Unusual Intermolecular “Through-Space” J Couplings in P–Se
Heterocycles
Paula Sanz Camacho,1 Kasun S. Athukorala Arachchige,1 Alexandra M. Z.
Slawin,1 Timothy F. G. Green,2 Jonathan R. Yates,2 Daniel M. Dawson,1 J.
Derek Woollins1,* and Sharon E. Ashbrook1,*
1
School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St
Andrews, Fife KY16 9ST UK
2
Department of Materials, University of Oxford, Oxford, OX1 3PH, UK
Supporting Information
S1. Experimental and theoretical methods
S2. Single crystal diffraction structures
S3. Full experimental 77Se NMR parameters
S4. 13C and 31P solid-state NMR and variable-temperature 77Se NMR
S5. DFT calculations and electronic coupling deformation density
S6. References
S1
S1. Experimental and theoretical methods
Unless otherwise stated all experiments were carried out under an oxygen- and
moisture-free nitrogen atmosphere using standard Schlenk techniques and glassware.
Reagents were obtained from commercial sources and used as received. Dry solvents were
collected from a MBraun solvent purification system. Elemental analyses were performed
by Stephen Boyer at the London Metropolitan University. Infrared spectra were recorded
for solids as KBr discs and oils on NaCl plates in the range 4000-300 cm–1 on a PerkinElmer System 2000 Fourier transform spectrometer. 1H and 13C solution-state NMR spectra
were recorded on a Bruker Avance 400 MHz spectrometer with chemical shifts (reported
in ppm) referenced to external (CH3)4Si or residual solvent peaks (CDCl3 δH = 7.26 ppm, δC
= 77.2 ppm).
77Se
and
31P
solution-state NMR spectra were recorded on a Jeol GSX 270
MHz spectrometer with chemical shifts (reported in ppm) referenced to external (CH 3)2Se
and 85% H3PO4, respectively. Assignments of
13C
and 1H NMR spectra were made with
the help of 1H-1H COSY and HSQC experiments. Coupling constants (J) are given in Hertz
(Hz). Electron ionisation (EI+) mass spectra were carried out by the EPSRC National Mass
Spectrometry Service, Swansea. The naphtho[1,8-cd]1,2-diselenole precursor was prepared
using the following standard literature procedures.S1
Naphtho[1,8-cd]1,2-diselenole tertbutylphosphine (1) : To a solution of naphtho[1,8cd]1,2-diselenole (2.0 g, 12 mmol) in THF (80 mL) was added dropwise a 1 M solution of
superhydride in THF (24 mL, 24 mmol). The mixture was stirred at room temperature for
15 min after which a solution of tertbutyldichlorophosphine (2.6 g, 16.4 mmol) in THF (15
mL) was added dropwise to the mixture. The resulting mixture was warmed to ∼66 °C
and left overnight. After the solvent was removed in vacuo, the reaction mixture was
extracted with hexane (250 mL), washed with distilled water (100 mL) and the organic
layer dried with magnesium sulfate and concentrated under reduced pressure. The
residue was passed through a shallow plug of dry silica and washed through with hexane
to afford the purified target compound as a brown-purple solid. Recrystallization of the
S2
target compound was obtained from hexane. (2.3 g, 48%); mp 85-88 °C; IR (KBr disk) : vmax
cm-1 : 2933s, 2852w, 2363s, 1655w, 1540s, 1455s, 1350s, 1192s, 804vs, 752vs, 565s, 439w,
420s; 1H {31P} NMR (400 MHz; CDCl3) ) δ (ppm) = 7.8 (dd, 3JHH = 7.2 Hz, 4JHH = 1.3 Hz, 2H,
Ar–H), 7.7 (dd, 3JHH = 8.3 Hz, 4JHH = 1.2 Hz, 2H, Ar–H), 7.3 (dd, 3JHH = 8.0 Hz, 3JHH = 7.3
Hz, 2H, Ar–H), 1.2 (s, 9H, 3  CH3); 13C {1H} NMR (100.6 MHz; CDCl3) δ (ppm): 134.9 (d, J
= 3.2 Hz, 2  Cq, Ar–C), 131.4 (d, J = 4.5 Hz, 2  CH, Ar–C), 130.2 (s, 2  CH, Ar–C), 125.5
(s, 2  CH, Ar–C), 124.8 (d, J = 10.6 Hz, 2  Cq, Ar–C), 38.4 (d, J = 44.3 Hz, Cq) 27.7 (d, J =
18.3 Hz, 3  CH3);
31P
{1H} NMR (109.4 MHz, CDCl3) δ (ppm)= 12.3 (t, 1J (31P,77Se) = 302
Hz); 77Se {1H} NMR (51.5 MHz, CDCl3) δ (ppm)= 210.2 (d, 1J (31P,77Se) = 302 Hz); MS (EI+):
m/z (%) 373.9 (15) [M+], 285.9 (85) [C10H6Se2+], 236.9 (100) [C10H6SeP], 205.6 (23) [C10H6Se],
126.0 (30) [C10H6], elemental analysis calculated (%) for C14H15PSe2 (372.16) : C 45.18, H
4.06. Found C 45.29, H 4.15.
Naphtho[1,8-cd]1,2-diselenole isopropylphosphine (2) : To a solution of naphtho[1,8cd]1,2-diselenole (2.0 g, 12.6 mmol) in THF (60 mL) was added dropwise a 1 M solution of
superhydride in THF (25.3 mL, 25.3 mmol). The mixture was stirred at room temperature
for 15 min, after which a solution of dicholoroisopropylphosphine (2.0 mL, 16.4 mmol) in
THF (10 mL) was added dropwise to the mixture. The resulting mixture was warmed to
∼66 °C and left overnight. After the solvent was removed in vacuo, the reaction mixture
was extracted with hexane (250 mL), washed with distilled water (100 mL) and the organic
layer dried with magnesium sulfate and concentrated under reduced pressure. Column
chromatography on silica gel (hexane) was performed to afford the purified target
compound as a brown-light solid. Recrystallization of the target compound was obtained
from hexane. (2.0 g, 45%); mp 83-91 °C; IR (KBr disk) : vmax cm-1 : 3422w, 2959w, 2854w,
1539w, 1487w, 1352w, 1191s, 1019w, 806vs, 750vs, 636w, 427s, 279w, 251s, 223s; 1H {31P}
NMR (400 MHz, CDCl3) δ (ppm) = 7.6 (m, 4H, Ar–H) 7.2 (dd, 3JHH = 7.1 Hz, 3JHH = 7.2 Hz,
2H, Ar–H) 1.8 (m, 1H, CH) 1.0 (d, J = 7.0 Hz , 2  CH3, 6H);
13C
{1H} NMR (100.6 MHz,
CDCl3) δ (ppm) = 135.1 (d, J = 3 Hz, Cq, Ar–C) 133.0 (d, J = 4.0 Hz, 2  CH, Ar–C) 130.6 (s,
2  CH, Ar–C) 129.5 (d, J = 3.6 Hz, Cq, Ar–C) 125.5 (s, 2  CH, Ar–C) 123.3 (d, J = 8.7 Hz,
S3
Cq, Ar–C) 30.2 (d, J = 35.3 Hz, CH) 19.3 (d, J = 21.9 Hz, 2  CH3);
31P
{1H} NMR (109.3
MHz, CDCl3) δ (ppm) = –3.4 (s, 1J (31P, 77Se) = 276 Hz); 77Se {1H} NMR (51.52 MHz, CDCl3)
δ (ppm) = 270.2 (s,1J (31P,
77Se)
= 276 Hz); MS (EI+): m/z (%) 359.9 (12) [M+], 285.8 (100)
[C10H6Se2+], 236.9 (82) [C10H6SeP], 205.9 (32) [C10H6Se], 126.0 (48) [C10H6]; elemental
analysis calculated (%) for C13H13PSe2 (358.14) : C 43.60, H 3.66. Found C 43.68, H 3.74.
Single crystal analysis
The X-ray crystal structure for compound 1 was determined at –148(1) °C using a
Rigaku MM007 high-brilliance RA generator (Mo Kα radiation, confocal optic) and Saturn
CCD system. At least a full hemisphere of data was collected using ω scans. Intensities
were corrected for Lorentz, polarization, and absorption. The X-ray crystal structure for
compound 2 was determined at –180(1) °C using a Rigaku MM007 high-brilliance RA
generator (Mo Kα radiation, confocal optic) and Mercury CCD system. At least a full
hemisphere of data was collected using ω scans. Intensities were corrected for Lorentz,
polarization, and absorption. Data for the complexes analyzed were collected and
processed using CrystalClear (Rigaku). Structures were solved by direct methods and
expanded using Fourier techniques. Non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were refined using the riding model. All calculations were performed
using the CrystalStructure crystallographic software package except for refinement, which
was performed using SHELXL-97. These X-ray data can be obtained free of charge via
ww.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax (+44) 1223-336-033; email:deposit@ccdc.cam.ac.uk. CCDC numbers 1057057 and 1057058.
Solid-state NMR measurements
Solid-state NMR measurements were performed using Bruker Avance III
spectrometers, operating at magnetic field strengths of 9.4, 14.1 and 20.0 T. Experiments
S4
were carried out using conventional 4- or 2.5-mm MAS probes, with MAS rates between 5
and 12.5 kHz. Detailed parameters for each of the spectra obtained are given in Table S1.1.
For 13C, transverse magnetization was obtained by cross-polarization (CP) from 1H using
ramped contact pulse durations of 5-10 ms, and two-pulse phase modulation (TPPM) 1H
decoupling during acquisition, in experiments carried out at 14.1 T. Chemical shifts are
quoted in ppm relative to (CH3)4Si at 0 ppm, using the CH3 resonance of L-alanine at 20.5
ppm as a secondary reference. For
31P,
MAS NMR spectra were acquired at 14.1 T, with
parameters given in Table S1.1. Chemical shifts are shown referenced relative to 85%
H3PO4 (aq) at 0 ppm, using BPO4 at –29.6 ppm as a secondary reference. For 77Se, CP MAS
experiments (using ramped contact pulse durations of 5-8 ms and TPPM 1H decoupling)
were carried out at 9.4, 14.1 and 20.0 T. Chemical shifts are referenced relative to (CH3)2Se
at 0 ppm, using the isotropic resonance of solid H2SeO3 at 1288.1 ppm as a secondary
reference. The position of the isotropic resonances within the spinning sideband patterns
were unambiguously determined by recording a second spectrum at a different MAS rate.
In some cases, spectra were also acquired with additional
decoupling. Experimental
77Se
31P
continuous wave (CW)
NMR parameters were determined by lineshape analysis
using Bruker Topspin software.
For controlled-temperature experiments between 0 and 50 C, recorded at 9.4 and
14.1 T, the sample temperature was controlled using a Bruker BCU-II chiller and Bruker
BVT/BVTB-3000 temperature controller and heater booster. The sample temperature
(including frictional heating effects arising from sample spinning) was calibrated using the
isotropic
87Rb
shift of solid RbCl, as described by Skibsted and Jakobsen.S2 The chemical
shift referencing for
87Rb
was relative to 0.01 M RbCl in D2O (the standard chemical shift
reference), rather than the 1 M RbCl in D2O reported by Skibsted and Jakobsen. However,
owing to a 4.85 ppm shift difference between the two concentrations (corresponding to a
temperature difference of ~134 K according to equation 1 of Ref. S1), using the more dilute
solution as a reference gave shifts for solid RbCl corresponding to significantly more
S5
realistic temperatures (i.e., within the operating range of the chiller), using equation 1 of
Ref. S1.
S6
Table S1.1 Experimental parameters (magnetic field strength, B0, MAS rate, CP contact
pulse duration, decoupling, number of transients averaged and recycle interval) for solidstate NMR experiments for compounds 1 and 2.
B0 /
Rotor size
MAS rate
Contact
T
/ mm
/ kHz
time / ms
Decoupling
Number of
Recycle
transients
interval / s
4096
3
8
30
1 Naphtho[1,8-cd]1,2-diselenole tertbutylphosphine
13C
14.1
4
12.5
10
31P
14.1
4
12.5
-
77Se
9.4
4
5
8
1H
TPPM
1872
3
14.1
4
12.5
8
1H
TPPM
23328
3
1H
TPPM
26400
3
15168
3
1024
10
8
30
14.1
4
12.5
8
20.0
2.5
12.5
5
1H
TPPM
-
31P
1H
CW
TPPM
2 Naphtho[1,8-cd]1,2-diselenole isopropylphosphine
13C
14.1
4
12.5
5
31P
14.1
4
12.5
-
77Se
9.4
4
5
8
1H
TPPM
5248
10
14.1
4
12.5
8
1H
TPPM
336
10
1H
TPPM
7880
10
17440
3
14.1
4
12.5
8
20.0
2.5
12.5
5
1H
TPPM
-
31P
1H
S7
CW
TPPM
Computational detail
The calculations of J-coupling were performed with the ultrasoft PAW J-coupling
methodS3 implemented in CASTEP 8.0S4 using the PBES5 functional to describe electronic
exchange-correlation, a planewave basis set described by a 50 Ry cut-off energy, a 2  2  2
k-point grid and a fine grid scale four times that of the standard grid scale. The default onthe-fly pseudopotential set was used, with both a Schrödinger (non-relativistic) and a
ZORA (scalar-relativistic) atomic solver used to generate the isolated atomic solutions. S6
The latter calculations include the effects of special relativity at the scalar-relativistic
ZORA level of theory. Prior to calculation of the J couplings the positions of the atoms
were optimized to minimise forces on the atoms, keeping the unit cell fixed. Calculations
were performed on the ARCHER UK National Supercomputing Service, supported by the
UK Car-Parrinello consortium (UKCP).
S8
S2. Single crystal diffraction structures
Compound 1
Data collection
A colorless platelet crystal of C14H15PSe2 having approximate dimensions of 0.12 
0.06  0.03 mm was mounted in a loop. All measurements were made on a Rigaku
Saturn70 diffractometer using graphite monochromated Mo-K radiation. The crystal-todetector distance was 40.00 mm.
Cell constants and an orientation matrix for data collection corresponded to a
primitive triclinic cell with dimensions:
a = 7.3880(15) Å
 = 107.355(8)°
b = 10.3745(19) Å
 = 107.255(8)°
c = 10.8099(19) Å
 = 106.126(8)°
V = 691.6(2) Å3
For Z = 2 and F.W. = 372.17, the calculated density is 1.787 g cm–3. Based on a statistical
analysis of intensity distribution, and the successful solution and refinement of the
structure, the space group was determined to be: P–1 (#2)
The data were collected at a temperature of –148 ± 1 °C to a maximum 2 value of
50.7°. A total of 315 oscillation images were collected. A sweep of data was done using 
scans from –100.0 to 80.0° in 1.00° steps, at  = 42.0° and  = 0.0°. The exposure rate was
40.0 [s/°]. The detector swing angle was –10.00°. A second sweep was performed using 
scans from –35.0 to 70.0° in 1.00° steps, at  = 42.0° and  = 240.0°. The exposure rate was
40.0 [s/°]. The detector swing angle was –10.00°. Another sweep was performed using 
scans from –20.0 to 10.0° in 1.00° steps, at  = 0.0° and  = 120.0°. The exposure rate was
40.0 [s/°]. The detector swing angle was –10.00. The crystal-to-detector distance was 40.00
mm. Readout was performed in the 0.070 mm pixel mode.
S9
Data reduction
Of the 5346 reflections were collected, where 2422 were unique (Rint = 0.0356);
equivalent reflections were merged. Data were collected and processed using CrystalClear
(Rigaku).S7 The linear absorption coefficient, , for Mo-K radiation is 54.378 cm–1. An
empirical absorption correction was applied which resulted in transmission factors
ranging from 0.629 to 0.849. The data were corrected for Lorentz and polarization effects.
Structure solution and refinement
The structure was solved by direct methodsS8 and expanded using Fourier
techniques. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were
refined using the riding model. The final cycle of full-matrix least-squares refinementF1 on
F2 was based on 2422 observed reflections and 154 variable parameters and converged
(largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement
factors of:
R1 =  ||Fo| – |Fc|| /  |Fo| = 0.0326
wR2 = [ ( w (Fo2 – Fc2)2)/  w(Fo2)2]1/2 = 0.0707
The goodness of fitF2 was 0.98. Unit weights were used. Plots of  w (|Fo| – |Fc|)2
versus |Fo|, reflection order in data collection, sin / and various classes of indices
showed no unusual trends. The maximum and minimum peaks on the final difference
Fourier map corresponded to 0.51 and –0.66 e Å–3, respectively.
Neutral atom scattering factors were taken from International Tables for
Crystallography (IT), Vol. C, Table 6.1.1.4.S9 Anomalous dispersion effects were included
in Fcalc;S10 the values for f' and f" were those of Creagh and McAuley.S11 The values for
the mass attenuation coefficients are those of Creagh and Hubbell.S12 All calculations were
performed using the CrystalStructureS13 crystallographic software package except for
S10
refinement, which was performed using SHELXL2013.S8
Compound 1
ORTEP at 50%
S11
Experimental details
A. Crystal data
Empirical Formula
C14H15PSe2
Formula Weight
372.17
Crystal Color, Habit
colorless, platelet
Crystal Dimensions
0.12  0.06  0.03 mm
Crystal System
triclinic
Lattice Type
Primitive
Lattice Parameters
a = 7.3880(15) Å
b = 10.3745(19) Å
c = 10.8099(19) Å
 = 107.355(8)°
 = 107.255(8)°
 = 106.126(8)°
V = 691.6(2) Å3
Space Group
P–1 (#2)
Z value
2
Dcalc
1.787 g cm–3
F000
364.00
(MoK)
54.378 cm–1
B. Intensity measurements
Diffractometer
Saturn70
Radiation
MoK ( = 0.71075 Å)
Voltage, Current
50 kV, 40 mA
Temperature
–148.0 °C
Detector Aperture
70.0  70.0 mm
Data Images
315 exposures
S12
 Oscillation Range ( = 42.0,  = 0.0)
–100.0 - 80.0°
Exposure Rate
40.0 s/°
Detector Swing Angle
–10.00°
 Oscillation Range ( = 42.0,  = 240.0)
–35.0 - 70.0°
Exposure Rate
40.0 s/°
Detector Swing Angle
–10.00°
 Oscillation Range ( = 0.0,  = 120.0)
–20.0 - 10.0°
Exposure Rate
40.0 s/°
Detector Swing Angle
–10.00°
Detector Position
40.00 mm
Pixel Size
0.070 mm
2max
50.0°
No. of Reflections Measured
Total: 5346
Unique: 2422 (Rint = 0.0356)
Corrections
Lorentz-polarization
Absorption
(trans. factors: 0.629 - 0.849)
C. Structure solution and refinement
Structure Solution
Direct Methods (SHELXS97)
Refinement
Full-matrix least-squares on F2
Function Minimized
 w (Fo2 – Fc2)2
Least Squares Weights
w = 1/ [2(Fo2) + (0.0267 . P)2 + 0.6478 . P]
where P = (Max(Fo2,0) + 2Fc2)/3
2max cutoff
50.0°
Anomalous Dispersion
All non-hydrogen atoms
No. Observations (All reflections)
2422
No. Variables
154
Reflection/Parameter Ratio
15.73
S13
Residuals: R1 (I > 2.00 (I))
0.0326
Residuals: R (All reflections)
0.0481
Residuals: wR2 (All reflections)
0.0707
Goodness of Fit Indicator
0.983
Max Shift/Error in Final Cycle
0.000
Maximum Peak in Final Diff. Map
0.51 e/Å–3
Minimum Peak in Final Diff. Map
–0.66 e/Å–3
Table S2.1. Atomic coordinates and Biso/Beq
atom
x
y
z
Beq
Se1
Se2
P1
C1
C2
C3
0.42240(7)
0.86228(6)
0.73444(17)
0.3163(7)
0.1041(7)
–0.0106(7)
0.87759(5)
0.95971(4)
0.87350(12)
0.7949(5)
0.7219(5)
0.6718(5)
0.31426(4)
0.26088(4)
0.39670(11)
0.1103(4)
0.0479(5)
–0.0986(5)
2.047(11)
1.774(10)
1.65(2)
1.73(7)
2.37(8)
2.57(9)
C4
C5
C6
C7
C8
C9
C10
C11
C12
0.0896(7)
0.3065(7)
0.4040(7)
0.6127(7)
0.7319(7)
0.6465(7)
0.4270(7)
0.6973(7)
0.5827(8)
0.6948(5)
0.7637(5)
0.7817(5)
0.8411(5)
0.8845(4)
0.8745(4)
0.8138(4)
0.6749(4)
0.6140(5)
–0.1815(4)
–0.1245(4)
–0.2166(4)
–0.1666(4)
–0.0233(4)
0.0718(4)
0.0241(4)
0.3367(4)
0.4174(5)
2.23(8)
1.79(7)
2.05(8)
2.17(8)
1.80(7)
1.66(7)
1.58(7)
1.78(7)
2.70(9)
C13
C14
0.5817(7)
0.9158(7)
0.5823(5)
0.6786(5)
0.1777(4)
0.3894(4)
2.03(8)
2.36(8)
Beq = 8/3 2(U11(aa*)2 + U22(bb*)2 + U33(cc*)2 + 2 U12(aa*bb*)cos  + 2 U13(aa*cc*)cos  + 2 U23(bb*cc*)cos )
S14
Table S2.2. Atomic coordinates and Biso involving hydrogen atoms
atom
x
y
z
Biso
H2
H3
H4
H6
H7
H8
H12A
0.03338
–0.15704
0.01164
0.32190
0.67732
0.87828
0.66033
0.70504
0.62216
0.66386
0.75180
0.85299
0.92250
0.67559
0.10575
–0.13933
–0.28022
–0.31450
–0.22881
0.01005
0.51980
2.846
3.081
2.673
2.464
2.608
2.157
3.236
H12B
H12C
H13A
H13B
H13C
H14A
H14B
H14C
0.44445
0.57014
0.44212
0.65591
0.57224
0.98866
0.90749
0.99116
0.61493
0.51270
0.58091
0.62477
0.48141
0.73879
0.57804
0.72140
0.38609
0.39792
0.14541
0.12825
0.15657
0.49229
0.36903
0.34071
3.236
3.236
2.437
2.437
2.437
2.831
2.831
2.831
S15
Table S2.3. Anisotropic displacement parameters
atom U11
U22
U33
U12
U13
U23
Se1
Se2
P1
C1
C2
C3
C4
0.0235(3)
0.0174(3)
0.0196(6)
0.020(3)
0.019(3)
0.016(3)
0.028(3)
0.0352(3)
0.0236(3)
0.0228(6)
0.023(2)
0.036(3)
0.032(3)
0.027(3)
0.0242(2)
0.0237(2)
0.0198(5)
0.025(2)
0.038(3)
0.040(3)
0.026(2)
0.0160(2)
0.0055(2)
0.0089(5)
0.013(2)
0.014(2)
0.010(2)
0.017(2)
0.0136(2)
0.00734(18)
0.0081(5)
0.0090(19)
0.014(2)
0.004(2)
0.005(2)
0.01129(19)
0.01006(18)
0.0079(5)
0.0101(18)
0.014(2)
0.010(2)
0.0068(19)
C5
C6
C7
C8
C9
C10
C11
C12
C13
0.022(3)
0.033(3)
0.039(3)
0.021(2)
0.025(3)
0.023(3)
0.026(3)
0.041(3)
0.029(3)
0.024(2)
0.026(3)
0.028(3)
0.021(2)
0.020(2)
0.016(2)
0.022(2)
0.033(3)
0.019(2)
0.025(2)
0.020(2)
0.026(2)
0.028(2)
0.024(2)
0.020(2)
0.019(2)
0.033(3)
0.025(2)
0.015(2)
0.017(2)
0.019(2)
0.008(2)
0.013(2)
0.010(2)
0.010(2)
0.013(2)
0.008(2)
0.0084(19)
0.009(2)
0.019(2)
0.0124(19)
0.0103(19)
0.0069(18)
0.0091(18)
0.019(2)
0.010(2)
0.0088(18)
0.0076(18)
0.015(2)
0.0113(19)
0.0113(18)
0.0056(17)
0.0083(18)
0.018(2)
0.0082(18)
C14
0.032(3)
0.025(3)
0.029(2)
0.014(2)
0.007(2)
0.0097(19)
The general temperature factor expression: exp(–2 (a* U11h
+ b* U22k
+ c* U33l
+ 2a*b*U12hk +
2a*c*U13hl + 2b*c*U23kl))
Table S2.4. Bond lengths (Å)
atom
atom
distance
atom
atom
distance
Se1
Se2
P1
C1
C3
C5
C6
C8
C11
P1
P1
C11
C10
C4
C6
C7
C9
C12
2.2291(15)
2.2326(15)
1.878(5)
1.431(7)
1.352(8)
1.417(8)
1.352(7)
1.369(7)
1.532(8)
Se1
Se2
C1
C2
C4
C5
C7
C9
C11
C1
C9
C2
C3
C5
C10
C8
C10
C13
1.919(4)
1.925(4)
1.377(6)
1.402(6)
1.405(6)
1.428(5)
1.390(6)
1.427(6)
1.514(5)
C11
C14
1.529(7)
S16
Table S2.5. Bond lengths involving hydrogens (Å)
atom
atom
distance
atom
atom
distance
C2
C4
C7
C12
C12
C13
C14
H2
H4
H7
H12A
H12C
H13B
H14A
0.950
0.950
0.950
0.980
0.980
0.980
0.980
C3
C6
C8
C12
C13
C13
C14
H3
H6
H8
H12B
H13A
H13C
H14B
0.950
0.950
0.950
0.980
0.980
0.980
0.980
C14
H14C
0.980
Table S2.6. Bond angles (°)
atom
atom
atom
angle
atom
atom
atom
angle
P1
Se1
Se2
Se1
P1
P1
C1
Se2
C11
107.40(16)
98.87(6)
106.74(17)
P1
Se1
Se1
Se2
P1
C1
C9
C11
C2
108.58(15)
107.36(14)
111.6(4)
Se1
C1
C3
C4
C5
C7
Se2
C1
C5
C1
C2
C4
C5
C6
C8
C9
C10
C10
C10
C3
C5
C10
C7
C9
C10
C5
C9
128.0(3)
121.8(5)
121.4(4)
120.4(5)
120.7(4)
122.6(4)
130.1(4)
117.0(4)
116.8(4)
C2
C2
C4
C6
C6
Se2
C8
C1
P1
C1
C3
C5
C5
C7
C9
C9
C10
C11
C10
C4
C6
C10
C8
C8
C10
C9
C12
120.0(4)
119.3(4)
119.1(4)
120.5(4)
119.4(5)
109.8(3)
120.0(4)
126.2(4)
105.2(3)
P1
C12
C13
C11
C11
C11
C13
C13
C14
115.4(4)
111.0(3)
110.4(4)
P1
C12
C11
C11
C14
C14
105.1(3)
109.4(4)
S17
Table S2.7. Bond angles involving hydrogens (°)
atom
atom
atom
angle
atom
atom
atom
angle
C1
C2
C3
C5
C6
C7
C11
C2
C3
C4
C6
C7
C8
C12
H2
H3
H4
H6
H7
H8
H12A
119.1
120.4
119.3
119.7
120.3
118.7
109.5
C3
C4
C5
C7
C8
C9
C11
C2
C3
C4
C6
C7
C8
C12
H2
H3
H4
H6
H7
H8
H12B
119.1
120.4
119.3
119.7
120.3
118.7
109.5
C11
H12A
C11
C11
H13A
C11
C11
H14A
C12
C12
C13
C13
C13
C14
C14
C14
H12C
H12C
H13A
H13C
H13C
H14A
H14C
H14C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
H12A
H12B
C11
H13A
H13B
C11
H14A
H14B
C12
C12
C13
C13
C13
C14
C14
C14
H12B
H12C
H13B
H13B
H13C
H14B
H14B
H14C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
S18
Table S2.8. Torsion angles (°)
atom1 atom2 atom3 atom4 angle
atom1 atom2 atom3 atom4 angle
P1
C1
P1
C9
Se1
Se1
Se2
Se1
Se1
Se2
Se2
P1
P1
P1
C1
P1
C9
P1
C11
C11
C11
C2
Se2
C8
Se1
C12
C14
C13
148.1(3)
45.43(15)
–160.1(2)
–39.65(17)
–67.3(2)
177.23(18)
–49.8(3)
P1
C1
P1
C9
Se1
Se2
Se2
Se1
Se1
Se2
Se2
P1
P1
P1
C1
P1
C9
P1
C11
C11
C11
C10
C11
C10
C11
C13
C12
C14
–38.6(4)
–65.31(16)
22.9(4)
71.59(17)
55.4(3)
–172.51(15)
72.0(2)
Se1
Se1
C2
C1
C3
C4
C4
C6
C5
C1
C1
C1
C2
C4
C5
C5
C5
C6
C2
C10
C10
C3
C5
C6
C10
C10
C7
C3
C9
C9
C4
C6
C7
C9
C9
C8
170.3(3)
13.3(7)
–173.9(4)
0.3(8)
178.4(4)
–176.8(4)
176.4(4)
–3.2(7)
0.1(7)
Se1
C2
C10
C2
C3
C4
C6
C10
C6
C1
C1
C1
C3
C4
C5
C5
C5
C7
C10
C10
C2
C4
C5
C10
C10
C6
C8
C5
C5
C3
C5
C10
C1
C1
C7
C9
–168.4(3)
4.4(7)
–3.6(8)
2.1(8)
–1.2(7)
–2.0(7)
178.4(4)
2.7(7)
–2.4(7)
C7
Se2
C8
C8
C9
C9
C9
C10
C10
Se2
C1
C1
–175.5(4)
–4.2(7)
179.2(4)
C7
Se2
C8
C8
C9
C9
C9
C10
C10
C10
C5
C5
1.8(7)
177.6(3)
1.0(6)
Torsion angles > 160° and <120° are excluded
Table S2.9. Intramolecular contacts less than 3.60 Å
atom
atom
distance
atom
atom
distance
Se1
Se2
C1
C2
C5
C7
C10
C9
C1
C4
C5
C8
C10
C13
3.488(5)
3.529(4)
2.789(6)
2.770(8)
2.756(6)
2.833(8)
3.551(7)
Se1
Se2
C1
C3
C6
C9
C12
C13
C13
C10
C9
C13
3.599(6)
3.567(4)
3.428(8)
2.833(6)
2.792(6)
3.510(7)
S19
Table S2.10. Intramolecular contacts less than 3.60 Å involving hydrogen
atom
atom
distance
atom
atom
distance
Se1
Se1
Se2
P1
P1
P1
C1
H2
H13A
H13B
H12A
H13A
H14A
H3
2.727
3.143
3.040
2.779
3.036
2.778
3.280
Se1
Se2
Se2
P1
P1
P1
C1
H12B
H8
H14C
H12B
H13B
H14C
H13A
3.080
2.666
3.140
2.877
3.020
2.868
2.715
C1
C2
C4
C5
C6
C8
C9
C10
C10
H13B
H13A
H6
H7
H8
H13B
H13A
H2
H6
3.438
3.298
2.602
3.268
3.216
3.549
3.435
3.287
3.324
C2
C4
C5
C6
C8
C9
C9
C10
C10
H4
H2
H3
H4
H6
H7
H13B
H4
H8
3.236
3.227
3.263
2.592
3.228
3.270
2.848
3.311
3.275
C10
C12
C12
C12
C13
C13
C13
C14
C14
C14
H13A
H13A
H13C
H14B
H12A
H12C
H14B
H12A
H12C
H13B
3.086
2.689
2.710
2.701
3.351
2.703
2.690
2.668
2.699
2.686
C10
C12
C12
C12
C13
C13
C13
C14
C14
C14
H13B
H13B
H14A
H14C
H12B
H14A
H14C
H12B
H13A
H13C
3.163
3.354
2.665
3.347
2.703
3.342
2.690
3.346
3.345
2.686
H2
H3
H6
H12A
H12A
H12A
H12B
H12B
H12C
H3
H4
H7
H13A
H14A
H14C
H13B
H14A
H13A
2.344
2.298
2.302
3.581
2.462
3.558
3.589
3.556
2.973
H2
H4
H7
H12A
H12A
H12B
H12B
H12B
H12C
H13A
H6
H8
H13C
H14B
H13A
H13C
H14B
H13B
3.561
2.402
2.326
3.597
2.970
2.513
3.005
3.598
3.600
H12C
H13C
2.537
H12C
H14A
2.962
S20
H12C
H14B
2.533
H12C
H14C
3.598
H13A
H13B
H13B
H13C
H14B
H14A
H14C
H14B
3.583
3.577
2.507
2.507
H13A
H13B
H13C
H13C
H14C
H14B
H14A
H14C
3.583
2.974
3.577
2.975
Table S2.11. Intermolecular contacts less than 3.60 Å
atom
atom
distance
atom
atom
distance
Se2
P1
C3
C7
C8
C10
C13
P11
P11
C83
C12
C34
C72
C136
3.5135(12)
3.5857(15)
3.366(8)
3.500(7)
3.366(8)
3.583(7)
3.365(6)
P1
C1
C5
C7
C9
C12
Se21
C72
C92
C102
C52
C125
3.5135(12)
3.500(7)
3.524(7)
3.583(7)
3.524(7)
3.535(8)
Symmetry operators:
(1) –X+2, –Y+2, –Z+1
(3) X–1, Y, Z
(5) –X+1, –Y+1, –Z+1
(2) –X+1, –Y+2, –Z
(4) X+1, Y, Z
(6) –X+1, –Y+1, –Z
S21
Table S2.12. Intermolecular contacts less than 3.60 Å involving hydrogens
atom
atom
distance
atom
atom
distance
Se1
Se2
Se2
P1
C2
C3
C3
H71
H23
H74
H14A5
H82
H72
H12B6
3.390
3.444
3.591
3.591
3.052
3.591
3.473
Se1
Se2
Se2
C1
C2
C3
C3
H14C2
H61
H14A5
H71
H14C2
H82
H13A6
3.287
3.583
3.079
3.474
3.505
2.959
3.302
C4
C4
C5
C6
C6
C7
C7
C8
C8
H13C7
H14B7
H14B7
H13C7
H14B7
H84
H12C7
H23
H84
3.477
2.960
3.297
3.026
3.354
3.413
3.364
3.519
2.951
C4
C5
C6
C6
C7
C7
C7
C8
C8
H14A8
H13C7
H12C7
H14A8
H33
H12A9
H13C7
H33
H13C7
3.576
2.883
3.191
3.492
3.223
3.483
3.292
3.077
3.407
C9
C12
C12
C13
C13
C14
C14
H2
H2
H13C7
H36
H12A11
H36
H13B7
H23
H610
C82
H82
3.350
3.263
3.414
3.086
2.976
3.490
3.378
3.519
3.098
C10
C12
C12
C13
C13
C14
H2
H2
H2
H13C7
H410
H12C11
H13A7
H13C7
H410
Se22
C142
H13A6
3.105
3.596
3.012
3.323
3.241
3.488
3.444
3.490
3.501
H2
H3
H3
H3
H3
H3
H3
H4
H4
H4
H13B2
C72
C126
H72
H12B6
H13A6
H13C6
C148
H12B6
H14A8
2.786
3.223
3.263
3.237
2.738
2.500
2.883
3.488
3.369
2.765
H2
H3
H3
H3
H3
H3
H4
H4
H4
H4
H14C2
C82
C136
H82
H12C6
H13B2
C128
H12A8
H12C8
H14B8
2.611
3.077
3.086
2.946
3.053
3.553
3.596
2.903
3.518
3.411
S22
H4
H14B7
2.704
H6
Se21
3.583
H6
H6
H6
H7
H7
H7
H7
H8
H8
H8
C148
H13C7
H14B8
Se11
C11
H33
H12A9
C23
C74
H23
3.378
3.479
3.372
3.390
3.474
3.237
2.734
3.052
3.413
3.098
H6
H6
H6
H7
H7
H7
H7
H8
H8
H8
H12C7
H14A8
H14B7
Se24
C33
H84
H12C7
C33
C84
H33
3.024
2.653
3.148
3.591
3.591
3.108
3.332
2.959
2.951
2.946
H8
H12A
H12A
H12A
H12A
H12B
H12B
H12C
H12C
H74
C712
H410
H12A11
H12C11
H36
H12A11
C67
C1211
3.108
3.483
2.903
3.570
2.756
2.738
3.423
3.191
3.012
H8
H12A
H12A
H12A
H12B
H12B
H12B
H12C
H12C
H84
C1211
H712
H12B11
C36
H46
H12C11
C77
H36
2.168
3.414
2.734
3.423
3.473
3.369
3.022
3.364
3.053
H12C
H12C
H12C
H13A
H13A
H13A
H13A
H13B
H13B
H410
H77
H12B11
C36
H26
H13A7
H13C7
H23
H13A7
3.518
3.332
3.022
3.302
3.501
3.560
3.096
2.786
2.817
H12C
H12C
H12C
H13A
H13A
H13A
H13B
H13B
H13B
H67
H12A11
H12C11
C137
H36
H13B7
C137
H33
H13B7
3.024
2.756
2.751
3.323
2.500
2.817
2.976
3.553
2.883
H13B
H13C
H13C
H13C
H13C
H13C
H13C
H14A
H14A
H14A
H13C7
C57
C77
C97
C137
H67
H13B7
Se25
C410
H410
2.720
2.883
3.292
3.350
3.241
3.479
2.720
3.079
3.576
2.765
H13C
H13C
H13C
H13C
H13C
H13C
H13C
H14A
H14A
H14A
C47
C67
C87
C107
H36
H13A7
H13C7
P15
C610
H610
3.477
3.026
3.407
3.105
2.883
3.096
3.407
3.591
3.492
2.653
S23
H14B
C47
2.960
H14B
C57
3.297
H14B
H14B
H14B
H14C
C67
H47
H67
C23
3.354
2.704
3.148
3.505
H14B
H14B
H14C
H14C
H410
H610
Se13
H23
3.411
3.372
3.287
2.611
Symmetry operators:
(1) –X+1, –Y+2, –Z
(3) X+1, Y, Z
(5) –X+2, –Y+2, –Z+1
(2) X–1, Y ,Z
(4) –X+2, –Y+2, –Z
(6) –X, –Y+1, –Z
(7) –X+1, –Y+1, –Z
(9) X, Y, Z–1
(11) –X+1, –Y+1, –Z+1
(8) X–1, Y, Z–1
(10) X+1, Y, Z+1
(12) X, Y, Z+1
S24
Compound 2
Data collection
A purple block crystal of C13H13PSe2 having approximate dimensions of 0.18  0.15
 0.05 mm was mounted in a loop. All measurements were made on a Rigaku Mercury70
diffractometer using filtered Mo-K radiation. The crystal-to-detector distance was 40.00
mm.
Cell constants and an orientation matrix for data collection corresponded to a
primitive triclinic cell with dimensions:
a = 7.6709(17) Å
 = 106.421(8)°
b = 9.404(2) Å
 = 104.690(7)°
c = 10.484(2) Å
 = 106.308(8)°
V = 649.1(3) Å3
For Z = 2 and F.W. = 358.14, the calculated density is 1.832 g cm–3. Based on a statistical
analysis of intensity distribution, and the successful solution and refinement of the
structure, the space group was determined to be: P–1 (#2)
The data were collected at a temperature of –180 ± 1 °C to a maximum 2 value of
50.7°. A total of 278 oscillation images were collected. A sweep of data was done using 
scans from –100.0 to 80.0° in 1.00° steps, at  = 0.0° and  = 0.0°. The exposure rate was 6.0
[s/°]. The detector swing angle was –10.00°. A second sweep was performed using  scans
from –26.0 to 23.0° in 1.00° steps, at  = –90.0° and  = 0.0°. The exposure rate was 6.0 [s/°].
The detector swing angle was –10.00°. Another sweep was performed using  scans from
–26.0 to 23.0° in 1.00° steps, at  = 90.0° and  = 90.0°. The exposure rate was 6.0 [s/°]. The
detector swing angle was –10.00. The crystal-to-detector distance was 40.00 mm. Readout
was performed in the 0.136 mm pixel mode.
Data reduction
S25
Of the 4193 reflections were collected, where 2322 were unique (Rint = 0.0281);
equivalent reflections were merged. Data were collected and processed using CrystalClear
(Rigaku).S7 The linear absorption coefficient, , for Mo-K radiation is 57.896 cm–1. An
empirical absorption correction was applied which resulted in transmission factors
ranging from 0.429 to 0.749. The data were corrected for Lorentz and polarization effects.
Structure solution and refinement
The structure was solved by direct methods and expanded using Fourier
techniques. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were
refined using the riding model. The final cycle of full-matrix least-squares refinementF1 on
F2 was based on 2221 observed reflections and 145 variable parameters and converged
(largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement
factors of:
R1 =  ||Fo| – |Fc|| /  |Fo| = 0.0294
wR2 = [ ( w (Fo2 – Fc2)2)/  w(Fo2)2]1/2 = 0.0467
The goodness of fitF2 was 0.95. Unit weights were used. Plots of  w (|Fo| – |Fc|)2
versus |Fo|, reflection order in data collection, sin / and various classes of indices
showed no unusual trends. The maximum and minimum peaks on the final difference
Fourier map corresponded to 0.37 and –0.38 e Å–3, respectively.
Neutral atom scattering factors were taken from International Tables for
Crystallography (IT), Vol. C, Table 6.1.1.4.S9 Anomalous dispersion effects were included
in Fcalc;S10 the values for f' and f" were those of Creagh and McAuley.S11 The values for
the mass attenuation coefficients are those of Creagh and Hubbell.S12 All calculations were
performed using the CrystalStructureS13 crystallographic software package except for
refinement, which was performed using SHELXL2013.S14
S26
Compound 2
ORTEP at 50%
S27
Experimental details
A. Crystal data
Empirical Formula
C13H13PSe2
Formula Weight
358.14
Crystal Color, Habit
purple, block
Crystal Dimensions
0.18  0.15  0.05 mm
Crystal System
triclinic
Lattice Type
Primitive
Lattice Parameters
a = 7.6709(17) Å
b = 9.404(2) Å
c = 10.484(2) Å
 = 106.421(8)°
 = 104.690(7)°
 = 106.308(8)°
V = 649.1(3) Å3
Space Group
P–1 (#2)
Z value
2
Dcalc
1.832 g cm–3
F000
348.00
(MoK)
57.896 cm–1
B. Intensity measurements
Diffractometer
Mercury70
Radiation
MoK ( = 0.71075 Å)
Voltage, Current
50 kV, 16 mA
Temperature
–180.0 °C
Detector Aperture
70.0  70.0 mm
Data Images
278 exposures
S28
 Oscillation Range ( = 0.0,  = 0.0)
0.0 - 180.0°
Exposure Rate
6.0 s/°
Detector Swing Angle
–10.00°
 Oscillation Range ( = –90.0,  = 0.0)
–26 - 23.0°
Exposure Rate
6.0 s/°
Detector Swing Angle
–10.00°
 Oscillation Range ( = –90.0,  = 90.0)
–26 - 23.0°
Exposure Rate
6.0 s/°
Detector Swing Angle
–10.00°
Detector Position
40.00 mm
Pixel Size
0.136 mm
2max
50.0°
No. of Reflections Measured
Total: 4082
Unique: 2221 (Rint = 0.0281)
Corrections
Lorentz-polarization
Absorption
(trans. factors: 0.429 - 0.749)
C. Structure solution and refinement
Structure Solution
Direct Methods (SHELXS97)
Refinement
Full-matrix least-squares on F2
Function Minimized
 w (Fo2 – Fc2)2
Least Squares Weights
w = 1/ [2(Fo2) + (0.0141 . P)2 + 0.000 . P]
where P = (Max(Fo2,0) + 2Fc2)/3
2max cutoff
50.0°
Anomalous Dispersion
All non-hydrogen atoms
No. Observations (All reflections)
2221
No. Variables
145
S29
Reflection/Parameter Ratio
15.32
Residuals: R1 (I > 2.00 (I))
0.0294
Residuals: R (All reflections)
0.0430
Residuals: wR2 (All reflections)
0.0467
Goodness of Fit Indicator
0.949
Max Shift/Error in Final Cycle
0.000
Maximum Peak in Final Diff. Map
0.37 e/Å–3
Minimum Peak in Final Diff. Map
–0.38 e/Å–3
Table S2.13. Atomic coordinates and Biso/Beq
atom
Se1
Se2
P1
C1
C2
x
0.33565(5)
0.00392(4)
0.31501(12)
0.2608(4)
0.3573(4)
y
0.85913(4)
0.95468(4)
1.07371(10)
0.7008(4)
0.5974(4)
z
0.53840(3)
0.66117(3)
0.68501(9)
0.6178(3)
0.5990(3)
Beq
1.832(9)
1.861(9)
1.646(17)
1.18(6)
1.63(6)
C3
C4
C5
C6
C7
C8
C9
C10
C11
0.3166(4)
0.1806(4)
0.0811(4)
–0.0585(4)
–0.1598(5)
–0.1254(4)
0.0068(4)
0.1167(4)
0.4521(4)
0.4651(4)
0.4378(4)
0.5423(4)
0.5072(4)
0.6011(4)
0.7370(4)
0.7756(4)
0.6766(4)
1.0895(4)
0.6368(3)
0.6984(3)
0.7233(3)
0.7887(3)
0.8138(4)
0.7776(3)
0.7128(3)
0.6827(3)
0.8648(3)
1.66(6)
1.67(6)
1.41(6)
1.91(7)
2.22(7)
1.82(7)
1.41(6)
1.12(6)
1.51(6)
C12
C13
0.4170(5)
0.6686(4)
1.2127(4)
1.1414(4)
0.9753(3)
0.8873(3)
2.70(8)
2.72(8)
Beq = 8/3 2(U11(aa*)2 + U22(bb*)2 + U33(cc*)2 + 2 U12(aa*bb*)cos  + 2 U13(aa*cc*)cos  + 2 U23(bb*cc*)cos )
S30
Table S2.14. Atomic coordinates and Biso involving hydrogen atoms
atom
x
y
z
Biso
H2
H3
H4
H6
H7
H8
H11
0.45513
0.38290
0.15253
–0.08026
–0.25437
–0.19520
0.40494
0.61744
0.39428
0.34764
0.41665
0.57578
0.80399
0.98296
0.55875
0.61995
0.72483
0.81482
0.85593
0.79840
0.87281
1.957
1.993
2.007
2.289
2.666
2.187
1.814
H12A
H12B
H12C
H13A
H13B
H13C
0.27756
0.48958
0.46129
0.68836
0.71397
0.74226
1.17747
1.22318
1.31656
1.06109
1.24498
1.15161
0.95934
1.07125
0.96629
0.81558
0.87788
0.98283
3.246
3.246
3.246
3.263
3.263
3.263
S31
Table S2.15. Anisotropic displacement parameters
atom
U11
U22
U33
U12
U13
U23
Se1
Se2
P1
C1
C2
C3
C4
0.0337(2)
0.02229(19)
0.0269(5)
0.0159(16)
0.0166(17)
0.0228(18)
0.0260(18)
0.0168(2)
0.0215(3)
0.0150(6)
0.009(2)
0.020(2)
0.018(2)
0.010(2)
0.0213(2)
0.0282(2)
0.0200(5)
0.0152(18)
0.0222(19)
0.025(2)
0.0191(19)
0.00743(17)
0.01175(17)
0.0074(4)
0.0003(15)
0.0050(17)
0.0128(17)
0.0033(17)
0.01487(18)
0.00519(17)
0.0075(4)
0.0034(15)
0.0089(16)
0.0086(17)
0.0002(17)
0.00803(17)
0.01127(18)
0.0073(4)
0.0044(15)
0.0036(17)
0.0079(17)
0.0037(16)
C5
C6
C7
C8
0.0177(17)
0.0271(19)
0.0224(19)
0.0161(18)
0.011(2)
0.016(2)
0.032(3)
0.025(2)
0.0175(18)
0.026(2)
0.030(2)
0.023(2)
–0.0000(16)
0.0030(17)
0.0049(18)
0.0078(17)
0.0022(16)
0.0101(18)
0.0159(18)
0.0073(17)
0.0037(16)
0.0085(17)
0.0116(19)
0.0023(18)
C9
C10
C11
C12
C13
0.0162(17)
0.0123(16)
0.0201(17)
0.041(2)
0.027(2)
0.015(2)
0.011(2)
0.015(2)
0.029(3)
0.039(3)
0.0156(17)
0.0114(17)
0.0205(19)
0.023(2)
0.030(2)
0.0016(16)
0.0003(15)
0.0050(16)
0.012(2)
0.006(2)
0.0028(16)
–0.0002(15)
0.0057(16)
0.005(2)
0.0078(19)
0.0031(16)
0.0006(15)
0.0068(16)
0.0031(19)
0.013(2)
The general temperature factor expression: exp(–2 (a* U11h
+ b* U22k
+ c* U33l
+ 2a*b*U12hk +
2a*c*U13hl + 2b*c*U23kl))
Table S2.16. Bond lengths (Å)
atom
atom
distance
atom
atom
distance
Se1
P1
2.2380(11)
Se1
C1
1.924(4)
Se2
P1
C1
C3
C5
C6
C8
C11
P1
C11
C10
C4
C6
C7
C9
C12
2.2471(11)
1.852(3)
1.437(5)
1.362(5)
1.424(5)
1.346(6)
1.380(5)
1.527(5)
Se2
C1
C2
C4
C5
C7
C9
C11
C9
C2
C3
C5
C10
C8
C10
C13
1.913(4)
1.379(5)
1.388(6)
1.412(5)
1.422(5)
1.408(6)
1.444(5)
1.527(5)
S32
Table S2.17. Bond lengths involving hydrogens (Å)
atom
atom
distance
atom
atom
distance
C2
C4
C7
C11
C12
C13
C13
H2
H4
H7
H11
H12B
H13A
H13C
0.950
0.950
0.950
1.000
0.980
0.980
0.980
C3
C6
C8
C12
C12
C13
H3
H6
H8
H12A
H12C
H13B
0.950
0.950
0.950
0.980
0.980
0.980
Table S2.18. Bond angles (°)
atom
atom
atom
angle
atom
atom
atom
angle
P1
Se1
Se2
Se1
Se1
P1
P1
C1
C1
Se2
C11
C10
102.69(10)
96.70(3)
102.51(11)
128.3(3)
P1
Se1
Se1
C2
Se2
P1
C1
C1
C9
C11
C2
C10
102.86(10)
103.49(12)
111.5(3)
120.1(3)
C1
C3
C4
C5
C7
Se2
C1
C5
P1
C2
C4
C5
C6
C8
C9
C10
C10
C11
C3
C5
C10
C7
C9
C10
C5
C9
C13
122.3(3)
120.6(4)
121.3(3)
120.6(4)
121.9(4)
127.9(3)
116.3(3)
116.8(3)
109.0(3)
C2
C4
C6
C6
Se2
C8
C1
P1
C12
C3
C5
C5
C7
C9
C9
C10
C11
C11
C4
C6
C10
C8
C8
C10
C9
C12
C13
119.3(4)
117.7(3)
121.0(3)
119.9(4)
112.1(3)
119.8(3)
126.9(3)
108.5(3)
110.6(2)
S33
Table S2.19. Bond angles involving hydrogens (°)
atom
atom
atom
angle
atom
atom
atom
angle
C1
C2
C3
C5
C6
C7
P1
C2
C3
C4
C6
C7
C8
C11
H2
H3
H4
H6
H7
H8
H11
118.8
120.3
119.7
119.7
120.1
119.0
109.6
C3
C4
C5
C7
C8
C9
C12
C2
C3
C4
C6
C7
C8
C11
H2
H3
H4
H6
H7
H8
H11
118.8
120.3
119.7
119.7
120.1
119.0
109.6
C13
C11
H12A
H12B
C11
H13A
H13B
C11
C12
C12
C12
C13
C13
C13
H11
H12B
H12B
H12C
H13B
H13B
H13C
109.6
109.5
109.5
109.5
109.5
109.5
109.5
C11
C11
H12A
C11
C11
H13A
C12
C12
C12
C13
C13
C13
H12A
H12C
H12C
H13A
H13C
H13C
109.5
109.5
109.5
109.5
109.5
109.5
S34
Table S2.20. Torsion angles (°)
atom1 atom2 atom3 atom4 angle
atom1 atom2 atom3 atom4 angle
P1
C1
P1
C9
Se1
Se2
Se1
Se1
Se1
Se2
Se2
P1
P1
C1
C1
P1
C9
P1
C11
C11
C2
C2
Se2
C8
Se1
C12
C12
C3
–147.30(12)
–55.27(9)
147.83(12)
55.76(10)
–169.60(14)
–69.46(17)
–174.71(16)
P1
C1
P1
C9
Se1
Se2
Se1
Se1
Se1
Se2
Se2
P1
P1
C1
C1
P1
C9
P1
C11
C11
C10
C10
C11
C10
C11
C13
C13
C5
36.26(18)
49.35(9)
–36.83(19)
–49.71(10)
69.94(19)
170.08(15)
175.57(14)
Se1
C2
C1
C3
C4
C4
C6
C5
C7
C1
C1
C2
C4
C5
C5
C5
C6
C8
C10
C10
C3
C5
C6
C10
C10
C7
C9
C9
C9
C4
C6
C7
C9
C9
C8
Se2
–5.4(3)
178.5(2)
–1.9(4)
–179.7(2)
–179.2(2)
179.86(19)
0.8(3)
–1.1(4)
174.63(19)
C2
C10
C2
C3
C4
C6
C10
C6
C7
C1
C1
C3
C4
C5
C5
C5
C7
C8
C10
C2
C4
C5
C10
C10
C6
C8
C9
C5
C3
C5
C10
C1
C1
C7
C9
C10
–0.6(3)
2.1(3)
0.2(4)
1.2(4)
–1.0(3)
179.92(19)
–0.1(3)
1.8(4)
–1.1(3)
Se2
C8
C9
C9
C10
C10
C1
C1
5.8(3)
–179.2(2)
Se2
C8
C9
C9
C10
C10
C5
C5
–175.16(14)
–0.1(3)
Torsion angles > 160° and <120° are excluded
Table S2.21. Intramolecular contacts less than 3.60 Å
atom
atom
distance
atom
atom
distance
Se1
Se2
C1
C2
C5
C7
C9
C1
C4
C5
C8
C10
3.516(4)
3.503(4)
2.793(5)
2.761(5)
2.772(5)
2.842(5)
Se1
Se2
C1
C3
C6
C9
C13
C12
C11
C10
C9
C11
3.594(3)
3.556(3)
3.454(4)
2.844(5)
2.808(6)
3.440(4)
S35
Table S2.22. Intramolecular contacts less than 3.60 Å involving hydrogen
atom
atom
distance
atom
atom
distance
Se1
Se1
Se2
P1
P1
C1
C1
H2
H13A
H11
H12A
H13A
H3
H13A
2.720
3.062
3.194
2.880
2.896
3.275
3.588
Se1
Se2
Se2
P1
P1
C1
C2
H11
H8
H12A
H12C
H13B
H11
H4
3.214
2.732
3.011
2.872
2.881
2.873
3.234
C4
C5
C6
C8
C9
C10
C10
C10
C12
H2
H3
H4
H6
H11
H2
H6
H11
H13B
3.224
3.271
2.581
3.245
2.855
3.294
3.329
2.846
2.701
C4
C5
C6
C9
C9
C10
C10
C12
C12
H6
H7
H8
H7
H12A
H4
H8
H13A
H13C
2.586
3.268
3.231
3.287
3.553
3.321
3.300
3.355
2.701
C13
C13
H3
H6
H11
H11
H11
H12A
H12B
H12A
H12C
H4
H7
H12A
H12C
H13B
H13B
H13A
3.355
2.701
2.312
2.293
2.375
2.877
2.877
3.592
3.592
C13
H2
H4
H7
H11
H11
H11
H12A
H12B
H12B
H3
H6
H8
H12B
H13A
H13C
H13C
H13B
2.701
2.326
2.379
2.345
2.385
2.375
2.385
3.592
2.987
H12B
H12C
H13C
H13B
2.522
2.522
H12C
H12C
H13A
H13C
3.592
2.987
S36
Table S2.23. Intermolecular contacts less than 3.60 Å
atom
atom
distance
atom
atom
distance
Se1
C2
C5
C9
Se11
C83
C12
C32
3.5369(8)
3.590(4)
3.485(3)
3.501(4)
C1
C3
C8
C52
C92
C24
3.485(3)
3.501(4)
3.590(4)
Symmetry operators:
(1) –X+1, –Y+2, –Z+1
(3) X+1, Y, Z
(2) –X, –Y+1, –Z+1
(4) X–1, Y, Z
S37
Table S2.24. Intermolecular contacts less than 3.60 Å involving hydrogens
atom
atom
distance
atom
atom
distance
Se1
Se2
P1
C1
C2
C2
C3
H61
H42
H32
H12B4
H35
H86
H25
3.509
3.355
3.207
3.091
3.403
3.201
3.091
Se2
Se2
P1
C2
C2
C2
C3
H31
H13A3
H42
H25
H76
H12B4
H76
3.590
3.452
3.134
3.136
3.571
3.116
3.175
C3
C4
C5
C6
C7
C7
C7
C8
C8
H12B4
H12C4
H13C4
H13B4
H23
H12A8
H13C4
H12A8
H13C4
3.216
3.491
3.208
3.447
3.519
3.186
3.125
3.244
3.014
C4
C5
C6
C6
C7
C7
C8
C8
C9
H12B4
H12B4
H13B7
H13C4
H33
H13B7
H23
H12B8
H31
3.227
3.160
3.117
3.202
3.246
3.519
3.106
3.599
3.540
C9
C10
C11
C12
C12
C13
C13
H2
H2
H13C4
H13C4
H12B4
H78
H114
H69
H114
C25
C76
3.044
3.157
3.316
3.027
3.123
3.169
3.166
3.136
3.519
C10
C11
C11
C12
C12
C13
C13
H2
H2
H12B4
H114
H13C4
H88
H13C4
H86
H12B4
C35
C86
3.121
3.030
3.357
3.264
3.492
3.566
3.492
3.091
3.106
H2
H2
H3
H3
H3
H3
H4
H4
H6
H6
H25
H76
Se21
C25
C91
H76
P110
H12C10
C137
H13A7
2.572
3.534
3.590
3.403
3.540
2.869
3.134
3.142
3.169
3.320
H2
H2
H3
H3
H3
H4
H4
H6
H6
H6
H35
H86
P110
C76
H25
Se210
H12A10
Se11
H611
H13B7
2.491
2.834
3.207
3.246
2.491
3.355
3.379
3.509
3.479
2.288
S38
H7
C23
3.571
H7
C33
3.175
H7
H7
H7
H7
H8
H8
H8
H8
H8
H11
C128
H33
H12B8
H12C8
C23
C133
H12A8
H13A3
H13C4
C124
3.027
2.869
3.035
2.890
3.201
3.566
2.740
2.779
3.480
3.123
H7
H7
H7
H7
H8
H8
H8
H8
H11
H11
H23
H12A8
H12C7
H13B7
C128
H23
H12B8
H13C3
C114
C134
3.534
2.652
3.454
3.130
3.264
2.834
2.910
3.526
3.030
3.166
H11
H11
H12A
H12A
H12A
H12A
H12B
H12B
H12B
H114
H12B4
C78
H42
H88
H13C4
C24
C44
C88
2.574
2.458
3.186
3.379
2.740
3.288
3.116
3.227
3.599
H11
H11
H12A
H12A
H12A
H12B
H12B
H12B
H12B
H12A4
H13C4
C88
H78
H114
C14
C34
C54
C104
3.563
2.513
3.244
2.652
3.563
3.091
3.216
3.160
3.121
H12B
H12B
H12B
H12B
H12C
H12C
H13A
H13A
H13B
C114
H78
H114
H13C4
H42
H78
Se26
H86
C69
3.316
3.035
2.458
3.278
3.142
2.890
3.452
2.779
3.117
H12B
H12B
H12B
H12C
H12C
H12C
H13A
H13A
H13B
C134
H88
H13A4
C44
H79
H12C12
H69
H12B4
C64
3.492
2.910
3.314
3.491
3.454
3.164
3.320
3.314
3.447
H13B
H13B
H13C
H13C
H13C
H13C
H13C
H13C
C79
H79
C64
C84
C104
C124
H84
H12A4
3.519
3.130
3.202
3.014
3.157
3.492
3.480
3.288
H13B
H13C
H13C
H13C
H13C
H13C
H13C
H13C
H69
C54
C74
C94
C114
H86
H114
H12B4
2.288
3.208
3.125
3.044
3.357
3.526
2.513
3.278
S39
Symmetry operators:
(1) –X, –Y+1, –Z+1
(3) X–1, Y, Z
(5) –X+1, –Y+1, –Z+1
(7) X–1, Y–1, Z
(9) X+1, Y+1, Z
(11) –X, –Y+1, –Z+2
(2) X, Y+1, Z
(4) –X+1, –Y+2, –Z+2
(6) X+1, Y, Z
(8) –X, –Y+2, –Z+2
(10) X, Y–1, Z
(12) –X+1, –Y+3, –Z+2
F1. Least Squares function minimized: (SHELXL2013)  w(Fo2 – Fc2)2, where w is the Least
Squares weights.
F2. Goodness of fit is defined as [w(Fo2 – Fc2)2/(No – Nv)]1/2, where No is the number of
observations and Nv is the number of variables.
S40
S3. Full experimental 77Se NMR parameters
Table S3.1 gives the NMR parameters extracted from the
77Se
solution-state and
solid-state NMR spectra of 1 and 2. The spectra were recorded at 14.1 T, with
31P
continuous wave decoupling at 12.5 kHz MAS. The principal components of the CSA
tensor are defined according to the convention, 11 > 22 > 33.S14 For 1, it was also possible
to get a fit of similar precision that resulted in the values shown in Table S3.2. It was not
possible to distinguish between these two fits with the data shown. While multiple-field
data may be useful to solve this problem, probe hardware capable of
31P/77Se
double
resonance experiments (and simultaneous 1H decoupling) was only available at 14.1 T.
Table S3.1 Experimental
77Se
NMR parameters (solution-state isotropic chemical shift,
isosoln, solid-state isotropic chemical shift, iso, principal tensor components, ii, span, ,
and skew, ) extracted from solution- and solid-state NMR spectra of 1 and 2.
Species
1
Se1
Se2
2
Se
isosoln
iso
11
22
33

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
179 (1)
492 (5)
23 (5)
23 (5)
470 (5)
–1.0 (0.1)
213 (1)
505 (5)
77 (5)
58 (5)
447 (5)
–0.9 (0.1)
280 (1)
672 (5)
84 (5)
83 (5)
589 (5)
–1 (0.1)
210.2
270.2
S41

Table S3.2 Experimental
77Se
NMR parameters (solution-state isotropic chemical shift,
isosoln, solid-state isotropic chemical shift, iso, principal tensor components, ii, span, ,
and skew, ) extracted from solution-state and solid-state NMR spectra of 1 (alternative
fitting).
Species
1
Se1
Se2
isosoln
iso
11
22
33

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
179 (1)
495 (5)
43 (5)
–1 (5)
496 (5)
–0.8 (0.1)
213 (1)
507 (5)
92 (5)
40 (5)
467(5)
–0.8 (0.1)
210.2
For 2, the change in the shape of the isotropic
77Se

resonance with external field
indicates the presence of two Se signals with slightly different isotropic shifts, both of
which experience a J coupling to
31P
in an AA’X spin system. In such a case, where the
resonances are overlapped, the total linewidth in Hz will be (JAX + JA’X)/2 + 0(iso(A) –
iso(A’)), where 0 is the Larmor frequency (= B0) of A and A’, and the isotropic shift
difference scales linearly with external field strength. In ppm, the linewidth will be (JAX +
JA’X)/20 + (iso(A) – iso(A’)) and the J coupling contribution scales inversely with external
field strength. Therefore, a plot of linewidth in Hz against 0 will yield a straight line with
gradient (iso(A) – iso(A’)) and y intercept (JAX + JA’X)/2, whereas a plot of linewidth in ppm
against 1/0 will yield a straight line with gradient (JAX + JA’X)/2 and y intercept (iso(A) –
iso(A’)). Both of these plots for 2 are shown in Figure S3.1 and, together, yield approximate
values for JSe1P + JSe2P = 616(54) Hz and isoSe1 – isoSe2 = 1.5(2) ppm, where the majority of
the uncertainty comes from the difficulty in determining (particularly at 9.4 T) the width
of the idealised “stick diagram” lineshape affected only by isotropic shifts and J couplings.
S42
Figure S3.1 plots of the linewidth of the isotropic 77Se resonance in (a) Hz and (b) ppm as a
function of (a) 0 and (b) 1/0. The lines of best fit and their formulae are shown in both
parts.
The case of two doublets in an AA’X system can readily be distinguished from
other possible cases that would lead to the triplet-like appearance of the 77Se spectra of 2 at
higher fields (14.1 and 20.0 T). A true triplet arising from an AX 2 system would have only
one isotropic shift and, therefore, the linewidth in Hz will be 2JAX and independent of
field. A doublet of doublets arising from AXX’ (i.e., as observed for Se1 of 1) would also
contain a single isotropic shift and the linewidth in Hz would be JAX+JAX’, and
independent of field. While both of these cases would give a linewidth in ppm that would
be inversely proportional to the external field strength, a plot of linewidth in ppm against
1/0 would yield a straight line that passed through the origin (as there is no shift
difference contribution to the linewidth).
S43
S4. 13C and 31P solid-state NMR spectra and variable-temperature 77Se NMR
Figure S4.1 shows the
13C
CP MAS NMR spectra of compounds 1 and 2, acquired
using the parameters given in Table S1.1.
Figure S4.1
13C
CP MAS NMR spectra of (a) 1 and (b) 2, acquired using the parameters
given in Table S1.1. Spinning sideband are marked *.
Figure S4.2 shows the 31P MAS NMR spectra of compounds 1 and 2, acquired using
the parameters given in Table S1.1. The coupling to the
S44
77Se
(7.6% abundance) is not
resolved, and no improvement in resolution is obtained when 1H decoupling is also
applied in acquisition.
a
1
50
1
0
0
50
0
−50
−1
0
0
−50
−1
0
0
−1
50
δ (ppm)
b
1
50
1
0
0
50
0
−1
50
δ (ppm)
Figure S4.2 31P MAS NMR spectra of (a) 1 and (b) 2, acquired using the parameters given
in Table S1.1.
Figures S4.3 and S4.4 show
77Se
CP MAS NMR spectra of 1 and 2, recorded as a
function of temperature. A significant shift to higher  is observed as the temperature
increases (accounting for the differing resonance positions in the spectra in Figure 1 of the
main text, where different rotor sizes and different spinning speeds were used). A very
small variation in the coupling may also be observed, but this is much more difficult to
S45
measure quantitatively owing to the change in linebroadening as the temperature
increases.
Figure S4.3
77Se
(14.1 T, 12.5 kHz) MAS NMR spectra of 1, acquired at varying
temperatures.
S46
Figure S4.4
77Se
(14.1 T, 12.5 kHz) MAS NMR spectra of 2, acquired at varying
temperatures.
S47
S5. DFT calculations and electronic coupling deformation density
Periodic planewave density functional theory (DFT) calculations were carried out
using the CASTEP code, version 8.0.S4 J coupling calculations, performed at both the nonrelativistic (Schrödinger) and scalar-relativistic levels of theory using the ZORA method,S6
are given in Table S5.1. Using ZORA was found to make a small difference to the
predicted couplings, generally resulting in an increase. However, ZORA and nonrelativistic calculations do predict a different order for the Se2-P through-bond and
through-space couplings.
Table S5.1 J couplings (TB = through bond, TS = through space) in 1 and 2 predicted by
DFT at the non-relativistic (NR) and scalar-relativistic ZORA levels of theory. Values given
are the largest coupling of that type.
Type
Compound 1
Compound 2
NR J / Hz
ZORA J / Hz
NR J / Hz
ZORA J / Hz
Se1-P
TB
–292.9
–289.7
–272.5
–271.63
Se1-P
TS
57.8
66.6
56.4
64.1
Se2-P
TB
–316.1
–324.0
–260.0
–261.4
Se2-P
TS
306.4
348.0
95.8
109.1
P-P
TS
143.2
147.6
12.5
11.5
Se1-Se2
TB
13.1
13.9
26.8
29.4
23.5
18.3
19.8
Se1-Se1
TS
109.6
123.7
121.7
136.3
Se2-Se2
TS
61.6
75.3
2.7
1.7
S48
The electronic coupling deformation density (CDD) is defined by Malkina and
Malkin in Ref. S15 as
 ACDD
, B (r ) 
 (r , A , B )   (r , A , B )
,
AB
(1)
where  (r , A , B ) is the ground state density of the following perturbed Hamiltonian
ˆ  H
ˆ 0  A H
ˆ AFC  BH
ˆ BFC .
H
(2)
Here, Ĥ 0 is the unperturbed ground-state Hamiltonian and Hˆ AFC is the Fermi-contact
operator acting on nucleus A. This can be easily implemented in a pseudopotential
electronic-structure code as a spin-dependent modification to the D 0 matrix of the
pseudopotential of the target nuclei. The value of  was chosen to be 102 .
S49
S6. References
S1. Fuller, A. L.; Knight, F. R.; Slawin, A. M. Z., Woollins, J. D. Eur. J. Inorg. Chem. 2010,
2010, 4043.
S2. Skibsted J.; Jakobsen, H. J. J. Phys. Chem. A, 1999, 103, 7958.
S3. Green, T. F. G.; Yates, J. R. J. Chem. Phys. 2014, 140, 234106.
S4. Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K. ; Payne,
M. C. Z. Kristall. 2005, 220, 567.
S5. Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.
S6. Autschbach, J.; Ziegler, T. J. Chem. Phys. 2000, 113, 936.
S7. CrystalClear: Data Collection and Processing Software, Rigaku Corporation (19982014). Tokyo 196-8666, Japan.
S8. Sheldrick, G. M. Acta Cryst. 2008, A64, 112.
S9. International Tables for Crystallography, Vol. C (1992). Ed. A. J. C. Wilson, Kluwer
Academic Publishers, Dordrecht, Netherlands, Table 6.1.1.4, pp. 572.
S10. Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781.
S11. Creagh, D. C.; McAuley, W. J.; "International Tables for Crystallography", Vol. C, (A.
J. C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992).
S12. Creagh, D. C.; Hubbell, J. H. "International Tables for Crystallography", Vol. C, (A. J.
C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992).
S13. CrystalStructure 4.1: Crystal Structure Analysis Package, Rigaku Corporation (20002014). Tokyo 196-8666, Japan.
S14. Mason, J. Solid State Nucl. Magn. Reson. 1992, 2, 285.
S16. Malkina, O. L., Malkin, V. G., Angew. Chemie Int. Ed. 2003, 42, 4335.
S50