Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Supplementary Information
Cooperative association of pyrazoles and phenols: a versatile binary
system†
Ishtvan Boldog,a Eduard B. Rusanov,a Joachim Sielerb and Konstantin V. Domasevitch*a
a
Inorganic Chemistry Department, Kiev University, Volodimirska Street 64, Kiev 01033, Ukraine
E-mail: dk@anorgchemie.univ.kiev.ua
b
Institut für Anorganische Chemie, Universität Leipzig, Linnéstraße 3, D-04103 Leipzig, Deutschland
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Expository clauses for Introduction
The conceptions of structure augmentation, decoration and other, mainly topological
transformations of the structure are repeatedly used for description of structures itself and the
description of the relations between them [M.O’Keeffe, M. Edaoudi, H.Li, T. Reineke, O.M.
Yaghi, J. of Solid State Chem., 152 (2000), 3]. Mostly, such uses can be formulated as static
scheme. In the present contribution, a dynamic scheme is used: the secondary molecular building
block (the prototypal H-bonded motif) is augmented in general way, and the augmented class is
further exploited – thus a non fixed design scheme is used.
In the main text, the H-bonded topologies, which is resulted by hydroxyl-augmentation,
introduced as “…it assumes existence of the classes of binary compounds based upon the
complementary combination of the H-bonding donating/accepting sites: {[--N–NH--]}{[--OH-]}{[--N–NH--]n[--OH--]m}”. Here, the  sign is used in the sense of free combination within
unique part of the motif, but formally the sign in that context can be used as a topology product
(but not as set product, where [--N–NH--]2[--OH--]2 and [--N–NH--] [--OH--] [--N–NH--] [-OH--] are not distinguished). The sigh of topology product may be consistent in case of trivial
choice of open parts ([--N–NH--] and [--OH--] are a minimal open parts), but the pertinence of
such artificial interpretation is questionable. In any cases, the shortened {[--N–NH--]n[--OH--]m}
expression means [--N–NH--]n1[--OH--]m1[--N–NH--]n2[--OH--]m2… n1,m1,n2, m2,…N
Experimental
The synthesis of 3,3´,5,5´-tetramethyl-4,4´-bipyrazolyl (Me4bpz) was carried on according
to the next scheme [W.L. Mosby, J.Chem.Soc., 1957, 3997]:
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Typical synthesis of pyrazole/phenol co-crystal:
Components in 1:1 molar ratio (usual weights were 50-100 mg) were dissolved in 5-10 ml
of MeOH and slowly evaporated in a period of 10-15 days until crystallization of app. 1/3-1/2 of
total amount of dissolved matter. This afforded high quality crystals of the molecular adducts
(i.e. 3,5-dimethylpyrazole-phenol, 3,3´,5,5´-tetramethyl-4,4´-bipyrazolyl-hydroquinone, etc) of
homogeneous morphology. Structures of six such compounds was determined and presented in
the contribution. Presence of water of crystallization in 2Me4bpz · 1,3,5-C6H3(OH)3 · H2O (6)
was conditioned by contact of the solution with air.
Bipyrazole and resorcinol do not form adducts under these conditions, but readily cocrystallize from chloroform as 1:1 complex Me4bpz· (m-C6H4(OH)2) 5.
We note that 3,5-dimethylpyrazole does not form co-crystals with resorcinol and
floroglucine under crystallization from alcohols, chloroform, dichloromethane, acetonitrile and
mixtures of the solvents.
Crystallography
X-ray diffraction data for 1 were collected using Stoe STADI-4 diffractometer psi-scan
based semi-empirical absorption correction was applied. The data for 2-6 were collected using
SMART CCD Siemens diffractometer, data frames were integrated using SAINT and adsorption
correction was applied (SADABS) in all cases. The structures were solved by direct methods and
refined by full-matrix least-squares techniques in the anisotropic approximation using SHELX97
Refinement
The refinements of all structures (1-6) were standard (SHELX-97 [G.M. Sheldrick,
SHELXL97, University of Göttingen, Germany, 1997]): all nonhydrogen atoms refined
anisotropically, no restraints were used. The hydrogen atoms were mainly constrained except
those involved in hydrogen bonds – the data quality was enough to refine them reasonably,
except structure of 3, where the hydrogen atoms were idealized and their equal delocalisation
over two positions was accounted as best simple and persistent model being in accordance with
Fourier difference synthesis. Other aromatic hydrogen atoms were constrained in ideal geometry
and refined in riding model with Uiso equal of 1.2 Ueq of bearing carbon atom. Hydrogen atoms
of methyl groups were processed with different modifications of ideal-geometry riding model
(Uiso equal of 1.5 Ueq). In all structures except of 5, the rotating group model was used. Common
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
feature of all structures is the complete circular disorder of methyl hydrogens that is clearly seen
from circular difference electron density syntheses. Account of the equal disorder as staggered
methyl group constraint effects in appreciable decreasing of the final R-factor, especially in
structures of 1,2,4, numerically app. 10%. Finally, the disordered methyl group model was kept
only in cases of 1,2 because the quantity of methyl groups equal two in this structures against
eight in case of 4 the last implies “disorder distribution (or diffusion)” in structure with
relatively high R and the correctness of such model seems disputable.
Atom numbering schemes and geometry of hydrogen bonding
Only the atom numbering schemes and hydrogen bond length and statistics are given
here. Detailed crystallographic information is given in the CIF file.
Me2pz · PhOH (1):
N1*
H11A
H10A
H4A H4E
0.5 / 0.5 disorder
C11
O1
C6
H4C
H4F
C4
C10
H4B H4D
H2
C3
N2
C9
H9A
C8
C7
C2
N1
H7A
H2A
H1
C1
H8A
O1*
H5A
H5E
C5
0.5 / 0.5 disorder
H5F
H5B
H5D
H5C
1:
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
N1-H1...O1(x, -y+1/2, z-1/2)
O1-H2...N2
0.91(3)
0.93(3)
2.01(3)
1.78(3)
2.916(3)
2.700(3)
173(3)
170(2)
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Me2pz · p-C6H4(OH)2 (2)
H4EH4C H4D
H4B
H4A
H4F
H7A
C8
H8A
C7
C6
C4
C3
O1
0.5 / 0.5 disorder
C2
H2
O2
H3
H2A
N2
C9
C10
C11
H11A
N1
C1
H1
H10A
H5B
H5F
O1*
O2*
C5 H5D
H5C
H5A H5E
0.5 / 0.5 disorder
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
N1-H1...O2(-x, y-1/2, -z+1/2)
O2-H3...O1(x+1/2, y, -z+1/2)
O1-H2...N2
0.896(15)
0.908(19)
0.95(2)
2.029(16)
1.79(2)
1.73(2)
2.8936(14)
2.6973(14)
2.6742(14)
161.8(14)
178.7(17)
171.1(18)
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
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Me4bpz · 2PhOH (3)
H24A
C24 C23
N3*
H23A
H5C
C25
H5B
C22
H25A
C20
H22A
C21
C1
H9B
C9
O1
H35A
H21
O2
C35 C30
H2B
C4
N3
C6
H4A
C10
H4C
H4B
H10A
C34
H34A
H2A
C31
C33
H33A
C3
C7
N4
H22
O1*
N2
C2
C8
H11
H1A
N1
H5A
H9A
H21A H9C
N2*
H12
C5
C32
H10C
H31A
H10B
N1*
H32A
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
O1-H11...O2
O2-H21...O1
O1-H12...N2(x-1/2, -y+1/2, z+1/2)
N2-H1B...O1(x+1/2, -y+1/2, z-1/2)
O2-H22...N4
N4-H2B...O2
N1-H1A...N3(x, y, z-1)
N3-H2A...N1(x, y, z+1)
1.05
0.79
1.10
0.86
0.98
0.83
0.90
0.88
1.60
1.94
1.88
2.04
1.72
1.86
1.96
1.97
2.647(3)
2.647(3)
2.887(3)
2.887(3)
2.681(4)
2.681(4)
2.825(2)
2.825(2)
173.4
148.8
150.4
169.0
166.1
169.9
162.2
166.9
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Me4bpz · p-C6H4(OH)2 (4)
N8*
H4A
H29A
C27*
C29
C29*
C27
C28
O3
N2
H1
C4 H4C
H4B H10A
C10
C3
H10B
H10C
N1
C2
C1
O4*
H26A
H5B
H9B
C22 C23
N4
C9
H14C
H3
H9C
C30*
H23A
H32A
H14B
N6 C13
C32
H20B
H14A
H20A C20
C31
C32*
C30
O1*
C14
H9A
H5A
H6
H22A
C8
C5
N7*
C25
C24 O2
N3 H2
H5C
H25A
C26
O1 H5
C21
C6
C7
H7
H27A
O2*
O2*
H20C
O4 H8
H30A
N5
C11
H15C
O3*
H15B
C15
H15A
C12
C16
N7
C17
C18
H19B
C19
H19A
N8
H4
N2*
H19C
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
N1-H1...O3
N3-H2...O1
N6-H3...N4
N8-H4...N2(x+1, y-1, z)
O1-H5...O2(x-1, y, z)
O2-H6...N7(-x+2, -y, -z)
O3-H7...O4(-x, -y+1, -z+1)
O4-H8...N5
0.91(3)
1.03(2)
0.86(3)
0.91(2)
0.85(3)
1.12(4)
0.98(3)
1.00(3)
1.89(3)
1.91(2)
2.02(3)
2.04(2)
1.92(3)
1.59(4)
1.65(3)
1.67(3)
2.792(2)
2.858(2)
2.864(2)
2.904(2)
2.763(3)
2.674(2)
2.624(2)
2.638(2)
170(2)
152(2)
164(2)
158(2)
168(3)
160(3)
171(3)
162(3)
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
The Centre National de la Recherche Scientifique, 2004
Me4bpz · m-C6H4(OH)2 (5)
N3*
N1*
H3
H16A
O1*
O1
H5C
C16
H9C
C11
C12
H15A
H14A
C13
C14
N4
H5A
H5B
C9
H9A
H12A
C15
C5
C1
H9B
N1
C8
H4
C7
C2
N2
H1
O2
O1*
H2
C3
N3 C6 C10 H10B
H4B
H4A
H10A
H10C
H4C
C4
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
N3-H2...O1(-x+1/2, y-1/2, z)
O1-H3...N1(-x+1/2, -y+1, z+1/2)
O2-H4...N4
0.87(3)
0.90(3)
0.99(4)
2.18(3)
1.86(3)
1.75(4)
2.943(2)
2.736(2)
2.736(3)
146(2)
163(2)
175(3)
Supplementary Material for New Journal of Chemistry
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2Me4bpz · 1,3,5-C6H3(OH)3 · H2O(6)
N5*
N1*
O2
O4
O1*
O4*
N2*
H9
H22A
O3*
N8
C26
H26A
H24AC24
H19B
C18
H20A
O1
C23
H4
N7
H5
C22
C21
O3
C25
H6
H2
C10
C6
N4
H10B
H19A
C16
C19 H15B
C20
C17
H20C
H15C
C15
H9A
C8
C9
C2
C11
H9C
C13
H14C
H14B C14
N5
H4A
C1
C3
N2
O1*
H5C
H7
N6
H5B
H9B
C4
H4B
H15A
C12
H14A
H4C
C7
O2*
H19C
H20B
H10A H10C
N3
O2*
N1
C5
H1
H5A
H3
N7*
N3*
D–H…A
d(D-H), Å
d(H---A), Å
d(D---A), Å
 DHA, ˚
O3-H6...O2(-x+1/2, -y, z+1/2)
O1-H5...N2(x-1/4, -y+1/4, z-5/4)
N1-H1...N3(x, y, z+1)
O2-H7...N5(x, y, z-1)
N4-H2...O3
N6-H3...N7(x, y, z+1)
O4-H8...O1(x-1/4, -y+1/4, z-1/4)
N8-H4...O4
0.84(2)
0.97(3)
0.95(3)
0.88(4)
0.97(3)
0.87(3)
0.96(5)
0.77(4)
1.88(2)
1.74(3)
1.94(3)
1.79(4)
1.89(3)
1.98(3)
1.95(5)
2.09(4)
2.639(2)
2.673(2)
2.874(3)
2.653(2)
2.853(2)
2.807(3)
2.873(3)
2.855(3)
149(2)
160(3)
166(2)
165(3)
171(3)
159(2)
162(4)
172(3)
Supplementary Material for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and
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The hydrogen bond lengths are distributed in the range of [2.624Å, 2.943Å]. In each
structure, there is a tendency to bimodal distribution of separations (maxima correspond to OH--N and NH---O types of interaction) with the difference of app. 0.2 Å. The summary histogram is
shown below:
5
Frequency
4
3
2
1
0
2,60
2,65
2,70
2,75
2,80
2,85
d(D-H...A) 2,60-2,96Å; =0,03Å
2,90
2,95