Zeitschrift
fUr Kristallographie,
The crystal
structure
Bd. 141, S. 1-10
(1975)
of mercury(II)phosphate,
Hg3(P04)2
By KARIN AURIVILLIUS and Bo ARNE NILSSON
University
(Received
of Lund
6 December
*
1974)
Auszug
Die Struktur
des Quecksilber(II)phosphates,
Hg3(P04)2,
wurde
mittels
symbolischer
Addition
und Fouriermethoden
bestimmt.
Durch Verfeinerung
aus 1491 unabhangigen
Zahlrohrintensitaten
wurde ein R-Faktor
von 0,043
erhalten.
Die Kristalle
sind monoklin,
die Raumgruppe
ist P 21/C, mit vier
Formeleinheiten
pro Elementarzelle
und
den folgenden
Zellpararnetern:
a = 9,737(2) A, b = 11,466(2) A, c = 6,406(1) A und j3 = 99,51(2)°.
Die Quecksilberatome
sind auf beinahe lineare Weise zweifach-koordiniert,
die Abstande
Quecksilber-Sauerstoff
schwanken
zwischen
2,06(1) A und
2,13(1) A und die O-Hg-O-Winkel
zwischen
163,4(4)° und 169,9(5)~. AIle
Sauerstoffatorne
gehoren
zu Phosphattetraedern.
Jedes Quecksilberatom
ist
an je ein Sauerstoffatom
von zwei Phosphattetraedern
gebunden
und jede
Phosphatgruppe
besitzt Bindungen
zu drei Quecksilberatomen.
Die Struktur
ist aus unendlichen,
einander durchdringenden
und gefalteten
Netzen rnit der Formel [Hg3(P04)2]n aufgebaut.
Die Netze werden aus endlosen
~/
-Hg-O-P-O-Hg--Ketten,
miteinander
durch zusatzliche
Quecksilberatome
verbunden, gebildet. Die Hg-O-Abstande
zwischen den N etzen sind > 2,42( 1)A.
Abstract
The structure
of mercury(II)phosphate,
Hg3(P04)2,
has been determined
by symbolic addition and Fourier methods and refined to an R value of 0.043
on the basis of 1491 independent
counter intensities.
The crystals
are monoclinic, space group P 21/c, with four formula units in a unit cell of the dimensions
a = 9.737(2), b = 11.466(2), c = 6.406(1) A and j3 = 99.51(2)°.
The mercury atoms are two-coordinated
in a nearly linear way; the mercury
to oxygen distances
vary between
2.06(1) and 2.13(1) A, and the O-Hg-O
angles between
163.4(4) and 169.9(5) 0. All oxygen atoms belong to phosphate
tetrahedra.
Each mercury
atom is bonded to one oxygen atom of each of two
phosphate
tetrahedra
and each phosphate
group is bonded to three mercury
atoms.
*
P.O.B.
Divisions of Inorganic
740, S.220 07 Lund
Z. Kristallogr. Bd. 141, 1/2
Chemistry.
7.
Chemical
Center,
University
of Lund,
2
KARIN
The
structure
AURIVILLIUS
is built
and
Eo ARNE
up of infinite,
NILSSON
interpenetrating
puckered
nets
V
formula [Hg3(P04)2]n, formed from endless -Hg-O-P-O-Hg-chains,
by additional
mercury
atoms.
The Hg-O
distances
between
the
nets
of
fused
are
> 2.42(1) A.
Introduction
In connection
with several
studies
on mercury
salts containing
pyramidal or tetrahedral anions (BJORNLUND, 1971, 1974; AURIVILLIUS, 1972), it was found of interest to investigate some mercury
phosphates. This paper deals with the structure of Hg3(P04)Z. Work
is in progress on a compound of formula Hgz(HzP04)z, containing
monovalent mercury.
Experimental
Single crystals of Hg3(P04)z were prepared according to two
different methods. First a synthesis suggested by KLEMENT and
HASELBEOK (1964) was tried, the procedure somewhat modified by
the present authors, using a more dilute solution of mercury(II)oxide
in phosphoric acid (3 g HgO in 50 ml concentrated H3P04). Another
method is to use an acidified solution of mercury(II)acetate
and
phosphoric acid (10 ml 0.3M Hg(C2H30Z)z, 10 ml 2.5M HN03, 10 ml
cone. H3P04). The crystallization
proceeds very slowly in the last
case, but gives a more well-formed product. The crystals thus obtained
were in the form of thin, colourless plates. Weissenberg photographs
showed the crystals to be monoclinic. The systematically
absent
reflections were hOl with 1 ¥- 2n and OkOwith k ¥- 2n, the extinctions
consistent with the space group P21/C. X-ray powder photographs
were taken in a Guinier- Hiigg focusing camera with CUKiXl radiation,
using aluminium as internal standard (a = 4.04934 A). The preliminary
values of the cell dimensions were refined by least-squares calculations.
The density was determined from the loss of weight in benzene. Some
crystal data are given in Table 1.
Table 1. Orystal data
Hg3(P04h,
Formula weight 791.8
Monoclinic,
P 21jc
a = 9.737(2), b = 11.466(2), c = 6.406(1) A,
f3 = 99.51(2)°,
V = 705.4A3, Z = 4.
Dm = 7.32, Dx = 7.45 g . cm-3
p, (MoKa)
=
669 cm-1
The crystal structure
of mercury(II)phosphate,
Hg3(P04)2
3
A single crystal with the dimensions 0.20 X 0.07 X 0.007 mm was
used for the intensity data collection on a Pailred linear diffractometer, using MoKiX radiation, monochromatized
by reflection off the
(002) planes of a graphite crystal, the monochromator
angle being
6.080. The crystal used was mounted along its longest edge, which
coincides with the direction of the crystallographic
b axis. The reflections of the layer lines hOl-h III were collected for the copper range,
(sinO)/). < 0.65, using the equi-inclination
and w-scan technique with
a scan rate of LOa/min. The scan range was 4.00 for all reflections.
The stationary background counts were measured for 40 see at each
end of the scan interval. The aperture size of the detector was 2.0°.
As a check of the electronic stability during the period of data collection, the intensity of two standard reflections, 400 and 050, were
measured at regular intervals. The fluctuation of their intensities was
random, and the values of (Imax - 1min)/lmax were less than 60/0.
A total of 2232 independent reflections were recorded (h > 0, k > 0).
209 reflections for which the two measured background values differed
more than 3.09 times the estimated standard deviations of their
difference were omitted. The integrated peak counts I were calculated
from the total integrated peak counts, the background counts and the
counting time in the usual way. 532 reflections with I < 2.58(1(1)
were considered unobserved. The values of (1(1) were based on counting
statistics. The remaining 1491 reflections were corrected for Lorentz,
polarization and absorption effects. The transmission factors, evaluated
by numerical integration, varied from 0.04 to 0.61.
structure determination and refinement
The positions of the heavy atoms were determined by symbolic
addition methods. The asymmetric part of the E map showed three
maxima of nearly the same height, indicating the positions of the
atoms Hg(1)-Hg(3)
ofthe unit cell. Least-squares refinement followed
by difference Fourier syntheses revealed the positions of the phosphorus
and oxygen atoms. The positional parameters,
the isotropic temperature factors and the inter-layer scale factors were then included
in a full-matrix least-squares refinement, minimizing L'wi(jFo 1- IFc J}2
with
weights
Wi
=
[(12(Fo)
+
a IFo 12]-1. A suitable
value
for a was
found from an analysis of the weighting scheme. The discrepancy
factors Rand Rw, defined by R = L'IIFol-IFcll/L'IFol
and Rw =
= [L'wi(IFo 1- IFc 1)2/L'wiIFo 12]112,converged to R = 0.064 and Rw =
1*
4
KARIN AURIVILLIUS
and
Bo ARNE
NILSSON
0.083. When anisotropic temperature
factors were introduced for
all atoms in a new refinement, the R value fell to 0.043 and Rw to
0.051. In the last cycle of refinement the value of a was 0.001. At the
end of the refinement the value of S was 0.99. The expression for
S (goodness of fit) is S = [L'wi(IFo 1- IFe !)2j(m - n)]1I2, where
=
Table 2. Atomic coordinates obtained in the final least-squares refinement
Estimated
standard
Atom
are given in parentheses
y
x
Hg(l)
Hg(2)
Hg(3)
P(l)
P(2)
0(11)
0(12)
0(13)
0(14)
0(21)
0(22)
0(23)
0(24)
Table
deviations
1.04137(7)
0.69987(7)
0.65409(7)
0.6109(4)
0.8972(4)
0.551(1)
0.716(1)
0.698(1)
0.492(1)
1.034( 1)
0.783(1)
0.916(1)
0.860(1)
3. Thermal
z
0.62072(5)
0.39641(6)
0.67005(6)
0.4010(4)
0.8666(3)
0.525( 1)
0.407(1)
0.356(1)
0.316(1)
0.798(1)
0.778(1)
0.940(1)
0.941(1)
parameters
{hj with estimated
standard
0.67502(8)
0.82674(8)
0.41226(9)
0.3051(5)
0.5987(5)
0.249(2)
0.511(2)
0.139(2)
0.317(2)
0.583(2)
0.632(2)
0.804(2)
0.399(2)
deviations
in parentheses.
The expression used is exp [- ([Jll . h2 + [J22 . k2 + [J33 . l2 + 2{312 . hk + 2{313 . hl
+ 2{323 . kl)J. The [Jijvalues are multiplied by 105 for Hg, 104for P and 103 for O.
The
root-mean-square
components,
axes of the ellipsoids
Atom
[J22
[Jll
I
Hg(l)
Hg(2)
Hg(3)
P(l)
P(2)
0(11)
0(12)
0(13)
0(14)
0(21)
0(22)
0(23)
0(24)
[J12
(333
I
276(6) 110(5) 734(12)
288(6) 282(5) 458(11)
341(6) 228(6) 794(12)
38(7)
19(4) 12(3)
6(3) 48(7)
14(3)
3(1)
3(1)
13(3)
1(1)
4(1)
6(2)
3(1)
3(1)
5(2)
3(1)
5(1)
8(2)
2(1)
1(1)
12(3)
1(1)
3(1)
8(2)
2(1)
8(2)
2(1)
1(1)
2(1)
8(2)
I
23(4)
29(4)
114(4)
-4(2)
0(2)
0(1)
0(1)
0(1)
-2(1)
1(1)
-1(1)
0(1)
0(1)
Ri> of thermal
vibration
along
of vibration
are also given
I
fJ13
fJ23
principal
R1
R2
R3
0.126A
0.139
0.155
0.104
0.100
0.183
0.162
0.142
0.199
0.155
0.158
0.138
0.136
0.083A
0.096
0.095
0.077
0.062
0.108
0.047
0.088
0.026
0.075
0.046
0.090
0.044
0.113A
0.114
0.115
0.088
0.081
0.145
0.112
0.124
0.132
0.119
0.119
0.109
0.108
1
33(4)
30(6)
49(6) -22(5)
171(7)
121(5)
5(4)
-2(3)
2(4)
-1(3)
1(1)
-1(2)
1(1)
1(1)
2(1)
0(1)
4(1)
-1(1)
1(1)
0(1)
1(1)
-1(1)
2(1)
-1(1)
0(1)
-1(1)
The crystal
structure
of mercury(II)phosphate,
Hga(P04)2
5
Table 4. Selected interatomic distances and angles in the structure of Hga(P04)2.
Estimated standard deviations are given in parentheses. For notations of the
atoms, cf. Table 2
Mercury
to oxygen
within
distances
2.11(1)
2.11( 1)
2.06(1)
2.06(1)
2.13(1)
2.12(1)
A
163.4( 4) 0
169.9(5)
163.9(5)
the nets
Hg-O
> 2.42(1)
Distances
A
and angles
A
P(1)-0(11)
-0(12)
-0(13)
-0(14)
Mean values
1.55(1)
0(1i)-0(1j)
2.43(2)2.57(2) A
0(11)-P(1)-0(12)
0(11)-P(1)-0(13)
0(11)-P(1)-0(14)
0(12)-P(1)-0(13)
0(12)-P(1)-0(14)
0(13)-P(1)-0(14)
angles
0(21)-Hg(1)-0(23)
0(13)-Hg(2)-0(12)
0(11)-Hg(3)-0(22)
the nets
Hg(1)-0(21)
Hg(1)-0(23)
Hg(2)-0(13)
Hg(2)-0(12)
Hg(3)-0(11)
Hg(3)-0(22)
between
O-Hg-O
1.53( 1)
1.55( 1)
1.53( 1)
1.541(6)
109.2(7)
111.8(7)
109.5(8)
104.0(6)
113.1(6)
109.3(7)
0
within
the P04 tetrahedra
P(2)-0(21)
-0(22)
-0(23)
-0(24)
1.56(1)
0(2i)-0(2j)
2.43(2)-
A
1.55( 1)
1.55( 1)
1.53( 1)
1.545(6)
2.58(2) A
0(21)-P(2)-0(22)
0(21)-P(2)-0(23)
0(21)-P(2)-0(24)
0(22)-P(2)-0(23)
0(22)-P(2)-0(24)
0(23)-P(2)-0(24)
108.3(6)
0
110.2(6)
108.3(6)
103.3(6)
113.9(6)
112.7(6)
m denotes the number of observations and n the number of parameters varied. Thus the errors seem to be correctly estimated. All
parameter shifts were less than 50;0 of the estimated standard deviations. Corrections for extinction and for anomalous dispersion were
not included in the calculations, however. A final three-dimensional
difference synthesis was calculated, with the contributions of all atoms
subtracted. The highest remaining peak had an approximate height
of 3 ej A3. The scattering factors were those of CROMER and W ABER
6
KARIN
Table
IF,II',[
1 k -9
1
2
3
107 110
';6 135
132 132
6
86 85
63 66
2 k -9
1 110 112
31
3,
'5
62
6'
5 189 187
3 k -9
2 181 174
53 38
3
6
57
66 '9
62
7
7
, k
-9
2
3
5
'8
80
67
78
82
61
5 k -9
68
1
k -8
2
0
8'
'5
2
3
,
'8
"
5
6
8
9
'8
87
'6
9'
88
'6
0
1
3,
"
'9
88
52
96
78
" 76"
'0
"k -8
,
8
10
11
1
2
3
5
6
7
10
11
,1
5
8
9
,
11
,2
8'
50
56 6J
5
7
"62 60
106 107
75 7J
5 k -7
1 131133
2 '93 195
J 172 172
5
'0 79
'5
81
6
8
10
11
7
79
8
52
2,
5
6
8
67
'0
51
'8 261
262
68 69
59 57
9
254
" "
'6
93 93
" 245
246
56
62
JJ
58 59
7 k -7
2 236 236
78 78
3
, 53
36
5
6.
7
11
1
2
J
7
10
52
" 175
'9
177
5 k -8
0 209 210
6
93
9'
k -8
0
121
1,
105 109
57 58
97 98
5
7
123
1
3,
8
2
1
2
3,
57 56
127 111t
51 57
215 220
5
6
8
50 52
230 2;2
246 250
9
'5
253
10
252
"
3 k -5
1
'99 214
201"
2 209
,J
5
6
10
11
5
7
k -5
67
57 56
"
155 157
123 125
79 79
101 105
89 91
5
8
9
10
11
5
10
53
'6
58 60
11
8
k
102
182
82
68
262
50
175
0
3,
6
7
8
11
9 k
0
,1
266
72
172
87
6
5'
51
63
9
10
k
149
..
,
8
9
10
'0
121
k
118
69
223
126
"
-5
116
72
227
200 205
62 66
209 213
,6
11
6
1
2
3,
"k
273
302
226
-5
277
311
225
68
174
133
60
112
58
-5
'0
5 171
6 135
-6
7
56
108
9 114
180 '11
56
83
7 k
65
259
2
3,
39
5'
" '0"
170
, 100
9'
172 173
-6
8 125 122
267
9 204 202
71 10
'7
168 11 112 112
"
81
8 k -5
..
3
8J 8J
58 , 123 126
" 5 78
'8
-6
6
77 7J
152
7 103 101
67
8 128 127
,
68
"
72
127
" '8
"
"k -7
5
6
51
53
86
139
9
89
7
10
11
58 65
152
'55 67
6'
72
96
..
93
"
'8
215
8
12
0
210
55
"
k -6
21.10 232
1 k -5
273
146
253
100
127
85
277
152
250
99
133
.J
OJ
"'
,
6
'2
58
50
"59
83 89
"
10 k -5
1
55
,2 127 129
9
,
6
8
9
11
IF,IIF,I
"
"
185
'8
181.1
80
89 '2
77
216 204
58 63
ARNE
70
67
160 151
92 95
11
93
96
78 80
7J 75
57 50
12 k -5
2
86
'8 61
3
7S
7 67 37
1 k -,
0 149 15'
2, 182 185
185 '91,.
65 6,
5
6 296 ;07
8 257 266
9 100 105
0
3
6
0 65
6'
1 108 109
106 104
65
6'
J7 55
197 200
129 128
134 138
124 126
99 98
,2
5
6
,
9
10
11
k -,
3
0 233
1 342
3, 275
177
5 240
6
69
7 115
8
95
11
60
,
0
2,
6
8
9
10
11
236
347
282
181
245
72
117
96
57
k -,
186
153
240
308
294
51
189
'92
157
242
313
298
58
189
38
5 "k -,
0
1
222
3,
125
129
99
109
55
22'~
2 2~~ 2~~
5
6
8
126
134
104
110
33
1\3 67
9
10
36 J2
6 k -,
0
62 6,
1')8
,1 194
58 60
5 106 104
6
56 61
7 100 103
8
'9
6,
9
10
11
7
0
1
2,
5
7 11.2lito
'0
6'
50
92 89
1'911;
63 61
220 215
8
50 38
63
9
'2
10 91 79
11 167 161
10 k -,
,
1
5
6
7
8
9
"
k -,
58 58
99 101
130 131
151
'55
116 115
77 73
12; 120
9' 9'
76
6' 105
112
83 81
11 k -,
0 221 200
1 160 150
3, 16" 156
158
100 1"7
95
100 106
68 25
5
7
9
12
k -,
163 148
118 136
0
,3
9
10
0
58
5J
275
278
1 235 233
2
60 ,6
J, 185 181
181 180
5
165
162
11
1)6 ';8
6 k -3
3,
6
7
IF,IIF,I
k
IF.IIF,I
k
315 ;18
1;11;1
235 2ltS
395 lto6
9
10
50 68
52
5'
k -2
10
11
285
,2 285
272 269 8 169 166
6
8
9
10
11
1
2
3,
5
6
8
11
1
J
6
8
}28
285
66
282
69
7 k
329
9
281t 10
65 11
279
66
0
-3
1
207
3,
'99
155
5
6
'58
,
132
8
59
128 10
11" 11
52
125 127
"
21.17254
, k -2
1
2
66 69
126 125
202
206
158
158
133
57
128
118
8 k -3
179 175
220 216
52 55
" "
63 53
9
10
72 70
11 141 al
9 k -3
1 68 53
2 170
'5'
3 118 118
100
137
13 k
0 116
,1 62
88
6
, 79
97
k
1 110
2 118
3 102
317 ;16
1t71
255
200
272
92
"'57
258
202
268
92
67
62
116
103
5 k
,3
6,
65
116
101
-2
'5
116 111
" 224
224
50 51
224 224
117 113
112 122
6
,
8
9
10
11
6
'5 '2
k -2
0 196 186
1
68 67
56
5
'2
'8
6 182 177
1lo3
2 120 120
60 55
7,
3
53
,
-,
6'
208 200
102 103
117 10 174 162
72 62
5
6
215
230
10 k -3
5'
87
7 126 120
1 215 205 10 100 99
'2
91
2 196 182 11 111 108
J, 175 165
7 k -2
-3
120 106
111
0 227 219
5 193 187
124
1 286 269
9 137 129
98
3, 195 187
11 k -3
, 173177
205 188
182
5 308 321
5 106 123
5
146141
6 127 133
134
147
8 '9"
9
8 165 173 11 126 111
8
k
-2
9 266 279
12 k
10 102 104
237
, 67 -372 01 263
11 120126
87 79
96 98
2, 140 119
7
2 k -3
86 86
8
251 231
1
463
6 249 238
13 k -3
"'41 256
2 246
8 287 271
1 125 134 10 158 156
3 414 428
2 153 153
5 206 207
9 k -2
6 106 108
102
,J 87
88 91
67
244
7
,0 222
92 91
157
9
5 129 126
" 6 145
11
91
6
58 J5
136 158
9'
6,
7
10 k -2
3 k -3
96 93
9
"
2 130 130
176
1 k -2
261270
'7"
8' 82
6 283 294
0 31.11.1349
86
80
1
1.136
457
103 100
7
'9
8 21.14248
2
68 69
'0
"51 53 ,J 210
'5 21lo
9
11 k -2
10 252 256
148 156
11 10') 113
0 129 124
5 )"9 366
,
, k -3
1
2
103 103
80 8J
97
,3
9'
218 222
5
6
8
'9
67 66
" 202
199
9
10
113111
21
55
63 62
208 212
128 123
8 k -,
IF,IIF,I
183 197 , 212 207
6 220 220 11 '33117
7
8
amplitudes
k
10
11
66
68
k -,
9
72 69
5
6
9
NILSSON
structure
IF,IIF,I
6
11 k -5
200 20-4
9' 99
75
'8 120
117
10 167 171.1
57
120 122
2 k -,
"
,
1
2
3,
Bo
and calculated
" ""18 2
S'
"k -5 3,
50
9 56 59
5
69 69 10 111111
1 k -6"
8
81 11
60 63
8'
202
58
9
'97
9 k -5
259
260 10 51 5'
181 184
1
175
178
11 k -6"
154 157
2 206 202
123 125
0
86 86
J 153 151
50
3 171171
100 106 ,, 63 71 5 138 134
'6
137
" 85
83
165
1'"
'9 '3
192
'90
158
122
146
125
59
7
2 k -6
226 227
1
9
10
and
k
8
" "
9
171
155
121
1lo9
12"
57
1
11.11 130
5
8
206
0
8 k -8
0,
202
1
3,
110
5
7
'0
0
6
7
!F,IIF,I
56
,2
56
5'
k -6
7
227 216
62 62
139 133
191 '90
"
10
5
111
'8
75
5. Observed
2
3 55
81 81
5
" ,J
6 1}6 135
6J 66
7
'6 104 65 205 209
8 107
" , 77 ,6
9 7J 68
'99193
62 58
86 92
114111.1
195 201
68
98
9' 153
"
156
6 k -6
0
2
211.1211
10 k -7
0
11
k -7
95 90
J7
52
" 55
3
6
7
9
10
11
2
3
29
, "k
-8
..
0
31
3
7
8
1
2
98 93
75 69
5
81 80
5
"
8J
8'
" 78
75
79 7J
8 k -7
69 69
135 138
117 111
72 75
9
1
2
39 6
,1 125
'8 124
9
9
249
10
173 175
,3
50
"'
6 k -7
2
6
7
8
9
10
11
1',11',1
3 k -6
132 133
193
'93
62 61
0 131 1}0
2 151 152
2 k -7
,3 187
5' 5'
187 186
'93
21t7 245
5
37
3'
1BIt 1BIt 6 235 238
6, 63
60 60
7
1l,.8
8 236 237
52 '5'39
73 76
9
66 59 10 125 125
65
, k -6
6'
3 k -7
0 305 ;111
60
1 258 262
86 90
196 200
" 180 3, 229 2JJ
180
88 85
5 146
193 6 J7 '5'37
'93
1101a
50
, k -7'2 8 82
8'
11
68 7J
93 92
5 k -6
86
'6
k -8
193 192
155 161
96 98
123 128
135 136
3
5
6
10
11
"k
-8
62 55
126 126
110112
184 181
68 69
132 133
2
3
6
7
10
11
1',11',1
AURIVILLIUS
5
k -3
1
357364
2
3,
180 177
33" 339
5
169
,
6
8
9
10
6,
169 167
96
"
J9
116
116
55
69 6,
" " ,2
8
9
~"
80
10
'~t ':~
11
2
. -2
0
369 376
2
3,
117
39
5
6
7
8
9
58 58 10
170
73 75
11
121
36
17217"
135 139
184 188
27
2' 57
60
179 187
23
51
53
"
3 k _2
0
J7 JJ
80
157
92
6 186
7
70
8 152
10 153
12 k
5
136
"
157
79
158
85
181
63
'55
159
-2
0
144
1
2
3,
143 152
75 68
175 183
83
8'
69 62
90 99
5
6
1J.6
7 150 161
11
96
13
,. ,
1
2
1 105 106
0
7
100
k -2
121125
66 7J
80
85
" 75
1 k -19'
2
470 523
2 k _1
::!21&
28 23'
3'
191 '98
";1". "56
188 194
31 28
235 235
;68 J8q
174
'7" _1
3 k
1
3,
5
6
7
8
9
10
""2 2,,6
""2
250
388 385
5 168 162
6 86 85
7
8
9
10
11
,
2,
184 180
71 69
J3 32
70 68
31 30
k -1
271 255
235 219
IF.IIF,I
11
189 196
61 65
k _1
2 169 176
3,
5
6
8
57 66
106 114
77 71
67 61
107 112
12 k _1
1
3
6
9
10
11
83
9'
96 100
102 111
60
'9 10;
101
75 82
13 k _1
1
2
3,
52 60
105 111
85 105
78 86
6 121122
7
'8 '5
8 101106
10
101 108
k -1
1 " 97 100
2
99 106
3
59
'9
2 k 0
62 52
5, 307 237
,5 177164
321 256
1}8 131
8
10
11
10
133 126
222 220
_1
5 k
,1
5
247 218
326 297
366 343
6
128
3
0
2
J,
6
57
k 0"
780 685
100 76
92 6,
540 "87
60 J9
123
7
83 75
242 226
307 291
117 105
117 109
6 k -1
1 415 358
2 223 206
3 41.10397
8
9
10
11
68
6
196
195
127
111
79
95
7 k
1 140
,3 220
10'
6 183
173
188
122
115
7
8
10
11
412
186
103
290
0
254
361
5
8
305 289
11
55 52
" 30
6 "k 0
0
233 221
7
8
9
10
11
,
5
6
7
8
9
11
"
,
8'
83
-1
111
87
189
159
193 170
197 188
173 162
8
2,
k
91
_1
204 187
88 9J
179 181
11711)
50 J7
9 k -1
1 '91 186
2 200 196
198
,
J
200
78 ,6
78 77
171.1168
59
5'
129 133
126 123
10
k -1
104
103
160 163
109 117
149 153
198 200
149
11.18
199 187
JJ
2
81
5
8
9
10
5
6
8
10
11
81
55
6' 180
438
'9'
198
109
299
5 k
0 274
1 384
3, 151.1
87 82 10
8
10
11
90
114102
83 77
141128
79 75
, k 0
1 214 188
81 72
2
3, 398 356
155
99
, 102
105 104
6 127 129
71 67
9J
8'
167 162
88
8'
7 k 0
0
63 60
1 150 11.13
7
8
9
11
2
159
158
6'
227
265
107
65
113
201
228
267
104
61
106
204
3 23" 227
67
5
6
7
8
9
10
11
8
k 0
'92 186
37" 378
59
'9 225
229
The
crystal
structure
ofmercury(II)phosphate,
Table 5.
1'.1/'.1
4 173 170
5 232 232
6 93 96
7 B2 83
B 136 138
10 63 70
11 81 B2
k
9
0
0
49
,1
BO n
76 BO
101
161
49
134
112
115
50
4
6
7
B
9
10
11
10
k
0
2
6
B
10
11
1
J
4
5
6
7
B
9
10
k
12
k
1)
k
0
1
2
J
4
6
7
10
0
57
70
152
B5
134
156
119
0
B4 96
59 5B
76 78
83 85
51
62
117131
67 71
57
53
0
2
J
4
6
k
1
90 95
221 227
31 J4
12.\ 126
1
1
2
3
4
k
1
36 38
100 102
202 195
146 148
2
k
,
686 781t
110 104
72 72
354 363
59 55
96 50
69
67
4J
..
3
k
209
97
152
356
245
46
302
295 285
1
195
38
11.16
349
2ltl
4J
299
IF.II'.I
3
4
5
6
k 1
63 50
283 261
55 46
185 177
109 103
73 73
90 91
57 66
0 k 2
0 239 21,.2
1 152 151
2 138 1111
7
8
g911t2
76
76
3
4
9
185 179
6
,
4
lJ..O
10
5
2
6
9
11
6
1
2
3
4
6
7
8
2
3
5
7
9
10
11
,
1
k
1
1
2
3
9
5
8
9
10
k
1
175 173
103 100
97
95
171& 173
227 230
126 126
217 223
55
53
10
2
3
4
5
6
7
8
10
11
1
2
3
k
1
172
159
219
99
68
158
127
98
105
177
156
232
100
68
163
129
101
104
k
1
62
61
50
52
52
53
80
74
77
77
66
62
61
52
65
65
102 109
120 127
9
6
7
8
9
'0
11
12
2
9
5
8
k
71
102
50
96
13
k
..
119
69
9
2
1
107 121t
82
78
106 111
69
74
..
3
0
2
3
4
6
7
B
9
10
11
2
45
2
211
k
2
65
46
249
186
166
121
329
170
31
81
206
597 625
66
66
111 107
402 1404
..
J5
1IIg
1"8
132 132
71
68
107 106
69
70
5
0
2
3
4
6
7
8
11
k
0
4
7
8
9
10
11
k
1
3
6
7
B
11
2
398
290
115
113
105
7'
75
7J
6B
114
2/,\6
129
240
1118
196
k
9
1
4
5
6
10
k
0
1
4
7
9
137
76
92
61
110
11
k
0,
93
123
71
160
50
57
132
156
69
141
2
3
4
5
6
7
10
11
12
k
0
1
2
3
4
5
6
8
10
131
134
57
70
147
116
105
130
56
1)
0
2
J
4
5
6
7
8
10
11
2
135
7J
84
61
104
2
86
127
82
156
40
9J
134
164
75
145
2
133
145
68
76
148
117
106
139
60
60
60
k
292
221
347
136
165
9J
66
160
2
5
6
8
9
10
11
2
2
k
1
9
1)0
236
144241t
141
189
k
244
68
250
47
29
110
113
93
102
1
2
3
5
7
8
9
10
1
2
2
188 169
107
95
162 153
115 108
69
7J
10
2
62
69
174 168
104
..
192 187
68
79
149 144
96
91
77
7J
71 66
k
421
312
122
107
105
B k
2
79
79
72
75
181 175
60
67
107 103
254 252
221 222
166 166
6
"
2
549
31
38
103
393
107
52
76
45
123
70
k
21)
71
4J
250
186
165
120
326
171
36
80
205
4
0
1
9
5
6
7
8
9
498
207
50
145
325
149 152
231 231
92
90
26
JJ
68
67
204 204
27
30
104 110
122 123
80
78
0
1
2
3
9
5
6
7
8
9
10
11
1
7J
105
55
102
k
0
1
2
3
4
5
6
7
B
10
"
k
5'7
39
38
104
375
104
52
79
10
194 184
58
45
69
72
B6
77
92
85
106 106
141 150
9
2
3
4
k
)47
205
/'.W.I
7
195 205
1t78
205
9B
141t
J08
0
1
2
3
9
5
6
7
8
1
189 173
181 162
267 243
74
9' 110
120
1.J8 155
111 101
B
,
k
JJ8
198
7
B
9
10
11
246
25'
159 156
395 378
111 118
91 111
327 312
192 181
7
,
k
'35
1
562 522
273 269
79
B4
132 127
1
4
5
6
8
9
10
0
154 165
12) 124
59
66
147
80
125
145
105
/'./1'./
10
5'
0
185198
145 152
124127
98 101
77 80
48
48
119.126
57 59
4J 50
0
1
2
3
4
5
6
B
10
1
3
4
5
6
8
9
107
161t
51
136
118
115
59 63
95 90
187 189
..
4J
B7 91
71 70
11
2
4
5
6
8
9
10
11
51
k
k
221
21.15
85
391.1
213
138
368
153
80
3
249
70
255
49
25
114
115
96
106
k
1
2
3
4
5
6
7
9
204 205
110 112
58
59
11
BO B9
4
k
1
2
3
5
6
7
9
10
,
k
3
110 106
181 178
76
77
334337
130 1}1
67
63
82
89
270 269
123 123
5
6
k
1
2
4
5
6
8
9
10
57
446
98
169
231
77
132
49
7
1
2
3
9
5
6
9
10
k
15'
120
55
79
175
7J
167
170
B
1
2
3
5
7
9
k
65
9
2
5
6
9
11
k
315
109
165
107
124
'0
k
79
0
0
1
2
3
57
446
16
171
224
68
128
5'
3
140
115
48
75
168
72
157
170
3
34
..
9' 150
157
103 114
104 108
105 114
3
1 168
119
298
3
223
115
4
350
172
5
11.11 9
169
173
10
108
96
11 k
67
165
63
126
3
81
220
81
252
69
86
12 k
1t09
218
lit 1
381
155
81
3
B5 B4
185 183
1431/t%
46
9J
3D
39
123 126
71
72
180 183
2
3
5
6
7
8
9
10
k
1'./1'.1
3
3
4
54
5
%82 6
81
7
61 11
B9
k
59
46'"
82
63
B4
3
285
1111
162
127
105
3
76
k
113
,
96
91
3
4
6
7
8
9
10
11
137
138
194
253
79
122
153
180
k
2
0
2
3
9
5
6
7
8
9
10
k
0
1
2
3
4
5
6
7
8
10
11
157
262
52
218
98
159
58
13 1
102
67
97
4
0
2
3
4
6
7
B
9
10
11
k
261
69
182
224
113
285
145
56
100
191
5
0
1
3
9
5
6
7
8
9
92
BB
134
tltJ
194
261
B5
121
156
183
4
k
9
162
269
51
224
57
167
60
136
103
66
98
4
272
72
183
230
115
292
1/'7
55
100
191
9
339 344
54
45
46
39
260 262
80
79
78
75
107 105
88
90
67
63
6
k
0
1
3
5
8
10
4
127 130
..
98
54
5J
87
79
139 143
97
49
k
7
166
175
136
71
223
105
72
136
0
3
4
5
7
8
10
11
B
0
3
9
4
117
166 170
115 115
55
58
51
5J
111115
213 218
65
57
61
63
72
76
105 110
3
4
300 303
399 1t13
80
83
1
2
3
77
132
67
84
64
334337
176 180
229 239
58 56
185 188
129 132
0
3
152
97
94
172
1M
115
7
(Continued)
1'.11'./
3
Hg3(P04)2
k
4
163
169
130
74
220
104
70
136
4
318 307
..
95
266 256
IF./I'.I
1'.11'./
129 132
122 115
71 65
9 k 4
0, 122 126
89 79
7
8
11
3
4
137
67
7
B
125 1'9
108 107
11
90
10
k
126
32
93
4
96 100
B7 B4
11
0
9
7
k
9
236 223
177 163
138 120
k
5
62
71
82
80
103 106
102 103
36
3' 121
116
128 131
39
J4
162 161&
0
2
3
9
5
6
8
9
10
11
1
1
2
J
4
6
7
8
10
11
k
61
87
119
209
181
B7
199
193
97
2
1
2
3
9
5
6
7
9
10
11
k
317
238
275
57
197
96
95
138
36
48
3
k
5
68
89
116
213
179
91
204
195
98
5
320
241
277
56
204
46
99
136
28
45
5
116 117
45
50
..
96
197 203
79
73
150 153
214 216
105 106
2
3
4
5
6
8
9
11
4
2
3
4
5
7
8
9
10
11
k
5
70
7'
..
92
141 145
103 105
91
93
110 114
..
95
63
55
59
55
5
1
2
3
4
5
7
9
10
11
k
187
120
172
40
162
55
121
123
4J
6
k
57
5
189
121
174
43
162
51
119
118
J9
5
55
2
4
5
6
8
9
10
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66
(1965) for neutral mercury and of HANSON et al. (1964) for neutral
phosphorus and oxygen. The final positional and thermal parameters,
together with the root-mean-square
components, are given in Tables 2
9
60
63
8
KARIN
AURIVILLIUS
and
Bo ARNE
NILSSON
and 3 and selected interatomic
distances and angles in Table 4.
Observed and calculated
structure
amplitudes
are presented in
Table 5.
Description and discussion of the structure
As seen from Table 4 the mercury atoms are each coordinated to
two oxygen atoms, the Hg-O
distances varying from 2.06(1) to
2.13(1) A and the O-Hg-O
angles from 163.4(4) to 169.9(5) 0. The
values of the distances are in good agreement with those found in
the infinite -O-Hg-Ochains of orthorhombic
HgO [2.04(3),
~/
2.07(3)A] (AURIVILLIUS,1956, 1964), and in the -Hg-O-Cr-O-Hgchains of HgCr04. t H20 [2.055(1), 2.064(1) A] (AURIVILLIUS and
STALHANDSKE).The values of the O-Hg-O
angles are more distorted
in the present compound, however [179.5(1.1)° in HgO; 179.95(5)° in
HgCr04 . t H20]. A dominant feature of the structure of Hg3(P04)2 is
thus the frequently occurring two-covalency of mercury(II).
The structure is built up of infinite puckered nets of formula
[Hg3(P04)2]n. Two such nets, related by t, run through the unit cell.
The nets are interpenetrating
and the Hg-O distances between them
are > 2.42(1) A.
~/
The nets are formed from fused endless chains -Hg-O-P-O-Hgin the following way: All oxygen atoms of the structure belong to
phosphate
tetrahedra;
one of them consists of the atoms P(l),
0(11)-0(14),
and the other of the atoms P(2), 0(21)-0(24).
Each
mercury atom is bonded to one oxygen atom of each of two phosphate
groups, while three oxygen atoms of each phosphate group are bonded
to mercury. The atoms Hg(l), bridging between the atoms 0(21) and
V
0(23), form separate endless -Hg-O-P-O-Hgchains related to
each other through t. They run approximately
parallel to [010].
In the same way, infinite chains, nearly parallel to [001], are formed
as the atoms Hg(2) bridge the atoms 0(12) and 0(13) (ct. Table 2 for
labelling of the atoms). The endless puckered nets are formed from
-0(21)-Hg(1)-0(23)and -0(12)-Hg(2)-0(13)chains, fused by
additional mercury atoms, Hg(3), which in turn are bonded to the
atoms 0(22) and 0(11). The fourth corner of each tetrahedron,
the
atom 0(24) or 0(14), is not bonded to any mercury atom at short
distance. The Hg-O distances within the nets are 2.06(1)-2.13(1)
A.
If the shortest mercury to oxygen distance between the nets of
2.42(1) A is also considered as a coordination distance, the structure
The crystal
structure
of mercury(II)phosphate,
Hg3(P04h
9
may be described as built up of a three-dimensional
network of
formula [Hg3(P04)2]n. A stereoscopic view of the structure is given
in Fig. 1.
The phosphate tetrahedra are rather regular (Table 3), the mean
P(1)-0
and P(2)-0
distances being 1.541(6) and 1.545(6) A, respectively. These values are in good agreement with mean P-O
values calculated from data given for other phosphates, e.g. LhP04
[1.546(3) A] (KEFFER et al., 1967), Mg3(P04)2 [1.527(3) A] (NORD and
Fig. 1. Stereoscopic
view along the c axis, showing two endless puckered
nets
of formula [Hg3(P04h]n,
related by I. The three mercury
atoms are indicated
as 1, 2 and 3. The nets are shadowed
and unshadowed
in the drawing.
The
c axis points against the reader
KIERKEGAARD, 1968) and Zn3(P04h [1.533 A] (CALVO,1965). There
is, however, a small tendency towards elongation of the P-O bonds
for the P-O-Hg
bridging oxygen atoms, the largest difference in the
bonds being about 3a in the distances (0.036 A). Much larger deformations of the tetrahedral
the elongation
groups
of the Cr-O
are found in e.g. HgCr04'
t H20,
bonds for the two Cr-O-Hg
V
where
bridging
oxygen atoms in the infinite -Hg-O-Cr-O-Hgchains amount to
. H20, one
(;::::;;;
60a
in
the
distances).
In
Hg(OH)2'
2
HgS04
0.12 A
oxygen atom of each sulfate tetrahedron bridges between sulfur and
mercury in the limited chains 0(S04)-Hg-0(OH)~Hg-0(OH)-Hg0(804), giving an elongation of 0.08 A (= 8a in the distances).
10
KARIN
AURIVILLIUS
and
Bo ARNE NILSSON
Acknowledgements
The authors wish to thank professor STURE FRONAEUSfor his kind
interest in our work. This work is part of a research project on salts
of heavy metals financially supported by the Swedish Natural Science
Research Council.
References
K. AURIVILLIUS (1956), The crystal structure
K.
K.
K.
G.
G.
C.
D.
H.
C.
R.
A.
of mercury(II)oxide
studied by
x-ray and neutron diffraction
methods.
Acta Chern. Scand. 10, 852-866.
AURIVILLIUS (1964), Least-squares
refinement
of the crystal structures
of
orthorhombic
HgO and of Hg202Na1.
Acta Chern. Scand. 18, 1305-1306.
AURIVILLIUS (1972), The crystal
structure
of mercury(II)chromate
hemihydrate HgCr04'
tH20.
Acta Chern. Scand. 26, 2113-2124.
AURIVILLIUS and C. STALHANDSKE, A neutron
diffraction
study of HgCr04
. tH20.
(In preparation).
BJORNLUND (1971), The crystal
structure
of Hg(OH)BrOa.
Acta Chern.
Scand. 25, 1645-1654.
BJORNLUND (1974), The crystal structure
of Hg(OHh
. 2HgS04' H20. Acta
Chern. Scand. A 28, 169-174.
CALVO (1965), The crystal structure
of IX-Zna(P04h.
Canad. J. Chern. 43,
436-445.
T. CROMER and 1. T. WABER (1965), Scattering
factors
computed
from
relativistic
Dirac-Slater
wave functions.
Acta Crystallogr.
18, 104-109.
P. HANSON, F. HERMAN, 1. D. LEA and S. SKILLMAN (1964), HFS atomic
scattering
factors.
Acta Crystallogr.
17, 1040-1044.
KEFFER, A. MIGHELL, F. MAUER, H. SWANSON and S. BLOCK (1967). The
crystal
structure
of twinned
low-temperature
lithium
phosphate.
Inorg.
Chern. 6, 119-125.
KLEMENT und H. HASELBECK (1964), Sauer und neutrale
Phosphate
und
Arsenate
einiger zweiwertiger
Metalle.
Z. anorg. allgem. Chern. 334, 27-36.
G. NORD and P. KIERKEGAARD (1968), The crystal structure
of Mga(P04h.
Acta Chern. Scand. 22, 1466-1474.