Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102005942/da1215sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102005942/da1215Isup2.hkl |
CCDC reference: 188599
NH4SCN (3.045 g, 40 mmol) and Hg(NO3)2·H2O (3.426 g, 10 mmol) were dissolved in water (20 ml) with stirring. To the colourless solution, an aqueous solution (10 ml) containing CdCl2·2.5H2O (2.284 g, 10 mmol) and N,N-dimethylacetamide (10 ml) were added simultaneously. After the colourless solution had been left standing at room temperature for a while, white precipitated (I) was separated. NB Light pink given below. The crystals used for the present X-ray structure analysis were obtained by slow cooling of a more dilute aqueous solution.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.
[CdHg(CNS)4(C4H9NO)2]2 | F(000) = 2720 |
Mr = 1439.11 | Dx = 2.071 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.829 (3) Å | Cell parameters from 39 reflections |
b = 16.1465 (19) Å | θ = 5.1–12.3° |
c = 19.282 (3) Å | µ = 7.95 mm−1 |
β = 91.27 (2)° | T = 293 K |
V = 4615.7 (12) Å3 | Prism, light pink |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Bruker P4 diffractometer | 4454 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −17→1 |
Absorption correction: ψ-scan (XSCANS; Siemens, 1996) | k = −1→19 |
Tmin = 0.094, Tmax = 0.204 | l = −22→22 |
9846 measured reflections | 3 standard reflections every 97 reflections |
8130 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
8127 reflections | (Δ/σ)max = 0.001 |
474 parameters | Δρmax = 1.37 e Å−3 |
453 restraints | Δρmin = −0.67 e Å−3 |
[CdHg(CNS)4(C4H9NO)2]2 | V = 4615.7 (12) Å3 |
Mr = 1439.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.829 (3) Å | µ = 7.95 mm−1 |
b = 16.1465 (19) Å | T = 293 K |
c = 19.282 (3) Å | 0.30 × 0.25 × 0.20 mm |
β = 91.27 (2)° |
Bruker P4 diffractometer | 4454 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (XSCANS; Siemens, 1996) | Rint = 0.032 |
Tmin = 0.094, Tmax = 0.204 | 3 standard reflections every 97 reflections |
9846 measured reflections | intensity decay: none |
8130 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 453 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.37 e Å−3 |
8127 reflections | Δρmin = −0.67 e Å−3 |
474 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Hg1 | 1.36927 (3) | 0.37772 (3) | 0.34635 (2) | 0.05643 (16) | |
Hg2 | 0.87973 (3) | 0.37879 (3) | 0.15394 (2) | 0.05513 (16) | |
Cd1 | 1.77057 (6) | 0.37456 (6) | 0.43507 (5) | 0.0612 (3) | |
Cd2 | 1.27093 (6) | 0.36851 (6) | 0.06063 (4) | 0.0578 (3) | |
S1 | 1.2355 (3) | 0.2825 (3) | 0.3362 (2) | 0.0947 (14) | |
S2 | 1.3149 (3) | 0.5123 (2) | 0.28955 (19) | 0.0783 (11) | |
S3 | 1.4994 (3) | 0.3144 (3) | 0.28013 (18) | 0.0803 (12) | |
S4 | 1.4337 (3) | 0.4065 (2) | 0.46408 (17) | 0.0755 (12) | |
S5 | 0.9327 (3) | 0.4031 (2) | 0.03357 (17) | 0.0736 (11) | |
S6 | 1.0173 (2) | 0.3503 (3) | 0.23095 (18) | 0.0880 (14) | |
S7 | 0.8043 (3) | 0.5099 (2) | 0.20020 (18) | 0.0731 (11) | |
S8 | 0.7707 (3) | 0.2606 (3) | 0.1705 (2) | 0.1046 (16) | |
N1 | 1.7542 (8) | 0.2950 (8) | 0.5347 (6) | 0.087 (3) | |
N2 | 1.6883 (8) | 0.4803 (8) | 0.4873 (6) | 0.080 (3) | |
N3 | 1.6325 (8) | 0.3351 (8) | 0.3814 (6) | 0.083 (3) | |
N4 | 1.7934 (9) | 0.4481 (8) | 0.3344 (6) | 0.082 (3) | |
N5 | 1.3098 (8) | 0.4504 (7) | 0.1547 (6) | 0.080 (3) | |
N6 | 1.1461 (7) | 0.3381 (7) | 0.1274 (6) | 0.078 (3) | |
N7 | 1.1817 (8) | 0.4673 (8) | 0.0071 (5) | 0.078 (3) | |
N8 | 1.2387 (8) | 0.2801 (8) | −0.0307 (6) | 0.091 (4) | |
C1 | 1.7627 (10) | 0.2737 (10) | 0.5907 (8) | 0.079 (4) | |
C2 | 1.6403 (9) | 0.5282 (9) | 0.5090 (6) | 0.062 (3) | |
C3 | 1.5773 (9) | 0.3250 (9) | 0.3405 (7) | 0.066 (3) | |
C4 | 1.7989 (9) | 0.4721 (8) | 0.2789 (7) | 0.065 (4) | |
C5 | 1.3104 (8) | 0.4761 (8) | 0.2100 (7) | 0.059 (3) | |
C6 | 1.0906 (8) | 0.3430 (9) | 0.1683 (7) | 0.066 (4) | |
C7 | 1.1365 (8) | 0.5209 (8) | −0.0116 (6) | 0.054 (3) | |
C8 | 1.2375 (9) | 0.2547 (9) | −0.0850 (8) | 0.072 (4) | |
O1 | 1.8627 (5) | 0.2752 (4) | 0.3921 (4) | 0.071 (2) | |
C9 | 1.8547 (5) | 0.2016 (5) | 0.3709 (6) | 0.060 (3) | |
C10 | 1.7629 (6) | 0.1607 (7) | 0.3651 (8) | 0.088 (5) | |
H10A | 1.7171 | 0.1998 | 0.3774 | 0.132* | |
H10B | 1.7611 | 0.1141 | 0.3959 | 0.132* | |
H10C | 1.7522 | 0.1423 | 0.3183 | 0.132* | |
N9 | 1.9254 (5) | 0.1582 (5) | 0.3566 (4) | 0.052 (2) | |
C11 | 1.9168 (8) | 0.0703 (6) | 0.3338 (7) | 0.086 (4) | |
H11A | 1.8541 | 0.0561 | 0.3289 | 0.129* | |
H11B | 1.9452 | 0.0349 | 0.3677 | 0.129* | |
H11C | 1.9455 | 0.0634 | 0.2900 | 0.129* | |
C12 | 2.0147 (6) | 0.1955 (7) | 0.3698 (7) | 0.091 (5) | |
H12A | 2.0075 | 0.2517 | 0.3849 | 0.137* | |
H12B | 2.0485 | 0.1947 | 0.3279 | 0.137* | |
H12C | 2.0464 | 0.1645 | 0.4051 | 0.137* | |
O2 | 1.8957 (5) | 0.4326 (5) | 0.4840 (4) | 0.080 (3) | |
C13 | 1.9203 (8) | 0.4460 (7) | 0.5460 (6) | 0.111 (4) | |
C14A | 1.8949 (19) | 0.5258 (13) | 0.5822 (11) | 0.129 (12) | 0.67 (6) |
H14A | 1.9184 | 0.5251 | 0.6290 | 0.194* | |
H14B | 1.8304 | 0.5308 | 0.5827 | 0.194* | |
H14C | 1.9197 | 0.5720 | 0.5578 | 0.194* | |
N10 | 1.9750 (8) | 0.3955 (6) | 0.5779 (5) | 0.126 (4) | |
C15 | 2.0103 (12) | 0.4140 (10) | 0.6491 (7) | 0.152 (6) | |
H15A | 2.0497 | 0.3702 | 0.6644 | 0.229* | |
H15B | 1.9608 | 0.4185 | 0.6802 | 0.229* | |
H15C | 2.0430 | 0.4653 | 0.6487 | 0.229* | |
C16 | 2.0074 (12) | 0.3231 (9) | 0.5393 (8) | 0.161 (7) | |
H16A | 1.9772 | 0.3206 | 0.4948 | 0.241* | |
H16B | 1.9950 | 0.2736 | 0.5649 | 0.241* | |
H16C | 2.0713 | 0.3279 | 0.5331 | 0.241* | |
O3 | 1.3701 (5) | 0.2762 (4) | 0.1064 (5) | 0.079 (3) | |
C17 | 1.3658 (5) | 0.2024 (5) | 0.1274 (6) | 0.059 (3) | |
C18 | 1.2762 (6) | 0.1639 (7) | 0.1456 (8) | 0.093 (5) | |
H18A | 1.2284 | 0.2023 | 0.1352 | 0.140* | |
H18B | 1.2763 | 0.1508 | 0.1942 | 0.140* | |
H18C | 1.2671 | 0.1142 | 0.1191 | 0.140* | |
N11 | 1.4388 (5) | 0.1598 (5) | 0.1384 (5) | 0.071 (3) | |
C19 | 1.4347 (8) | 0.0738 (6) | 0.1662 (7) | 0.095 (5) | |
H19A | 1.3734 | 0.0602 | 0.1766 | 0.142* | |
H19B | 1.4714 | 0.0700 | 0.2078 | 0.142* | |
H19C | 1.4567 | 0.0357 | 0.1323 | 0.142* | |
C20 | 1.5251 (6) | 0.1965 (7) | 0.1183 (7) | 0.091 (5) | |
H20A | 1.5150 | 0.2518 | 0.1014 | 0.137* | |
H20B | 1.5513 | 0.1636 | 0.0825 | 0.137* | |
H20C | 1.5655 | 0.1983 | 0.1579 | 0.137* | |
O4 | 1.3884 (6) | 0.4234 (6) | 0.0020 (5) | 0.096 (3) | |
C21 | 1.3953 (8) | 0.4817 (7) | −0.0411 (5) | 0.118 (4) | |
C22 | 1.3765 (12) | 0.5704 (7) | −0.0202 (7) | 0.136 (5) | |
H22A | 1.3501 | 0.5712 | 0.0248 | 0.204* | |
H22B | 1.3355 | 0.5952 | −0.0534 | 0.204* | |
H22C | 1.4319 | 0.6012 | −0.0187 | 0.204* | |
N12 | 1.4303 (10) | 0.4684 (7) | −0.1011 (5) | 0.138 (5) | |
C23 | 1.4509 (13) | 0.5384 (9) | −0.1485 (7) | 0.148 (6) | |
H23A | 1.4351 | 0.5898 | −0.1268 | 0.221* | |
H23B | 1.4167 | 0.5322 | −0.1910 | 0.221* | |
H23C | 1.5141 | 0.5384 | −0.1582 | 0.221* | |
C24 | 1.4483 (15) | 0.3822 (8) | −0.1212 (8) | 0.187 (9) | |
H24A | 1.4315 | 0.3457 | −0.0844 | 0.281* | |
H24B | 1.5114 | 0.3757 | −0.1300 | 0.281* | |
H24C | 1.4139 | 0.3689 | −0.1625 | 0.281* | |
C14B | 1.894 (6) | 0.490 (6) | 0.612 (5) | 0.16 (3)* | 0.33 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0552 (3) | 0.0658 (4) | 0.0481 (3) | 0.0001 (3) | −0.0028 (2) | 0.0014 (3) |
Hg2 | 0.0547 (3) | 0.0634 (3) | 0.0474 (3) | 0.0042 (3) | 0.0044 (2) | −0.0002 (3) |
Cd1 | 0.0612 (6) | 0.0636 (6) | 0.0588 (5) | 0.0152 (6) | −0.0003 (4) | −0.0044 (5) |
Cd2 | 0.0562 (5) | 0.0601 (6) | 0.0573 (5) | 0.0120 (5) | 0.0034 (4) | 0.0054 (5) |
S1 | 0.084 (3) | 0.117 (4) | 0.082 (3) | −0.034 (3) | −0.027 (2) | 0.023 (3) |
S2 | 0.102 (3) | 0.062 (2) | 0.070 (2) | 0.016 (2) | −0.020 (2) | −0.0057 (19) |
S3 | 0.070 (2) | 0.114 (3) | 0.057 (2) | 0.017 (2) | 0.0013 (17) | −0.017 (2) |
S4 | 0.078 (2) | 0.095 (3) | 0.0530 (19) | 0.037 (2) | −0.0159 (17) | −0.0202 (19) |
S5 | 0.088 (3) | 0.081 (3) | 0.0523 (18) | 0.036 (2) | 0.0233 (18) | 0.0152 (18) |
S6 | 0.062 (2) | 0.147 (4) | 0.055 (2) | 0.024 (3) | 0.0001 (16) | 0.017 (2) |
S7 | 0.083 (3) | 0.072 (3) | 0.065 (2) | 0.021 (2) | 0.012 (2) | 0.0090 (19) |
S8 | 0.133 (4) | 0.109 (4) | 0.073 (3) | −0.060 (3) | 0.025 (3) | −0.009 (3) |
N1 | 0.080 (8) | 0.094 (8) | 0.087 (7) | 0.017 (6) | 0.015 (6) | 0.023 (7) |
N2 | 0.077 (7) | 0.098 (8) | 0.065 (7) | 0.029 (6) | 0.002 (6) | −0.024 (6) |
N3 | 0.061 (6) | 0.087 (8) | 0.100 (8) | 0.016 (6) | −0.011 (5) | −0.023 (7) |
N4 | 0.105 (9) | 0.075 (8) | 0.067 (6) | 0.024 (6) | 0.017 (6) | −0.003 (5) |
N5 | 0.095 (8) | 0.070 (7) | 0.073 (6) | 0.012 (6) | −0.012 (6) | 0.002 (5) |
N6 | 0.054 (6) | 0.077 (8) | 0.103 (8) | 0.025 (5) | 0.015 (5) | 0.015 (6) |
N7 | 0.077 (7) | 0.089 (8) | 0.068 (7) | 0.033 (6) | 0.005 (5) | 0.013 (6) |
N8 | 0.091 (8) | 0.091 (8) | 0.092 (7) | 0.022 (6) | −0.002 (6) | −0.026 (7) |
C1 | 0.078 (10) | 0.084 (11) | 0.076 (8) | 0.022 (9) | 0.026 (8) | 0.015 (8) |
C2 | 0.057 (8) | 0.079 (10) | 0.051 (7) | 0.014 (7) | 0.001 (6) | −0.006 (7) |
C3 | 0.062 (6) | 0.066 (9) | 0.068 (8) | 0.005 (7) | 0.007 (5) | −0.012 (7) |
C4 | 0.077 (9) | 0.045 (8) | 0.072 (7) | 0.016 (7) | −0.004 (8) | −0.005 (6) |
C5 | 0.053 (7) | 0.063 (9) | 0.061 (6) | 0.016 (7) | −0.012 (6) | 0.012 (5) |
C6 | 0.044 (6) | 0.081 (9) | 0.073 (8) | 0.012 (7) | −0.001 (5) | 0.010 (8) |
C7 | 0.055 (5) | 0.059 (5) | 0.050 (5) | 0.002 (4) | 0.006 (4) | 0.002 (4) |
C8 | 0.058 (8) | 0.061 (9) | 0.098 (9) | 0.003 (7) | −0.010 (8) | −0.027 (8) |
O1 | 0.071 (5) | 0.058 (5) | 0.085 (6) | 0.013 (4) | 0.008 (5) | −0.018 (5) |
C9 | 0.056 (6) | 0.063 (7) | 0.061 (7) | 0.010 (6) | −0.005 (6) | −0.009 (6) |
C10 | 0.055 (6) | 0.072 (10) | 0.137 (13) | 0.010 (7) | −0.002 (9) | −0.024 (10) |
N9 | 0.054 (5) | 0.048 (5) | 0.056 (6) | 0.004 (5) | 0.008 (5) | −0.006 (5) |
C11 | 0.113 (12) | 0.065 (8) | 0.080 (10) | 0.009 (8) | 0.024 (9) | −0.027 (8) |
C12 | 0.050 (7) | 0.078 (10) | 0.144 (14) | 0.005 (7) | 0.007 (9) | 0.023 (10) |
O2 | 0.066 (5) | 0.086 (7) | 0.090 (6) | −0.007 (5) | 0.006 (4) | −0.019 (5) |
C13 | 0.109 (6) | 0.113 (6) | 0.111 (6) | −0.015 (4) | 0.000 (4) | −0.006 (4) |
C14A | 0.13 (2) | 0.14 (2) | 0.11 (2) | −0.024 (18) | 0.029 (19) | −0.047 (17) |
N10 | 0.093 (10) | 0.149 (12) | 0.136 (9) | −0.023 (8) | −0.007 (8) | 0.015 (8) |
C15 | 0.151 (8) | 0.160 (8) | 0.146 (7) | −0.004 (5) | −0.010 (5) | 0.002 (5) |
C16 | 0.161 (8) | 0.158 (7) | 0.164 (8) | 0.007 (5) | 0.000 (5) | −0.004 (5) |
O3 | 0.062 (5) | 0.061 (5) | 0.115 (7) | 0.018 (4) | 0.000 (5) | 0.017 (5) |
C17 | 0.064 (6) | 0.054 (7) | 0.058 (7) | 0.009 (6) | −0.006 (6) | −0.004 (6) |
C18 | 0.091 (8) | 0.058 (9) | 0.132 (13) | 0.010 (8) | 0.019 (10) | 0.026 (9) |
N11 | 0.082 (6) | 0.052 (6) | 0.079 (7) | 0.018 (5) | −0.007 (6) | −0.005 (6) |
C19 | 0.098 (12) | 0.062 (8) | 0.122 (13) | 0.023 (8) | −0.024 (10) | 0.012 (9) |
C20 | 0.060 (7) | 0.107 (12) | 0.106 (12) | −0.005 (8) | −0.014 (8) | −0.018 (10) |
O4 | 0.073 (6) | 0.098 (7) | 0.119 (7) | 0.003 (5) | 0.014 (5) | 0.019 (6) |
C21 | 0.109 (6) | 0.126 (6) | 0.119 (6) | −0.009 (5) | −0.002 (4) | 0.005 (4) |
C22 | 0.136 (7) | 0.126 (6) | 0.146 (7) | 0.003 (5) | −0.004 (5) | 0.005 (5) |
N12 | 0.135 (6) | 0.145 (6) | 0.134 (5) | −0.003 (5) | 0.002 (4) | 0.007 (4) |
C23 | 0.145 (8) | 0.151 (7) | 0.146 (7) | −0.009 (5) | 0.003 (5) | 0.013 (5) |
C24 | 0.18 (2) | 0.134 (9) | 0.25 (2) | 0.008 (17) | −0.007 (19) | −0.050 (13) |
Hg1—S4 | 2.487 (3) | C11—H11A | 0.9600 |
Hg1—S1 | 2.514 (4) | C11—H11B | 0.9600 |
Hg1—S3 | 2.551 (4) | C11—H11C | 0.9600 |
Hg1—S2 | 2.557 (4) | C12—H12A | 0.9600 |
Hg2—S5 | 2.498 (3) | C12—H12B | 0.9600 |
Hg2—S8 | 2.527 (4) | C12—H12C | 0.9600 |
Hg2—S6 | 2.538 (4) | O2—C13 | 1.260 (8) |
Hg2—S7 | 2.564 (4) | C13—N10 | 1.296 (6) |
Cd1—O2 | 2.266 (9) | C13—C14B | 1.51 (8) |
Cd1—O1 | 2.276 (6) | C13—C14A | 1.516 (9) |
Cd1—N4 | 2.307 (12) | C14A—H14A | 0.9600 |
Cd1—N1 | 2.329 (12) | C14A—H14B | 0.9600 |
Cd1—N2 | 2.339 (11) | C14A—H14C | 0.9600 |
Cd1—N3 | 2.360 (12) | N10—C16 | 1.471 (9) |
Cd2—O3 | 2.259 (7) | N10—C15 | 1.490 (9) |
Cd2—O4 | 2.277 (8) | C15—H15A | 0.9600 |
Cd2—N7 | 2.302 (11) | C15—H15B | 0.9600 |
Cd2—N5 | 2.308 (12) | C15—H15C | 0.9600 |
Cd2—N8 | 2.308 (12) | C16—H16A | 0.9600 |
Cd2—N6 | 2.330 (11) | C16—H16B | 0.9600 |
S1—C8i | 1.632 (15) | C16—H16C | 0.9600 |
S2—C5 | 1.642 (14) | O3—C17 | 1.260 (8) |
S3—C3 | 1.631 (14) | C17—N11 | 1.296 (6) |
S4—C2ii | 1.616 (13) | C17—C18 | 1.516 (9) |
S5—C7iii | 1.649 (13) | C18—H18A | 0.9600 |
S6—C6 | 1.647 (13) | C18—H18B | 0.9600 |
S7—C4iv | 1.640 (14) | C18—H18C | 0.9600 |
S8—C1v | 1.637 (15) | N11—C20 | 1.471 (9) |
N1—C1 | 1.137 (15) | N11—C19 | 1.490 (9) |
N2—C2 | 1.136 (14) | C19—H19A | 0.9600 |
N3—C3 | 1.136 (15) | C19—H19B | 0.9600 |
N4—C4 | 1.142 (14) | C19—H19C | 0.9600 |
N5—C5 | 1.144 (14) | C20—H20A | 0.9600 |
N6—C6 | 1.156 (14) | C20—H20B | 0.9600 |
N7—C7 | 1.148 (14) | C20—H20C | 0.9600 |
N8—C8 | 1.125 (15) | O4—C21 | 1.261 (8) |
C1—S8vi | 1.637 (15) | C21—N12 | 1.296 (6) |
C2—S4ii | 1.616 (13) | C21—C22 | 1.516 (9) |
C4—S7vii | 1.640 (14) | C22—H22A | 0.9600 |
C7—S5iii | 1.649 (13) | C22—H22B | 0.9600 |
C8—S1viii | 1.632 (15) | C22—H22C | 0.9600 |
O1—C9 | 1.260 (8) | N12—C24 | 1.471 (9) |
C9—N9 | 1.296 (6) | N12—C23 | 1.490 (9) |
C9—C10 | 1.516 (9) | C23—H23A | 0.9600 |
C10—H10A | 0.9600 | C23—H23B | 0.9600 |
C10—H10B | 0.9600 | C23—H23C | 0.9600 |
C10—H10C | 0.9600 | C24—H24A | 0.9600 |
N9—C12 | 1.471 (9) | C24—H24B | 0.9600 |
N9—C11 | 1.490 (9) | C24—H24C | 0.9600 |
S4—Hg1—S1 | 118.14 (14) | N9—C12—H12A | 109.5 |
S4—Hg1—S3 | 104.62 (12) | N9—C12—H12B | 109.5 |
S1—Hg1—S3 | 108.69 (15) | H12A—C12—H12B | 109.5 |
S4—Hg1—S2 | 110.07 (12) | N9—C12—H12C | 109.5 |
S1—Hg1—S2 | 104.23 (14) | H12A—C12—H12C | 109.5 |
S3—Hg1—S2 | 111.17 (13) | H12B—C12—H12C | 109.5 |
S5—Hg2—S8 | 116.84 (14) | C13—O2—Cd1 | 133.0 (9) |
S5—Hg2—S6 | 107.87 (12) | O2—C13—N10 | 120.4 (7) |
S8—Hg2—S6 | 107.28 (16) | O2—C13—C14B | 143 (4) |
S5—Hg2—S7 | 110.02 (11) | N10—C13—C14B | 94 (4) |
S8—Hg2—S7 | 107.14 (15) | O2—C13—C14A | 120.9 (7) |
S6—Hg2—S7 | 107.28 (14) | N10—C13—C14A | 118.5 (7) |
O2—Cd1—O1 | 87.2 (3) | C14B—C13—C14A | 31 (4) |
O2—Cd1—N4 | 90.2 (4) | C13—C14A—H14A | 109.5 |
O1—Cd1—N4 | 87.5 (4) | C13—C14A—H14B | 109.5 |
O2—Cd1—N1 | 89.1 (4) | H14A—C14A—H14B | 109.5 |
O1—Cd1—N1 | 89.2 (4) | C13—C14A—H14C | 109.5 |
N4—Cd1—N1 | 176.6 (4) | H14A—C14A—H14C | 109.5 |
O2—Cd1—N2 | 87.1 (4) | H14B—C14A—H14C | 109.5 |
O1—Cd1—N2 | 174.0 (4) | C13—N10—C16 | 118.0 (7) |
N4—Cd1—N2 | 94.3 (4) | C13—N10—C15 | 120.9 (7) |
N1—Cd1—N2 | 89.0 (4) | C16—N10—C15 | 120.9 (6) |
O2—Cd1—N3 | 171.2 (4) | N10—C15—H15A | 109.5 |
O1—Cd1—N3 | 99.9 (3) | N10—C15—H15B | 109.5 |
N4—Cd1—N3 | 85.0 (5) | H15A—C15—H15B | 109.5 |
N1—Cd1—N3 | 96.2 (5) | N10—C15—H15C | 109.5 |
N2—Cd1—N3 | 86.0 (4) | H15A—C15—H15C | 109.5 |
O3—Cd2—O4 | 87.3 (3) | H15B—C15—H15C | 109.5 |
O3—Cd2—N7 | 174.1 (4) | N10—C16—H16A | 109.5 |
O4—Cd2—N7 | 86.9 (4) | N10—C16—H16B | 109.5 |
O3—Cd2—N5 | 85.5 (4) | H16A—C16—H16B | 109.5 |
O4—Cd2—N5 | 89.3 (4) | N10—C16—H16C | 109.5 |
N7—Cd2—N5 | 94.9 (4) | H16A—C16—H16C | 109.5 |
O3—Cd2—N8 | 90.7 (4) | H16B—C16—H16C | 109.5 |
O4—Cd2—N8 | 90.5 (4) | C17—O3—Cd2 | 135.4 (6) |
N7—Cd2—N8 | 88.8 (4) | O3—C17—N11 | 120.5 (7) |
N5—Cd2—N8 | 176.2 (4) | O3—C17—C18 | 120.9 (7) |
O3—Cd2—N6 | 99.4 (3) | N11—C17—C18 | 118.5 (7) |
O4—Cd2—N6 | 169.1 (4) | C17—C18—H18A | 109.5 |
N7—Cd2—N6 | 86.5 (4) | C17—C18—H18B | 109.5 |
N5—Cd2—N6 | 82.8 (4) | H18A—C18—H18B | 109.5 |
N8—Cd2—N6 | 97.9 (4) | C17—C18—H18C | 109.5 |
C8i—S1—Hg1 | 98.9 (5) | H18A—C18—H18C | 109.5 |
C5—S2—Hg1 | 95.9 (5) | H18B—C18—H18C | 109.5 |
C3—S3—Hg1 | 97.6 (5) | C17—N11—C20 | 118.1 (7) |
C2ii—S4—Hg1 | 99.5 (5) | C17—N11—C19 | 120.9 (7) |
C7iii—S5—Hg2 | 98.5 (4) | C20—N11—C19 | 120.9 (6) |
C6—S6—Hg2 | 96.9 (4) | N11—C19—H19A | 109.5 |
C4iv—S7—Hg2 | 92.6 (5) | N11—C19—H19B | 109.5 |
C1v—S8—Hg2 | 99.7 (5) | H19A—C19—H19B | 109.5 |
C1—N1—Cd1 | 159.8 (14) | N11—C19—H19C | 109.5 |
C2—N2—Cd1 | 172.5 (12) | H19A—C19—H19C | 109.5 |
C3—N3—Cd1 | 161.4 (12) | H19B—C19—H19C | 109.5 |
C4—N4—Cd1 | 167.8 (12) | N11—C20—H20A | 109.5 |
C5—N5—Cd2 | 159.6 (12) | N11—C20—H20B | 109.5 |
C6—N6—Cd2 | 161.7 (12) | H20A—C20—H20B | 109.5 |
C7—N7—Cd2 | 171.5 (11) | N11—C20—H20C | 109.5 |
C8—N8—Cd2 | 159.3 (14) | H20A—C20—H20C | 109.5 |
N1—C1—S8vi | 177.0 (17) | H20B—C20—H20C | 109.5 |
N2—C2—S4ii | 175.6 (13) | C21—O4—Cd2 | 133.8 (8) |
N3—C3—S3 | 177.4 (15) | O4—C21—N12 | 120.3 (7) |
N4—C4—S7vii | 177.6 (13) | O4—C21—C22 | 120.8 (7) |
N5—C5—S2 | 178.1 (13) | N12—C21—C22 | 118.3 (7) |
N6—C6—S6 | 175.9 (13) | C21—C22—H22A | 109.5 |
N7—C7—S5iii | 175.9 (12) | C21—C22—H22B | 109.5 |
N8—C8—S1viii | 179.9 (19) | H22A—C22—H22B | 109.5 |
C9—O1—Cd1 | 136.8 (5) | C21—C22—H22C | 109.5 |
O1—C9—N9 | 120.5 (7) | H22A—C22—H22C | 109.5 |
O1—C9—C10 | 120.8 (6) | H22B—C22—H22C | 109.5 |
N9—C9—C10 | 118.6 (7) | C21—N12—C24 | 118.1 (7) |
C9—C10—H10A | 109.5 | C21—N12—C23 | 120.9 (7) |
C9—C10—H10B | 109.5 | C24—N12—C23 | 121.0 (6) |
H10A—C10—H10B | 109.5 | N12—C23—H23A | 109.5 |
C9—C10—H10C | 109.5 | N12—C23—H23B | 109.5 |
H10A—C10—H10C | 109.5 | H23A—C23—H23B | 109.5 |
H10B—C10—H10C | 109.5 | N12—C23—H23C | 109.5 |
C9—N9—C12 | 118.1 (7) | H23A—C23—H23C | 109.5 |
C9—N9—C11 | 120.9 (7) | H23B—C23—H23C | 109.5 |
C12—N9—C11 | 120.8 (6) | N12—C24—H24A | 109.5 |
N9—C11—H11A | 109.5 | N12—C24—H24B | 109.5 |
N9—C11—H11B | 109.5 | H24A—C24—H24B | 109.5 |
H11A—C11—H11B | 109.5 | N12—C24—H24C | 109.5 |
N9—C11—H11C | 109.5 | H24A—C24—H24C | 109.5 |
H11A—C11—H11C | 109.5 | H24B—C24—H24C | 109.5 |
H11B—C11—H11C | 109.5 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+1; (iii) −x+2, −y+1, −z; (iv) x−1, y, z; (v) x−1, −y+1/2, z−1/2; (vi) x+1, −y+1/2, z+1/2; (vii) x+1, y, z; (viii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [CdHg(CNS)4(C4H9NO)2]2 |
Mr | 1439.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.829 (3), 16.1465 (19), 19.282 (3) |
β (°) | 91.27 (2) |
V (Å3) | 4615.7 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.95 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ-scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.094, 0.204 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9846, 8130, 4454 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.121, 1.00 |
No. of reflections | 8127 |
No. of parameters | 474 |
No. of restraints | 453 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.37, −0.67 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
Hg1—S4 | 2.487 (3) | S2—C5 | 1.642 (14) |
Hg1—S1 | 2.514 (4) | S3—C3 | 1.631 (14) |
Hg1—S3 | 2.551 (4) | S4—C2ii | 1.616 (13) |
Hg1—S2 | 2.557 (4) | S5—C7iii | 1.649 (13) |
Hg2—S5 | 2.498 (3) | S6—C6 | 1.647 (13) |
Hg2—S8 | 2.527 (4) | S7—C4iv | 1.640 (14) |
Hg2—S6 | 2.538 (4) | S8—C1v | 1.637 (15) |
Hg2—S7 | 2.564 (4) | N1—C1 | 1.137 (15) |
Cd1—O2 | 2.266 (9) | N2—C2 | 1.136 (14) |
Cd1—O1 | 2.276 (6) | N3—C3 | 1.136 (15) |
Cd1—N4 | 2.307 (12) | N4—C4 | 1.142 (14) |
Cd1—N1 | 2.329 (12) | N5—C5 | 1.144 (14) |
Cd1—N2 | 2.339 (11) | N6—C6 | 1.156 (14) |
Cd1—N3 | 2.360 (12) | N7—C7 | 1.148 (14) |
Cd2—O3 | 2.259 (7) | N8—C8 | 1.125 (15) |
Cd2—O4 | 2.277 (8) | C1—S8vi | 1.637 (15) |
Cd2—N7 | 2.302 (11) | C2—S4ii | 1.616 (13) |
Cd2—N5 | 2.308 (12) | C4—S7vii | 1.640 (14) |
Cd2—N8 | 2.308 (12) | C7—S5iii | 1.649 (13) |
Cd2—N6 | 2.330 (11) | C8—S1viii | 1.632 (15) |
S1—C8i | 1.632 (15) | ||
S4—Hg1—S1 | 118.14 (14) | N1—Cd1—N3 | 96.2 (5) |
S4—Hg1—S3 | 104.62 (12) | N2—Cd1—N3 | 86.0 (4) |
S1—Hg1—S3 | 108.69 (15) | O3—Cd2—O4 | 87.3 (3) |
S4—Hg1—S2 | 110.07 (12) | O3—Cd2—N7 | 174.1 (4) |
S1—Hg1—S2 | 104.23 (14) | O4—Cd2—N7 | 86.9 (4) |
S3—Hg1—S2 | 111.17 (13) | O3—Cd2—N5 | 85.5 (4) |
S5—Hg2—S8 | 116.84 (14) | O4—Cd2—N5 | 89.3 (4) |
S5—Hg2—S6 | 107.87 (12) | N7—Cd2—N5 | 94.9 (4) |
S8—Hg2—S6 | 107.28 (16) | O3—Cd2—N8 | 90.7 (4) |
S5—Hg2—S7 | 110.02 (11) | O4—Cd2—N8 | 90.5 (4) |
S8—Hg2—S7 | 107.14 (15) | N7—Cd2—N8 | 88.8 (4) |
S6—Hg2—S7 | 107.28 (14) | N5—Cd2—N8 | 176.2 (4) |
O2—Cd1—O1 | 87.2 (3) | O3—Cd2—N6 | 99.4 (3) |
O2—Cd1—N4 | 90.2 (4) | O4—Cd2—N6 | 169.1 (4) |
O1—Cd1—N4 | 87.5 (4) | N7—Cd2—N6 | 86.5 (4) |
O2—Cd1—N1 | 89.1 (4) | N5—Cd2—N6 | 82.8 (4) |
O1—Cd1—N1 | 89.2 (4) | N8—Cd2—N6 | 97.9 (4) |
N4—Cd1—N1 | 176.6 (4) | N1—C1—S8vi | 177.0 (17) |
O2—Cd1—N2 | 87.1 (4) | N2—C2—S4ii | 175.6 (13) |
O1—Cd1—N2 | 174.0 (4) | N3—C3—S3 | 177.4 (15) |
N4—Cd1—N2 | 94.3 (4) | N4—C4—S7vii | 177.6 (13) |
N1—Cd1—N2 | 89.0 (4) | N5—C5—S2 | 178.1 (13) |
O2—Cd1—N3 | 171.2 (4) | N6—C6—S6 | 175.9 (13) |
O1—Cd1—N3 | 99.9 (3) | N7—C7—S5iii | 175.9 (12) |
N4—Cd1—N3 | 85.0 (5) | N8—C8—S1viii | 179.9 (19) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+1; (iii) −x+2, −y+1, −z; (iv) x−1, y, z; (v) x−1, −y+1/2, z−1/2; (vi) x+1, −y+1/2, z+1/2; (vii) x+1, y, z; (viii) x, −y+1/2, z−1/2. |
In recent years, the preparation and characterization of infinite two- and three-dimensional networks has spawned much interest, since these networks may have electronic, magnetic, optical or catalytic applications (Batten & Robson, 1998). Various pseudohalide and pseudochalcogenide ions, such as CN-, OCN-, SCN-, SeCN-, TeCN-, CNO-, N3-, CN22- and SN22-, have been used for designing infinite networks (Cortes et al., 1997; Kitazawa et al., 1994; Yuan et al., 1997; Zhang et al., 2000; Becker & Jansen, 2001). Because of their versatility as monodentate, bidentate or bridging ligands, pseudohalide or pseudochalcogenide ions can be used to build multi-dimensional framework structures connecting one metal atom to another.
Group IIB metal complexes have been extensively studied, mainly due to the capability of these d10 metal ions to adopt different modes of coordination determined by considerations of size, as well as by electrostatic and covalent bonding forces. The presence of pseudohalide and pseudochalcogenide ions introduces some additional degrees of freedom, as seen in the title complex, (I), a novel Lewis base adduct of cadmium mercury thiocyanate (CMTC). \sch
According to the hard and soft acid and bases (HSAB) concept (Pearson, 1966; Balarew & Duhlew, 1984), the harder metals show a pronounced affinity for coordination with harder ligands, while softer metals prefer coordination with softer ligands. In the structure of (I), each hard CdII is coordinated by four hard SCN N atoms and two DMA O atoms. Each soft HgII is coordinated by four of the softer S ligands (SCN). Each CdII is octahedrally coordinated and each HgII is tetrahedrally coordinated.
Both CdII centres exhibit slight distortions from ideal geometry. The Cd1—N bond lengths [range 2.288 (12)–2.347 (11) Å] are longer than the Cd2—N distances [range 2.297 (13)–2.339 (10) Å], but all are shorter than the sum of ionic radii (2.41 Å; Shannon, 1976). This is partly because the assumed valence of the N atom is not appropriate, since the charge on the SCN- ion is highly delocalized. The Cd1—O and Cd2—O bond lengths [2.258 (8) and 2.269 (9), and 2.259 (9) and 2.273 (9) Å, respectively] are somewhat smaller than the Cd—N distances. The bond angles N—Cd1—N, N—Cd2—N, O—Cd1—N and O—Cd2—N (between adjacent atoms) are 84.9 (5)–96.2 (4)°, 82.8 (4)–97.6 (4)°, 87.4 (4)–100.1 (4)° and 85.7 (4)–99.4 (3)°, respectively, with average values of 90.0, 90.2, 90.6 and 90.5°, respectively. The O1—Cd1—O2 and O3—Cd2—O4 angles are 86.7 (3) and 86.5 (3)°, respectively, slightly smaller than the ideal octahedral angle.
Each of the two crystallographically independent HgII centres is tetrahedrally coordinated by four SCN S atoms. The tetrahedra are slightly deformed, with Hg1—S and Hg2—S bond lengths in the range 2.486 (3)–2.558 (4) Å and 2.502 (3)–2.562 (4) Å, respectively, averaging 2.526 and 2.534 Å, respectively. The former is slightly shorter than the latter, and both are much shorter than the sum of the ionic radii (2.80 Å; Shannon, 1976), also likely due to considerable delocalization of the charge on the SCN- ion. The S—Hg1—S and S—Hg2—S bond angles [104.18 (14)–118.02 (13)° and 107.09 (14)–116.80 (13)°, respectively] deviate somewhat from the typical tetrahedral angle.
The average C—S—Hg angle is 97.4°, which is normal compared with CMTC [97.6 (3)°]. Although the C2—N2—Cd1 [172.5 (12)°] and C7—N7—Cd2 [172.1 (10)°] bond angles are similar to those in CMTC [171.3 (8)°], the remaining C—N—Cd bond angles are significantly smaller and exhibit a significant bending. The SCN groups are quasi-linear [N—C—S angles 175.0 (10)–178.8 (15)°], which is the striking feature of these kinds of complexes: the –S═C═N– bridges connect bimetals, forming infinite two- or three-dimensional networks; a three-dimensional network is formed in (I). This feature is most important, as it confers high physicochemical stability and other desirable properties on these complexes.