Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011902/qd0024sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011902/qd0024Isup2.hkl |
CCDC reference: 152647
Cd(NO3)2·4H2O (0.31 g, 1 mmol), KSCN (O.17 g, 2 mmol) and diphenylthiourea (0.46 g, 2 mmol) were dissolved in a small volume of ethanol. The mixture was heated until the white material which formed was completely dissolved. After filtration, the solution was allowed to evaporate slowly; crystals deposited after several days.
Although the β angle is almost 90°, the cell is not orthorhombic. The checking program PLATON (Spek, 1990) did not find a symmetry higher than orthorhombic; indeed, if the data were averaged in an orthorhombic setting, the Rint exceeded 0.2. As a TWIN (a, −b, −c) instruction did not lower the R index much, its use was discarded. H atoms were placed in calculated idealized positions and allowed to ride on their attached non-H atoms (N—H = 0.86 Å and C—H = 0.93 Å). The water H atoms were placed at calculated positions using the HYDROGEN (Nardelli, 1999) option in the WinGX suite (Farrugia, 2000). The slightly low completeness of the reflection data, 91.7%, is due to the incompleteness of the region of 25 < θ < 28.91°.
Data collection: R3m Software (Siemens, 1990); cell refinement: R3m Software; data reduction: R3m Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
[Cd(NCS)2(C13H12N2S)2]·2H2O | F(000) = 732 |
Mr = 721.20 | Dx = 1.540 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.643 (2) Å | Cell parameters from 25 reflections |
b = 15.625 (8) Å | θ = 7.0–15.0° |
c = 17.641 (8) Å | µ = 1.01 mm−1 |
β = 89.98 (4)° | T = 298 K |
V = 1555 (1) Å3 | Parallelepiped, colorless |
Z = 2 | 0.40 × 0.22 × 0.20 mm |
Siemens R3m four-circle diffractometer | 2848 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 28.9°, θmin = 2.6° |
ω scans | h = 0→7 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = 0→20 |
Tmin = 0.609, Tmax = 0.676 | l = −24→23 |
4131 measured reflections | 2 standard reflections every 120 reflections |
3765 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.3895P] where P = (Fo2 + 2Fc2)/3 |
3765 reflections | (Δ/σ)max < 0.001 |
188 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Cd(NCS)2(C13H12N2S)2]·2H2O | V = 1555 (1) Å3 |
Mr = 721.20 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.643 (2) Å | µ = 1.01 mm−1 |
b = 15.625 (8) Å | T = 298 K |
c = 17.641 (8) Å | 0.40 × 0.22 × 0.20 mm |
β = 89.98 (4)° |
Siemens R3m four-circle diffractometer | 2848 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.028 |
Tmin = 0.609, Tmax = 0.676 | 2 standard reflections every 120 reflections |
4131 measured reflections | intensity decay: none |
3765 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.44 e Å−3 |
3765 reflections | Δρmin = −0.40 e Å−3 |
188 parameters |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.5000 | 0.5000 | 0.5000 | 0.0346 (1) | |
S1 | 0.2242 (1) | 0.50856 (6) | 0.37042 (4) | 0.0477 (2) | |
S2 | 0.6907 (1) | 0.36619 (5) | 0.43860 (4) | 0.0377 (2) | |
O1w | 0.7507 (9) | 0.0194 (3) | 0.5304 (2) | 0.119 (2) | |
N1 | −0.2007 (5) | 0.5787 (2) | 0.4231 (2) | 0.047 (1) | |
N2 | 0.8030 (5) | 0.2088 (2) | 0.4829 (1) | 0.039 (1) | |
N3 | 0.5688 (5) | 0.2840 (2) | 0.5653 (1) | 0.042 (1) | |
C1 | −0.0230 (5) | 0.5505 (2) | 0.4020 (2) | 0.035 (1) | |
C2 | 0.6876 (5) | 0.2820 (2) | 0.4998 (2) | 0.033 (1) | |
C3 | 0.9456 (5) | 0.1941 (2) | 0.4166 (2) | 0.036 (1) | |
C4 | 0.8850 (6) | 0.1275 (2) | 0.3691 (2) | 0.047 (1) | |
C5 | 1.0279 (7) | 0.1082 (2) | 0.3075 (2) | 0.056 (1) | |
C6 | 1.2267 (7) | 0.1555 (2) | 0.2932 (2) | 0.054 (1) | |
C7 | 1.2846 (6) | 0.2228 (2) | 0.3403 (2) | 0.053 (1) | |
C8 | 1.1446 (6) | 0.2427 (2) | 0.4026 (2) | 0.044 (1) | |
C9 | 0.5827 (6) | 0.2187 (2) | 0.6225 (2) | 0.038 (1) | |
C10 | 0.4059 (7) | 0.1590 (2) | 0.6303 (2) | 0.055 (1) | |
C11 | 0.4251 (8) | 0.0973 (3) | 0.6862 (2) | 0.071 (1) | |
C12 | 0.6209 (8) | 0.0949 (3) | 0.7332 (2) | 0.062 (1) | |
C13 | 0.7919 (8) | 0.1546 (3) | 0.7260 (2) | 0.064 (1) | |
C14 | 0.7754 (7) | 0.2169 (2) | 0.6705 (2) | 0.052 (1) | |
H1w1 | 0.6974 | −0.0235 | 0.5552 | 0.050* | |
H1w2 | 0.8643 | 0.0401 | 0.5604 | 0.050* | |
H2 | 0.7901 | 0.1673 | 0.5147 | 0.058* | |
H3 | 0.4780 | 0.3272 | 0.5737 | 0.063* | |
H4 | 0.7489 | 0.0956 | 0.3784 | 0.070* | |
H5 | 0.9882 | 0.0629 | 0.2757 | 0.084* | |
H6 | 1.3227 | 0.1423 | 0.2520 | 0.081* | |
H7 | 1.4190 | 0.2553 | 0.3302 | 0.079* | |
H8 | 1.1844 | 0.2881 | 0.4343 | 0.065* | |
H10 | 0.2748 | 0.1600 | 0.5983 | 0.083* | |
H11 | 0.3052 | 0.0570 | 0.6923 | 0.106* | |
H12 | 0.6347 | 0.0523 | 0.7697 | 0.093* | |
H13 | 0.9217 | 0.1539 | 0.7585 | 0.096* | |
H14 | 0.8946 | 0.2576 | 0.6656 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0336 (2) | 0.0313 (2) | 0.0388 (2) | 0.0068 (1) | 0.0024 (1) | −0.0004 (1) |
S1 | 0.0369 (4) | 0.0695 (6) | 0.0366 (4) | 0.0169 (4) | −0.0002 (3) | −0.0088 (4) |
S2 | 0.0477 (4) | 0.0314 (4) | 0.0340 (4) | 0.0075 (3) | 0.0058 (3) | 0.0013 (3) |
O1w | 0.162 (4) | 0.099 (3) | 0.097 (3) | 0.036 (3) | 0.035 (3) | 0.036 (2) |
N1 | 0.035 (1) | 0.047 (2) | 0.058 (2) | 0.007 (1) | 0.006 (1) | 0.003 (1) |
N2 | 0.049 (2) | 0.029 (1) | 0.039 (1) | 0.006 (1) | 0.012 (1) | 0.002 (1) |
N3 | 0.047 (2) | 0.037 (1) | 0.042 (1) | 0.012 (1) | 0.012 (1) | 0.004 (1) |
C1 | 0.034 (2) | 0.037 (2) | 0.034 (2) | 0.002 (1) | 0.000 (1) | 0.001 (1) |
C2 | 0.033 (1) | 0.030 (1) | 0.037 (2) | 0.002 (1) | 0.002 (1) | −0.003 (1) |
C3 | 0.037 (2) | 0.033 (2) | 0.037 (2) | 0.004 (1) | 0.004 (1) | −0.001 (1) |
C4 | 0.049 (2) | 0.041 (2) | 0.051 (2) | −0.004 (2) | 0.006 (2) | −0.006 (2) |
C5 | 0.065 (2) | 0.053 (2) | 0.050 (2) | −0.002 (2) | 0.005 (2) | −0.017 (2) |
C6 | 0.057 (2) | 0.062 (2) | 0.043 (2) | 0.006 (2) | 0.013 (2) | −0.008 (2) |
C7 | 0.041 (2) | 0.059 (2) | 0.059 (2) | −0.005 (2) | 0.013 (2) | −0.004 (2) |
C8 | 0.039 (2) | 0.045 (2) | 0.047 (2) | 0.001 (1) | 0.003 (1) | −0.009 (1) |
C9 | 0.043 (2) | 0.032 (1) | 0.038 (2) | 0.004 (1) | 0.012 (1) | 0.000 (1) |
C10 | 0.048 (2) | 0.060 (2) | 0.058 (2) | −0.011 (2) | 0.005 (2) | 0.007 (2) |
C11 | 0.080 (3) | 0.057 (2) | 0.074 (3) | −0.023 (2) | 0.031 (2) | 0.006 (2) |
C12 | 0.086 (3) | 0.051 (2) | 0.049 (2) | 0.013 (2) | 0.020 (2) | 0.011 (2) |
C13 | 0.068 (3) | 0.075 (3) | 0.048 (2) | 0.014 (2) | 0.003 (2) | 0.014 (2) |
C14 | 0.053 (2) | 0.055 (2) | 0.047 (2) | −0.006 (2) | 0.005 (2) | 0.006 (2) |
Cd1—N1i | 2.491 (3) | C9—C14 | 1.379 (5) |
Cd1—N1ii | 2.491 (3) | C10—C11 | 1.385 (5) |
Cd1—S1 | 2.769 (2) | C11—C12 | 1.382 (6) |
Cd1—S1iii | 2.769 (2) | C12—C13 | 1.348 (6) |
Cd1—S2 | 2.589 (1) | C13—C14 | 1.383 (5) |
Cd1—S2iii | 2.589 (1) | O1w—H1w1 | 0.8600 |
S1—C1 | 1.639 (3) | O1w—H1w2 | 0.8900 |
S2—C2 | 1.701 (3) | N2—H2 | 0.8600 |
N1—C1 | 1.157 (4) | N3—H3 | 0.8600 |
N2—C2 | 1.349 (4) | C4—H4 | 0.9300 |
N2—C3 | 1.438 (4) | C5—H5 | 0.9300 |
N3—C2 | 1.336 (4) | C6—H6 | 0.9300 |
N3—C9 | 1.438 (4) | C7—H7 | 0.9300 |
C3—C8 | 1.379 (4) | C8—H8 | 0.9300 |
C3—C4 | 1.378 (4) | C10—H10 | 0.9300 |
C4—C5 | 1.387 (4) | C11—H11 | 0.9300 |
C5—C6 | 1.367 (5) | C12—H12 | 0.9300 |
C6—C7 | 1.380 (5) | C13—H13 | 0.9300 |
C7—C8 | 1.388 (4) | C14—H14 | 0.9300 |
C9—C10 | 1.373 (5) | ||
N1i—Cd1—N1ii | 180.0 | C10—C9—N3 | 120.8 (3) |
N1i—Cd1—S2iii | 96.4 (1) | C14—C9—N3 | 119.3 (3) |
N1ii—Cd1—S2iii | 83.7 (1) | C9—C10—C11 | 119.1 (4) |
N1i—Cd1—S2 | 83.7 (1) | C12—C11—C10 | 120.6 (4) |
N1ii—Cd1—S2 | 96.4 (1) | C13—C12—C11 | 119.9 (4) |
S2iii—Cd1—S2 | 180.0 | C12—C13—C14 | 120.3 (4) |
N1i—Cd1—S1 | 84.7 (1) | C9—C14—C13 | 120.2 (4) |
N1ii—Cd1—S1 | 95.3 (1) | H1w1—O1w—H1w2 | 103.6 |
S2iii—Cd1—S1 | 94.2 (1) | C2—N2—H2 | 117.1 |
S2—Cd1—S1 | 85.8 (1) | C3—N2—H2 | 117.1 |
N1i—Cd1—S1iii | 95.3 (1) | C2—N3—H3 | 117.9 |
N1ii—Cd1—S1iii | 84.7 (1) | C9—N3—H3 | 117.9 |
S2iii—Cd1—S1iii | 85.8 (1) | C3—C4—H4 | 120.1 |
S2—Cd1—S1iii | 94.2 (1) | C5—C4—H4 | 120.1 |
S1—Cd1—S1iii | 180.0 | C6—C5—H5 | 119.9 |
C1—S1—Cd1 | 102.6 (1) | C4—C5—H5 | 119.9 |
C2—S2—Cd1 | 110.8 (1) | C5—C6—H6 | 120.1 |
C1—N1—Cd1iv | 125.1 (2) | C7—C6—H6 | 120.1 |
C2—N2—C3 | 125.8 (2) | C6—C7—H7 | 119.6 |
C2—N3—C9 | 124.3 (2) | C8—C7—H7 | 119.6 |
N1—C1—S1 | 178.3 (3) | C3—C8—H8 | 120.6 |
N3—C2—N2 | 116.9 (3) | C7—C8—H8 | 120.6 |
N3—C2—S2 | 122.4 (2) | C9—C10—H10 | 120.4 |
N2—C2—S2 | 120.7 (2) | C11—C10—H10 | 120.4 |
C8—C3—C4 | 120.6 (3) | C12—C11—H11 | 119.7 |
C8—C3—N2 | 120.9 (3) | C10—C11—H11 | 119.7 |
C4—C3—N2 | 118.4 (3) | C13—C12—H12 | 120.1 |
C3—C4—C5 | 119.7 (3) | C11—C12—H12 | 120.1 |
C6—C5—C4 | 120.3 (3) | C12—C13—H13 | 119.8 |
C5—C6—C7 | 119.7 (3) | C14—C13—H13 | 119.8 |
C6—C7—C8 | 120.8 (3) | C9—C14—H14 | 119.9 |
C3—C8—C7 | 118.8 (3) | C13—C14—H14 | 119.9 |
C10—C9—C14 | 119.9 (3) | ||
N1i—Cd1—S1—C1 | −127.0 (1) | C2—N2—C3—C4 | −121.8 (3) |
N1ii—Cd1—S1—C1 | 53.0 (1) | C8—C3—C4—C5 | 1.2 (5) |
S2iii—Cd1—S1—C1 | −31.0 (1) | N2—C3—C4—C5 | −175.8 (3) |
S2—Cd1—S1—C1 | 149.1 (1) | C3—C4—C5—C6 | −0.7 (6) |
S1iii—Cd1—S1—C1 | 136 (100) | C4—C5—C6—C7 | −0.3 (6) |
N1i—Cd1—S2—C2 | 146.3 (1) | C5—C6—C7—C8 | 0.7 (6) |
N1ii—Cd1—S2—C2 | −33.7 (1) | C4—C3—C8—C7 | −0.7 (5) |
S2iii—Cd1—S2—C2 | −77.3 (2) | N2—C3—C8—C7 | 176.2 (3) |
S1—Cd1—S2—C2 | −128.5 (1) | C6—C7—C8—C3 | −0.2 (6) |
S1iii—Cd1—S2—C2 | 51.5 (1) | C2—N3—C9—C10 | −101.9 (4) |
Cd1iv—N1—C1—S1 | 65 (11) | C2—N3—C9—C14 | 78.7 (4) |
Cd1—S1—C1—N1 | −138 (11) | C14—C9—C10—C11 | −0.4 (5) |
C9—N3—C2—N2 | 8.8 (5) | N3—C9—C10—C11 | −179.8 (3) |
C9—N3—C2—S2 | −172.5 (2) | C9—C10—C11—C12 | −0.8 (6) |
C3—N2—C2—N3 | −178.3 (3) | C10—C11—C12—C13 | 1.8 (6) |
C3—N2—C2—S2 | 3.0 (4) | C11—C12—C13—C14 | −1.7 (6) |
Cd1—S2—C2—N3 | 9.3 (3) | C10—C9—C14—C13 | 0.6 (5) |
Cd1—S2—C2—N2 | −172.1 (2) | N3—C9—C14—C13 | 180.0 (3) |
C2—N2—C3—C8 | 61.3 (4) | C12—C13—C14—C9 | 0.5 (6) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NCS)2(C13H12N2S)2]·2H2O |
Mr | 721.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 5.643 (2), 15.625 (8), 17.641 (8) |
β (°) | 89.98 (4) |
V (Å3) | 1555 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.01 |
Crystal size (mm) | 0.40 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Siemens R3m four-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.609, 0.676 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4131, 3765, 2848 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.680 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.097, 1.04 |
No. of reflections | 3765 |
No. of parameters | 188 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.40 |
Computer programs: R3m Software (Siemens, 1990), R3m Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cd1—N1i | 2.491 (3) | Cd1—S1iii | 2.769 (2) |
Cd1—N1ii | 2.491 (3) | Cd1—S2 | 2.589 (1) |
Cd1—S1 | 2.769 (2) | Cd1—S2iii | 2.589 (1) |
N1i—Cd1—N1ii | 180.0 | S2iii—Cd1—S1 | 94.2 (1) |
N1i—Cd1—S2iii | 96.4 (1) | S2—Cd1—S1 | 85.8 (1) |
N1ii—Cd1—S2iii | 83.7 (1) | N1i—Cd1—S1iii | 95.3 (1) |
N1i—Cd1—S2 | 83.7 (1) | N1ii—Cd1—S1iii | 84.7 (1) |
N1ii—Cd1—S2 | 96.4 (1) | S2iii—Cd1—S1iii | 85.8 (1) |
S2iii—Cd1—S2 | 180.0 | S2—Cd1—S1iii | 94.2 (1) |
N1i—Cd1—S1 | 84.7 (1) | S1—Cd1—S1iii | 180.0 |
N1ii—Cd1—S1 | 95.3 (1) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
In cadmium thiocyanate, briding by both pseudohalide groups leads to the formation of eight-membered rings that are connected through the Cd atoms, which show trans-N2S4 octahedral coordination (Cannas et al., 1976). In the 1/2 complexes with sulfur-donor ligands, the Cd atoms retain such a coordination characteristic, as noted in the bis(ethylene)thiourea complex (Cavalca et al., 1960). The phenylthiourea complex of cadmium thiocyanate displays a one-dimensional chain structure, whereas the cadmium chloride complex exists as a monomeric entity (Yang et al., 2000). Replacing the phenylthiourea ligand by the somewhat bulkier diphenylthiourea (DPTU) donor ligand leads to the formation of a similar chain motif; however, the title compound, (I), crystallizes with lattice water that only weakly holds the chains together. There is only one hydrogen bond from the water molecule to an N atom of the DPTU ligand.
The Cd atom is octahedrally coordinated by two S atoms of two monodentate DPTU ligands, two S atoms of two thiocyanato anions, and two N ends of other thiocyanate anions. The bridging behavior of the thiocyanate group in the formation of eight-membered rings has been documented in other systems (Chen et al., 1999; Ram et al., 1981; Taniguchi et al., 1987). The Cd—S and Cd—N bond distances fall within the range reported for other octahedral cadmium–thiocyanate complexes (Bigoli et al., 1972; Cavalca et al., 1960; Chen et al., 1999; Ram et al., 1981; Taniguchi et al., 1987; Tian et al., 1997; Yang et al., 2000).