catena-Poly­[[[bis(N,N'-di­phenyl­thio­urea)­cadmium(II)]-di-[mu]-thio­cyanato] dihydrate]

Bridging by the two thio­cyanato groups in centrosymmetric six-coordinate bis­(thio­cyanato)­bis­(di­phenyl­thio­urea)­cad­mium(II) dihydrate leads tothe formation of eight-membered [Cd-SCN[rightwards arrow]Cd-SCN[rightwards arrow]] rings that are linked at the metal atom to furnish chains running parallel to the a axis, i.e {[Cd(NCS)₂(C₁₃H₁₂N₂S)₂]·2H₂O}_n.

S1. Comment

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).

S2. Experimental

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.

S3. Refinement

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 R_int 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°.

Computing details

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.

catena-Bis(thiocyanato)bis(diphenylthiourea)cadmium(II) dihydrate

Crystal data

[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) Å^3	Parallelepiped, colorless
Z = 2	0.40 × 0.22 × 0.20 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 0.3895P] where P = (Fo^2 + 2Fc^2)/3
3765 reflections	(Δ/σ)max < 0.001
188 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cd1—N1^i	2.491 (3)	C9—C14	1.379 (5)
Cd1—N1^ii	2.491 (3)	C10—C11	1.385 (5)
Cd1—S1	2.769 (2)	C11—C12	1.382 (6)
Cd1—S1^iii	2.769 (2)	C12—C13	1.348 (6)
Cd1—S2	2.589 (1)	C13—C14	1.383 (5)
Cd1—S2^iii	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)
N1^i—Cd1—N1^ii	180.0	C10—C9—N3	120.8 (3)
N1^i—Cd1—S2^iii	96.4 (1)	C14—C9—N3	119.3 (3)
N1^ii—Cd1—S2^iii	83.7 (1)	C9—C10—C11	119.1 (4)
N1^i—Cd1—S2	83.7 (1)	C12—C11—C10	120.6 (4)
N1^ii—Cd1—S2	96.4 (1)	C13—C12—C11	119.9 (4)
S2^iii—Cd1—S2	180.0	C12—C13—C14	120.3 (4)
N1^i—Cd1—S1	84.7 (1)	C9—C14—C13	120.2 (4)
N1^ii—Cd1—S1	95.3 (1)	H1w1—O1w—H1w2	103.6
S2^iii—Cd1—S1	94.2 (1)	C2—N2—H2	117.1
S2—Cd1—S1	85.8 (1)	C3—N2—H2	117.1
N1^i—Cd1—S1^iii	95.3 (1)	C2—N3—H3	117.9
N1^ii—Cd1—S1^iii	84.7 (1)	C9—N3—H3	117.9
S2^iii—Cd1—S1^iii	85.8 (1)	C3—C4—H4	120.1
S2—Cd1—S1^iii	94.2 (1)	C5—C4—H4	120.1
S1—Cd1—S1^iii	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—Cd1^iv	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)
N1^i—Cd1—S1—C1	−127.0 (1)	C2—N2—C3—C4	−121.8 (3)
N1^ii—Cd1—S1—C1	53.0 (1)	C8—C3—C4—C5	1.2 (5)
S2^iii—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)
S1^iii—Cd1—S1—C1	136 (100)	C4—C5—C6—C7	−0.3 (6)
N1^i—Cd1—S2—C2	146.3 (1)	C5—C6—C7—C8	0.7 (6)
N1^ii—Cd1—S2—C2	−33.7 (1)	C4—C3—C8—C7	−0.7 (5)
S2^iii—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)
S1^iii—Cd1—S2—C2	51.5 (1)	C2—N3—C9—C10	−101.9 (4)
Cd1^iv—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1w	0.86	2.34	3.090 (5)	146