catena-Poly[[bis­(pyridine-κN)cadmium]-di-μ2-thio­cyanato-κ2N:S;κ2S:N]

Boeckmann, J.; Jess, I.; Näther, C.

doi:10.1107/S1600536811009871

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m481

doi:10.1107/S1600536811009871

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catena-Poly[[bis(pyridine-κN)cadmium]-di-μ₂-thiocyanato-κ²N:S;κ²S:N]

Jan Boeckmann,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24098 Kiel, Germany
^*Correspondence e-mail: jboeckmann@ac.uni-kiel.de

(Received 15 March 2011; accepted 16 March 2011; online 26 March 2011)

The asymmetric unit of the title compound, [Cd(NCS)₂(C₅H₅N)₂]_n, consists of two crystallographically independent Cd^II cations, four thiocyanato anions and four pyridine ligands. The Cd^II atoms are each coordinated by four N atoms from two pyridine ligands and two thiocyanato anions, each in a mutually cis orientation, and by two S atoms from two adjacent thiocyanato anions within a slightly distorted octahedral coordination environment. The Cd^II atoms are μ-1,3-bridged via the thiocyanato anions into polymeric chains parallel to [001]. The Cd^II⋯Cd^II intrachain separations range between 5.9688 (6) and 6.0195 (6) Å, whereas the shortest Cd^II⋯Cd^II interchain separations are 7.8272 (7) and 8.6312 (6) Å.

Related literature

For related structures see: Boeckmann & Näther (2010 ); Chen et al. (2005 ); Foner et al. (1975 ); Marsh et al. (2002 ); Porai-Koshits & Tishchenko (1960 ); Reller & Oswald (1986 ); Taniguchi et al. (1987 ); Zhu et al. (2008 ).

Experimental

Crystal data

[Cd(NCS)₂(C₅H₅N)₂]
M_r = 386.76
Triclinic, $[P \overline 1]$
a = 7.8272 (4) Å
b = 8.6242 (4) Å
c = 23.705 (1) Å
α = 84.890 (3)°
β = 89.520 (4)°
γ = 63.070 (3)°
V = 1420.06 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 293 K
0.15 × 0.11 × 0.07 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) T_min = 0.779, T_max = 0.874
21468 measured reflections
5998 independent reflections
4613 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.083
S = 1.17
5998 reflections
343 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Selected bond angles (°)

N1—C1—S1	178.5 (4)
N3—C3—S3	179.1 (5)
N2—C2—S2	179.7 (5)
N4—C4—S4	178.8 (5)

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009871/bt5493sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009871/bt5493Isup2.hkl

checkCIF report

Comment top

The structure determination of the title compound was performed as a part of a project on the synthesis of new one-dimensional coordination compounds (Boeckmann & Näther, 2010). Within this project we have reacted cadmium(II)chloride with potassium(I)thiocyanate and pyridine in water, which leads to the phase pure formation of catena-poly[bis(µ₂-thiocyanato-N, S)-bis(pyridine-N)cadmium(II)].

The title compound crystallizes in the centrosymmetric triclinic space group P1 with four formula units in the unit cell. In the crystal structure each of the two crystallographically independent cadmium atoms is surrounded by four N-atoms of two pyridine ligands and two thiocyanato anions, each in mutually cis orientation, and by two S-atoms of two adjacent thiocyanato anions in a slightly distorted octahedral geometry (Fig. 1 and Tab. 1). The thiocyanato anions bridge the metal cations forming one-dimensional chains (Fig. 2), which elongate along the crystallographic c axis. These chains are arranged in a staggered form and further linked by weak S···S interactions into layers which are located in the ac plane (Fig. 3). A compound of similar composition [Cd(NCS)₂(pyridine)₂]_n has already been described (Taniguchi et al., 1987) and reported to crystallize in the centrosymmetric triclinic space group P1 with six formula units in the unit cell. However, Marsh et al. (2002) found that the triclinic cell can be transformed to a C-centered monoclinic cell with Z = 12. It must be noted that in both cases only unit-cell parameters but no atomic coordinates are reported. Similiar one-dimensional coordination polymers with different transition metals have also been reported (Chen et al. (2005); Foner et al. (1975); Porai-Koshits & Tishchenko (1960); Reller & Oswald (1986); Zhu et al. (2008).

Related literature top

For related structures see: Boeckmann & Näther (2010); Chen et al. (2005); Foner et al.(1975); Marsh et al. (2002); Porai-Koshits & Tishchenko (1960); Reller & Oswald (1986); Taniguchi et al. (1987); Zhu et al. (2008).

Experimental top

The title compound was prepared by the reaction of 91.60 mg CdCl₂ (0.50 mmol), 97.2 mg KSCN (1.00 mmol) and 20.2 µL pyridine (0.25 mmol) in 1.50 ml water at RT in a closed 3 ml snap cap vial. After one week colourless needles of the title compound were obtained.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : Crystal structure of the title compund with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x + 1, -y + 2, -z + 1; ii = -x + 1, -y + 2, -z.
	Fig. 2. : Packing diagram of the title compound with view along the crystallographic a axis onto the one-dimensional polymeric chains.
	Fig. 3. : Packing diagram of the title compound with view along the crystallographic b axis onto the layers located in the ac plane.

catena-Poly[[bis(pyridine-κN)cadmium]-di-µ₂- thiocyanato-κ²N:S;κ²S:N] top

Crystal data top

[Cd(NCS)₂(C₅H₅N)₂]	Z = 4
M_r = 386.76	F(000) = 760
Triclinic, P1	D_x = 1.809 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8272 (4) Å	Cell parameters from 21468 reflections
b = 8.6242 (4) Å	θ = 1.7–26.8°
c = 23.705 (1) Å	µ = 1.82 mm⁻¹
α = 84.890 (3)°	T = 293 K
β = 89.520 (4)°	Needle, colourless
γ = 63.070 (3)°	0.15 × 0.11 × 0.07 mm
V = 1420.06 (11) Å³

Data collection top

Stoe IPDS-2 diffractometer	5998 independent reflections
Radiation source: fine-focus sealed tube	4613 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
ω scans	θ_max = 26.8°, θ_min = 1.7°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −9→9
T_min = 0.779, T_max = 0.874	k = −10→10
21468 measured reflections	l = −29→29

Refinement top

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0176P)² + 0.9412P] where P = (F_o² + 2F_c²)/3
5998 reflections	(Δ/σ)_max < 0.001
343 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[Cd(NCS)₂(C₅H₅N)₂]	γ = 63.070 (3)°
M_r = 386.76	V = 1420.06 (11) Å³
Triclinic, P1	Z = 4
a = 7.8272 (4) Å	Mo Kα radiation
b = 8.6242 (4) Å	µ = 1.82 mm⁻¹
c = 23.705 (1) Å	T = 293 K
α = 84.890 (3)°	0.15 × 0.11 × 0.07 mm
β = 89.520 (4)°

Data collection top

Stoe IPDS-2 diffractometer	5998 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	4613 reflections with I > 2σ(I)
T_min = 0.779, T_max = 0.874	R_int = 0.071
21468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.17	Δρ_max = 0.60 e Å⁻³
5998 reflections	Δρ_min = −0.75 e Å⁻³
343 parameters

Special details top

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.55905 (5)	0.97050 (4)	0.375033 (15)	0.03786 (11)
Cd2	0.44978 (6)	0.99144 (5)	0.125075 (15)	0.03970 (11)
S1	0.8352 (2)	0.93622 (19)	0.45431 (6)	0.0470 (3)
S3	0.2004 (2)	0.9601 (2)	0.20176 (6)	0.0542 (4)
S2	0.8141 (2)	0.9986 (2)	0.29930 (6)	0.0479 (3)
S4	0.1714 (2)	1.0203 (2)	0.04890 (7)	0.0542 (4)
N1	0.6266 (7)	1.0543 (6)	0.5514 (2)	0.0483 (11)
N3	0.3481 (7)	0.9946 (6)	0.3040 (2)	0.0501 (12)
N2	0.6584 (7)	0.9716 (6)	0.1968 (2)	0.0512 (12)
N11	0.4113 (6)	1.2780 (5)	0.37531 (19)	0.0424 (10)
N21	0.7184 (7)	0.6634 (5)	0.3729 (2)	0.0452 (11)
N31	0.2874 (7)	1.2985 (6)	0.1265 (2)	0.0494 (12)
N41	0.5944 (7)	0.6842 (6)	0.1253 (2)	0.0511 (12)
C1	0.7117 (7)	1.0078 (6)	0.5111 (2)	0.0371 (11)
C3	0.2885 (7)	0.9809 (6)	0.2618 (2)	0.0380 (11)
C2	0.7225 (7)	0.9828 (6)	0.2393 (2)	0.0382 (11)
C4	0.2834 (8)	1.0002 (6)	−0.0110 (2)	0.0386 (11)
C11	0.3248 (9)	1.3573 (7)	0.4204 (3)	0.0548 (15)
H11	0.3199	1.2890	0.4524	0.066*
C13	0.2505 (10)	1.6376 (7)	0.3758 (3)	0.0653 (18)
H13	0.1991	1.7580	0.3764	0.078*
C14	0.3353 (10)	1.5601 (8)	0.3289 (3)	0.0614 (17)
H14	0.3396	1.6272	0.2964	0.074*
C15	0.4150 (9)	1.3809 (7)	0.3299 (3)	0.0538 (14)
H15	0.4738	1.3290	0.2976	0.065*
C21	0.8169 (9)	0.5864 (7)	0.3292 (3)	0.0543 (15)
H21	0.8185	0.6566	0.2972	0.065*
C22	0.9167 (10)	0.4081 (8)	0.3286 (3)	0.0624 (17)
H22	0.9840	0.3597	0.2969	0.075*
C23	0.9157 (9)	0.3043 (8)	0.3745 (3)	0.0623 (17)
H23	0.9842	0.1835	0.3751	0.075*
C24	0.8136 (11)	0.3782 (8)	0.4199 (3)	0.0664 (18)
H24	0.8091	0.3092	0.4518	0.080*
C25	0.7165 (10)	0.5588 (7)	0.4175 (3)	0.0561 (15)
H25	0.6466	0.6094	0.4486	0.067*
C31	0.2529 (10)	1.3725 (8)	0.1749 (3)	0.0601 (16)
H31	0.3017	1.3017	0.2086	0.072*
C33	0.0767 (10)	1.6554 (8)	0.1281 (4)	0.0691 (19)
H33	0.0063	1.7757	0.1287	0.083*
C34	0.1113 (11)	1.5804 (8)	0.0782 (3)	0.075 (2)
H34	0.0647	1.6488	0.0439	0.090*
C35	0.2159 (10)	1.4025 (8)	0.0794 (3)	0.0636 (17)
H35	0.2377	1.3525	0.0453	0.076*
C41	0.6102 (10)	0.6087 (8)	0.0777 (3)	0.0619 (17)
H41	0.5715	0.6788	0.0435	0.074*
C42	0.6816 (11)	0.4304 (9)	0.0770 (3)	0.074 (2)
H42	0.6885	0.3819	0.0430	0.088*
C43	0.7418 (10)	0.3267 (8)	0.1266 (4)	0.0678 (19)
H43	0.7921	0.2061	0.1270	0.081*
C44	0.7273 (12)	0.4020 (9)	0.1756 (4)	0.075 (2)
H44	0.7653	0.3340	0.2102	0.090*
C45	0.6555 (10)	0.5800 (8)	0.1730 (3)	0.0624 (17)
H45	0.6494	0.6303	0.2066	0.075*
C32	0.1479 (12)	1.5493 (8)	0.1769 (4)	0.074 (2)
H32	0.1254	1.5965	0.2116	0.088*
C12	0.2420 (10)	1.5359 (8)	0.4219 (3)	0.0677 (19)
H12	0.1810	1.5863	0.4541	0.081*
N4	0.3589 (8)	0.9870 (7)	−0.0535 (2)	0.0531 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0446 (2)	0.03687 (19)	0.0315 (2)	−0.01765 (16)	0.00348 (18)	−0.00516 (15)
Cd2	0.0456 (3)	0.0426 (2)	0.0309 (2)	−0.01997 (17)	0.00095 (18)	−0.00324 (16)
S1	0.0417 (8)	0.0603 (8)	0.0370 (8)	−0.0204 (6)	0.0045 (6)	−0.0103 (6)
S3	0.0585 (10)	0.0841 (10)	0.0350 (8)	−0.0451 (8)	0.0040 (7)	−0.0085 (7)
S2	0.0482 (8)	0.0707 (9)	0.0340 (8)	−0.0345 (7)	0.0035 (6)	−0.0085 (6)
S4	0.0474 (9)	0.0867 (10)	0.0348 (8)	−0.0355 (8)	0.0032 (7)	−0.0087 (7)
N1	0.050 (3)	0.062 (3)	0.039 (3)	−0.030 (2)	0.005 (2)	−0.007 (2)
N3	0.053 (3)	0.068 (3)	0.036 (3)	−0.033 (2)	0.001 (2)	−0.007 (2)
N2	0.051 (3)	0.069 (3)	0.037 (3)	−0.031 (2)	−0.003 (2)	−0.004 (2)
N11	0.042 (3)	0.043 (2)	0.039 (3)	−0.0169 (19)	−0.001 (2)	−0.0019 (18)
N21	0.052 (3)	0.040 (2)	0.043 (3)	−0.020 (2)	0.000 (2)	−0.0059 (19)
N31	0.052 (3)	0.044 (2)	0.050 (3)	−0.020 (2)	0.001 (2)	−0.003 (2)
N41	0.050 (3)	0.043 (2)	0.056 (3)	−0.018 (2)	0.003 (3)	−0.002 (2)
C1	0.038 (3)	0.033 (2)	0.040 (3)	−0.018 (2)	−0.003 (2)	0.003 (2)
C3	0.037 (3)	0.037 (2)	0.037 (3)	−0.014 (2)	0.006 (2)	−0.002 (2)
C2	0.035 (3)	0.037 (2)	0.042 (3)	−0.016 (2)	0.009 (2)	−0.001 (2)
C4	0.040 (3)	0.039 (2)	0.039 (3)	−0.019 (2)	−0.008 (2)	−0.001 (2)
C11	0.060 (4)	0.049 (3)	0.047 (3)	−0.017 (3)	0.007 (3)	−0.004 (2)
C13	0.064 (4)	0.034 (3)	0.086 (5)	−0.014 (3)	−0.007 (4)	0.001 (3)
C14	0.069 (4)	0.048 (3)	0.066 (4)	−0.028 (3)	−0.006 (3)	0.014 (3)
C15	0.057 (4)	0.052 (3)	0.048 (4)	−0.021 (3)	0.004 (3)	0.002 (2)
C21	0.063 (4)	0.049 (3)	0.050 (4)	−0.024 (3)	0.007 (3)	−0.009 (3)
C22	0.067 (4)	0.051 (3)	0.069 (5)	−0.023 (3)	0.011 (3)	−0.023 (3)
C23	0.055 (4)	0.044 (3)	0.082 (5)	−0.016 (3)	−0.006 (3)	−0.013 (3)
C24	0.089 (5)	0.045 (3)	0.059 (4)	−0.027 (3)	−0.006 (4)	0.005 (3)
C25	0.072 (4)	0.050 (3)	0.043 (3)	−0.024 (3)	0.002 (3)	−0.005 (2)
C31	0.071 (4)	0.051 (3)	0.054 (4)	−0.024 (3)	−0.005 (3)	−0.006 (3)
C33	0.066 (4)	0.046 (3)	0.093 (6)	−0.023 (3)	0.001 (4)	−0.008 (4)
C34	0.081 (5)	0.052 (4)	0.073 (5)	−0.018 (3)	−0.009 (4)	0.015 (3)
C35	0.074 (4)	0.055 (4)	0.052 (4)	−0.021 (3)	−0.001 (3)	−0.001 (3)
C41	0.075 (4)	0.048 (3)	0.052 (4)	−0.018 (3)	0.004 (3)	−0.007 (3)
C42	0.080 (5)	0.063 (4)	0.072 (5)	−0.025 (4)	0.010 (4)	−0.025 (4)
C43	0.062 (4)	0.048 (3)	0.090 (6)	−0.024 (3)	0.005 (4)	0.002 (3)
C44	0.091 (6)	0.058 (4)	0.068 (5)	−0.029 (4)	−0.006 (4)	0.012 (3)
C45	0.074 (5)	0.052 (3)	0.057 (4)	−0.026 (3)	−0.008 (3)	0.001 (3)
C32	0.093 (6)	0.050 (4)	0.074 (5)	−0.027 (4)	0.006 (4)	−0.019 (3)
C12	0.076 (5)	0.046 (3)	0.064 (5)	−0.011 (3)	0.004 (4)	−0.011 (3)
N4	0.054 (3)	0.076 (3)	0.035 (3)	−0.035 (2)	0.007 (2)	−0.008 (2)

Geometric parameters (Å, º) top

Cd1—N3	2.298 (5)	C13—H13	0.9300
Cd1—N1ⁱ	2.317 (5)	C14—C15	1.378 (8)
Cd1—N11	2.365 (4)	C14—H14	0.9300
Cd1—N21	2.367 (4)	C15—H15	0.9300
Cd1—S2	2.7508 (15)	C21—C22	1.375 (8)
Cd1—S1	2.7715 (16)	C21—H21	0.9300
Cd2—N4ⁱⁱ	2.303 (5)	C22—C23	1.349 (10)
Cd2—N2	2.309 (5)	C22—H22	0.9300
Cd2—N41	2.363 (4)	C23—C24	1.361 (9)
Cd2—N31	2.366 (4)	C23—H23	0.9300
Cd2—S3	2.7416 (16)	C24—C25	1.385 (8)
Cd2—S4	2.7503 (17)	C24—H24	0.9300
S1—C1	1.647 (5)	C25—H25	0.9300
S3—C3	1.646 (6)	C31—C32	1.371 (9)
S2—C2	1.642 (6)	C31—H31	0.9300
S4—C4	1.643 (6)	C33—C32	1.360 (11)
N1—C1	1.156 (6)	C33—C34	1.365 (11)
N1—Cd1ⁱ	2.317 (5)	C33—H33	0.9300
N3—C3	1.144 (7)	C34—C35	1.371 (9)
N2—C2	1.159 (7)	C34—H34	0.9300
N11—C11	1.329 (7)	C35—H35	0.9300
N11—C15	1.342 (7)	C41—C42	1.379 (8)
N21—C21	1.326 (7)	C41—H41	0.9300
N21—C25	1.332 (7)	C42—C43	1.358 (11)
N31—C35	1.318 (8)	C42—H42	0.9300
N31—C31	1.329 (8)	C43—C44	1.360 (11)
N41—C45	1.324 (8)	C43—H43	0.9300
N41—C41	1.331 (8)	C44—C45	1.370 (9)
C4—N4	1.153 (7)	C44—H44	0.9300
C11—C12	1.378 (8)	C45—H45	0.9300
C11—H11	0.9300	C32—H32	0.9300
C13—C14	1.357 (10)	C12—H12	0.9300
C13—C12	1.360 (10)	N4—Cd2ⁱⁱ	2.303 (5)

N3—Cd1—N1ⁱ	95.37 (17)	C14—C13—H13	120.6
N3—Cd1—N11	90.26 (17)	C12—C13—H13	120.6
N1ⁱ—Cd1—N11	91.19 (16)	C13—C14—C15	119.2 (6)
N3—Cd1—N21	90.51 (17)	C13—C14—H14	120.4
N1ⁱ—Cd1—N21	91.07 (16)	C15—C14—H14	120.4
N11—Cd1—N21	177.54 (15)	N11—C15—C14	122.9 (6)
N3—Cd1—S2	92.60 (12)	N11—C15—H15	118.6
N1ⁱ—Cd1—S2	172.02 (13)	C14—C15—H15	118.6
N11—Cd1—S2	88.36 (11)	N21—C21—C22	123.3 (6)
N21—Cd1—S2	89.27 (12)	N21—C21—H21	118.3
N3—Cd1—S1	175.47 (12)	C22—C21—H21	118.3
N1ⁱ—Cd1—S1	89.01 (13)	C23—C22—C21	119.1 (6)
N11—Cd1—S1	90.83 (12)	C23—C22—H22	120.4
N21—Cd1—S1	88.23 (12)	C21—C22—H22	120.4
S2—Cd1—S1	83.03 (4)	C22—C23—C24	119.3 (6)
N4ⁱⁱ—Cd2—N2	94.30 (17)	C22—C23—H23	120.3
N4ⁱⁱ—Cd2—N41	91.31 (18)	C24—C23—H23	120.3
N2—Cd2—N41	91.26 (18)	C23—C24—C25	118.4 (6)
N4ⁱⁱ—Cd2—N31	91.68 (17)	C23—C24—H24	120.8
N2—Cd2—N31	90.34 (17)	C25—C24—H24	120.8
N41—Cd2—N31	176.50 (16)	N21—C25—C24	123.2 (6)
N4ⁱⁱ—Cd2—S3	174.04 (13)	N21—C25—H25	118.4
N2—Cd2—S3	91.52 (13)	C24—C25—H25	118.4
N41—Cd2—S3	87.27 (13)	N31—C31—C32	122.4 (7)
N31—Cd2—S3	89.57 (12)	N31—C31—H31	118.8
N4ⁱⁱ—Cd2—S4	92.06 (14)	C32—C31—H31	118.8
N2—Cd2—S4	173.51 (13)	C32—C33—C34	118.1 (6)
N41—Cd2—S4	89.88 (14)	C32—C33—H33	120.9
N31—Cd2—S4	88.19 (13)	C34—C33—H33	120.9
S3—Cd2—S4	82.16 (5)	C33—C34—C35	118.8 (7)
C1—S1—Cd1	103.53 (19)	C33—C34—H34	120.6
C3—S3—Cd2	101.98 (18)	C35—C34—H34	120.6
C2—S2—Cd1	101.04 (17)	N31—C35—C34	123.6 (6)
C4—S4—Cd2	101.36 (19)	N31—C35—H35	118.2
C1—N1—Cd1ⁱ	152.4 (4)	C34—C35—H35	118.2
C3—N3—Cd1	161.5 (4)	N41—C41—C42	122.6 (6)
C2—N2—Cd2	163.6 (4)	N41—C41—H41	118.7
C11—N11—C15	116.7 (5)	C42—C41—H41	118.7
C11—N11—Cd1	122.2 (4)	C43—C42—C41	119.1 (7)
C15—N11—Cd1	121.1 (4)	C43—C42—H42	120.5
C21—N21—C25	116.7 (5)	C41—C42—H42	120.5
C21—N21—Cd1	123.0 (4)	C42—C43—C44	119.0 (6)
C25—N21—Cd1	120.3 (4)	C42—C43—H43	120.5
C35—N31—C31	117.2 (5)	C44—C43—H43	120.5
C35—N31—Cd2	121.2 (4)	C43—C44—C45	118.7 (7)
C31—N31—Cd2	121.4 (4)	C43—C44—H44	120.7
C45—N41—C41	117.1 (5)	C45—C44—H44	120.7
C45—N41—Cd2	121.6 (4)	N41—C45—C44	123.6 (7)
C41—N41—Cd2	121.3 (4)	N41—C45—H45	118.2
N1—C1—S1	178.5 (4)	C44—C45—H45	118.2
N3—C3—S3	179.1 (5)	C33—C32—C31	119.8 (7)
N2—C2—S2	179.7 (5)	C33—C32—H32	120.1
N4—C4—S4	178.8 (5)	C31—C32—H32	120.1
N11—C11—C12	123.2 (6)	C13—C12—C11	119.2 (6)
N11—C11—H11	118.4	C13—C12—H12	120.4
C12—C11—H11	118.4	C11—C12—H12	120.4
C14—C13—C12	118.8 (5)	C4—N4—Cd2ⁱⁱ	162.1 (4)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₅H₅N)₂]
M_r	386.76
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.8272 (4), 8.6242 (4), 23.705 (1)
α, β, γ (°)	84.890 (3), 89.520 (4), 63.070 (3)
V (Å³)	1420.06 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.82
Crystal size (mm)	0.15 × 0.11 × 0.07

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.779, 0.874
No. of measured, independent and observed [I > 2σ(I)] reflections	21468, 5998, 4613
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.083, 1.17
No. of reflections	5998
No. of parameters	343
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.75

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011).

Selected bond angles (º) top

N1—C1—S1	178.5 (4)	N2—C2—S2	179.7 (5)
N3—C3—S3	179.1 (5)	N4—C4—S4	178.8 (5)

Acknowledgements

We gratefully acknowledge financial support by the DFG (project number NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for the opportunity to use of his experimental facility.

References

Boeckmann, J. & Näther, C. (2010). Dalton Trans. pp. 11019–11026. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany Google Scholar
Chen, G., Bai, Z.-P. & Qu, S.-J. (2005). Acta Cryst. E61, m2718–m2719. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Foner, S., Frankel, R. B., McNiff, J. E. J., Reiff, W. M., Little, B. F. & Long, G. J. (1975). AIP Conf. Proc. 24, 363–364. CrossRef Google Scholar
Marsh, R. E., Kapon, M., Hu, S. & Herbstein, F. H. (2002). Acta Cryst. B58, 62–77. CSD CrossRef CAS IUCr Journals Google Scholar
Porai-Koshits, M. A. & Tishchenko, G. N. (1960). Crystallogr. Rep. 4, 239–239. Google Scholar
Reller, A. & Oswald, H.-R. (1986). J. Solid State Chem. 62, 306–316. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Taniguchi, M., Sugita, Y. & Ouchi, A. (1987). Bull. Chem. Soc. Jpn, 60, 1321–1326. CrossRef CAS Web of Science Google Scholar
Zhu, L., Xu, D., Wang, X. & Yu, G. (2008). J. Chem. Crystallogr. 38, 609–612. CSD CrossRef CAS Google Scholar