catena-Poly[[bis­(2-meth­oxy­aniline-κN)cadmium]-di-μ-thio­cyanato-κ2N:S;κ2S:N]

Chemli, R.; Kamoun, S.; Roisnel, T.

doi:10.1107/S1600536813010738

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m292-m293

https://doi.org/10.1107/S1600536813010738

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catena-Poly[[bis(2-methoxyaniline-κN)cadmium]-di-μ-thiocyanato-κ²N:S;κ²S:N]

Rakia Chemli,^a Slaheddine Kamoun ^a ^* and Thierry Roisnel ^b

^aLaboratoire de Génie des Matériaux et Environnement, École Nationale d'Ingénieurs de Sfax, BP 1173, Sfax, Tunisia, and ^bCentre de Diffractométrie X, UMR 6226 CNRS Unitée Sciences, Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France
^*Correspondence e-mail: slah.kamoun@gmail.com

(Received 13 April 2013; accepted 19 April 2013; online 27 April 2013)

The structure of the title compound, [Cd(NCS)₂(C₇H₉NO)₂]_n, consists of cadmium–thiocyanate layers parallel to the ab plane. Pairs of Cd^II ions are bridged by two end-to-end inversely bridging μ-NCS-N:S thiocyanate groups, forming a two-dimensional network with the remaining two trans positions of the octahedrally coordinated Cd^II ions occupied by the N atoms of two neutral 2-methoxyaniline ligands. The crystal structure is stabilized by intralayer N—H⋯S hydrogen bonds.

Related literature

For related structures, see: Wöhlert et al. (2012 , 2013 ); Bai et al. (2011 ); Yang et al. (2001 ). For HSCN synthesis, see: Bartlett et al. (1969 ). For the effects of substituents on the internal angles of the benzene ring, see: Domenicano & Murray-Rust (1979 ). For non-linear optical and luminescence properties of related compounds, see: Chen et al. (2000 ); Bai et al. (2011). For electric and dielectric properties of related compounds, see: Karoui et al. (2013 ).

Experimental

Crystal data

[Cd(NCS)₂(C₇H₉NO)₂]
M_r = 474.89
Orthorhombic, P b c a
a = 6.6860 (2) Å
b = 23.3658 (7) Å
c = 24.3281 (8) Å
V = 3800.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 150 K
0.33 × 0.18 × 0.11 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.741, T_max = 0.859
16897 measured reflections
4210 independent reflections
3262 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.055
S = 1.02
4210 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N2	2.2724 (19)
Cd1—N1	2.3142 (18)
Cd1—N11	2.3653 (17)
Cd1—N21	2.3718 (17)
Cd1—S1ⁱ	2.7306 (6)
Cd1—S2ⁱⁱ	2.7449 (6)
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11A⋯S2ⁱⁱⁱ	0.92	2.50	3.4182 (17)	174
N21—H21B⋯S1^iv	0.92	2.66	3.5637 (18)	169
Symmetry codes: (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813010738/rz5058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010738/rz5058Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813010738/rz5058Isup3.cdx

checkCIF report

Comment top

The crystal engineering of inorganic-organic hybrid coordination polymers is currently one of the most active fields in coordination chemistry, supramolecular and materials chemistry. These compounds attract significant attention for their architectures and topologies (Yang et al., 2001). Hybrid inorganic-organic thiocyanate materials exhibit interesting physical properties such electrical conductivity and dielectric relaxation process (Karoui et al., 2013) and may have potential applications in non-linear optics and luminescence (Chen et al., 2000; Bai et al., 2011). Herein we report the structure of a new polymeric hybrid title compound

As shown in Fig. 1, each cadmium atom, which sits on general position, is coordinated by two trans N-bonded and two trans S-bonded thiocyanato anions. Two trans-coordinated 2-methoxy aniline ligands complete the octahedral coordination geometry around cadmium. The crystal structure of the title compound consists of both simply and doubly µ-1,3-SCN–bridged two dimensional networks parallel to the ab plane with terminal neutral 2-methoxyaniline ligands (Fig. 2). In the CdN₄S₂ core, the Cd—N and Cd—S bonds span the range 2.2724 (19)–2.3718 (17) Å and 2.7306 (6)–2.7449 (6) Å, respectively (Table 1). These values are in good agreement with those observed in other similar complexes (Wöhlert et al., 2012, 2013; Yang et al., 2001). The bond angles involving the cadmium(II) cation range from 84.29 (6) to 95.50 (7)° and from 174.91 (2) to 175.76 (6)°. The double-bridging role of S1/C1/N1 anions gives rise to eight-membered Cd₂(SCN)₂ rings in a chair conformation because of the almost linear SCN groups (S1–C1–N1 angle = 178.76 (21)°). The distance between adjacent Cd atoms in the Cd₂(SCN)₂ rings is 5.9127 (4) Å. Again, these rings built up a 2-D sheet through their corner-sharing action at the two cadmium atoms via the linear S2/C2/N2 anions (S1–C1–N1 angle = 177.96 (21)°) and give rise to thirty-membered [Cd₆(µ-SCN-N,S)₈] macrocycles as subunits, as shown in Fig. 2. The bond angles in the phenyl groups deviate significantly from the idealized value of 120° due to the effect of the substituent. In fact, it was established that the angular deformations of phenyl groups can be described as a sum of the effects of the different substituents (Domenicano & Murray-Rust, 1979). The phenyl rings of both independent 2-methoxyaniline ligands are planar with the greatest deviation from the six-atoms least-square plane of 0.0029 Å and 0.0073 Å. They are well ordered with C–C–C angles in agreement with the expected sp² hybridation. The π-π interactions between phenyl rings may be neglected (>4 Å); in fact the shortest distances between the centroids of the rings are: Cg1 ··· Cg1ⁱ = 5.6130 (14) Å; Cg1 ··· Cg2ⁱⁱ = 5.5949 (14) Å (Cg1 and Cg2 are the centroids of the C12–C17 and C22–C27 rings, respectively; symmetry codes: (i) -0.5+x, +y, 1.5-z; 2.-x, -y, 1.-z). The major contributions to the cohesion and the stability of the polymeric structure is the presence of intralayer N—H···S hydrogen bonds which include two relatively long contacts, with H···S and N..S distances ranging from 2.50 to 2.66 Å and 3.4182 (17) Å to 3.5637 (18) Å, respectively (Table 2).

Related literature top

For related structures, see: Wöhlert et al. (2012, 2013); Bai et al. (2011); Yang et al. (2001). For HSCN synthesis, see: Bartlett et al. (1969). For the effects of substituents on the internal angles of the benzene ring, see: Domenicano & Murray-Rust (1979). For non-linear optical and luminescence properties of related compounds, see: Chen et al. (2000); Bai et al. (2011). For electric and dielectric properties of related compounds, see: Karoui et al. (2013).

Experimental top

To 25 ml of an aqueous solution of thiocyanic acid (0.8 M) prepared using the published procedure (Bartlett et al., 1969) an appropriate amount of cadmium carbonate (1.664 g, 10 mmol) was added and refluxed for 3 h. After cooling, 25 ml of methanol and 2.3 ml of a solution of 2-methoxyaniline (8.64 M) was added. The resulting solution was heated under reflux for 1 h and left to stand at ambient temperature. Well shaped colourless crystals were obtained after 2 h on slow evaporation of the solvent. They were washed with diethyl ether and dried over P₂O₅.

Structure description top

For related structures, see: Wöhlert et al. (2012, 2013); Bai et al. (2011); Yang et al. (2001). For HSCN synthesis, see: Bartlett et al. (1969). For the effects of substituents on the internal angles of the benzene ring, see: Domenicano & Murray-Rust (1979). For non-linear optical and luminescence properties of related compounds, see: Chen et al. (2000); Bai et al. (2011). For electric and dielectric properties of related compounds, see: Karoui et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Crystal structure of the title compound, showing the coordination around the Cd²⁺ cation with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View at z=0 of the two-dimensional layer structure of the inorganic coordination polymer parallel to the ab plane. The organic ligands are omitted for clarity.

catena-Poly[[bis(2-methoxyaniline-κN)cadmium]-di-µ-thiocyanato-κ²N:S;κ²S:N] top

Crystal data top

[Cd(NCS)₂(C₇H₉NO)₂]	F(000) = 1904
M_r = 474.89	D_x = 1.660 Mg m⁻³ D_m = 1.593 Mg m⁻³ D_m measured by flotation
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5155 reflections
a = 6.6860 (2) Å	θ = 3.1–27.4°
b = 23.3658 (7) Å	µ = 1.39 mm⁻¹
c = 24.3281 (8) Å	T = 150 K
V = 3800.6 (2) Å³	Prism, colourless
Z = 8	0.33 × 0.18 × 0.11 mm

Data collection top

Bruker APEXII diffractometer	3262 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
CCD rotation images, thin slices scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −29→30
T_min = 0.741, T_max = 0.859	l = −31→20
16897 measured reflections	2 standard reflections every 120 min
4210 independent reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0184P)² + 1.4548P] where P = (F_o² + 2F_c²)/3
4210 reflections	(Δ/σ)_max = 0.004
228 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cd(NCS)₂(C₇H₉NO)₂]	V = 3800.6 (2) Å³
M_r = 474.89	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 6.6860 (2) Å	µ = 1.39 mm⁻¹
b = 23.3658 (7) Å	T = 150 K
c = 24.3281 (8) Å	0.33 × 0.18 × 0.11 mm

Data collection top

Bruker APEXII diffractometer	4210 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	3262 reflections with I > 2σ(I)
T_min = 0.741, T_max = 0.859	R_int = 0.031
16897 measured reflections	2 standard reflections every 120 min

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.055	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
4210 reflections	Δρ_min = −0.38 e Å⁻³
228 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	0.99993 (2)	0.126200 (7)	0.508711 (7)	0.02024 (6)
S1	0.68873 (8)	−0.06757 (2)	0.53717 (3)	0.03279 (16)
C1	0.7845 (3)	−0.00256 (9)	0.53832 (8)	0.0191 (5)
N1	0.8515 (3)	0.04293 (8)	0.54015 (8)	0.0253 (4)
S2	1.17331 (8)	0.32408 (2)	0.44237 (3)	0.02739 (14)
N2	1.1259 (3)	0.21155 (8)	0.48030 (8)	0.0266 (4)
C2	1.1461 (3)	0.25807 (9)	0.46565 (9)	0.0193 (5)
N11	1.1959 (2)	0.13518 (7)	0.58919 (7)	0.0213 (4)
H11A	1.3247	0.1440	0.5789	0.026*
H11B	1.1478	0.1657	0.6092	0.026*
C12	1.2028 (3)	0.08631 (9)	0.62450 (9)	0.0220 (5)
C13	1.3485 (3)	0.04507 (10)	0.61900 (10)	0.0312 (6)
H13	1.4520	0.0498	0.5926	0.037*
C14	1.3446 (4)	−0.00363 (11)	0.65207 (11)	0.0412 (7)
H14	1.4466	−0.0317	0.6488	0.049*
C15	1.1926 (5)	−0.01091 (11)	0.68948 (11)	0.0441 (7)
H15	1.1889	−0.0445	0.7115	0.053*
C16	1.0444 (4)	0.03030 (12)	0.69545 (9)	0.0362 (6)
H16	0.9394	0.0249	0.7213	0.043*
C17	1.0510 (3)	0.07931 (10)	0.66349 (9)	0.0258 (5)
O18	0.9195 (2)	0.12405 (7)	0.66597 (7)	0.0344 (4)
C19	0.7522 (4)	0.11868 (13)	0.70215 (11)	0.0478 (8)
H19A	0.6797	0.0833	0.6938	0.072*
H19B	0.6628	0.1515	0.6972	0.072*
H19C	0.7994	0.1176	0.7403	0.072*
N21	0.8084 (3)	0.10925 (8)	0.42829 (7)	0.0240 (4)
H21A	0.8731	0.0813	0.4085	0.029*
H21B	0.6879	0.0941	0.4393	0.029*
C22	0.7653 (3)	0.15518 (10)	0.39121 (9)	0.0230 (5)
C23	0.5968 (3)	0.18854 (10)	0.39643 (9)	0.0281 (5)
H23	0.5026	0.1805	0.4246	0.034*
C24	0.5637 (4)	0.23401 (11)	0.36050 (10)	0.0344 (6)
H24	0.4466	0.2568	0.3640	0.041*
C25	0.7010 (4)	0.24592 (11)	0.31981 (10)	0.0380 (6)
H25	0.6786	0.2771	0.2955	0.046*
C26	0.8727 (4)	0.21251 (11)	0.31418 (9)	0.0346 (6)
H26	0.9674	0.2209	0.2862	0.042*
C27	0.9044 (3)	0.16704 (10)	0.34953 (9)	0.0269 (5)
O28	1.0642 (2)	0.13068 (7)	0.34823 (7)	0.0348 (4)
C29	1.1988 (4)	0.13507 (13)	0.30289 (10)	0.0446 (7)
H29A	1.1241	0.1312	0.2684	0.067*
H29B	1.2992	0.1046	0.3053	0.067*
H29C	1.2655	0.1724	0.3038	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02022 (9)	0.01308 (9)	0.02743 (10)	−0.00211 (6)	0.00012 (7)	0.00258 (7)
S1	0.0237 (3)	0.0153 (3)	0.0594 (4)	−0.0043 (2)	0.0168 (3)	−0.0044 (3)
C1	0.0164 (9)	0.0193 (12)	0.0217 (11)	0.0047 (9)	0.0036 (9)	0.0024 (10)
N1	0.0238 (9)	0.0161 (10)	0.0361 (11)	0.0001 (8)	0.0062 (9)	0.0016 (9)
S2	0.0211 (3)	0.0175 (3)	0.0435 (3)	−0.0045 (2)	−0.0093 (3)	0.0096 (3)
N2	0.0265 (10)	0.0169 (10)	0.0364 (11)	−0.0047 (8)	0.0035 (9)	0.0010 (9)
C2	0.0143 (9)	0.0202 (12)	0.0235 (11)	−0.0014 (9)	−0.0001 (9)	−0.0028 (10)
N11	0.0192 (8)	0.0177 (10)	0.0272 (10)	−0.0018 (8)	0.0048 (8)	−0.0019 (8)
C12	0.0241 (10)	0.0196 (11)	0.0224 (11)	−0.0026 (9)	−0.0044 (9)	−0.0025 (10)
C13	0.0339 (12)	0.0283 (13)	0.0314 (13)	0.0025 (11)	−0.0080 (11)	−0.0051 (12)
C14	0.0588 (17)	0.0254 (14)	0.0392 (15)	0.0107 (13)	−0.0238 (14)	−0.0068 (13)
C15	0.077 (2)	0.0220 (14)	0.0334 (15)	−0.0083 (14)	−0.0267 (15)	0.0048 (12)
C16	0.0501 (15)	0.0380 (16)	0.0205 (12)	−0.0184 (13)	−0.0058 (11)	0.0031 (12)
C17	0.0309 (11)	0.0254 (13)	0.0211 (11)	−0.0053 (10)	−0.0024 (10)	−0.0010 (11)
O18	0.0304 (8)	0.0399 (11)	0.0330 (9)	0.0006 (8)	0.0131 (8)	0.0038 (8)
C19	0.0336 (14)	0.070 (2)	0.0400 (16)	−0.0100 (14)	0.0149 (12)	−0.0017 (16)
N21	0.0248 (9)	0.0219 (10)	0.0253 (10)	−0.0043 (8)	0.0037 (8)	−0.0030 (9)
C22	0.0289 (11)	0.0201 (12)	0.0201 (11)	−0.0065 (10)	−0.0032 (9)	−0.0052 (10)
C23	0.0294 (12)	0.0292 (13)	0.0259 (12)	−0.0053 (11)	−0.0023 (10)	−0.0073 (11)
C24	0.0422 (13)	0.0243 (13)	0.0366 (14)	0.0016 (12)	−0.0112 (12)	−0.0102 (12)
C25	0.0625 (17)	0.0245 (14)	0.0270 (13)	−0.0068 (13)	−0.0123 (13)	0.0007 (12)
C26	0.0503 (15)	0.0342 (15)	0.0194 (12)	−0.0115 (13)	0.0036 (11)	−0.0036 (12)
C27	0.0312 (12)	0.0263 (13)	0.0231 (12)	−0.0055 (11)	−0.0005 (10)	−0.0060 (11)
O28	0.0319 (8)	0.0434 (11)	0.0290 (9)	0.0008 (8)	0.0089 (7)	−0.0014 (8)
C29	0.0358 (14)	0.066 (2)	0.0321 (14)	−0.0049 (14)	0.0089 (12)	−0.0082 (14)

Geometric parameters (Å, º) top

Cd1—N2	2.2724 (19)	C16—H16	0.9500
Cd1—N1	2.3142 (18)	C17—O18	1.367 (3)
Cd1—N11	2.3653 (17)	O18—C19	1.429 (3)
Cd1—N21	2.3718 (17)	C19—H19A	0.9800
Cd1—S1ⁱ	2.7306 (6)	C19—H19B	0.9800
Cd1—S2ⁱⁱ	2.7449 (6)	C19—H19C	0.9800
S1—C1	1.649 (2)	N21—C22	1.431 (3)
S1—Cd1ⁱ	2.7306 (6)	N21—H21A	0.9200
C1—N1	1.154 (3)	N21—H21B	0.9200
S2—C2	1.653 (2)	C22—C23	1.376 (3)
S2—Cd1ⁱⁱⁱ	2.7449 (5)	C22—C27	1.403 (3)
N2—C2	1.152 (3)	C23—C24	1.394 (3)
N11—C12	1.430 (3)	C23—H23	0.9500
N11—H11A	0.9200	C24—C25	1.379 (3)
N11—H11B	0.9200	C24—H24	0.9500
C12—C13	1.377 (3)	C25—C26	1.395 (3)
C12—C17	1.399 (3)	C25—H25	0.9500
C13—C14	1.394 (3)	C26—C27	1.383 (3)
C13—H13	0.9500	C26—H26	0.9500
C14—C15	1.375 (4)	C27—O28	1.365 (3)
C14—H14	0.9500	O28—C29	1.427 (3)
C15—C16	1.389 (4)	C29—H29A	0.9800
C15—H15	0.9500	C29—H29B	0.9800
C16—C17	1.385 (3)	C29—H29C	0.9800

N2—Cd1—N1	175.76 (6)	O18—C17—C16	125.9 (2)
N2—Cd1—N11	88.20 (6)	O18—C17—C12	114.0 (2)
N1—Cd1—N11	92.22 (6)	C16—C17—C12	120.0 (2)
N2—Cd1—N21	95.50 (7)	C17—O18—C19	117.6 (2)
N1—Cd1—N21	84.29 (6)	O18—C19—H19A	109.5
N11—Cd1—N21	175.44 (6)	O18—C19—H19B	109.5
N2—Cd1—S1ⁱ	91.92 (5)	H19A—C19—H19B	109.5
N1—Cd1—S1ⁱ	92.31 (4)	O18—C19—H19C	109.5
N11—Cd1—S1ⁱ	87.74 (4)	H19A—C19—H19C	109.5
N21—Cd1—S1ⁱ	89.47 (5)	H19B—C19—H19C	109.5
N2—Cd1—S2ⁱⁱ	93.16 (5)	C22—N21—Cd1	120.21 (13)
N1—Cd1—S2ⁱⁱ	82.60 (4)	C22—N21—H21A	107.3
N11—Cd1—S2ⁱⁱ	92.54 (4)	Cd1—N21—H21A	107.3
N21—Cd1—S2ⁱⁱ	89.92 (5)	C22—N21—H21B	107.3
S1ⁱ—Cd1—S2ⁱⁱ	174.914 (18)	Cd1—N21—H21B	107.3
C1—S1—Cd1ⁱ	99.97 (7)	H21A—N21—H21B	106.9
N1—C1—S1	178.8 (2)	C23—C22—C27	119.8 (2)
C1—N1—Cd1	158.10 (18)	C23—C22—N21	122.1 (2)
C2—S2—Cd1ⁱⁱⁱ	109.52 (7)	C27—C22—N21	118.0 (2)
C2—N2—Cd1	164.95 (17)	C22—C23—C24	120.3 (2)
N2—C2—S2	178.0 (2)	C22—C23—H23	119.9
C12—N11—Cd1	116.38 (13)	C24—C23—H23	119.9
C12—N11—H11A	108.2	C25—C24—C23	119.9 (2)
Cd1—N11—H11A	108.2	C25—C24—H24	120.0
C12—N11—H11B	108.2	C23—C24—H24	120.0
Cd1—N11—H11B	108.2	C24—C25—C26	120.4 (2)
H11A—N11—H11B	107.3	C24—C25—H25	119.8
C13—C12—C17	119.8 (2)	C26—C25—H25	119.8
C13—C12—N11	121.6 (2)	C27—C26—C25	119.7 (2)
C17—C12—N11	118.52 (19)	C27—C26—H26	120.2
C12—C13—C14	120.1 (2)	C25—C26—H26	120.2
C12—C13—H13	119.9	O28—C27—C26	125.7 (2)
C14—C13—H13	119.9	O28—C27—C22	114.4 (2)
C15—C14—C13	119.8 (2)	C26—C27—C22	120.0 (2)
C15—C14—H14	120.1	C27—O28—C29	117.82 (19)
C13—C14—H14	120.1	O28—C29—H29A	109.5
C14—C15—C16	120.7 (2)	O28—C29—H29B	109.5
C14—C15—H15	119.6	H29A—C29—H29B	109.5
C16—C15—H15	119.6	O28—C29—H29C	109.5
C17—C16—C15	119.4 (2)	H29A—C29—H29C	109.5
C17—C16—H16	120.3	H29B—C29—H29C	109.5
C15—C16—H16	120.3

N11—Cd1—N1—C1	−141.7 (4)	C13—C12—C17—C16	−1.7 (3)
N21—Cd1—N1—C1	35.3 (4)	N11—C12—C17—C16	175.03 (19)
S1ⁱ—Cd1—N1—C1	−53.9 (4)	C16—C17—O18—C19	−4.3 (3)
S2ⁱⁱ—Cd1—N1—C1	126.0 (4)	C12—C17—O18—C19	176.0 (2)
N11—Cd1—N2—C2	−122.1 (7)	N2—Cd1—N21—C22	−16.79 (16)
N21—Cd1—N2—C2	60.6 (7)	N1—Cd1—N21—C22	158.96 (16)
S1ⁱ—Cd1—N2—C2	150.2 (7)	S1ⁱ—Cd1—N21—C22	−108.66 (15)
S2ⁱⁱ—Cd1—N2—C2	−29.6 (7)	S2ⁱⁱ—Cd1—N21—C22	76.39 (15)
N2—Cd1—N11—C12	−171.56 (15)	Cd1—N21—C22—C23	−90.3 (2)
N1—Cd1—N11—C12	12.66 (14)	Cd1—N21—C22—C27	87.6 (2)
S1ⁱ—Cd1—N11—C12	−79.56 (14)	C27—C22—C23—C24	0.0 (3)
S2ⁱⁱ—Cd1—N11—C12	95.35 (14)	N21—C22—C23—C24	177.95 (19)
Cd1—N11—C12—C13	91.3 (2)	C22—C23—C24—C25	−0.5 (3)
Cd1—N11—C12—C17	−85.4 (2)	C23—C24—C25—C26	0.4 (4)
C17—C12—C13—C14	0.2 (3)	C24—C25—C26—C27	0.3 (4)
N11—C12—C13—C14	−176.4 (2)	C25—C26—C27—O28	179.3 (2)
C12—C13—C14—C15	1.3 (4)	C25—C26—C27—C22	−0.8 (3)
C13—C14—C15—C16	−1.2 (4)	C23—C22—C27—O28	−179.42 (19)
C14—C15—C16—C17	−0.3 (4)	N21—C22—C27—O28	2.6 (3)
C15—C16—C17—O18	−178.0 (2)	C23—C22—C27—C26	0.6 (3)
C15—C16—C17—C12	1.7 (3)	N21—C22—C27—C26	−177.39 (19)
C13—C12—C17—O18	178.09 (19)	C26—C27—O28—C29	−8.1 (3)
N11—C12—C17—O18	−5.2 (3)	C22—C27—O28—C29	172.00 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···S2ⁱⁱⁱ	0.92	2.50	3.4182 (17)	174
N21—H21B···S1^iv	0.92	2.66	3.5637 (18)	169
N11—H11B···O18	0.92	2.28	2.641 (2)	103
N21—H21A···O28	0.92	2.26	2.640 (2)	104

Symmetry codes: (iii) x+1/2, −y+1/2, −z+1; (iv) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₇H₉NO)₂]
M_r	474.89
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	6.6860 (2), 23.3658 (7), 24.3281 (8)
V (Å³)	3800.6 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.39
Crystal size (mm)	0.33 × 0.18 × 0.11

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.741, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	16897, 4210, 3262
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.055, 1.02
No. of reflections	4210
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.38

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Berndt, 2001) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cd1—N2	2.2724 (19)	Cd1—N21	2.3718 (17)
Cd1—N1	2.3142 (18)	Cd1—S1ⁱ	2.7306 (6)
Cd1—N11	2.3653 (17)	Cd1—S2ⁱⁱ	2.7449 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···S2ⁱⁱⁱ	0.92	2.50	3.4182 (17)	174.3
N21—H21B···S1^iv	0.92	2.66	3.5637 (18)	169.4

Symmetry codes: (iii) x+1/2, −y+1/2, −z+1; (iv) −x+1, −y, −z+1.

Acknowledgements

The authors gratefully acknowledge the support of the Tunisian Ministry of Higher Education and Scientific Research.

References

Bai, Y., Hu, X., Dang, D., Bi, F. & Niu, J. (2011). Spectrochim. Acta, 78, 70–73. CSD CrossRef Google Scholar
Bartlett, H. E., Jurriaanse, A. & De Haas, K. (1969). Can. J. Chem. 47, 2981–2986. CrossRef CAS Web of Science Google Scholar
Brandenburg, K. & Berndt, M. (2001). DIAMOND. Crystal Impact, Bonn, Germany. Google Scholar
Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, H., Zhang, L., Cai, Z., Guang Yanga, G. & Chen, X. (2000). J. Chem. Soc. Dalton Trans. pp. 2463–2466. Web of Science CSD CrossRef Google Scholar
Domenicano, A. & Murray-Rust, P. (1979). Tetrahedron Lett. 24, 2283–2286. CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Karoui, S., Kamoun, S. & Jouini, A. (2013). J. Solid State Chem. 197, 60–68. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Boeckmann, J., Jess, I. & Näther, C. (2012). CrystEngComm, 14, 5412–5420. Google Scholar
Wöhlert, S., Jess, I. & Näther, C. (2013). Z. Anorg. Allg. Chem. 639, 385–391. Google Scholar
Yang, G., Zhu, H., Liang, B. & Chen, X. (2001). J. Chem. Soc. Dalton Trans. pp. 580–585. Web of Science CSD CrossRef Google Scholar

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