Crystal structure of catena-poly[[[bis­(pyridine-4-carbo­thio­amide-κN1)cadmium]-di-μ-thio­cyanato-κ2N:S;κ2S:N] methanol disolvate]

Neumann, T.; Jess, I.; Näther, C.

doi:10.1107/S2056989016002632

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ISSN: 2056-9890

Volume 72| Part 3| March 2016| Pages 370-373

doi:10.1107/S2056989016002632

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Crystal structure of catena-poly[[[bis(pyridine-4-carbothioamide-κN¹)cadmium]-di-μ-thiocyanato-κ²N:S;κ²S:N] methanol disolvate]

Tristan Neumann,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 6, D-24118 Kiel, Germany
^*Correspondence e-mail: t.neumann@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 February 2016; accepted 15 February 2016; online 20 February 2016)

The asymmetric unit of the polymeric title compound, {[Cd(NCS)₂(C₆H₆N₂S)]·2CH₃OH}_n, consists of one cadmium(II) cation that is located on a centre of inversion as well as one thiocyanate anion, one pyridine-4-carbothioamide ligand and one methanol molecule in general positions. The Cd^II cations are octahedrally coordinated by the pyridine N atom of two pyridine-4-carbothioamide ligands and by the S and N atoms of four thiocyanate anions and are linked into chains along [010] by pairs of anionic ligands. These chains are further linked into layers extending along (201) by intermolecular N—H⋯O and O—H⋯S hydrogen bonds. One of the amino H atoms of the pyridine-4-carbothioamide ligand is hydrogen-bonded to the O atom of a methanol molecule, and a symmetry-related methanol molecule is the donor group to the S atom of another pyridine-4-carbothioamide ligand whereby each of the pyridine-4-carbothioamide ligands forms two pairs of centrosymmetric N—H⋯S and O—H⋯S hydrogen bonds. The methanol molecules are equally disordered over two orientations.

Keywords: crystal structure; cadmium thiocyanate; coordination polymer; pyridine-4-carbothioamide; hydrogen bonding.

CCDC reference: 1453442

1. Chemical context

Thiocyanato anions are versatile ligands that can coordinate to metal cations in different ways (Näther et al., 2013 ). In this context, compounds in which paramagnetic metal cations are linked into chains by μ-1,3 bridging anionic ligands are of special interest, because they can show different magnetic behavior (Palion-Gazda et al., 2015 ). This is the case e.g. for compounds of general composition M(NCS)₂(L)₂ (M = Mn, Fe, Co and Ni; L = pyridine derivative) that frequently show cooperative magnetic properties like ferromagnetic or antiferromagnetic ordering or a slow relaxation of the magnetization indicative for single chain magnetic behavior (Näther et al., 2013; Wöhlert et al., 2011 ; Boeckmann & Näther, 2012 ; Werner et al., 2015a ,b ). Unfortunately, compounds with a bridging coordination are frequently less stable than those in which these anionic ligands are only N-terminally coordinating. Hence, we have developed an alternative synthesis procedure which is based on thermal decomposition of suitable precursor compounds and leads directly to the formation of the desired compounds (Näther et al., 2013). However, following this procedure only microcrystalline materials are obtained. This is the reason why we are also interested in the diamagnetic cadmium analogues. This metal cation is much more chalcophilic than most paramagnetic cations, which means that the desired compounds with a bridging coordination of the anionic ligands can easily be crystallized and characterized by single crystal X-ray diffraction (Wöhlert et al., 2013 ). In several cases, the resulting structures are isotypic to the paramagnetic analogues and therefore the latter can be refined by the Rietveld method using the crystallographic data of the respective Cd^II compound (Wöhlert et al., 2013). In the scope of our systematic work, we became interested in pyridine-4-carbothioamide as another ligand that was reacted with cadmium(II) thiocyanate to give the title compound.

2. Structural commentary

The asymmetric unit of the title compound, [Cd(NCS)₂(C₆H₆N₂S)]·2CH₃OH, consists of a Cd^II cation that is located on a centre of inversion as well as one thiocyanato anion, one pyridine-4-carbothioamide ligand and one methanol molecule in general positions. The Cd^II cation is sixfold coordinated by two N-bonding pyridinethioamide ligands as well as two N- and two S-coordinating thiocyanate anions in an all trans distorted octahedral environment (Fig. 1). As expected, the Cd—N bond length to the negatively charged thiocyanate anion is significantly shorter than to the pyridine-4-carbothioamide N atom; the Cd—S bond length is within the normal range (Table 1). The Cd^II cations are linked by centrosymmetric pairs of anionic ligands into chains along [010] (Fig. 2). The methanol molecule is equally disordered over two orientations.

Table 1
Selected bond lengths (Å)

Cd1—N1	2.3212 (18)	Cd1—S1ⁱ	2.7174 (6)
Cd1—N11	2.3576 (18)
Symmetry code: (i) x, y-1, z.

Figure 1
The coordination of the Cd^II cation in the structure of the title compound; the two orientations of the methanol solvent molecule are shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x, y + 1, z; (iii) −x + 1, −y + 2, −z + 1.]

Figure 2
View of a Cd–thiocyanate chain in the crystal structure of the title compound.

3. Supramolecular features

In the crystal structure, the neutral chains are linked into layers extending along (201) by intermolecular N—H⋯O and O—H⋯S hydrogen bonding via the methanol solvent molecules (Fig. 3). Each pyridine-4-carbothioamide ligand of neighbouring chains makes one N—H⋯O hydrogen bond to the hydroxyl O atom that acts as an acceptor, and one O—H⋯S hydrogen bond between the hydroxyl H atom and the S atom of the pyridine-4-carbothioamide ligand (Fig. 3 and Table 2). The hydrogen-bonding geometry is very similar for the two disordered and slightly differently oriented methanol molecules (Table 2). This arrangement leads to 12-membered rings [graph-set notation R₄⁴(12); Etter et al., 1990 ] in which four donor and four acceptors are involved (Fig. 2 and Table 2). There are additional C—H⋯N, C—H⋯S and N—H⋯S interactions of much weaker nature that consolidate the three-dimensional network (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N1ⁱⁱ	0.95	2.69	3.335 (3)	126
C12—H12⋯S1ⁱⁱⁱ	0.95	2.86	3.762 (2)	158
C15—H15⋯N1	0.95	2.54	3.230 (3)	130
N12—H12B⋯O1^iv	0.88	2.02	2.883 (10)	165
N12—H12B⋯O1′^iv	0.88	1.88	2.740 (12)	165
N12—H12A⋯S1^v	0.88	2.90	3.560 (3)	133
N12—H12A⋯S11^vi	0.88	2.87	3.522 (2)	132
O1—H1⋯S11	0.84	2.53	3.351 (12)	165
O1′—H1′⋯S11	0.84	2.46	3.250 (12)	156
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (v) $[x, -y+2, z+{\script{1\over 2}}]$ ; (vi) x, y+1, z.

Figure 3
View of one layer in the crystal structure of the title compound with hydrogen bonds shown as dashed lines. Only one orientation of the disordered methanol molecule is shown.

4. Database survey

According to the Cambridge Structural Database (Version 5.36, last update 2015; Groom & Allen, 2014 ) no coordination compounds with pyridine-4-carbothioamide have been structurally characterized. There is only one crystal structure of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967 ; Eccles et al., 2014 ). The crystal structure of the protonated ligand 4-thiocarbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014 ).

5. Synthesis and crystallization

CdSO₄·3/8H₂O was purchased from Merck and pyridine-4-carbothioamide and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Cd(NCS)₂ was synthesized by stirring 17.5 g (57.0 mmol) Ba(NCS)₂·3H₂O and 14.6 g (57.0 mmol) CdSO₄·3/8H₂O in 300 ml water at room temperature for 3 h. The white residue of BaSO₄ was filtered off and the resulting solution dried at 353 K. The homogeneity of the product was checked by X-ray powder diffraction and elemental analysis. The title compound was obtained by reaction of 11.4 mg Cd(NCS)₂ (0.05 mmol) with 27.6 mg pyridine-4-carbothioamide (0.2 mmol) in boiling methanol (2 ml). Crystals suitable for single-crystal x-ray diffraction formed after cooling.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The C—H, O—H and N—H hydrogen atoms were located in a difference map but were positioned with idealized geometry (methyl and O—H hydrogen atoms allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C, N) (1.5 for methyl and O—H hydrogen atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.98 Å for methyl, N—H = 0.88 Å and O—H = 0.84 Å, respectively. The methanol molecule is equally disordered over two orientations and was refined using a split model using SAME restraints (Sheldrick, 2015 ).

Table 3
Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₆H₆N₂S)]·2CH₄O
M_r	1138.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	25.1891 (10), 5.8729 (2), 15.5080 (6)
β (°)	90.124 (3)
V (Å³)	2294.14 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.34
Crystal size (mm)	0.18 × 0.14 × 0.10

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008 )
T_min, T_max	0.644, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections	15896, 2515, 2208
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.067, 1.06
No. of reflections	2515
No. of parameters	156
No. of restraints	37
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.47
Computer programs: X-AREA (Stoe, 2008), SHELXS97 and XP in SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1453442

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989016002632/wm5271sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016002632/wm5271Isup2.hkl

checkCIF report

Chemical context top

Thiocyanato anions are versatile ligands that can coordinate to metal cations in different ways (Näther et al., 2013). In this context, compounds in which paramagnetic metal cations are linked into chains by µ-1,3 bridging anionic ligands are of special interest, because they can show different magnetic behavior (Palion-Gazda et al., 2015). This is the case e.g. for compounds of general composition M(NCS)₂(L)₂ (M = Mn, Fe, Co and Ni; L = pyridine derivative) that frequently show cooperative magnetic properties like ferromagnetic or antiferromagnetic ordering or a slow relaxation of the magnetization indicative for single chain magnetic behavior (Näther et al., 2013; Wöhlert et al., 2011; Boeckmann & Näther, 2012; Werner et al., 2015a,b). Unfortunately, compounds with a bridging coordination are frequently less stable than those in which these anionic ligands are only N-terminally coordinating. Hence, we have developed an alternative synthesis procedure which is based on thermal decomposition of suitable precursor compounds and leads directly to the formation of the desired compounds (Näther et al., 2013). However, following this procedure only microcrystalline materials are obtained. This is the reason why we are also interested in the diamagnetic cadmium analogues. This metal cation is much more chalcophilic than most paramagnetic cations, which means that the desired compounds with a bridging coordination of the anionic ligands can easily be crystallized and characterized by single-crystal X-ray diffraction (Wöhlert et al., 2013). In several cases, the resulting structures are isotypic to the paramagnetic analogues and therefore the latter can be refined by the Rietveld method using the crystallographic data of the respective Cd^II compound (Wöhlert et al., 2013). In the scope of our systematic work, we became interested in pyridine-4-carbothioamide as another ligand that was reacted with cadmium(II) thiocyanate to give the title compound.

Structural commentary top

The asymmetric unit of the title compound, [Cd(NCS)₂(C₆H₆N₂S)]·2CH₃OH, consists of a Cd^II cation that is located on a centre of inversion as well as one thiocyanato anion, one pyridine-4-carbothioamide ligand and one methanol molecule in general positions. The Cd^II cation is sixfold coordinated by two N-bonding pyridinethioamide ligands as well as two N– and two S-coordinating thiocyanato anions in an all trans distorted octahedral environment (Fig. 1). As expected, the Cd—N bond length to the negatively charged thiocyanato anion is significantly shorter than to the pyridine-4-carbothioamide N atom; the Cd—S bond length is within the normal range (Table 1). The Cd^II cations are linked by centrosymmetric pairs of anionic ligands into chains along [010] (Fig. 2). The methanol molecule is equally disordered over two orientations.

Supramolecular features top

In the crystal structure, the neutral chains are linked into layers extending along (201) by intermolecular N—H···O and O—H···S hydrogen bonding via the methanol solvent molecules (Fig. 3). Each pyridine-4-carbothioamide ligand of neighbouring chains makes one N—H···O hydrogen bond to the hydroxyl O atom that acts as an acceptor, and one O—H···S hydrogen bond between the hydroxyl H atom and the S atom of the pyridine-4-carbothioamide ligand (Fig. 3 and Table 2). The hydrogen-bonding geometry is very similar for the two disordered and slightly differently oriented methanol molecules (Table 2). This arrangement leads to 12-membered rings [graph-set notation R⁴₄(12); Etter et al., 1990] in which four donor and four acceptors are involved (Fig. 2 and Table 3). There are additional C—H···N, C—H···S and N—H···S interactions of much weaker nature that consolidate the three-dimensional network (Table 3).

Database survey top

According to the Cambridge Structural Database (Version 5.36, last update 2015; Groom & Allen, 2014) no coordination compounds with pyridine-4-carbothioamide have been structurally characterized. There is only one crystal structure of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967; Eccles et al., 2014). The crystal structure of the protonated ligand 4-thiocarbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014).

Synthesis and crystallization top

CdSO₄·3/8H₂O was purchased from Merck and pyridine-4-carbothioamide and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Cd(NCS)₂ was synthesized by stirring 17.5 g (57.0 mmol) Ba(NCS)₂·3H₂O and 14.6 g (57.0 mmol) CdSO₄·3/8 H₂O in 300 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and dried at 353 K. The homogeneity of the product was checked by X-ray powder diffraction and elemental analysis. The title compound was obtained by reaction of 11.4 mg C d(NCS)₂ (0.05 mmol) with 27.6 mg pyridine-4-carbothioamide (0.2 mmol) in boiling methanol (2 ml). Crystals suitable for single-crystal X-ray diffraction formed after cooling.

Refinement details top

Structure description top

Thiocyanato anions are versatile ligands that can coordinate to metal cations in different ways (Näther et al., 2013). In this context, compounds in which paramagnetic metal cations are linked into chains by µ-1,3 bridging anionic ligands are of special interest, because they can show different magnetic behavior (Palion-Gazda et al., 2015). This is the case e.g. for compounds of general composition M(NCS)₂(L)₂ (M = Mn, Fe, Co and Ni; L = pyridine derivative) that frequently show cooperative magnetic properties like ferromagnetic or antiferromagnetic ordering or a slow relaxation of the magnetization indicative for single chain magnetic behavior (Näther et al., 2013; Wöhlert et al., 2011; Boeckmann & Näther, 2012; Werner et al., 2015a,b). Unfortunately, compounds with a bridging coordination are frequently less stable than those in which these anionic ligands are only N-terminally coordinating. Hence, we have developed an alternative synthesis procedure which is based on thermal decomposition of suitable precursor compounds and leads directly to the formation of the desired compounds (Näther et al., 2013). However, following this procedure only microcrystalline materials are obtained. This is the reason why we are also interested in the diamagnetic cadmium analogues. This metal cation is much more chalcophilic than most paramagnetic cations, which means that the desired compounds with a bridging coordination of the anionic ligands can easily be crystallized and characterized by single-crystal X-ray diffraction (Wöhlert et al., 2013). In several cases, the resulting structures are isotypic to the paramagnetic analogues and therefore the latter can be refined by the Rietveld method using the crystallographic data of the respective Cd^II compound (Wöhlert et al., 2013). In the scope of our systematic work, we became interested in pyridine-4-carbothioamide as another ligand that was reacted with cadmium(II) thiocyanate to give the title compound.

The asymmetric unit of the title compound, [Cd(NCS)₂(C₆H₆N₂S)]·2CH₃OH, consists of a Cd^II cation that is located on a centre of inversion as well as one thiocyanato anion, one pyridine-4-carbothioamide ligand and one methanol molecule in general positions. The Cd^II cation is sixfold coordinated by two N-bonding pyridinethioamide ligands as well as two N– and two S-coordinating thiocyanato anions in an all trans distorted octahedral environment (Fig. 1). As expected, the Cd—N bond length to the negatively charged thiocyanato anion is significantly shorter than to the pyridine-4-carbothioamide N atom; the Cd—S bond length is within the normal range (Table 1). The Cd^II cations are linked by centrosymmetric pairs of anionic ligands into chains along [010] (Fig. 2). The methanol molecule is equally disordered over two orientations.

According to the Cambridge Structural Database (Version 5.36, last update 2015; Groom & Allen, 2014) no coordination compounds with pyridine-4-carbothioamide have been structurally characterized. There is only one crystal structure of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967; Eccles et al., 2014). The crystal structure of the protonated ligand 4-thiocarbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014).

Synthesis and crystallization top

CdSO₄·3/8H₂O was purchased from Merck and pyridine-4-carbothioamide and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Cd(NCS)₂ was synthesized by stirring 17.5 g (57.0 mmol) Ba(NCS)₂·3H₂O and 14.6 g (57.0 mmol) CdSO₄·3/8 H₂O in 300 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and dried at 353 K. The homogeneity of the product was checked by X-ray powder diffraction and elemental analysis. The title compound was obtained by reaction of 11.4 mg C d(NCS)₂ (0.05 mmol) with 27.6 mg pyridine-4-carbothioamide (0.2 mmol) in boiling methanol (2 ml). Crystals suitable for single-crystal X-ray diffraction formed after cooling.

Refinement details top

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The coordination of the Cd^II cation in the structure of the title compound; the two orientations of the methanol solvent molecule are shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x, y + 1, z; (iii) −x + 1, −y + 2, −z + 1.]
	Fig. 2. View of a Cd–thiocyanate chain in the crystal structure of the title compound.
	Fig. 3. View of one layer in the crystal structure of the title compound with hydrogen bonds shown as dashed lines. Only one orientation of the disordered methanol molecule is shown.

catena-Poly[[[bis(pyridine-4-carbothioamide-κN¹)cadmium]-di-µ-thiocyanato-κ²N:S;κ²S:N] methanol disolvate] top

Crystal data top

[Cd(NCS)₂(C₆H₆N₂S)]·2CH₄O	F(000) = 1144
M_r = 1138.04	D_x = 1.647 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.1891 (10) Å	Cell parameters from 16834 reflections
b = 5.8729 (2) Å	θ = 1.3–27°
c = 15.5080 (6) Å	µ = 1.34 mm⁻¹
β = 90.124 (3)°	T = 200 K
V = 2294.14 (15) Å³	Block, colorless
Z = 2	0.18 × 0.14 × 0.10 mm

Data collection top

Stoe IPDS-2 diffractometer	2208 reflections with I > 2σ(I)
ω scans	R_int = 0.032
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	θ_max = 27.0°, θ_min = 1.6°
T_min = 0.644, T_max = 0.800	h = −32→32
15896 measured reflections	k = −7→7
2515 independent reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0471P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.067	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.41 e Å⁻³
2515 reflections	Δρ_min = −0.47 e Å⁻³
156 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
37 restraints	Extinction coefficient: 0.0015 (2)

Crystal data top

[Cd(NCS)₂(C₆H₆N₂S)]·2CH₄O	V = 2294.14 (15) Å³
M_r = 1138.04	Z = 2
Monoclinic, C2/c	Mo Kα radiation
a = 25.1891 (10) Å	µ = 1.34 mm⁻¹
b = 5.8729 (2) Å	T = 200 K
c = 15.5080 (6) Å	0.18 × 0.14 × 0.10 mm
β = 90.124 (3)°

Data collection top

Stoe IPDS-2 diffractometer	2515 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	2208 reflections with I > 2σ(I)
T_min = 0.644, T_max = 0.800	R_int = 0.032
15896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	37 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
2515 reflections	Δρ_min = −0.47 e Å⁻³
156 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.5000	0.5000	0.5000	0.02964 (10)
N1	0.45141 (7)	0.8201 (3)	0.46141 (12)	0.0363 (4)
C1	0.44617 (9)	1.0011 (3)	0.43255 (13)	0.0317 (4)
S1	0.43930 (2)	1.25424 (10)	0.38878 (4)	0.04069 (15)
N11	0.43968 (8)	0.4286 (3)	0.61284 (12)	0.0361 (4)
C11	0.44093 (9)	0.2407 (4)	0.66130 (15)	0.0426 (5)
H11	0.4684	0.1332	0.6514	0.051*
C12	0.40419 (9)	0.1946 (4)	0.72524 (14)	0.0405 (5)
H12	0.4060	0.0563	0.7569	0.049*
C13	0.36515 (9)	0.3512 (4)	0.74238 (13)	0.0353 (5)
C14	0.36407 (12)	0.5485 (4)	0.6943 (2)	0.0542 (7)
H14	0.3381	0.6623	0.7050	0.065*
C15	0.40177 (12)	0.5776 (5)	0.62990 (18)	0.0532 (7)
H15	0.4002	0.7124	0.5962	0.064*
C16	0.32407 (9)	0.3067 (4)	0.81005 (14)	0.0366 (5)
N12	0.31373 (11)	0.4768 (4)	0.86169 (16)	0.0540 (6)
H12A	0.3305	0.6070	0.8554	0.065*
H12B	0.2900	0.4610	0.9028	0.065*
S11	0.29342 (3)	0.05620 (11)	0.81316 (4)	0.04527 (16)
O1	0.2777 (4)	0.0596 (16)	1.0276 (8)	0.067 (3)	0.5
H1	0.2760	0.0718	0.9737	0.100*	0.5
C17	0.3143 (5)	−0.101 (3)	1.0489 (13)	0.062 (3)	0.5
H17A	0.3476	−0.0703	1.0185	0.093*	0.5
H17B	0.3010	−0.2520	1.0324	0.093*	0.5
H17C	0.3206	−0.0978	1.1113	0.093*	0.5
O1'	0.2639 (4)	−0.0102 (19)	1.0155 (8)	0.079 (3)	0.5
H1'	0.2637	0.0358	0.9642	0.118*	0.5
C17'	0.3144 (8)	−0.019 (4)	1.0447 (17)	0.113 (8)	0.5
H17D	0.3348	0.1072	1.0201	0.169*	0.5
H17E	0.3306	−0.1640	1.0274	0.169*	0.5
H17F	0.3146	−0.0074	1.1077	0.169*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03369 (13)	0.02444 (13)	0.03081 (13)	−0.00052 (8)	0.00757 (8)	0.00137 (8)
N1	0.0362 (9)	0.0302 (10)	0.0427 (10)	0.0018 (7)	0.0035 (8)	0.0034 (8)
C1	0.0325 (10)	0.0329 (11)	0.0298 (9)	−0.0004 (8)	0.0016 (8)	−0.0038 (8)
S1	0.0504 (3)	0.0295 (3)	0.0421 (3)	−0.0022 (2)	−0.0116 (2)	0.0059 (2)
N11	0.0383 (10)	0.0333 (9)	0.0366 (9)	−0.0026 (8)	0.0111 (8)	0.0000 (8)
C11	0.0392 (12)	0.0483 (13)	0.0404 (11)	0.0086 (10)	0.0107 (9)	0.0094 (10)
C12	0.0404 (12)	0.0444 (13)	0.0368 (11)	0.0058 (10)	0.0090 (9)	0.0105 (10)
C13	0.0377 (11)	0.0342 (11)	0.0341 (10)	−0.0052 (9)	0.0090 (9)	−0.0034 (8)
C14	0.0611 (16)	0.0340 (12)	0.0677 (17)	0.0117 (11)	0.0367 (14)	0.0063 (12)
C15	0.0667 (17)	0.0303 (11)	0.0628 (16)	0.0054 (12)	0.0336 (14)	0.0104 (11)
C16	0.0364 (11)	0.0380 (11)	0.0353 (10)	0.0017 (9)	0.0096 (9)	0.0005 (9)
N12	0.0645 (15)	0.0432 (12)	0.0543 (13)	−0.0078 (10)	0.0297 (11)	−0.0077 (10)
S11	0.0490 (3)	0.0376 (3)	0.0493 (3)	−0.0070 (3)	0.0158 (3)	0.0009 (3)
O1	0.066 (6)	0.063 (4)	0.072 (6)	0.006 (3)	0.043 (5)	0.005 (3)
C17	0.045 (5)	0.091 (7)	0.050 (5)	0.008 (4)	−0.004 (3)	0.005 (5)
O1'	0.059 (5)	0.127 (10)	0.050 (3)	0.006 (5)	0.019 (3)	0.019 (5)
C17'	0.084 (10)	0.18 (2)	0.077 (10)	0.001 (11)	0.003 (7)	−0.013 (12)

Geometric parameters (Å, º) top

Cd1—N1ⁱ	2.3212 (18)	C14—C15	1.390 (3)
Cd1—N1	2.3212 (18)	C14—H14	0.9500
Cd1—N11ⁱ	2.3575 (18)	C15—H15	0.9500
Cd1—N11	2.3576 (18)	C16—N12	1.307 (3)
Cd1—S1ⁱⁱ	2.7174 (6)	C16—S11	1.662 (2)
Cd1—S1ⁱⁱⁱ	2.7174 (6)	N12—H12A	0.8800
N1—C1	1.161 (3)	N12—H12B	0.8800
C1—S1	1.643 (2)	O1—C17	1.361 (13)
S1—Cd1^iv	2.7174 (6)	O1—H1	0.8400
N11—C15	1.322 (3)	C17—H17A	0.9800
N11—C11	1.335 (3)	C17—H17B	0.9800
C11—C12	1.385 (3)	C17—H17C	0.9800
C11—H11	0.9500	O1'—C17'	1.351 (15)
C12—C13	1.373 (3)	O1'—H1'	0.8400
C12—H12	0.9500	C17'—H17D	0.9800
C13—C14	1.378 (3)	C17'—H17E	0.9800
C13—C16	1.498 (3)	C17'—H17F	0.9800

N1ⁱ—Cd1—N1	180.00 (9)	C12—C13—C16	121.0 (2)
N1ⁱ—Cd1—N11ⁱ	89.72 (7)	C14—C13—C16	120.8 (2)
N1—Cd1—N11ⁱ	90.28 (7)	C13—C14—C15	118.6 (2)
N1ⁱ—Cd1—N11	90.28 (7)	C13—C14—H14	120.7
N1—Cd1—N11	89.72 (7)	C15—C14—H14	120.7
N11ⁱ—Cd1—N11	180.0	N11—C15—C14	123.9 (2)
N1ⁱ—Cd1—S1ⁱⁱ	91.67 (5)	N11—C15—H15	118.1
N1—Cd1—S1ⁱⁱ	88.33 (5)	C14—C15—H15	118.1
N11ⁱ—Cd1—S1ⁱⁱ	89.20 (5)	N12—C16—C13	115.8 (2)
N11—Cd1—S1ⁱⁱ	90.80 (5)	N12—C16—S11	124.43 (17)
N1ⁱ—Cd1—S1ⁱⁱⁱ	88.33 (5)	C13—C16—S11	119.74 (16)
N1—Cd1—S1ⁱⁱⁱ	91.67 (5)	C16—N12—H12A	120.0
N11ⁱ—Cd1—S1ⁱⁱⁱ	90.80 (5)	C16—N12—H12B	120.0
N11—Cd1—S1ⁱⁱⁱ	89.20 (5)	H12A—N12—H12B	120.0
S1ⁱⁱ—Cd1—S1ⁱⁱⁱ	180.0	C17—O1—H1	109.5
C1—N1—Cd1	154.23 (17)	O1—C17—H17A	109.5
N1—C1—S1	178.2 (2)	O1—C17—H17B	109.5
C1—S1—Cd1^iv	99.19 (7)	H17A—C17—H17B	109.5
C15—N11—C11	116.8 (2)	O1—C17—H17C	109.5
C15—N11—Cd1	119.86 (16)	H17A—C17—H17C	109.5
C11—N11—Cd1	123.37 (15)	H17B—C17—H17C	109.5
N11—C11—C12	123.3 (2)	C17'—O1'—H1'	109.5
N11—C11—H11	118.3	O1'—C17'—H17D	109.5
C12—C11—H11	118.3	O1'—C17'—H17E	109.5
C13—C12—C11	119.2 (2)	H17D—C17'—H17E	109.5
C13—C12—H12	120.4	O1'—C17'—H17F	109.5
C11—C12—H12	120.4	H17D—C17'—H17F	109.5
C12—C13—C14	118.2 (2)	H17E—C17'—H17F	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N1ⁱ	0.95	2.69	3.335 (3)	126
C12—H12···S1^v	0.95	2.86	3.762 (2)	158
C15—H15···N1	0.95	2.54	3.230 (3)	130
N12—H12B···O1^vi	0.88	2.02	2.883 (10)	165
N12—H12B···O1′^vi	0.88	1.88	2.740 (12)	165
N12—H12A···S1^vii	0.88	2.90	3.560 (3)	133
N12—H12A···S11^iv	0.88	2.87	3.522 (2)	132
O1—H1···S11	0.84	2.53	3.351 (12)	165
O1′—H1′···S11	0.84	2.46	3.250 (12)	156

Symmetry codes: (i) −x+1, −y+1, −z+1; (iv) x, y+1, z; (v) x, −y+1, z+1/2; (vi) −x+1/2, −y+1/2, −z+2; (vii) x, −y+2, z+1/2.

Selected bond lengths (Å) top

Cd1—N1	2.3212 (18)	Cd1—S1ⁱ	2.7174 (6)
Cd1—N11	2.3576 (18)

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N1ⁱⁱ	0.95	2.69	3.335 (3)	125.9
C12—H12···S1ⁱⁱⁱ	0.95	2.86	3.762 (2)	157.9
C15—H15···N1	0.95	2.54	3.230 (3)	129.8
N12—H12B···O1^iv	0.88	2.02	2.883 (10)	165.4
N12—H12B···O1'^iv	0.88	1.88	2.740 (12)	164.7
N12—H12A···S1^v	0.88	2.90	3.560 (3)	132.7
N12—H12A···S11^vi	0.88	2.87	3.522 (2)	131.8
O1—H1···S11	0.84	2.53	3.351 (12)	165.4
O1'—H1'···S11	0.84	2.46	3.250 (12)	156.2

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

Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₆H₆N₂S)]·2CH₄O
M_r	1138.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	25.1891 (10), 5.8729 (2), 15.5080 (6)
β (°)	90.124 (3)
V (Å³)	2294.14 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.18 × 0.14 × 0.10

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008)
T_min, T_max	0.644, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections	15896, 2515, 2208
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.067, 1.06
No. of reflections	2515
No. of parameters	156
No. of restraints	37
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.47

Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Acknowledgements

This project was supported by the Deutsche Forschungsgemeinschaft (project No. NA 720/5–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

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