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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 370-373

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

CROSSMARK_Color_square_no_text.svg

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 CdII 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.

1. Chemical context

Thio­cyanato anions are versatile ligands that can coordinate to metal cations in different ways (Näther et al., 2013[Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696-2714.]). 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[Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380-2388.]). 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[Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696-2714.]; Wöhlert et al., 2011[Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920-6923.]; Boeckmann & Näther, 2012[Boeckmann, J. & Näther, C. (2012). Polyhedron, 31, 587-595.]; Werner et al., 2015a[Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893-2901.],b[Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015b). Dalton Trans. 44, 14149-14158.]). 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[Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696-2714.]). 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[Wöhlert, S., Peters, L. & Näther, C. (2013). Dalton Trans. 42, 10746-10758.]). 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 CdII compound (Wöhlert et al., 2013[Wöhlert, S., Peters, L. & Näther, C. (2013). Dalton Trans. 42, 10746-10758.]). 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.

[Scheme 1]

2. Structural commentary

The asymmetric unit of the title compound, [Cd(NCS)2(C6H6N2S)]·2CH3OH, consists of a CdII 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 CdII 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[link]). 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[link]). The CdII cations are linked by centrosymmetric pairs of anionic ligands into chains along [010] (Fig. 2[link]). 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]
Figure 1
The coordination of the CdII 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]
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[link]). 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[link] and Table 2[link]). The hydrogen-bonding geometry is very similar for the two disordered and slightly differently oriented methanol mol­ecules (Table 2[link]). This arrangement leads to 12-membered rings [graph-set notation R44(12); Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]] in which four donor and four acceptors are involved (Fig. 2[link] and Table 2[link]). 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[link]).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯O1iv 0.88 2.02 2.883 (10) 165
N12—H12B⋯O1′iv 0.88 1.88 2.740 (12) 165
N12—H12A⋯S1v 0.88 2.90 3.560 (3) 133
N12—H12A⋯S11vi 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]
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[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) 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[Colleter, J. C. & Gadret, M. (1967). Bull. Soc. Chim. Fr. pp. 3463-3469.]; Eccles et al., 2014[Eccles, K. S., Morrison, R. E., Maguire, A. R. & Lawrence, S. E. (2014). Cryst. Growth Des. 14, 2753-2762.]). The crystal structure of the protonated ligand 4-thio­carbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014[Shotonwa, I. O. & Boeré, R. T. (2014). Acta Cryst. E70, o340-o341.]).

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[link]. 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 Uiso(H) = 1.2Ueq(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[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Table 3
Experimental details

Crystal data
Chemical formula [Cd(NCS)2(C6H6N2S)]·2CH4O
Mr 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)
V3) 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[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.])
Tmin, Tmax 0.644, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections 15896, 2515, 2208
Rint 0.032
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.41, −0.47
Computer programs: X-AREA (Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]), SHELXS97 and XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 CdII 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 CdII 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 CdII 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 CdII 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

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 Uiso(H) = 1.2Ueq(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).

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 CdII 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 CdII 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 CdII 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 CdII cations are linked by centrosymmetric pairs of anionic ligands into chains along [010] (Fig. 2). The methanol molecule is equally disordered over two orientations.

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).

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

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 Uiso(H) = 1.2Ueq(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).

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
[Figure 1] Fig. 1. The coordination of the CdII 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] Fig. 2. View of a Cd–thiocyanate chain in the crystal structure of the title compound.
[Figure 3] 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)]·2CH4OF(000) = 1144
Mr = 1138.04Dx = 1.647 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 25.1891 (10) ÅCell parameters from 16834 reflections
b = 5.8729 (2) Åθ = 1.3–27°
c = 15.5080 (6) ŵ = 1.34 mm1
β = 90.124 (3)°T = 200 K
V = 2294.14 (15) Å3Block, colorless
Z = 20.18 × 0.14 × 0.10 mm
Data collection top
Stoe IPDS-2
diffractometer
2208 reflections with I > 2σ(I)
ω scansRint = 0.032
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
θmax = 27.0°, θmin = 1.6°
Tmin = 0.644, Tmax = 0.800h = 3232
15896 measured reflectionsk = 77
2515 independent reflectionsl = 1919
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.0471P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.41 e Å3
2515 reflectionsΔρmin = 0.47 e Å3
156 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
37 restraintsExtinction coefficient: 0.0015 (2)
Crystal data top
[Cd(NCS)2(C6H6N2S)]·2CH4OV = 2294.14 (15) Å3
Mr = 1138.04Z = 2
Monoclinic, C2/cMo Kα radiation
a = 25.1891 (10) ŵ = 1.34 mm1
b = 5.8729 (2) ÅT = 200 K
c = 15.5080 (6) Å0.18 × 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)
Tmin = 0.644, Tmax = 0.800Rint = 0.032
15896 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02637 restraints
wR(F2) = 0.067H-atom parameters constrained
S = 1.06Δρmax = 0.41 e Å3
2515 reflectionsΔρmin = 0.47 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cd10.50000.50000.50000.02964 (10)
N10.45141 (7)0.8201 (3)0.46141 (12)0.0363 (4)
C10.44617 (9)1.0011 (3)0.43255 (13)0.0317 (4)
S10.43930 (2)1.25424 (10)0.38878 (4)0.04069 (15)
N110.43968 (8)0.4286 (3)0.61284 (12)0.0361 (4)
C110.44093 (9)0.2407 (4)0.66130 (15)0.0426 (5)
H110.46840.13320.65140.051*
C120.40419 (9)0.1946 (4)0.72524 (14)0.0405 (5)
H120.40600.05630.75690.049*
C130.36515 (9)0.3512 (4)0.74238 (13)0.0353 (5)
C140.36407 (12)0.5485 (4)0.6943 (2)0.0542 (7)
H140.33810.66230.70500.065*
C150.40177 (12)0.5776 (5)0.62990 (18)0.0532 (7)
H150.40020.71240.59620.064*
C160.32407 (9)0.3067 (4)0.81005 (14)0.0366 (5)
N120.31373 (11)0.4768 (4)0.86169 (16)0.0540 (6)
H12A0.33050.60700.85540.065*
H12B0.29000.46100.90280.065*
S110.29342 (3)0.05620 (11)0.81316 (4)0.04527 (16)
O10.2777 (4)0.0596 (16)1.0276 (8)0.067 (3)0.5
H10.27600.07180.97370.100*0.5
C170.3143 (5)0.101 (3)1.0489 (13)0.062 (3)0.5
H17A0.34760.07031.01850.093*0.5
H17B0.30100.25201.03240.093*0.5
H17C0.32060.09781.11130.093*0.5
O1'0.2639 (4)0.0102 (19)1.0155 (8)0.079 (3)0.5
H1'0.26370.03580.96420.118*0.5
C17'0.3144 (8)0.019 (4)1.0447 (17)0.113 (8)0.5
H17D0.33480.10721.02010.169*0.5
H17E0.33060.16401.02740.169*0.5
H17F0.31460.00741.10770.169*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03369 (13)0.02444 (13)0.03081 (13)0.00052 (8)0.00757 (8)0.00137 (8)
N10.0362 (9)0.0302 (10)0.0427 (10)0.0018 (7)0.0035 (8)0.0034 (8)
C10.0325 (10)0.0329 (11)0.0298 (9)0.0004 (8)0.0016 (8)0.0038 (8)
S10.0504 (3)0.0295 (3)0.0421 (3)0.0022 (2)0.0116 (2)0.0059 (2)
N110.0383 (10)0.0333 (9)0.0366 (9)0.0026 (8)0.0111 (8)0.0000 (8)
C110.0392 (12)0.0483 (13)0.0404 (11)0.0086 (10)0.0107 (9)0.0094 (10)
C120.0404 (12)0.0444 (13)0.0368 (11)0.0058 (10)0.0090 (9)0.0105 (10)
C130.0377 (11)0.0342 (11)0.0341 (10)0.0052 (9)0.0090 (9)0.0034 (8)
C140.0611 (16)0.0340 (12)0.0677 (17)0.0117 (11)0.0367 (14)0.0063 (12)
C150.0667 (17)0.0303 (11)0.0628 (16)0.0054 (12)0.0336 (14)0.0104 (11)
C160.0364 (11)0.0380 (11)0.0353 (10)0.0017 (9)0.0096 (9)0.0005 (9)
N120.0645 (15)0.0432 (12)0.0543 (13)0.0078 (10)0.0297 (11)0.0077 (10)
S110.0490 (3)0.0376 (3)0.0493 (3)0.0070 (3)0.0158 (3)0.0009 (3)
O10.066 (6)0.063 (4)0.072 (6)0.006 (3)0.043 (5)0.005 (3)
C170.045 (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—N1i2.3212 (18)C14—C151.390 (3)
Cd1—N12.3212 (18)C14—H140.9500
Cd1—N11i2.3575 (18)C15—H150.9500
Cd1—N112.3576 (18)C16—N121.307 (3)
Cd1—S1ii2.7174 (6)C16—S111.662 (2)
Cd1—S1iii2.7174 (6)N12—H12A0.8800
N1—C11.161 (3)N12—H12B0.8800
C1—S11.643 (2)O1—C171.361 (13)
S1—Cd1iv2.7174 (6)O1—H10.8400
N11—C151.322 (3)C17—H17A0.9800
N11—C111.335 (3)C17—H17B0.9800
C11—C121.385 (3)C17—H17C0.9800
C11—H110.9500O1'—C17'1.351 (15)
C12—C131.373 (3)O1'—H1'0.8400
C12—H120.9500C17'—H17D0.9800
C13—C141.378 (3)C17'—H17E0.9800
C13—C161.498 (3)C17'—H17F0.9800
N1i—Cd1—N1180.00 (9)C12—C13—C16121.0 (2)
N1i—Cd1—N11i89.72 (7)C14—C13—C16120.8 (2)
N1—Cd1—N11i90.28 (7)C13—C14—C15118.6 (2)
N1i—Cd1—N1190.28 (7)C13—C14—H14120.7
N1—Cd1—N1189.72 (7)C15—C14—H14120.7
N11i—Cd1—N11180.0N11—C15—C14123.9 (2)
N1i—Cd1—S1ii91.67 (5)N11—C15—H15118.1
N1—Cd1—S1ii88.33 (5)C14—C15—H15118.1
N11i—Cd1—S1ii89.20 (5)N12—C16—C13115.8 (2)
N11—Cd1—S1ii90.80 (5)N12—C16—S11124.43 (17)
N1i—Cd1—S1iii88.33 (5)C13—C16—S11119.74 (16)
N1—Cd1—S1iii91.67 (5)C16—N12—H12A120.0
N11i—Cd1—S1iii90.80 (5)C16—N12—H12B120.0
N11—Cd1—S1iii89.20 (5)H12A—N12—H12B120.0
S1ii—Cd1—S1iii180.0C17—O1—H1109.5
C1—N1—Cd1154.23 (17)O1—C17—H17A109.5
N1—C1—S1178.2 (2)O1—C17—H17B109.5
C1—S1—Cd1iv99.19 (7)H17A—C17—H17B109.5
C15—N11—C11116.8 (2)O1—C17—H17C109.5
C15—N11—Cd1119.86 (16)H17A—C17—H17C109.5
C11—N11—Cd1123.37 (15)H17B—C17—H17C109.5
N11—C11—C12123.3 (2)C17'—O1'—H1'109.5
N11—C11—H11118.3O1'—C17'—H17D109.5
C12—C11—H11118.3O1'—C17'—H17E109.5
C13—C12—C11119.2 (2)H17D—C17'—H17E109.5
C13—C12—H12120.4O1'—C17'—H17F109.5
C11—C12—H12120.4H17D—C17'—H17F109.5
C12—C13—C14118.2 (2)H17E—C17'—H17F109.5
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z; (iii) x+1, y+2, z+1; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···N1i0.952.693.335 (3)126
C12—H12···S1v0.952.863.762 (2)158
C15—H15···N10.952.543.230 (3)130
N12—H12B···O1vi0.882.022.883 (10)165
N12—H12B···O1vi0.881.882.740 (12)165
N12—H12A···S1vii0.882.903.560 (3)133
N12—H12A···S11iv0.882.873.522 (2)132
O1—H1···S110.842.533.351 (12)165
O1—H1···S110.842.463.250 (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—N12.3212 (18)Cd1—S1i2.7174 (6)
Cd1—N112.3576 (18)
Symmetry code: (i) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···N1ii0.952.693.335 (3)125.9
C12—H12···S1iii0.952.863.762 (2)157.9
C15—H15···N10.952.543.230 (3)129.8
N12—H12B···O1iv0.882.022.883 (10)165.4
N12—H12B···O1'iv0.881.882.740 (12)164.7
N12—H12A···S1v0.882.903.560 (3)132.7
N12—H12A···S11vi0.882.873.522 (2)131.8
O1—H1···S110.842.533.351 (12)165.4
O1'—H1'···S110.842.463.250 (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
Mr1138.04
Crystal system, space groupMonoclinic, C2/c
Temperature (K)200
a, b, c (Å)25.1891 (10), 5.8729 (2), 15.5080 (6)
β (°) 90.124 (3)
V3)2294.14 (15)
Z2
Radiation typeMo Kα
µ (mm1)1.34
Crystal size (mm)0.18 × 0.14 × 0.10
Data collection
DiffractometerStoe IPDS2
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe, 2008)
Tmin, Tmax0.644, 0.800
No. of measured, independent and
observed [I > 2σ(I)] reflections
15896, 2515, 2208
Rint0.032
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.067, 1.06
No. of reflections2515
No. of parameters156
No. of restraints37
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

References

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