Crystal structure of catena-poly[[[bis-(pyridine-4-carbo-thio-amide-κN (1))cadmium]-di-μ-thio-cyanato-κ(2) N:S;κ(2) S:N] methanol disolvate].

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 thio-cyanate anion, one pyridine-4-carbo-thio-amide ligand and one methanol mol-ecule in general positions. The Cd(II) cations are octa-hedrally coordinated by the pyridine N atom of two pyridine-4-carbo-thio-amide ligands and by the S and N atoms of four thio-cyanate anions and are linked into chains along [010] by pairs of anionic ligands. These chains are further linked into layers extending along (201) by inter-molecular N-H⋯O and O-H⋯S hydrogen bonds. One of the amino H atoms of the pyridine-4-carbo-thio-amide ligand is hydrogen-bonded to the O atom of a methanol mol-ecule, and a symmetry-related methanol mol-ecule is the donor group to the S atom of another pyridine-4-carbo-thio-amide ligand whereby each of the pyridine-4-carbo-thio-amide ligands forms two pairs of centrosymmetric N-H⋯S and O-H⋯S hydrogen bonds. The methanol mol-ecules are equally disordered over two orientations.

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., 2015 ▸). 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

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 ▸). 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 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.

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.]

Table 1

Selected bond lengths (Å)

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

Symmetry code: (i) .

Figure 2

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

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 (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 ▸).

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.

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⋯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) ; (iii) ; (iv) ; (v) ; (vi) .

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 ▸).

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.

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[F 2 > 2σ(F 2)], wR(F 2), 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 ▸), SHELXS97 and XP in SHELXTL (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016002632/wm5271sup1.cif

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

CCDC reference: 1453442

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cd(NCS)2(C6H6N2S)]·2CH4O	F(000) = 1144
Mr = 1138.04	Dx = 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

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

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(Fo2) + (0.0471P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.41 e Å−3
2515 reflections	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq	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

	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)

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—Cd1iv	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—Cd1iv	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

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···S1v	0.95	2.86	3.762 (2)	158
C15—H15···N1	0.95	2.54	3.230 (3)	130
N12—H12B···O1vi	0.88	2.02	2.883 (10)	165
N12—H12B···O1′vi	0.88	1.88	2.740 (12)	165
N12—H12A···S1vii	0.88	2.90	3.560 (3)	133
N12—H12A···S11iv	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