research communications
catena-poly[[[bis(pyridine-4-carbothioamide-κN1)cadmium]-di-μ-thiocyanato-κ2N:S;κ2S:N] methanol disolvate]
ofaInstitut 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
The 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.
of the polymeric title compound, {[Cd(NCS)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 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.
2. Structural commentary
The 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.
of the title compound, [Cd(NCS)3. Supramolecular features
In the 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).
the neutral chains are linked into layers extending along (201) by intermolecular N—H⋯O and O—H⋯S hydrogen bonding4. 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 of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967; Eccles et al., 2014). The 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 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. details
Crystal data, data collection and structure . 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).
details are summarized in Table 3
|
Supporting information
CCDC reference: 1453442
10.1107/S2056989016002632/wm5271sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002632/wm5271Isup2.hkl
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
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
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
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
of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967; Eccles et al., 2014). The of the protonated ligand 4-thiocarbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014).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
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.Crystal data, data collection and structure
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).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
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
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
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
of the ligand itself reported at room temperature and at 100 K (Colleter & Gadret, 1967; Eccles et al., 2014). The of the protonated ligand 4-thiocarbamoylpyridinium iodide was also reported recently (Shotonwa & Boeré, 2014).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
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. detailsCrystal data, data collection and structure
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).Data collection: X-AREA (Stoe, 2008); cell
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).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.] | |
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. |
[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) |
[Cd(NCS)2(C6H6N2S)]·2CH4O | V = 2294.14 (15) Å3 |
Mr = 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)° |
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 = 0.800 | Rint = 0.032 |
15896 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 37 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.41 e Å−3 |
2515 reflections | Δρmin = −0.47 e Å−3 |
156 parameters |
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 |
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. |
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 |
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. |
Cd1—N1 | 2.3212 (18) | Cd1—S1i | 2.7174 (6) |
Cd1—N11 | 2.3576 (18) |
Symmetry code: (i) x, y−1, z. |
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···O1iv | 0.88 | 2.02 | 2.883 (10) | 165.4 |
N12—H12B···O1'iv | 0.88 | 1.88 | 2.740 (12) | 164.7 |
N12—H12A···S1v | 0.88 | 2.90 | 3.560 (3) | 132.7 |
N12—H12A···S11vi | 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 |
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) |
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) |
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 (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 |
Δρmax, Δρmin (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.
References
Boeckmann, J. & Näther, C. (2012). Polyhedron, 31, 587–595. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Colleter, J. C. & Gadret, M. (1967). Bull. Soc. Chim. Fr. pp. 3463–3469. Google Scholar
Eccles, K. S., Morrison, R. E., Maguire, A. R. & Lawrence, S. E. (2014). Cryst. Growth Des. 14, 2753–2762. CSD CrossRef CAS Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696–2714. Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shotonwa, I. O. & Boeré, R. T. (2014). Acta Cryst. E70, o340–o341. CSD CrossRef IUCr Journals Google Scholar
Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893–2901. CSD CrossRef CAS PubMed Google Scholar
Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015b). Dalton Trans. 44, 14149–14158. CSD CrossRef CAS PubMed 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., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920–6923. Google Scholar
Wöhlert, S., Peters, L. & Näther, C. (2013). Dalton Trans. 42, 10746–10758. PubMed Google Scholar
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