supplementary materials


bt6838 scheme

Acta Cryst. (2012). E68, m1338    [ doi:10.1107/S1600536812040913 ]

Poly[([mu]-1,3-thiocyanato-[kappa]N,S)(isonicotinato-[kappa]N,O)(ethanol-[kappa]O)cadmium(II)]

T. Neumann, J. Werner, I. Jess and C. Näther

Abstract top

In the crystal structure of the title compound, [Cd(NCS)(C6H4NO2)(C2H5OH)]n, the Cd2+ cation is coordinated by one N and two O atoms of two symmetry-related isonicotinate anions, one ethanol molecule and two [mu]-1,3-bridging thiocyanate anions in a distorted octahedral N2O3S geometry. The metal cations are [mu]-1,3-bridged via thiocyanate anions into chains that are further connected into layers parallel to the ab plane by bridging isonicotinate anions. The layers are stacked along the c axis. The crystal structure is stabilized by O-H...O hydrogen bonds.

Comment top

The structure of the title compound was prepared within a project on the synthesis of transition metal thiocyanato coordination polymers in which the metal cations are µ-1,3 bridged by the anionic ligands (Näther & Greve, 2003; Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). In the course of our investigations crystals of the title compound were obtained and characterized by single-crystal X-ray diffraction.

In the crystal structure the cadmium(II) cations are coordinated by one N and two O atoms of two µ-1,3,6 bridging isonicotinato anions which are related by symmetry, one N and one S atom of two symmetry-related µ-1,3 bridging thiocyanato anions and one O atom of an ethanol molecule (Fig. 1). The coordination polyhedron of the cadmium cations can be described as a slightly distorted octahedron (Table 1).

The Cd2+ cations are µ-1,3 bridged by thiocyanato anions into chains, which elongate in the direction of the crystallographic a axis. These chains are bridged by µ-1,3,6 bridging isonicotinato anions into layers in the direction of the crystallographic b axis and the layers are stacked along the crystallographic c axis (Fig. 2).

The shortest Cd···Cd distances within the layers amounts to 5.7778 (3) Å and to 9.2393 (4) Å. It must be noted that according to research in the CCDC database (ConQuest Ver.1.14; Allen, 2002) one coordination compound based on Cd(NCS)2, isonicotinato anions and thiocyanato anions is known, in which ethanol is exchanged by water. The overall coordination topology is similar but this compound is not isotypic to the title compound (Yang et al., 2001).

The crystal structure is stabilized by an O—H···O hydrogen bond.

Related literature top

For general background information, including details of thermal decomposition reactions and magnetic properties, see: Näther & Greve (2003); Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For related structures, see: Yang et al. (2001). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Potassium thiocyanate and isonicotinic acid were purchased from Alfa Aesar, Cd(SO4)2.4H2O was obtained from Merck. The Cd(NCS)2 was prepared by stirring Ba(NCS)2.3H2O (3.076 g, 10 mmol) and CdSO4.8/3H2O (2.566 g, 10 mmol) in water (100 ml). The white precipitate of BaSO4 was filtered off and the water was removed from the filtrate by heating. The final product was dried at 80°C. The homogeneity of the product was investigated by X-ray powder diffraction. The title compound was prepared by the reaction of 34.3 mg Cd(NCS)2(0.15 mmol) and 36.9 mg isonicotinic acid (0.30 mmol) in 2 ml ethanol at 80°C in a closed 10 ml glass culture tube. After several days colourless needles of the title compound were obtained.

Refinement top

The C—H H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with Uiso(H) = 1.2Ueq(C) for aromatic H atoms (1.5 for methyl H atoms) using a riding model with C—H = 0.93 Å (aromatic H atoms) and with C—H = 0.96 Å (methyl H atoms). The O—H H atom was located in difference map, its bond length set to ideal value of 0.82 Å and finally it was refined using a riding model with Uiso(H) = 1.2Ueq(O).

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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x + 1, y + 1/2, -z + 3/2.
[Figure 2] Fig. 2. Crystal structure of the title compound with view in the direction of the crystallographic c axis.
Poly[(µ-1,3-thiocyanato-κN,S)(isonicotinato- κN,O)(ethanol-κO)cadmium(II)] top
Crystal data top
[Cd(NCS)(C6H4NO2)(C2H6O)]F(000) = 664
Mr = 338.65Dx = 1.845 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.7778 (2) ÅCell parameters from 17537 reflections
b = 16.1804 (6) Åθ = 2.0–28.0°
c = 13.0855 (6) ŵ = 1.96 mm1
β = 94.685 (3)°T = 293 K
V = 1219.24 (8) Å3Needle, colourless
Z = 40.28 × 0.10 × 0.04 mm
Data collection top
Stoe IPDS-1
diffractometer
2920 independent reflections
Radiation source: fine-focus sealed tube2545 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ scansθmax = 28.0°, θmin = 2.0°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
h = 77
Tmin = 0.803, Tmax = 0.931k = 2121
17537 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0288P)2 + 0.6822P]
where P = (Fo2 + 2Fc2)/3
2920 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
[Cd(NCS)(C6H4NO2)(C2H6O)]V = 1219.24 (8) Å3
Mr = 338.65Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.7778 (2) ŵ = 1.96 mm1
b = 16.1804 (6) ÅT = 293 K
c = 13.0855 (6) Å0.28 × 0.10 × 0.04 mm
β = 94.685 (3)°
Data collection top
Stoe IPDS-1
diffractometer
2920 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
2545 reflections with I > 2σ(I)
Tmin = 0.803, Tmax = 0.931Rint = 0.032
17537 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.38 e Å3
S = 1.06Δρmin = 0.44 e Å3
2920 reflectionsAbsolute structure: ?
145 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.14587 (3)0.856111 (10)0.668028 (15)0.04089 (7)
N10.1966 (4)0.8771 (2)0.5822 (2)0.0667 (8)
C10.3839 (5)0.87582 (19)0.5463 (2)0.0492 (6)
S10.65079 (13)0.87510 (7)0.49397 (6)0.0662 (2)
N110.7272 (4)0.48256 (13)0.77586 (18)0.0432 (5)
C110.5200 (6)0.49095 (17)0.7245 (3)0.0578 (8)
H110.44170.44370.70050.069*
C120.4168 (5)0.56691 (17)0.7052 (2)0.0540 (7)
H120.27220.57020.66870.065*
C130.5275 (4)0.63720 (15)0.7401 (2)0.0396 (5)
C140.7445 (5)0.62913 (15)0.7913 (2)0.0480 (6)
H140.82750.67570.81450.058*
C150.8372 (5)0.55133 (16)0.8077 (2)0.0490 (6)
H150.98340.54660.84260.059*
C160.4083 (5)0.71974 (15)0.7252 (2)0.0426 (5)
O110.2091 (4)0.71926 (12)0.67857 (18)0.0592 (5)
O120.5052 (3)0.78408 (11)0.75867 (17)0.0510 (5)
O210.0682 (4)0.84635 (14)0.81279 (16)0.0572 (5)
H1O10.20250.83100.79960.086*
C210.0069 (7)0.8386 (3)0.9186 (3)0.0778 (11)
H21A0.14540.87200.93270.093*
H21B0.04970.78150.93240.093*
C220.1619 (11)0.8630 (4)0.9880 (4)0.129 (2)
H22A0.09820.85521.05740.193*
H22B0.29900.82980.97570.193*
H22C0.20100.92010.97710.193*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03291 (10)0.03170 (10)0.05680 (12)0.00051 (7)0.00408 (7)0.00070 (8)
N10.0336 (12)0.098 (2)0.0675 (16)0.0051 (13)0.0028 (11)0.0164 (15)
C10.0382 (14)0.0617 (17)0.0476 (14)0.0037 (12)0.0028 (11)0.0077 (12)
S10.0357 (3)0.1101 (7)0.0514 (4)0.0010 (4)0.0046 (3)0.0062 (4)
N110.0401 (11)0.0317 (10)0.0569 (13)0.0011 (8)0.0020 (10)0.0014 (9)
C110.0541 (17)0.0349 (13)0.080 (2)0.0018 (12)0.0226 (16)0.0042 (13)
C120.0452 (15)0.0390 (13)0.0739 (19)0.0016 (12)0.0192 (14)0.0019 (13)
C130.0386 (12)0.0341 (11)0.0466 (13)0.0009 (10)0.0053 (10)0.0031 (10)
C140.0381 (13)0.0320 (12)0.0724 (18)0.0039 (10)0.0043 (12)0.0003 (11)
C150.0381 (13)0.0376 (13)0.0692 (18)0.0013 (10)0.0074 (13)0.0007 (12)
C160.0408 (13)0.0357 (12)0.0517 (14)0.0007 (10)0.0052 (11)0.0057 (11)
O110.0486 (11)0.0379 (10)0.0880 (15)0.0055 (9)0.0130 (11)0.0024 (10)
O120.0483 (11)0.0317 (9)0.0721 (13)0.0001 (8)0.0004 (9)0.0024 (8)
O210.0479 (11)0.0665 (14)0.0564 (12)0.0085 (10)0.0011 (9)0.0004 (10)
C210.072 (2)0.092 (3)0.066 (2)0.011 (2)0.0128 (18)0.0078 (19)
C220.125 (5)0.201 (7)0.059 (2)0.049 (4)0.002 (3)0.000 (3)
Geometric parameters (Å, º) top
Cd1—N12.220 (3)C12—H120.9300
Cd1—O112.247 (2)C13—C141.379 (4)
Cd1—N11i2.275 (2)C13—C161.508 (3)
Cd1—O212.351 (2)C14—C151.378 (4)
Cd1—O122.583 (2)C14—H140.9300
Cd1—S1ii2.6644 (9)C15—H150.9300
Cd1—C162.746 (3)C16—O121.245 (3)
N1—C11.144 (4)C16—O111.258 (3)
C1—S11.635 (3)O21—C211.422 (4)
S1—Cd1iii2.6644 (9)O21—H1O10.8199
N11—C111.331 (4)C21—C221.441 (7)
N11—C151.331 (3)C21—H21A0.9700
N11—Cd1iv2.275 (2)C21—H21B0.9700
C11—C121.380 (4)C22—H22A0.9600
C11—H110.9300C22—H22B0.9600
C12—C131.365 (4)C22—H22C0.9600
N1—Cd1—O11108.39 (10)C12—C13—C14117.8 (2)
N1—Cd1—N11i106.05 (11)C12—C13—C16119.9 (2)
O11—Cd1—N11i145.09 (8)C14—C13—C16122.3 (2)
N1—Cd1—O2184.95 (9)C15—C14—C13119.2 (2)
O11—Cd1—O2188.73 (8)C15—C14—H14120.4
N11i—Cd1—O2188.70 (8)C13—C14—H14120.4
N1—Cd1—O12161.97 (10)N11—C15—C14123.0 (2)
O11—Cd1—O1253.60 (7)N11—C15—H15118.5
N11i—Cd1—O1291.82 (7)C14—C15—H15118.5
O21—Cd1—O1293.19 (7)O12—C16—O11122.9 (2)
N1—Cd1—S1ii89.26 (8)O12—C16—C13120.5 (2)
O11—Cd1—S1ii94.89 (7)O11—C16—C13116.6 (2)
N11i—Cd1—S1ii91.09 (6)O12—C16—Cd169.29 (14)
O21—Cd1—S1ii173.91 (6)O11—C16—Cd153.83 (13)
O12—Cd1—S1ii92.90 (5)C13—C16—Cd1169.39 (19)
N1—Cd1—C16135.24 (11)C16—O11—Cd199.30 (16)
O11—Cd1—C1626.87 (8)C16—O12—Cd183.93 (15)
N11i—Cd1—C16118.58 (8)C21—O21—Cd1130.7 (2)
O21—Cd1—C1692.37 (8)C21—O21—H1O1112.8
O12—Cd1—C1626.78 (7)Cd1—O21—H1O1113.7
S1ii—Cd1—C1693.06 (6)O21—C21—C22114.9 (3)
C1—N1—Cd1168.3 (3)O21—C21—H21A108.5
N1—C1—S1179.2 (3)C22—C21—H21A108.5
C1—S1—Cd1iii96.29 (10)O21—C21—H21B108.5
C11—N11—C15117.4 (2)C22—C21—H21B108.5
C11—N11—Cd1iv120.52 (17)H21A—C21—H21B107.5
C15—N11—Cd1iv121.17 (18)C21—C22—H22A109.5
N11—C11—C12122.7 (3)C21—C22—H22B109.5
N11—C11—H11118.7H22A—C22—H22B109.5
C12—C11—H11118.7C21—C22—H22C109.5
C13—C12—C11119.8 (3)H22A—C22—H22C109.5
C13—C12—H12120.1H22B—C22—H22C109.5
C11—C12—H12120.1
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y, z; (iii) x1, y, z; (iv) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H1O1···O12iii0.821.892.703 (3)172
Symmetry code: (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H1O1···O12i0.82001.89002.703 (3)172.00
Symmetry code: (i) x1, y, z.
Acknowledgements top

The authors gratefully acknowledge financial support from the DFG (project No. NA720/3-1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

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Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.

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