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Acta Cryst. (2007). E63, m2478    [ doi:10.1107/S1600536807043024 ]

Tetraaquabis(thiocyanato-[kappa]N)cobalt(II) hexamethylenetetramine (1/2) cocrystal

X.-L. Li, D.-Z. Niu and Z.-S. Lu

Abstract top

In the crystal structure of the title compound, [Co(H2O)4(NCS)2]·2C6H12N4, the six-coordinated CoII atom lies on a special position of mmm site symmetry and the hexamethylenetetramine molecule about a special position of \overline{4} site symmetry. The two entities interact through an O-H...N hydrogen bond to form a three-dimensional network.

Comment top

Thiocyanate ion has played an important role in constructing heteronuclear complexes in our systems. (Li, Tong et al.,2004; Li, Zhao et al., 2004). Herein is described a crystal structure of thiocyanate complex, [Co(NCS)2(H2O)4]·2(C6H12N4). The cell contains two same units of the title compound. A perspective drawing of the complex with atomic numbering scheme is depicted in Fig. 1 and selected bonding parameters are presented in Table 1.

The cobalt atom locates in a slightly disordered CoN2O4 octahedral coordination geometry. Each hmt connects with four [Co(NCS)2(H2O)4] units and each [Co(NCS)2(H2O)4] unit connects with eight hmt molecules through O—H···N hydrogen bonds leading to 3-D network.

Related literature top

For related compounds, see Li, Tong et al. (2004); Li, Zhao et al. (2004).

Experimental top

AgNO3 (0.68 g, 4.0 mmol), NH4SCN (0.61 g, 4.0 mmol) and hmt (1.4 g, 10 mmol) were added to a stired CoCl2·6H2O (0.47 g, 2.0 mmol) solution in acetonitrile, respectively. The mixture was stirred in r.t. for 12 h. After filtration, the filtrate was disposed to stand in the air. A few days later, purple-red single crystals suitable for X-ray diffraction were obtained.

Refinement top

The positions of hydrogen atoms were generated geometrically (C—H bond fixed at 0.96 Å) expect those connected to O1w atoms which are generated according to the fourier map, assigned isotropic thermal parameters and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1996); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures top
[Figure 1] Fig. 1. A view of the complex with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Tetraaquabis(thiocyanato-κN)cobalt(II) hexamethylenetetramine (1/2) cocrystal top
Crystal data top
[Co(H2O)4(NCS)2]·2C6H12N4Z = 2
Mr = 527.55F000 = 554
Tetragonal, P42/mnmDx = 1.418 Mg m−3
Hall symbol: -P 4n 2nMo Kα radiation
λ = 0.71073 Å
a = 9.4846 (4) ÅCell parameters from 200 reflections
b = 9.4846 Åθ = 2.6–25.1º
c = 13.7339 (6) ŵ = 0.90 mm−1
α = 90ºT = 293 (2) K
β = 90ºPrism, purple-red
γ = 90º0.43 × 0.40 × 0.25 mm
V = 1235.47 (7) Å3
Data collection top
Siemens SMART
diffractometer		625 independent reflections
Radiation source: fine-focus sealed tube554 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 293(2) Kθmax = 25.1º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→11
Tmin = 0.685, Tmax = 0.798k = −11→11
2871 measured reflectionsl = −16→10
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034  w = 1/[σ2(Fo2) + (0.0614P)2 + 0.8126P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.100(Δ/σ)max = 0.01
S = 1.06Δρmax = 0.33 e Å−3
626 reflectionsΔρmin = −0.46 e Å−3
58 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.052 (5)
Secondary atom site location: difference Fourier map
Crystal data top
[Co(H2O)4(NCS)2]·2C6H12N4γ = 90º
Mr = 527.55V = 1235.47 (7) Å3
Tetragonal, P42/mnmZ = 2
a = 9.4846 (4) ÅMo Kα
b = 9.4846 ŵ = 0.90 mm−1
c = 13.7339 (6) ÅT = 293 (2) K
α = 90º0.43 × 0.40 × 0.25 mm
β = 90º
Data collection top
Siemens SMART
diffractometer		625 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		554 reflections with I > 2σ(I)
Tmin = 0.685, Tmax = 0.798Rint = 0.024
2871 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03458 parameters
wR(F2) = 0.100H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.33 e Å−3
626 reflectionsΔρmin = −0.46 e Å−3
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.

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 > σ(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
Co0.50000.50000.50000.0295 (4)
S10.86349 (9)0.86349 (9)0.50000.0606 (5)
O1W0.3901 (3)0.6099 (3)0.3938 (3)0.0960 (13)
H10.39900.71140.38100.115*
N10.6560 (3)0.6560 (3)0.50000.0413 (9)
C10.7427 (3)0.7427 (3)0.50000.0348 (10)
N20.1198 (3)0.5440 (3)0.31207 (17)0.0558 (7)
C20.00000.50000.3713 (3)0.0637 (13)
H2−0.023 (4)0.572 (4)0.409 (2)0.081 (11)*
C30.1598 (3)0.4253 (4)0.2505 (3)0.0632 (9)
H3A0.179 (4)0.350 (4)0.293 (3)0.078 (11)*
H3B0.243 (4)0.457 (4)0.212 (3)0.079 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0285 (4)0.0285 (4)0.0315 (5)−0.0055 (3)0.0000.000
S10.0445 (6)0.0445 (6)0.0930 (11)−0.0205 (6)0.0000.000
O1W0.0788 (14)0.0788 (14)0.131 (3)−0.0392 (18)−0.0664 (18)0.0664 (18)
N10.0391 (14)0.0391 (14)0.046 (2)−0.0050 (18)0.0000.000
C10.0322 (15)0.0322 (15)0.040 (2)−0.0018 (19)0.0000.000
N20.0523 (14)0.0631 (15)0.0520 (13)0.0067 (11)−0.0179 (11)−0.0131 (11)
C20.095 (4)0.065 (3)0.0310 (18)0.031 (2)0.0000.000
C30.0467 (17)0.071 (2)0.072 (2)0.0158 (15)0.0021 (14)−0.0125 (17)
Geometric parameters (Å, °) top
Co—O1Wi2.074 (3)N2—C21.459 (3)
Co—O1Wii2.074 (3)N2—C3iv1.459 (4)
Co—O1W2.074 (3)N2—C31.458 (4)
Co—O1Wiii2.074 (3)C2—N2v1.459 (3)
Co—N1ii2.092 (4)C2—H20.88 (3)
Co—N12.092 (4)C3—N2vi1.459 (4)
S1—C11.621 (5)C3—H3A0.94 (4)
O1W—H10.9821C3—H3B0.99 (4)
N1—C11.163 (6)
O1Wi—Co—O1Wii89.4 (3)Co—O1W—H1125.1
O1Wi—Co—O1W90.6 (3)C1—N1—Co180.0
O1Wii—Co—O1W180.0N1—C1—S1179.999 (1)
O1Wi—Co—O1Wiii180.0C2—N2—C3iv108.4 (2)
O1Wii—Co—O1Wiii90.6 (3)C2—N2—C3107.8 (2)
O1W—Co—O1Wiii89.4 (3)C3iv—N2—C3108.44 (18)
O1Wi—Co—N1ii90.0N2—C2—N2v112.2 (3)
O1Wii—Co—N1ii90.0N2—C2—H2107 (2)
O1W—Co—N1ii90.0N2v—C2—H2111 (2)
O1Wiii—Co—N1ii90.0N2vi—C3—N2111.8 (3)
O1Wi—Co—N190.0N2vi—C3—H3A107 (2)
O1Wii—Co—N190.0N2—C3—H3A106 (2)
O1W—Co—N190.0N2vi—C3—H3B112 (2)
O1Wiii—Co—N190.0N2—C3—H3B106 (2)
N1ii—Co—N1180.0H3A—C3—H3B114 (3)
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y, −z+1; (iv) −y+1/2, x+1/2, −z+1/2; (v) −x, −y+1, z; (vi) y−1/2, −x+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···N2vii0.981.942.867 (3)157.1
Symmetry codes: (vii) −y+1, −x+1, z.
Table 1
Selected geometric parameters (°) top
O1Wi—Co—O1W90.6 (3)C1—N1—Co180.0
O1W—Co—O1Wii89.4 (3)N1—C1—S1179.999 (1)
Symmetry codes: (i) −x+1, −y+1, z; (ii) x, y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···N2iii0.981.942.867 (3)157.1
Symmetry codes: (iii) −y+1, −x+1, z.
Acknowledgements top

This work is supported by the Natural Science Foundation of Xuzhou Normal University (05XLB09).

references
References top

Bruker (1999). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Li, X. L., Tong, M. L., Niu, D. Z. & Chen, J. T. (2004). Chin. J. Chem. . 22, 64–68.

Li, X. L., Zhao, C. C., Chen, J. T. & Du, W. X. (2004). Chin. J. Chem. . 22, 533–536.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1996). SAINT and SMART. Software Reference Manual. Siemens Energy and Automation Inc., Madison, Wisconsin, USA.