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Acta Cryst. (2007). E63, m856    [ doi:10.1107/S1600536807007805 ]

trans-Bis(aniline-[kappa]N)dichlorobis(ethanol-[kappa]O)cobalt(II)

W. Clegg and N. C. Martin

Abstract top

The title compound, [CoCl2(C6H7N)2(C2H6O)2], was obtained unintentionally as the product of an attempted synthesis of a polycarboxylate-bridged network complex of cobalt(II) using aniline as a base to deprotonate the organic acid. The molecule is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry. Molecules are linked by O-H...Cl and N-H...Cl hydrogen bonds involving all the potential donors, generating sheets parallel to (001). The phenyl rings protrude on both sides of these sheets and have normal hydrophobic contacts with each other, involving no intercalation or stacking interactions.

Comment top

The molecule of the title complex, (I) (Fig. 1), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry, cis angles deviating from 90° by less than 4°.

Molecules are linked by O—H···Cl and N—H···Cl hydrogen bonds involving all potential donors, generating sheets parallel to (001), as shown in Fig. 2. The phenyl rings protrude on both sides of these sheets and have normal hydrophobic contacts with each other, involving no intercalation or stacking interactions.

The corresponding four-coordinate complex without ethanol has tetrahedral geometry (Burrow et al., 1997), with layers of molecules linked by N—H···Cl hydrogen bonds.

Related literature top

The corresponding four-coordinate complex without ethanol has tetrahedral geometry (Burrow et al., 1997), with layers of molecules linked by N—H···Cl hydrogen bonds.

Experimental top

The title compound was obtained unintentionally as the product of an attempted synthesis of a polymeric network complex of cobalt with pyromellitic acid, using vapour diffusion of aniline into an ethanol solution of cobalt(II) chloride and pyromellitic acid at room temperature.

Refinement top

H atoms bonded to N and O atoms were located in a difference map and refined with distance restraints of O—H = 0.84 (2) and N—H = 0.87 (2) Å, and with Uiso(H) = 1.2Ueq(N,O). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the c axis, showing one layer of molecules connected by O—H···Cl and N—H···Cl hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted.
trans-Bis(aniline-κN)dichlorobis(ethanol-κO)cobalt(II) top
Crystal data top
[CoCl2(C6H7N)2(C2H6O)2]Z = 1
Mr = 408.22F000 = 213
Triclinic, P1Dx = 1.469 Mg m−3
a = 5.8166 (16) ÅMo Kα radiation
λ = 0.71073 Å
b = 6.8339 (19) ÅCell parameters from 2052 reflections
c = 12.263 (3) Åθ = 3.1–28.6º
α = 87.642 (5)ºµ = 1.23 mm−1
β = 81.726 (5)ºT = 160 (2) K
γ = 73.017 (5)ºBlock, pink
V = 461.3 (2) Å30.30 × 0.20 × 0.04 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1583 independent reflections
Radiation source: sealed tube1278 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
Detector resolution: 8.192 pixels mm-1θmax = 25.0º
T = 160(2) Kθmin = 1.7º
thin–slice ω scansh = −6→6
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		k = −8→7
Tmin = 0.710, Tmax = 0.950l = −14→14
2296 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.0677P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1583 reflectionsΔρmax = 0.82 e Å−3
116 parametersΔρmin = −0.95 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[CoCl2(C6H7N)2(C2H6O)2]γ = 73.017 (5)º
Mr = 408.22V = 461.3 (2) Å3
Triclinic, P1Z = 1
a = 5.8166 (16) ÅMo Kα
b = 6.8339 (19) ŵ = 1.23 mm−1
c = 12.263 (3) ÅT = 160 (2) K
α = 87.642 (5)º0.30 × 0.20 × 0.04 mm
β = 81.726 (5)º
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1583 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1278 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.950Rint = 0.027
2296 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0403 restraints
wR(F2) = 0.105H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.82 e Å−3
1583 reflectionsΔρmin = −0.95 e Å−3
116 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.50000.50000.50000.0127 (2)
Cl0.26740 (13)0.26735 (11)0.45695 (6)0.0178 (2)
O0.2256 (4)0.5979 (3)0.63639 (18)0.0165 (5)
H1O0.095 (4)0.608 (5)0.613 (3)0.020*
C10.2075 (6)0.7554 (5)0.7133 (3)0.0215 (8)
H1A0.14620.89070.67870.026*
H1B0.37100.74420.73190.026*
C20.0399 (7)0.7412 (6)0.8177 (3)0.0291 (9)
H2A−0.12180.75120.79950.044*
H2B0.02870.85320.86740.044*
H2C0.10410.60990.85390.044*
N0.2846 (5)0.7522 (4)0.4102 (2)0.0158 (6)
H1C0.293 (7)0.860 (3)0.444 (3)0.019*
H1D0.139 (3)0.743 (5)0.432 (3)0.019*
C30.3387 (6)0.7559 (4)0.2928 (3)0.0153 (7)
C40.5275 (6)0.8296 (5)0.2440 (3)0.0225 (8)
H40.61840.88030.28850.027*
C50.5829 (7)0.8292 (5)0.1308 (3)0.0267 (8)
H50.71120.88110.09790.032*
C60.4557 (7)0.7549 (5)0.0649 (3)0.0292 (9)
H60.49580.7547−0.01300.035*
C70.2666 (7)0.6797 (5)0.1139 (3)0.0274 (8)
H70.17770.62730.06920.033*
C80.2086 (6)0.6813 (5)0.2273 (3)0.0209 (8)
H80.07890.63110.26030.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0061 (3)0.0094 (3)0.0209 (4)0.0015 (2)−0.0035 (2)−0.0010 (2)
Cl0.0090 (4)0.0140 (4)0.0297 (5)−0.0008 (3)−0.0050 (3)−0.0037 (3)
O0.0090 (12)0.0161 (11)0.0240 (13)−0.0006 (9)−0.0058 (10)−0.0030 (9)
C10.0161 (18)0.0168 (17)0.031 (2)−0.0030 (14)−0.0039 (15)−0.0049 (14)
C20.029 (2)0.0248 (19)0.031 (2)−0.0056 (16)0.0007 (17)−0.0067 (16)
N0.0097 (14)0.0112 (13)0.0248 (16)0.0009 (11)−0.0049 (12)−0.0015 (11)
C30.0124 (17)0.0069 (14)0.0227 (17)0.0036 (12)−0.0032 (13)0.0009 (12)
C40.0173 (19)0.0158 (16)0.035 (2)−0.0046 (14)−0.0069 (15)0.0042 (14)
C50.0185 (19)0.0197 (18)0.036 (2)0.0002 (15)0.0019 (16)0.0078 (15)
C60.030 (2)0.0197 (18)0.028 (2)0.0065 (16)−0.0001 (16)0.0035 (15)
C70.030 (2)0.0189 (17)0.032 (2)−0.0016 (15)−0.0120 (16)−0.0043 (15)
C80.0184 (18)0.0155 (17)0.0280 (19)−0.0030 (14)−0.0042 (14)−0.0004 (14)
Geometric parameters (Å, °) top
Co—Cl2.4836 (9)N—H1C0.873 (10)
Co—Cli2.4835 (9)N—H1D0.869 (10)
Co—O2.120 (2)N—C31.431 (4)
Co—Oi2.120 (2)C3—C41.388 (5)
Co—N2.175 (3)C3—C81.382 (5)
Co—Ni2.175 (3)C4—H40.950
O—H1O0.833 (10)C4—C51.378 (5)
O—C11.431 (4)C5—H50.950
C1—H1A0.990C5—C61.372 (6)
C1—H1B0.990C6—H60.950
C1—C21.512 (5)C6—C71.396 (6)
C2—H2A0.980C7—H70.950
C2—H2B0.980C7—C81.383 (5)
C2—H2C0.980C8—H80.950
Cl—Co—Cli180H2A—C2—H2B109.5
Cl—Co—O86.06 (6)H2A—C2—H2C109.5
Cli—Co—Oi86.06 (7)H2B—C2—H2C109.5
Cli—Co—O93.94 (7)Co—N—H1C103 (2)
Cl—Co—Oi93.94 (6)Co—N—H1D101 (2)
Cl—Co—N92.33 (8)Co—N—C3118.62 (19)
Cli—Co—N87.67 (8)H1C—N—H1D106 (3)
Cli—Co—Ni92.33 (8)H1C—N—C3115 (2)
Cl—Co—Ni87.67 (8)H1D—N—C3112 (2)
O—Co—Oi180N—C3—C4119.9 (3)
O—Co—N86.22 (10)N—C3—C8120.5 (3)
Oi—Co—N93.78 (10)C4—C3—C8119.6 (3)
Oi—Co—Ni86.22 (10)C3—C4—H4120.1
O—Co—Ni93.78 (10)C3—C4—C5119.9 (3)
N—Co—Ni180H4—C4—C5120.1
Co—O—H1O106 (3)C4—C5—H5119.5
Co—O—C1126.4 (2)C4—C5—C6121.1 (4)
H1O—O—C1113 (3)H5—C5—C6119.5
O—C1—H1A109.3C5—C6—H6120.4
O—C1—H1B109.3C5—C6—C7119.1 (4)
O—C1—C2111.8 (3)H6—C6—C7120.4
H1A—C1—H1B107.9C6—C7—H7119.9
H1A—C1—C2109.3C6—C7—C8120.1 (3)
H1B—C1—C2109.3H7—C7—C8119.9
C1—C2—H2A109.5C3—C8—C7120.2 (3)
C1—C2—H2B109.5C3—C8—H8119.9
C1—C2—H2C109.5C7—C8—H8119.9
Cl—Co—O—C1−177.0 (2)Co—N—C3—C896.5 (3)
Cli—Co—O—C13.0 (2)N—C3—C4—C5178.7 (3)
N—Co—O—C1−84.4 (2)C8—C3—C4—C50.4 (5)
Ni—Co—O—C195.6 (2)C3—C4—C5—C6−0.6 (5)
Co—O—C1—C2−162.3 (2)C4—C5—C6—C70.3 (5)
Cl—Co—N—C3−79.7 (2)C5—C6—C7—C80.3 (5)
Cli—Co—N—C3100.3 (2)N—C3—C8—C7−178.1 (3)
O—Co—N—C3−165.6 (2)C4—C3—C8—C70.2 (5)
Oi—Co—N—C314.4 (2)C6—C7—C8—C3−0.5 (5)
Co—N—C3—C4−81.7 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O—H1O···Clii0.833 (10)2.306 (14)3.114 (2)163 (3)
N—H1C···Cliii0.873 (10)2.756 (18)3.560 (3)154 (3)
N—H1D···Clii0.869 (10)2.574 (13)3.422 (3)165 (3)
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x, y+1, z.
Table 1
Selected geometric parameters (Å, °) top
Co—Cl2.4836 (9)Co—N2.175 (3)
Co—O2.120 (2)
Cl—Co—O86.06 (6)O—Co—N86.22 (10)
Cl—Co—N92.33 (8)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O—H1O···Cli0.833 (10)2.306 (14)3.114 (2)163 (3)
N—H1C···Clii0.873 (10)2.756 (18)3.560 (3)154 (3)
N—H1D···Cli0.869 (10)2.574 (13)3.422 (3)165 (3)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z.
Acknowledgements top

The authors thank the EPSRC for financial support.

references
References top

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Burrow, R. A., Horner, M., Lang, L. S., Neves, A. & Vencato, I. (1997). Z. Kristallogr. New Cryst. Struct. 212, 41–41.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.