trans-Bis(aniline-κN)dichloro­bis(ethanol-κO)cobalt(II)

Clegg, W.; Martin, N.C.

doi:10.1107/S1600536807007805

metal-organic compounds

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Volume 63| Part 3| March 2007| Page m856

https://doi.org/10.1107/S1600536807007805

trans-Bis(aniline-κN)dichlorobis(ethanol-κO)cobalt(II)

William Clegg ^a ^* and Nicola C. Martin ^a

^aSchool of Natural Sciences (Chemistry), Newcastle University, Newcastle upon Tyne NE1 7RU, England
^*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 8 February 2007; accepted 15 February 2007; online 28 February 2007)

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.

Related literature

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

Crystal data

[CoCl₂(C₆H₇N)₂(C₂H₆O)₂]
M_r = 408.22
Triclinic, $[P \overline 1]$
a = 5.8166 (16) Å
b = 6.8339 (19) Å
c = 12.263 (3) Å
α = 87.642 (5)°
β = 81.726 (5)°
γ = 73.017 (5)°
V = 461.3 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 160 (2) K
0.30 × 0.20 × 0.04 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.710, T_max = 0.950
2296 measured reflections
1583 independent reflections
1278 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.03
1583 reflections
116 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co—Cl	2.4836 (9)
Co—O	2.120 (2)
Co—N	2.175 (3)

Cl—Co—O	86.06 (6)
Cl—Co—N	92.33 (8)
O—Co—N	86.22 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O—H1O⋯Clⁱ	0.833 (10)	2.306 (14)	3.114 (2)	163 (3)
N—H1C⋯Clⁱⁱ	0.873 (10)	2.756 (18)	3.560 (3)	154 (3)
N—H1D⋯Clⁱ	0.869 (10)	2.574 (13)	3.422 (3)	165 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y+1, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807007805/wn2117sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007805/wn2117Isup2.hkl

checkCIF report

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.

Structure description 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.

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

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	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
M_r = 408.22	F(000) = 213
Triclinic, P1	D_x = 1.469 Mg m⁻³
a = 5.8166 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.8339 (19) Å	Cell parameters from 2052 reflections
c = 12.263 (3) Å	θ = 3.1–28.6°
α = 87.642 (5)°	µ = 1.23 mm⁻¹
β = 81.726 (5)°	T = 160 K
γ = 73.017 (5)°	Block, pink
V = 461.3 (2) Å³	0.30 × 0.20 × 0.04 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1583 independent reflections
Radiation source: sealed tube	1278 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 1.7°
thin–slice ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −8→7
T_min = 0.710, T_max = 0.950	l = −14→14
2296 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0677P)²] where P = (F_o² + 2F_c²)/3
1583 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.82 e Å⁻³
3 restraints	Δρ_min = −0.95 e Å⁻³

Crystal data top

[CoCl₂(C₆H₇N)₂(C₂H₆O)₂]	γ = 73.017 (5)°
M_r = 408.22	V = 461.3 (2) Å³
Triclinic, P1	Z = 1
a = 5.8166 (16) Å	Mo Kα radiation
b = 6.8339 (19) Å	µ = 1.23 mm⁻¹
c = 12.263 (3) Å	T = 160 K
α = 87.642 (5)°	0.30 × 0.20 × 0.04 mm
β = 81.726 (5)°

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)
T_min = 0.710, T_max = 0.950	R_int = 0.027
2296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	3 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.82 e Å⁻³
1583 reflections	Δρ_min = −0.95 e Å⁻³
116 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co	0.5000	0.5000	0.5000	0.0127 (2)
Cl	0.26740 (13)	0.26735 (11)	0.45695 (6)	0.0178 (2)
O	0.2256 (4)	0.5979 (3)	0.63639 (18)	0.0165 (5)
H1O	0.095 (4)	0.608 (5)	0.613 (3)	0.020*
C1	0.2075 (6)	0.7554 (5)	0.7133 (3)	0.0215 (8)
H1A	0.1462	0.8907	0.6787	0.026*
H1B	0.3710	0.7442	0.7319	0.026*
C2	0.0399 (7)	0.7412 (6)	0.8177 (3)	0.0291 (9)
H2A	−0.1218	0.7512	0.7995	0.044*
H2B	0.0287	0.8532	0.8674	0.044*
H2C	0.1041	0.6099	0.8539	0.044*
N	0.2846 (5)	0.7522 (4)	0.4102 (2)	0.0158 (6)
H1C	0.293 (7)	0.860 (3)	0.444 (3)	0.019*
H1D	0.139 (3)	0.743 (5)	0.432 (3)	0.019*
C3	0.3387 (6)	0.7559 (4)	0.2928 (3)	0.0153 (7)
C4	0.5275 (6)	0.8296 (5)	0.2440 (3)	0.0225 (8)
H4	0.6184	0.8803	0.2885	0.027*
C5	0.5829 (7)	0.8292 (5)	0.1308 (3)	0.0267 (8)
H5	0.7112	0.8811	0.0979	0.032*
C6	0.4557 (7)	0.7549 (5)	0.0649 (3)	0.0292 (9)
H6	0.4958	0.7547	−0.0130	0.035*
C7	0.2666 (7)	0.6797 (5)	0.1139 (3)	0.0274 (8)
H7	0.1777	0.6273	0.0692	0.033*
C8	0.2086 (6)	0.6813 (5)	0.2273 (3)	0.0209 (8)
H8	0.0789	0.6311	0.2603	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0061 (3)	0.0094 (3)	0.0209 (4)	0.0015 (2)	−0.0035 (2)	−0.0010 (2)
Cl	0.0090 (4)	0.0140 (4)	0.0297 (5)	−0.0008 (3)	−0.0050 (3)	−0.0037 (3)
O	0.0090 (12)	0.0161 (11)	0.0240 (13)	−0.0006 (9)	−0.0058 (10)	−0.0030 (9)
C1	0.0161 (18)	0.0168 (17)	0.031 (2)	−0.0030 (14)	−0.0039 (15)	−0.0049 (14)
C2	0.029 (2)	0.0248 (19)	0.031 (2)	−0.0056 (16)	0.0007 (17)	−0.0067 (16)
N	0.0097 (14)	0.0112 (13)	0.0248 (16)	0.0009 (11)	−0.0049 (12)	−0.0015 (11)
C3	0.0124 (17)	0.0069 (14)	0.0227 (17)	0.0036 (12)	−0.0032 (13)	0.0009 (12)
C4	0.0173 (19)	0.0158 (16)	0.035 (2)	−0.0046 (14)	−0.0069 (15)	0.0042 (14)
C5	0.0185 (19)	0.0197 (18)	0.036 (2)	0.0002 (15)	0.0019 (16)	0.0078 (15)
C6	0.030 (2)	0.0197 (18)	0.028 (2)	0.0065 (16)	−0.0001 (16)	0.0035 (15)
C7	0.030 (2)	0.0189 (17)	0.032 (2)	−0.0016 (15)	−0.0120 (16)	−0.0043 (15)
C8	0.0184 (18)	0.0155 (17)	0.0280 (19)	−0.0030 (14)	−0.0042 (14)	−0.0004 (14)

Geometric parameters (Å, º) top

Co—Cl	2.4836 (9)	N—H1C	0.873 (10)
Co—Clⁱ	2.4835 (9)	N—H1D	0.869 (10)
Co—O	2.120 (2)	N—C3	1.431 (4)
Co—Oⁱ	2.120 (2)	C3—C4	1.388 (5)
Co—N	2.175 (3)	C3—C8	1.382 (5)
Co—Nⁱ	2.175 (3)	C4—H4	0.950
O—H1O	0.833 (10)	C4—C5	1.378 (5)
O—C1	1.431 (4)	C5—H5	0.950
C1—H1A	0.990	C5—C6	1.372 (6)
C1—H1B	0.990	C6—H6	0.950
C1—C2	1.512 (5)	C6—C7	1.396 (6)
C2—H2A	0.980	C7—H7	0.950
C2—H2B	0.980	C7—C8	1.383 (5)
C2—H2C	0.980	C8—H8	0.950

Cl—Co—Clⁱ	180	H2A—C2—H2B	109.5
Cl—Co—O	86.06 (6)	H2A—C2—H2C	109.5
Clⁱ—Co—Oⁱ	86.06 (7)	H2B—C2—H2C	109.5
Clⁱ—Co—O	93.94 (7)	Co—N—H1C	103 (2)
Cl—Co—Oⁱ	93.94 (6)	Co—N—H1D	101 (2)
Cl—Co—N	92.33 (8)	Co—N—C3	118.62 (19)
Clⁱ—Co—N	87.67 (8)	H1C—N—H1D	106 (3)
Clⁱ—Co—Nⁱ	92.33 (8)	H1C—N—C3	115 (2)
Cl—Co—Nⁱ	87.67 (8)	H1D—N—C3	112 (2)
O—Co—Oⁱ	180	N—C3—C4	119.9 (3)
O—Co—N	86.22 (10)	N—C3—C8	120.5 (3)
Oⁱ—Co—N	93.78 (10)	C4—C3—C8	119.6 (3)
Oⁱ—Co—Nⁱ	86.22 (10)	C3—C4—H4	120.1
O—Co—Nⁱ	93.78 (10)	C3—C4—C5	119.9 (3)
N—Co—Nⁱ	180	H4—C4—C5	120.1
Co—O—H1O	106 (3)	C4—C5—H5	119.5
Co—O—C1	126.4 (2)	C4—C5—C6	121.1 (4)
H1O—O—C1	113 (3)	H5—C5—C6	119.5
O—C1—H1A	109.3	C5—C6—H6	120.4
O—C1—H1B	109.3	C5—C6—C7	119.1 (4)
O—C1—C2	111.8 (3)	H6—C6—C7	120.4
H1A—C1—H1B	107.9	C6—C7—H7	119.9
H1A—C1—C2	109.3	C6—C7—C8	120.1 (3)
H1B—C1—C2	109.3	H7—C7—C8	119.9
C1—C2—H2A	109.5	C3—C8—C7	120.2 (3)
C1—C2—H2B	109.5	C3—C8—H8	119.9
C1—C2—H2C	109.5	C7—C8—H8	119.9

Cl—Co—O—C1	−177.0 (2)	Co—N—C3—C8	96.5 (3)
Clⁱ—Co—O—C1	3.0 (2)	N—C3—C4—C5	178.7 (3)
N—Co—O—C1	−84.4 (2)	C8—C3—C4—C5	0.4 (5)
Nⁱ—Co—O—C1	95.6 (2)	C3—C4—C5—C6	−0.6 (5)
Co—O—C1—C2	−162.3 (2)	C4—C5—C6—C7	0.3 (5)
Cl—Co—N—C3	−79.7 (2)	C5—C6—C7—C8	0.3 (5)
Clⁱ—Co—N—C3	100.3 (2)	N—C3—C8—C7	−178.1 (3)
O—Co—N—C3	−165.6 (2)	C4—C3—C8—C7	0.2 (5)
Oⁱ—Co—N—C3	14.4 (2)	C6—C7—C8—C3	−0.5 (5)
Co—N—C3—C4	−81.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H1O···Clⁱⁱ	0.83 (1)	2.31 (1)	3.114 (2)	163 (3)
N—H1C···Clⁱⁱⁱ	0.87 (1)	2.76 (2)	3.560 (3)	154 (3)
N—H1D···Clⁱⁱ	0.87 (1)	2.57 (1)	3.422 (3)	165 (3)

Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₆H₇N)₂(C₂H₆O)₂]
M_r	408.22
Crystal system, space group	Triclinic, P1
Temperature (K)	160
a, b, c (Å)	5.8166 (16), 6.8339 (19), 12.263 (3)
α, β, γ (°)	87.642 (5), 81.726 (5), 73.017 (5)
V (Å³)	461.3 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.30 × 0.20 × 0.04

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.710, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	2296, 1583, 1278
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.03
No. of reflections	1583
No. of parameters	116
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.95

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.

Selected geometric parameters (Å, º) top

Co—Cl	2.4836 (9)	Co—N	2.175 (3)
Co—O	2.120 (2)

Cl—Co—O	86.06 (6)	O—Co—N	86.22 (10)
Cl—Co—N	92.33 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H1O···Clⁱ	0.833 (10)	2.306 (14)	3.114 (2)	163 (3)
N—H1C···Clⁱⁱ	0.873 (10)	2.756 (18)	3.560 (3)	154 (3)
N—H1D···Clⁱ	0.869 (10)	2.574 (13)	3.422 (3)	165 (3)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z.

Acknowledgements

The authors thank the EPSRC for financial support.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burrow, R. A., Horner, M., Lang, L. S., Neves, A. & Vencato, I. (1997). Z. Kristallogr. New Cryst. Struct. 212, 41–41. CrossRef CAS Google Scholar
Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar

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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Page m856

https://doi.org/10.1107/S1600536807007805

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

trans-Bis(aniline-κN)di­chloro­bis­(ethanol-κO)cobalt(II)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

trans-Bis(aniline-κN)dichlorobis(ethanol-κO)cobalt(II)