Chloridobis(dimethyl­glyoximato-κ2N,N′)(ethyl pyridine-4-carboxyl­ate-κN)cobalt(III) chloro­form monosolvate

Wang, N.; Sun, X.; Wan, D.; Chen, J.; Li, B.

doi:10.1107/S1600536812002449

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m204-m205

doi:10.1107/S1600536812002449

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Chloridobis(dimethylglyoximato-κ²N,N′)(ethyl pyridine-4-carboxylate-κN)cobalt(III) chloroform monosolvate

Ning Wang,^a ^* Xuzhuo Sun,^a Dongjin Wan,^a Jing Chen ^a and Bo Li ^a

^aHenan University of Technology, School of Chemistry and Chemical Engineering, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: ssdyok@yahoo.com.cn

(Received 5 January 2012; accepted 19 January 2012; online 25 January 2012)

The title compound, [Co(C₄H₇N₂O₂)₂Cl(C₈H₉NO₂)]·CHCl₃, was synthesized as a model complex of vitamin B₁₂. The Co^III cation displays an approximately octahedral coordination environment, being displaced by 0.0240 (15) Å from the mean plane of the four N atoms of the equatorial plane. The O—H distances in the dimethylglyoximate hydroxy groups are 0.89 (6) and 1.14 (6) Å; such long O—H bonds are very common in cobaloxime derivatives. Weak classical O—H⋯N and non-classical C—H⋯Cl hydrogen-bonding interactions further consolidate the crystal packing.

Related literature

For background on the chemistry of cobaloximes, see: Schrayzer (1968 ); Zangrando et al. (2003 ). For applications of cobaloximes in proton reduction, see: Razavet et al. (2005 ). For related structures, see: Bhuyan et al. (2007 ); Dutta et al. (2009 ); Mandal & Gupta (2005 , 2007 ); William et al. (1973 ). For NMR research on O—H⋯O bridges, see: Bakac & Espenson (1984 ). For deprotonation of O—H⋯O bridges by BF₃·Et₂O, see: Magnuson & Weber (1974 ).

Experimental

Crystal data

[Co(C₄H₇N₂O₂)₂Cl(C₈H₉NO₂)]·CHCl₃
M_r = 595.14
Orthorhombic, P b c a
a = 10.053 (3) Å
b = 22.357 (7) Å
c = 23.099 (8) Å
V = 5192 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 293 K
0.29 × 0.14 × 0.06 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.829, T_max = 0.935
24393 measured reflections
4558 independent reflections
3483 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.158
S = 1.08
4558 reflections
310 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4	1.14 (6)	1.37 (6)	2.495 (4)	168 (5)
O2—H2⋯N4	1.14 (6)	2.10 (6)	3.004 (4)	133 (4)
O1—H1⋯O3	0.89 (6)	1.60 (6)	2.486 (4)	177 (6)
O1—H1⋯N3	0.89 (6)	2.25 (6)	3.000 (4)	142 (5)
C17—H17A⋯Cl1	0.98	2.49	3.437 (6)	163
C6—H6C⋯Cl1ⁱ	0.96	2.79	3.675 (5)	153
Symmetry code: (i) -x, -y, -z+1.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002449/zl2444sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002449/zl2444Isup2.hkl

checkCIF report

Comment top

The cobaloximes have extensively been used to mimic the vitamin B₁₂ coenzyme (Schrayzer, 1968). Recently they also are used to catalyze proton reduction as a functional model of hydrogenase (Razavet et al., 2005). The title compound, [Co(dmgH)₂(4-(COOEt)C₅H₄N)Cl], was prepared as previously described (William et al., 1973). The cobalt atom is coordinated in a distorted-octahedral geometry by four nitrogen atoms of the pseudomacrocyclic [(dmgH)₂]^2- ligand in the equatorial plane and by one chlorine atom and a nitrogen atom of ethyl isonicotinate, respectively, in mutually trans positions (N5—Co—Cl1 = 179.33° (10)). The cobalt atom which is linked to four nitrogen atoms belonging to the equatorial plane, displays an approximately octahedral coordination. The mean Co—N bond length is 1.898 Å (3). The mean O—O distance between neighboring dimethylglyoximato oxygen atoms is 2.491 Å (5). These ligands form strong O—H···O bridges with each other which is very common in cobaloxime derivatives. The presence of the O—H···O bridging moieties in cobaloxime derivatives ensures coplanarity of the two ligand molecules and promotes the stability of the cobaloxime molecule (Zangrando et al., 2003). The existence of O—H···O bridging is supported by the NMR data and further substantiated by their chemical behavior with BF₃.Et₂O in readily forming an O—BF₂—O system by deprotonation of the O—H···O bridge (Bakac & Espenson, 1984; Magnuson & Weber, 1974). The distance between O2 and H2 is 1.14 (6) Å indicating a strongly hydrogen bonded nearly symmetric O—H···O system (Bhuyan et al., 2007; Dutta et al., 2009; Mandal & Gupta, 2005, 2007). The Co atom is 0.0240 Å (15) out of the mean plane of the four nitrogen atoms. The plane of the four nitrogen atoms is practically planar.

Related literature top

For background on the chemistry of cobaloximes, see: Schrayzer (1968); Zangrando et al. (2003). For applications of cobaloximes in proton reduction, see: Razavet et al. (2005). For related structures, see: Bhuyan et al. (2007); Dutta et al. (2009); Mandal & Gupta (2005, 2007); William et al. (1973). For NMR research on O—H···O bridges, see: Bakac & Espenson (1984). For deprotonation of O—H···O bridges by BF₃.Et₂O, see: Magnuson & Weber (1974).

Experimental top

Co(dmgH)(dmgH₂)Cl, (3.6 g, 0.01 mol) and ethyl isonicotinate (3.0 g, 0.02 mol) were added to chloroform (90 ml) (William et al.,1973). The suspension was stirred for 20 minutes. Then water (30 ml) was added to the flask and the mixture was vigorously stirred for 2 h. The aqueous layer was discarded and the chloroform layer filtered and extracted with water until the washings were nearly colorless. The solution was reduced in volume and the product precipitated by addition of ethanol (95%); yield 69%. Brown single crystals of [Co(dmgH)₂(4-(COOEt)C₅H₄N)Cl] were grown from a CHCl₃/ethyl acetate solution (v:v = 1:1). ¹H NMR (400 MHz, CDCl₃): δ 8.45 (d, 6.4 Hz, 2 H, o-H_py), 7.75 (d, 6 Hz, 2 H, m-H_py), 4.38 (q, 7.2 Hz, 2 H, CH₂), 2.30 (s, 12 H, N=CCH₃), 1.35 (t, 7.0 Hz, 3 H, CH₃).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Chloridobis(dimethylglyoximato-κ²N,N')(ethyl pyridine-4-carboxylate-κN)cobalt(III) chloroform monosolvate top

Crystal data top

[Co(C₄H₇N₂O₂)₂Cl(C₈H₉NO₂)]·CHCl₃	F(000) = 2432
M_r = 595.14	D_x = 1.523 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5509 reflections
a = 10.053 (3) Å	θ = 2.4–24.8°
b = 22.357 (7) Å	µ = 1.11 mm⁻¹
c = 23.099 (8) Å	T = 293 K
V = 5192 (3) Å³	Needle, brown
Z = 8	0.29 × 0.14 × 0.06 mm

Data collection top

Bruker APEXII area-detector diffractometer	4558 independent reflections
Radiation source: fine-focus sealed tube	3483 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→9
T_min = 0.829, T_max = 0.935	k = −26→26
24393 measured reflections	l = −27→24

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0892P)² + 4.4304P] where P = (F_o² + 2F_c²)/3
4558 reflections	(Δ/σ)_max = 0.001
310 parameters	Δρ_max = 1.25 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Co(C₄H₇N₂O₂)₂Cl(C₈H₉NO₂)]·CHCl₃	V = 5192 (3) Å³
M_r = 595.14	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.053 (3) Å	µ = 1.11 mm⁻¹
b = 22.357 (7) Å	T = 293 K
c = 23.099 (8) Å	0.29 × 0.14 × 0.06 mm

Data collection top

Bruker APEXII area-detector diffractometer	4558 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3483 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.935	R_int = 0.039
24393 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.25 e Å⁻³
4558 reflections	Δρ_min = −0.78 e Å⁻³
310 parameters

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

	x	y	z	U_iso*/U_eq
Co1	0.23591 (5)	0.00646 (2)	0.63484 (2)	0.03477 (19)
Cl1	0.08443 (9)	0.07824 (5)	0.62035 (4)	0.0473 (3)
N2	0.2686 (3)	0.00560 (14)	0.55381 (14)	0.0387 (7)
N4	0.3608 (3)	0.06594 (13)	0.65679 (12)	0.0364 (7)
O2	0.3577 (3)	0.04186 (12)	0.52883 (11)	0.0489 (7)
N3	0.1977 (3)	0.00927 (14)	0.71495 (13)	0.0407 (7)
N5	0.3706 (3)	−0.05592 (13)	0.64728 (13)	0.0406 (7)
O4	0.4372 (3)	0.09421 (12)	0.61771 (11)	0.0473 (7)
O3	0.1032 (3)	−0.02516 (14)	0.73944 (11)	0.0558 (7)
C4	0.3647 (4)	0.07978 (16)	0.71110 (15)	0.0384 (8)
N1	0.1090 (3)	−0.05257 (15)	0.61321 (13)	0.0443 (8)
C2	0.2011 (4)	−0.03273 (18)	0.52384 (15)	0.0438 (9)
O1	0.0261 (3)	−0.07852 (15)	0.65120 (13)	0.0617 (9)
C3	0.2708 (3)	0.04442 (17)	0.74594 (16)	0.0406 (9)
C1	0.1055 (4)	−0.06658 (18)	0.55898 (16)	0.0478 (10)
C6	0.2193 (5)	−0.0395 (2)	0.45984 (18)	0.0661 (13)
H6A	0.3024	−0.0591	0.4522	0.099*
H6B	0.2193	−0.0008	0.4420	0.099*
H6C	0.1478	−0.0630	0.4443	0.099*
C7	0.2605 (4)	0.0476 (2)	0.81032 (17)	0.0580 (12)
H7A	0.1723	0.0599	0.8210	0.087*
H7B	0.3238	0.0760	0.8248	0.087*
H7C	0.2787	0.0089	0.8266	0.087*
C9	0.4808 (4)	−0.05867 (19)	0.61441 (18)	0.0514 (10)
H9A	0.4920	−0.0307	0.5850	0.062*
C8	0.4506 (4)	0.12779 (18)	0.73592 (18)	0.0522 (10)
H8A	0.5049	0.1446	0.7059	0.078*
H8B	0.5065	0.1111	0.7655	0.078*
H8C	0.3955	0.1585	0.7524	0.078*
C10	0.5774 (4)	−0.10112 (19)	0.6225 (2)	0.0571 (11)
H10A	0.6512	−0.1022	0.5982	0.069*
C13	0.3583 (4)	−0.09637 (18)	0.68994 (17)	0.0518 (10)
H13A	0.2825	−0.0953	0.7130	0.062*
C5	0.0100 (5)	−0.1112 (2)	0.5347 (2)	0.0683 (13)
H5A	−0.0506	−0.1237	0.5645	0.102*
H5B	0.0582	−0.1452	0.5205	0.102*
H5C	−0.0389	−0.0933	0.5035	0.102*
C11	0.5646 (5)	−0.14251 (19)	0.66696 (19)	0.0548 (11)
C12	0.4530 (5)	−0.1392 (2)	0.70090 (19)	0.0601 (12)
H12A	0.4414	−0.1659	0.7313	0.072*
O5	0.7541 (4)	−0.1941 (2)	0.6368 (2)	0.1054 (16)
O6	0.6596 (6)	−0.2213 (2)	0.7205 (2)	0.134 (2)
C14	0.6648 (6)	−0.1899 (2)	0.6788 (3)	0.0737 (15)
C15	0.8560 (7)	−0.2399 (3)	0.6427 (4)	0.130 (3)
H15A	0.8681	−0.2498	0.6833	0.156*
H15B	0.9399	−0.2252	0.6277	0.156*
C16	0.8152 (9)	−0.2930 (4)	0.6107 (3)	0.127 (3)
H16A	0.8815	−0.3236	0.6149	0.191*
H16B	0.8053	−0.2831	0.5705	0.191*
H16C	0.7318	−0.3072	0.6256	0.191*
Cl2	0.3288 (3)	0.21423 (11)	0.52934 (9)	0.1438 (9)
Cl3	0.2763 (2)	0.24725 (11)	0.64763 (12)	0.1451 (11)
Cl4	0.0658 (2)	0.24578 (13)	0.56700 (13)	0.1782 (13)
C17	0.2161 (6)	0.2156 (3)	0.5858 (2)	0.0785 (15)
H17A	0.1983	0.1736	0.5954	0.094*
H2	0.406 (6)	0.064 (3)	0.568 (3)	0.105 (19)*
H1	0.053 (6)	−0.060 (3)	0.683 (3)	0.10 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0347 (3)	0.0443 (3)	0.0253 (3)	−0.0059 (2)	0.00124 (18)	0.00086 (19)
Cl1	0.0387 (5)	0.0631 (6)	0.0401 (5)	0.0045 (4)	−0.0007 (4)	0.0016 (4)
N2	0.0389 (17)	0.0465 (18)	0.0306 (17)	−0.0038 (14)	0.0041 (12)	0.0030 (13)
N4	0.0354 (16)	0.0430 (16)	0.0308 (16)	−0.0006 (13)	−0.0008 (12)	0.0025 (13)
O2	0.0527 (17)	0.0618 (17)	0.0321 (14)	−0.0127 (14)	0.0075 (12)	0.0021 (12)
N3	0.0389 (17)	0.0536 (19)	0.0296 (16)	−0.0037 (14)	0.0033 (13)	0.0034 (13)
N5	0.0424 (17)	0.0409 (17)	0.0384 (17)	−0.0040 (14)	−0.0010 (13)	0.0012 (13)
O4	0.0460 (15)	0.0562 (16)	0.0398 (15)	−0.0164 (13)	0.0049 (11)	0.0074 (12)
O3	0.0506 (17)	0.0802 (19)	0.0366 (15)	−0.0215 (15)	0.0116 (12)	0.0071 (14)
C4	0.0384 (19)	0.0416 (19)	0.035 (2)	0.0047 (16)	−0.0036 (15)	0.0002 (15)
N1	0.0430 (18)	0.0542 (19)	0.0358 (18)	−0.0111 (15)	−0.0005 (13)	0.0029 (14)
C2	0.052 (2)	0.051 (2)	0.0293 (18)	−0.0015 (18)	−0.0021 (17)	−0.0057 (17)
O1	0.065 (2)	0.078 (2)	0.0422 (17)	−0.0358 (17)	0.0040 (14)	0.0046 (16)
C3	0.037 (2)	0.056 (2)	0.0287 (18)	0.0056 (17)	−0.0011 (15)	−0.0013 (17)
C1	0.052 (2)	0.055 (2)	0.037 (2)	−0.0067 (19)	−0.0063 (17)	−0.0052 (18)
C6	0.075 (3)	0.090 (4)	0.033 (2)	−0.014 (3)	0.003 (2)	−0.013 (2)
C7	0.057 (3)	0.086 (3)	0.031 (2)	−0.006 (2)	0.0015 (17)	−0.005 (2)
C9	0.047 (2)	0.051 (2)	0.056 (3)	0.0002 (19)	0.0069 (19)	0.0105 (19)
C8	0.056 (2)	0.056 (2)	0.044 (2)	−0.007 (2)	−0.0107 (19)	−0.0058 (18)
C10	0.049 (2)	0.054 (2)	0.068 (3)	0.004 (2)	0.004 (2)	0.002 (2)
C13	0.059 (3)	0.054 (2)	0.042 (2)	−0.001 (2)	0.0035 (18)	0.0085 (19)
C5	0.081 (3)	0.070 (3)	0.053 (3)	−0.029 (3)	−0.013 (2)	−0.007 (2)
C11	0.061 (3)	0.048 (2)	0.055 (3)	0.003 (2)	−0.015 (2)	−0.002 (2)
C12	0.080 (3)	0.052 (2)	0.048 (3)	0.001 (2)	−0.006 (2)	0.012 (2)
O5	0.074 (3)	0.078 (3)	0.164 (5)	0.031 (2)	0.017 (3)	0.036 (3)
O6	0.180 (5)	0.134 (4)	0.089 (3)	0.091 (4)	−0.008 (3)	0.028 (3)
C14	0.084 (4)	0.057 (3)	0.081 (4)	0.016 (3)	−0.028 (3)	0.000 (3)
C15	0.086 (5)	0.098 (5)	0.207 (9)	0.052 (4)	0.016 (5)	0.038 (6)
C16	0.151 (8)	0.114 (6)	0.118 (6)	0.072 (6)	0.003 (5)	0.020 (5)
Cl2	0.159 (2)	0.167 (2)	0.1055 (15)	0.0384 (17)	0.0411 (14)	0.0400 (13)
Cl3	0.1212 (16)	0.178 (2)	0.1355 (19)	0.0474 (15)	−0.0562 (14)	−0.0717 (16)
Cl4	0.1211 (17)	0.229 (3)	0.185 (3)	0.0840 (18)	−0.0778 (17)	−0.087 (2)
C17	0.081 (4)	0.079 (4)	0.075 (4)	−0.007 (3)	−0.009 (3)	0.001 (3)

Geometric parameters (Å, º) top

Co1—N3	1.891 (3)	C7—H7C	0.9600
Co1—N4	1.898 (3)	C9—C10	1.370 (6)
Co1—N2	1.901 (3)	C9—H9A	0.9300
Co1—N1	1.902 (3)	C8—H8A	0.9600
Co1—N5	1.965 (3)	C8—H8B	0.9600
Co1—Cl1	2.2375 (12)	C8—H8C	0.9600
N2—C2	1.294 (5)	C10—C11	1.389 (6)
N2—O2	1.339 (4)	C10—H10A	0.9300
N4—C4	1.293 (5)	C13—C12	1.374 (6)
N4—O4	1.344 (4)	C13—H13A	0.9300
O2—H2	1.14 (6)	C5—H5A	0.9600
N3—C3	1.292 (5)	C5—H5B	0.9600
N3—O3	1.347 (4)	C5—H5C	0.9600
N5—C13	1.343 (5)	C11—C12	1.371 (6)
N5—C9	1.345 (5)	C11—C14	1.487 (6)
O4—H2	1.37 (6)	C12—H12A	0.9300
C4—C3	1.471 (5)	O5—C14	1.325 (7)
C4—C8	1.492 (5)	O5—C15	1.454 (7)
N1—C1	1.292 (5)	O6—C14	1.194 (7)
N1—O1	1.342 (4)	C15—C16	1.456 (11)
C2—C1	1.468 (6)	C15—H15A	0.9700
C2—C6	1.497 (5)	C15—H15B	0.9700
O1—H1	0.89 (6)	C16—H16A	0.9600
C3—C7	1.492 (5)	C16—H16B	0.9600
C1—C5	1.493 (6)	C16—H16C	0.9600
C6—H6A	0.9600	Cl2—C17	1.728 (6)
C6—H6B	0.9600	Cl3—C17	1.705 (6)
C6—H6C	0.9600	Cl4—C17	1.712 (6)
C7—H7A	0.9600	C17—H17A	0.9800
C7—H7B	0.9600

N3—Co1—N4	81.36 (13)	H7A—C7—H7B	109.5
N3—Co1—N2	177.80 (13)	C3—C7—H7C	109.5
N4—Co1—N2	98.96 (13)	H7A—C7—H7C	109.5
N3—Co1—N1	98.27 (13)	H7B—C7—H7C	109.5
N4—Co1—N1	179.30 (14)	N5—C9—C10	122.6 (4)
N2—Co1—N1	81.39 (13)	N5—C9—H9A	118.7
N3—Co1—N5	91.17 (13)	C10—C9—H9A	118.7
N4—Co1—N5	90.15 (13)	C4—C8—H8A	109.5
N2—Co1—N5	91.00 (13)	C4—C8—H8B	109.5
N1—Co1—N5	90.45 (14)	H8A—C8—H8B	109.5
N3—Co1—Cl1	89.10 (10)	C4—C8—H8C	109.5
N4—Co1—Cl1	89.28 (9)	H8A—C8—H8C	109.5
N2—Co1—Cl1	88.73 (10)	H8B—C8—H8C	109.5
N1—Co1—Cl1	90.12 (11)	C9—C10—C11	119.8 (4)
N5—Co1—Cl1	179.33 (10)	C9—C10—H10A	120.1
C2—N2—O2	121.4 (3)	C11—C10—H10A	120.1
C2—N2—Co1	116.3 (3)	N5—C13—C12	122.7 (4)
O2—N2—Co1	122.3 (2)	N5—C13—H13A	118.6
C4—N4—O4	121.5 (3)	C12—C13—H13A	118.6
C4—N4—Co1	116.6 (2)	C1—C5—H5A	109.5
O4—N4—Co1	121.9 (2)	C1—C5—H5B	109.5
N2—O2—H2	102 (3)	H5A—C5—H5B	109.5
C3—N3—O3	121.0 (3)	C1—C5—H5C	109.5
C3—N3—Co1	116.5 (3)	H5A—C5—H5C	109.5
O3—N3—Co1	122.4 (2)	H5B—C5—H5C	109.5
C13—N5—C9	117.3 (4)	C12—C11—C10	117.6 (4)
C13—N5—Co1	121.5 (3)	C12—C11—C14	119.2 (5)
C9—N5—Co1	121.2 (3)	C10—C11—C14	123.2 (5)
N4—O4—H2	102 (2)	C11—C12—C13	120.0 (4)
N4—C4—C3	112.5 (3)	C11—C12—H12A	120.0
N4—C4—C8	124.3 (3)	C13—C12—H12A	120.0
C3—C4—C8	123.2 (3)	C14—O5—C15	117.3 (5)
C1—N1—O1	120.8 (3)	O6—C14—O5	125.3 (5)
C1—N1—Co1	116.2 (3)	O6—C14—C11	122.5 (6)
O1—N1—Co1	123.0 (2)	O5—C14—C11	112.1 (5)
N2—C2—C1	112.9 (3)	O5—C15—C16	109.1 (7)
N2—C2—C6	122.1 (4)	O5—C15—H15A	109.9
C1—C2—C6	125.0 (4)	C16—C15—H15A	109.9
N1—O1—H1	99 (4)	O5—C15—H15B	109.9
N3—C3—C4	112.9 (3)	C16—C15—H15B	109.9
N3—C3—C7	122.8 (4)	H15A—C15—H15B	108.3
C4—C3—C7	124.3 (3)	C15—C16—H16A	109.5
N1—C1—C2	113.1 (3)	C15—C16—H16B	109.5
N1—C1—C5	122.9 (4)	H16A—C16—H16B	109.5
C2—C1—C5	123.9 (4)	C15—C16—H16C	109.5
C2—C6—H6A	109.5	H16A—C16—H16C	109.5
C2—C6—H6B	109.5	H16B—C16—H16C	109.5
H6A—C6—H6B	109.5	Cl3—C17—Cl4	111.2 (3)
C2—C6—H6C	109.5	Cl3—C17—Cl2	114.0 (3)
H6A—C6—H6C	109.5	Cl4—C17—Cl2	113.2 (4)
H6B—C6—H6C	109.5	Cl3—C17—H17A	105.9
C3—C7—H7A	109.5	Cl4—C17—H17A	105.9
C3—C7—H7B	109.5	Cl2—C17—H17A	105.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	1.14 (6)	1.37 (6)	2.495 (4)	168 (5)
O2—H2···N4	1.14 (6)	2.10 (6)	3.004 (4)	133 (4)
O1—H1···O3	0.89 (6)	1.60 (6)	2.486 (4)	177 (6)
O1—H1···N3	0.89 (6)	2.25 (6)	3.000 (4)	142 (5)
C17—H17A···Cl1	0.98	2.49	3.437 (6)	163
C6—H6C···Cl1ⁱ	0.96	2.79	3.675 (5)	153

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Co(C₄H₇N₂O₂)₂Cl(C₈H₉NO₂)]·CHCl₃
M_r	595.14
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.053 (3), 22.357 (7), 23.099 (8)
V (Å³)	5192 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.29 × 0.14 × 0.06

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.829, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	24393, 4558, 3483
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.158, 1.08
No. of reflections	4558
No. of parameters	310
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.25, −0.78

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	1.14 (6)	1.37 (6)	2.495 (4)	168 (5)
O2—H2···N4	1.14 (6)	2.10 (6)	3.004 (4)	133 (4)
O1—H1···O3	0.89 (6)	1.60 (6)	2.486 (4)	177 (6)
O1—H1···N3	0.89 (6)	2.25 (6)	3.000 (4)	142 (5)
C17—H17A···Cl1	0.98	2.49	3.437 (6)	163
C6—H6C···Cl1ⁱ	0.96	2.79	3.675 (5)	153

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

We are grateful to the Chinese National Natural Science Foundation (grant No. 21101057), the Science Foundation of the Education Department of Henan Province (No. 2011B150006) and the Doctoral Fund of Henan University of Technology (No. 2009BS053).

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