Dichlorido(dimethyl­glyoximato-κ²N,N′)(dimethyl­glyoxime-κ²N,N′)cobalt(III)

In the title compound, [Co(C₄H₇N₂O₂)Cl₂(C₄H₈N₂O₂)], the Co^III ion has a distorted octa­hedral coordination environment. The equatorial plane consists of four N atoms, two each from the dimethyl­glyoxime and dimethyl­glyoximate ligands, while the two axial positions are occupied by two chloride ions. Strong intra­molecular O—H...O hydrogen bonds are observed between the dimethyl­glyoxime and dimethyl­glyoximate ligands. Mol­ecules are linked into a chain running along the [101] direction by O—H...O and C—H...Cl hydrogen bonds. The chains are cross-linked through inter­molecular C—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.025
• wR factor = 0.058
• Data-to-parameter ratio = 29.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co     -   Cl2     ..      10.54 su

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT128_ALERT_4_C Non-standard setting of Space-group Pc      ....      Pn
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co     -   Cl1     ..       7.22 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co     -   N3      ..       5.67 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           37.24
           From the CIF: _reflns_number_total               5284
           Count of symmetry unique reflns         3517
           Completeness (_total/calc)            150.24%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1767
           Fraction of Friedel pairs measured     0.502
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Dimethylglyoximatocobalt(III) complexes, generally known as cobaloximes, have been studied extensively as model compounds for vitamine-B₁₂ (Trommel et al., 2001; Ohkubo & Fukuzumi, 2005). Most of the work on cobaloximes include electron-transfer reactions (Dayalan & Vijayaraghavan, 2001) and catalytic activity (Razavelt et al., 2005) in solution. There are few literature evidences relating the structural aspects of cobaloximes (Gupta et al., 2000; Gupta et al., 2001; Gupta et al., 2004). We report here the synthesis and X-ray crystal structure of the title compoud.

The coordination geometry around the Co^III ion can be described as a slightly distorted octahedron. The axial positions are occupied by the chloride ions. The glyoxime moieties are individually planar. The Co^III ion and the four N atoms of dimethylglyoxime ligands are approximately coplanar. The Co—N and Co—Cl bond lengths are normal (Table 1), and are comparable with the corresponding values observed in a related complex (Lee et al., 2007).

Strong intramolecular O—H···O hydrogen bonds are observed between the dimethylglyoxime and dimethylglyoximate ligands (Table 2). The crystal packing is stabilized by O—H···O and C—H···Cl hydrogen bonds. Atoms O2 and C4 of the molecule at (x, y, z) act as donors to atoms O1 and Cl1, respectively, of the molecule at (-1/2 + x, -y, -1/2 + z). These two hydrogen bonds form a chain running along the [1 0 1] direction. The chains are cross-linked through C—H···Cl intermolecular hydrogen bonds.

Related literature

For related literature, see: Dayalan & Vijayaraghavan (2001); Lee et al. (2007); Gupta et al. (2000, 2001, 2004); Ohkubo & Fukuzumi (2005); Razavelt et al. (2005). Trommel et al. (2001).

S2. Experimental

Cobalt(II) chloride hexahydrate was thoroughly grinded and exposed to microwave for 30 s. Dehydrated cobalt(II) chloride (1.3 g) was mixed with dimethyl glyoxime (2.32 g). The mixture was intimately grinded and made into a paste using acetone and exposed to microwave radiation for 60 s. The microwave treated reaction mixture was exposed to atmosphere, till it became green. The green coloured product was recrystallized from acetone. Single crystals were obtained by slow evaporation of the acetone solution.

S3. Refinement

All H atoms were fixed geometrically (O—H = 0.82 Å and C—H = 0.96 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C,O).

Computing details

Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: APEX2 (Bruker–Nonius, 2004); data reduction: SAINT (Bruker–Nonius, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

Fig. 1. The structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitary radii.

Dichlorido(dimethylglyoximato-κ²N,N')(dimethylglyoxime- κ²N,N')cobalt(III)

Crystal data

[Co(C4H7N2O2)Cl2(C4H8N2O2)]	F(000) = 368
Mr = 361.07	Dx = 1.763 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 3586 reflections
a = 8.1901 (2) Å	θ = 2.8–37.2°
b = 8.1261 (2) Å	µ = 1.67 mm^−1
c = 10.4463 (3) Å	T = 293 K
β = 102.007 (1)°	Plate, green
V = 680.03 (3) Å^3	0.20 × 0.12 × 0.12 mm
Z = 2

Data collection

Bruker–Nonius Kappa APEXII CCD diffractometer	5284 independent reflections
Radiation source: fine-focus sealed tube	4711 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω and ϕ scans	θmax = 37.2°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→13
Tmin = 0.786, Tmax = 0.819	k = −13→13
10990 measured reflections	l = −17→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0235P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.023
5284 reflections	Δρmax = 0.56 e Å^−3
179 parameters	Δρmin = −0.29 e Å^−3
2 restraints	Absolute structure: Flack (1983), 2067 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (7)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2744 (2)	−0.2411 (2)	0.7384 (2)	0.0354 (4)
H1A	0.3762	−0.3016	0.7436	0.053*
H1B	0.1848	−0.2974	0.6812	0.053*
H1C	0.2497	−0.2325	0.8241	0.053*
C2	0.29345 (19)	−0.07336 (17)	0.68614 (15)	0.0255 (3)
C3	0.15626 (19)	0.01410 (18)	0.60187 (15)	0.0259 (3)
C4	−0.0162 (2)	−0.0517 (2)	0.56788 (19)	0.0362 (4)
H4A	−0.0912	0.0339	0.5290	0.054*
H4B	−0.0486	−0.0908	0.6457	0.054*
H4C	−0.0207	−0.1408	0.5069	0.054*
C5	0.5786 (2)	0.6808 (2)	0.5132 (2)	0.0353 (4)
H5A	0.6540	0.6827	0.4541	0.053*
H5B	0.6213	0.7497	0.5873	0.053*
H5C	0.4712	0.7208	0.4691	0.053*
C6	0.5617 (2)	0.50905 (17)	0.55842 (15)	0.0264 (3)
C7	0.70180 (19)	0.41674 (18)	0.63553 (16)	0.0266 (3)
C8	0.8762 (2)	0.4804 (2)	0.6649 (2)	0.0411 (4)
H8A	0.8866	0.5647	0.7305	0.062*
H8B	0.9027	0.5253	0.5867	0.062*
H8C	0.9518	0.3921	0.6966	0.062*
Cl1	0.36969 (5)	0.33736 (5)	0.79458 (4)	0.03361 (8)
Cl2	0.48754 (5)	0.09885 (5)	0.44061 (4)	0.03422 (9)
Co	0.42858 (2)	0.21491 (2)	0.618650 (19)	0.02055 (4)
N1	0.43373 (15)	0.00641 (15)	0.70278 (13)	0.0232 (2)
N2	0.20367 (15)	0.15171 (15)	0.56038 (12)	0.0242 (2)
N3	0.65689 (16)	0.27610 (14)	0.67399 (13)	0.0249 (2)
N4	0.42440 (16)	0.42760 (15)	0.53841 (13)	0.0257 (2)
O1	0.57344 (14)	−0.05436 (13)	0.77384 (12)	0.0303 (2)
O2	0.09198 (16)	0.24162 (15)	0.46980 (13)	0.0301 (2)
H2	0.0688	0.1904	0.4008	0.045*
O3	0.77626 (15)	0.18097 (16)	0.74654 (14)	0.0362 (3)
H3	0.7352	0.0934	0.7628	0.054*
O4	0.28559 (16)	0.50431 (15)	0.46882 (14)	0.0378 (3)
H4	0.2091	0.4377	0.4506	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0400 (9)	0.0242 (7)	0.0421 (10)	−0.0089 (7)	0.0088 (8)	0.0041 (7)
C2	0.0304 (7)	0.0209 (5)	0.0252 (7)	−0.0042 (5)	0.0061 (6)	−0.0010 (5)
C3	0.0278 (7)	0.0254 (6)	0.0247 (7)	−0.0041 (5)	0.0061 (5)	−0.0038 (5)
C4	0.0295 (8)	0.0382 (8)	0.0401 (9)	−0.0097 (7)	0.0052 (6)	−0.0017 (7)
C5	0.0420 (10)	0.0239 (6)	0.0423 (10)	−0.0035 (7)	0.0138 (8)	0.0061 (7)
C6	0.0352 (7)	0.0208 (5)	0.0250 (7)	−0.0012 (5)	0.0108 (6)	0.0010 (5)
C7	0.0266 (7)	0.0249 (6)	0.0284 (7)	−0.0044 (5)	0.0060 (6)	−0.0009 (6)
C8	0.0336 (8)	0.0405 (9)	0.0493 (11)	−0.0137 (7)	0.0085 (7)	0.0027 (8)
Cl1	0.0474 (2)	0.02841 (16)	0.02782 (18)	0.00147 (15)	0.01415 (16)	−0.00198 (14)
Cl2	0.0435 (2)	0.03213 (17)	0.02942 (18)	−0.00460 (16)	0.01298 (16)	−0.00663 (15)
Co	0.02324 (7)	0.01784 (6)	0.02009 (7)	−0.00196 (6)	0.00338 (5)	0.00024 (6)
N1	0.0265 (6)	0.0198 (5)	0.0229 (6)	−0.0016 (4)	0.0040 (4)	0.0001 (4)
N2	0.0249 (6)	0.0231 (5)	0.0229 (6)	−0.0003 (5)	0.0011 (4)	−0.0002 (5)
N3	0.0257 (5)	0.0213 (5)	0.0265 (6)	−0.0010 (4)	0.0028 (5)	0.0003 (5)
N4	0.0313 (6)	0.0225 (5)	0.0231 (6)	0.0021 (5)	0.0050 (5)	0.0031 (4)
O1	0.0290 (5)	0.0268 (5)	0.0320 (6)	0.0008 (4)	−0.0010 (4)	0.0085 (4)
O2	0.0293 (6)	0.0312 (5)	0.0260 (5)	0.0023 (4)	−0.0027 (4)	−0.0016 (4)
O3	0.0286 (6)	0.0295 (5)	0.0462 (8)	0.0009 (5)	−0.0020 (5)	0.0101 (5)
O4	0.0339 (6)	0.0338 (6)	0.0420 (7)	0.0040 (5)	−0.0002 (5)	0.0115 (6)

Geometric parameters (Å, º)

C1—C2	1.489 (2)	C7—C8	1.490 (2)
C1—H1A	0.96	C8—H8A	0.96
C1—H1B	0.96	C8—H8B	0.96
C1—H1C	0.96	C8—H8C	0.96
C2—N1	1.2990 (19)	Cl1—Co	2.2292 (4)
C2—C3	1.460 (2)	Cl2—Co	2.2261 (4)
C3—N2	1.2881 (18)	Co—N2	1.8870 (12)
C3—C4	1.483 (2)	Co—N3	1.9048 (13)
C4—H4A	0.96	Co—N1	1.9051 (12)
C4—H4B	0.96	Co—N4	1.9181 (12)
C4—H4C	0.96	N1—O1	1.3231 (17)
C5—C6	1.489 (2)	N1—O1	1.3231 (17)
C5—H5A	0.96	N2—O2	1.3805 (17)
C5—H5B	0.96	N3—O3	1.3489 (17)
C5—H5C	0.96	N4—O4	1.3659 (17)
C6—N4	1.284 (2)	O2—H2	0.82
C6—C7	1.464 (2)	O3—H3	0.82
C7—N3	1.2901 (18)	O4—H4	0.82
C2—C1—H1A	109.5	H8A—C8—H8C	109.5
C2—C1—H1B	109.5	H8B—C8—H8C	109.5
H1A—C1—H1B	109.5	N2—Co—N3	178.64 (6)
C2—C1—H1C	109.5	N2—Co—N1	80.40 (5)
H1A—C1—H1C	109.5	N3—Co—N1	99.56 (5)
H1B—C1—H1C	109.5	N2—Co—N4	100.18 (5)
N1—C2—C3	112.72 (13)	N3—Co—N4	79.90 (5)
N1—C2—C1	124.42 (15)	N1—Co—N4	178.48 (6)
C3—C2—C1	122.72 (13)	N2—Co—Cl2	88.97 (4)
N2—C3—C2	112.18 (13)	N3—Co—Cl2	89.67 (4)
N2—C3—C4	124.84 (15)	N1—Co—Cl2	91.19 (4)
C2—C3—C4	122.98 (13)	N4—Co—Cl2	90.23 (4)
C3—C4—H4A	109.5	N2—Co—Cl1	91.34 (4)
C3—C4—H4B	109.5	N3—Co—Cl1	90.02 (4)
H4A—C4—H4B	109.5	N1—Co—Cl1	90.26 (4)
C3—C4—H4C	109.5	N4—Co—Cl1	88.33 (4)
H4A—C4—H4C	109.5	Cl2—Co—Cl1	178.550 (17)
H4B—C4—H4C	109.5	C2—N1—O1	121.76 (12)
C6—C5—H5A	109.5	C2—N1—O1	121.76 (12)
C6—C5—H5B	109.5	C2—N1—Co	116.61 (11)
H5A—C5—H5B	109.5	O1—N1—Co	121.62 (9)
C6—C5—H5C	109.5	O1—N1—Co	121.62 (9)
H5A—C5—H5C	109.5	C3—N2—O2	119.14 (12)
H5B—C5—H5C	109.5	C3—N2—Co	118.04 (11)
N4—C6—C7	112.65 (13)	O2—N2—Co	122.70 (9)
N4—C6—C5	124.55 (16)	C7—N3—O3	117.54 (13)
C7—C6—C5	122.77 (14)	C7—N3—Co	117.53 (11)
N3—C7—C6	112.57 (13)	O3—N3—Co	124.89 (9)
N3—C7—C8	124.50 (15)	C6—N4—O4	117.09 (12)
C6—C7—C8	122.93 (14)	C6—N4—Co	117.25 (11)
C7—C8—H8A	109.5	O4—N4—Co	125.52 (9)
C7—C8—H8B	109.5	N2—O2—H2	109.5
H8A—C8—H8B	109.5	N3—O3—H3	109.5
C7—C8—H8C	109.5	N4—O4—H4	109.5
N1—C2—C3—N2	0.71 (19)	N4—Co—N2—C3	−176.40 (11)
C1—C2—C3—N2	−175.17 (14)	Cl2—Co—N2—C3	93.56 (11)
N1—C2—C3—C4	179.90 (14)	Cl1—Co—N2—C3	−87.86 (11)
C1—C2—C3—C4	4.0 (2)	N1—Co—N2—O2	−173.82 (12)
N4—C6—C7—N3	−3.70 (19)	N4—Co—N2—O2	7.61 (12)
C5—C6—C7—N3	174.29 (15)	Cl2—Co—N2—O2	−82.44 (11)
N4—C6—C7—C8	176.17 (15)	Cl1—Co—N2—O2	96.15 (11)
C5—C6—C7—C8	−5.8 (2)	C6—C7—N3—O3	−179.68 (13)
C3—C2—N1—O1	−178.56 (13)	C8—C7—N3—O3	0.5 (2)
C1—C2—N1—O1	−2.8 (2)	C6—C7—N3—Co	2.60 (17)
C3—C2—N1—O1	−178.56 (13)	C8—C7—N3—Co	−177.27 (13)
C1—C2—N1—O1	−2.8 (2)	N1—Co—N3—C7	−179.35 (11)
C3—C2—N1—Co	1.02 (16)	N4—Co—N3—C7	−0.79 (11)
C1—C2—N1—Co	176.83 (13)	Cl2—Co—N3—C7	89.50 (11)
N2—Co—N1—C2	−1.70 (11)	Cl1—Co—N3—C7	−89.08 (11)
N3—Co—N1—C2	179.68 (11)	N1—Co—N3—O3	3.11 (13)
Cl2—Co—N1—C2	−90.45 (11)	N4—Co—N3—O3	−178.33 (13)
Cl1—Co—N1—C2	89.61 (10)	Cl2—Co—N3—O3	−88.04 (12)
N2—Co—N1—O1	177.89 (12)	Cl1—Co—N3—O3	93.37 (12)
N3—Co—N1—O1	−0.74 (12)	C7—C6—N4—O4	179.09 (13)
Cl2—Co—N1—O1	89.14 (11)	C5—C6—N4—O4	1.1 (2)
Cl1—Co—N1—O1	−90.80 (11)	C7—C6—N4—Co	3.19 (17)
N2—Co—N1—O1	177.89 (12)	C5—C6—N4—Co	−174.76 (13)
N3—Co—N1—O1	−0.74 (12)	N2—Co—N4—C6	179.87 (11)
Cl2—Co—N1—O1	89.14 (11)	N3—Co—N4—C6	−1.51 (11)
Cl1—Co—N1—O1	−90.80 (11)	Cl2—Co—N4—C6	−91.14 (11)
C2—C3—N2—O2	173.96 (13)	Cl1—Co—N4—C6	88.81 (11)
C4—C3—N2—O2	−5.2 (2)	N2—Co—N4—O4	4.35 (13)
C2—C3—N2—Co	−2.17 (17)	N3—Co—N4—O4	−177.02 (13)
C4—C3—N2—Co	178.66 (12)	Cl2—Co—N4—O4	93.35 (12)
N1—Co—N2—C3	2.17 (11)	Cl1—Co—N4—O4	−86.70 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.82	1.81	2.5875 (16)	158
O4—H4···O2	0.82	1.89	2.6604 (18)	156
O2—H2···O1^i	0.82	1.73	2.5297 (17)	163
C4—H4C···Cl1^i	0.96	2.73	3.6473 (19)	160
C5—H5A···Cl1^ii	0.96	2.67	3.6317 (18)	175

Symmetry codes: (i) x−1/2, −y, z−1/2; (ii) x+1/2, −y+1, z−1/2.