Aqua-bromidobis(dimethyl-glyoximato)cobalt(III).

In the title complex, [CoBr(C(4)H(7)N(2)O(2))(2)(H(2)O)], a crystallo-graphic mirror plane bis-ects the mol-ecule, perpendicular to the glyoximate ligands. The geometry around the cobalt(III) atom is approximately octa-hedral with the four glyoximate N atoms forming the square base. A bromide ion and the O atom of a water mol-ecule occupy the remaining coordination sites. The N-Co-N bite angles are 82.18 (4) and 80.03 (16)°. The glyoximate moieties form strong intra-molecular O-H⋯O hydrogen bonds. The coordinated water mol-ecule forms an inter-molecular O-H⋯O hydrogen bond with a glyoximate O atom, thereby generating supra-molecular chains parallel to [010].

Related literature

For related complexes, see: Ohkubo & Fukuzumi (2005 ▶); Randall & Alberty (1970 ▶); Schrauzer (1968 ▶); Trommel et al. (2001 ▶). For similar structures, see: Bernstein et al. (1995 ▶); Mégnamisi-Bélombé et al. (1983 ▶); Meera et al. (2009 ▶); Ramesh et al. (2008 ▶). For the preparation of similar complexes, see: Vijayraghavan & Dayalan (1992 ▶). For spectroscopic studies related to the title complex, see: Folgando et al. (1986 ▶); Khan et al. (1997 ▶); Lopez et al. (1986 ▶).

Experimental

Crystal data

[CoBr(C4H7N2O2)2(H2O)]

M = 387.09

Monoclinic,

a = 7.5903 (3) Å

b = 8.8816 (4) Å

c = 10.5343 (5) Å

β = 96.137 (3)°

V = 706.09 (5) Å3

Z = 2

Mo Kα radiation

μ = 4.07 mm−1

T = 293 K

0.15 × 0.10 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 1999 ▶) T min = 0.581, T max = 0.687

7395 measured reflections

1480 independent reflections

1298 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.096

S = 1.22

1480 reflections

101 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.01 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008) ▶; software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008877/fj2399sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008877/fj2399Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CoBr(C4H7N2O2)2(H2O)]	F(000) = 388
Mr = 387.09	Dx = 1.821 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 3745 reflections
a = 7.5903 (3) Å	θ = 2.7–30.7°
b = 8.8816 (4) Å	µ = 4.07 mm−1
c = 10.5343 (5) Å	T = 293 K
β = 96.137 (3)°	Block, brown
V = 706.09 (5) Å3	0.15 × 0.10 × 0.10 mm
Z = 2

Bruker Kappa APEXII CCD diffractometer	1480 independent reflections
Radiation source: fine-focus sealed tube	1298 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω and φ scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker 1999)	h = −9→9
Tmin = 0.581, Tmax = 0.687	k = −10→9
7395 measured reflections	l = −12→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ2(Fo2) + (0.0564P)2 + 0.1583P] where P = (Fo2 + 2Fc2)/3
1480 reflections	(Δ/σ)max = 0.001
101 parameters	Δρmax = 1.01 e Å−3
2 restraints	Δρmin = −0.54 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.7937 (4)	0.3331 (3)	0.5395 (3)	0.0330 (6)
C2	0.8935 (4)	0.4238 (4)	0.6415 (3)	0.0487 (8)
H2A	0.8818	0.5288	0.6207	0.073*
H2B	1.0164	0.3960	0.6486	0.073*
H2C	0.8469	0.4052	0.7213	0.073*
C3	0.3600 (4)	0.1669 (4)	0.1163 (3)	0.0448 (8)
C4	0.2476 (6)	0.0761 (5)	0.0221 (4)	0.0726 (13)
H4A	0.2737	−0.0288	0.0358	0.109*
H4B	0.2709	0.1038	−0.0626	0.109*
H4C	0.1250	0.0942	0.0318	0.109*
N1	0.6996 (3)	0.3893 (2)	0.4417 (2)	0.0302 (5)
N2	0.4668 (3)	0.1117 (3)	0.2069 (2)	0.0374 (6)
O1	0.6810 (3)	0.5377 (2)	0.4230 (2)	0.0395 (5)
O2	0.4819 (3)	−0.0402 (3)	0.2186 (2)	0.0501 (6)
O3	0.3771 (4)	0.2500	0.4145 (3)	0.0314 (6)
Co1	0.58731 (6)	0.2500	0.32505 (5)	0.02601 (18)
Br1	0.83644 (6)	0.2500	0.20942 (4)	0.04048 (18)
H2	0.557 (4)	−0.051 (4)	0.293 (2)	0.059 (12)*
H3	0.366 (5)	0.173 (3)	0.460 (3)	0.050 (10)*

	U11	U22	U33	U12	U13	U23
C1	0.0234 (13)	0.0376 (16)	0.0391 (15)	−0.0028 (12)	0.0091 (11)	−0.0058 (12)
C2	0.0354 (17)	0.060 (2)	0.0503 (18)	−0.0080 (15)	0.0039 (14)	−0.0164 (17)
C3	0.0321 (15)	0.068 (2)	0.0356 (16)	−0.0038 (15)	0.0097 (13)	−0.0091 (15)
C4	0.054 (2)	0.106 (4)	0.056 (2)	−0.018 (2)	0.0022 (19)	−0.030 (2)
N1	0.0284 (12)	0.0230 (12)	0.0415 (13)	−0.0032 (9)	0.0139 (10)	−0.0029 (10)
N2	0.0327 (13)	0.0388 (15)	0.0430 (14)	−0.0053 (11)	0.0140 (11)	−0.0082 (11)
O1	0.0446 (12)	0.0229 (10)	0.0538 (13)	−0.0022 (9)	0.0180 (10)	−0.0031 (9)
O2	0.0540 (15)	0.0376 (13)	0.0604 (15)	−0.0075 (11)	0.0142 (12)	−0.0163 (11)
O3	0.0300 (14)	0.0259 (15)	0.0401 (16)	0.000	0.0130 (12)	0.000
Co1	0.0251 (3)	0.0227 (3)	0.0312 (3)	0.000	0.0076 (2)	0.000
Br1	0.0364 (3)	0.0432 (3)	0.0441 (3)	0.000	0.01498 (19)	0.000

C1—N1	1.289 (4)	C4—H4C	0.9600
C1—C1i	1.476 (6)	N1—O1	1.338 (3)
C1—C2	1.485 (4)	N1—Co1	1.883 (2)
C2—H2A	0.9600	N2—O2	1.358 (3)
C2—H2B	0.9600	N2—Co1	1.911 (2)
C2—H2C	0.9600	O2—H2	0.921 (10)
C3—N2	1.283 (4)	O3—Co1	1.938 (3)
C3—C3i	1.475 (7)	O3—H3	0.85 (3)
C3—C4	1.477 (4)	Co1—N1i	1.883 (2)
C4—H4A	0.9600	Co1—N2i	1.911 (2)
C4—H4B	0.9600	Co1—Br1	2.3563 (6)
N1—C1—C1i	112.79 (16)	C3—N2—O2	119.2 (3)
N1—C1—C2	124.4 (3)	C3—N2—Co1	117.3 (2)
C1i—C1—C2	122.85 (19)	O2—N2—Co1	123.3 (2)
C1—C2—H2A	109.5	N2—O2—H2	103 (2)
C1—C2—H2B	109.5	Co1—O3—H3	114 (3)
H2A—C2—H2B	109.5	N1—Co1—N1i	82.18 (14)
C1—C2—H2C	109.5	N1—Co1—N2i	98.88 (11)
H2A—C2—H2C	109.5	N1i—Co1—N2i	178.29 (10)
H2B—C2—H2C	109.5	N1—Co1—N2	178.29 (10)
N2—C3—C3i	112.51 (19)	N1i—Co1—N2	98.88 (11)
N2—C3—C4	124.4 (4)	N2i—Co1—N2	80.03 (16)
C3i—C3—C4	123.1 (2)	N1—Co1—O3	91.24 (9)
C3—C4—H4A	109.5	N1i—Co1—O3	91.24 (9)
C3—C4—H4B	109.5	N2i—Co1—O3	87.40 (10)
H4A—C4—H4B	109.5	N2—Co1—O3	87.40 (10)
C3—C4—H4C	109.5	N1—Co1—Br1	90.29 (7)
H4A—C4—H4C	109.5	N1i—Co1—Br1	90.29 (7)
H4B—C4—H4C	109.5	N2i—Co1—Br1	91.04 (7)
C1—N1—O1	122.7 (2)	N2—Co1—Br1	91.04 (7)
C1—N1—Co1	116.1 (2)	O3—Co1—Br1	177.97 (9)
O1—N1—Co1	121.18 (18)
C1i—C1—N1—O1	179.81 (18)	C1—N1—Co1—O3	91.1 (2)
C2—C1—N1—O1	−0.7 (4)	O1—N1—Co1—O3	−88.7 (2)
C1i—C1—N1—Co1	0.02 (19)	C1—N1—Co1—Br1	−90.28 (19)
C2—C1—N1—Co1	179.5 (2)	O1—N1—Co1—Br1	89.92 (19)
C3i—C3—N2—O2	−179.62 (19)	C3—N2—Co1—N1i	174.1 (2)
C4—C3—N2—O2	0.8 (5)	O2—N2—Co1—N1i	−2.4 (2)
C3i—C3—N2—Co1	3.8 (2)	C3—N2—Co1—N2i	−4.6 (3)
C4—C3—N2—Co1	−175.8 (3)	O2—N2—Co1—N2i	178.98 (17)
C1—N1—Co1—N1i	0.0 (2)	C3—N2—Co1—O3	83.2 (2)
O1—N1—Co1—N1i	−179.82 (14)	O2—N2—Co1—O3	−93.2 (2)
C1—N1—Co1—N2i	178.6 (2)	C3—N2—Co1—Br1	−95.5 (2)
O1—N1—Co1—N2i	−1.2 (2)	O2—N2—Co1—Br1	88.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.92 (1)	1.58 (1)	2.494 (3)	169 (4)
O3—H3···O1ii	0.85 (3)	1.79 (3)	2.616 (3)	167 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.92 (1)	1.58 (1)	2.494 (3)	169 (4)
O3—H3⋯O1ii	0.85 (3)	1.79 (3)	2.616 (3)	167 (4)

Symmetry codes: (i) ; (ii) .