Bis­(di­methyl­glyoximato-N,N')(ethanol-O)­nitro­cobalt(III), [Co(Hdmg)₂(NO₂)(EtOH)]

In the distorted octahedral title complex, [Co(NO₂)(C₂H₆O)(C₄H₇N₂O₂)₂], the Co atom is coordinated to two chelating ligands in the equatorial plane, with nitro and ethanol groups occupying the axial positions. In addition to the asymmetric intramolecular hydrogen bridges between the equatorial ligands, strong intermolecular hydrogen bonds result in a pairwise arrangement of the mol­ecules with respect to a crystallographic inversion center.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.108
• Data-to-parameter ratio = 18.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART); data reduction: SAINT+ (Bruker, 1999); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXTL.

Bis(dimethylglyoximato-N,N')(ethanol-O)nitrocobalt(III)

Crystal data

[Co(NO2)(C2H6O)(C4H7N2O2)2]	F(000) = 792
Mr = 381.24	Dx = 1.585 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9591 (5) Å	Cell parameters from 14412 reflections
b = 16.614 (1) Å	θ = 2.3–28.3°
c = 10.7359 (6) Å	µ = 1.12 mm^−1
β = 91.83 (1)°	T = 293 K
V = 1597.18 (16) Å^3	Block, red
Z = 4	0.48 × 0.28 × 0.18 mm

Data collection

CCD area-detector diffractometer	3973 independent reflections
Radiation source: fine-focus sealed tube	3166 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.694, Tmax = 0.818	k = −22→22
14412 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0578P)^2] where P = (Fo^2 + 2Fc^2)/3
3973 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. The values of Tmin and Tmax are 0.757793 and 1.000000 from SADABS.

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
Co1	0.03317 (3)	0.111866 (17)	0.77851 (3)	0.02689 (11)
N1	−0.0166 (2)	0.00306 (11)	0.80836 (18)	0.0307 (4)
O1	0.07775 (19)	−0.04591 (9)	0.86995 (16)	0.0390 (4)
C1	−0.1473 (3)	−0.02007 (14)	0.7679 (2)	0.0366 (5)
C10	−0.2062 (4)	−0.10297 (16)	0.7823 (3)	0.0565 (8)
H10A	−0.1316	−0.1361	0.8270	0.073*
H10B	−0.2279	−0.1263	0.6998	0.073*
H10C	−0.2979	−0.1012	0.8295	0.073*
N2	−0.1613 (2)	0.11227 (12)	0.70546 (19)	0.0350 (4)
O2	−0.2237 (2)	0.17886 (12)	0.65415 (18)	0.0489 (5)
H3	−0.112 (6)	0.232 (3)	0.678 (5)	0.138 (18)*
C2	−0.2327 (3)	0.04459 (16)	0.7064 (2)	0.0385 (6)
C20	−0.3853 (3)	0.0329 (2)	0.6501 (3)	0.0601 (8)
H20A	−0.4209	0.0836	0.6134	0.078*
H20B	−0.4532	0.0157	0.7147	0.078*
H20C	−0.3821	−0.0084	0.5851	0.078*
N3	0.0798 (2)	0.22294 (12)	0.75714 (18)	0.0339 (4)
O3	−0.0189 (2)	0.27485 (11)	0.70831 (17)	0.0466 (5)
C3	0.2055 (3)	0.24753 (14)	0.8064 (2)	0.0372 (6)
C30	0.2495 (4)	0.33382 (16)	0.8169 (3)	0.0558 (8)
H30A	0.1718	0.3675	0.7771	0.073*
H30B	0.3441	0.3422	0.7754	0.073*
H30C	0.2615	0.3485	0.9050	0.073*
N4	0.2295 (2)	0.11306 (12)	0.85173 (19)	0.0343 (4)
O4	0.3035 (2)	0.04706 (12)	0.89606 (19)	0.0492 (5)
H4	0.233 (4)	0.007 (2)	0.891 (3)	0.074 (11)*
C4	0.2980 (3)	0.18165 (16)	0.8565 (2)	0.0383 (6)
C40	0.4532 (3)	0.1922 (2)	0.9051 (3)	0.0547 (8)
H40A	0.4931	0.1401	0.9332	0.071*
H40B	0.4544	0.2299	0.9753	0.071*
H40C	0.5150	0.2135	0.8390	0.071*
N5	0.1112 (2)	0.08453 (13)	0.62156 (19)	0.0375 (5)
O5	0.0725 (3)	0.12254 (14)	0.53058 (19)	0.0657 (6)
O6	0.2030 (3)	0.03062 (13)	0.6172 (2)	0.0679 (7)
O7	−0.0450 (2)	0.14082 (11)	0.94361 (16)	0.0369 (4)
H7	−0.045 (3)	0.1072 (17)	0.990 (3)	0.043 (9)*
C5	−0.1526 (3)	0.20259 (16)	0.9717 (3)	0.0424 (6)
H5A	−0.2275	0.1804	1.0268	0.055*
H5B	−0.2041	0.2201	0.8944	0.055*
C6	−0.0777 (4)	0.27351 (18)	1.0335 (3)	0.0612 (9)
H6A	−0.1521	0.3153	1.0488	0.080*
H6B	−0.0014	0.2950	0.9792	0.080*
H6C	−0.0307	0.2566	1.1129	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02679 (18)	0.02646 (17)	0.02730 (17)	−0.00076 (12)	−0.00098 (12)	0.00304 (12)
N1	0.0341 (11)	0.0274 (9)	0.0307 (10)	0.0014 (8)	0.0033 (8)	0.0028 (8)
O1	0.0443 (10)	0.0308 (8)	0.0420 (10)	0.0082 (8)	0.0056 (8)	0.0100 (7)
C1	0.0393 (14)	0.0354 (12)	0.0354 (13)	−0.0076 (11)	0.0040 (11)	−0.0033 (10)
C10	0.064 (2)	0.0415 (15)	0.064 (2)	−0.0187 (14)	−0.0001 (16)	0.0000 (13)
N2	0.0331 (11)	0.0382 (11)	0.0332 (11)	0.0030 (9)	−0.0059 (9)	0.0025 (8)
O2	0.0439 (11)	0.0503 (11)	0.0515 (11)	0.0130 (9)	−0.0126 (9)	0.0111 (9)
C2	0.0320 (13)	0.0484 (14)	0.0349 (13)	−0.0042 (11)	−0.0026 (10)	−0.0041 (11)
C20	0.0398 (16)	0.072 (2)	0.068 (2)	−0.0101 (15)	−0.0137 (15)	−0.0092 (17)
N3	0.0414 (12)	0.0310 (10)	0.0295 (10)	−0.0016 (9)	0.0028 (9)	0.0045 (8)
O3	0.0583 (12)	0.0325 (9)	0.0484 (11)	0.0066 (9)	−0.0047 (10)	0.0117 (8)
C3	0.0431 (14)	0.0366 (13)	0.0325 (12)	−0.0099 (11)	0.0088 (11)	−0.0027 (10)
C30	0.072 (2)	0.0416 (14)	0.0539 (17)	−0.0210 (15)	0.0107 (16)	−0.0029 (13)
N4	0.0293 (10)	0.0371 (10)	0.0361 (11)	0.0015 (9)	−0.0025 (9)	0.0017 (8)
O4	0.0401 (11)	0.0484 (11)	0.0582 (12)	0.0083 (9)	−0.0124 (9)	0.0070 (9)
C4	0.0343 (13)	0.0503 (15)	0.0307 (12)	−0.0081 (11)	0.0044 (10)	−0.0048 (11)
C40	0.0378 (15)	0.074 (2)	0.0522 (17)	−0.0139 (14)	−0.0050 (13)	−0.0099 (15)
N5	0.0386 (12)	0.0411 (11)	0.0331 (11)	−0.0046 (9)	0.0050 (9)	−0.0011 (9)
O5	0.0798 (17)	0.0847 (16)	0.0328 (10)	0.0169 (13)	0.0052 (11)	0.0131 (10)
O6	0.0845 (17)	0.0673 (14)	0.0534 (13)	0.0302 (13)	0.0244 (12)	0.0018 (11)
O7	0.0470 (11)	0.0336 (9)	0.0304 (9)	0.0076 (8)	0.0052 (8)	0.0054 (7)
C5	0.0341 (14)	0.0494 (15)	0.0440 (15)	0.0088 (11)	0.0032 (11)	0.0050 (12)
C6	0.066 (2)	0.0488 (16)	0.070 (2)	0.0029 (15)	0.0223 (17)	−0.0183 (15)

Geometric parameters (Å, º)

Co1—N2	1.888 (2)	C3—C4	1.465 (4)
Co1—N1	1.8918 (18)	C3—C30	1.490 (3)
Co1—N5	1.900 (2)	C30—H30A	0.9800
Co1—N4	1.904 (2)	C30—H30B	0.9800
Co1—N3	1.908 (2)	C30—H30C	0.9800
Co1—O7	1.9856 (17)	N4—C4	1.295 (3)
N1—C1	1.293 (3)	N4—O4	1.360 (3)
N1—O1	1.334 (2)	O4—H4	0.92 (4)
C1—C2	1.464 (4)	C4—C40	1.480 (4)
C1—C10	1.485 (3)	C40—H40A	0.9800
C10—H10A	0.9800	C40—H40B	0.9800
C10—H10B	0.9800	C40—H40C	0.9800
C10—H10C	0.9800	N5—O5	1.205 (3)
N2—C2	1.294 (3)	N5—O6	1.218 (3)
N2—O2	1.349 (3)	O7—C5	1.447 (3)
O2—H3	1.36 (5)	O7—H7	0.75 (3)
C2—C20	1.490 (4)	C5—C6	1.500 (4)
C20—H20A	0.9800	C5—H5A	0.9800
C20—H20B	0.9800	C5—H5B	0.9800
C20—H20C	0.9800	C6—H6A	0.9800
N3—C3	1.295 (3)	C6—H6B	0.9800
N3—O3	1.331 (3)	C6—H6C	0.9800
O3—H3	1.13 (5)
N2—Co1—N1	81.61 (8)	O3—N3—Co1	121.94 (16)
N2—Co1—N5	89.61 (9)	N3—O3—H3	100 (3)
N1—Co1—N5	90.99 (9)	N3—C3—C4	112.9 (2)
N2—Co1—N4	179.19 (9)	N3—C3—C30	124.0 (3)
N1—Co1—N4	99.20 (8)	C4—C3—C30	123.1 (3)
N5—Co1—N4	90.43 (9)	C3—C30—H30A	109.5
N2—Co1—N3	98.60 (9)	C3—C30—H30B	109.5
N1—Co1—N3	176.92 (8)	H30A—C30—H30B	109.5
N5—Co1—N3	92.08 (9)	C3—C30—H30C	109.5
N4—Co1—N3	80.59 (9)	H30A—C30—H30C	109.5
N2—Co1—O7	91.31 (8)	H30B—C30—H30C	109.5
N1—Co1—O7	89.34 (8)	C4—N4—O4	118.1 (2)
N5—Co1—O7	179.05 (9)	C4—N4—Co1	117.15 (17)
N4—Co1—O7	88.65 (8)	O4—N4—Co1	124.77 (16)
N3—Co1—O7	87.59 (8)	N4—O4—H4	103 (2)
C1—N1—O1	122.52 (19)	N4—C4—C3	112.4 (2)
C1—N1—Co1	116.29 (17)	N4—C4—C40	123.9 (3)
O1—N1—Co1	121.18 (15)	C3—C4—C40	123.7 (2)
N1—C1—C2	112.8 (2)	C4—C40—H40A	109.5
N1—C1—C10	124.2 (2)	C4—C40—H40B	109.5
C2—C1—C10	123.0 (2)	H40A—C40—H40B	109.5
C1—C10—H10A	109.5	C4—C40—H40C	109.5
C1—C10—H10B	109.5	H40A—C40—H40C	109.5
H10A—C10—H10B	109.5	H40B—C40—H40C	109.5
C1—C10—H10C	109.5	O5—N5—O6	122.1 (2)
H10A—C10—H10C	109.5	O5—N5—Co1	119.31 (18)
H10B—C10—H10C	109.5	O6—N5—Co1	118.55 (18)
C2—N2—O2	121.2 (2)	C5—O7—Co1	127.90 (16)
C2—N2—Co1	116.33 (17)	C5—O7—H7	112 (2)
O2—N2—Co1	122.50 (16)	Co1—O7—H7	115 (2)
N2—O2—H3	99 (2)	O7—C5—C6	110.9 (2)
N2—C2—C1	113.0 (2)	O7—C5—H5A	109.4
N2—C2—C20	123.9 (3)	C6—C5—H5A	109.4
C1—C2—C20	123.1 (2)	O7—C5—H5B	109.4
C2—C20—H20A	109.5	C6—C5—H5B	109.4
C2—C20—H20B	109.5	H5A—C5—H5B	108.0
H20A—C20—H20B	109.5	C5—C6—H6A	109.5
C2—C20—H20C	109.5	C5—C6—H6B	109.5
H20A—C20—H20C	109.5	H6A—C6—H6B	109.5
H20B—C20—H20C	109.5	C5—C6—H6C	109.5
C3—N3—O3	121.0 (2)	H6A—C6—H6C	109.5
C3—N3—Co1	116.56 (17)	H6B—C6—H6C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	1.13 (5)	1.36 (5)	2.486 (3)	175 (5)
O4—H4···O1	0.92 (4)	1.66 (4)	2.554 (3)	166 (3)
O7—H7···O1^i	0.75 (3)	1.85 (3)	2.572 (2)	163 (3)

Symmetry code: (i) −x, −y, −z+2.