Bis(1,5-diphenyl-carbazonato)di-methano-lcobalt(II).

The structure of the title compound, [Co(C(13)H(11)N(4)O)(2)(CH(3)OH)(2)], is a mononuclear six-coordinated octa-hedral cobalt(II) complex of C(i) mol-ecular symmetry. The Co(II) ion is coordinated by two N atoms and two O atoms from two 1,5-biphenyl-carbazide ligands, and two O atoms from two methanol molecules. Two diphenyl-carbazidate ligands and the central Co(II) ion form the basal plane, with the two methanol mol-ecules located in axial positions. The crystal packing is defined by bifurcated O-H⋯N hydrogen bonding and intra-molecular N-H⋯O inter-actions.

Related literature

For the use of biphenyl­carbazide for the analytical determination of chromium in biological materials, see: Yarbro & Flaschka (1976 ▶). For its coordination modes, see: Feigl (1924 ▶); n class="Chemical">Shafranskii & Mal’kova (1975a ▶,b ▶); Martynova et al. (1985 ▶); Turkington & Tracy (1958 ▶); Deshpande & Jain (1988 ▶). For related literature, see: Pankaj & Chauhan (2004 ▶); Sollott & Peterson (1969 ▶); Cazeneuve (1900a ▶,b ▶).

Experimental

Crystal data

[Co(C13H11N4O)2(CH4O)2]

M = 601.53

Monoclinic,

a = 6.492 (2) Å

b = 8.926 (3) Å

c = 25.159 (9) Å

β = 92.372 (6)°

V = 1456.7 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.64 mm−1

T = 296 K

0.35 × 0.28 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.808, T max = 0.847

6990 measured reflections

2564 independent reflections

2037 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.08

2564 reflections

196 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809055305/kp2244sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055305/kp2244Isup2.hkl

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

[Co(C13H11N4O)2(CH4O)2]	F(000) = 626
Mr = 601.53	Dx = 1.371 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2392 reflections
a = 6.492 (2) Å	θ = 2.4–24.6°
b = 8.926 (3) Å	µ = 0.64 mm−1
c = 25.159 (9) Å	T = 296 K
β = 92.372 (6)°	Block, clear violet
V = 1456.7 (9) Å3	0.35 × 0.28 × 0.27 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	2564 independent reflections
Radiation source: fine-focus sealed tube	2037 reflections with I > 2σ(I)
graphite	Rint = 0.046
phi and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
Tmin = 0.808, Tmax = 0.847	k = −10→10
6990 measured reflections	l = −20→29

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0652P)2 + 0.0401P] where P = (Fo2 + 2Fc2)/3
2564 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.43 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
Co1	1.0000	1.0000	1.0000	0.03524 (19)
C1	0.8530 (5)	0.7374 (3)	1.09426 (11)	0.0528 (7)
H1	0.9758	0.7899	1.0914	0.063*
C2	0.8241 (6)	0.6473 (4)	1.13836 (11)	0.0640 (9)
H2	0.9270	0.6404	1.1651	0.077*
C3	0.6446 (6)	0.5688 (4)	1.14251 (13)	0.0642 (9)
H3	0.6256	0.5087	1.1721	0.077*
C4	0.4933 (5)	0.5785 (4)	1.10342 (14)	0.0720 (10)
H4	0.3721	0.5241	1.1064	0.086*
C5	0.5185 (5)	0.6687 (4)	1.05925 (13)	0.0634 (9)
H5	0.4145	0.6753	1.0328	0.076*
C6	0.7007 (4)	0.7492 (3)	1.05484 (10)	0.0382 (6)
C7	0.6545 (4)	0.9405 (3)	0.93219 (10)	0.0367 (6)
C8	0.4192 (4)	1.0503 (3)	0.80937 (10)	0.0437 (6)
C9	0.2276 (5)	0.9825 (3)	0.80672 (13)	0.0584 (8)
H9	0.1907	0.9157	0.8330	0.070*
C10	0.0906 (6)	1.0150 (4)	0.76451 (14)	0.0710 (10)
H10	−0.0385	0.9697	0.7627	0.085*
C11	0.1441 (6)	1.1139 (4)	0.72520 (13)	0.0719 (10)
H11	0.0509	1.1361	0.6972	0.086*
C12	0.3356 (6)	1.1794 (4)	0.72765 (11)	0.0648 (9)
H12	0.3720	1.2450	0.7009	0.078*
C13	0.4753 (5)	1.1491 (3)	0.76934 (10)	0.0538 (7)
H13	0.6047	1.1940	0.7707	0.065*
C14	0.9161 (6)	1.3027 (4)	1.06416 (16)	0.0849 (12)
H14A	1.0319	1.2726	1.0866	0.127*
H14B	0.8090	1.3405	1.0857	0.127*
H14C	0.9580	1.3797	1.0403	0.127*
N1	0.7412 (3)	0.8471 (2)	1.01157 (8)	0.0359 (5)
N2	0.6030 (3)	0.8460 (2)	0.97330 (8)	0.0391 (5)
N3	0.5120 (3)	0.9360 (3)	0.89297 (8)	0.0411 (5)
N4	0.5597 (4)	1.0247 (3)	0.85196 (9)	0.0463 (6)
O1	0.8187 (3)	1.0213 (2)	0.93292 (7)	0.0438 (5)
O2	0.8423 (3)	1.1797 (2)	1.03493 (9)	0.0570 (6)
H4'	0.660 (5)	1.073 (3)	0.8563 (11)	0.048 (9)*
H2'	0.720 (6)	1.167 (4)	1.0382 (13)	0.084 (12)*

	U11	U22	U33	U12	U13	U23
Co1	0.0269 (3)	0.0445 (3)	0.0341 (3)	−0.0019 (2)	−0.00083 (18)	−0.0004 (2)
C1	0.0589 (19)	0.0546 (17)	0.0445 (16)	−0.0123 (14)	−0.0024 (14)	0.0054 (13)
C2	0.088 (3)	0.0600 (19)	0.0428 (16)	−0.0077 (18)	−0.0077 (16)	0.0091 (14)
C3	0.086 (3)	0.0534 (18)	0.0543 (19)	−0.0007 (18)	0.0204 (18)	0.0125 (15)
C4	0.057 (2)	0.074 (2)	0.086 (3)	−0.0096 (18)	0.0160 (19)	0.029 (2)
C5	0.0419 (17)	0.076 (2)	0.073 (2)	−0.0062 (16)	0.0013 (15)	0.0258 (17)
C6	0.0402 (14)	0.0368 (13)	0.0382 (14)	0.0022 (11)	0.0080 (11)	−0.0002 (11)
C7	0.0284 (13)	0.0454 (13)	0.0362 (13)	0.0017 (11)	0.0003 (10)	−0.0023 (11)
C8	0.0474 (17)	0.0479 (15)	0.0352 (14)	0.0059 (12)	−0.0044 (12)	−0.0064 (11)
C9	0.064 (2)	0.0593 (19)	0.0508 (18)	−0.0049 (15)	−0.0145 (15)	0.0038 (14)
C10	0.066 (2)	0.078 (2)	0.066 (2)	−0.0084 (18)	−0.0298 (17)	0.0024 (18)
C11	0.087 (3)	0.071 (2)	0.0549 (19)	0.013 (2)	−0.0312 (18)	−0.0007 (18)
C12	0.093 (3)	0.0605 (19)	0.0408 (17)	0.0102 (18)	−0.0044 (16)	0.0036 (14)
C13	0.0610 (19)	0.0583 (18)	0.0420 (15)	0.0018 (15)	0.0001 (13)	−0.0031 (13)
C14	0.058 (2)	0.084 (3)	0.113 (3)	−0.0036 (19)	0.015 (2)	−0.047 (2)
N1	0.0296 (11)	0.0426 (12)	0.0355 (11)	0.0026 (9)	0.0028 (9)	−0.0024 (9)
N2	0.0313 (11)	0.0472 (13)	0.0386 (12)	0.0003 (9)	0.0013 (9)	−0.0009 (10)
N3	0.0342 (12)	0.0524 (13)	0.0365 (12)	−0.0015 (10)	−0.0017 (9)	−0.0010 (10)
N4	0.0397 (14)	0.0592 (16)	0.0394 (13)	−0.0065 (12)	−0.0059 (10)	0.0034 (11)
O1	0.0355 (10)	0.0560 (12)	0.0395 (10)	−0.0074 (9)	−0.0035 (8)	0.0049 (8)
O2	0.0295 (11)	0.0635 (13)	0.0786 (15)	−0.0035 (10)	0.0100 (10)	−0.0232 (11)

Co1—O1i	2.0263 (18)	C8—C9	1.383 (4)
Co1—O1	2.0263 (18)	C8—N4	1.397 (3)
Co1—O2	2.114 (2)	C8—C13	1.398 (4)
Co1—O2i	2.114 (2)	C9—C10	1.387 (4)
Co1—N1i	2.193 (2)	C9—H9	0.9300
Co1—N1	2.193 (2)	C10—C11	1.381 (5)
C1—C6	1.375 (4)	C10—H10	0.9300
C1—C2	1.389 (4)	C11—C12	1.373 (5)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.368 (5)	C12—C13	1.384 (4)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.363 (5)	C13—H13	0.9300
C3—H3	0.9300	C14—O2	1.395 (4)
C4—C5	1.387 (4)	C14—H14A	0.9600
C4—H4	0.9300	C14—H14B	0.9600
C5—C6	1.392 (4)	C14—H14C	0.9600
C5—H5	0.9300	N1—N2	1.289 (3)
C6—N1	1.429 (3)	N3—N4	1.347 (3)
C7—O1	1.286 (3)	N4—H4'	0.78 (3)
C7—N3	1.325 (3)	O2—H2'	0.81 (4)
C7—N2	1.386 (3)
O1i—Co1—O1	179.999 (1)	C9—C8—N4	121.6 (3)
O1i—Co1—O2	89.97 (8)	C9—C8—C13	120.1 (3)
O1—Co1—O2	90.03 (8)	N4—C8—C13	118.3 (3)
O1i—Co1—O2i	90.03 (8)	C8—C9—C10	119.5 (3)
O1—Co1—O2i	89.97 (8)	C8—C9—H9	120.2
O2—Co1—O2i	179.997 (1)	C10—C9—H9	120.2
O1i—Co1—N1i	75.34 (7)	C11—C10—C9	120.7 (3)
O1—Co1—N1i	104.66 (7)	C11—C10—H10	119.7
O2—Co1—N1i	88.27 (8)	C9—C10—H10	119.7
O2i—Co1—N1i	91.73 (8)	C12—C11—C10	119.6 (3)
O1i—Co1—N1	104.66 (7)	C12—C11—H11	120.2
O1—Co1—N1	75.34 (7)	C10—C11—H11	120.2
O2—Co1—N1	91.73 (8)	C11—C12—C13	121.0 (3)
O2i—Co1—N1	88.27 (8)	C11—C12—H12	119.5
N1i—Co1—N1	180.0	C13—C12—H12	119.5
C6—C1—C2	120.2 (3)	C12—C13—C8	119.1 (3)
C6—C1—H1	119.9	C12—C13—H13	120.4
C2—C1—H1	119.9	C8—C13—H13	120.4
C3—C2—C1	120.1 (3)	O2—C14—H14A	109.5
C3—C2—H2	120.0	O2—C14—H14B	109.5
C1—C2—H2	120.0	H14A—C14—H14B	109.5
C4—C3—C2	120.2 (3)	O2—C14—H14C	109.5
C4—C3—H3	119.9	H14A—C14—H14C	109.5
C2—C3—H3	119.9	H14B—C14—H14C	109.5
C3—C4—C5	120.6 (3)	N2—N1—C6	114.8 (2)
C3—C4—H4	119.7	N2—N1—Co1	114.78 (15)
C5—C4—H4	119.7	C6—N1—Co1	130.38 (16)
C4—C5—C6	119.5 (3)	N1—N2—C7	111.8 (2)
C4—C5—H5	120.3	C7—N3—N4	112.2 (2)
C6—C5—H5	120.3	N3—N4—C8	121.3 (3)
C1—C6—C5	119.4 (3)	N3—N4—H4'	116 (2)
C1—C6—N1	116.5 (2)	C8—N4—H4'	122 (2)
C5—C6—N1	124.1 (3)	C7—O1—Co1	114.33 (15)
O1—C7—N3	125.5 (2)	C14—O2—Co1	130.91 (19)
O1—C7—N2	123.8 (2)	C14—O2—H2'	112 (3)
N3—C7—N2	110.8 (2)	Co1—O2—H2'	116 (3)
C6—C1—C2—C3	0.6 (5)	O1—Co1—N1—C6	178.9 (2)
C1—C2—C3—C4	0.1 (5)	O2—Co1—N1—C6	−91.5 (2)
C2—C3—C4—C5	−0.5 (6)	O2i—Co1—N1—C6	88.5 (2)
C3—C4—C5—C6	0.4 (5)	N1i—Co1—N1—C6	−89 (10)
C2—C1—C6—C5	−0.8 (4)	C6—N1—N2—C7	−178.5 (2)
C2—C1—C6—N1	178.5 (3)	Co1—N1—N2—C7	1.8 (2)
C4—C5—C6—C1	0.3 (5)	O1—C7—N2—N1	−1.2 (3)
C4—C5—C6—N1	−178.9 (3)	N3—C7—N2—N1	179.1 (2)
N4—C8—C9—C10	177.9 (3)	O1—C7—N3—N4	1.5 (4)
C13—C8—C9—C10	−0.9 (5)	N2—C7—N3—N4	−178.9 (2)
C8—C9—C10—C11	0.1 (5)	C7—N3—N4—C8	−172.2 (2)
C9—C10—C11—C12	0.7 (5)	C9—C8—N4—N3	−1.8 (4)
C10—C11—C12—C13	−0.8 (5)	C13—C8—N4—N3	177.1 (3)
C11—C12—C13—C8	0.0 (5)	N3—C7—O1—Co1	179.6 (2)
C9—C8—C13—C12	0.9 (4)	N2—C7—O1—Co1	−0.1 (3)
N4—C8—C13—C12	−178.0 (3)	O1i—Co1—O1—C7	129 (3)
C1—C6—N1—N2	174.5 (2)	O2—Co1—O1—C7	−90.99 (18)
C5—C6—N1—N2	−6.3 (4)	O2i—Co1—O1—C7	89.01 (18)
C1—C6—N1—Co1	−5.9 (3)	N1i—Co1—O1—C7	−179.21 (17)
C5—C6—N1—Co1	173.3 (2)	N1—Co1—O1—C7	0.79 (17)
O1i—Co1—N1—N2	178.49 (15)	O1i—Co1—O2—C14	44.4 (3)
O1—Co1—N1—N2	−1.51 (15)	O1—Co1—O2—C14	−135.6 (3)
O2—Co1—N1—N2	88.07 (17)	O2i—Co1—O2—C14	−89 (4)
O2i—Co1—N1—N2	−91.93 (17)	N1i—Co1—O2—C14	−30.9 (3)
N1i—Co1—N1—N2	91 (10)	N1—Co1—O2—C14	149.1 (3)
O1i—Co1—N1—C6	−1.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4'···O1	0.78 (3)	2.20 (3)	2.587 (3)	111 (2)
O2—H2'···N2ii	0.81 (4)	2.11 (4)	2.899 (3)	166 (3)
O2—H2'···N3ii	0.81 (4)	2.52 (4)	3.161 (3)	138 (3)

Table 1

Selected bond lengths (Å)

Co1—O1	2.0263 (18)
Co1—O2	2.114 (2)
Co1—N1	2.193 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4′⋯O1	0.78 (3)	2.20 (3)	2.587 (3)	111 (2)
O2—H2′⋯N2i	0.81 (4)	2.11 (4)	2.899 (3)	166 (3)
O2—H2′⋯N3i	0.81 (4)	2.52 (4)	3.161 (3)	138 (3)

Symmetry code: (i) .