Bis[2-(benzimidazol-2-yl)phenolato-κ²N,O]cobalt(II)

In the title compound, [Co(C₁₃H₉N₂O)₂], the coordination geometry of the Co^II atom is distorted tetra­hedral; the Co atom lies on a twofold axis. Adjacent mol­ecules are linked by N—H...O hydrogen bonds into a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.114
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.490
           From the CIF: _refine_ls_abs_structure_Flack_su    0.030
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.49
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.19
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.51 Ratio

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           28.31
           From the CIF: _reflns_number_total               2669
           Count of symmetry unique reflns         1683
           Completeness (_total/calc)            158.59%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       986
           Fraction of Friedel pairs measured     0.586
           Are heavy atom types Z>Si present        yes

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

   2 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

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S1. Comment

2-(Benzimidazol-2-yl)phenol is a bidentate heterocycle that possesses a benzimidazole nitrogen and a phenol oxygen site, and it also has an additional hydrogen-bond donor unit (NH) (Crane et al., 1995).

In the structure of (I), the Co^II atom lies on a twofold axis and is coordinated by two N atoms and two O atoms to give a distorted tetrahedral geometry (Fig. 1). The benzimidazole and phenol groups are nearly planar as the dihedral angle between them is 3.6 (2)°. The angle between the two ligand planes is 83.10 (5)°. The complexes are linked by N—H···O hydrogen bonds [N···O = 2.809 (3) Å] into a three-dimensional network structure.

S2. Experimental

Cobalt nitrate hexahydrate (0.146 g, 0.5 mmol) and 2-(benzimidazol-2-yl)phenol (0.210 g, 1 mmol) were dissolved in ethanol (3 ml) and water (15 ml). The solution was placed in a 23 ml Teflon-lined stainless steel Parr bomb. The bomb was heated at 433 K for 120 h. The cooled mixture yielded red crystals of (I); these were washed with water and then dried in air (yield ca 70%).

S3. Refinement

The crystal is a racemic twin, can be refined in P4₁2₁2 with a Flack (1983) parameter of 0.49 (3) and in P4₃2₁2 with a Flack parameter of 0.52 (2). As the Flack parameter of the former is slightly lower, the space group P4₁2₁2 was chosen. All H atoms were positioned geometrically and refined with a riding model, with distances C—H = 0.93 Å and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), with displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radii. [symmetry code: (i) y, x, −z].

Bis[2-(benzimidazol-2-yl)phenolato-κ²N,O] cobalt(II)

Crystal data

[Co(C13H9N2O)2]	Dx = 1.420 Mg m^−3
Mr = 477.37	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 1671 reflections
Hall symbol: P 4abw 2nw	θ = 3.0–25.4°
a = 9.9452 (3) Å	µ = 0.80 mm^−1
c = 22.581 (2) Å	T = 293 K
V = 2233.4 (2) Å^3	Block, red
Z = 4	0.17 × 0.15 × 0.14 mm
F(000) = 980

Data collection

Bruker CCD area-detector diffractometer	2669 independent reflections
Radiation source: fine-focus sealed tube	2346 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
Tmin = 0.876, Tmax = 0.896	k = −12→10
15456 measured reflections	l = −29→29

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0615P)^2 + 0.7603P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
2669 reflections	Δρmax = 0.49 e Å^−3
150 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Absolute structure: Flack (1983), 986 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.49 (3)

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
Co1	0.37726 (4)	0.37726 (4)	0.0000	0.03744 (16)
O1	0.2037 (2)	0.4154 (2)	−0.03236 (9)	0.0456 (5)
N1	0.2675 (3)	0.6494 (3)	0.12591 (13)	0.0510 (7)
H1	0.2064	0.6959	0.1434	0.061*
N2	0.3659 (2)	0.5170 (2)	0.06036 (10)	0.0396 (5)
C1	0.1079 (3)	0.4912 (3)	−0.00874 (12)	0.0409 (6)
C2	0.1249 (3)	0.5715 (3)	0.04303 (12)	0.0416 (6)
C3	0.0171 (3)	0.6494 (4)	0.06224 (16)	0.0591 (9)
H3	0.0287	0.7045	0.0951	0.071*
C4	−0.1050 (4)	0.6481 (5)	0.0347 (2)	0.0726 (11)
H4	−0.1752	0.7009	0.0488	0.087*
C5	−0.1229 (4)	0.5677 (4)	−0.01408 (18)	0.0693 (11)
H5	−0.2064	0.5649	−0.0326	0.083*
C6	−0.0187 (4)	0.4914 (4)	−0.03585 (16)	0.0559 (8)
H6	−0.0327	0.4387	−0.0693	0.067*
C7	0.2512 (3)	0.5771 (3)	0.07535 (12)	0.0373 (6)
C8	0.4003 (3)	0.6350 (4)	0.14439 (14)	0.0511 (8)
C9	0.4700 (4)	0.6868 (5)	0.19162 (19)	0.0786 (13)
H9	0.4287	0.7427	0.2192	0.094*
C10	0.6028 (4)	0.6528 (6)	0.1964 (2)	0.0936 (16)
H10	0.6531	0.6869	0.2277	0.112*
C11	0.6642 (4)	0.5686 (5)	0.1556 (2)	0.0853 (14)
H11	0.7547	0.5474	0.1603	0.102*
C12	0.5946 (3)	0.5155 (4)	0.10820 (17)	0.0635 (10)
H12	0.6355	0.4580	0.0812	0.076*
C13	0.4605 (3)	0.5521 (3)	0.10286 (12)	0.0434 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03945 (19)	0.03945 (19)	0.0334 (2)	0.0056 (2)	0.00447 (15)	−0.00447 (15)
O1	0.0435 (12)	0.0504 (12)	0.0428 (10)	0.0063 (9)	−0.0075 (9)	−0.0115 (9)
N1	0.0430 (14)	0.0604 (19)	0.0496 (13)	0.0091 (12)	0.0040 (11)	−0.0198 (13)
N2	0.0363 (12)	0.0446 (13)	0.0378 (11)	0.0047 (10)	0.0029 (10)	−0.0059 (9)
C1	0.0385 (15)	0.0407 (14)	0.0436 (14)	−0.0007 (11)	−0.0009 (12)	0.0066 (12)
C2	0.0370 (13)	0.0460 (14)	0.0419 (13)	0.0032 (13)	0.0045 (12)	0.0022 (11)
C3	0.0457 (18)	0.072 (2)	0.0595 (18)	0.0157 (16)	0.0040 (15)	−0.0063 (17)
C4	0.041 (2)	0.096 (3)	0.080 (2)	0.0243 (19)	0.0017 (17)	0.003 (2)
C5	0.0386 (17)	0.086 (3)	0.083 (3)	0.0074 (18)	−0.0125 (18)	0.009 (2)
C6	0.0483 (19)	0.064 (2)	0.0552 (18)	−0.0013 (16)	−0.0123 (15)	0.0017 (16)
C7	0.0382 (14)	0.0387 (14)	0.0350 (12)	0.0021 (11)	0.0055 (11)	−0.0029 (11)
C8	0.0436 (17)	0.060 (2)	0.0500 (15)	0.0008 (15)	−0.0017 (12)	−0.0136 (14)
C9	0.072 (3)	0.091 (3)	0.073 (2)	0.004 (2)	−0.013 (2)	−0.037 (2)
C10	0.068 (3)	0.126 (4)	0.087 (3)	−0.003 (3)	−0.029 (2)	−0.037 (3)
C11	0.049 (2)	0.110 (4)	0.097 (3)	0.010 (2)	−0.026 (2)	−0.014 (3)
C12	0.044 (2)	0.081 (3)	0.066 (2)	0.0119 (17)	−0.0029 (15)	−0.0134 (19)
C13	0.0398 (17)	0.0484 (18)	0.0421 (13)	−0.0019 (12)	0.0010 (12)	−0.0037 (13)

Geometric parameters (Å, º)

Co1—O1^i	1.912 (2)	C4—C5	1.372 (6)
Co1—O1	1.912 (2)	C4—H4	0.9300
Co1—N2	1.950 (2)	C5—C6	1.375 (6)
Co1—N2^i	1.950 (2)	C5—H5	0.9300
O1—C1	1.327 (3)	C6—H6	0.9300
N1—C7	1.359 (4)	C8—C9	1.373 (5)
N1—C8	1.392 (4)	C8—C13	1.385 (4)
N1—H1	0.8600	C9—C10	1.368 (6)
N2—C7	1.331 (3)	C9—H9	0.9300
N2—C13	1.388 (4)	C10—C11	1.387 (7)
C1—C6	1.400 (4)	C10—H10	0.9300
C1—C2	1.426 (4)	C11—C12	1.380 (6)
C2—C3	1.392 (4)	C11—H11	0.9300
C2—C7	1.454 (4)	C12—C13	1.388 (4)
C3—C4	1.364 (5)	C12—H12	0.9300
C3—H3	0.9300
O1^i—Co1—O1	120.25 (13)	C4—C5—H5	119.7
O1—Co1—N2	94.22 (9)	C6—C5—H5	119.7
O1^i—Co1—N2	112.81 (9)	C5—C6—C1	121.5 (3)
O1^i—Co1—N2^i	94.22 (9)	C5—C6—H6	119.3
O1—Co1—N2^i	112.81 (9)	C1—C6—H6	119.3
N2—Co1—N2^i	124.83 (15)	N2—C7—N1	110.4 (3)
C1—O1—Co1	127.38 (18)	N2—C7—C2	126.6 (2)
C7—N1—C8	108.1 (2)	N1—C7—C2	123.0 (3)
C7—N1—H1	126.0	C9—C8—C13	122.1 (3)
C8—N1—H1	126.0	C9—C8—N1	132.3 (3)
C7—N2—C13	107.0 (2)	C13—C8—N1	105.6 (3)
C7—N2—Co1	123.2 (2)	C10—C9—C8	117.1 (4)
C13—N2—Co1	128.55 (19)	C10—C9—H9	121.4
O1—C1—C6	118.1 (3)	C8—C9—H9	121.4
O1—C1—C2	124.2 (3)	C9—C10—C11	121.5 (4)
C6—C1—C2	117.7 (3)	C9—C10—H10	119.2
C3—C2—C1	118.4 (3)	C11—C10—H10	119.2
C3—C2—C7	119.2 (3)	C12—C11—C10	121.7 (4)
C1—C2—C7	122.4 (3)	C12—C11—H11	119.2
C4—C3—C2	122.6 (4)	C10—C11—H11	119.2
C4—C3—H3	118.7	C11—C12—C13	116.7 (4)
C2—C3—H3	118.7	C11—C12—H12	121.6
C3—C4—C5	119.2 (4)	C13—C12—H12	121.6
C3—C4—H4	120.4	C8—C13—C12	120.9 (3)
C5—C4—H4	120.4	C8—C13—N2	109.0 (3)
C4—C5—C6	120.7 (3)	C12—C13—N2	130.2 (3)
O1^i—Co1—O1—C1	106.6 (2)	Co1—N2—C7—C2	−13.5 (4)
N2—Co1—O1—C1	−13.0 (2)	C8—N1—C7—N2	0.0 (4)
N2^i—Co1—O1—C1	−143.7 (2)	C8—N1—C7—C2	−178.7 (3)
O1^i—Co1—N2—C7	−110.1 (2)	C3—C2—C7—N2	−174.7 (3)
O1—Co1—N2—C7	15.3 (2)	C1—C2—C7—N2	3.8 (5)
N2^i—Co1—N2—C7	136.9 (2)	C3—C2—C7—N1	3.9 (5)
O1^i—Co1—N2—C13	55.1 (3)	C1—C2—C7—N1	−177.6 (3)
O1—Co1—N2—C13	−179.6 (3)	C7—N1—C8—C9	179.2 (4)
N2^i—Co1—N2—C13	−57.9 (2)	C7—N1—C8—C13	0.1 (4)
Co1—O1—C1—C6	−171.5 (2)	C13—C8—C9—C10	−0.3 (7)
Co1—O1—C1—C2	7.7 (4)	N1—C8—C9—C10	−179.2 (4)
O1—C1—C2—C3	178.2 (3)	C8—C9—C10—C11	−0.6 (8)
C6—C1—C2—C3	−2.6 (4)	C9—C10—C11—C12	0.2 (9)
O1—C1—C2—C7	−0.3 (4)	C10—C11—C12—C13	0.9 (8)
C6—C1—C2—C7	178.9 (3)	C9—C8—C13—C12	1.5 (6)
C1—C2—C3—C4	2.3 (5)	N1—C8—C13—C12	−179.3 (3)
C7—C2—C3—C4	−179.1 (4)	C9—C8—C13—N2	−179.4 (4)
C2—C3—C4—C5	−0.4 (7)	N1—C8—C13—N2	−0.2 (4)
C3—C4—C5—C6	−1.3 (7)	C11—C12—C13—C8	−1.7 (6)
C4—C5—C6—C1	1.0 (6)	C11—C12—C13—N2	179.3 (4)
O1—C1—C6—C5	−179.8 (3)	C7—N2—C13—C8	0.2 (4)
C2—C1—C6—C5	1.0 (5)	Co1—N2—C13—C8	−166.9 (2)
C13—N2—C7—N1	−0.2 (3)	C7—N2—C13—C12	179.3 (4)
Co1—N2—C7—N1	167.8 (2)	Co1—N2—C13—C12	12.2 (5)
C13—N2—C7—C2	178.6 (3)

Symmetry code: (i) y, x, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^ii	0.86	2.07	2.809 (3)	144

Symmetry code: (ii) −y+1/2, x+1/2, z+1/4.