Bis[2-(cyclo­pentyl­imino­meth­yl)-4-nitro­phenolato-κ2N2,O]cobalt(II)

Xu, M.; Wei, Y.-J.; Wang, F.-W.

doi:10.1107/S1600536811002194

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m245

doi:10.1107/S1600536811002194

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Bis[2-(cyclopentyliminomethyl)-4-nitrophenolato-κ²N²,O]cobalt(II)

Mai Xu,^a ^* Yi-Jun Wei ^a and Feng-Wu Wang ^a

^aDepartment of Chemistry, Huainan Normal College, Huainan 232001, People's Republic of China
^*Correspondence e-mail: xumaimai@126.com

(Received 11 January 2011; accepted 14 January 2011; online 22 January 2011)

In the title compound, [Co(C₁₂H₁₃N₂O₃)₂], the Co^II ion is situated on a twofold rotation axis and is coordinated by two N and two O atoms from two symmetry-related Schiff base 2-(cyclopentyliminomethyl)-4-nitrophenolate ligands (L) in a distorted tetrahedral geometry. The cyclopentyl ring in L is disordered over two conformations in a 0.640 (19):0.360 (19) ratio.

Related literature

For background to Schiff bases and their complexes, see: Salehzadeh et al. (2010 ). For cobalt(II/III) complexes with Schiff base ligands, see: Nejo et al. (2010 ); Shahabadi et al. (2010 ). For the Schiff base complexes we have reported, see: Wei et al. (2008 ); Wang et al. (2007 ). For similar cobalt(II) complexes with Schiff bases, see: Bahron et al. (1994 ); Elerman et al. (1996 ).

Experimental

Crystal data

[Co(C₁₂H₁₃N₂O₃)₂]
M_r = 525.42
Orthorhombic, F d d d
a = 18.057 (2) Å
b = 18.792 (2) Å
c = 30.070 (4) Å
V = 10203 (2) Å³
Z = 16
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 298 K
0.17 × 0.13 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.888, T_max = 0.919
13092 measured reflections
2381 independent reflections
1143 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.182
S = 0.92
2381 reflections
196 parameters
66 restraints
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002194/cv5039sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002194/cv5039Isup2.hkl

checkCIF report

Comment top

The condensation reaction of aromatic carbaldehydes with primary amines has been shown to offer an easy and inexpensive way of forming a variety of polydentate Schiff base ligands (Salehzadeh et al., 2010). Cobalt(II/III) complexes with Schiff base ligands have been studied extensively due to their interesting structures and wide applications (Nejo et al., 2010; Shahabadi et al., 2010). As a continuation of our work on Schiff base complexes (Wei et al., 2008; Wang et al., 2007), the title mononuclear cobalt(II) complex (Fig. 1) is reported here.

The complex is located on a twofold rotational axis. The tetrahedral coordination sphere of Co^II atom in the complex is formed by two imino N atoms and two phenolate O atoms from two Schiff base ligands. The coordinate bond distances are typical and comparable with the values in other similar cobalt(II) complexes with Schiff bases (Bahron et al., 1994; Elerman et al., 1996). The coordinate bond angles are in the range 96.06 (14)–123.0 (2)°, indicating a distorted tetrahedral geometry.

Related literature top

For background to Schiff bases and their complexes, see: Salehzadeh et al. (2010). For cobalt(II/III) complexes with Schiff base ligands, see: Nejo et al. (2010); Shahabadi et al. (2010). For the Schiff base complexes we have reported, see: Wei et al. (2008); Wang et al. (2007). For similar cobalt(II) complexes with Schiff bases, see: Bahron et al. (1994); Elerman et al. (1996).

Experimental top

The title complex was obtained by stirring of 5-nitrosalicylaldehyde (0.1 mmol, 16.7 mg), cyclopentylamine (0.1 mmol, 8.5 mg), and cobalt(II) acetate (0.1 mmol, 24.9 mg) in methanol (20 ml) for 30 min at room temperature. The reaction mixture was fitered. Brown block-shaped single crystals suitable for X-ray diffraction were formed from the filtrate after a few days.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. Unlabeled atoms are related with the labeled ones by symmetry operation (3/4 - x, 7/4 - y, z). Only major parts of the disordered cyclopentyl rings are shown.

Bis[2-(cyclopentyliminomethyl)-4-nitrophenolato- κ²N²,O]cobalt(II) top

Crystal data top

[Co(C₁₂H₁₃N₂O₃)₂]	D_x = 1.368 Mg m⁻³
M_r = 525.42	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fddd	Cell parameters from 1748 reflections
a = 18.057 (2) Å	θ = 2.3–24.5°
b = 18.792 (2) Å	µ = 0.72 mm⁻¹
c = 30.070 (4) Å	T = 298 K
V = 10203 (2) Å³	Block, brown
Z = 16	0.17 × 0.13 × 0.12 mm
F(000) = 4368

Data collection top

Bruker SMART CCD area-detector diffractometer	2381 independent reflections
Radiation source: fine-focus sealed tube	1143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.099
ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −21→18
T_min = 0.888, T_max = 0.919	k = −20→22
13092 measured reflections	l = −29→36

Refinement top

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.1016P)²] where P = (F_o² + 2F_c²)/3
2381 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 0.67 e Å⁻³
66 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Co(C₁₂H₁₃N₂O₃)₂]	V = 10203 (2) Å³
M_r = 525.42	Z = 16
Orthorhombic, Fddd	Mo Kα radiation
a = 18.057 (2) Å	µ = 0.72 mm⁻¹
b = 18.792 (2) Å	T = 298 K
c = 30.070 (4) Å	0.17 × 0.13 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2381 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1143 reflections with I > 2σ(I)
T_min = 0.888, T_max = 0.919	R_int = 0.099
13092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	66 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 0.92	Δρ_max = 0.67 e Å⁻³
2381 reflections	Δρ_min = −0.29 e Å⁻³
196 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.3750	0.8750	0.69805 (4)	0.0616 (4)
N1	0.4685 (2)	0.8513 (2)	0.66652 (14)	0.0627 (11)
N2	0.5105 (3)	0.5346 (2)	0.69096 (17)	0.0724 (13)
O1	0.36714 (17)	0.78730 (16)	0.72938 (12)	0.0692 (10)
O2	0.4809 (2)	0.47999 (19)	0.70349 (16)	0.0979 (14)
O3	0.5686 (3)	0.53537 (19)	0.66859 (15)	0.0857 (12)
C1	0.4679 (3)	0.7286 (2)	0.69236 (16)	0.0532 (12)
C2	0.4045 (3)	0.7292 (2)	0.71991 (18)	0.0593 (13)
C3	0.3787 (3)	0.6643 (3)	0.73778 (18)	0.0673 (14)
H3	0.3373	0.6643	0.7562	0.081*
C4	0.4134 (3)	0.6022 (3)	0.72853 (19)	0.0686 (15)
H4	0.3952	0.5599	0.7403	0.082*
C5	0.4751 (3)	0.6013 (2)	0.70195 (18)	0.0603 (14)
C6	0.5035 (3)	0.6637 (3)	0.68422 (16)	0.0601 (13)
H6	0.5462	0.6624	0.6669	0.072*
C7	0.4979 (3)	0.7890 (2)	0.67028 (17)	0.0625 (14)
H7	0.5439	0.7829	0.6570	0.075*
C8	0.5093 (3)	0.9036 (2)	0.63903 (19)	0.0792 (18)	0.360 (19)
H8A	0.5478	0.8772	0.6231	0.095*	0.360 (19)
C9	0.4576 (10)	0.9360 (6)	0.6035 (5)	0.058 (6)	0.360 (19)
H9A	0.4097	0.9126	0.6038	0.069*	0.360 (19)
H9B	0.4790	0.9313	0.5741	0.069*	0.360 (19)
C10	0.4500 (11)	1.0153 (7)	0.6166 (8)	0.105 (8)	0.360 (19)
H10A	0.4142	1.0219	0.6402	0.127*	0.360 (19)
H10B	0.4363	1.0445	0.5913	0.127*	0.360 (19)
C11	0.5309 (11)	1.0318 (8)	0.6328 (8)	0.084 (8)	0.360 (19)
H11A	0.5651	1.0349	0.6080	0.101*	0.360 (19)
H11B	0.5329	1.0758	0.6497	0.101*	0.360 (19)
C12	0.5479 (14)	0.9666 (7)	0.6625 (8)	0.065 (8)	0.360 (19)
H12A	0.6009	0.9585	0.6645	0.078*	0.360 (19)
H12B	0.5282	0.9733	0.6922	0.078*	0.360 (19)
C8'	0.5093 (3)	0.9036 (2)	0.63903 (19)	0.0792 (18)	0.640 (19)
H8'A	0.5543	0.8822	0.6267	0.095*	0.640 (19)
C9'	0.4605 (12)	0.9347 (7)	0.6014 (6)	0.184 (12)	0.640 (19)
H9'A	0.4088	0.9361	0.6102	0.220*	0.640 (19)
H9'B	0.4651	0.9068	0.5744	0.220*	0.640 (19)
C10'	0.4914 (9)	1.0109 (6)	0.5946 (4)	0.109 (5)	0.640 (19)
H10C	0.4549	1.0420	0.5811	0.131*	0.640 (19)
H10D	0.5359	1.0106	0.5765	0.131*	0.640 (19)
C11'	0.5087 (10)	1.0337 (5)	0.6438 (4)	0.104 (6)	0.640 (19)
H11C	0.5496	1.0671	0.6444	0.124*	0.640 (19)
H11D	0.4657	1.0563	0.6569	0.124*	0.640 (19)
C12'	0.5288 (9)	0.9665 (5)	0.6696 (4)	0.075 (5)	0.640 (19)
H12C	0.5007	0.9639	0.6971	0.090*	0.640 (19)
H12D	0.5811	0.9662	0.6768	0.090*	0.640 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0590 (6)	0.0357 (5)	0.0903 (8)	0.0076 (4)	0.000	0.000
N1	0.062 (3)	0.041 (2)	0.086 (3)	0.0031 (19)	0.002 (2)	0.006 (2)
N2	0.080 (3)	0.040 (3)	0.097 (4)	0.007 (2)	−0.019 (3)	0.001 (3)
O1	0.073 (2)	0.0385 (19)	0.097 (3)	0.0136 (17)	0.015 (2)	0.0044 (17)
O2	0.100 (3)	0.038 (2)	0.155 (4)	0.007 (2)	−0.010 (3)	0.001 (2)
O3	0.097 (3)	0.060 (2)	0.100 (3)	0.026 (2)	−0.008 (3)	−0.005 (2)
C1	0.051 (3)	0.038 (3)	0.070 (3)	0.006 (2)	−0.003 (3)	−0.003 (2)
C2	0.063 (3)	0.042 (3)	0.073 (3)	0.007 (2)	−0.014 (3)	0.002 (2)
C3	0.069 (3)	0.044 (3)	0.089 (4)	0.002 (3)	0.011 (3)	0.008 (3)
C4	0.073 (4)	0.040 (3)	0.093 (4)	−0.002 (3)	−0.003 (3)	0.014 (3)
C5	0.065 (3)	0.036 (3)	0.080 (4)	0.009 (2)	−0.014 (3)	−0.002 (2)
C6	0.057 (3)	0.047 (3)	0.077 (4)	0.012 (2)	−0.008 (3)	−0.004 (2)
C7	0.055 (3)	0.044 (3)	0.088 (4)	0.003 (2)	0.007 (3)	0.002 (3)
C8	0.071 (4)	0.048 (3)	0.119 (5)	0.004 (3)	0.024 (3)	0.014 (3)
C9	0.076 (10)	0.050 (8)	0.048 (8)	−0.032 (6)	−0.013 (7)	0.022 (6)
C10	0.101 (11)	0.111 (11)	0.104 (12)	0.025 (8)	0.000 (9)	0.008 (8)
C11	0.089 (11)	0.062 (10)	0.100 (12)	0.003 (7)	0.014 (9)	−0.009 (8)
C12	0.059 (11)	0.052 (10)	0.083 (11)	−0.004 (7)	0.017 (8)	0.001 (7)
C8'	0.071 (4)	0.048 (3)	0.119 (5)	0.004 (3)	0.024 (3)	0.014 (3)
C9'	0.189 (14)	0.174 (14)	0.188 (14)	−0.040 (9)	−0.001 (9)	0.020 (9)
C10'	0.110 (8)	0.093 (7)	0.126 (9)	0.011 (6)	−0.001 (7)	0.037 (6)
C11'	0.120 (10)	0.067 (7)	0.125 (9)	−0.008 (6)	0.024 (8)	0.015 (6)
C12'	0.054 (7)	0.067 (7)	0.105 (8)	−0.022 (5)	0.003 (6)	0.011 (5)

Geometric parameters (Å, º) top

Co1—O1ⁱ	1.904 (3)	C8—H8A	0.9800
Co1—O1	1.904 (3)	C9—C10	1.548 (10)
Co1—N1ⁱ	1.987 (4)	C9—H9A	0.9700
Co1—N1	1.987 (4)	C9—H9B	0.9700
N1—C7	1.291 (5)	C10—C11	1.571 (10)
N1—C8	1.480 (6)	C10—H10A	0.9700
N2—O2	1.217 (5)	C10—H10B	0.9700
N2—O3	1.248 (6)	C11—C12	1.549 (10)
N2—C5	1.444 (6)	C11—H11A	0.9700
O1—C2	1.314 (5)	C11—H11B	0.9700
C1—C6	1.401 (6)	C12—H12A	0.9700
C1—C2	1.413 (7)	C12—H12B	0.9700
C1—C7	1.422 (6)	C9'—C10'	1.551 (9)
C2—C3	1.411 (6)	C9'—H9'A	0.9700
C3—C4	1.353 (7)	C9'—H9'B	0.9700
C3—H3	0.9300	C10'—C11'	1.569 (9)
C4—C5	1.371 (7)	C10'—H10C	0.9700
C4—H4	0.9300	C10'—H10D	0.9700
C5—C6	1.387 (7)	C11'—C12'	1.527 (8)
C6—H6	0.9300	C11'—H11C	0.9700
C7—H7	0.9300	C11'—H11D	0.9700
C8—C9	1.544 (9)	C12'—H12C	0.9700
C8—C12	1.545 (10)	C12'—H12D	0.9700

O1ⁱ—Co1—O1	120.7 (2)	C8—C9—H9A	110.8
O1ⁱ—Co1—N1ⁱ	96.06 (14)	C10—C9—H9A	110.8
O1—Co1—N1ⁱ	111.50 (16)	C8—C9—H9B	110.8
O1ⁱ—Co1—N1	111.50 (16)	C10—C9—H9B	110.8
O1—Co1—N1	96.06 (14)	H9A—C9—H9B	108.8
N1ⁱ—Co1—N1	123.0 (2)	C9—C10—C11	100.8 (10)
C7—N1—C8	116.5 (4)	C9—C10—H10A	111.6
C7—N1—Co1	120.7 (3)	C11—C10—H10A	111.6
C8—N1—Co1	122.7 (3)	C9—C10—H10B	111.6
O2—N2—O3	123.0 (5)	C11—C10—H10B	111.6
O2—N2—C5	117.9 (5)	H10A—C10—H10B	109.4
O3—N2—C5	119.1 (5)	C12—C11—C10	101.9 (10)
C2—O1—Co1	125.0 (3)	C12—C11—H11A	111.4
C6—C1—C2	118.8 (5)	C10—C11—H11A	111.4
C6—C1—C7	116.0 (5)	C12—C11—H11B	111.4
C2—C1—C7	125.1 (4)	C10—C11—H11B	111.4
O1—C2—C3	117.8 (5)	H11A—C11—H11B	109.3
O1—C2—C1	123.3 (4)	C8—C12—C11	104.7 (9)
C3—C2—C1	118.9 (4)	C8—C12—H12A	110.8
C4—C3—C2	121.0 (5)	C11—C12—H12A	110.8
C4—C3—H3	119.5	C8—C12—H12B	110.8
C2—C3—H3	119.5	C11—C12—H12B	110.8
C3—C4—C5	120.4 (5)	H12A—C12—H12B	108.9
C3—C4—H4	119.8	C10'—C9'—H9'A	111.0
C5—C4—H4	119.8	C10'—C9'—H9'B	111.0
C4—C5—C6	120.9 (4)	H9'A—C9'—H9'B	109.0
C4—C5—N2	120.3 (5)	C9'—C10'—C11'	101.5 (9)
C6—C5—N2	118.8 (5)	C9'—C10'—H10C	111.5
C5—C6—C1	120.0 (5)	C11'—C10'—H10C	111.5
C5—C6—H6	120.0	C9'—C10'—H10D	111.5
C1—C6—H6	120.0	C11'—C10'—H10D	111.5
N1—C7—C1	127.5 (5)	H10C—C10'—H10D	109.3
N1—C7—H7	116.2	C12'—C11'—C10'	107.5 (8)
C1—C7—H7	116.2	C12'—C11'—H11C	110.2
N1—C8—C9	110.3 (8)	C10'—C11'—H11C	110.2
N1—C8—C12	118.6 (11)	C12'—C11'—H11D	110.2
C9—C8—C12	106.7 (8)	C10'—C11'—H11D	110.2
N1—C8—H8A	106.9	H11C—C11'—H11D	108.5
C9—C8—H8A	106.9	C11'—C12'—H12C	110.5
C12—C8—H8A	106.9	C11'—C12'—H12D	110.5
C8—C9—C10	104.9 (8)	H12C—C12'—H12D	108.7

Symmetry code: (i) −x+3/4, −y+7/4, z.

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₁₃N₂O₃)₂]
M_r	525.42
Crystal system, space group	Orthorhombic, Fddd
Temperature (K)	298
a, b, c (Å)	18.057 (2), 18.792 (2), 30.070 (4)
V (Å³)	10203 (2)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.17 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.888, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	13092, 2381, 1143
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.182, 0.92
No. of reflections	2381
No. of parameters	196
No. of restraints	66
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.29

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Acknowledgements

We acknowledge Huainan Normal College for supporting this work.

References

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