Diaqua­bis­(1H-imidazole-4-carboxyl­ato-κ² N ³,O)cobalt(II)

Abstract

The title compound, [Co(C₄H₃N₂O₂)₂(H₂O)₂], contains a Co^II cation on a twofold rotation axis, exhibiting a distorted octa­hedral coordination geometry. The equatorial plane is formed by two N,O-bidentate 1H-imidazole-4-carboxyl­ate ligands and the axial positions are occupied by water mol­ecules. The crystal packing consists of a three-dimensional network stabilized by O—H⋯O and N—H⋯O hydrogen bonds, together with weak π–π inter­actions [centroid–centroid distance = 3.577 (2) Å] between the imidazole rings.

Related literature  

For the isostructural zinc(II) and cadmium(II) complexes, see: Yin et al. (2009 ▶); Shuai et al. (2011 ▶). For related homoleptic compounds, see: Kondo et al. (2003 ▶); Gryz et al. (2007 ▶); Zheng et al. (2011 ▶).

Experimental  

Crystal data  

• [Co(C₄H₃N₂O₂)₂(H₂O)₂]

• M _r = 317.13

• Orthorhombic,

• a = 7.1236 (16) Å

• b = 11.6305 (2) Å

• c = 13.5496 (4) Å

• V = 1122.6 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 1.56 mm⁻¹

• T = 100 K

• 0.09 × 0.04 × 0.03 mm

Data collection  

• Agilent SuperNova (single source at offset) diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.947, T _max = 1.000

• 2396 measured reflections

• 1162 independent reflections

• 1025 reflections with I > 2σ(I)

• R _int = 0.018

Refinement  

• R[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 0.063

• S = 1.08

• 1162 reflections

• 95 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Co1—N3	2.0763 (17)
Co1—O1W	2.1074 (15)
Co1—O1	2.1774 (14)

N3—Co1—N3i	97.39 (9)
N3—Co1—O1W	98.62 (6)
N3—Co1—O1	78.47 (6)
O1W—Co1—O1	83.04 (6)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ii	0.88	1.89	2.766 (2)	172
O1W—H1WA⋯O2iii	0.86 (2)	1.91 (2)	2.760 (2)	171 (3)
O1W—H1WB⋯O2iv	0.85 (2)	1.98 (2)	2.812 (2)	167 (2)

Symmetry codes: (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The title compound, [Co(C₄H₃N₂O₂)₂(H₂O)₂] crystallizes in the orthorhombic crystal system, space group Pccn, and it is isostructural with the zinc and cadmium complexes previously reported by Yin et al. (2009) and Shuai et al. (2011). As expected, the Co—O and Co—N distances (Table 1) are similar to those of the Zn^II analogue and shorter than those of the Cd^II derivative. Table 2 summarizes the geometrical parameters of the O—H···O and N—H···O hydrogen bonding interactions. The centroid-to-centroid distance between interacting imidazole rings is 3.577 (2) Å.

Experimental

To a solution of CoCl₂.6H₂O (12 mg, 0.05 mmol) in 15 ml of water 4-imidazole carboxylic acid (6 mg, 0.05 mmol) was added and the resulting solution was stirred for 30 min at room temperature. Prismatic red crystals were obtained by slow evaporation after several days. IR (cm^-1): 3148 (s), 2934 (s), 1685 (m), 1588 (vs), 1555 (vs), 1528 (s), 1462 (s), 1406 (vs), 1333 (m), 1234 (s), 1177 (m), 1101 (m), 1005 (m), 930 (m), 845 (m), 820 (m), 791 (m), 731 (w), 658 (s), 610 (m), 492 (m).

Refinement

All atoms except H were refined anisotropically. H atoms of the water molecule were located in a Fourier difference map and refined isotropically with O—H bond lengths restrained to 0.84 (2) Å. All imidazole H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N).

Figures

Fig. 1.

Molecular structure of [Co(C4H3N2O2)2(H2O)2] showing atom labelling for the asymmetric unit and 50% probability displacement ellipsoids.

Fig. 2.

View of the crystal packing along the crystallographic a axis (hydrogen bonds represented as dashed lines).

Crystal data

[Co(C4H3N2O2)2(H2O)2]	F(000) = 644
Mr = 317.13	Dx = 1.876 Mg m−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1055 reflections
a = 7.1236 (16) Å	θ = 1.8–28.1°
b = 11.6305 (2) Å	µ = 1.56 mm−1
c = 13.5496 (4) Å	T = 100 K
V = 1122.6 (3) Å3	Prism, red
Z = 4	0.09 × 0.04 × 0.03 mm

Data collection

Agilent SuperNova (single source at offset) diffractometer	1162 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1025 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 16.2439 pixels mm-1	θmax = 26.5°, θmin = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→14
Tmin = 0.947, Tmax = 1.000	l = −5→17
2396 measured reflections

Refinement

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)] = 0.027	Hydrogen site location: difference Fourier map
wR(F2) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0201P)2 + 1.0008P] where P = (Fo2 + 2Fc2)/3
1162 reflections	(Δ/σ)max < 0.001
95 parameters	Δρmax = 0.32 e Å−3
2 restraints	Δρmin = −0.25 e Å−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.75	0.25	0.13009 (3)	0.00874 (13)
O1W	0.8972 (2)	0.09575 (13)	0.15593 (11)	0.0140 (3)
O1	0.54278 (18)	0.17114 (12)	0.22690 (10)	0.0120 (3)
O2	0.26134 (18)	0.08371 (12)	0.22474 (10)	0.0113 (3)
N3	0.5553 (2)	0.18870 (15)	0.02894 (12)	0.0107 (4)
N1	0.3584 (2)	0.12877 (15)	−0.08496 (13)	0.0125 (4)
H1	0.3094	0.1157	−0.1435	0.015*
C4	0.4058 (3)	0.13338 (17)	0.07356 (15)	0.0098 (4)
C6	0.4028 (3)	0.12899 (16)	0.18291 (15)	0.0096 (4)
C5	0.2836 (3)	0.09571 (18)	0.00325 (15)	0.0118 (4)
H5	0.1697	0.0549	0.0136	0.014*
C2	0.5204 (3)	0.18489 (18)	−0.06678 (15)	0.0123 (4)
H2	0.5989	0.2173	−0.1162	0.015*
H1WA	1.007 (3)	0.099 (3)	0.180 (2)	0.047 (9)*
H1WB	0.847 (4)	0.050 (2)	0.1974 (17)	0.039 (9)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0080 (2)	0.0098 (2)	0.0084 (2)	−0.00165 (15)	0	0
O1W	0.0110 (8)	0.0146 (8)	0.0163 (8)	−0.0018 (6)	−0.0014 (7)	0.0039 (7)
O1	0.0102 (7)	0.0140 (7)	0.0116 (7)	−0.0016 (6)	−0.0011 (6)	−0.0008 (6)
O2	0.0087 (7)	0.0137 (7)	0.0116 (7)	−0.0007 (6)	0.0021 (6)	0.0019 (6)
N3	0.0095 (8)	0.0111 (9)	0.0115 (8)	−0.0003 (7)	0.0013 (7)	0.0009 (7)
N1	0.0130 (9)	0.0151 (9)	0.0094 (8)	−0.0007 (7)	−0.0031 (7)	−0.0005 (7)
C4	0.0101 (10)	0.0072 (10)	0.0120 (10)	0.0000 (8)	0.0007 (8)	0.0006 (8)
C6	0.0105 (10)	0.0071 (9)	0.0113 (10)	0.0041 (8)	0.0009 (8)	0.0000 (8)
C5	0.0122 (10)	0.0113 (10)	0.0118 (9)	−0.0007 (8)	0.0012 (9)	0.0001 (9)
C2	0.0121 (10)	0.0137 (11)	0.0111 (10)	−0.0008 (8)	0.0005 (8)	0.0009 (9)

Geometric parameters (Å, º)

Co1—N3	2.0763 (17)	N3—C2	1.321 (3)
Co1—N3i	2.0763 (17)	N3—C4	1.383 (2)
Co1—O1Wi	2.1074 (15)	N1—C2	1.349 (3)
Co1—O1W	2.1074 (15)	N1—C5	1.364 (3)
Co1—O1i	2.1774 (14)	N1—H1	0.88
Co1—O1	2.1774 (14)	C4—C5	1.363 (3)
O1W—H1WA	0.849 (17)	C4—C6	1.483 (3)
O1W—H1WB	0.853 (17)	C5—H5	0.95
O1—C6	1.261 (2)	C2—H2	0.95
O2—C6	1.271 (2)
N3—Co1—N3i	97.39 (9)	C2—N3—C4	105.60 (17)
N3—Co1—O1Wi	93.98 (6)	C2—N3—Co1	141.72 (15)
N3i—Co1—O1Wi	98.62 (6)	C4—N3—Co1	112.67 (13)
N3—Co1—O1W	98.62 (6)	C2—N1—C5	108.11 (17)
N3i—Co1—O1W	93.98 (6)	C2—N1—H1	125.9
O1Wi—Co1—O1W	160.87 (9)	C5—N1—H1	125.9
N3—Co1—O1i	174.42 (6)	C5—C4—N3	109.62 (18)
N3i—Co1—O1i	78.47 (6)	C5—C4—C6	132.70 (18)
O1Wi—Co1—O1i	83.04 (6)	N3—C4—C6	117.64 (17)
O1W—Co1—O1i	85.47 (6)	O1—C6—O2	125.27 (18)
N3—Co1—O1	78.47 (6)	O1—C6—C4	116.60 (17)
N3i—Co1—O1	174.42 (6)	O2—C6—C4	118.13 (17)
O1Wi—Co1—O1	85.47 (6)	C4—C5—N1	105.79 (17)
O1W—Co1—O1	83.04 (6)	C4—C5—H5	127.1
O1i—Co1—O1	105.91 (7)	N1—C5—H5	127.1
Co1—O1W—H1WA	119 (2)	N3—C2—N1	110.87 (18)
Co1—O1W—H1WB	115.7 (19)	N3—C2—H2	124.6
H1WA—O1W—H1WB	100 (3)	N1—C2—H2	124.6
C6—O1—Co1	114.52 (12)
N3—Co1—O1—C6	−1.93 (13)	Co1—N3—C4—C5	179.84 (13)
N3i—Co1—O1—C6	−44.3 (6)	C2—N3—C4—C6	−177.35 (18)
O1Wi—Co1—O1—C6	93.08 (13)	Co1—N3—C4—C6	1.8 (2)
O1W—Co1—O1—C6	−102.24 (13)	Co1—O1—C6—O2	−176.57 (15)
O1i—Co1—O1—C6	174.51 (15)	Co1—O1—C6—C4	3.4 (2)
N3i—Co1—N3—C2	−5.2 (2)	C5—C4—C6—O1	178.9 (2)
O1Wi—Co1—N3—C2	94.1 (2)	N3—C4—C6—O1	−3.6 (3)
O1W—Co1—N3—C2	−100.4 (2)	C5—C4—C6—O2	−1.1 (3)
O1i—Co1—N3—C2	36.6 (7)	N3—C4—C6—O2	176.37 (17)
O1—Co1—N3—C2	178.6 (2)	N3—C4—C5—N1	−0.3 (2)
N3i—Co1—N3—C4	176.15 (16)	C6—C4—C5—N1	177.4 (2)
O1Wi—Co1—N3—C4	−84.61 (14)	C2—N1—C5—C4	−0.2 (2)
O1W—Co1—N3—C4	80.96 (14)	C4—N3—C2—N1	−0.8 (2)
O1i—Co1—N3—C4	−142.1 (6)	Co1—N3—C2—N1	−179.56 (16)
O1—Co1—N3—C4	−0.06 (13)	C5—N1—C2—N3	0.7 (2)
C2—N3—C4—C5	0.7 (2)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ii	0.88	1.89	2.766 (2)	172
O1W—H1WA···O2iii	0.86 (2)	1.91 (2)	2.760 (2)	171 (3)
O1W—H1WB···O2iv	0.85 (2)	1.98 (2)	2.812 (2)	167 (2)

Symmetry codes: (ii) −x+1/2, y, z−1/2; (iii) x+1, y, z; (iv) x+1/2, −y, −z+1/2.