Diaqua­bis­(1H-imidazole-4-carboxyl­ato-κ2N3,O)cobalt(II)

Artetxe, B.; San Felices, L.; Pache, A.; Reinoso, S.; Gutiérrez-Zorrilla, J.M.

doi:10.1107/S1600536813000330

metal-organic compounds

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Volume 69| Part 2| February 2013| Page m94

doi:10.1107/S1600536813000330

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Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O)cobalt(II)

Beñat Artetxe,^a Leire San Felices,^a Aroa Pache,^a Santiago Reinoso ^a and Juan M. Gutiérrez-Zorrilla ^a ^*

^aDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad de País Vasco, UPV/EHU, PO Box 644, E-48080 Bilbao, Spain
^*Correspondence e-mail: juanma.zorrilla@ehu.es

(Received 18 December 2012; accepted 4 January 2013; online 9 January 2013)

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, P c c n
a = 7.1236 (16) Å
b = 11.6305 (2) Å
c = 13.5496 (4) Å
V = 1122.6 (3) Å³
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[F² > 2σ(F²)] = 0.027
wR(F²) = 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

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) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z]$ .

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⋯O2^iv	0.85 (2)	1.98 (2)	2.812 (2)	167 (2)
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[x+{\script{1\over 2}}, -y, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813000330/zj2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000330/zj2099Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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).

Figures top

	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).

(I) top

Crystal data top

[Co(C₄H₃N₂O₂)₂(H₂O)₂]	F(000) = 644
M_r = 317.13	D_x = 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 top

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	R_int = 0.018
Detector resolution: 16.2439 pixels mm^-1	θ_max = 26.5°, θ_min = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→14
T_min = 0.947, T_max = 1.000	l = −5→17
2396 measured reflections

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)] = 0.027	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(F_o²) + (0.0201P)² + 1.0008P] where P = (F_o² + 2F_c²)/3
1162 reflections	(Δ/σ)_max < 0.001
95 parameters	Δρ_max = 0.32 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Co(C₄H₃N₂O₂)₂(H₂O)₂]	V = 1122.6 (3) Å³
M_r = 317.13	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.1236 (16) Å	µ = 1.56 mm⁻¹
b = 11.6305 (2) Å	T = 100 K
c = 13.5496 (4) Å	0.09 × 0.04 × 0.03 mm

Data collection top

Agilent SuperNova (single source at offset) diffractometer	1162 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1025 reflections with I > 2σ(I)
T_min = 0.947, T_max = 1.000	R_int = 0.018
2396 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	2 restraints
wR(F²) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.32 e Å⁻³
1162 reflections	Δρ_min = −0.25 e Å⁻³
95 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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···O2^iv	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.

Experimental details

Crystal data
Chemical formula	[Co(C₄H₃N₂O₂)₂(H₂O)₂]
M_r	317.13
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	100
a, b, c (Å)	7.1236 (16), 11.6305 (2), 13.5496 (4)
V (Å³)	1122.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.56
Crystal size (mm)	0.09 × 0.04 × 0.03

Data collection
Diffractometer	Agilent SuperNova (single source at offset) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.947, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2396, 1162, 1025
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.063, 1.08
No. of reflections	1162
No. of parameters	95
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25

Computer programs: CrysAlis PRO (Agilent, 2011), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

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

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

Symmetry code: (i) −x+3/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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.

Acknowledgements

This work was financially supported by Eusko Jaurlaritza/Gobierno Vasco (grant Nos. IT477-10 and S-PE11UN062) and the Universidad de País Vasco UPV/EHU (grant No. UFI11/53). BA and AP thank EJ/GV for their predoctoral fellowships.

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