Diaqua­bis­(5-methyl-1,2-oxazole-3-car­box­yl­ato-κ2N,O3)cobalt(II) dihydrate

Wang, Y.; Zhao, J.

doi:10.1107/S1600536811053414

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m69

doi:10.1107/S1600536811053414

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Diaquabis(5-methyl-1,2-oxazole-3-carboxylato-κ²N,O³)cobalt(II) dihydrate

Yan Wang ^a ^* and Jing Zhao ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 3 December 2011; accepted 12 December 2011; online 21 December 2011)

In the title compound, [Co(C₅H₄NO₃)₂(H₂O)₂]·2H₂O, the coordination polyhedron around the six-coordinate Co^II ion is formed by two equatorial 5-methylisoxazole-3-carboxylate ligands in an N,O³-bidentate fashion through the isoxazole N atom and a carboxylate O atom, and by two axial water ligands. The asymmetric unit consists of half of the complex and one water molecule (the full comlex being completed by application of inversion). In the crystal, the water molecules participate in the formation of an intricate three-dimensional network of hydrogen bonds involving the coordinated water molecule and the carboxylate groups.

Related literature

For a related structure, see: Luo et al. (2011 ).

Experimental

Crystal data

[Co(C₅H₄NO₃)₂(H₂O)₂]·2H₂O
M_r = 383.18
Monoclinic, P 2₁ /n
a = 5.260 (3) Å
b = 18.528 (10) Å
c = 8.077 (4) Å
β = 103.707 (6)°
V = 764.9 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.983, T_max = 0.983
5217 measured reflections
1344 independent reflections
1202 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.078
S = 1.06
1344 reflections
123 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱ	0.83 (5)	2.07 (5)	2.890 (3)	172 (4)
O4—H4B⋯O1ⁱⁱ	0.83 (4)	2.03 (4)	2.853 (3)	172 (3)
O3—H3B⋯O2ⁱⁱ	0.82 (4)	2.07 (4)	2.852 (3)	161 (3)
O3—H3A⋯O4	0.76 (3)	1.95 (3)	2.696 (3)	167 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053414/vm2142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053414/vm2142Isup2.hkl

checkCIF report

Comment top

Isoxazole derivatives are versatile ligands towards transition metal ions both in man-made and natural systems. They are not only used as (bio)catalysts but also for dioxygen transport and electron storage (Luo et al., 2011). As part of our interest in isoxazole derivatives, we report here the crystal structure of a new cobalt complex.

The molecular structure of the title compound is shown in Fig. 1. All non-H atoms, except O3 and O4, are located in the same plane with an r.m.s. deviation of 0.0247 Å.

The coordination polyhedron around the six coordinated central Co^II ion is described as a octahedron, formed by two equatorial 5-methylisoxazole-3-carboxylates in an O, N bidentate fashion through the isoxazole nitrogen and the carboxylate oxygen atoms and by two axial water ligands.

The title compound forms a three-dimensional structure via intermolecular O—H···O hydrogen bonds interactions (Table 1, Fig. 2).

Related literature top

For a related structure, see: Luo et al. (2011).

Experimental top

0.06 g CoCl₂.6H₂O (mg) was added to a methanol solution of 0.06 g 5-methyl-3-isoxazolecarboxylic acid and stirred for three h at room temperature. The resulting solution was filtered off and allowed to evaporate at room temperature. Pillar pink crystals of the title compound were obtained within 3 days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Symmetry code: (A) -x+1, -y, -z+1.
	Fig. 2. A packing view down the a axis showing the three dimensional network. Intermolecular hydrogen bonds are shown as dashed lines.

Diaquabis(5-methyl-1,2-oxazole-3-carboxylato- κ²N,O³)cobalt(II) dihydrate top

Crystal data top

[Co(C₅H₄NO₃)₂(H₂O)₂]·2H₂O	F(000) = 394
M_r = 383.18	D_x = 1.664 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1344 reflections
a = 5.260 (3) Å	θ = 2.2–25.0°
b = 18.528 (10) Å	µ = 1.18 mm⁻¹
c = 8.077 (4) Å	T = 296 K
β = 103.707 (6)°	Pillar, pink
V = 764.9 (7) Å³	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	1344 independent reflections
Radiation source: fine-focus sealed tube	1202 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
CCD_Profile_fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −22→22
T_min = 0.983, T_max = 0.983	l = −9→9
5217 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0428P)² + 0.2614P] where P = (F_o² + 2F_c²)/3
1344 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Co(C₅H₄NO₃)₂(H₂O)₂]·2H₂O	V = 764.9 (7) Å³
M_r = 383.18	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.260 (3) Å	µ = 1.18 mm⁻¹
b = 18.528 (10) Å	T = 296 K
c = 8.077 (4) Å	0.20 × 0.20 × 0.20 mm
β = 103.707 (6)°

Data collection top

Rigaku SCXmini diffractometer	1344 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1202 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.983	R_int = 0.034
5217 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.28 e Å⁻³
1344 reflections	Δρ_min = −0.38 e Å⁻³
123 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
Co1	0.5000	0.0000	0.5000	0.02592 (16)
O1	0.8288 (3)	0.18878 (7)	0.38174 (19)	0.0361 (4)
O5	0.0881 (3)	0.06221 (8)	0.16193 (19)	0.0345 (4)
O2	0.7638 (3)	0.08451 (7)	0.50526 (17)	0.0293 (3)
N1	0.3171 (3)	0.06356 (9)	0.2896 (2)	0.0312 (4)
O3	0.3032 (4)	0.05798 (10)	0.6557 (2)	0.0369 (4)
C5	0.6992 (4)	0.13440 (10)	0.3955 (3)	0.0266 (4)
C4	0.4387 (4)	0.12311 (10)	0.2705 (3)	0.0270 (4)
C3	0.2957 (4)	0.16322 (12)	0.1325 (3)	0.0330 (5)
H3	0.3393	0.2077	0.0937	0.040*
C1	−0.1485 (5)	0.13125 (15)	−0.0775 (3)	0.0462 (6)
H1A	−0.1458	0.1782	−0.1275	0.069*
H1B	−0.3060	0.1259	−0.0382	0.069*
H1C	−0.1427	0.0949	−0.1612	0.069*
C2	0.0819 (4)	0.12328 (12)	0.0685 (3)	0.0313 (5)
O4	0.3191 (4)	0.20264 (10)	0.6234 (3)	0.0511 (5)
H3A	0.332 (6)	0.0981 (18)	0.655 (4)	0.051 (9)*
H3B	0.144 (8)	0.0564 (18)	0.623 (5)	0.081 (12)*
H4B	0.175 (8)	0.2028 (19)	0.555 (5)	0.080 (12)*
H4A	0.309 (7)	0.232 (2)	0.698 (5)	0.093 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0265 (2)	0.0213 (2)	0.0275 (3)	−0.00130 (14)	0.00157 (17)	0.00343 (14)
O1	0.0380 (8)	0.0292 (8)	0.0374 (9)	−0.0093 (6)	0.0014 (7)	0.0050 (7)
O5	0.0321 (8)	0.0325 (8)	0.0324 (8)	−0.0032 (6)	−0.0051 (6)	0.0006 (6)
O2	0.0287 (7)	0.0267 (7)	0.0290 (8)	−0.0024 (6)	−0.0002 (6)	0.0046 (6)
N1	0.0300 (9)	0.0284 (9)	0.0301 (10)	−0.0019 (7)	−0.0030 (7)	0.0033 (7)
O3	0.0360 (10)	0.0318 (10)	0.0424 (10)	0.0002 (7)	0.0082 (7)	−0.0041 (7)
C5	0.0281 (10)	0.0244 (10)	0.0269 (11)	−0.0005 (8)	0.0059 (8)	−0.0007 (8)
C4	0.0297 (10)	0.0254 (10)	0.0252 (11)	−0.0006 (8)	0.0052 (8)	0.0007 (8)
C3	0.0374 (11)	0.0294 (11)	0.0305 (11)	0.0014 (9)	0.0048 (9)	0.0085 (9)
C1	0.0409 (13)	0.0579 (16)	0.0329 (13)	0.0074 (11)	−0.0051 (10)	0.0006 (11)
C2	0.0344 (11)	0.0343 (11)	0.0234 (11)	0.0064 (9)	0.0031 (9)	0.0012 (9)
O4	0.0483 (11)	0.0376 (10)	0.0598 (12)	0.0073 (8)	−0.0024 (9)	−0.0118 (9)

Geometric parameters (Å, º) top

Co1—O2ⁱ	2.0860 (16)	O3—H3B	0.82 (4)
Co1—O2	2.0860 (16)	C5—C4	1.512 (3)
Co1—N1ⁱ	2.1035 (18)	C4—C3	1.401 (3)
Co1—N1	2.1035 (18)	C3—C2	1.343 (3)
Co1—O3ⁱ	2.1038 (18)	C3—H3	0.9300
Co1—O3	2.1038 (18)	C1—C2	1.485 (3)
O1—C5	1.236 (2)	C1—H1A	0.9600
O5—C2	1.356 (3)	C1—H1B	0.9600
O5—N1	1.388 (2)	C1—H1C	0.9600
O2—C5	1.270 (2)	O4—H4B	0.83 (4)
N1—C4	1.303 (3)	O4—H4A	0.83 (5)
O3—H3A	0.76 (3)

O2ⁱ—Co1—O2	180.00 (5)	Co1—O3—H3B	113 (3)
O2ⁱ—Co1—N1ⁱ	76.76 (6)	H3A—O3—H3B	103 (3)
O2—Co1—N1ⁱ	103.24 (6)	O1—C5—O2	126.42 (19)
O2ⁱ—Co1—N1	103.24 (6)	O1—C5—C4	119.00 (17)
O2—Co1—N1	76.76 (6)	O2—C5—C4	114.57 (16)
N1ⁱ—Co1—N1	180.0	N1—C4—C3	110.96 (18)
O2ⁱ—Co1—O3ⁱ	91.37 (8)	N1—C4—C5	115.51 (17)
O2—Co1—O3ⁱ	88.63 (8)	C3—C4—C5	133.53 (18)
N1ⁱ—Co1—O3ⁱ	90.08 (8)	C2—C3—C4	104.87 (19)
N1—Co1—O3ⁱ	89.92 (8)	C2—C3—H3	127.6
O2ⁱ—Co1—O3	88.63 (8)	C4—C3—H3	127.6
O2—Co1—O3	91.37 (8)	C2—C1—H1A	109.5
N1ⁱ—Co1—O3	89.92 (8)	C2—C1—H1B	109.5
N1—Co1—O3	90.08 (8)	H1A—C1—H1B	109.5
O3ⁱ—Co1—O3	180.00 (7)	C2—C1—H1C	109.5
C2—O5—N1	107.48 (15)	H1A—C1—H1C	109.5
C5—O2—Co1	117.73 (12)	H1B—C1—H1C	109.5
C4—N1—O5	106.92 (16)	C3—C2—O5	109.77 (18)
C4—N1—Co1	115.26 (13)	C3—C2—C1	134.6 (2)
O5—N1—Co1	137.76 (13)	O5—C2—C1	115.60 (19)
Co1—O3—H3A	112 (2)	H4B—O4—H4A	106 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱⁱ	0.83 (5)	2.07 (5)	2.890 (3)	172 (4)
O4—H4B···O1ⁱⁱⁱ	0.83 (4)	2.03 (4)	2.853 (3)	172 (3)
O3—H3B···O2ⁱⁱⁱ	0.82 (4)	2.07 (4)	2.852 (3)	161 (3)
O3—H3A···O4	0.76 (3)	1.95 (3)	2.696 (3)	167 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(C₅H₄NO₃)₂(H₂O)₂]·2H₂O
M_r	383.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.260 (3), 18.528 (10), 8.077 (4)
β (°)	103.707 (6)
V (Å³)	764.9 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.983, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	5217, 1344, 1202
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.078, 1.06
No. of reflections	1344
No. of parameters	123
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.38

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.83 (5)	2.07 (5)	2.890 (3)	172 (4)
O4—H4B···O1ⁱⁱ	0.83 (4)	2.03 (4)	2.853 (3)	172 (3)
O3—H3B···O2ⁱⁱ	0.82 (4)	2.07 (4)	2.852 (3)	161 (3)
O3—H3A···O4	0.76 (3)	1.95 (3)	2.696 (3)	167 (3)

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

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Luo, Y.-H., Qian, X.-M., Gao, G., Li, J.-F. & Mao, S.-L. (2011). Acta Cryst. E67, m172. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar