Diaqua-bis(5-carb-oxy-1H-pyrazole-3-carboxyl-ato-κN,O)cobalt(II) dihydrate.

In the title complex, [Co(C(5)H(3)N(2)O(4))(2)(H(2)O)(2)]·2H(2)O, the Co(II) ion lies on an inversion center and is coordinated in a distorted octa-hedral environment. In the crystal structure, complex and water mol-ecules are linked into a three-dimensional network by O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For a mononuclear zinc(II) complex with a pyrazole-3,5-dicarboxyl­ato ligand, see: Xie et al. (2006 ▶) and for a cobalt(III) complex with a 5-carb­oxy-1H-pyrazole-3-carboxyl­ato ligand, see: Xie et al. (2007 ▶). The 3,5-pyrazole­dicarboxylic acid ligand is asymmetric and has six potential coordination sites which can act to link together metal centers through a number of bridging modes, see: King et al. (2004 ▶). A variety of complexes containing this ligand have been reported, see: Frisch & Cahill (2005 ▶); King et al. (2003 ▶, 2004 ▶); Li et al. (2005 ▶); Pan, Ching et al. (2001 ▶); Pan, Frydel et al. (2001 ▶).

Experimental

Crystal data

[Co(C5H3N2O4)2(H2O)2]·2H2O

M = 441.18

Monoclinic,

a = 10.030 (3) Å

b = 12.483 (4) Å

c = 6.827 (2) Å

β = 108.641 (4)°

V = 809.9 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.14 mm−1

T = 291 K

0.32 × 0.27 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.713, T max = 0.854

5748 measured reflections

1502 independent reflections

1331 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.142

S = 1.12

1502 reflections

129 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.84 e Å−3

Δρmin = −0.44 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029456/lh2869sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029456/lh2869Isup2.hkl

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

[Co(C5H3N2O4)2(H2O)2]·2H2O	F(000) = 450
Mr = 441.18	Dx = 1.809 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2747 reflections
a = 10.030 (3) Å	θ = 2.7–27.9°
b = 12.483 (4) Å	µ = 1.14 mm−1
c = 6.827 (2) Å	T = 291 K
β = 108.641 (4)°	Block, orange
V = 809.9 (5) Å3	0.32 × 0.27 × 0.14 mm
Z = 2

Bruker SMART CCD diffractometer	1502 independent reflections
Radiation source: fine-focus sealed tube	1331 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.713, Tmax = 0.854	k = −15→15
5748 measured reflections	l = −8→8

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0775P)2 + 1.4115P] where P = (Fo2 + 2Fc2)/3
1502 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.84 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co1	0.5000	1.0000	0.0000	0.0227 (3)
O1	0.5183 (3)	0.8358 (2)	−0.0667 (5)	0.0308 (6)
O2	0.6657 (3)	0.6977 (2)	−0.0142 (5)	0.0337 (7)
O3	1.1998 (3)	0.9569 (3)	0.3134 (5)	0.0408 (8)
O4	1.0960 (3)	1.1105 (2)	0.3529 (5)	0.0366 (7)
H4	1.1772	1.1324	0.3977	0.055*
O5	0.4797 (3)	0.9554 (3)	0.2803 (5)	0.0378 (7)
H1W	0.4031	0.9594	0.3020	0.045*
H2W	0.5296	0.9069	0.3484	0.045*
O6	0.7621 (4)	0.2301 (3)	0.2670 (8)	0.0684 (13)
H3W	0.7617	0.2926	0.3116	0.082*
N1	0.7187 (3)	0.9727 (3)	0.1137 (5)	0.0238 (7)
N2	0.8371 (3)	1.0290 (2)	0.1925 (5)	0.0237 (7)
H2	0.8402	1.0958	0.2251	0.028*
C1	0.6402 (4)	0.7957 (3)	−0.0049 (6)	0.0239 (8)
C2	0.7586 (4)	0.8723 (3)	0.0850 (6)	0.0232 (7)
C3	0.9054 (4)	0.8646 (3)	0.1462 (6)	0.0255 (8)
H3	0.9595	0.8047	0.1422	0.031*
C4	0.9519 (4)	0.9668 (3)	0.2143 (6)	0.0246 (8)
C5	1.0964 (4)	1.0103 (3)	0.2981 (6)	0.0264 (8)
H4W	0.678 (12)	0.232 (9)	0.182 (18)	0.19 (4)*

	U11	U22	U33	U12	U13	U23
Co1	0.0135 (4)	0.0169 (4)	0.0356 (4)	0.0024 (2)	0.0049 (3)	0.0001 (3)
O1	0.0156 (13)	0.0203 (13)	0.0522 (17)	0.0011 (10)	0.0046 (11)	−0.0035 (12)
O2	0.0203 (14)	0.0210 (14)	0.0535 (18)	0.0006 (10)	0.0031 (12)	−0.0062 (12)
O3	0.0198 (15)	0.0342 (16)	0.066 (2)	0.0006 (12)	0.0106 (14)	−0.0041 (15)
O4	0.0207 (14)	0.0269 (15)	0.0568 (19)	−0.0042 (11)	0.0048 (13)	−0.0063 (13)
O5	0.0292 (16)	0.0418 (17)	0.0443 (16)	0.0129 (13)	0.0143 (13)	0.0130 (14)
O6	0.041 (2)	0.0318 (19)	0.124 (4)	0.0026 (15)	0.014 (2)	−0.010 (2)
N1	0.0136 (15)	0.0210 (15)	0.0344 (17)	0.0010 (12)	0.0041 (12)	−0.0024 (12)
N2	0.0159 (15)	0.0154 (14)	0.0379 (17)	−0.0022 (12)	0.0059 (13)	−0.0025 (13)
C1	0.0170 (17)	0.0197 (18)	0.0327 (19)	−0.0005 (14)	0.0047 (15)	−0.0014 (14)
C2	0.0167 (17)	0.0185 (17)	0.0329 (19)	−0.0012 (14)	0.0056 (15)	−0.0014 (14)
C3	0.0171 (17)	0.0183 (18)	0.039 (2)	0.0018 (13)	0.0066 (15)	−0.0005 (15)
C4	0.0154 (17)	0.0236 (18)	0.0336 (19)	0.0010 (14)	0.0064 (14)	0.0008 (15)
C5	0.0205 (19)	0.0238 (19)	0.033 (2)	−0.0021 (14)	0.0065 (16)	0.0010 (15)

Co1—O5i	2.065 (3)	O5—H2W	0.8277
Co1—O5	2.065 (3)	O6—H3W	0.8380
Co1—N1	2.108 (3)	O6—H4W	0.85 (11)
Co1—N1i	2.108 (3)	N1—N2	1.336 (4)
Co1—O1i	2.120 (3)	N1—C2	1.349 (5)
Co1—O1	2.120 (3)	N2—C4	1.358 (5)
O1—C1	1.262 (5)	N2—H2	0.8600
O2—C1	1.256 (5)	C1—C2	1.495 (5)
O3—C5	1.209 (5)	C2—C3	1.400 (5)
O4—C5	1.306 (5)	C3—C4	1.386 (5)
O4—H4	0.8200	C3—H3	0.9300
O5—H1W	0.8288	C4—C5	1.481 (5)
O5i—Co1—O5	180	N2—N1—C2	106.3 (3)
O5i—Co1—N1	89.16 (12)	N2—N1—Co1	138.6 (3)
O5—Co1—N1	90.84 (12)	C2—N1—Co1	114.8 (2)
O5i—Co1—N1i	90.84 (12)	N1—N2—C4	110.9 (3)
O5—Co1—N1i	89.16 (12)	N1—N2—H2	124.6
N1—Co1—N1i	180	C4—N2—H2	124.6
O5i—Co1—O1i	88.82 (12)	O2—C1—O1	124.1 (3)
O5—Co1—O1i	91.18 (12)	O2—C1—C2	119.7 (3)
N1—Co1—O1i	103.22 (11)	O1—C1—C2	116.2 (3)
N1i—Co1—O1i	76.78 (11)	N1—C2—C3	110.7 (3)
O5i—Co1—O1	91.18 (12)	N1—C2—C1	114.8 (3)
O5—Co1—O1	88.82 (12)	C3—C2—C1	134.5 (3)
N1—Co1—O1	76.78 (11)	C4—C3—C2	104.3 (3)
N1i—Co1—O1	103.22 (11)	C4—C3—H3	127.9
O1i—Co1—O1	180	C2—C3—H3	127.9
C1—O1—Co1	116.9 (2)	N2—C4—C3	107.9 (3)
C5—O4—H4	109.5	N2—C4—C5	121.6 (3)
Co1—O5—H1W	121.4	C3—C4—C5	130.6 (3)
Co1—O5—H2W	119.8	O3—C5—O4	125.8 (4)
H1W—O5—H2W	111.9	O3—C5—C4	122.5 (3)
H3W—O6—H4W	95.7	O4—C5—C4	111.7 (3)
O5i—Co1—O1—C1	92.3 (3)	Co1—N1—C2—C3	174.1 (3)
O5—Co1—O1—C1	−87.7 (3)	N2—N1—C2—C1	−179.5 (3)
N1—Co1—O1—C1	3.4 (3)	Co1—N1—C2—C1	−5.3 (4)
N1i—Co1—O1—C1	−176.6 (3)	O2—C1—C2—N1	−171.3 (4)
O5i—Co1—N1—N2	81.6 (4)	O1—C1—C2—N1	8.3 (5)
O5—Co1—N1—N2	−98.4 (4)	O2—C1—C2—C3	9.5 (7)
O1i—Co1—N1—N2	−6.9 (4)	O1—C1—C2—C3	−170.8 (4)
O1—Co1—N1—N2	173.1 (4)	N1—C2—C3—C4	0.1 (4)
O5i—Co1—N1—C2	−90.0 (3)	C1—C2—C3—C4	179.3 (4)
O5—Co1—N1—C2	90.0 (3)	N1—N2—C4—C3	−0.1 (4)
O1i—Co1—N1—C2	−178.6 (3)	N1—N2—C4—C5	179.8 (3)
O1—Co1—N1—C2	1.4 (3)	C2—C3—C4—N2	0.0 (4)
C2—N1—N2—C4	0.2 (4)	C2—C3—C4—C5	−179.9 (4)
Co1—N1—N2—C4	−171.9 (3)	N2—C4—C5—O3	−178.0 (4)
Co1—O1—C1—O2	172.5 (3)	C3—C4—C5—O3	1.9 (7)
Co1—O1—C1—C2	−7.2 (4)	N2—C4—C5—O4	2.7 (5)
N2—N1—C2—C3	−0.2 (4)	C3—C4—C5—O4	−177.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ii	0.82	1.73	2.535 (4)	169
O5—H1W···O3iii	0.83	2.07	2.887 (4)	171
O5—H2W···O2iv	0.83	1.91	2.726 (4)	171
O6—H4W···O1v	0.85 (11)	2.06 (11)	2.828 (5)	149 (10)
O6—H3W···O3vi	0.84	2.30	2.932 (5)	132
N2—H2···O6vii	0.86	1.91	2.714 (5)	155

Co1—O5	2.065 (3)
Co1—N1	2.108 (3)
Co1—O1	2.120 (3)
O1—C1	1.262 (5)
O2—C1	1.256 (5)

O5i—Co1—O5	180
O5—Co1—N1	90.84 (12)
O5—Co1—N1i	89.16 (12)
N1—Co1—N1i	180
O5—Co1—O1i	91.18 (12)
N1—Co1—O1i	103.22 (11)
O5—Co1—O1	88.82 (12)
N1—Co1—O1	76.78 (11)
O1i—Co1—O1	180

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ii	0.82	1.73	2.535 (4)	169
O5—H1W⋯O3iii	0.83	2.07	2.887 (4)	171
O5—H2W⋯O2iv	0.83	1.91	2.726 (4)	171
O6—H4W⋯O1v	0.85 (11)	2.06 (11)	2.828 (5)	149 (10)
O6—H3W⋯O3vi	0.84	2.30	2.932 (5)	132
N2—H2⋯O6vii	0.86	1.91	2.714 (5)	155

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .