Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl-κN²)picolinato-κ²N,O]cobalt(II) 2.5-hydrate

In the title compound, [Co(C₁₁H₉ClN₃O₂)₂]·2.5H₂O, the Co^II atom, which lies on a twofold rotation axis, is coordinated by four N atoms and two O atoms from two ligands in a distorted octa­hedral geometry. In the crystal structure, mol­ecules are linked together by inter­molecular O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• R factor = 0.041
• wR factor = 0.130
• Data-to-parameter ratio = 13.2

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S1. Comment

In recent years, there has been an increasing interest in the coordination chemistry due to the increased recognition of it's role in catalysis enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). We report here the crystal structure of a new cobalt(II) complex with the ligand 6-(3-chloro- (3,5-dimethyl-1H-pyrazol-1-yl)) picolinic acid(CDPA).(I) (Fig.1).

The title compound, (I), consists of a central mononuclear cobalt(II) complex together with two uncoordinated water molecules. The Co atom is coordinated by four N atoms and two O atoms from the two CDPA ligands. The Co^II atom is a slightly distorted octahedral environment. The Co—O bond length is 2.090 (2) Å, The Co—N distances range from 2.071 (2) to 2.129 (3) Å, i.e. normal values. The C1—C2 bond length is 1.529 (5) Å, being in the normal C—C ranges in cobalt carboxylate complexes.The angles around Co^II atom are from 74.49 (10) to 167.64 (15)°. The CDPA molecule acts as a bidentate ligand.

In the title compound, the oxygen atoms contribute to the formation of intermolecular hydrogen bonds involving water O3w atom, as well as carboxyl O2 atom and carboxyl O1 atom (Table 2).

Related literature

For related literature, see: Bhatia et al. (1981); Costamagna et al. (1992).

S2. Experimental

3-Chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid, and CoCl₂. 6H₂O were available commercially and were used without further purification. Equimolar 6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinic acid (1 mmol, 217 mg) was dissolved in anhydrous alcohol (15 ml). The mixture was stirred to give a clear solution, To this solution was added CoCl₂.6H₂O (0.5 mmol, 119 mg) in anhydrous alcohol (10 ml). After keeping the resulting solution in air to evaporate about half of the solvents, dark red prisms of the title compound were formed. The crystals were isolated, washed with alcohol three times and dried in a vacuum desiccator using silica gel (Yield 75%). Elemental analysis: found: C, 53.708; H, 4.20; N, 17.04; O, 13.22; calc. for C₂₂H₂₀Co_N6_O4: C, 53.78; H, 4.10; N, 17.10; O, 13.02

S3. Refinement

All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with N—H and C—H distances of 0.90 Å and 0.96 Å, respectively. They were treated as riding atoms, with U_iso(H) = 1.2U_eq(C), U_iso(H) = 1.2U_eq(N) and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The structure of the title compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of (I) showing the hydrogen bonded interactions as dashed lines.

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl-κN²)picolinato- κ²N,O]cobalt(II) 2.5-hydrate

Crystal data

[Co(C11H9ClN3O2)2]·2.5H2O	F(000) = 1240
Mr = 605.29	Dx = 1.532 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3006 reflections
a = 20.207 (3) Å	θ = 2.2–28.0°
b = 11.7918 (13) Å	µ = 0.91 mm^−1
c = 14.3531 (16) Å	T = 293 K
β = 129.875 (2)°	Block, red
V = 2624.6 (5) Å^3	0.52 × 0.39 × 0.37 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2305 independent reflections
Radiation source: fine-focus sealed tube	1847 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→23
Tmin = 0.649, Tmax = 0.730	k = −14→9
6384 measured reflections	l = −16→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0624P)^2 + 4.5881P] where P = (Fo^2 + 2Fc^2)/3
2305 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.0000	0.88230 (5)	0.2500	0.0405 (2)
Cl1	0.25684 (7)	0.64296 (9)	0.28440 (10)	0.0700 (3)
N1	0.12695 (15)	0.8634 (2)	0.3226 (2)	0.0400 (6)
N2	0.15784 (15)	1.0115 (2)	0.4471 (2)	0.0435 (6)
N3	0.06995 (15)	1.0112 (2)	0.3844 (2)	0.0450 (7)
O1	−0.00805 (14)	0.7608 (2)	0.1370 (2)	0.0584 (7)
O2	0.0689 (2)	0.6276 (3)	0.1374 (4)	0.0981 (12)
O3	0.0520 (3)	0.4551 (4)	0.4323 (5)	0.160 (2)
H3A	0.0156	0.5085	0.4053	0.192*
H3B	0.0605	0.4261	0.4934	0.192*
O4	0.0000	0.3204 (11)	0.2500	0.118 (4)	0.50
H4A	0.0167	0.3626	0.3096	0.142*	0.50
C1	0.0613 (2)	0.7152 (3)	0.1753 (3)	0.0539 (9)
C2	0.1436 (2)	0.7766 (3)	0.2794 (3)	0.0430 (7)
C3	0.2279 (2)	0.7541 (3)	0.3311 (3)	0.0489 (8)
C4	0.2934 (2)	0.8222 (4)	0.4251 (3)	0.0614 (10)
H4	0.3503	0.8078	0.4595	0.074*
C5	0.2752 (2)	0.9103 (4)	0.4677 (3)	0.0578 (10)
H5	0.3186	0.9570	0.5300	0.069*
C6	0.18908 (19)	0.9271 (3)	0.4139 (3)	0.0427 (7)
C7	0.2919 (3)	1.1245 (4)	0.6132 (4)	0.0785 (14)
H7A	0.3035	1.1900	0.6614	0.118*
H7B	0.3102	1.1387	0.5669	0.118*
H7C	0.3227	1.0604	0.6654	0.118*
C8	0.1967 (2)	1.1000 (3)	0.5284 (3)	0.0519 (9)
C9	0.1331 (2)	1.1555 (4)	0.5161 (3)	0.0591 (10)
H9	0.1394	1.2196	0.5589	0.071*
C10	0.0553 (2)	1.0985 (3)	0.4266 (3)	0.0503 (8)
C11	−0.0344 (3)	1.1244 (4)	0.3785 (4)	0.0714 (12)
H11A	−0.0708	1.0598	0.3348	0.107*
H11B	−0.0565	1.1885	0.3250	0.107*
H11C	−0.0333	1.1413	0.4448	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0225 (3)	0.0521 (4)	0.0380 (4)	0.000	0.0152 (3)	0.000
Cl1	0.0582 (6)	0.0774 (7)	0.0825 (7)	0.0267 (5)	0.0489 (6)	0.0137 (5)
N1	0.0260 (12)	0.0485 (16)	0.0385 (14)	0.0019 (11)	0.0175 (11)	0.0032 (11)
N2	0.0247 (12)	0.0551 (17)	0.0372 (14)	−0.0030 (12)	0.0137 (11)	−0.0024 (12)
N3	0.0254 (13)	0.0600 (18)	0.0404 (14)	0.0003 (12)	0.0169 (11)	−0.0028 (13)
O1	0.0334 (12)	0.0703 (17)	0.0556 (15)	−0.0012 (11)	0.0212 (11)	−0.0165 (12)
O2	0.0618 (19)	0.095 (2)	0.125 (3)	−0.0092 (17)	0.054 (2)	−0.056 (2)
O3	0.135 (4)	0.127 (4)	0.243 (6)	0.037 (3)	0.133 (4)	0.064 (4)
O4	0.084 (7)	0.139 (10)	0.111 (8)	0.000	0.053 (7)	0.000
C1	0.042 (2)	0.059 (2)	0.056 (2)	−0.0016 (17)	0.0292 (17)	−0.0095 (17)
C2	0.0363 (16)	0.0491 (19)	0.0426 (17)	0.0051 (14)	0.0247 (15)	0.0072 (14)
C3	0.0405 (18)	0.058 (2)	0.0521 (19)	0.0134 (16)	0.0315 (16)	0.0133 (16)
C4	0.0261 (16)	0.083 (3)	0.063 (2)	0.0117 (18)	0.0236 (17)	0.011 (2)
C5	0.0263 (16)	0.079 (3)	0.052 (2)	−0.0006 (17)	0.0179 (16)	−0.0035 (19)
C6	0.0285 (15)	0.0522 (19)	0.0378 (16)	−0.0001 (14)	0.0168 (14)	0.0042 (14)
C7	0.039 (2)	0.084 (3)	0.081 (3)	−0.020 (2)	0.024 (2)	−0.026 (2)
C8	0.0371 (18)	0.057 (2)	0.0472 (19)	−0.0088 (16)	0.0204 (16)	−0.0071 (16)
C9	0.051 (2)	0.061 (2)	0.056 (2)	−0.0064 (18)	0.0305 (19)	−0.0133 (18)
C10	0.0389 (18)	0.060 (2)	0.0471 (19)	0.0011 (16)	0.0254 (16)	−0.0026 (16)
C11	0.048 (2)	0.085 (3)	0.073 (3)	0.004 (2)	0.035 (2)	−0.020 (2)

Geometric parameters (Å, º)

Co1—N1	2.071 (2)	C1—C2	1.529 (5)
Co1—N1^i	2.071 (2)	C2—C3	1.380 (4)
Co1—O1	2.090 (2)	C3—C4	1.388 (5)
Co1—O1^i	2.090 (2)	C4—C5	1.371 (6)
Co1—N3	2.129 (3)	C4—H4	0.9300
Co1—N3^i	2.129 (3)	C5—C6	1.393 (4)
Cl1—C3	1.735 (4)	C5—H5	0.9300
N1—C6	1.323 (4)	C7—C8	1.504 (5)
N1—C2	1.346 (4)	C7—H7A	0.9600
N2—C8	1.375 (4)	C7—H7B	0.9600
N2—N3	1.384 (3)	C7—H7C	0.9600
N2—C6	1.414 (4)	C8—C9	1.350 (5)
N3—C10	1.321 (4)	C9—C10	1.408 (5)
O1—C1	1.252 (4)	C9—H9	0.9300
O2—C1	1.221 (4)	C10—C11	1.499 (5)
O3—H3A	0.8500	C11—H11A	0.9600
O3—H3B	0.8502	C11—H11B	0.9600
O4—H4A	0.8500	C11—H11C	0.9600
N1—Co1—N1^i	167.64 (15)	C2—C3—Cl1	122.9 (3)
N1—Co1—O1	76.79 (9)	C4—C3—Cl1	117.7 (3)
N1^i—Co1—O1	94.64 (10)	C5—C4—C3	120.7 (3)
N1—Co1—O1^i	94.64 (10)	C5—C4—H4	119.6
N1^i—Co1—O1^i	76.79 (9)	C3—C4—H4	119.6
O1—Co1—O1^i	93.49 (16)	C4—C5—C6	117.2 (3)
N1—Co1—N3	74.49 (10)	C4—C5—H5	121.4
N1^i—Co1—N3	114.91 (10)	C6—C5—H5	121.4
O1—Co1—N3	150.26 (9)	N1—C6—C5	121.5 (3)
O1^i—Co1—N3	96.33 (11)	N1—C6—N2	112.9 (3)
N1—Co1—N3^i	114.91 (10)	C5—C6—N2	125.6 (3)
N1^i—Co1—N3^i	74.49 (10)	C8—C7—H7A	109.5
O1—Co1—N3^i	96.33 (11)	C8—C7—H7B	109.5
O1^i—Co1—N3^i	150.26 (9)	H7A—C7—H7B	109.5
N3—Co1—N3^i	88.88 (15)	C8—C7—H7C	109.5
C6—N1—C2	122.0 (3)	H7A—C7—H7C	109.5
C6—N1—Co1	121.3 (2)	H7B—C7—H7C	109.5
C2—N1—Co1	116.4 (2)	C9—C8—N2	106.2 (3)
C8—N2—N3	110.5 (3)	C9—C8—C7	129.0 (4)
C8—N2—C6	133.1 (3)	N2—C8—C7	124.8 (3)
N3—N2—C6	116.3 (2)	C8—C9—C10	107.5 (3)
C10—N3—N2	105.8 (3)	C8—C9—H9	126.3
C10—N3—Co1	139.3 (2)	C10—C9—H9	126.3
N2—N3—Co1	114.9 (2)	N3—C10—C9	110.0 (3)
C1—O1—Co1	116.5 (2)	N3—C10—C11	120.5 (3)
H3A—O3—H3B	108.2	C9—C10—C11	129.5 (3)
O2—C1—O1	126.4 (4)	C10—C11—H11A	109.5
O2—C1—C2	117.8 (3)	C10—C11—H11B	109.5
O1—C1—C2	115.8 (3)	H11A—C11—H11B	109.5
N1—C2—C3	119.0 (3)	C10—C11—H11C	109.5
N1—C2—C1	112.0 (3)	H11A—C11—H11C	109.5
C3—C2—C1	129.0 (3)	H11B—C11—H11C	109.5
C2—C3—C4	119.4 (3)
N1^i—Co1—N1—C6	−137.3 (2)	Co1—N1—C2—C1	5.0 (3)
O1—Co1—N1—C6	175.8 (3)	O2—C1—C2—N1	−172.3 (4)
O1^i—Co1—N1—C6	−91.7 (3)	O1—C1—C2—N1	7.8 (5)
N3—Co1—N1—C6	3.6 (2)	O2—C1—C2—C3	7.4 (6)
N3^i—Co1—N1—C6	84.9 (3)	O1—C1—C2—C3	−172.4 (3)
N1^i—Co1—N1—C2	36.9 (2)	N1—C2—C3—C4	−0.9 (5)
O1—Co1—N1—C2	−10.1 (2)	C1—C2—C3—C4	179.4 (3)
O1^i—Co1—N1—C2	82.4 (2)	N1—C2—C3—Cl1	178.8 (2)
N3—Co1—N1—C2	177.7 (2)	C1—C2—C3—Cl1	−0.9 (5)
N3^i—Co1—N1—C2	−101.0 (2)	C2—C3—C4—C5	0.8 (6)
C8—N2—N3—C10	0.1 (4)	Cl1—C3—C4—C5	−179.0 (3)
C6—N2—N3—C10	−177.7 (3)	C3—C4—C5—C6	0.8 (6)
C8—N2—N3—Co1	177.8 (2)	C2—N1—C6—C5	2.4 (5)
C6—N2—N3—Co1	0.0 (3)	Co1—N1—C6—C5	176.2 (3)
N1—Co1—N3—C10	174.9 (4)	C2—N1—C6—N2	−178.4 (3)
N1^i—Co1—N3—C10	−13.7 (4)	Co1—N1—C6—N2	−4.6 (4)
O1—Co1—N3—C10	159.4 (3)	C4—C5—C6—N1	−2.4 (5)
O1^i—Co1—N3—C10	−92.1 (4)	C4—C5—C6—N2	178.5 (3)
N3^i—Co1—N3—C10	58.6 (3)	C8—N2—C6—N1	−174.4 (3)
N1—Co1—N3—N2	−1.7 (2)	N3—N2—C6—N1	2.8 (4)
N1^i—Co1—N3—N2	169.7 (2)	C8—N2—C6—C5	4.8 (6)
O1—Co1—N3—N2	−17.2 (4)	N3—N2—C6—C5	−178.0 (3)
O1^i—Co1—N3—N2	91.4 (2)	N3—N2—C8—C9	−0.3 (4)
N3^i—Co1—N3—N2	−118.0 (2)	C6—N2—C8—C9	177.0 (3)
N1—Co1—O1—C1	15.0 (3)	N3—N2—C8—C7	178.8 (4)
N1^i—Co1—O1—C1	−156.0 (3)	C6—N2—C8—C7	−3.9 (6)
O1^i—Co1—O1—C1	−79.0 (3)	N2—C8—C9—C10	0.4 (4)
N3—Co1—O1—C1	30.3 (4)	C7—C8—C9—C10	−178.7 (4)
N3^i—Co1—O1—C1	129.1 (3)	N2—N3—C10—C9	0.1 (4)
Co1—O1—C1—O2	163.4 (4)	Co1—N3—C10—C9	−176.7 (3)
Co1—O1—C1—C2	−16.8 (4)	N2—N3—C10—C11	−180.0 (3)
C6—N1—C2—C3	−0.7 (5)	Co1—N3—C10—C11	3.3 (6)
Co1—N1—C2—C3	−174.8 (2)	C8—C9—C10—N3	−0.3 (5)
C6—N1—C2—C1	179.1 (3)	C8—C9—C10—C11	179.8 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^i	0.85	1.98	2.825 (8)	172
O3—H3B···O2^ii	0.85	2.06	2.907 (8)	172
O4—H4A···O3	0.85	1.79	2.636 (8)	178

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