Tetra-aqua-bis-[3-(pyridin-4-yl)benzoato-κN]cobalt(II).

In the title compound, [Co(C(12)H(8)NO(2))(2)(H(2)O)(4)], the Co atom lies on a twofold rotation axis and has an N(2)O(4) octa-hedral coordination environment formed by four O atoms of water mol-ecules in the equatorial plane and two apical N atoms of pyridine groups. An intricate three-dimensional supra-molecular network is formed by multiple O-H⋯O hydrogen bonds between the coordinated water mol-ecules and the uncoordinated carboxyl-ate groups.

Related literature

For the design of metal-organic complexes, see: Ruben et al. (2003 ▶). For pyridyl-multicarboxyl­ate-metal frameworks, see: Huang et al. (2007 ▶). For similar pyridyl­benzoate complexes, see: Luo et al. (2007 ▶). For self-effacement of carboxyl­ate groups in coordination chemistry, see: Lu et al. (2008 ▶).

Experimental

Crystal data

[Co(C12H8NO2)2(H2O)4]

M = 527.38

Monoclinic,

a = 24.642 (10) Å

b = 7.128 (3) Å

c = 13.822 (6) Å

β = 112.660 (7)°

V = 2240.4 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.82 mm−1

T = 296 K

0.27 × 0.21 × 0.17 mm

Data collection

Siemens SMART CCD diffractometer

4423 measured reflections

1974 independent reflections

1499 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.131

S = 1.02

1974 reflections

171 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1994 ▶); 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: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046496/yk2023sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046496/yk2023Isup2.hkl

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

[Co(C12H8NO2)2(H2O)4]	F(000) = 1092
Mr = 527.38	Dx = 1.564 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 981 reflections
a = 24.642 (10) Å	θ = 3.0–21.3°
b = 7.128 (3) Å	µ = 0.82 mm−1
c = 13.822 (6) Å	T = 296 K
β = 112.660 (7)°	Block, red
V = 2240.4 (16) Å3	0.27 × 0.21 × 0.17 mm
Z = 4

Siemens SMART CCD diffractometer	1499 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
graphite	θmax = 25.0°, θmin = 1.8°
ω scan	h = −23→29
4423 measured reflections	k = −8→8
1974 independent reflections	l = −14→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0755P)2] where P = (Fo2 + 2Fc2)/3
1974 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.63 e Å−3
4 restraints	Δρmin = −0.43 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	0.30197 (9)	0.2500	0.0294 (3)
O1	0.46997 (11)	0.0853 (4)	0.13933 (19)	0.0381 (6)
O2	0.46824 (11)	0.5033 (4)	0.1285 (2)	0.0407 (6)
O3	0.09455 (11)	0.2256 (4)	0.0359 (2)	0.0515 (8)
O4	0.03868 (11)	0.2931 (4)	0.1240 (2)	0.0455 (7)
N1	0.41603 (12)	0.3126 (4)	0.2633 (2)	0.0322 (7)
C1	0.08769 (15)	0.2741 (5)	0.1173 (3)	0.0355 (9)
C2	0.14247 (15)	0.3156 (5)	0.2136 (3)	0.0306 (8)
C3	0.13890 (16)	0.3628 (5)	0.3077 (3)	0.0383 (9)
H3	0.1017	0.3689	0.3134	0.046*
C4	0.18993 (16)	0.4014 (6)	0.3940 (3)	0.0404 (9)
H4	0.1876	0.4354	0.4587	0.049*
C5	0.24431 (15)	0.3905 (5)	0.3862 (3)	0.0365 (8)
H5	0.2790	0.4165	0.4459	0.044*
C6	0.24867 (14)	0.3419 (5)	0.2920 (3)	0.0297 (8)
C7	0.19680 (14)	0.3043 (5)	0.2059 (3)	0.0302 (8)
H7	0.1988	0.2703	0.1409	0.036*
C8	0.30666 (14)	0.3304 (5)	0.2826 (3)	0.0300 (8)
C9	0.35800 (15)	0.2917 (5)	0.3676 (3)	0.0342 (8)
H9	0.3569	0.2698	0.4346	0.041*
C10	0.41091 (15)	0.2848 (5)	0.3551 (3)	0.0347 (8)
H10	0.4456	0.2590	0.4149	0.042*
C11	0.36609 (15)	0.3493 (5)	0.1809 (3)	0.0355 (9)
H11	0.3683	0.3688	0.1144	0.043*
C12	0.31186 (15)	0.3603 (5)	0.1876 (3)	0.0364 (9)
H12	0.2779	0.3884	0.1269	0.044*
H1A	0.4545 (17)	0.127 (6)	0.0779 (15)	0.055*
H1B	0.4919 (15)	−0.001 (4)	0.136 (3)	0.055*
H2B	0.4916 (15)	0.591 (4)	0.133 (3)	0.055*
H2A	0.4530 (17)	0.448 (6)	0.0706 (18)	0.055*

	U11	U22	U33	U12	U13	U23
Co1	0.0181 (4)	0.0332 (4)	0.0371 (4)	0.000	0.0107 (3)	0.000
O1	0.0348 (15)	0.0390 (16)	0.0428 (14)	0.0036 (12)	0.0175 (12)	−0.0014 (12)
O2	0.0293 (14)	0.0402 (17)	0.0484 (15)	−0.0077 (11)	0.0101 (12)	0.0059 (13)
O3	0.0313 (15)	0.074 (2)	0.0434 (15)	0.0003 (13)	0.0077 (12)	−0.0062 (14)
O4	0.0228 (14)	0.0398 (15)	0.0731 (19)	0.0005 (11)	0.0173 (13)	−0.0009 (13)
N1	0.0222 (15)	0.0333 (17)	0.0402 (17)	0.0000 (12)	0.0110 (13)	−0.0020 (13)
C1	0.0241 (19)	0.0287 (19)	0.051 (2)	0.0019 (15)	0.0120 (16)	0.0076 (17)
C2	0.0240 (18)	0.0275 (18)	0.0398 (18)	0.0035 (14)	0.0118 (15)	0.0058 (15)
C3	0.031 (2)	0.043 (2)	0.048 (2)	0.0082 (16)	0.0229 (17)	0.0083 (17)
C4	0.034 (2)	0.054 (3)	0.0377 (19)	0.0040 (18)	0.0179 (16)	−0.0032 (18)
C5	0.0264 (19)	0.043 (2)	0.039 (2)	−0.0014 (16)	0.0107 (15)	−0.0029 (17)
C6	0.0219 (17)	0.0283 (19)	0.0401 (19)	0.0009 (14)	0.0133 (15)	0.0010 (15)
C7	0.0247 (18)	0.0315 (19)	0.0367 (18)	−0.0017 (15)	0.0146 (15)	−0.0006 (15)
C8	0.0210 (17)	0.0280 (19)	0.0416 (19)	−0.0007 (14)	0.0128 (15)	−0.0026 (15)
C9	0.0242 (18)	0.047 (2)	0.0324 (18)	−0.0023 (16)	0.0114 (15)	−0.0004 (16)
C10	0.0222 (18)	0.043 (2)	0.0361 (19)	−0.0020 (15)	0.0081 (15)	−0.0005 (16)
C11	0.0224 (18)	0.048 (2)	0.0370 (19)	−0.0006 (15)	0.0122 (15)	0.0002 (16)
C12	0.0238 (18)	0.044 (2)	0.040 (2)	0.0017 (16)	0.0114 (15)	−0.0008 (17)

Co1—O1	2.098 (3)	C3—C4	1.387 (5)
Co1—O1i	2.098 (3)	C3—H3	0.9500
Co1—O2i	2.117 (3)	C4—C5	1.387 (5)
Co1—O2	2.117 (3)	C4—H4	0.9500
Co1—N1	2.148 (3)	C5—C6	1.390 (5)
Co1—N1i	2.148 (3)	C5—H5	0.9500
O1—H1A	0.840 (10)	C6—C7	1.396 (5)
O1—H1B	0.836 (10)	C6—C8	1.487 (5)
O2—H2B	0.835 (10)	C7—H7	0.9500
O2—H2A	0.840 (10)	C8—C9	1.383 (5)
O3—C1	1.249 (5)	C8—C12	1.383 (5)
O4—C1	1.254 (4)	C9—C10	1.381 (5)
N1—C10	1.337 (4)	C9—H9	0.9500
N1—C11	1.342 (4)	C10—H10	0.9500
C1—C2	1.516 (5)	C11—C12	1.377 (5)
C2—C3	1.378 (5)	C11—H11	0.9500
C2—C7	1.386 (5)	C12—H12	0.9500
O1—Co1—O1i	85.18 (15)	C2—C3—C4	119.6 (3)
O1—Co1—O2i	175.22 (10)	C2—C3—H3	120.2
O1i—Co1—O2i	90.11 (11)	C4—C3—H3	120.2
O1—Co1—O2	90.11 (11)	C3—C4—C5	120.3 (3)
O1i—Co1—O2	175.22 (10)	C3—C4—H4	119.8
O2i—Co1—O2	94.61 (15)	C5—C4—H4	119.8
O1—Co1—N1	90.43 (10)	C4—C5—C6	120.8 (3)
O1i—Co1—N1	92.54 (10)	C4—C5—H5	119.6
O2i—Co1—N1	88.98 (10)	C6—C5—H5	119.6
O2—Co1—N1	88.28 (10)	C5—C6—C7	118.0 (3)
O1—Co1—N1i	92.54 (10)	C5—C6—C8	121.3 (3)
O1i—Co1—N1i	90.43 (10)	C7—C6—C8	120.6 (3)
O2i—Co1—N1i	88.28 (10)	C2—C7—C6	121.2 (3)
O2—Co1—N1i	88.98 (10)	C2—C7—H7	119.4
N1—Co1—N1i	175.97 (15)	C6—C7—H7	119.4
Co1—O1—H1A	112 (3)	C9—C8—C12	116.6 (3)
Co1—O1—H1B	122 (3)	C9—C8—C6	122.1 (3)
H1A—O1—H1B	104 (4)	C12—C8—C6	121.2 (3)
Co1—O2—H2B	114 (3)	C10—C9—C8	119.9 (3)
Co1—O2—H2A	109 (3)	C10—C9—H9	120.0
H2B—O2—H2A	118 (4)	C8—C9—H9	120.0
C10—N1—C11	116.3 (3)	N1—C10—C9	123.5 (3)
C10—N1—Co1	121.5 (2)	N1—C10—H10	118.2
C11—N1—Co1	122.2 (2)	C9—C10—H10	118.2
O3—C1—O4	124.4 (4)	N1—C11—C12	123.3 (3)
O3—C1—C2	117.5 (3)	N1—C11—H11	118.3
O4—C1—C2	118.1 (3)	C12—C11—H11	118.3
C3—C2—C7	120.1 (3)	C11—C12—C8	120.2 (3)
C3—C2—C1	121.1 (3)	C11—C12—H12	119.9
C7—C2—C1	118.8 (3)	C8—C12—H12	119.9

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ii	0.84 (1)	1.89 (2)	2.692 (4)	159 (4)
O2—H2A···O3ii	0.84 (1)	1.94 (2)	2.741 (4)	160 (4)
O1—H1B···O4iii	0.84 (1)	1.91 (1)	2.743 (4)	177 (4)
O2—H2B···O4iv	0.84 (1)	1.89 (1)	2.714 (4)	172 (4)

Co1—O1	2.098 (3)
Co1—O2	2.117 (3)
Co1—N1	2.148 (3)

O1—Co1—O1i	85.18 (15)
O1—Co1—O2	90.11 (11)
O1i—Co1—O2	175.22 (10)
O2i—Co1—O2	94.61 (15)
O1—Co1—N1	90.43 (10)
O1i—Co1—N1	92.54 (10)
O2i—Co1—N1	88.98 (10)
O2—Co1—N1	88.28 (10)
O2—Co1—N1i	88.98 (10)
N1—Co1—N1i	175.97 (15)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ii	0.84 (1)	1.89 (2)	2.692 (4)	159 (4)
O2—H2A⋯O3ii	0.84 (1)	1.94 (2)	2.741 (4)	160 (4)
O1—H1B⋯O4iii	0.84 (1)	1.91 (1)	2.743 (4)	177 (4)
O2—H2B⋯O4iv	0.84 (1)	1.89 (1)	2.714 (4)	172 (4)

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