Tetra-aqua-bis-(2-methyl-1H-imidazole-κN)cobalt(II) naphthalene-1,5-disulfonate.

In the title complex, [Co(C(4)H(6)N(2))(2)(H(2)O)(4)](C(10)H(6)O(6)S(2)), the cation and anion both reside on crystallographic inversion centers, such that the asymmetric unit comprises one half cation and one half anion. The central Co(II) ion is coordinated by four water mol-ecules and two 2-methyl-imidazole ligands, resulting in a trans-octa-hedral coordination geometry. The existence of strong N-H⋯O and O-H⋯O hydrogen-bonding inter-actions gives rise to a three-dimensional structure.

Related literature

For general background to ferroelectric metal-organic frameworks, see: Wu et al. (2011 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010) ▶; Fu et al. (2009 ▶).

Experimental

Crystal data

[Co(C4H6N2)2(H2O)4](C10H6O6S2)

M = 581.48

Monoclinic,

a = 8.0260 (16) Å

b = 12.923 (3) Å

c = 11.658 (2) Å

β = 99.27 (3)°

V = 1193.5 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.96 mm−1

T = 293 K

0.3 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.489, T max = 1.000

12041 measured reflections

2729 independent reflections

2558 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.073

S = 1.09

2729 reflections

177 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.27 e Å−3

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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104548X/fj2459sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104548X/fj2459Isup2.hkl

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

[Co(C4H6N2)2(H2O)4](C10H6O6S2)	F(000) = 602
Mr = 581.48	Dx = 1.618 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3450 reflections
a = 8.0260 (16) Å	θ = 6.2–55.3°
b = 12.923 (3) Å	µ = 0.96 mm−1
c = 11.658 (2) Å	T = 293 K
β = 99.27 (3)°	Block, pink
V = 1193.5 (4) Å3	0.3 × 0.3 × 0.2 mm
Z = 2

Rigaku Mercury CCD diffractometer	2729 independent reflections
Radiation source: fine-focus sealed tube	2558 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
Tmin = 0.489, Tmax = 1.000	k = −16→16
12041 measured reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.0283P)2 + 0.6244P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
2729 reflections	Δρmax = 0.30 e Å−3
177 parameters	Δρmin = −0.27 e Å−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0260 (17)

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
C1	1.0422 (2)	0.82564 (13)	0.59914 (16)	0.0329 (4)
H1A	1.0320	0.7642	0.6389	0.039*
C2	0.91065 (19)	0.89391 (12)	0.58123 (13)	0.0237 (3)
C3	0.92275 (18)	0.98928 (11)	0.52102 (14)	0.0221 (3)
C4	0.7893 (2)	1.06210 (13)	0.50084 (16)	0.0304 (4)
H4C	0.6886	1.0486	0.5278	0.036*
C5	0.8068 (2)	1.15174 (14)	0.44245 (18)	0.0376 (4)
H5C	0.7178	1.1986	0.4299	0.045*
C6	0.1443 (2)	1.11040 (14)	0.80184 (15)	0.0351 (4)
H6B	0.0598	1.1600	0.7984	0.042*
C7	0.2652 (3)	1.10886 (16)	0.73404 (17)	0.0411 (4)
H7B	0.2799	1.1559	0.6761	0.049*
C8	0.2985 (2)	0.97570 (14)	0.85354 (17)	0.0349 (4)
C9	0.3757 (3)	0.88003 (18)	0.9091 (2)	0.0561 (6)
H9A	0.3124	0.8573	0.9677	0.084*
H9B	0.4901	0.8940	0.9442	0.084*
H9C	0.3746	0.8269	0.8515	0.084*
Co1	0.0000	1.0000	1.0000	0.02367 (11)
H4	0.217 (4)	0.8773 (10)	1.141 (2)	0.074 (9)*
H5	0.233 (3)	0.9781 (17)	1.1808 (15)	0.058 (8)*
H6	0.118 (3)	1.169 (2)	1.1307 (16)	0.072 (9)*
H7	0.006 (2)	1.2076 (11)	1.0401 (18)	0.039 (6)*
N1	0.3618 (2)	1.02391 (14)	0.76803 (14)	0.0405 (4)
H1B	0.4490	1.0044	0.7394	0.049*
N2	0.16477 (19)	1.02694 (11)	0.87765 (13)	0.0310 (3)
O1	0.05471 (19)	1.15356 (9)	1.06915 (12)	0.0378 (3)
O2	0.20133 (17)	0.94019 (10)	1.12236 (12)	0.0356 (3)
O3	0.60123 (15)	0.83245 (10)	0.52393 (11)	0.0341 (3)
O4	0.66384 (16)	0.94058 (10)	0.69426 (11)	0.0378 (3)
O5	0.76184 (17)	0.76414 (10)	0.70195 (12)	0.0396 (3)
S1	0.72008 (5)	0.85486 (3)	0.62836 (3)	0.02460 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0290 (8)	0.0262 (8)	0.0442 (10)	0.0024 (7)	0.0079 (7)	0.0075 (7)
C2	0.0199 (7)	0.0238 (7)	0.0278 (8)	−0.0024 (6)	0.0052 (6)	−0.0018 (6)
C3	0.0178 (7)	0.0225 (7)	0.0259 (7)	−0.0013 (5)	0.0031 (6)	−0.0029 (6)
C4	0.0197 (7)	0.0304 (8)	0.0426 (9)	0.0035 (6)	0.0097 (7)	0.0026 (7)
C5	0.0253 (8)	0.0317 (9)	0.0572 (12)	0.0098 (7)	0.0111 (8)	0.0098 (8)
C6	0.0412 (10)	0.0322 (9)	0.0334 (9)	−0.0028 (7)	0.0111 (8)	0.0004 (7)
C7	0.0494 (11)	0.0433 (11)	0.0333 (9)	−0.0123 (9)	0.0142 (8)	−0.0024 (8)
C8	0.0334 (9)	0.0347 (9)	0.0394 (10)	−0.0020 (7)	0.0148 (8)	−0.0073 (7)
C9	0.0531 (13)	0.0455 (12)	0.0764 (16)	0.0166 (10)	0.0304 (12)	0.0034 (11)
Co1	0.02407 (17)	0.02192 (17)	0.02595 (17)	0.00133 (11)	0.00684 (12)	0.00013 (11)
N1	0.0364 (9)	0.0496 (9)	0.0405 (9)	−0.0068 (7)	0.0215 (7)	−0.0112 (7)
N2	0.0325 (8)	0.0285 (7)	0.0346 (8)	−0.0008 (6)	0.0134 (6)	−0.0015 (6)
O1	0.0499 (8)	0.0237 (6)	0.0364 (7)	0.0016 (5)	−0.0035 (6)	−0.0006 (5)
O2	0.0363 (7)	0.0313 (7)	0.0365 (7)	0.0043 (5)	−0.0022 (5)	−0.0040 (5)
O3	0.0273 (6)	0.0388 (7)	0.0354 (7)	−0.0091 (5)	0.0028 (5)	−0.0059 (5)
O4	0.0373 (7)	0.0389 (7)	0.0416 (7)	−0.0062 (5)	0.0197 (6)	−0.0141 (6)
O5	0.0402 (7)	0.0370 (7)	0.0431 (7)	−0.0047 (6)	0.0115 (6)	0.0119 (6)
S1	0.0228 (2)	0.0253 (2)	0.0269 (2)	−0.00531 (14)	0.00757 (15)	−0.00294 (14)

C1—C2	1.366 (2)	C8—C9	1.484 (3)
C1—C5i	1.406 (2)	C9—H9A	0.9600
C1—H1A	0.9300	C9—H9B	0.9600
C2—C3	1.429 (2)	C9—H9C	0.9600
C2—S1	1.7795 (16)	Co1—O2ii	2.1215 (14)
C3—C4	1.417 (2)	Co1—O2	2.1215 (14)
C3—C3i	1.432 (3)	Co1—N2	2.1242 (15)
C4—C5	1.362 (2)	Co1—N2ii	2.1242 (15)
C4—H4C	0.9300	Co1—O1ii	2.1603 (13)
C5—C1i	1.406 (2)	Co1—O1	2.1603 (13)
C5—H5C	0.9300	N1—H1B	0.8600
C6—C7	1.347 (3)	O1—H6	0.837 (10)
C6—N2	1.387 (2)	O1—H7	0.843 (9)
C6—H6B	0.9300	O2—H4	0.845 (10)
C7—N1	1.365 (3)	O2—H5	0.844 (10)
C7—H7B	0.9300	O3—S1	1.4498 (13)
C8—N2	1.329 (2)	O4—S1	1.4605 (12)
C8—N1	1.343 (2)	O5—S1	1.4596 (13)
C2—C1—C5i	120.04 (16)	O2—Co1—N2	91.27 (6)
C2—C1—H1A	120.0	O2ii—Co1—N2ii	91.27 (6)
C5i—C1—H1A	120.0	O2—Co1—N2ii	88.73 (6)
C1—C2—C3	121.33 (14)	N2—Co1—N2ii	180.000 (1)
C1—C2—S1	116.83 (12)	O2ii—Co1—O1ii	89.81 (5)
C3—C2—S1	121.73 (11)	O2—Co1—O1ii	90.19 (5)
C4—C3—C2	123.03 (14)	N2—Co1—O1ii	90.63 (6)
C4—C3—C3i	119.19 (17)	N2ii—Co1—O1ii	89.37 (6)
C2—C3—C3i	117.78 (17)	O2ii—Co1—O1	90.19 (5)
C5—C4—C3	120.77 (15)	O2—Co1—O1	89.81 (5)
C5—C4—H4C	119.6	N2—Co1—O1	89.37 (6)
C3—C4—H4C	119.6	N2ii—Co1—O1	90.63 (6)
C4—C5—C1i	120.88 (16)	O1ii—Co1—O1	180.0
C4—C5—H5C	119.6	C8—N1—C7	108.86 (16)
C1i—C5—H5C	119.6	C8—N1—H1B	125.6
C7—C6—N2	109.89 (17)	C7—N1—H1B	125.6
C7—C6—H6B	125.1	C8—N2—C6	105.61 (15)
N2—C6—H6B	125.1	C8—N2—Co1	132.19 (13)
C6—C7—N1	105.70 (17)	C6—N2—Co1	122.19 (12)
C6—C7—H7B	127.2	Co1—O1—H6	127.2 (19)
N1—C7—H7B	127.2	Co1—O1—H7	124.0 (15)
N2—C8—N1	109.93 (17)	H6—O1—H7	109 (2)
N2—C8—C9	128.11 (18)	Co1—O2—H4	126 (2)
N1—C8—C9	121.95 (18)	Co1—O2—H5	115.3 (18)
C8—C9—H9A	109.5	H4—O2—H5	110 (3)
C8—C9—H9B	109.5	O3—S1—O5	113.01 (8)
H9A—C9—H9B	109.5	O3—S1—O4	112.08 (8)
C8—C9—H9C	109.5	O5—S1—O4	111.17 (8)
H9A—C9—H9C	109.5	O3—S1—C2	106.22 (8)
H9B—C9—H9C	109.5	O5—S1—C2	106.38 (8)
O2ii—Co1—O2	180.0	O4—S1—C2	107.53 (7)
O2ii—Co1—N2	88.73 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H4···O5iii	0.85 (1)	1.97 (1)	2.815 (2)	174 (3)
O2—H5···O4iv	0.84 (1)	1.88 (1)	2.7149 (19)	171 (3)
O1—H6···O5iv	0.84 (1)	2.21 (1)	3.026 (2)	167 (3)
O1—H7···O3v	0.84 (1)	1.92 (1)	2.7661 (18)	179 (2)
N1—H1B···O4	0.86	2.06	2.906 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H4⋯O5i	0.85 (1)	1.97 (1)	2.815 (2)	174 (3)
O2—H5⋯O4ii	0.84 (1)	1.88 (1)	2.7149 (19)	171 (3)
O1—H6⋯O5ii	0.84 (1)	2.21 (1)	3.026 (2)	167 (3)
O1—H7⋯O3iii	0.84 (1)	1.92 (1)	2.7661 (18)	179 (2)
N1—H1B⋯O4	0.86	2.06	2.906 (2)	170

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