catena-Poly[[[diaqua­cobalt(II)]-μ-(E)-1,2-bis­(4-pyrid­yl)ethyl­ene-κ²N:N′] bis­(4-amino­benzene­sulfonate) hexa­hydrate]

In the title compound, {[Co(C₁₂H₁₀N₂)(H₂O)₂](C₆H₆NO₃S)₂·6H₂O}_n, a cobalt coordination polymer, the repeat unit comprises a cobalt complex cation, two 4-amino­benzene­sulfonate anions and six uncoordinated water mol­ecules. In the doubly charged cobalt cation, each Co atom lies on a center of symmetry and is six-coordinated in a distorted octa­hedral geometry formed by four O atoms of four coordinated water mol­ecules, and two N atoms from two (E)-1,2-bis­(4-pyrid­yl)ethyl­ene (bpe) ligands. The bpe ligands bridge the Co atoms, forming a one-dimensional linear chain. Inter­molecular O—H...O, O—H...N and N—H...O hydrogen-bonding inter­actions stabilize this chain structure.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.051
• wR factor = 0.155
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1B    ..  H4W     ..       1.40 Ang.

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Co1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.41
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O2     -   H4W    ...       1.03 Ang.
PLAT415_ALERT_2_C Short Inter D-H..H-X       H4W    ..  H9      ..       2.11 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            N2  -CO1 -N2  -C5     13.00 10.00   3.765   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N2  -CO1 -N2  -C4   -166.00 10.00   3.765   1.555   1.555   1.555

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (2)       1.92
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......        144

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In the previous literatures, the complexes containing 4-aminobenzenesulfonate as monodentate ligand (Du & Li, 2007., Gunderman et al., 1996; Huang et al., 2004; Starynowicz, 1992) have been reported. In our paper, we describe another new compound (I) in which 4-aminobenzenesulfonate does not participate in coordination, (Fig. 1).

Compound (I) is a Co coordination polymer and the structural unit is comprised of a cobalt complex cation, two 4-aminobenzenesulfonate anions and six uncoordinated water molecules.

In the doubly charged cobalt cation, each Co symmetrical center has distorted octahedral geometry, formed by four O atoms of four coordinated water molecules, two N atoms from two (E)-1,2-bis(4-pyridyl)ethylene (bpe) ligands (Table 1). The bpe ligand plays as a bridging ligand linking neighbouring Co^II atoms into a one-dimensional linear chain with the Co1···Co1(-x + 1, y, z) separation distance of 13.435 (2) Å.

4-Aaminobenzenesulfonate anions here does not take part in coordination but involve in intermolecular hydrogen bonds with coordinated and uncoordinated water molecules (Table 2). The chain structure is stabilized via these hydrogen bonding interactions and as well as electrostatic force (Fig. 2).

Related literature

For related literature, see: Du & Li (2007); Gunderman et al. (1996); Huang et al. (2004); Starynowicz (1992).

S2. Experimental

A 10 ml water solution of Co(Cl)₂.6H₂O (0.238 g,1 mmol) was dropped into 10 ml me thanol solution of (E)-1,2-bis(4-pyridyl)ethylene (0.182 g,1 mmol) and 4-aminobenzenesulfonic acid (0.346 g, 2 mmol) and then the mixture was stirred for 5 h at 343 K.The filtrate was stayed in air for about two weeks to obtain red block-shaped crystals. Analysis, found (%): C 39.42, H 5.15, N 7.71, S 8.82. C₂₄H₃₈CoN₄O₁₄S₂ requires(%): C 39.47, H 5.21, N 7.67, S 8.77. [CCDC: 656072].

S3. Refinement

H atoms bonded to C and N were positioned geometrically with C—H distance of 0.93Å and N—H of 0.86 Å, respectively, and treated as riding atoms, with U_iso(H) =1.2U_eq(C or N). The O—H hydrogen atoms were located in a difference Fourier map and refined isotropically, with O—H distance in the range of 0.8250–1.0288 Å.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures

	Fig. 1. The segment of the polymeric structure of (I) with atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The uncoordinated water molecules have been omitted. [Symmetry codes: (A) -x + 2, -y + 1, -z; (B) -x + 1, -y + 1, -z; (C) -1 + x, y, z.]
	Fig. 2. Packing diagram of (I), showing the hydrogen bonds as dashed lines. H atoms on C atoms have been omitted for clarity.

catena-Poly[[[diaquacobalt(II)]-µ-(E)-1,2-bis(4- pyridyl)ethylene-κ²N:N'] bis(4-aminobenzenesulfonate) hexahydrate]

Crystal data

[Co(C12H10N2)(H2O)2](C6H6NO3S)2·6H2O	F(000) = 762
Mr = 729.63	Dx = 1.485 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2927 reflections
a = 13.4351 (15) Å	θ = 2.7–24.2°
b = 7.9688 (9) Å	µ = 0.72 mm^−1
c = 15.7183 (18) Å	T = 291 K
β = 104.133 (1)°	Block, red
V = 1631.9 (3) Å^3	0.30 × 0.20 × 0.09 mm
Z = 2

Data collection

Bruker APEX II CCD area-detector diffractometer	3035 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −16→16
Tmin = 0.814, Tmax = 0.941	k = −9→9
12048 measured reflections	l = −19→19

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0893P)^2 + 1.4053P] where P = (Fo^2 + 2Fc^2)/3
3035 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.83 e Å^−3
144 restraints	Δρmin = −0.49 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
Co1	1.0000	0.5000	0.0000	0.0305 (2)
S1	0.20531 (8)	−0.04540 (13)	0.13300 (7)	0.0519 (3)
O1	1.00684 (18)	0.2545 (4)	0.0220 (2)	0.0587 (8)
H1W	0.9589	0.1931	−0.0039	0.088*
H2W	1.0497	0.2017	0.0588	0.088*
O2	0.7714 (5)	0.9228 (9)	0.0977 (4)	0.160 (2)
H3W	0.8184	0.8814	0.1386	0.240*
H4W	0.6946	0.9382	0.0949	0.240*
O3	0.0514 (2)	0.5633 (4)	0.1577 (2)	0.0614 (8)
H5W	0.1010	0.6284	0.1636	0.092*
H6W	0.0534	0.5159	0.2058	0.092*
O4	0.0764 (3)	0.2844 (5)	0.2693 (3)	0.1046 (13)
H7W	0.1093	0.1920	0.2643	0.157*
H8W	0.0185	0.2582	0.2756	0.157*
O5	0.1560 (3)	0.1016 (5)	0.1560 (3)	0.0924 (12)
O6	0.1664 (3)	−0.0819 (6)	0.0398 (2)	0.0910 (12)
O7	0.1974 (2)	−0.1889 (4)	0.1860 (2)	0.0788 (10)
N1	0.6514 (3)	0.0765 (6)	0.2018 (3)	0.0829 (13)
H1A	0.6824	0.1329	0.2472	0.099*
H1B	0.6858	0.0332	0.1678	0.099*
N2	0.8530 (2)	0.4986 (3)	0.0078 (2)	0.0392 (7)
C1	0.5415 (3)	0.4745 (5)	0.0290 (3)	0.0447 (9)
H1D	0.5320	0.4262	0.0803	0.054*
C2	0.6476 (3)	0.4871 (4)	0.0201 (3)	0.0412 (8)
C3	0.6745 (3)	0.5588 (5)	−0.0527 (3)	0.0457 (9)
H3	0.6241	0.6045	−0.0981	0.055*
C4	0.7758 (3)	0.5612 (5)	−0.0566 (3)	0.0436 (8)
H4	0.7920	0.6080	−0.1057	0.052*
C5	0.8270 (3)	0.4325 (5)	0.0778 (2)	0.0435 (8)
H5	0.8787	0.3896	0.1232	0.052*
C6	0.7273 (3)	0.4256 (5)	0.0855 (3)	0.0445 (8)
H6	0.7133	0.3787	0.1355	0.053*
C7	0.3369 (3)	0.0009 (4)	0.1491 (3)	0.0453 (9)
C8	0.3922 (3)	−0.0651 (5)	0.0940 (3)	0.0513 (10)
H8	0.3588	−0.1266	0.0451	0.062*
C9	0.4968 (3)	−0.0405 (6)	0.1107 (3)	0.0560 (10)
H9	0.5338	−0.0872	0.0737	0.067*
C10	0.5476 (3)	0.0555 (6)	0.1838 (3)	0.0554 (10)
C11	0.4897 (3)	0.1229 (5)	0.2368 (3)	0.0590 (11)
H11	0.5221	0.1879	0.2847	0.071*
C12	0.3864 (3)	0.0969 (5)	0.2209 (3)	0.0544 (10)
H12	0.3493	0.1431	0.2580	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0108 (3)	0.0324 (4)	0.0491 (4)	−0.0001 (2)	0.0086 (2)	0.0038 (3)
S1	0.0409 (6)	0.0450 (6)	0.0632 (7)	−0.0035 (4)	0.0003 (5)	0.0099 (4)
O1	0.0310 (14)	0.0484 (16)	0.088 (2)	−0.0015 (11)	−0.0011 (13)	0.0101 (14)
O2	0.145 (5)	0.218 (6)	0.127 (4)	0.059 (4)	0.053 (4)	0.037 (4)
O3	0.0460 (16)	0.0704 (18)	0.0687 (19)	−0.0153 (14)	0.0159 (14)	0.0019 (15)
O4	0.130 (3)	0.093 (3)	0.105 (3)	−0.007 (3)	0.056 (3)	0.009 (2)
O5	0.066 (2)	0.071 (2)	0.142 (3)	0.0020 (18)	0.030 (2)	−0.008 (2)
O6	0.059 (2)	0.131 (3)	0.068 (2)	−0.034 (2)	−0.0116 (17)	0.011 (2)
O7	0.0564 (19)	0.064 (2)	0.103 (2)	−0.0148 (15)	−0.0042 (17)	0.0334 (18)
N1	0.056 (2)	0.101 (3)	0.086 (3)	−0.032 (2)	0.006 (2)	−0.008 (3)
N2	0.0248 (14)	0.0424 (16)	0.0510 (17)	−0.0017 (11)	0.0105 (12)	0.0015 (13)
C1	0.0292 (18)	0.054 (2)	0.053 (2)	−0.0032 (15)	0.0133 (15)	0.0029 (17)
C2	0.0265 (17)	0.0450 (19)	0.054 (2)	−0.0030 (14)	0.0146 (15)	−0.0021 (15)
C3	0.0240 (17)	0.058 (2)	0.054 (2)	0.0029 (15)	0.0083 (15)	0.0109 (18)
C4	0.0272 (17)	0.053 (2)	0.051 (2)	0.0019 (15)	0.0106 (15)	0.0101 (17)
C5	0.0260 (17)	0.053 (2)	0.052 (2)	0.0009 (15)	0.0094 (15)	0.0081 (17)
C6	0.0273 (17)	0.056 (2)	0.050 (2)	−0.0014 (16)	0.0099 (15)	0.0059 (17)
C7	0.044 (2)	0.0371 (19)	0.048 (2)	−0.0065 (15)	−0.0004 (16)	0.0065 (15)
C8	0.052 (2)	0.050 (2)	0.047 (2)	−0.0099 (18)	0.0013 (17)	−0.0044 (17)
C9	0.055 (2)	0.064 (2)	0.047 (2)	−0.011 (2)	0.0091 (18)	0.0040 (18)
C10	0.047 (2)	0.055 (2)	0.057 (2)	−0.0178 (19)	0.0005 (19)	0.0111 (19)
C11	0.058 (2)	0.053 (2)	0.056 (2)	−0.0100 (19)	−0.004 (2)	−0.0114 (19)
C12	0.052 (2)	0.051 (2)	0.055 (2)	−0.0014 (18)	0.0025 (18)	−0.0072 (18)

Geometric parameters (Å, º)

Co1—O1^i	1.985 (3)	N2—C4	1.354 (5)
Co1—O1	1.985 (3)	C1—C1^ii	1.321 (8)
Co1—N2^i	2.009 (3)	C1—C2	1.469 (5)
Co1—N2^i	2.009 (3)	C1—H1D	0.9300
Co1—O3^ii	2.458 (3)	C2—C6	1.380 (5)
Co1—O3^ii	2.458 (3)	C2—C3	1.403 (5)
S1—O7	1.434 (3)	C3—C4	1.378 (5)
S1—O5	1.435 (4)	C3—H3	0.9300
S1—O6	1.460 (4)	C4—H4	0.9300
S1—C7	1.763 (4)	C5—C6	1.375 (5)
O1—H1W	0.8319	C5—H5	0.9300
O1—H2W	0.8250	C6—H6	0.9300
O2—H3W	0.8496	C7—C8	1.376 (6)
O2—H4W	1.0288	C7—C12	1.391 (5)
O3—H5W	0.8322	C8—C9	1.379 (6)
O3—H6W	0.8390	C8—H8	0.9300
O4—H7W	0.8721	C9—C10	1.411 (6)
O4—H8W	0.8349	C9—H9	0.9300
N1—C10	1.364 (6)	C10—C11	1.378 (7)
N1—H1A	0.8600	C11—C12	1.365 (6)
N1—H1B	0.8600	C11—H11	0.9300
N2—C5	1.341 (5)	C12—H12	0.9300
O1^i—Co1—O1	179.998 (1)	C6—C2—C1	120.0 (3)
O1^i—Co1—N2^i	89.33 (11)	C3—C2—C1	123.6 (3)
O1—Co1—N2^i	90.67 (11)	C4—C3—C2	119.7 (3)
O1^i—Co1—N2	90.67 (11)	C4—C3—H3	120.2
O1—Co1—N2	89.33 (11)	C2—C3—H3	120.2
N2^i—Co1—N2	180.0	N2—C4—C3	123.1 (3)
O1—Co1—N2	89.33 (11)	N2—C4—H4	118.4
N2^i—Co1—N2	180.0	C3—C4—H4	118.4
O3^ii—Co1—O3^ii	180.0	N2—C5—C6	122.8 (3)
O3^ii—Co1—N2^i	88.75 (11)	N2—C5—H5	118.6
O3—Co1—N2^i	172.76 (9)	C6—C5—H5	118.6
O7—S1—O5	113.6 (3)	C5—C6—C2	121.1 (4)
O7—S1—O6	111.4 (2)	C5—C6—H6	119.5
O5—S1—O6	110.0 (3)	C2—C6—H6	119.5
O7—S1—C7	107.27 (18)	C8—C7—C12	119.8 (4)
O5—S1—C7	107.6 (2)	C8—C7—S1	120.4 (3)
O6—S1—C7	106.7 (2)	C12—C7—S1	119.7 (3)
Co1—O1—H1W	119.9	C7—C8—C9	120.5 (4)
Co1—O1—H2W	128.3	C7—C8—H8	119.8
H1W—O1—H2W	111.5	C9—C8—H8	119.8
H3W—O2—H4W	129.1	C8—C9—C10	120.0 (4)
H5W—O3—H6W	109.4	C8—C9—H9	120.0
H7W—O4—H8W	107.9	C10—C9—H9	120.0
C10—N1—H1A	120.0	N1—C10—C11	121.7 (4)
C10—N1—H1B	120.0	N1—C10—C9	120.1 (5)
H1A—N1—H1B	120.0	C11—C10—C9	118.2 (4)
C5—N2—C4	116.9 (3)	C12—C11—C10	121.9 (4)
C5—N2—Co1	120.6 (2)	C12—C11—H11	119.0
C4—N2—Co1	122.5 (2)	C10—C11—H11	119.0
C1^ii—C1—C2	126.1 (5)	C11—C12—C7	119.6 (4)
C1^ii—C1—H1D	116.9	C11—C12—H12	120.2
C2—C1—H1D	116.9	C7—C12—H12	120.2
C6—C2—C3	116.4 (3)
O1^i—Co1—N2—C5	−126.6 (3)	C1—C2—C6—C5	178.6 (4)
O1—Co1—N2—C5	53.4 (3)	O7—S1—C7—C8	92.7 (4)
N2^i—Co1—N2—C5	13 (10)	O5—S1—C7—C8	−144.7 (4)
O1^i—Co1—N2—C4	54.1 (3)	O6—S1—C7—C8	−26.8 (4)
O1—Co1—N2—C4	−125.9 (3)	O7—S1—C7—C12	−83.6 (4)
N2^i—Co1—N2—C4	−166 (10)	O5—S1—C7—C12	38.9 (4)
C1^ii—C1—C2—C6	−178.8 (5)	O6—S1—C7—C12	156.8 (3)
C1^ii—C1—C2—C3	0.9 (8)	C12—C7—C8—C9	1.8 (6)
C6—C2—C3—C4	1.4 (6)	S1—C7—C8—C9	−174.6 (3)
C1—C2—C3—C4	−178.3 (4)	C7—C8—C9—C10	−1.2 (6)
C5—N2—C4—C3	−0.2 (6)	C8—C9—C10—N1	178.3 (4)
Co1—N2—C4—C3	179.0 (3)	C8—C9—C10—C11	−0.2 (6)
C2—C3—C4—N2	−0.8 (6)	N1—C10—C11—C12	−177.4 (4)
C4—N2—C5—C6	0.6 (6)	C9—C10—C11—C12	1.0 (7)
Co1—N2—C5—C6	−178.7 (3)	C10—C11—C12—C7	−0.5 (7)
N2—C5—C6—C2	0.1 (6)	C8—C7—C12—C11	−0.9 (6)
C3—C2—C6—C5	−1.1 (6)	S1—C7—C12—C11	175.5 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O6^iii	0.83	1.86	2.674 (4)	164
O1—H2W···O5^iv	0.83	1.99	2.806 (5)	173
O2—H3W···O4^v	0.85	1.92	2.771 (7)	179
O2—H4W···N1^vi	1.03	2.20	2.841 (8)	118
O3—H5W···O7^vi	0.83	1.92	2.743 (4)	168
O3—H6W···O4	0.84	2.08	2.800 (5)	143
O4—H7W···O5	0.87	2.08	2.714 (6)	129
O4—H8W···O3^vii	0.83	2.21	2.886 (5)	139
N1—H1A···O7^v	0.86	2.21	2.997 (5)	152
N1—H1B···O2^viii	0.86	1.98	2.841 (8)	175

Symmetry codes: (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) x, y+1, z; (vii) −x, y−1/2, −z+1/2; (viii) x, y−1, z.