Triaqua­(2,2′-bipyridine)(2-sulfonatobenzoato)cobalt(II)

In the title compound, [Co(C₇H₄O₅S)(C₁₀H₈N₂)(H₂O)₃], the Co^II atom has a distorted octa­hedral geometry formed by three aqua O atoms, one carboxyl­ate O atom from a 2-sulfonatobenzoate dianion and two N atoms of a 2,2′-bipyridine ligand. Inter­molecular O—H...O hydrogen bonds link the mononuclear units into a two-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.023
• wR factor = 0.057
• Data-to-parameter ratio = 9.9

checkCIF/PLATON results

No syntax errors found



Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.98
           From the CIF: _reflns_number_total               2602
           Count of symmetry unique reflns         1897
           Completeness (_total/calc)            137.16%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       705
           Fraction of Friedel pairs measured     0.372
           Are heavy atom types Z>Si present        yes

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

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

---

S1. Comment

Like other sulfobenzoic acids, such as 4-sulfobenzoic acid (Zhang et al., 2005) and 5-sulfoisophthalic acid (Li et al., 2005; Xiao & Morsali, 2005; Yuan et al., 2004), which show diverse coordination modes, 2-sulfobenzoic acid (o-H₂sb) is also a versatile ligand and can function variously as a monodentate, bidentate or tridentate ligand; it can also bridge or chelate (Li & Yang, 2004; Su et al., 2005; Xiao et al., 2005). Here, we represent the title compound [Co(2,2'-bipy)(o-sb)(H₂O)₃] (2,2'-bipy is 2,2'-bipyridine), (I), in which the o-sb²⁻ dianion functions in a monodentate coordination mode.

In (I), the Co^II atom is in a distorted octahedral environment formed by three aqua O atoms, one carboxylate O atom from an o-sb²⁻ dianion and two N atoms of a 2,2'-bipyridine ligand (Fig. 1 and Table 1). The o-sb²⁻ ligand coordinates to the Co^II centre in a monodentate mode, which is the same as observed in the previously reported compound [Mn(phen)₂(o-sb)(H₂O)]·3H₂O (phen is 1,10-phenanthroline; Xiao, 2005). The dihedral angle between the planes of the o-sb²⁻ ring and its carboxylate group is 59.7 (1)°, which is comparable with that in [Mn(phen)₂(o-sb)(H₂O)]·3H₂O and much larger than that in [Ni(o-sb)(bpe)(H₂O)₂]·0.25H₂O (Xiao et al., 2005). The dihedral angle between the o-sb²⁻ ring and the mean plane of the 2,2'-bipyridine rings is 50.6 (2)°.

The stability of the crystal structure of (I) is enhanced significantly by hydrogen-bonding interactions (Table 2). There are three intramolecular hydrogen bonds between the coordinated water molecule and the uncoordinated carboxylate O atom (O8—H8B···O2), and between the coordinated water molecule and the uncoordinated sulfonate group (O7—H7A···O3 and O6—H6A···O4). Additional O6—H6B···O2, O8—H8A···O3 and O7—H7B···O5 intermolecular hydrogen bonds link neighbouring mononuclear units into a two-dimensional network structure (Fig. 2).

S2. Experimental

An aqueous solution (10 ml) of CoCl₂·6H₂O (0.20 mmol, 0.047 g) was added slowly to a solution (10 ml) of N,N-dimethylformamide containing 2,2'-bipyridine (0.20 mmol, 0.031 g) and 2-sulfobenzoic acid (0.20 mmol, 0.037 g). Red crystals of (I) suitable for X-ray diffraction analysis were obtained on allowing the solution to stand at room temperature for about two months.

S3. Refinement

Water H atoms were located in a difference map and refined with distance restraints O—H = 0.82 (1) Å and with U_iso(H) = 1.5U_eq(O). Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The coordination environment of the Co^II atom in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the two-dimensional network structure formed by hydrogen bonding interactions (shown as dashed lines). For clarity, the 2,2'-bipyridine ligands have been omitted.

Triaqua(2,2'-bipyridine)(2-sulfonatobenzoato)cobalt(II)

Crystal data

[Co(C7H4O5S)(C10H8N2)(H2O)3]	F(000) = 482
Mr = 469.32	Dx = 1.610 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 1079 reflections
a = 7.4546 (7) Å	θ = 2.5–25.2°
b = 12.3272 (11) Å	µ = 1.04 mm^−1
c = 10.5333 (9) Å	T = 298 K
β = 90.142 (11)°	Block, red
V = 967.95 (15) Å^3	0.32 × 0.25 × 0.17 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2602 independent reflections
Radiation source: fine-focus sealed tube	2565 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→9
Tmin = 0.731, Tmax = 0.843	k = −15→15
5336 measured reflections	l = −12→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0228P)^2 + 0.0468P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2602 reflections	Δρmax = 0.21 e Å^−3
262 parameters	Δρmin = −0.24 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 1897 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (10)

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	0.75555 (3)	0.81413 (2)	0.06926 (3)	0.02901 (9)
S1	0.64956 (9)	0.81690 (5)	0.48475 (6)	0.03447 (16)
O1	0.5925 (2)	0.73049 (14)	0.19754 (18)	0.0325 (4)
O2	0.3141 (2)	0.79215 (16)	0.1713 (2)	0.0439 (5)
O3	0.5840 (3)	0.90778 (14)	0.40835 (18)	0.0408 (5)
O4	0.8146 (3)	0.77107 (16)	0.4378 (2)	0.0451 (5)
O5	0.6566 (4)	0.84418 (17)	0.6185 (2)	0.0542 (6)
O6	0.9540 (2)	0.74925 (15)	0.18803 (18)	0.0395 (4)
H6A	0.9241	0.7567	0.2625	0.059*
H6B	1.0609	0.7648	0.1895	0.059*
O7	0.7481 (3)	0.95047 (14)	0.18624 (19)	0.0438 (5)
H7A	0.7120	0.9423	0.2591	0.066*
H7B	0.7213	1.0130	0.1678	0.066*
O8	0.5243 (3)	0.86858 (15)	−0.02745 (19)	0.0432 (5)
H8A	0.5205	0.9320	−0.0504	0.065*
H8B	0.4422	0.8408	0.0127	0.065*
N1	0.9399 (3)	0.88320 (16)	−0.0602 (2)	0.0330 (5)
N2	0.7909 (3)	0.68890 (15)	−0.0661 (2)	0.0339 (5)
C1	1.0184 (4)	0.9796 (2)	−0.0480 (3)	0.0414 (6)
H1	0.9844	1.0236	0.0195	0.050*
C2	1.1471 (4)	1.0173 (2)	−0.1300 (3)	0.0472 (7)
H2	1.1987	1.0853	−0.1185	0.057*
C3	1.1972 (5)	0.9526 (2)	−0.2289 (4)	0.0531 (7)
H3	1.2852	0.9758	−0.2853	0.064*
C4	1.1176 (4)	0.8534 (3)	−0.2446 (3)	0.0481 (7)
H4	1.1498	0.8088	−0.3121	0.058*
C5	0.9878 (4)	0.82048 (19)	−0.1581 (3)	0.0338 (6)
C6	0.8982 (4)	0.7123 (2)	−0.1650 (3)	0.0348 (6)
C7	0.9237 (4)	0.6398 (2)	−0.2631 (3)	0.0463 (7)
H7	0.9935	0.6588	−0.3328	0.056*
C8	0.8447 (5)	0.5390 (3)	−0.2566 (3)	0.0543 (8)
H8	0.8638	0.4883	−0.3205	0.065*
C9	0.7380 (5)	0.5142 (2)	−0.1553 (3)	0.0527 (8)
H9	0.6842	0.4464	−0.1490	0.063*
C10	0.7115 (4)	0.5914 (2)	−0.0626 (3)	0.0456 (7)
H10	0.6356	0.5753	0.0049	0.055*
C11	0.4336 (3)	0.74470 (19)	0.2331 (2)	0.0298 (5)
C12	0.3883 (3)	0.69362 (17)	0.3601 (3)	0.0295 (5)
C13	0.4818 (3)	0.71406 (19)	0.4726 (3)	0.0311 (5)
C14	0.4466 (4)	0.6548 (2)	0.5817 (3)	0.0441 (7)
H14	0.5070	0.6705	0.6568	0.053*
C15	0.3208 (4)	0.5720 (3)	0.5783 (3)	0.0542 (8)
H15	0.3018	0.5295	0.6499	0.065*
C16	0.2240 (4)	0.5524 (2)	0.4694 (3)	0.0511 (8)
H16	0.1377	0.4979	0.4683	0.061*
C17	0.2547 (4)	0.6135 (2)	0.3619 (3)	0.0376 (6)
H17	0.1858	0.6015	0.2896	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02392 (16)	0.03124 (16)	0.03187 (18)	−0.00049 (14)	0.00387 (12)	0.00286 (16)
S1	0.0420 (4)	0.0302 (3)	0.0312 (4)	−0.0030 (3)	−0.0010 (3)	−0.0011 (3)
O1	0.0233 (9)	0.0372 (9)	0.0370 (10)	0.0008 (7)	0.0073 (7)	0.0057 (8)
O2	0.0233 (10)	0.0626 (12)	0.0458 (12)	0.0052 (9)	0.0035 (8)	0.0154 (10)
O3	0.0539 (13)	0.0290 (8)	0.0394 (11)	−0.0014 (8)	0.0037 (9)	0.0001 (8)
O4	0.0348 (11)	0.0483 (10)	0.0522 (12)	−0.0018 (9)	−0.0030 (9)	0.0038 (10)
O5	0.0810 (17)	0.0447 (10)	0.0368 (12)	−0.0108 (11)	−0.0035 (11)	−0.0051 (10)
O6	0.0239 (9)	0.0530 (11)	0.0417 (11)	0.0022 (8)	0.0007 (7)	0.0091 (9)
O7	0.0606 (13)	0.0328 (9)	0.0380 (11)	0.0009 (9)	0.0081 (9)	0.0027 (8)
O8	0.0344 (10)	0.0496 (11)	0.0457 (12)	0.0040 (9)	−0.0008 (8)	0.0121 (9)
N1	0.0285 (11)	0.0326 (10)	0.0378 (12)	−0.0026 (8)	0.0016 (9)	0.0055 (9)
N2	0.0313 (12)	0.0314 (11)	0.0389 (13)	−0.0027 (9)	0.0003 (10)	0.0034 (9)
C1	0.0402 (16)	0.0341 (13)	0.0499 (17)	−0.0039 (12)	−0.0027 (13)	0.0044 (12)
C2	0.0360 (15)	0.0421 (15)	0.0636 (19)	−0.0106 (12)	−0.0026 (14)	0.0164 (15)
C3	0.0386 (15)	0.0601 (16)	0.0606 (18)	−0.0075 (16)	0.0109 (13)	0.0188 (18)
C4	0.0434 (16)	0.0515 (16)	0.0494 (18)	−0.0011 (14)	0.0159 (13)	0.0084 (14)
C5	0.0298 (14)	0.0370 (13)	0.0346 (14)	0.0009 (10)	0.0032 (11)	0.0054 (11)
C6	0.0321 (14)	0.0354 (12)	0.0370 (15)	0.0008 (11)	0.0006 (11)	0.0046 (11)
C7	0.0509 (19)	0.0456 (15)	0.0422 (16)	0.0018 (14)	0.0088 (13)	−0.0004 (13)
C8	0.057 (2)	0.0491 (17)	0.056 (2)	0.0025 (15)	−0.0057 (16)	−0.0159 (15)
C9	0.0540 (19)	0.0417 (16)	0.062 (2)	−0.0129 (14)	−0.0073 (17)	−0.0023 (16)
C10	0.0453 (17)	0.0395 (14)	0.0518 (18)	−0.0117 (12)	0.0012 (13)	0.0097 (13)
C11	0.0262 (13)	0.0289 (11)	0.0344 (14)	−0.0014 (10)	0.0023 (10)	−0.0034 (10)
C12	0.0233 (13)	0.0257 (11)	0.0396 (15)	0.0057 (9)	0.0084 (10)	−0.0014 (10)
C13	0.0302 (13)	0.0281 (11)	0.0350 (14)	0.0041 (10)	0.0097 (10)	0.0019 (10)
C14	0.0454 (17)	0.0485 (15)	0.0384 (16)	0.0035 (13)	0.0076 (12)	0.0059 (13)
C15	0.0558 (19)	0.0539 (18)	0.053 (2)	−0.0030 (15)	0.0173 (16)	0.0232 (15)
C16	0.0414 (17)	0.0427 (15)	0.069 (2)	−0.0089 (13)	0.0157 (15)	0.0083 (15)
C17	0.0305 (14)	0.0342 (13)	0.0482 (17)	−0.0014 (11)	0.0095 (11)	−0.0014 (12)

Geometric parameters (Å, º)

Co1—O7	2.085 (2)	C2—H2	0.9300
Co1—O1	2.092 (2)	C3—C4	1.370 (5)
Co1—O6	2.094 (2)	C3—H3	0.9300
Co1—O8	2.112 (2)	C4—C5	1.390 (4)
Co1—N1	2.115 (2)	C4—H4	0.9300
Co1—N2	2.118 (2)	C5—C6	1.494 (4)
S1—O4	1.441 (2)	C6—C7	1.379 (4)
S1—O5	1.450 (2)	C7—C8	1.377 (4)
S1—O3	1.4634 (18)	C7—H7	0.9300
S1—C13	1.785 (3)	C8—C9	1.365 (5)
O1—C11	1.255 (3)	C8—H8	0.9300
O2—C11	1.249 (3)	C9—C10	1.378 (4)
O6—H6A	0.8202	C9—H9	0.9300
O6—H6B	0.8199	C10—H10	0.9300
O7—H7A	0.8198	C11—C12	1.517 (4)
O7—H7B	0.8195	C12—C13	1.397 (4)
O8—H8A	0.8194	C12—C17	1.403 (4)
O8—H8B	0.8196	C13—C14	1.387 (4)
N1—C1	1.331 (3)	C14—C15	1.387 (5)
N1—C5	1.338 (4)	C14—H14	0.9300
N2—C10	1.340 (3)	C15—C16	1.377 (5)
N2—C6	1.345 (4)	C15—H15	0.9300
C1—C2	1.372 (4)	C16—C17	1.379 (4)
C1—H1	0.9300	C16—H16	0.9300
C2—C3	1.364 (5)	C17—H17	0.9300
O7—Co1—O1	90.00 (8)	C2—C3—H3	120.1
O7—Co1—O6	88.49 (8)	C4—C3—H3	120.1
O1—Co1—O6	80.58 (7)	C3—C4—C5	118.9 (3)
O7—Co1—O8	90.41 (8)	C3—C4—H4	120.6
O1—Co1—O8	89.66 (7)	C5—C4—H4	120.6
O6—Co1—O8	170.18 (8)	N1—C5—C4	121.5 (2)
O7—Co1—N1	94.23 (8)	N1—C5—C6	115.7 (2)
O1—Co1—N1	173.49 (7)	C4—C5—C6	122.7 (3)
O6—Co1—N1	94.57 (8)	N2—C6—C7	121.6 (2)
O8—Co1—N1	95.25 (8)	N2—C6—C5	114.8 (2)
O7—Co1—N2	171.44 (9)	C7—C6—C5	123.6 (3)
O1—Co1—N2	98.51 (8)	C8—C7—C6	119.2 (3)
O6—Co1—N2	92.05 (8)	C8—C7—H7	120.4
O8—Co1—N2	90.49 (8)	C6—C7—H7	120.4
N1—Co1—N2	77.21 (8)	C9—C8—C7	119.4 (3)
O4—S1—O5	113.16 (14)	C9—C8—H8	120.3
O4—S1—O3	113.37 (12)	C7—C8—H8	120.3
O5—S1—O3	111.66 (12)	C8—C9—C10	118.9 (3)
O4—S1—C13	107.17 (11)	C8—C9—H9	120.6
O5—S1—C13	105.05 (14)	C10—C9—H9	120.6
O3—S1—C13	105.68 (12)	N2—C10—C9	122.4 (3)
C11—O1—Co1	132.32 (16)	N2—C10—H10	118.8
Co1—O6—H6A	109.6	C9—C10—H10	118.8
Co1—O6—H6B	127.4	O2—C11—O1	125.7 (2)
H6A—O6—H6B	102.7	O2—C11—C12	119.7 (2)
Co1—O7—H7A	117.6	O1—C11—C12	114.5 (2)
Co1—O7—H7B	128.6	C13—C12—C17	118.0 (2)
H7A—O7—H7B	104.9	C13—C12—C11	124.2 (2)
Co1—O8—H8A	118.3	C17—C12—C11	117.5 (2)
Co1—O8—H8B	103.2	C14—C13—C12	120.9 (2)
H8A—O8—H8B	121.7	C14—C13—S1	116.5 (2)
C1—N1—C5	118.2 (2)	C12—C13—S1	122.56 (19)
C1—N1—Co1	125.7 (2)	C13—C14—C15	119.6 (3)
C5—N1—Co1	115.97 (16)	C13—C14—H14	120.2
C10—N2—C6	118.4 (2)	C15—C14—H14	120.2
C10—N2—Co1	125.5 (2)	C16—C15—C14	120.4 (3)
C6—N2—Co1	116.07 (16)	C16—C15—H15	119.8
N1—C1—C2	123.3 (3)	C14—C15—H15	119.8
N1—C1—H1	118.3	C17—C16—C15	120.1 (3)
C2—C1—H1	118.3	C17—C16—H16	120.0
C3—C2—C1	118.3 (3)	C15—C16—H16	120.0
C3—C2—H2	120.8	C16—C17—C12	120.9 (3)
C1—C2—H2	120.8	C16—C17—H17	119.6
C2—C3—C4	119.7 (3)	C12—C17—H17	119.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8B···O2	0.82	2.02	2.780 (3)	155
O8—H8A···O3^i	0.82	2.08	2.873 (3)	164
O7—H7B···O5^i	0.82	1.90	2.717 (3)	178
O7—H7A···O3	0.82	1.89	2.692 (3)	167
O6—H6B···O2^ii	0.82	1.93	2.741 (3)	173
O6—H6A···O4	0.82	2.03	2.842 (3)	172

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