Triaqua­(3-carb­oxy-5-sulfonatobenzoato-κO1)(1,10-phenanthroline-κ2N,N′)cobalt(II) monohydrate

Zhang, B.-Y.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536808019843

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m986

doi:10.1107/S1600536808019843

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Triaqua(3-carboxy-5-sulfonatobenzoato-κO¹)(1,10-phenanthroline-κ²N,N′)cobalt(II) monohydrate

Bing-Yu Zhang,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 27 June 2008; accepted 29 June 2008; online 5 July 2008)

In the title compound, [Co(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)₃]·H₂O, the Co^II cation is coordinated by one sulfoisophthalate dianion, one bidentate phenathroline (phen) molecule and three water molecules in a distorted cis-CoN₂O₄ octahedral geometry. In the crystal structure, aromatic π–π stacking occurs [centroid–centroid distances 3.7630 (14) and 3.7269 (15) Å], as well as an extensive O—H⋯O and C—H⋯O hydrogen-bonding network

Related literature

For related structures, see: Li et al. (2005 ); Liu et al. (2006 ).

Experimental

Crystal data

[Co(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)₃]·H₂O
M_r = 555.37
Monoclinic, P 2₁ /n
a = 10.9968 (13) Å
b = 13.9358 (18) Å
c = 15.870 (2) Å
β = 109.645 (14)°
V = 2290.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 295 (2) K
0.36 × 0.24 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.740, T_max = 0.835
25103 measured reflections
4490 independent reflections
3416 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.06
4490 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected bond lengths (Å)

Co—O1	2.0730 (16)
Co—O5	2.1070 (17)
Co—O6	2.1663 (17)
Co—O7	2.1277 (16)
Co—N1	2.1198 (19)
Co—N2	2.141 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O6ⁱ	0.95	2.11	2.881 (3)	137
O1W—H1B⋯O11ⁱⁱ	0.96	1.93	2.873 (3)	165
O4—H4A⋯O1W	0.93	1.71	2.621 (3)	166
O5—H5A⋯O13ⁱⁱⁱ	0.84	1.86	2.695 (3)	175
O5—H5B⋯O3^iv	0.86	1.94	2.798 (2)	174
O6—H6A⋯O3^v	0.81	2.08	2.803 (2)	149
O6—H6B⋯O12^vi	0.85	1.95	2.790 (3)	173
O7—H7A⋯O2	0.86	1.73	2.579 (3)	168
O7—H7B⋯O11ⁱⁱⁱ	0.84	2.03	2.859 (2)	172
C1—H1⋯O5^iv	0.93	2.56	3.249 (3)	131
C2—H2⋯O13^vii	0.93	2.59	3.506 (4)	167
C3—H3⋯O2^vii	0.93	2.48	3.399 (3)	168
C6—H6⋯O1W^viii	0.93	2.59	3.391 (4)	145
C9—H9⋯O12^viii	0.93	2.47	3.373 (4)	164
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+2; (iii) -x, -y, -z+1; (iv) -x+1, -y, -z+1; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) x+1, y, z; (viii) x, y, z-1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019843/hb2753sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019843/hb2753Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of aromatic π–π stacking in coordination complexes (Li et al., 2005; Liu et al., 2006), the title Co^II compound, (I), incorporating the sulfoisophthalate ligand has been prepared and its crystal structure is reported here (Fig. 1).

The Co^II cation in (I) is coordinated by one sulfoisophthalate dianion, one bidentate phenathroline (phen) molecule and three water molecules in a distorted CoN₂O₄ octahedral geometry (Table 1). Among the two carboxyl groups of the sulfoisophthalate, the C13-carboxyl group is deprotonated and the difference between C13—O1 and C13—O2 bond distances is small whereas the C20-carboxyl group is not deprotonated and the difference between the C20—O3 and C20—O4 bond distances is larger (Table 1).

This is in agreement with those found in related structures, e.g. catena-((µ₃-5-carboxy-3-sulfonatobenzoato)aqua(phenanthroline)lead(II) monohydrate (Li et al., 2005) and bis(µ₂-aqua)hexaaquabis(5-sulfoisophthalato)dicadmium(II) (Liu et al., 2006). The C13-carboxyl group is hydrogen bonded (as an acceptor) to the coordinated water molecule while the C20-carboxylo group is hydrogen bonded (as a donor) to the uncoordinated water molecule (Fig. 1). An extensive O—H···O and C—H···O hydrogen bonding network helps to consolidate the packing (Table 2).

A partially overlapped arrangement is observed between nearly parallel phen ring system and the benzene ring of the sulfoisophthalate dianion from an adjacent complex (Fig. 2). The centroid-to-centroid distances of 3.7630 (14) Å between the N1-pyridine and C16ⁱ-benzene rings and 3.7269 (15) Å between the C6-benzene and C16ⁱ-benzene rings [symmetry code: (i) 1 - x, -y, 1 - z] indicate the existence of π–π stacking between phen and sulfoisophthalate of the adjacent molecule.

Related literature top

For related structures, see: Li et al. (2005); Liu et al. (2006).

Experimental top

A water–ethanol solution (15 ml, 2:1 v/v) containing monosodium 5-sulfoisophthalate (0.27 g, 1 mmol), sodium carbonate (0.053 g, 0.5 mmol), 1,10-phenanthroline (0.10 g, 0.5 mmol) and cobalt nitrate hexahydrate (0.29 g, 1 mmol) was refluxed for 3 h. After cooling to room temperature the solution was filtered. Red prisms of (I) were obtained from the filtrate after one week.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) with 40% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding.
	Fig. 2. A diagram showing π–π stacking between aromatic rings [symmetry code: (i) 1 - x, -y, 1 - z].

Triaqua(3-carboxy-5-sulfonatobenzoato-κO¹)(1,10-phenanthroline- κ²N,N')cobalt(II) monohydrate top

Crystal data top

[Co(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)₃]·H₂O	F(000) = 1140
M_r = 555.37	D_x = 1.611 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6846 reflections
a = 10.9968 (13) Å	θ = 2.0–25.0°
b = 13.9358 (18) Å	µ = 0.91 mm⁻¹
c = 15.870 (2) Å	T = 295 K
β = 109.645 (14)°	Prism, red
V = 2290.4 (5) Å³	0.36 × 0.24 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4490 independent reflections
Radiation source: fine-focus sealed tube	3416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 10.0 pixels mm^-1	θ_max = 26.0°, θ_min = 2.0°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→16
T_min = 0.740, T_max = 0.835	l = −18→19
25103 measured reflections

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0494P)² + 0.1783P] where P = (F_o² + 2F_c²)/3
4490 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Co(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)₃]·H₂O	V = 2290.4 (5) Å³
M_r = 555.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.9968 (13) Å	µ = 0.91 mm⁻¹
b = 13.9358 (18) Å	T = 295 K
c = 15.870 (2) Å	0.36 × 0.24 × 0.20 mm
β = 109.645 (14)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4490 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3416 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.835	R_int = 0.051
25103 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.06	Δρ_max = 0.40 e Å⁻³
4490 reflections	Δρ_min = −0.28 e Å⁻³
316 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Co	0.32537 (3)	0.13651 (2)	0.35952 (2)	0.03134 (12)
S	0.05040 (5)	0.06815 (4)	0.78134 (4)	0.03161 (16)
N1	0.52786 (18)	0.12769 (13)	0.38882 (13)	0.0321 (4)
N2	0.3431 (2)	0.14723 (15)	0.22955 (13)	0.0387 (5)
O1	0.32643 (15)	0.12435 (12)	0.48995 (11)	0.0367 (4)
O2	0.11757 (17)	0.14036 (17)	0.47225 (13)	0.0674 (7)
O3	0.63866 (15)	0.09338 (13)	0.80484 (11)	0.0418 (4)
O4	0.55844 (17)	0.09929 (17)	0.91585 (12)	0.0585 (6)
H4A	0.6392	0.0966	0.9595	0.088*
O5	0.30048 (15)	−0.01239 (12)	0.33733 (11)	0.0386 (4)
H5A	0.2252	−0.0345	0.3241	0.058*
H5B	0.3245	−0.0352	0.2950	0.058*
O6	0.35517 (15)	0.28948 (12)	0.38099 (11)	0.0388 (4)
H6A	0.2923	0.3108	0.3420	0.058*
H6B	0.4197	0.3111	0.3694	0.058*
O7	0.12326 (15)	0.16385 (12)	0.31242 (11)	0.0405 (4)
H7A	0.1099	0.1588	0.3629	0.061*
H7B	0.0742	0.1278	0.2734	0.061*
O11	0.05105 (16)	−0.03233 (12)	0.80684 (11)	0.0435 (4)
O12	0.07483 (16)	0.13193 (13)	0.85730 (12)	0.0444 (5)
O13	−0.06484 (15)	0.09361 (14)	0.70756 (12)	0.0465 (5)
O1W	0.7986 (2)	0.1114 (2)	1.02278 (15)	0.0893 (9)
H1A	0.8596	0.1380	0.9985	0.134*
H1B	0.8576	0.0794	1.0741	0.134*
C1	0.6184 (2)	0.11688 (18)	0.46861 (17)	0.0395 (6)
H1	0.5929	0.1065	0.5181	0.047*
C2	0.7504 (3)	0.12047 (19)	0.4809 (2)	0.0488 (7)
H2	0.8108	0.1121	0.5377	0.059*
C3	0.7901 (2)	0.13620 (18)	0.4096 (2)	0.0482 (7)
H3	0.8777	0.1396	0.4175	0.058*
C4	0.6977 (2)	0.14729 (16)	0.32399 (19)	0.0393 (6)
C5	0.7295 (3)	0.16124 (19)	0.2445 (2)	0.0497 (7)
H5	0.8156	0.1661	0.2486	0.060*
C6	0.6364 (3)	0.16742 (19)	0.1640 (2)	0.0527 (8)
H6	0.6597	0.1761	0.1134	0.063*
C7	0.5023 (3)	0.16096 (18)	0.15414 (18)	0.0446 (7)
C8	0.4010 (3)	0.1641 (2)	0.07230 (19)	0.0596 (8)
H8	0.4191	0.1708	0.0194	0.071*
C9	0.2766 (3)	0.1574 (2)	0.0696 (2)	0.0637 (9)
H9	0.2094	0.1578	0.0151	0.076*
C10	0.2509 (3)	0.1500 (2)	0.14981 (19)	0.0537 (8)
H10	0.1653	0.1468	0.1473	0.064*
C11	0.4678 (2)	0.15056 (17)	0.23164 (17)	0.0349 (6)
C12	0.5665 (2)	0.14201 (16)	0.31698 (16)	0.0323 (5)
C13	0.2328 (2)	0.12619 (17)	0.51846 (16)	0.0348 (6)
C14	0.2602 (2)	0.10967 (16)	0.61750 (15)	0.0305 (5)
C15	0.1576 (2)	0.09694 (17)	0.64978 (16)	0.0320 (5)
H15	0.0731	0.0971	0.6102	0.038*
C16	0.1814 (2)	0.08409 (16)	0.74032 (15)	0.0293 (5)
C17	0.3073 (2)	0.08407 (16)	0.80040 (16)	0.0317 (5)
H17	0.3226	0.0759	0.8613	0.038*
C18	0.4098 (2)	0.09629 (17)	0.76915 (15)	0.0312 (5)
C19	0.3862 (2)	0.10878 (17)	0.67763 (16)	0.0313 (5)
H19	0.4551	0.1165	0.6567	0.038*
C20	0.5461 (2)	0.09713 (18)	0.83179 (16)	0.0351 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.02507 (18)	0.0439 (2)	0.0262 (2)	−0.00116 (13)	0.01016 (14)	0.00125 (14)
S	0.0246 (3)	0.0425 (3)	0.0300 (3)	−0.0027 (2)	0.0122 (3)	−0.0003 (3)
N1	0.0287 (10)	0.0399 (11)	0.0287 (11)	0.0004 (8)	0.0110 (9)	0.0012 (9)
N2	0.0379 (12)	0.0501 (13)	0.0271 (12)	0.0012 (10)	0.0095 (10)	0.0028 (9)
O1	0.0289 (9)	0.0581 (11)	0.0255 (9)	0.0008 (7)	0.0122 (7)	0.0025 (8)
O2	0.0307 (10)	0.141 (2)	0.0324 (11)	0.0098 (11)	0.0125 (9)	0.0141 (12)
O3	0.0264 (9)	0.0628 (11)	0.0378 (10)	−0.0036 (8)	0.0130 (8)	−0.0111 (9)
O4	0.0326 (10)	0.1136 (17)	0.0280 (10)	−0.0016 (11)	0.0086 (8)	−0.0058 (11)
O5	0.0324 (9)	0.0489 (10)	0.0370 (10)	−0.0058 (7)	0.0149 (8)	−0.0054 (8)
O6	0.0271 (8)	0.0478 (10)	0.0438 (10)	0.0009 (7)	0.0149 (8)	0.0058 (8)
O7	0.0306 (9)	0.0577 (11)	0.0318 (10)	−0.0018 (8)	0.0085 (8)	−0.0016 (8)
O11	0.0412 (10)	0.0457 (10)	0.0476 (11)	−0.0046 (8)	0.0205 (9)	0.0054 (9)
O12	0.0374 (10)	0.0588 (12)	0.0421 (11)	−0.0031 (8)	0.0200 (9)	−0.0150 (9)
O13	0.0248 (9)	0.0721 (13)	0.0401 (11)	−0.0009 (8)	0.0077 (8)	0.0100 (9)
O1W	0.0410 (12)	0.174 (3)	0.0463 (14)	−0.0109 (14)	0.0059 (10)	0.0314 (15)
C1	0.0319 (13)	0.0495 (15)	0.0355 (15)	0.0006 (11)	0.0093 (12)	0.0020 (12)
C2	0.0343 (14)	0.0544 (17)	0.0490 (18)	0.0024 (12)	0.0025 (13)	0.0004 (14)
C3	0.0264 (13)	0.0477 (16)	0.071 (2)	0.0014 (11)	0.0164 (14)	−0.0012 (14)
C4	0.0380 (14)	0.0310 (13)	0.0588 (18)	0.0015 (10)	0.0291 (14)	0.0002 (12)
C5	0.0503 (17)	0.0424 (16)	0.072 (2)	0.0004 (13)	0.0416 (17)	−0.0008 (14)
C6	0.077 (2)	0.0411 (15)	0.064 (2)	0.0034 (14)	0.0561 (19)	0.0034 (14)
C7	0.0640 (19)	0.0398 (15)	0.0406 (16)	0.0052 (13)	0.0316 (15)	0.0040 (12)
C8	0.089 (3)	0.063 (2)	0.0345 (17)	0.0117 (18)	0.0306 (17)	0.0098 (14)
C9	0.078 (2)	0.078 (2)	0.0265 (16)	0.0079 (18)	0.0057 (16)	0.0064 (15)
C10	0.0482 (17)	0.072 (2)	0.0343 (16)	0.0018 (15)	0.0059 (14)	0.0050 (14)
C11	0.0438 (15)	0.0335 (13)	0.0340 (14)	0.0020 (10)	0.0217 (12)	0.0021 (10)
C12	0.0350 (13)	0.0287 (12)	0.0389 (15)	−0.0009 (10)	0.0199 (12)	−0.0017 (10)
C13	0.0285 (13)	0.0493 (15)	0.0285 (13)	−0.0020 (11)	0.0123 (11)	0.0011 (11)
C14	0.0306 (12)	0.0347 (12)	0.0286 (13)	−0.0025 (10)	0.0132 (11)	−0.0027 (10)
C15	0.0261 (12)	0.0389 (13)	0.0317 (13)	−0.0010 (10)	0.0108 (10)	−0.0026 (11)
C16	0.0277 (12)	0.0329 (12)	0.0305 (13)	−0.0019 (9)	0.0139 (10)	−0.0022 (10)
C17	0.0305 (12)	0.0397 (14)	0.0276 (13)	−0.0024 (10)	0.0134 (11)	−0.0007 (10)
C18	0.0287 (12)	0.0345 (12)	0.0298 (13)	−0.0038 (10)	0.0089 (10)	−0.0022 (10)
C19	0.0270 (12)	0.0401 (13)	0.0320 (13)	−0.0019 (10)	0.0166 (10)	−0.0016 (11)
C20	0.0269 (12)	0.0452 (14)	0.0328 (14)	−0.0028 (11)	0.0096 (11)	−0.0012 (11)

Geometric parameters (Å, º) top

Co—O1	2.0730 (16)	C2—C3	1.361 (4)
Co—O5	2.1070 (17)	C2—H2	0.9300
Co—O6	2.1663 (17)	C3—C4	1.405 (4)
Co—O7	2.1277 (16)	C3—H3	0.9300
Co—N1	2.1198 (19)	C4—C12	1.411 (3)
Co—N2	2.141 (2)	C4—C5	1.431 (4)
S—O11	1.4569 (18)	C5—C6	1.345 (4)
S—O12	1.4482 (18)	C5—H5	0.9300
S—O13	1.4509 (17)	C6—C7	1.432 (4)
S—C16	1.783 (2)	C6—H6	0.9300
N1—C1	1.330 (3)	C7—C8	1.399 (4)
N1—C12	1.359 (3)	C7—C11	1.411 (3)
N2—C10	1.330 (3)	C8—C9	1.357 (4)
N2—C11	1.361 (3)	C8—H8	0.9300
O1—C13	1.257 (3)	C9—C10	1.398 (4)
O2—C13	1.248 (3)	C9—H9	0.9300
O3—C20	1.231 (3)	C10—H10	0.9300
O4—C20	1.295 (3)	C11—C12	1.428 (3)
O4—H4A	0.9257	C13—C14	1.515 (3)
O5—H5A	0.8416	C14—C19	1.393 (3)
O5—H5B	0.8608	C14—C15	1.399 (3)
O6—H6A	0.8129	C15—C16	1.383 (3)
O6—H6B	0.8463	C15—H15	0.9300
O7—H7A	0.8645	C16—C17	1.392 (3)
O7—H7B	0.8385	C17—C18	1.386 (3)
O1W—H1A	0.9530	C17—H17	0.9300
O1W—H1B	0.9630	C18—C19	1.398 (3)
C1—C2	1.399 (4)	C18—C20	1.495 (3)
C1—H1	0.9300	C19—H19	0.9300

O1—Co—O5	92.48 (6)	C12—C4—C5	118.9 (3)
O1—Co—N1	97.09 (7)	C6—C5—C4	120.8 (3)
O5—Co—N1	92.72 (7)	C6—C5—H5	119.6
O1—Co—O7	91.14 (6)	C4—C5—H5	119.6
O5—Co—O7	93.21 (6)	C5—C6—C7	121.8 (3)
N1—Co—O7	169.64 (7)	C5—C6—H6	119.1
O1—Co—N2	174.74 (7)	C7—C6—H6	119.1
O5—Co—N2	87.51 (7)	C8—C7—C11	116.7 (3)
N1—Co—N2	77.66 (8)	C8—C7—C6	124.7 (3)
O7—Co—N2	94.11 (7)	C11—C7—C6	118.7 (3)
O1—Co—O6	88.49 (6)	C9—C8—C7	120.5 (3)
O5—Co—O6	178.49 (6)	C9—C8—H8	119.8
N1—Co—O6	86.00 (6)	C7—C8—H8	119.8
O7—Co—O6	87.93 (6)	C8—C9—C10	119.1 (3)
N2—Co—O6	91.43 (7)	C8—C9—H9	120.4
O12—S—O13	112.88 (11)	C10—C9—H9	120.4
O12—S—O11	112.12 (11)	N2—C10—C9	123.1 (3)
O13—S—O11	112.37 (11)	N2—C10—H10	118.5
O12—S—C16	106.31 (11)	C9—C10—H10	118.5
O13—S—C16	105.58 (11)	N2—C11—C7	123.1 (2)
O11—S—C16	106.98 (10)	N2—C11—C12	117.3 (2)
C1—N1—C12	118.0 (2)	C7—C11—C12	119.6 (2)
C1—N1—Co	127.59 (17)	N1—C12—C4	122.8 (2)
C12—N1—Co	114.17 (15)	N1—C12—C11	117.1 (2)
C10—N2—C11	117.5 (2)	C4—C12—C11	120.1 (2)
C10—N2—Co	129.16 (19)	O2—C13—O1	125.8 (2)
C11—N2—Co	113.33 (16)	O2—C13—C14	116.3 (2)
C13—O1—Co	128.88 (16)	O1—C13—C14	118.0 (2)
C20—O4—H4A	120.8	C19—C14—C15	119.1 (2)
Co—O5—H5A	117.7	C19—C14—C13	121.1 (2)
Co—O5—H5B	116.0	C15—C14—C13	119.7 (2)
H5A—O5—H5B	101.8	C16—C15—C14	120.2 (2)
Co—O6—H6A	101.2	C16—C15—H15	119.9
Co—O6—H6B	114.2	C14—C15—H15	119.9
H6A—O6—H6B	105.4	C15—C16—C17	120.6 (2)
Co—O7—H7A	98.2	C15—C16—S	120.11 (17)
Co—O7—H7B	119.3	C17—C16—S	119.32 (17)
H7A—O7—H7B	111.6	C18—C17—C16	119.7 (2)
H1A—O1W—H1B	99.1	C18—C17—H17	120.1
N1—C1—C2	122.5 (2)	C16—C17—H17	120.1
N1—C1—H1	118.7	C17—C18—C19	119.9 (2)
C2—C1—H1	118.7	C17—C18—C20	121.2 (2)
C3—C2—C1	119.8 (3)	C19—C18—C20	119.0 (2)
C3—C2—H2	120.1	C14—C19—C18	120.5 (2)
C1—C2—H2	120.1	C14—C19—H19	119.8
C2—C3—C4	119.5 (2)	C18—C19—H19	119.8
C2—C3—H3	120.3	O3—C20—O4	123.1 (2)
C4—C3—H3	120.3	O3—C20—C18	122.0 (2)
C3—C4—C12	117.3 (2)	O4—C20—C18	114.8 (2)
C3—C4—C5	123.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O6ⁱ	0.95	2.11	2.881 (3)	137
O1W—H1B···O11ⁱⁱ	0.96	1.93	2.873 (3)	165
O4—H4A···O1W	0.93	1.71	2.621 (3)	166
O5—H5A···O13ⁱⁱⁱ	0.84	1.86	2.695 (3)	175
O5—H5B···O3^iv	0.86	1.94	2.798 (2)	174
O6—H6A···O3^v	0.81	2.08	2.803 (2)	149
O6—H6B···O12^vi	0.85	1.95	2.790 (3)	173
O7—H7A···O2	0.86	1.73	2.579 (3)	168
O7—H7B···O11ⁱⁱⁱ	0.84	2.03	2.859 (2)	172
C1—H1···O5^iv	0.93	2.56	3.249 (3)	131
C2—H2···O13^vii	0.93	2.59	3.506 (4)	167
C3—H3···O2^vii	0.93	2.48	3.399 (3)	168
C6—H6···O1W^viii	0.93	2.59	3.391 (4)	145
C9—H9···O12^viii	0.93	2.47	3.373 (4)	164

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)₃]·H₂O
M_r	555.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	10.9968 (13), 13.9358 (18), 15.870 (2)
β (°)	109.645 (14)
V (Å³)	2290.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.36 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.740, 0.835
No. of measured, independent and observed [I > 2σ(I)] reflections	25103, 4490, 3416
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.06
No. of reflections	4490
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.28

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Co—O1	2.0730 (16)	Co—O7	2.1277 (16)
Co—O5	2.1070 (17)	Co—N1	2.1198 (19)
Co—O6	2.1663 (17)	Co—N2	2.141 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O6ⁱ	0.95	2.11	2.881 (3)	137
O1W—H1B···O11ⁱⁱ	0.96	1.93	2.873 (3)	165
O4—H4A···O1W	0.93	1.71	2.621 (3)	166
O5—H5A···O13ⁱⁱⁱ	0.84	1.86	2.695 (3)	175
O5—H5B···O3^iv	0.86	1.94	2.798 (2)	174
O6—H6A···O3^v	0.81	2.08	2.803 (2)	149
O6—H6B···O12^vi	0.85	1.95	2.790 (3)	173
O7—H7A···O2	0.86	1.73	2.579 (3)	168
O7—H7B···O11ⁱⁱⁱ	0.84	2.03	2.859 (2)	172
C1—H1···O5^iv	0.93	2.56	3.249 (3)	131
C2—H2···O13^vii	0.93	2.59	3.506 (4)	167
C3—H3···O2^vii	0.93	2.48	3.399 (3)	168
C6—H6···O1W^viii	0.93	2.59	3.391 (4)	145
C9—H9···O12^viii	0.93	2.47	3.373 (4)	164

Acknowledgements

This work was supported by the ZIJIN project of Zhejiang University, China.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, X.-H., Xiao, H.-P., Zhang, Q. & Hu, M.-L. (2005). Acta Cryst. C61, m130–m132. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Liu, Q.-Y., Wang, Y.-L. & Xu, L. (2006). Eur. J. Inorg. Chem. pp. 4843–4851. Web of Science CSD CrossRef Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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