Hexa­kis­(μ2-4-amino-3,5-dimethyl-4H-1,2,4-triazole)hexa­aqua­tricobalt(II) naphthalene-1,5-disulfonate tetra­chloride

Gu, Z.-G.; Wang, B.-X.; Pang, C.-Y.; Bao, F.-F.

doi:10.1107/S1600536812020417

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m862

https://doi.org/10.1107/S1600536812020417

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Hexakis(μ₂-4-amino-3,5-dimethyl-4H-1,2,4-triazole)hexaaquatricobalt(II) naphthalene-1,5-disulfonate tetrachloride

Zhi-Guo Gu,^a ^* Bao-Xiang Wang,^a Chun-Yan Pang ^a and Fei-Fei Bao ^a

^aSchool of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, People's Republic of China
^*Correspondence e-mail: zhiguogu@jiangnan.edu.cn

(Received 29 March 2012; accepted 7 May 2012; online 2 June 2012)

In the centrosymmetric trinuclear cation of the title compound, [Co₃(C₄H₈N₄)₆(H₂O)₆](C₁₀H₆O₆S₂)Cl₄, the three Co^II atoms are bridged by six triazole molecules via the N atoms in the 1,2-positions. The central Co^II atom, lying on an inversion center, is coordinated by six triazole N atoms while the terminal Co^II atoms are coordinated by three triazole N atoms and three water O atoms in a distorted octahedral geometry. The naphthalenedisulfonate anion is also centrosymmetric. The four chloride counter anions are half-occupied; the H atoms of the amino groups show an occupancy of 2/3. O—H⋯Cl, O—H⋯O and N—H⋯O hydrogen bonds link the complex cations and the chloride and naphthalene-1,5-disulfonate anions.

Related literature

For the structure of the title cation as hydrated nitrate salt, see: Tong et al. (2011 ).

Experimental

Crystal data

[Co₃(C₄H₈N₄)₆(H₂O)₆](C₁₀H₆O₆S₂)Cl₄
M_r = 1385.82
Triclinic, $[P \overline 1]$
a = 11.1641 (4) Å
b = 12.2744 (5) Å
c = 13.2265 (5) Å
α = 106.924 (2)°
β = 99.622 (3)°
γ = 103.452 (2)°
V = 1631.79 (11) Å³
Z = 1
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 100 K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.763, T_max = 0.815
23481 measured reflections
6410 independent reflections
5057 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.108
S = 1.06
6410 reflections
386 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1X⋯Cl3ⁱ	0.98	2.06	2.765 (3)	127
O1W—H1Y⋯Cl3ⁱⁱ	0.98	1.89	2.701 (3)	138
O2W—H2X⋯Cl1	0.98	2.28	2.929 (3)	122
O2W—H2Y⋯Cl3ⁱⁱ	0.98	2.82	3.749 (3)	158
O3W—H3X⋯O2ⁱⁱⁱ	0.98	1.89	2.773 (3)	148
O3W—H3Y⋯Cl4ⁱⁱⁱ	0.98	2.18	3.114 (3)	159
N8—H8A⋯O3ⁱ	0.91	2.21	3.009 (3)	146
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z-1; (iii) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812020417/hy2535sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812020417/hy2535Isup2.hkl

checkCIF report

Comment top

A recent study has reported a centrosymmetric trinuclear cobalt nitrate complex of 4-amino-3,5-dimethanyl-1,2,4-triazole (C₄H₈N₄), which crystallizes in the monoclinic system, P2₁/n space group (Tong et al., 2011). The charge of the hexavalent cation, [Co₃(C₄H₈N₄)₆(H₂O)₆]⁶⁺, is balanced by the nitrate anions. In the trinuclear unit of the title compound, the central Co^II atom and two terminal Co^II atoms are bridged by six triazole ligands (Fig. 1). The central Co^II atom, lying on an inversion center, is coordinated by six N atoms from the triazole ligands whereas each terminal Co^II atom completes its octahedral geometry by three water molecules. The title compound displays a similar structure to the previuosly reported cobalt analogs (Tong et al., 2011), but it crystallizes in the triclinic system, P1 space group. The charge of the trinuclear cation is balanced by one naphthalene-1,5-disulfonate dianion and four chloride anions. O—H···Cl, O—H···O and N—H···O hydrogen bonds link the complex cations, chloride and naphthalene-1,5-disulfonate anions (Table 1).

Related literature top

For the structure of the title cation as hydrated nitrate salt, see: Tong et al. (2011).

Experimental top

A 20 ml ethanol solution of 4-amino-3,5-dimethanyl-1,2,4-triazole (0.6 mmol) was mixed with a 10 ml aqueous solution of CoCl₂.6H₂O (0.3 mmol). naphthalene-1,5-disulfonate acid (0.1 mmol) in 5 ml of ethanol was added to this reaction mixture with continuous stirring. The resulting solution was filtered and left to stand at room temperature. Pink bolck-shaped crystals of the title compound were obtained by slow evaporation of the solvent within two weeks (yield: 48%).

Structure description top

For the structure of the title cation as hydrated nitrate salt, see: Tong et al. (2011).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 2-x, -y, 2-z.]

Hexakis(µ₂-4-amino-3,5-dimethyl-4H- 1,2,4-triazole)hexaaquatricobalt(II) naphthalene-1,5-disulfonate tetrachloride top

Crystal data top

[Co₃(C₄H₈N₄)₆(H₂O)₆](C₁₀H₆O₆S₂)Cl₄	Z = 1
M_r = 1385.82	F(000) = 715
Triclinic, P1	D_x = 1.410 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.1641 (4) Å	Cell parameters from 3738 reflections
b = 12.2744 (5) Å	θ = 2.2–25.7°
c = 13.2265 (5) Å	µ = 1.05 mm⁻¹
α = 106.924 (2)°	T = 100 K
β = 99.622 (3)°	Block, pink
γ = 103.452 (2)°	0.26 × 0.22 × 0.20 mm
V = 1631.79 (11) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	6410 independent reflections
Radiation source: sealed tube	5057 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.763, T_max = 0.815	k = −15→15
23481 measured reflections	l = −16→16

Refinement top

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0427P)² + 2.0543P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6410 reflections	Δρ_max = 0.67 e Å⁻³
386 parameters	Δρ_min = −0.75 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0020 (5)

Crystal data top

[Co₃(C₄H₈N₄)₆(H₂O)₆](C₁₀H₆O₆S₂)Cl₄	γ = 103.452 (2)°
M_r = 1385.82	V = 1631.79 (11) Å³
Triclinic, P1	Z = 1
a = 11.1641 (4) Å	Mo Kα radiation
b = 12.2744 (5) Å	µ = 1.05 mm⁻¹
c = 13.2265 (5) Å	T = 100 K
α = 106.924 (2)°	0.26 × 0.22 × 0.20 mm
β = 99.622 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	6410 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	5057 reflections with I > 2σ(I)
T_min = 0.763, T_max = 0.815	R_int = 0.043
23481 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.06	Δρ_max = 0.67 e Å⁻³
6410 reflections	Δρ_min = −0.75 e Å⁻³
386 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
Co1	0.63106 (4)	0.64428 (4)	0.31065 (4)	0.02470 (13)
Co2	0.5000	0.5000	0.5000	0.02126 (15)
O1W	0.5966 (2)	0.56654 (19)	0.14192 (17)	0.0265 (5)
H1X	0.5055	0.5253	0.1106	0.040*
H1Y	0.6234	0.6285	0.1105	0.040*
O2W	0.6118 (2)	0.79286 (19)	0.27619 (18)	0.0261 (5)
H2X	0.6232	0.8578	0.3444	0.039*
H2Y	0.5942	0.7753	0.1971	0.039*
O3W	0.8229 (2)	0.70517 (19)	0.31226 (18)	0.0268 (5)
H3X	0.8292	0.7098	0.2406	0.040*
H3Y	0.8764	0.7196	0.3845	0.040*
N1	0.6573 (2)	0.4793 (2)	0.3235 (2)	0.0223 (6)
N2	0.6086 (2)	0.4269 (2)	0.3951 (2)	0.0215 (5)
N3	0.7090 (2)	0.3163 (2)	0.3066 (2)	0.0213 (5)
N4	0.7638 (3)	0.2234 (2)	0.2677 (2)	0.0229 (6)
H4A	0.7329	0.1885	0.1940	0.034*	0.667
H4B	0.7436	0.1680	0.3001	0.034*	0.667
H4C	0.8499	0.2545	0.2842	0.034*	0.667
N5	0.4307 (2)	0.5840 (2)	0.2976 (2)	0.0223 (6)
N6	0.3797 (2)	0.5345 (2)	0.3702 (2)	0.0210 (5)
N7	0.2246 (2)	0.5399 (2)	0.2502 (2)	0.0214 (5)
N8	0.0988 (2)	0.5242 (2)	0.1957 (2)	0.0233 (6)
H8A	0.0997	0.5532	0.1398	0.035*	0.667
H8B	0.0604	0.5640	0.2434	0.035*	0.667
H8C	0.0549	0.4451	0.1687	0.035*	0.667
N9	0.6756 (2)	0.7319 (2)	0.4850 (2)	0.0234 (6)
N10	0.6331 (2)	0.6759 (2)	0.5555 (2)	0.0214 (5)
N11	0.7398 (2)	0.8597 (2)	0.6501 (2)	0.0228 (6)
N12	0.7993 (3)	0.9696 (2)	0.7368 (2)	0.0302 (7)
H12A	0.8319	1.0268	0.7095	0.045*	0.667
H12B	0.8632	0.9615	0.7839	0.045*	0.667
H12C	0.7411	0.9911	0.7727	0.045*	0.667
C1	0.7852 (3)	0.4237 (3)	0.1853 (3)	0.0292 (7)
H1D	0.8529	0.5001	0.2143	0.044*
H1E	0.7246	0.4222	0.1217	0.044*
H1F	0.8225	0.3584	0.1635	0.044*
C2	0.7179 (3)	0.4095 (3)	0.2710 (2)	0.0213 (6)
C3	0.6427 (3)	0.3295 (3)	0.3836 (2)	0.0204 (6)
C4	0.6189 (3)	0.2409 (3)	0.4412 (2)	0.0206 (6)
H4D	0.5658	0.2627	0.4911	0.031*
H4E	0.7003	0.2410	0.4829	0.031*
H4F	0.5751	0.1611	0.3874	0.031*
C5	0.3332 (3)	0.6312 (3)	0.1326 (3)	0.0209 (6)
H5D	0.4186	0.6815	0.1396	0.031*
H5E	0.2731	0.6780	0.1321	0.031*
H5F	0.3068	0.5630	0.0642	0.031*
C6	0.3351 (3)	0.5871 (3)	0.2273 (2)	0.0219 (6)
C7	0.2558 (3)	0.5085 (3)	0.3398 (2)	0.0219 (6)
C8	0.1563 (3)	0.4586 (3)	0.3906 (3)	0.0287 (7)
H8D	0.1968	0.4413	0.4533	0.043*
H8E	0.0959	0.3850	0.3367	0.043*
H8F	0.1110	0.5169	0.4150	0.043*
C9	0.8092 (3)	0.9393 (3)	0.5089 (3)	0.0281 (7)
H9A	0.7569	0.9922	0.5030	0.042*
H9B	0.8251	0.9038	0.4377	0.042*
H9C	0.8905	0.9853	0.5627	0.042*
C10	0.7414 (3)	0.8433 (3)	0.5442 (2)	0.0211 (6)
C11	0.6736 (3)	0.7529 (3)	0.6545 (2)	0.0231 (7)
C12	0.6622 (3)	0.7396 (3)	0.7613 (3)	0.0245 (7)
H12D	0.6123	0.6577	0.7490	0.037*
H12E	0.6196	0.7953	0.7974	0.037*
H12F	0.7473	0.7569	0.8079	0.037*
S1	1.06020 (7)	0.26397 (7)	0.94747 (6)	0.02274 (18)
O1	1.1780 (2)	0.32512 (18)	1.03387 (17)	0.0229 (5)
O2	1.0829 (2)	0.21065 (18)	0.84071 (17)	0.0222 (5)
O3	0.9768 (2)	0.33792 (18)	0.94574 (17)	0.0238 (5)
C13	0.7946 (3)	0.0438 (3)	1.0283 (2)	0.0211 (6)
H13	0.7140	0.0431	1.0427	0.025*
C14	0.8632 (3)	0.1383 (3)	1.0024 (3)	0.0235 (7)
H14	0.8283	0.2011	0.9992	0.028*
C15	0.9796 (3)	0.1417 (3)	0.9818 (3)	0.0229 (7)
C16	1.0358 (3)	0.0482 (3)	0.9874 (3)	0.0226 (6)
C17	1.1565 (3)	0.0484 (3)	0.9670 (3)	0.0245 (7)
H17	1.2041	0.1126	0.9501	0.029*
Cl1	0.45668 (16)	0.91733 (15)	0.39605 (14)	0.0331 (4)	0.50
Cl2	0.47349 (13)	0.01196 (12)	0.18426 (11)	0.0180 (3)	0.50
Cl3	0.57922 (14)	0.65370 (13)	0.97649 (13)	0.0249 (3)	0.50
Cl4	0.95318 (12)	0.22467 (12)	0.48318 (11)	0.0172 (3)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0198 (2)	0.0236 (2)	0.0234 (2)	0.00047 (17)	0.00243 (17)	0.00400 (18)
Co2	0.0170 (3)	0.0209 (3)	0.0225 (3)	0.0040 (2)	0.0033 (2)	0.0048 (2)
O1W	0.0259 (12)	0.0256 (11)	0.0212 (11)	0.0007 (9)	0.0044 (9)	0.0047 (9)
O2W	0.0255 (12)	0.0253 (11)	0.0179 (11)	−0.0031 (9)	0.0005 (9)	0.0047 (9)
O3W	0.0229 (12)	0.0313 (12)	0.0218 (11)	0.0013 (9)	0.0037 (9)	0.0094 (10)
N1	0.0169 (13)	0.0225 (13)	0.0235 (14)	0.0027 (10)	0.0053 (11)	0.0043 (11)
N2	0.0226 (13)	0.0186 (12)	0.0208 (13)	0.0064 (10)	0.0067 (11)	0.0024 (10)
N3	0.0245 (13)	0.0222 (13)	0.0171 (13)	0.0120 (11)	0.0064 (11)	0.0022 (10)
N4	0.0327 (15)	0.0256 (14)	0.0203 (13)	0.0210 (12)	0.0139 (11)	0.0085 (11)
N5	0.0223 (14)	0.0188 (13)	0.0214 (14)	0.0036 (10)	0.0026 (11)	0.0039 (10)
N6	0.0180 (13)	0.0211 (13)	0.0213 (13)	0.0045 (10)	0.0047 (10)	0.0047 (11)
N7	0.0188 (13)	0.0228 (13)	0.0201 (13)	0.0043 (10)	0.0037 (10)	0.0059 (11)
N8	0.0166 (13)	0.0243 (13)	0.0256 (14)	0.0034 (10)	−0.0009 (11)	0.0092 (11)
N9	0.0232 (14)	0.0245 (13)	0.0205 (13)	0.0048 (11)	0.0048 (11)	0.0070 (11)
N10	0.0196 (13)	0.0203 (13)	0.0206 (13)	0.0054 (10)	0.0033 (10)	0.0029 (11)
N11	0.0217 (13)	0.0240 (13)	0.0172 (13)	0.0037 (11)	0.0059 (10)	0.0012 (10)
N12	0.0273 (15)	0.0239 (14)	0.0193 (14)	−0.0075 (11)	0.0020 (11)	−0.0079 (11)
C1	0.0257 (17)	0.0386 (19)	0.0260 (17)	0.0113 (15)	0.0110 (14)	0.0111 (15)
C2	0.0212 (15)	0.0205 (15)	0.0180 (15)	0.0050 (12)	0.0011 (12)	0.0036 (12)
C3	0.0204 (15)	0.0189 (14)	0.0169 (15)	0.0054 (12)	0.0011 (12)	0.0011 (12)
C4	0.0187 (15)	0.0227 (15)	0.0230 (16)	0.0110 (12)	0.0063 (12)	0.0074 (13)
C5	0.0148 (14)	0.0225 (15)	0.0265 (16)	0.0034 (12)	0.0041 (12)	0.0125 (13)
C6	0.0221 (16)	0.0212 (15)	0.0148 (15)	0.0014 (12)	0.0024 (12)	0.0003 (12)
C7	0.0194 (16)	0.0245 (15)	0.0153 (15)	0.0025 (12)	0.0023 (12)	0.0018 (12)
C8	0.0263 (17)	0.0353 (18)	0.0307 (18)	0.0078 (14)	0.0070 (14)	0.0217 (15)
C9	0.0279 (17)	0.0238 (16)	0.0290 (18)	0.0020 (13)	0.0129 (14)	0.0052 (14)
C10	0.0240 (16)	0.0233 (15)	0.0147 (14)	0.0075 (12)	0.0069 (12)	0.0034 (12)
C11	0.0246 (16)	0.0223 (15)	0.0190 (15)	0.0064 (13)	0.0062 (13)	0.0023 (12)
C12	0.0239 (16)	0.0196 (15)	0.0242 (16)	0.0021 (12)	0.0050 (13)	0.0032 (13)
S1	0.0218 (4)	0.0219 (4)	0.0222 (4)	0.0040 (3)	0.0031 (3)	0.0076 (3)
O1	0.0187 (11)	0.0242 (11)	0.0227 (11)	0.0010 (9)	0.0035 (9)	0.0088 (9)
O2	0.0221 (11)	0.0241 (11)	0.0225 (11)	0.0046 (9)	0.0091 (9)	0.0108 (9)
O3	0.0239 (11)	0.0239 (11)	0.0273 (12)	0.0080 (9)	0.0003 (9)	0.0169 (9)
C13	0.0220 (15)	0.0191 (15)	0.0184 (15)	0.0072 (12)	0.0050 (12)	0.0002 (12)
C14	0.0200 (16)	0.0253 (16)	0.0215 (16)	0.0072 (13)	0.0035 (12)	0.0032 (13)
C15	0.0238 (16)	0.0169 (14)	0.0246 (16)	0.0019 (12)	0.0058 (13)	0.0055 (12)
C16	0.0195 (15)	0.0212 (15)	0.0207 (15)	0.0032 (12)	0.0002 (12)	0.0028 (12)
C17	0.0237 (16)	0.0220 (15)	0.0225 (16)	0.0017 (13)	0.0042 (13)	0.0051 (13)
Cl1	0.0314 (9)	0.0308 (8)	0.0284 (9)	−0.0015 (7)	0.0048 (7)	0.0074 (7)
Cl2	0.0182 (7)	0.0195 (7)	0.0128 (6)	0.0016 (5)	0.0015 (5)	0.0050 (5)
Cl3	0.0226 (7)	0.0253 (8)	0.0287 (8)	0.0041 (6)	0.0114 (6)	0.0115 (6)
Cl4	0.0133 (6)	0.0211 (7)	0.0223 (7)	0.0067 (5)	0.0008 (5)	0.0155 (6)

Geometric parameters (Å, º) top

Co1—O2W	2.053 (2)	N12—H12A	0.9100
Co1—O1W	2.084 (2)	N12—H12B	0.9100
Co1—O3W	2.092 (2)	N12—H12C	0.9100
Co1—N5	2.146 (3)	C1—C2	1.490 (4)
Co1—N9	2.156 (3)	C1—H1D	0.9800
Co1—N1	2.162 (3)	C1—H1E	0.9800
Co2—N2ⁱ	2.132 (3)	C1—H1F	0.9800
Co2—N2	2.132 (3)	C3—C4	1.501 (4)
Co2—N10	2.151 (2)	C4—H4D	0.9800
Co2—N10ⁱ	2.151 (2)	C4—H4E	0.9800
Co2—N6ⁱ	2.201 (3)	C4—H4F	0.9800
Co2—N6	2.201 (3)	C5—C6	1.502 (4)
O1W—H1X	0.9796	C5—H5D	0.9800
O1W—H1Y	0.9802	C5—H5E	0.9800
O2W—H2X	0.9801	C5—H5F	0.9800
O2W—H2Y	0.9797	C7—C8	1.494 (4)
O3W—H3X	0.9793	C8—H8D	0.9800
O3W—H3Y	0.9807	C8—H8E	0.9800
N1—C2	1.325 (4)	C8—H8F	0.9800
N1—N2	1.404 (4)	C9—C10	1.485 (4)
N2—C3	1.312 (4)	C9—H9A	0.9800
N3—C2	1.346 (4)	C9—H9B	0.9800
N3—C3	1.350 (4)	C9—H9C	0.9800
N3—N4	1.423 (3)	C11—C12	1.492 (4)
N4—H4A	0.9100	C12—H12D	0.9800
N4—H4B	0.9100	C12—H12E	0.9800
N4—H4C	0.9100	C12—H12F	0.9800
N5—C6	1.308 (4)	S1—O3	1.445 (2)
N5—N6	1.407 (3)	S1—O1	1.462 (2)
N6—C7	1.308 (4)	S1—O2	1.464 (2)
N7—C6	1.358 (4)	S1—C15	1.781 (3)
N7—C7	1.366 (4)	C13—C17ⁱⁱ	1.377 (4)
N7—N8	1.409 (3)	C13—C14	1.398 (4)
N8—H8A	0.9100	C13—H13	0.9500
N8—H8B	0.9100	C14—C15	1.365 (4)
N8—H8C	0.9100	C14—H14	0.9500
N9—C10	1.319 (4)	C15—C16	1.444 (4)
N9—N10	1.391 (3)	C16—C17	1.417 (5)
N10—C11	1.302 (4)	C16—C16ⁱⁱ	1.425 (6)
N11—C10	1.359 (4)	C17—C13ⁱⁱ	1.377 (4)
N11—C11	1.369 (4)	C17—H17	0.9500
N11—N12	1.416 (3)

O2W—Co1—O1W	84.31 (9)	H12A—N12—H12B	109.5
O2W—Co1—O3W	86.35 (9)	N11—N12—H12C	109.5
O1W—Co1—O3W	86.73 (9)	H12A—N12—H12C	109.5
O2W—Co1—N5	90.77 (9)	H12B—N12—H12C	109.5
O1W—Co1—N5	89.79 (9)	C2—C1—H1D	109.5
O3W—Co1—N5	175.68 (9)	C2—C1—H1E	109.5
O2W—Co1—N9	94.08 (9)	H1D—C1—H1E	109.5
O1W—Co1—N9	176.90 (9)	C2—C1—H1F	109.5
O3W—Co1—N9	90.53 (9)	H1D—C1—H1F	109.5
N5—Co1—N9	92.89 (10)	H1E—C1—H1F	109.5
O2W—Co1—N1	171.49 (10)	N1—C2—N3	108.6 (3)
O1W—Co1—N1	87.76 (9)	N1—C2—C1	128.7 (3)
O3W—Co1—N1	90.13 (9)	N3—C2—C1	122.7 (3)
N5—Co1—N1	92.27 (9)	N2—C3—N3	108.8 (3)
N9—Co1—N1	93.70 (10)	N2—C3—C4	130.0 (3)
N2ⁱ—Co2—N2	180.00 (11)	N3—C3—C4	121.1 (3)
N2ⁱ—Co2—N10	87.58 (9)	C3—C4—H4D	109.5
N2—Co2—N10	92.42 (10)	C3—C4—H4E	109.5
N2ⁱ—Co2—N10ⁱ	92.42 (10)	H4D—C4—H4E	109.5
N2—Co2—N10ⁱ	87.58 (9)	C3—C4—H4F	109.5
N10—Co2—N10ⁱ	180.0	H4D—C4—H4F	109.5
N2ⁱ—Co2—N6ⁱ	93.28 (9)	H4E—C4—H4F	109.5
N2—Co2—N6ⁱ	86.72 (9)	C6—C5—H5D	109.5
N10—Co2—N6ⁱ	87.17 (9)	C6—C5—H5E	109.5
N10ⁱ—Co2—N6ⁱ	92.83 (9)	H5D—C5—H5E	109.5
N2ⁱ—Co2—N6	86.72 (9)	C6—C5—H5F	109.5
N2—Co2—N6	93.28 (9)	H5D—C5—H5F	109.5
N10—Co2—N6	92.83 (9)	H5E—C5—H5F	109.5
N10ⁱ—Co2—N6	87.17 (9)	N5—C6—N7	109.2 (3)
N6ⁱ—Co2—N6	180.000 (1)	N5—C6—C5	130.4 (3)
Co1—O1W—H1X	109.4	N7—C6—C5	120.4 (3)
Co1—O1W—H1Y	109.6	N6—C7—N7	108.7 (3)
H1X—O1W—H1Y	109.5	N6—C7—C8	129.9 (3)
Co1—O2W—H2X	109.4	N7—C7—C8	121.4 (3)
Co1—O2W—H2Y	109.5	C7—C8—H8D	109.5
H2X—O2W—H2Y	141.1	C7—C8—H8E	109.5
Co1—O3W—H3X	109.3	H8D—C8—H8E	109.5
Co1—O3W—H3Y	109.6	C7—C8—H8F	109.5
H3X—O3W—H3Y	141.1	H8D—C8—H8F	109.5
C2—N1—N2	106.9 (2)	H8E—C8—H8F	109.5
C2—N1—Co1	130.1 (2)	C10—C9—H9A	109.5
N2—N1—Co1	123.00 (18)	C10—C9—H9B	109.5
C3—N2—N1	107.4 (2)	H9A—C9—H9B	109.5
C3—N2—Co2	129.0 (2)	C10—C9—H9C	109.5
N1—N2—Co2	123.60 (18)	H9A—C9—H9C	109.5
C2—N3—C3	108.1 (2)	H9B—C9—H9C	109.5
C2—N3—N4	123.8 (2)	N9—C10—N11	108.1 (3)
C3—N3—N4	128.1 (2)	N9—C10—C9	129.2 (3)
N3—N4—H4A	109.5	N11—C10—C9	122.8 (3)
N3—N4—H4B	109.5	N10—C11—N11	108.2 (3)
H4A—N4—H4B	109.5	N10—C11—C12	131.1 (3)
N3—N4—H4C	109.5	N11—C11—C12	120.7 (3)
H4A—N4—H4C	109.5	C11—C12—H12D	109.5
H4B—N4—H4C	109.5	C11—C12—H12E	109.5
C6—N5—N6	107.3 (2)	H12D—C12—H12E	109.5
C6—N5—Co1	129.4 (2)	C11—C12—H12F	109.5
N6—N5—Co1	123.37 (18)	H12D—C12—H12F	109.5
C7—N6—N5	107.7 (2)	H12E—C12—H12F	109.5
C7—N6—Co2	130.1 (2)	O3—S1—O1	112.19 (13)
N5—N6—Co2	122.12 (18)	O3—S1—O2	113.46 (13)
C6—N7—C7	107.2 (2)	O1—S1—O2	112.75 (13)
C6—N7—N8	128.9 (3)	O3—S1—C15	106.52 (14)
C7—N7—N8	123.9 (2)	O1—S1—C15	105.66 (13)
N7—N8—H8A	109.5	O2—S1—C15	105.50 (14)
N7—N8—H8B	109.5	C17ⁱⁱ—C13—C14	120.3 (3)
H8A—N8—H8B	109.5	C17ⁱⁱ—C13—H13	119.9
N7—N8—H8C	109.5	C14—C13—H13	119.9
H8A—N8—H8C	109.5	C15—C14—C13	121.1 (3)
H8B—N8—H8C	109.5	C15—C14—H14	119.5
C10—N9—N10	107.7 (2)	C13—C14—H14	119.5
C10—N9—Co1	129.0 (2)	C14—C15—C16	120.7 (3)
N10—N9—Co1	123.31 (18)	C14—C15—S1	118.5 (2)
C11—N10—N9	108.3 (2)	C16—C15—S1	120.8 (2)
C11—N10—Co2	127.8 (2)	C17—C16—C16ⁱⁱ	119.7 (4)
N9—N10—Co2	123.28 (18)	C17—C16—C15	122.7 (3)
C10—N11—C11	107.6 (2)	C16ⁱⁱ—C16—C15	117.6 (4)
C10—N11—N12	123.8 (3)	C13ⁱⁱ—C17—C16	120.6 (3)
C11—N11—N12	128.5 (3)	C13ⁱⁱ—C17—H17	119.7
N11—N12—H12A	109.5	C16—C17—H17	119.7
N11—N12—H12B	109.5

O1W—Co1—N1—C2	42.1 (3)	Co1—N1—C2—N3	179.84 (19)
O3W—Co1—N1—C2	−44.6 (3)	N2—N1—C2—C1	179.3 (3)
N5—Co1—N1—C2	131.8 (3)	Co1—N1—C2—C1	−1.0 (5)
N9—Co1—N1—C2	−135.2 (3)	C3—N3—C2—N1	−0.7 (3)
O1W—Co1—N1—N2	−138.2 (2)	N4—N3—C2—N1	−179.8 (3)
O3W—Co1—N1—N2	135.1 (2)	C3—N3—C2—C1	−180.0 (3)
N5—Co1—N1—N2	−48.5 (2)	N4—N3—C2—C1	0.9 (4)
N9—Co1—N1—N2	44.5 (2)	N1—N2—C3—N3	−1.0 (3)
C2—N1—N2—C3	0.6 (3)	Co2—N2—C3—N3	178.92 (19)
Co1—N1—N2—C3	−179.2 (2)	N1—N2—C3—C4	178.6 (3)
C2—N1—N2—Co2	−179.37 (19)	Co2—N2—C3—C4	−1.4 (5)
Co1—N1—N2—Co2	0.9 (3)	C2—N3—C3—N2	1.1 (3)
N10—Co2—N2—C3	132.7 (3)	N4—N3—C3—N2	−179.8 (3)
N10ⁱ—Co2—N2—C3	−47.3 (3)	C2—N3—C3—C4	−178.6 (3)
N6ⁱ—Co2—N2—C3	45.7 (3)	N4—N3—C3—C4	0.5 (5)
N6—Co2—N2—C3	−134.3 (3)	N6—N5—C6—N7	−1.0 (3)
N10—Co2—N2—N1	−47.3 (2)	Co1—N5—C6—N7	−179.58 (19)
N10ⁱ—Co2—N2—N1	132.7 (2)	N6—N5—C6—C5	179.7 (3)
N6ⁱ—Co2—N2—N1	−134.3 (2)	Co1—N5—C6—C5	1.1 (5)
N6—Co2—N2—N1	45.7 (2)	C7—N7—C6—N5	0.9 (3)
O2W—Co1—N5—C6	40.3 (3)	N8—N7—C6—N5	−179.4 (3)
O1W—Co1—N5—C6	−44.0 (3)	C7—N7—C6—C5	−179.7 (3)
N9—Co1—N5—C6	134.5 (3)	N5—N6—C7—N7	−0.2 (3)
N1—Co1—N5—C6	−131.7 (3)	Co2—N6—C7—N7	−175.57 (19)
O2W—Co1—N5—N6	−138.0 (2)	N5—N6—C7—C8	−177.4 (3)
O1W—Co1—N5—N6	137.7 (2)	Co2—N6—C7—C8	7.3 (5)
N9—Co1—N5—N6	−43.9 (2)	C6—N7—C7—N6	−0.4 (3)
N1—Co1—N5—N6	49.9 (2)	N8—N7—C7—N6	179.9 (3)
C6—N5—N6—C7	0.8 (3)	C6—N7—C7—C8	177.1 (3)
Co1—N5—N6—C7	179.4 (2)	N8—N7—C7—C8	−2.7 (5)
C6—N5—N6—Co2	176.57 (19)	N10—N9—C10—N11	−1.1 (3)
Co1—N5—N6—Co2	−4.8 (3)	Co1—N9—C10—N11	177.3 (2)
N2ⁱ—Co2—N6—C7	−48.8 (3)	N10—N9—C10—C9	178.4 (3)
N2—Co2—N6—C7	131.2 (3)	Co1—N9—C10—C9	−3.2 (5)
N10—Co2—N6—C7	−136.2 (3)	C11—N11—C10—N9	1.9 (4)
N10ⁱ—Co2—N6—C7	43.8 (3)	N12—N11—C10—N9	−178.9 (3)
N2ⁱ—Co2—N6—N5	136.4 (2)	C11—N11—C10—C9	−177.7 (3)
N2—Co2—N6—N5	−43.6 (2)	N12—N11—C10—C9	1.5 (5)
N10—Co2—N6—N5	49.0 (2)	N9—N10—C11—N11	1.3 (3)
N10ⁱ—Co2—N6—N5	−131.0 (2)	Co2—N10—C11—N11	−169.8 (2)
O2W—Co1—N9—C10	−35.7 (3)	N9—N10—C11—C12	−176.3 (3)
O3W—Co1—N9—C10	50.7 (3)	Co2—N10—C11—C12	12.5 (5)
N5—Co1—N9—C10	−126.7 (3)	C10—N11—C11—N10	−2.0 (4)
N1—Co1—N9—C10	140.9 (3)	N12—N11—C11—N10	178.9 (3)
O2W—Co1—N9—N10	142.5 (2)	C10—N11—C11—C12	175.9 (3)
O3W—Co1—N9—N10	−131.1 (2)	N12—N11—C11—C12	−3.2 (5)
N5—Co1—N9—N10	51.5 (2)	C17ⁱⁱ—C13—C14—C15	−0.3 (5)
N1—Co1—N9—N10	−41.0 (2)	C13—C14—C15—C16	−0.7 (5)
C10—N9—N10—C11	−0.2 (3)	C13—C14—C15—S1	179.1 (2)
Co1—N9—N10—C11	−178.7 (2)	O3—S1—C15—C14	−1.7 (3)
C10—N9—N10—Co2	171.5 (2)	O1—S1—C15—C14	117.8 (3)
Co1—N9—N10—Co2	−7.0 (3)	O2—S1—C15—C14	−122.6 (3)
N2ⁱ—Co2—N10—C11	41.0 (3)	O3—S1—C15—C16	178.2 (2)
N2—Co2—N10—C11	−139.0 (3)	O1—S1—C15—C16	−62.3 (3)
N6ⁱ—Co2—N10—C11	−52.4 (3)	O2—S1—C15—C16	57.3 (3)
N6—Co2—N10—C11	127.6 (3)	C14—C15—C16—C17	−179.7 (3)
N2ⁱ—Co2—N10—N9	−128.9 (2)	S1—C15—C16—C17	0.4 (4)
N2—Co2—N10—N9	51.1 (2)	C14—C15—C16—C16ⁱⁱ	1.4 (5)
N6ⁱ—Co2—N10—N9	137.7 (2)	S1—C15—C16—C16ⁱⁱ	−178.5 (3)
N6—Co2—N10—N9	−42.3 (2)	C16ⁱⁱ—C16—C17—C13ⁱⁱ	−0.1 (5)
N2—N1—C2—N3	0.1 (3)	C15—C16—C17—C13ⁱⁱ	−179.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···Cl3ⁱ	0.98	2.06	2.765 (3)	127
O1W—H1Y···Cl3ⁱⁱⁱ	0.98	1.89	2.701 (3)	138
O2W—H2X···Cl1	0.98	2.28	2.929 (3)	122
O2W—H2Y···Cl3ⁱⁱⁱ	0.98	2.82	3.749 (3)	158
O3W—H3X···O2^iv	0.98	1.89	2.773 (3)	148
O3W—H3Y···Cl4^iv	0.98	2.18	3.114 (3)	159
N8—H8A···O3ⁱ	0.91	2.21	3.009 (3)	146

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

Experimental details

Crystal data
Chemical formula	[Co₃(C₄H₈N₄)₆(H₂O)₆](C₁₀H₆O₆S₂)Cl₄
M_r	1385.82
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	11.1641 (4), 12.2744 (5), 13.2265 (5)
α, β, γ (°)	106.924 (2), 99.622 (3), 103.452 (2)
V (Å³)	1631.79 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.05
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.763, 0.815
No. of measured, independent and observed [I > 2σ(I)] reflections	23481, 6410, 5057
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.108, 1.06
No. of reflections	6410
No. of parameters	386
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.75

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···Cl3ⁱ	0.98	2.06	2.765 (3)	127
O1W—H1Y···Cl3ⁱⁱ	0.98	1.89	2.701 (3)	138
O2W—H2X···Cl1	0.98	2.28	2.929 (3)	122
O2W—H2Y···Cl3ⁱⁱ	0.98	2.82	3.749 (3)	158
O3W—H3X···O2ⁱⁱⁱ	0.98	1.89	2.773 (3)	148
O3W—H3Y···Cl4ⁱⁱⁱ	0.98	2.18	3.114 (3)	159
N8—H8A···O3ⁱ	0.91	2.21	3.009 (3)	146

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21101078), the Program for New Century Excellent Talents in Universities of China (NCET-11–0657), the Natural Science Foundation of Jiangsu Province (BK2011143), the Fundamental Research Funds for the Central Universities (JUSRP21111), the State Key Laboratory of Coordination Chemistry of Nanjing University and the Scientific Research Foundation of Jiangnan University (20101951).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tong, Y.-Z., Wang, Q.-L., Si, M., Qi, J., Yan, S.-P., Yang, G.-M., Cheng, P. & Liao, D.-Z. (2011). Polyhedron, 30, 3151–3157. Web of Science CSD CrossRef CAS Google Scholar

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