catena-Poly[piperazinium [diaqua­cobalt(II)-μ-benzene-1,3,5-tricaboxylato-tetra­aqua­cobalt(II)-μ-benzene-1,3,5-tricaboxylato] dihydrate]

Wei, W.; Dong, Y.; Han, J.; Chang, H.

doi:10.1107/S160053680503970X

catena-Poly[piperazinium [diaquacobalt(II)-μ-benzene-1,3,5-tricaboxylato-tetraaquacobalt(II)-μ-benzene-1,3,5-tricaboxylato] dihydrate]

The title polymer, {(C₄H₁₂N₂)[Co₂(C₉H₃O₆)₂(H₂O)₆]·2H₂O}_n, contains two independent Co^II atoms, both of which are located on inversion centres. The benzene-1,3,5-tricarboxylate ligand bridges the Co^II atoms in two coordination modes to form a one-dimensional polymeric zigzag chain structure. The zigzag chains are connected via O—H

O and N—H

O hydrogen bonds to form a three-dimensional network. This determination corrects a previous report which formulated this compound as (C₄H₁₀N₂)_n[C₁₈H₂₀Co₂O₁₈]_n·2nH₂O [Chen & Liu (2004). Chem. J. Chin. Univ. 25, 1189–1193].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680503970X/ci6711sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680503970X/ci6711Isup2.hkl Contains datablock I

CCDC reference: 296535

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.036
wR factor = 0.098
Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.638     0.883
            Tmin(prime) and Tmax expected:      0.776     0.883
            RR(prime) =      0.822
            Please check that your absorption correction is appropriate.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT417_ALERT_2_C Short Inter D-H..H-D       H7B    ..  H11B    ..       2.11 Ang.

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Benzene-1,3,5-tricarboxylate (BTC) usually plays the role of a bridging ligand in metal complexes. We present here the crystal structure of the title Co^II complex, [(C₁₈H₁₈Co₂O₁₈)²⁻]_n.n[C₄H₁₂N₂]²⁺.2nH₂O, (I). This determination corrects a previous report which formulated this compound as [C₁₈H₂₀Co₂O₁₈]_n.n[C₄H₁₀N₂].2nH₂O, (II) (Chen & Liu, 2004). In compound (II), the C—O bond lengths [1.251 and 1.262 Å] of the uncoordinated carboxyl groups clearly indicate proton transfer from them to a piperazine ring, resulting in a [C₄H₁₂N₂]²⁺ cation. However, in (II), the components were reported as neutral. In (I), the proton transfer is taken into account, and the protons are assigned to the piperazine ring.

Compound (I) contains two independent Co^II atoms, which are located at the centres of different centrosymmetric CoO₆ octahedra (Fig. 1). Each BTC ligand bridges two Co^II atoms to form a polymeric zigzag chain, and these are further linked via O—H···O hydrogen bonds to form a three-dimensional network (Table 1). The two carboxylate groups of the BTC ligand coordinate to Co^II atoms, one in a monodentate fashion and the other in a bidentate chelating fashion. The third carboxylate group is not coordinated to Co^II. The packing of the chains forms quadrilateral pores, which are occupied by C₄H₁₂N₂]²⁺ cations and free water molecules (Fig. 2).

Experimental top

An aqueous solution (10 ml) of benzene-1,3,5-tricarboxylic acid (0.210 g), terephthalic acid (0.166 g) and piperazine hexahydrate (0.132 g) was mixed with an aqueous solution (5 ml) of cobalt nitrate hexahydrate (0.292 g) with continuous stirring. The mixture was sealed in a 40 ml Teflon-lined stainless steel vessel and heated at 453 K for 96 h under autogenous conditions. After cooling to room temperature, the resulting product was filtered off to obtain pale-red crystals of (I) (about 76.2% yield, based on the Co source). Spectroscopic analysis: IR (KBr, ν, cm⁻¹): 3120, 2445, 2345, 1610, 1532, 1454, 1429, 1363, 1202, 1087, 754, 712, 542, 521, 459. Elemental analysis, calculated for C₁₁H₁₇N Co O₁₀: C 34.54, H 4.48, N 3.66%; found: C 34.45, H 4.51, N 3.62%.

Computing details top

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

Figures top

	Fig. 1. Part of the polymeric structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffixes A, B and C are generated by the symmetry operations (−x, 2 − y, −z), (2 − x, 1 − y,-z) and (−x, 1 − y, 1 − z), respectively.
	Fig. 2. The crystal packing of (I), viewed along the a axis.

catena-Poly[piperazinium [diaquacobalt(II)-µ-benzene-1,3,5-tricaboxylato-tetraaquacobalt(II)-µ-benzene- 1,3,5-tricaboxylato] dihydrate] top

Crystal data top

(C₄H₁₂N₂)[Co₂(C₉H₃O₆)₂(H₂O)₆]·2H₂O	Z = 1
M_r = 764.38	F(000) = 394
Triclinic, P1	D_x = 1.764 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1443 (11) Å	Cell parameters from 1224 reflections
b = 10.5308 (16) Å	θ = 2.1–25.0°
c = 10.5385 (16) Å	µ = 1.25 mm⁻¹
α = 110.753 (2)°	T = 293 K
β = 102.521 (2)°	Block, pale-red
γ = 91.351 (2)°	0.20 × 0.12 × 0.10 mm
V = 719.40 (19) Å³

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	2503 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.638, T_max = 0.883	k = −12→12
3896 measured reflections	l = −8→12

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0626P)²] where P = (F_o² + 2F_c²)/3
2503 reflections	(Δ/σ)_max = 0.001
211 parameters	Δρ_max = 0.56 e Å⁻³
12 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Co₂(C₉H₃O₆)₂(H₂O)₆]·2H₂O	γ = 91.351 (2)°
M_r = 764.38	V = 719.40 (19) Å³
Triclinic, P1	Z = 1
a = 7.1443 (11) Å	Mo Kα radiation
b = 10.5308 (16) Å	µ = 1.25 mm⁻¹
c = 10.5385 (16) Å	T = 293 K
α = 110.753 (2)°	0.20 × 0.12 × 0.10 mm
β = 102.521 (2)°

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	2503 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1957 reflections with I > 2σ(I)
T_min = 0.638, T_max = 0.883	R_int = 0.015
3896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	12 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.01	Δρ_max = 0.56 e Å⁻³
2503 reflections	Δρ_min = −0.56 e Å⁻³
211 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
Co1	0.0000	1.0000	0.0000	0.01768 (17)
Co2	0.0000	0.5000	0.5000	0.02347 (18)
O1	0.1519 (3)	0.6995 (2)	0.6363 (2)	0.0266 (5)
O2	0.0267 (3)	0.6506 (2)	0.4138 (2)	0.0288 (5)
O3	0.1060 (3)	0.9742 (2)	0.18822 (19)	0.0241 (5)
O4	0.2732 (3)	1.1785 (2)	0.3085 (2)	0.0289 (5)
O5	0.6055 (3)	1.2898 (2)	0.8111 (2)	0.0322 (6)
O6	0.5058 (3)	1.1671 (2)	0.9223 (2)	0.0291 (5)
O7	0.2534 (3)	0.4354 (2)	0.4549 (2)	0.0356 (6)
H7A	0.2522	0.3504	0.4100	0.053*
H7B	0.3036	0.4780	0.4133	0.053*
O8	0.1637 (3)	0.8460 (2)	−0.0887 (2)	0.0249 (5)
H8A	0.1686	0.8175	−0.1740	0.037*
H8B	0.2771	0.8528	−0.0390	0.037*
O9	0.2139 (3)	1.1639 (2)	0.0473 (2)	0.0225 (5)
H9A	0.3049	1.1501	0.0054	0.034*
H9B	0.2622	1.1769	0.1326	0.034*
C1	0.1986 (4)	0.8720 (3)	0.5422 (3)	0.0187 (6)
C2	0.1654 (4)	0.9058 (3)	0.4244 (3)	0.0183 (6)
H2	0.0936	0.8428	0.3398	0.022*
C3	0.2369 (4)	1.0315 (3)	0.4298 (3)	0.0170 (6)
C4	0.3451 (4)	1.1244 (3)	0.5569 (3)	0.0191 (6)
H4	0.3963	1.2084	0.5614	0.023*
C5	0.3778 (4)	1.0939 (3)	0.6769 (3)	0.0178 (6)
C6	0.3053 (4)	0.9673 (3)	0.6696 (3)	0.0196 (7)
H6	0.3277	0.9459	0.7496	0.024*
C7	0.1223 (4)	0.7339 (3)	0.5306 (3)	0.0208 (7)
C8	0.2030 (4)	1.0652 (3)	0.3004 (3)	0.0189 (6)
C9	0.5054 (4)	1.1914 (3)	0.8138 (3)	0.0211 (7)
C10	0.8829 (5)	0.5889 (3)	0.0791 (3)	0.0296 (8)
H10A	0.7579	0.5663	0.0130	0.036*
H10B	0.8703	0.6591	0.1652	0.036*
C11	0.9435 (5)	0.4647 (3)	0.1073 (3)	0.0321 (8)
H11C	1.0621	0.4892	0.1802	0.038*
H11D	0.8450	0.4291	0.1401	0.038*
N1	0.9741 (4)	0.3578 (3)	−0.0211 (3)	0.0288 (6)
H1A	0.8612	0.3291	−0.0857	0.035*
H1B	1.0165	0.2857	−0.0010	0.035*
O11	0.4461 (4)	0.5031 (3)	0.2864 (3)	0.0631 (9)
H11A	0.4503	0.5576	0.2435	0.095*
H11B	0.5514	0.5066	0.3442	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0185 (3)	0.0199 (3)	0.0140 (3)	−0.0025 (2)	−0.0002 (2)	0.0082 (2)
Co2	0.0272 (3)	0.0197 (3)	0.0211 (3)	−0.0054 (3)	0.0012 (3)	0.0079 (3)
O1	0.0365 (13)	0.0242 (12)	0.0194 (11)	−0.0059 (10)	0.0034 (9)	0.0109 (9)
O2	0.0387 (13)	0.0219 (12)	0.0217 (11)	−0.0096 (10)	0.0006 (10)	0.0078 (10)
O3	0.0295 (12)	0.0258 (12)	0.0142 (10)	−0.0051 (10)	−0.0026 (9)	0.0093 (9)
O4	0.0418 (14)	0.0233 (13)	0.0207 (11)	−0.0086 (10)	0.0014 (10)	0.0112 (10)
O5	0.0306 (13)	0.0300 (13)	0.0275 (12)	−0.0142 (11)	−0.0088 (10)	0.0108 (11)
O6	0.0195 (11)	0.0478 (15)	0.0166 (11)	−0.0076 (10)	−0.0033 (9)	0.0131 (10)
O7	0.0348 (13)	0.0239 (13)	0.0484 (14)	−0.0004 (10)	0.0128 (11)	0.0123 (11)
O8	0.0216 (11)	0.0336 (13)	0.0159 (10)	0.0039 (10)	0.0003 (9)	0.0072 (9)
O9	0.0190 (11)	0.0303 (13)	0.0182 (10)	−0.0033 (9)	0.0016 (8)	0.0109 (9)
C1	0.0168 (15)	0.0197 (16)	0.0198 (15)	−0.0009 (12)	0.0041 (12)	0.0077 (13)
C2	0.0169 (15)	0.0202 (16)	0.0158 (14)	−0.0002 (12)	0.0006 (12)	0.0062 (12)
C3	0.0145 (14)	0.0225 (16)	0.0153 (14)	0.0007 (12)	0.0033 (11)	0.0086 (12)
C4	0.0166 (15)	0.0189 (15)	0.0232 (15)	−0.0022 (12)	0.0034 (12)	0.0105 (13)
C5	0.0119 (14)	0.0226 (16)	0.0175 (14)	−0.0010 (12)	0.0019 (11)	0.0068 (13)
C6	0.0179 (15)	0.0260 (17)	0.0173 (14)	−0.0005 (13)	0.0040 (12)	0.0111 (13)
C7	0.0207 (15)	0.0213 (16)	0.0181 (15)	−0.0019 (13)	0.0026 (12)	0.0061 (13)
C8	0.0168 (15)	0.0230 (17)	0.0175 (15)	0.0028 (13)	0.0048 (12)	0.0077 (13)
C9	0.0142 (14)	0.0249 (17)	0.0210 (15)	−0.0013 (13)	0.0002 (12)	0.0072 (13)
C10	0.0264 (17)	0.0300 (19)	0.0260 (17)	−0.0041 (14)	−0.0003 (14)	0.0069 (15)
C11	0.039 (2)	0.0311 (19)	0.0225 (16)	−0.0068 (16)	0.0004 (14)	0.0107 (15)
N1	0.0329 (15)	0.0219 (15)	0.0269 (14)	−0.0048 (12)	−0.0044 (12)	0.0106 (12)
O11	0.0496 (18)	0.077 (2)	0.071 (2)	−0.0133 (16)	−0.0056 (15)	0.0500 (18)

Geometric parameters (Å, º) top

Co1—O3	2.0787 (19)	O9—H9B	0.85
Co1—O3ⁱ	2.0787 (19)	C1—C2	1.383 (4)
Co1—O8	2.088 (2)	C1—C6	1.399 (4)
Co1—O8ⁱ	2.088 (2)	C1—C7	1.495 (4)
Co1—O9	2.1210 (19)	C2—C3	1.385 (4)
Co1—O9ⁱ	2.1210 (19)	C2—H2	0.93
Co2—O7	2.041 (2)	C3—C4	1.391 (4)
Co2—O7ⁱⁱ	2.041 (2)	C3—C8	1.500 (4)
Co2—O2ⁱⁱ	2.111 (2)	C4—C5	1.386 (4)
Co2—O2	2.111 (2)	C4—H4	0.93
Co2—O1ⁱⁱ	2.175 (2)	C5—C6	1.389 (4)
Co2—O1	2.175 (2)	C5—C9	1.517 (4)
Co2—C7ⁱⁱ	2.480 (3)	C6—H6	0.93
Co2—C7	2.480 (3)	C10—N1ⁱⁱⁱ	1.489 (4)
O1—C7	1.266 (3)	C10—C11	1.494 (5)
O2—C7	1.262 (3)	C10—H10A	0.97
O3—C8	1.267 (3)	C10—H10B	0.97
O4—C8	1.251 (3)	C11—N1	1.486 (4)
O5—C9	1.256 (4)	C11—H11C	0.97
O6—C9	1.258 (4)	C11—H11D	0.97
O7—H7A	0.85	N1—C10ⁱⁱⁱ	1.489 (4)
O7—H7B	0.85	N1—H1A	0.90
O8—H8A	0.85	N1—H1B	0.90
O8—H8B	0.85	O11—H11A	0.85
O9—H9A	0.85	O11—H11B	0.85

O3—Co1—O3ⁱ	180.0	Co1—O9—H9A	119.0
O3—Co1—O8	87.26 (8)	Co1—O9—H9B	99.1
O3ⁱ—Co1—O8	92.74 (8)	H9A—O9—H9B	107.7
O3—Co1—O8ⁱ	92.74 (8)	C2—C1—C6	119.2 (3)
O3ⁱ—Co1—O8ⁱ	87.26 (8)	C2—C1—C7	119.5 (3)
O8—Co1—O8ⁱ	180.000 (1)	C6—C1—C7	121.3 (3)
O3—Co1—O9	93.22 (8)	C1—C2—C3	121.4 (3)
O3ⁱ—Co1—O9	86.78 (8)	C1—C2—H2	119.3
O8—Co1—O9	95.51 (8)	C3—C2—H2	119.3
O8ⁱ—Co1—O9	84.49 (8)	C2—C3—C4	118.7 (3)
O3—Co1—O9ⁱ	86.78 (8)	C2—C3—C8	120.6 (3)
O3ⁱ—Co1—O9ⁱ	93.22 (8)	C4—C3—C8	120.6 (3)
O8—Co1—O9ⁱ	84.49 (8)	C5—C4—C3	121.0 (3)
O8ⁱ—Co1—O9ⁱ	95.51 (8)	C5—C4—H4	119.5
O9—Co1—O9ⁱ	180.00 (11)	C3—C4—H4	119.5
O7—Co2—O7ⁱⁱ	180.00 (14)	C4—C5—C6	119.5 (3)
O7—Co2—O2ⁱⁱ	90.77 (9)	C4—C5—C9	121.2 (3)
O7ⁱⁱ—Co2—O2ⁱⁱ	89.23 (9)	C6—C5—C9	119.1 (3)
O7—Co2—O2	89.23 (9)	C5—C6—C1	120.1 (3)
O7ⁱⁱ—Co2—O2	90.77 (9)	C5—C6—H6	119.9
O2ⁱⁱ—Co2—O2	180.0	C1—C6—H6	119.9
O7—Co2—O1ⁱⁱ	90.37 (9)	O2—C7—O1	119.6 (3)
O7ⁱⁱ—Co2—O1ⁱⁱ	89.63 (9)	O2—C7—C1	119.5 (3)
O2ⁱⁱ—Co2—O1ⁱⁱ	61.26 (8)	O1—C7—C1	120.9 (2)
O2—Co2—O1ⁱⁱ	118.74 (8)	O2—C7—Co2	58.34 (15)
O7—Co2—O1	89.63 (9)	O1—C7—Co2	61.25 (15)
O7ⁱⁱ—Co2—O1	90.37 (9)	C1—C7—Co2	177.1 (2)
O2ⁱⁱ—Co2—O1	118.74 (8)	O4—C8—O3	124.2 (3)
O2—Co2—O1	61.26 (8)	O4—C8—C3	118.9 (2)
O1ⁱⁱ—Co2—O1	180.00 (8)	O3—C8—C3	116.9 (3)
O7—Co2—C7ⁱⁱ	91.33 (9)	O5—C9—O6	124.3 (3)
O7ⁱⁱ—Co2—C7ⁱⁱ	88.67 (9)	O5—C9—C5	118.1 (3)
O2ⁱⁱ—Co2—C7ⁱⁱ	30.58 (9)	O6—C9—C5	117.5 (3)
O2—Co2—C7ⁱⁱ	149.42 (9)	N1ⁱⁱⁱ—C10—C11	111.0 (3)
O1ⁱⁱ—Co2—C7ⁱⁱ	30.69 (8)	N1ⁱⁱⁱ—C10—H10A	109.4
O1—Co2—C7ⁱⁱ	149.31 (8)	C11—C10—H10A	109.4
O7—Co2—C7	88.67 (9)	N1ⁱⁱⁱ—C10—H10B	109.4
O7ⁱⁱ—Co2—C7	91.33 (9)	C11—C10—H10B	109.4
O2ⁱⁱ—Co2—C7	149.42 (9)	H10A—C10—H10B	108.0
O2—Co2—C7	30.58 (9)	N1—C11—C10	110.7 (3)
O1ⁱⁱ—Co2—C7	149.31 (8)	N1—C11—H11C	109.5
O1—Co2—C7	30.69 (8)	C10—C11—H11C	109.5
C7ⁱⁱ—Co2—C7	180.0	N1—C11—H11D	109.5
C7—O1—Co2	88.06 (17)	C10—C11—H11D	109.5
C7—O2—Co2	91.08 (18)	H11C—C11—H11D	108.1
C8—O3—Co1	125.94 (19)	C11—N1—C10ⁱⁱⁱ	111.1 (2)
Co2—O7—H7A	116.6	C11—N1—H1A	109.4
Co2—O7—H7B	114.5	C10ⁱⁱⁱ—N1—H1A	109.4
H7A—O7—H7B	107.5	C11—N1—H1B	109.4
Co1—O8—H8A	124.2	C10ⁱⁱⁱ—N1—H1B	109.4
Co1—O8—H8B	114.2	H1A—N1—H1B	108.0
H8A—O8—H8B	108.2	H11A—O11—H11B	113.6

O7—Co2—O1—C7	88.03 (18)	Co2—O1—C7—O2	2.2 (3)
O7ⁱⁱ—Co2—O1—C7	−91.97 (18)	Co2—O1—C7—C1	−177.9 (3)
O2ⁱⁱ—Co2—O1—C7	178.70 (17)	C2—C1—C7—O2	−0.8 (4)
O2—Co2—O1—C7	−1.30 (17)	C6—C1—C7—O2	−179.9 (3)
C7ⁱⁱ—Co2—O1—C7	180.000 (1)	C2—C1—C7—O1	179.3 (3)
O7—Co2—O2—C7	−88.70 (19)	C6—C1—C7—O1	0.1 (4)
O7ⁱⁱ—Co2—O2—C7	91.30 (19)	O7—Co2—C7—O2	90.73 (19)
O1ⁱⁱ—Co2—O2—C7	−178.70 (17)	O7ⁱⁱ—Co2—C7—O2	−89.27 (19)
O1—Co2—O2—C7	1.30 (17)	O2ⁱⁱ—Co2—C7—O2	180.000 (1)
C7ⁱⁱ—Co2—O2—C7	180.000 (1)	O1ⁱⁱ—Co2—C7—O2	2.2 (3)
O8—Co1—O3—C8	120.4 (2)	O1—Co2—C7—O2	−177.8 (3)
O8ⁱ—Co1—O3—C8	−59.6 (2)	O7—Co2—C7—O1	−91.51 (17)
O9—Co1—O3—C8	25.1 (2)	O7ⁱⁱ—Co2—C7—O1	88.49 (17)
O9ⁱ—Co1—O3—C8	−154.9 (2)	O2ⁱⁱ—Co2—C7—O1	−2.2 (3)
C6—C1—C2—C3	0.5 (4)	O2—Co2—C7—O1	177.8 (3)
C7—C1—C2—C3	−178.6 (3)	O1ⁱⁱ—Co2—C7—O1	180.000 (2)
C1—C2—C3—C4	0.4 (4)	Co1—O3—C8—O4	−10.9 (4)
C1—C2—C3—C8	178.7 (3)	Co1—O3—C8—C3	170.14 (18)
C2—C3—C4—C5	−1.4 (4)	C2—C3—C8—O4	−178.5 (3)
C8—C3—C4—C5	−179.7 (3)	C4—C3—C8—O4	−0.2 (4)
C3—C4—C5—C6	1.5 (4)	C2—C3—C8—O3	0.5 (4)
C3—C4—C5—C9	176.4 (3)	C4—C3—C8—O3	178.7 (3)
C4—C5—C6—C1	−0.6 (4)	C4—C5—C9—O5	−11.3 (4)
C9—C5—C6—C1	−175.5 (3)	C6—C5—C9—O5	163.6 (3)
C2—C1—C6—C5	−0.5 (4)	C4—C5—C9—O6	169.7 (3)
C7—C1—C6—C5	178.7 (3)	C6—C5—C9—O6	−15.5 (4)
Co2—O2—C7—O1	−2.3 (3)	N1ⁱⁱⁱ—C10—C11—N1	−56.1 (4)
Co2—O2—C7—C1	177.8 (2)	C10—C11—N1—C10ⁱⁱⁱ	56.1 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5^iv	0.90	1.86	2.751 (4)	168
N1—H1B···O9^v	0.90	2.03	2.880 (4)	157
N1—H1B···O8^vi	0.90	2.42	3.011 (4)	124
O7—H7A···O4^vii	0.85	1.78	2.622 (3)	173
O7—H7B···O11	0.85	1.93	2.733 (4)	157
O8—H8A···O1^viii	0.85	1.91	2.740 (3)	162
O8—H8B···O6^ix	0.85	1.83	2.657 (3)	166
O9—H9A···O6^viii	0.85	1.87	2.703 (3)	165
O9—H9B···O4	0.85	1.83	2.640 (3)	158
O11—H11A···O5^ix	0.85	1.91	2.722 (4)	158
O11—H11B···O7^x	0.85	2.14	2.934 (4)	156

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[Co₂(C₉H₃O₆)₂(H₂O)₆]·2H₂O
M_r	764.38
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1443 (11), 10.5308 (16), 10.5385 (16)
α, β, γ (°)	110.753 (2), 102.521 (2), 91.351 (2)
V (Å³)	719.40 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.25
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.638, 0.883
No. of measured, independent and observed [I > 2σ(I)] reflections	3896, 2503, 1957
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.01
No. of reflections	2503
No. of parameters	211
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.56

Computer programs: APEX2 (Bruker, 1997), APEX2, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.