Piperazinium hexa­aqua­cobalt(II) bis­[bis­(pyridine-2,6-dicarboxylato)cobaltate(II)] octa­hydrate

Aghabozorg, H.; Attar Gharamaleki, J.; Ghadermazi, M.; Ghasemikhah, P.; Soleimannejad, J.

doi:10.1107/S1600536807025640

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Piperazinium hexaaquacobalt(II) bis[bis(pyridine-2,6-dicarboxylato)cobaltate(II)] octahydrate

H. Aghabozorg, J. Attar Gharamaleki, M. Ghadermazi, P. Ghasemikhah and J. Soleimannejad

The title compound, (C₄H₁₂N₂)[Co(H₂O)₆][Co(C₇H₃O₄)₂]₂·8H₂O, was obtained by the reaction of cobalt(II) nitrate hexahydrate with the proton-transfer compound piperazinediium pyridine-2,6-dicarboxylate or (pipzH₂)(pydc) (where pipz is piperazine and pydcH₂ is pyridine-2,6-dicarboxylic acid) in aqueous solution. The anionic complex, [Co(pydc)₂]²⁻, features six-coordinate Co^II with a distorted octahedral geometry. The structure also contains hexaaquacobalt(II) cations (site symmetry $\overline{1}$ ), and piperazinium (site symmetry $\overline{1}$ ) as counter-ions and eight uncoordinated water molecules. The torsion angles indicate that the (pydc)²⁻ units are almost perpendicular to each other. In the crystal structure, extensive O—H

O, N—H

O and C—H

O hydrogen bonds, as well as ion pairing and distances for π–π interactions between anion fragments, play an important role in stabilizing the structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025640/om2127sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025640/om2127Isup2.hkl Contains datablock I

CCDC reference: 654699

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.003 Å
R factor = 0.036
wR factor = 0.097
Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H10B   ..  H14A    ..       2.11 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C8     ..  C10     ..       3.10 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          7
              H2 O

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C32 H52 Co3 N6 O30
            Atom count from _chemical_formula_moiety:C32 H52 Co3 N2 O30
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (2)       2.11
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co2         (2)       1.88

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Non-covalent interactions including hydrogen bonds are of great importance in stabilizing the structures of different compounds in solid state. We have so far synthesized several proton transfer compounds (Aghabozorg et al., 2006b; Manteghi et al., 2007) and their metal-organic complexes (Aghabozorg et al., 2006c; Aghabozorg et al., 2006 d; Aghabozorg et al., 2006 e; Aghabozorg et al., 2007). A wide range of various hydrogen bonds was observed in these compounds and water molecules were involved in hydrogen bonding formation of some of these structures.

Here, we report on the synthesis and X-ray crystal structure of the title compound, (I). The molecular structure of the compound (I) is shown in Fig. 1. The intermolecular hydrogen bond distances are listed in Table 1. This compound crystallizes in the triclinic system, space group P 1 with one formula in the unit cell. The most important feature of the title compound is the formation of both anionic [Co(pydc)₂]^2- and cationic [Co(H₂O)₆]²⁺ complexes (site symmetry 1), and (pipzH₂)²⁺ ion (site symmetry 1), simultaneously. In the anionic complex, [Co(pydc)₂]^2-, the metal ion is hexacoordinated by two nitrogen atoms N1, and N2 and four oxygen atoms O2, O3, O6 and O7 of carboxylate groups of two (pydc)^2- fragments which act as tridentate ligands. N1 and N2 atoms of the two (pydc)^2- fragments occupy the axial positions, while oxygen atoms form the equatorial plane. The N1—Co2—N2 angle revealed with a 14.88° deviation from linearity.

The mean Co—N and Co—O bond lengths for Co2 are 2.0147 (18) and 2.1575 (17) Å, respectively and are consistent with the corresponding data reported in the literature (Aghabozorg et al., 2006a). According to bond lengths, bond and torsion angles, arrangement of the six donor atoms around Co2 is distorted octahedral.

The dihedral angel between the two planes of Co2N2O6 and N2Co2O2 [86.81 (9)°] indicate that two dianionic (pydc)^2- units are almost perpendicular to each other.

In the cationic complex, [Co(H₂O)₆]²⁺, the metal ion is hexacoordinated by six oxygen atoms of water molecules with a nearly octahedral geometry around the central atom. The extensive O—H···O, N—H···O and C—H···O hydrogen bonds between [Co(H₂O)₆]²⁺, [Co(pydc)₂]^2-, (pipzH₂)²⁺ and uncoordinated water molecules play an important role in stabilizing and architecture of the crystal (Table 1). The intermolecular forces in this compound consist of hydrogen bonding and ion pairing as well as π-π stacking between anion-anion fragments (3.5277 (15) Å -x, -y + 2, -z + 1) (Fig. 2) (Aghabozorg, et al., 2006f). These interactions result in the formation of a supramolecular structure based on a hydrogen-bonded network.

Related literature top

The reaction between Co(NO₃)₂·6H₂O and the proton-transfer compound (GH)₂(pydc) (G is guanidine) in a 1:2 molar ratio leads to the formation of red crystals of (GH)₂[Co(H₂O)₆][Co(pydc)₂]₂ (Aghabozorg et al., 2006a).

For related literature, see: Aghabozorg et al. (2006b, 2006c, 2006d, 2006e, 2006f, 2007); Manteghi et al. (2007).

Experimental top

The proton transfer compound, (pipzH₂)(pydc), was prepared by the reaction of pyridine-2,6-dicarboxylic acid, pydcH₂, with piperazine, (pipz). The reaction between Co(NO₃)₂·6H₂O (143 mg, 0.5 mmol) in water (25 ml) and the proton transfer compound, (pipzH₂)(pydc) (253 mg, 1.0 mmol) in water (25 ml), in a 1:2 molar ratio was carried out and a purple crystalline compound was obtained by the slow evaporation of the solvent at room temperature.

Structure description top

The dihedral angel between the two planes of Co2N2O6 and N2Co2O2 [86.81 (9)°] indicate that two dianionic (pydc)^2- units are almost perpendicular to each other.

For related literature, see: Aghabozorg et al. (2006b, 2006c, 2006d, 2006e, 2006f, 2007); Manteghi et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. Molecular structure of compound (I), displacement ellipsoids are at the 50% probability level. The rest of fragments could be generated by symmetry. [symmetry codes: (a) -x, -y + 1, -z + 1, (b) -x, -y, -z].
	Fig. 2. π-π Stacking interactions between two aromatic rings of (I). The average distance between the planes is 3.5277 (15) Å (-x, 2 - y, 1 - z).

Piperazinium hexaaquacobalt(II) bis[bis(pyridine-2,6-dicarboxylato)cobaltate(II)] octahydrate top

Crystal data top

(C₄H₁₂N₂)[Co(H₂O)₆][Co(C₇H₃O₄)₂]₂·8H₂O	Z = 1
M_r = 1177.59	F(000) = 607
Triclinic, P1	D_x = 1.710 Mg m⁻³
a = 8.4682 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9287 (14) Å	Cell parameters from 7659 reflections
c = 12.9091 (15) Å	θ = 2.5–27.5°
α = 63.478 (2)°	µ = 1.18 mm⁻¹
β = 78.683 (2)°	T = 150 K
γ = 83.063 (2)°	Block, purple
V = 1143.3 (2) Å³	0.50 × 0.48 × 0.20 mm

Data collection top

Bruker SMART 1000 diffractometer	5061 independent reflections
Radiation source: fine-focus sealed tube	4261 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 100 pixels mm^-1	θ_max = 27.6°, θ_min = 1.8°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −15→15
T_min = 0.589, T_max = 0.798	l = −16→16
9953 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0549P)² + 0.4524P] where P = (F_o² + 2F_c²)/3
5061 reflections	(Δ/σ)_max < 0.001
322 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Co(H₂O)₆][Co(C₇H₃O₄)₂]₂·8H₂O	γ = 83.063 (2)°
M_r = 1177.59	V = 1143.3 (2) Å³
Triclinic, P1	Z = 1
a = 8.4682 (10) Å	Mo Kα radiation
b = 11.9287 (14) Å	µ = 1.18 mm⁻¹
c = 12.9091 (15) Å	T = 150 K
α = 63.478 (2)°	0.50 × 0.48 × 0.20 mm
β = 78.683 (2)°

Data collection top

Bruker SMART 1000 diffractometer	5061 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	4261 reflections with I > 2σ(I)
T_min = 0.589, T_max = 0.798	R_int = 0.025
9953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.06	Δρ_max = 0.59 e Å⁻³
5061 reflections	Δρ_min = −0.62 e Å⁻³
322 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	0.5000	0.5000	0.01842 (11)
Co2	0.22003 (4)	0.25036 (2)	0.23467 (2)	0.01670 (9)
N1	0.2066 (2)	0.08823 (16)	0.38145 (15)	0.0165 (4)
N2	0.2792 (2)	0.38844 (16)	0.07167 (15)	0.0163 (4)
N3	−0.1311 (2)	0.04921 (17)	0.05881 (16)	0.0210 (4)
H3B	−0.1022	0.0221	0.1301	0.025*
H3A	−0.2268	0.0916	0.0558	0.025*
O1	−0.0037 (2)	−0.05806 (14)	0.26917 (13)	0.0238 (3)
O2	0.0688 (2)	0.13971 (13)	0.20204 (13)	0.0224 (3)
O3	0.32424 (19)	0.29185 (13)	0.35241 (13)	0.0201 (3)
O4	0.4158 (2)	0.19928 (15)	0.52370 (14)	0.0243 (4)
O5	−0.03682 (19)	0.58947 (14)	0.11407 (14)	0.0237 (3)
O6	0.04162 (19)	0.39324 (13)	0.22919 (13)	0.0204 (3)
O7	0.4431 (2)	0.17914 (14)	0.16162 (13)	0.0238 (4)
O8	0.61077 (19)	0.21798 (14)	−0.00623 (13)	0.0242 (4)
O9	−0.2103 (2)	0.48680 (15)	0.61912 (15)	0.0303 (4)
H9B	−0.2614	0.5548	0.6339	0.036*
H9A	−0.2648	0.4103	0.6613	0.036*
O10	0.1082 (2)	0.58551 (14)	0.57348 (14)	0.0229 (3)
H10B	0.2198	0.5651	0.5762	0.028*
H10A	0.0612	0.5788	0.6491	0.028*
O11	0.0824 (2)	0.32105 (14)	0.61321 (15)	0.0293 (4)
H11B	0.1654	0.3186	0.6542	0.035*
H11A	0.0526	0.2378	0.6368	0.035*
O12	0.5233 (2)	−0.07835 (16)	0.24549 (15)	0.0348 (4)
H12B	0.4914	0.0070	0.2255	0.042*
H12A	0.5606	−0.1126	0.3188	0.042*
O13	0.4299 (2)	0.5784 (2)	0.5563 (3)	0.0603 (7)
H13B	0.4766	0.5256	0.5199	0.072*
H13A	0.4914	0.6496	0.5330	0.072*
O14	0.2727 (3)	0.3327 (2)	0.7521 (2)	0.0516 (6)
H14A	0.3261	0.4091	0.7047	0.062*
H14B	0.1995	0.3646	0.7995	0.062*
O15	0.6190 (3)	0.27236 (17)	−0.23945 (16)	0.0410 (5)
H15D	0.5929	0.1973	−0.2399	0.049*
H15C	0.6323	0.2384	−0.1595	0.049*
C1	0.0628 (3)	0.02551 (19)	0.27641 (18)	0.0193 (4)
C2	0.1404 (3)	−0.00853 (18)	0.38368 (18)	0.0175 (4)
C3	0.1429 (3)	−0.12571 (19)	0.47785 (19)	0.0207 (5)
H3	0.0966	−0.1949	0.4788	0.025*
C4	0.2147 (3)	−0.1393 (2)	0.57052 (19)	0.0226 (5)
H4	0.2170	−0.2185	0.6366	0.027*
C5	0.2834 (3)	−0.03764 (19)	0.56740 (19)	0.0196 (4)
H5	0.3331	−0.0459	0.6305	0.024*
C6	0.2773 (3)	0.07649 (19)	0.46932 (18)	0.0169 (4)
C7	0.3451 (3)	0.19821 (19)	0.44923 (18)	0.0182 (4)
C8	0.0529 (3)	0.49527 (19)	0.13425 (19)	0.0184 (4)
C9	0.1906 (3)	0.49543 (18)	0.04015 (18)	0.0168 (4)
C10	0.2280 (3)	0.59417 (19)	−0.07070 (19)	0.0197 (4)
H10	0.1656	0.6706	−0.0934	0.024*
C11	0.3584 (3)	0.5779 (2)	−0.14681 (18)	0.0208 (5)
H11	0.3864	0.6439	−0.2228	0.025*
C12	0.4488 (3)	0.4653 (2)	−0.11257 (19)	0.0204 (4)
H12	0.5380	0.4530	−0.1645	0.024*
C13	0.4050 (3)	0.37179 (19)	−0.00081 (18)	0.0172 (4)
C14	0.4942 (3)	0.24579 (19)	0.05474 (19)	0.0192 (4)
C15	−0.0037 (3)	0.1319 (2)	−0.0319 (2)	0.0249 (5)
H15B	0.0112	0.2018	−0.0137	0.030*
H15A	−0.0383	0.1681	−0.1098	0.030*
C16	0.1531 (3)	0.0588 (2)	−0.0353 (2)	0.0243 (5)
H16B	0.2351	0.1139	−0.0976	0.029*
H16A	0.1920	0.0278	0.0407	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0220 (2)	0.01281 (19)	0.0190 (2)	−0.00347 (15)	0.00298 (16)	−0.00748 (16)
Co2	0.02253 (17)	0.01160 (14)	0.01341 (15)	−0.00183 (11)	−0.00085 (11)	−0.00368 (11)
N1	0.0185 (9)	0.0144 (8)	0.0159 (8)	−0.0020 (7)	−0.0002 (7)	−0.0067 (7)
N2	0.0190 (9)	0.0137 (8)	0.0152 (8)	−0.0009 (7)	−0.0023 (7)	−0.0055 (7)
N3	0.0226 (10)	0.0197 (9)	0.0189 (9)	0.0052 (7)	−0.0026 (7)	−0.0086 (7)
O1	0.0345 (9)	0.0176 (7)	0.0211 (8)	−0.0064 (7)	−0.0063 (7)	−0.0079 (6)
O2	0.0332 (9)	0.0150 (7)	0.0180 (7)	−0.0048 (6)	−0.0057 (6)	−0.0047 (6)
O3	0.0271 (8)	0.0146 (7)	0.0173 (7)	−0.0036 (6)	−0.0031 (6)	−0.0054 (6)
O4	0.0292 (9)	0.0227 (8)	0.0234 (8)	−0.0021 (7)	−0.0093 (7)	−0.0097 (6)
O5	0.0250 (8)	0.0154 (7)	0.0282 (8)	0.0028 (6)	−0.0015 (7)	−0.0093 (6)
O6	0.0249 (8)	0.0161 (7)	0.0162 (7)	−0.0003 (6)	−0.0001 (6)	−0.0050 (6)
O7	0.0301 (9)	0.0169 (7)	0.0172 (7)	0.0036 (6)	−0.0003 (6)	−0.0035 (6)
O8	0.0243 (9)	0.0231 (8)	0.0205 (8)	0.0070 (6)	0.0002 (6)	−0.0088 (6)
O9	0.0312 (9)	0.0205 (8)	0.0359 (9)	−0.0071 (7)	0.0143 (8)	−0.0159 (7)
O10	0.0258 (8)	0.0220 (8)	0.0232 (8)	−0.0054 (6)	0.0027 (6)	−0.0133 (6)
O11	0.0369 (10)	0.0152 (7)	0.0337 (9)	−0.0031 (7)	−0.0124 (8)	−0.0055 (7)
O12	0.0580 (13)	0.0203 (8)	0.0270 (9)	0.0056 (8)	−0.0138 (8)	−0.0099 (7)
O13	0.0295 (11)	0.0450 (12)	0.122 (2)	−0.0093 (9)	0.0042 (13)	−0.0545 (14)
O14	0.0386 (12)	0.0798 (16)	0.0611 (14)	0.0221 (11)	−0.0193 (10)	−0.0538 (13)
O15	0.0647 (14)	0.0318 (10)	0.0238 (9)	−0.0193 (9)	−0.0017 (9)	−0.0077 (8)
C1	0.0230 (11)	0.0175 (10)	0.0160 (10)	−0.0014 (8)	0.0004 (8)	−0.0073 (8)
C2	0.0189 (10)	0.0147 (9)	0.0168 (10)	−0.0012 (8)	0.0009 (8)	−0.0064 (8)
C3	0.0232 (11)	0.0147 (9)	0.0218 (11)	−0.0036 (8)	−0.0011 (9)	−0.0061 (8)
C4	0.0256 (12)	0.0151 (10)	0.0199 (10)	0.0002 (9)	−0.0021 (9)	−0.0019 (8)
C5	0.0203 (11)	0.0186 (10)	0.0177 (10)	0.0009 (8)	−0.0030 (8)	−0.0063 (8)
C6	0.0160 (10)	0.0175 (10)	0.0155 (9)	0.0000 (8)	0.0009 (8)	−0.0072 (8)
C7	0.0172 (10)	0.0178 (10)	0.0199 (10)	−0.0004 (8)	0.0008 (8)	−0.0100 (8)
C8	0.0206 (11)	0.0154 (9)	0.0212 (10)	−0.0035 (8)	−0.0029 (8)	−0.0093 (8)
C9	0.0204 (10)	0.0133 (9)	0.0182 (10)	−0.0024 (8)	−0.0046 (8)	−0.0071 (8)
C10	0.0235 (11)	0.0142 (9)	0.0203 (10)	−0.0013 (8)	−0.0062 (9)	−0.0053 (8)
C11	0.0259 (12)	0.0166 (10)	0.0156 (10)	−0.0045 (9)	−0.0029 (8)	−0.0027 (8)
C12	0.0212 (11)	0.0203 (10)	0.0178 (10)	−0.0026 (8)	−0.0011 (8)	−0.0070 (8)
C13	0.0197 (10)	0.0145 (9)	0.0168 (10)	−0.0010 (8)	−0.0021 (8)	−0.0066 (8)
C14	0.0209 (11)	0.0166 (10)	0.0201 (10)	0.0010 (8)	−0.0051 (8)	−0.0076 (8)
C15	0.0363 (14)	0.0130 (9)	0.0214 (11)	−0.0015 (9)	0.0004 (10)	−0.0057 (8)
C16	0.0256 (12)	0.0251 (11)	0.0242 (11)	−0.0084 (9)	0.0005 (9)	−0.0123 (9)

Geometric parameters (Å, º) top

Co1—O10ⁱ	2.0522 (16)	O11—H11A	0.9499
Co1—O10	2.0522 (16)	O12—H12B	0.9500
Co1—O9ⁱ	2.0824 (16)	O12—H12A	0.9500
Co1—O9	2.0824 (16)	O13—H13B	0.9499
Co1—O11	2.1056 (16)	O13—H13A	0.9500
Co1—O11ⁱ	2.1056 (15)	O14—H14A	0.9501
Co2—N1	2.0098 (17)	O14—H14B	0.9499
Co2—N2	2.0204 (17)	O15—H15D	0.9499
Co2—O6	2.1224 (15)	O15—H15C	0.9501
Co2—O3	2.1534 (16)	C1—C2	1.518 (3)
Co2—O2	2.1623 (16)	C2—C3	1.385 (3)
Co2—O7	2.1927 (16)	C3—C4	1.384 (3)
N1—C2	1.330 (3)	C3—H3	0.9500
N1—C6	1.330 (3)	C4—C5	1.388 (3)
N2—C13	1.332 (3)	C4—H4	0.9500
N2—C9	1.335 (3)	C5—C6	1.389 (3)
N3—C16ⁱⁱ	1.488 (3)	C5—H5	0.9500
N3—C15	1.495 (3)	C6—C7	1.520 (3)
N3—H3B	0.9024	C8—C9	1.510 (3)
N3—H3A	0.9001	C9—C10	1.394 (3)
O1—C1	1.249 (3)	C10—C11	1.384 (3)
O2—C1	1.269 (2)	C10—H10	0.9500
O3—C7	1.278 (3)	C11—C12	1.393 (3)
O4—C7	1.233 (3)	C11—H11	0.9500
O5—C8	1.232 (3)	C12—C13	1.384 (3)
O6—C8	1.282 (2)	C12—H12	0.9500
O7—C14	1.262 (3)	C13—C14	1.523 (3)
O8—C14	1.246 (3)	C15—C16	1.503 (3)
O9—H9B	0.9500	C15—H15B	0.9900
O9—H9A	0.9499	C15—H15A	0.9900
O10—H10B	0.9501	C16—N3ⁱⁱ	1.488 (3)
O10—H10A	0.9501	C16—H16B	0.9900
O11—H11B	0.9501	C16—H16A	0.9900

O10ⁱ—Co1—O10	180.000 (1)	H14A—O14—H14B	95.2
O10ⁱ—Co1—O9ⁱ	89.89 (7)	H15D—O15—H15C	98.0
O10—Co1—O9ⁱ	90.11 (7)	O1—C1—O2	125.5 (2)
O10ⁱ—Co1—O9	90.11 (7)	O1—C1—C2	118.72 (18)
O10—Co1—O9	89.89 (7)	O2—C1—C2	115.76 (19)
O9ⁱ—Co1—O9	180.000 (1)	N1—C2—C3	121.1 (2)
O10ⁱ—Co1—O11	88.04 (7)	N1—C2—C1	113.09 (17)
O10—Co1—O11	91.96 (7)	C3—C2—C1	125.8 (2)
O9ⁱ—Co1—O11	88.93 (7)	C4—C3—C2	118.2 (2)
O9—Co1—O11	91.07 (7)	C4—C3—H3	120.9
O10ⁱ—Co1—O11ⁱ	91.96 (7)	C2—C3—H3	120.9
O10—Co1—O11ⁱ	88.04 (7)	C3—C4—C5	120.31 (19)
O9ⁱ—Co1—O11ⁱ	91.07 (7)	C3—C4—H4	119.8
O9—Co1—O11ⁱ	88.93 (7)	C5—C4—H4	119.8
O11—Co1—O11ⁱ	180.0	C4—C5—C6	118.0 (2)
N1—Co2—N2	165.15 (7)	C4—C5—H5	121.0
N1—Co2—O6	117.76 (6)	C6—C5—H5	121.0
N2—Co2—O6	76.99 (6)	N1—C6—C5	120.9 (2)
N1—Co2—O3	76.50 (6)	N1—C6—C7	113.00 (17)
N2—Co2—O3	107.36 (6)	C5—C6—C7	126.0 (2)
O6—Co2—O3	87.84 (6)	O4—C7—O3	125.7 (2)
N1—Co2—O2	76.73 (6)	O4—C7—C6	119.32 (18)
N2—Co2—O2	101.16 (7)	O3—C7—C6	114.95 (19)
O6—Co2—O2	95.55 (6)	O5—C8—O6	126.4 (2)
O3—Co2—O2	151.30 (6)	O5—C8—C9	118.87 (18)
N1—Co2—O7	89.59 (6)	O6—C8—C9	114.73 (18)
N2—Co2—O7	75.79 (6)	N2—C9—C10	120.6 (2)
O6—Co2—O7	152.52 (6)	N2—C9—C8	113.56 (17)
O3—Co2—O7	96.68 (6)	C10—C9—C8	125.86 (19)
O2—Co2—O7	93.31 (6)	C11—C10—C9	118.23 (19)
C2—N1—C6	121.47 (18)	C11—C10—H10	120.9
C2—N1—Co2	118.78 (14)	C9—C10—H10	120.9
C6—N1—Co2	119.43 (14)	C10—C11—C12	120.36 (19)
C13—N2—C9	121.70 (18)	C10—C11—H11	119.8
C13—N2—Co2	119.90 (14)	C12—C11—H11	119.8
C9—N2—Co2	118.39 (14)	C13—C12—C11	118.1 (2)
C16ⁱⁱ—N3—C15	110.72 (17)	C13—C12—H12	120.9
C16ⁱⁱ—N3—H3B	110.6	C11—C12—H12	120.9
C15—N3—H3B	108.7	N2—C13—C12	121.02 (19)
C16ⁱⁱ—N3—H3A	106.0	N2—C13—C14	113.12 (18)
C15—N3—H3A	110.2	C12—C13—C14	125.8 (2)
H3B—N3—H3A	110.6	O8—C14—O7	125.70 (19)
C1—O2—Co2	114.35 (14)	O8—C14—C13	118.81 (19)
C7—O3—Co2	115.43 (14)	O7—C14—C13	115.48 (19)
C8—O6—Co2	116.30 (13)	N3—C15—C16	110.58 (17)
C14—O7—Co2	115.18 (13)	N3—C15—H15B	109.5
Co1—O9—H9B	124.4	C16—C15—H15B	109.5
Co1—O9—H9A	120.9	N3—C15—H15A	109.5
H9B—O9—H9A	114.8	C16—C15—H15A	109.5
Co1—O10—H10B	115.3	H15B—C15—H15A	108.1
Co1—O10—H10A	118.6	N3ⁱⁱ—C16—C15	110.06 (19)
H10B—O10—H10A	106.0	N3ⁱⁱ—C16—H16B	109.6
Co1—O11—H11B	116.5	C15—C16—H16B	109.6
Co1—O11—H11A	134.4	N3ⁱⁱ—C16—H16A	109.6
H11B—O11—H11A	109.0	C15—C16—H16A	109.6
H12B—O12—H12A	108.2	H16B—C16—H16A	108.2
H13B—O13—H13A	112.9

N2—Co2—N1—C2	−74.0 (3)	O2—C1—C2—N1	−1.3 (3)
O6—Co2—N1—C2	98.84 (16)	O1—C1—C2—C3	−1.1 (3)
O3—Co2—N1—C2	179.05 (17)	O2—C1—C2—C3	177.4 (2)
O2—Co2—N1—C2	9.51 (15)	N1—C2—C3—C4	0.7 (3)
O7—Co2—N1—C2	−83.98 (16)	C1—C2—C3—C4	−177.9 (2)
N2—Co2—N1—C6	99.7 (3)	C2—C3—C4—C5	−0.7 (3)
O6—Co2—N1—C6	−87.52 (16)	C3—C4—C5—C6	0.1 (3)
O3—Co2—N1—C6	−7.31 (15)	C2—N1—C6—C5	−0.5 (3)
O2—Co2—N1—C6	−176.85 (17)	Co2—N1—C6—C5	−173.96 (16)
O7—Co2—N1—C6	89.66 (16)	C2—N1—C6—C7	180.00 (18)
N1—Co2—N2—C13	−5.8 (4)	Co2—N1—C6—C7	6.5 (2)
O6—Co2—N2—C13	−179.31 (17)	C4—C5—C6—N1	0.5 (3)
O3—Co2—N2—C13	97.16 (17)	C4—C5—C6—C7	180.0 (2)
O2—Co2—N2—C13	−86.12 (17)	Co2—O3—C7—O4	173.03 (17)
O7—Co2—N2—C13	4.49 (16)	Co2—O3—C7—C6	−5.8 (2)
N1—Co2—N2—C9	174.9 (2)	N1—C6—C7—O4	−178.97 (19)
O6—Co2—N2—C9	1.46 (16)	C5—C6—C7—O4	1.6 (3)
O3—Co2—N2—C9	−82.07 (17)	N1—C6—C7—O3	0.0 (3)
O2—Co2—N2—C9	94.65 (16)	C5—C6—C7—O3	−179.5 (2)
O7—Co2—N2—C9	−174.74 (17)	Co2—O6—C8—O5	−179.05 (18)
N1—Co2—O2—C1	−9.99 (15)	Co2—O6—C8—C9	1.4 (2)
N2—Co2—O2—C1	154.97 (15)	C13—N2—C9—C10	−0.2 (3)
O6—Co2—O2—C1	−127.24 (15)	Co2—N2—C9—C10	179.05 (16)
O3—Co2—O2—C1	−31.6 (2)	C13—N2—C9—C8	179.58 (19)
O7—Co2—O2—C1	78.80 (15)	Co2—N2—C9—C8	−1.2 (2)
N1—Co2—O3—C7	7.07 (15)	O5—C8—C9—N2	−179.8 (2)
N2—Co2—O3—C7	−158.05 (15)	O6—C8—C9—N2	−0.2 (3)
O6—Co2—O3—C7	126.30 (15)	O5—C8—C9—C10	−0.1 (3)
O2—Co2—O3—C7	28.7 (2)	O6—C8—C9—C10	179.6 (2)
O7—Co2—O3—C7	−80.89 (15)	N2—C9—C10—C11	0.2 (3)
N1—Co2—O6—C8	−179.67 (15)	C8—C9—C10—C11	−179.5 (2)
N2—Co2—O6—C8	−1.55 (15)	C9—C10—C11—C12	0.1 (3)
O3—Co2—O6—C8	106.82 (15)	C10—C11—C12—C13	−0.5 (3)
O2—Co2—O6—C8	−101.75 (15)	C9—N2—C13—C12	−0.3 (3)
O7—Co2—O6—C8	6.5 (2)	Co2—N2—C13—C12	−179.48 (16)
N1—Co2—O7—C14	170.69 (16)	C9—N2—C13—C14	177.03 (19)
N2—Co2—O7—C14	−6.67 (16)	Co2—N2—C13—C14	−2.2 (2)
O6—Co2—O7—C14	−14.7 (2)	C11—C12—C13—N2	0.6 (3)
O3—Co2—O7—C14	−112.95 (16)	C11—C12—C13—C14	−176.3 (2)
O2—Co2—O7—C14	94.01 (16)	Co2—O7—C14—O8	−173.99 (19)
Co2—O2—C1—O1	−172.74 (18)	Co2—O7—C14—C13	7.5 (2)
Co2—O2—C1—C2	8.9 (2)	N2—C13—C14—O8	177.5 (2)
C6—N1—C2—C3	−0.1 (3)	C12—C13—C14—O8	−5.4 (3)
Co2—N1—C2—C3	173.36 (16)	N2—C13—C14—O7	−3.9 (3)
C6—N1—C2—C1	178.64 (18)	C12—C13—C14—O7	173.3 (2)
Co2—N1—C2—C1	−7.9 (2)	C16ⁱⁱ—N3—C15—C16	−57.7 (3)
O1—C1—C2—N1	−179.8 (2)	N3—C15—C16—N3ⁱⁱ	57.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1	0.90	1.92	2.808 (2)	167
N3—H3A···O8ⁱⁱⁱ	0.90	1.91	2.772 (2)	159
O9—H9B···O3ⁱ	0.95	1.92	2.855 (2)	168
O9—H9A···O15^iv	0.95	1.82	2.767 (2)	171
O10—H10B···O13	0.95	1.76	2.683 (3)	162
O10—H10A···O6ⁱ	0.95	1.79	2.719 (2)	166
O11—H11B···O14	0.95	1.77	2.692 (3)	163
O11—H11A···O1^v	0.95	1.98	2.906 (2)	163
O12—H12B···O7	0.95	1.87	2.808 (2)	171
O12—H12A···O4^vi	0.95	1.86	2.795 (2)	166
O13—H13B···O13^vii	0.95	1.92	2.868 (5)	179
O13—H13A···O4^vii	0.95	1.83	2.770 (3)	171
O14—H14B···O5ⁱ	0.95	1.79	2.732 (3)	170
O14—H14A···O13	0.95	2.20	3.123 (4)	164
O15—H15D···O12^viii	0.95	1.86	2.772 (3)	161
O15—H15C···O8	0.95	1.86	2.770 (2)	161

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[Co(H₂O)₆][Co(C₇H₃O₄)₂]₂·8H₂O
M_r	1177.59
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	8.4682 (10), 11.9287 (14), 12.9091 (15)
α, β, γ (°)	63.478 (2), 78.683 (2), 83.063 (2)
V (Å³)	1143.3 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.50 × 0.48 × 0.20

Data collection
Diffractometer	Bruker SMART 1000
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.589, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	9953, 5061, 4261
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.06
No. of reflections	5061
No. of parameters	322
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.62

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1	0.90	1.92	2.808 (2)	166.8
N3—H3A···O8ⁱ	0.90	1.91	2.772 (2)	159.1
O9—H9B···O3ⁱⁱ	0.95	1.92	2.855 (2)	168.4
O9—H9A···O15ⁱⁱⁱ	0.95	1.82	2.767 (2)	170.7
O10—H10B···O13	0.95	1.76	2.683 (3)	162.1
O10—H10A···O6ⁱⁱ	0.95	1.79	2.719 (2)	165.5
O11—H11B···O14	0.95	1.77	2.692 (3)	162.8
O11—H11A···O1^iv	0.95	1.98	2.906 (2)	163.1
O12—H12B···O7	0.95	1.87	2.808 (2)	170.8
O12—H12A···O4^v	0.95	1.86	2.795 (2)	165.5
O13—H13B···O13^vi	0.95	1.92	2.868 (5)	178.9
O13—H13A···O4^vi	0.95	1.83	2.770 (3)	171.1
O14—H14B···O5ⁱⁱ	0.95	1.79	2.732 (3)	170.4
O14—H14A···O13	0.95	2.20	3.123 (4)	164.3
O15—H15D···O12^vii	0.95	1.86	2.772 (3)	161.2
O15—H15C···O8	0.95	1.86	2.770 (2)	160.5

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

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