Bis(N,N′-dimethyl­ethylenediammonium) tris­(oxalato-κ2O1,O2)cobaltate(II) dihydrate: an ion-pair complex

Gaye, P.A.; Sy, A.; Thiam, I.E.; Gaye, M.; Retailleau, P.

doi:10.1107/S1600536811031357

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1269

doi:10.1107/S1600536811031357

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Bis(N,N′-dimethylethylenediammonium) tris(oxalato-κ²O¹,O²)cobaltate(II) dihydrate: an ion-pair complex

Papa Aly Gaye,^a ^* Adama Sy,^a Ibrahima Elhadj Thiam,^a Mohamed Gaye ^a and Pascal Retailleau ^b

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bICSN-CNRS, Laboratoire de Cristallochimie, 1 Avenue la Terasse, 91198 Gift sur Yvette, France
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 11 July 2011; accepted 3 August 2011; online 27 August 2011)

The Co^II ion in the title complex, (C₄H₁₄N₂)₂[Co(C₂O₄)₃]·2H₂O, is coordinated by three oxalate ions, resulting in a distorted octahedral geometry. Two uncoordinated water molecules are present in asymmetric unit. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds between the different entities stabilize the crystal structure.

Related literature

For related structures: see Diallo et al. (2008 ); Gaye et al. (2011 ); Hao et al. (2010 ); Kelly et al. (2005 ); Zhang et al., (2009 ).

Experimental

Crystal data

(C₄H₁₄N₂)₂[Co(C₂O₄)₃]·2H₂O
M_r = 539.37
Monoclinic, P 2₁ /c
a = 12.625 (3) Å
b = 13.411 (4) Å
c = 16.996 (2) Å
β = 125.91 (2)°
V = 2330.7 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.50 × 0.48 × 0.26 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.720, T_max = 0.800
9121 measured reflections
5342 independent reflections
4178 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.133
S = 1.05
5333 reflections
302 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9N1⋯O8	0.90	1.86	2.668 (3)	148
O14—H14O⋯O7	0.96	1.94	2.876 (4)	163
N7—H7NB⋯O1	0.90	1.90	2.769 (3)	161
O13—H13W⋯O10	0.96	1.91	2.755 (3)	146
N10—H10M⋯O11ⁱ	0.90	1.94	2.814 (3)	165
N10—H10N⋯O9ⁱⁱ	0.90	1.83	2.721 (3)	173
N9—H9N2⋯O13ⁱⁱⁱ	0.90	1.80	2.679 (3)	163
N8—H8NA⋯O6^iv	0.90	1.94	2.829 (3)	170
N8—H8NB⋯O7^v	0.90	2.07	2.916 (3)	156
N8—H8NB⋯O8^v	0.90	2.25	2.801 (3)	119
N7—H7NA⋯O12^vi	0.90	1.97	2.751 (3)	144
O13—H13O⋯O12^vii	0.95	1.75	2.698 (3)	174
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) -x, -y, -z; (vii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999 ); cell refinement: DENZO and COLLECT; data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031357/bt5577sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031357/bt5577Isup2.hkl

checkCIF report

Comment top

The title salt, (C₄H₁₄N₂)₂[Co(C₂O₄)₃](H₂ O)₂, was obtained as an unexpected product by reaction of the employed ligand (C₆H₁₀N₂O₂)_n, in a methanolic medium. The hydrolytically unstable cyclic ligand apparently is oxidatively hydrolyzed in the presence of metal ions, leading to the oxalate dianion (Diallo et al., 2008; Kelly et al., 2005). This species, which is generated in situ, acts with cobat(II) ions resulting in the formation of the title compound. A similar reaction was found elsewhere (Zhang et al., 2009). Recently, we published the structure of an organic-inorganic hybrid salt involving the dimethylethylenediammonium cation, [C₄H₁₄N₂]²⁺ and complex anion, [Cu(C₂O₄)₂]^2- (Gaye et al., 2011). A homologous salt, with [Co(C₂O₄)₃]^4- as the anionic moiety is reported here. The Fig. 1 shows the dimethylethylenediammonium cation, [C₄H₂₄N₂]²⁺, and the complex anion, [Co(C₂O₄)₃]^4-. The asymmetric unit contains two organic cations, one anion and two water molecules. The geometrical parameters of the [C₄H₂₄N₂]⁺, cation are similar to those found in salt with the [Cu(C₂O₄)₂]^2- cationic complex (Gaye et al., 2011). The Co^II ion of the complex anion adopts a distorted octahedral coordination involving four equatorial O atoms (O1, O2, O4, O5) two quasi axial O atoms (O3, O6) of oxalate ligands (Fig. 1). The equatorial Co–O distances are 2.1009 (17) Å (Co–O1), 2.0751 (18) Å (Co–O2), 2.0693 (17) (13) Å (Co–O4) and 2.0659 (17) Å (Co–O5) respectively, and are significantly longer than the axial Co–O distance of 2.1163 (19) Å (Co–O3), 2.1070 (17) Å (Co–O6). The bond distances in the complex anion are comparable with those reported for the [Co^III(Hbiim)₃]₂[Co^II₃(ox)₃].4H₂O compound (Hao et al., 2010), where Hbiim is 2,2'-biimidazole and ox is oxalate. Two lattice water molecules are also present in the asymmetric unit. In the crystal structure, intramolecular N–H···O_ox hydrogen bonds connect the ionic entities. O_water–H···O_ox hydrogen bonds are also observed (Table 2).

Related literature top

For related structures: see Diallo et al. (2008); Gaye et al. (2011); Hao et al. (2010); Kelly et al. (2005); Zhang et al., (2009).

Experimental top

In a 50 ml round bottom flask introduce Dimethyl oxalate (2.36 g, 0.020 mol) dissolved in ethanol (10 ml). N,N'-dimethyl-1,2-diaminoethane (1.77 g, 0.020 mol) in ethanol (10 ml), was added to yield immediately a quantitative precipitate. The white precipitate formed, was separated by filtration, washed with methanol and ether and dried under vacuum (Yield 3.32 g, 58.5%); m.p.=240 °C. ¹H NMR in CDCl₃, δ (p.p.m.): 3.1, s, 12H, –CH3; 3.5, s, 8H, –CH₂. ¹³C NMR in CDCl₃, δ (p.p.m.): 34.86, N—CH₃, 46.12, N—CH₂, 157.56, C=O. IR (cm^-1) 1598 (C=O), 1284 (C—N). Anal. Calc. for C₁₂H₂₀N₄O₄ (%): C, 50.62; H, 7.11; N, 19.68. Found: C, 50.60; H, 7.09; N, 19.71. Mass spectrum (m/z) 284, 162, 134, 106, 78. Into a methanolic solution (5 ml) of cobalt chloride hexahydratee (0.2974 g, 1.25 mmol) was added a methanolic solution (10 ml) of the ligand prepared above (0.3554 g, 1.25 mmol). The resulting mixture is heated at 60°C for thirty minutes. The pink solution was filtered and then allowed to evaporate slowly in an open atmosphere. After two days, pink crystals suitable for X-ray analysis were obtained. The crystals were separated, washed with cold methanol and dried (yield: 83%); Anal. Calc. for C₁₄H₃₂CoN₄O₁₄(%): C, 31.18; H, 5.98; N, 10.39. Found: C, 31.16; H, 6.01; N, 10.37. Selected IR data (cm^-1, KBr pellet): 3335, 1635, 1601, 1580, 1193, 765.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. An ORTEP view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level.

Bis(N,N'-dimethylethylenediammonium) tris(oxalato-κ²O¹,O²)cobaltate(II) dihydrate top

Crystal data top

(C₄H₁₄N₂)₂[Co(C₂O₄)₃]·2H₂O	F(000) = 1132
M_r = 539.37	D_x = 1.537 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71070 Å
a = 12.625 (3) Å	Cell parameters from 5427 reflections
b = 13.411 (4) Å	θ = 0.4–27.5°
c = 16.996 (2) Å	µ = 0.81 mm⁻¹
β = 125.91 (2)°	T = 293 K
V = 2330.7 (11) Å³	Cube, pink
Z = 4	0.50 × 0.48 × 0.26 mm

Data collection top

Nonius KappaCCD diffractometer	5342 independent reflections
Radiation source: fine-focus sealed tube, Nonius Kappa CCD	4178 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −16→17
T_min = 0.720, T_max = 0.800	l = −21→22
9121 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)] = 0.047	Hydrogen site location: difference Fourier map
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0615P)² + 2.554P] where P = (F_o² + 2F_c²)/3
5333 reflections	(Δ/σ)_max = 0.001
302 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

(C₄H₁₄N₂)₂[Co(C₂O₄)₃]·2H₂O	V = 2330.7 (11) Å³
M_r = 539.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.625 (3) Å	µ = 0.81 mm⁻¹
b = 13.411 (4) Å	T = 293 K
c = 16.996 (2) Å	0.50 × 0.48 × 0.26 mm
β = 125.91 (2)°

Data collection top

Nonius KappaCCD diffractometer	5342 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	4178 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.800	R_int = 0.018
9121 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	Δρ_max = 1.24 e Å⁻³
5333 reflections	Δρ_min = −0.48 e Å⁻³
302 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	0.19856 (3)	0.25025 (2)	0.04584 (2)	0.02870 (12)
O1	0.1066 (2)	0.28305 (14)	0.11324 (14)	0.0380 (4)
O2	0.1676 (2)	0.40241 (14)	0.02043 (14)	0.0373 (4)
O3	0.38888 (19)	0.27837 (17)	0.17225 (13)	0.0404 (5)
O4	0.30589 (18)	0.24570 (14)	−0.01047 (13)	0.0341 (4)
O5	0.19519 (17)	0.09766 (13)	0.06110 (12)	0.0326 (4)
O6	0.02190 (17)	0.21331 (13)	−0.08801 (13)	0.0342 (4)
O7	0.0523 (2)	0.41384 (16)	0.16340 (16)	0.0492 (5)
O8	0.1380 (2)	0.53582 (14)	0.08303 (15)	0.0423 (5)
O9	0.5759 (2)	0.33994 (19)	0.20796 (14)	0.0520 (6)
O10	0.4998 (2)	0.2882 (2)	0.02668 (16)	0.0600 (7)
O11	0.09729 (19)	−0.03816 (13)	−0.02854 (13)	0.0358 (4)
O12	−0.0938 (2)	0.07973 (15)	−0.17267 (13)	0.0477 (5)
C1	0.0942 (3)	0.3754 (2)	0.12066 (18)	0.0321 (5)
C2	0.1363 (3)	0.44434 (19)	0.06991 (18)	0.0319 (5)
C3	0.4665 (3)	0.3009 (2)	0.15178 (18)	0.0335 (6)
C4	0.4215 (3)	0.2767 (2)	0.04675 (18)	0.0328 (5)
C5	0.1060 (2)	0.05329 (18)	−0.01538 (16)	0.0268 (5)
C6	0.0010 (2)	0.12061 (18)	−0.09993 (17)	0.0288 (5)
C11	0.4502 (4)	0.9703 (3)	0.1245 (3)	0.0728 (11)
H11A	0.5370	0.9437	0.1670	0.109*
H11B	0.4438	1.0308	0.1516	0.109*
H11C	0.4316	0.9839	0.0621	0.109*
N10	0.3537 (3)	0.8959 (2)	0.11339 (17)	0.0477 (6)
H10N	0.3732	0.8813	0.1722	0.057*
H10M	0.2729	0.9225	0.0771	0.057*
C12	0.3555 (4)	0.8048 (3)	0.0674 (3)	0.0550 (8)
H12A	0.4417	0.7746	0.1064	0.066*
H12B	0.3337	0.8194	0.0035	0.066*
C13	0.2585 (3)	0.7372 (3)	0.0593 (2)	0.0548 (9)
H13A	0.1719	0.7653	0.0144	0.066*
H13B	0.2744	0.7310	0.1222	0.066*
N9	0.2635 (3)	0.6321 (2)	0.02300 (19)	0.0516 (7)
H9N1	0.2019	0.5941	0.0192	0.062*
H9N2	0.2412	0.6386	−0.0377	0.062*
C14	0.3862 (4)	0.5786 (4)	0.0800 (3)	0.0795 (13)
H14A	0.4520	0.6153	0.0807	0.119*
H14B	0.3757	0.5141	0.0518	0.119*
H14C	0.4122	0.5709	0.1452	0.119*
O13	0.7540 (2)	0.3562 (2)	0.14165 (16)	0.0632 (7)
H13O	0.8069	0.3745	0.2082	0.095*
H13W	0.6669	0.3440	0.1227	0.095*
O14	0.2551 (4)	0.4143 (3)	0.3690 (2)	0.1119 (14)
H14O	0.1813	0.4028	0.3031	0.168*
H14W	0.2973	0.3604	0.4146	0.168*
N8	−0.1051 (2)	0.12399 (17)	0.28323 (16)	0.0366 (5)
H8NA	−0.0724	0.1751	0.3256	0.044*
H8NB	−0.0788	0.0667	0.3173	0.044*
N7	0.1385 (2)	0.11853 (17)	0.22373 (15)	0.0323 (5)
H7NA	0.1035	0.0668	0.1821	0.039*
H7NB	0.1129	0.1752	0.1888	0.039*
C7	0.2830 (3)	0.1114 (3)	0.2847 (2)	0.0470 (7)
H7A	0.3200	0.1654	0.3304	0.070*
H7B	0.3126	0.1149	0.2441	0.070*
H7C	0.3098	0.0491	0.3191	0.070*
C8	0.0909 (3)	0.1176 (2)	0.2861 (2)	0.0435 (7)
H8C	0.1306	0.1720	0.3325	0.052*
H8D	0.1152	0.0554	0.3218	0.052*
C9	−0.0551 (3)	0.1289 (2)	0.2227 (2)	0.0431 (7)
H9A	−0.0790	0.1923	0.1889	0.052*
H9B	−0.0944	0.0761	0.1745	0.052*
C10	−0.2507 (3)	0.1290 (3)	0.2196 (2)	0.0522 (8)
H10A	−0.2781	0.1938	0.1902	0.078*
H10B	−0.2828	0.1173	0.2579	0.078*
H10C	−0.2849	0.0792	0.1698	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02854 (19)	0.02694 (19)	0.02907 (19)	−0.00288 (13)	0.01603 (15)	−0.00256 (13)
O1	0.0469 (11)	0.0303 (9)	0.0484 (11)	−0.0013 (9)	0.0343 (10)	0.0026 (8)
O2	0.0533 (11)	0.0260 (9)	0.0479 (11)	−0.0014 (8)	0.0383 (10)	−0.0007 (8)
O3	0.0336 (10)	0.0596 (13)	0.0273 (9)	−0.0106 (9)	0.0175 (8)	−0.0065 (9)
O4	0.0287 (9)	0.0466 (11)	0.0263 (9)	−0.0050 (8)	0.0157 (7)	−0.0088 (7)
O5	0.0323 (9)	0.0259 (9)	0.0267 (8)	0.0001 (7)	0.0101 (7)	0.0016 (7)
O6	0.0315 (9)	0.0238 (9)	0.0313 (9)	0.0001 (7)	0.0095 (8)	0.0033 (7)
O7	0.0695 (15)	0.0436 (12)	0.0593 (13)	0.0075 (11)	0.0517 (12)	0.0045 (10)
O8	0.0601 (13)	0.0273 (10)	0.0505 (12)	−0.0033 (9)	0.0385 (11)	−0.0035 (8)
O9	0.0340 (11)	0.0808 (17)	0.0327 (10)	−0.0197 (11)	0.0148 (9)	−0.0160 (10)
O10	0.0396 (12)	0.107 (2)	0.0396 (12)	−0.0170 (13)	0.0268 (10)	−0.0131 (12)
O11	0.0424 (10)	0.0249 (9)	0.0337 (9)	0.0000 (8)	0.0188 (8)	0.0001 (7)
O12	0.0432 (11)	0.0347 (11)	0.0292 (10)	−0.0058 (9)	0.0010 (9)	−0.0006 (8)
C1	0.0327 (13)	0.0331 (13)	0.0326 (13)	0.0011 (11)	0.0203 (11)	0.0018 (10)
C2	0.0355 (14)	0.0286 (13)	0.0332 (13)	−0.0005 (10)	0.0210 (11)	0.0006 (10)
C3	0.0303 (13)	0.0386 (15)	0.0258 (12)	−0.0009 (11)	0.0133 (10)	−0.0023 (10)
C4	0.0292 (13)	0.0390 (14)	0.0273 (12)	−0.0012 (11)	0.0150 (11)	−0.0022 (10)
C5	0.0282 (12)	0.0255 (12)	0.0252 (11)	0.0004 (9)	0.0147 (10)	0.0018 (9)
C6	0.0293 (12)	0.0262 (12)	0.0254 (11)	−0.0004 (10)	0.0128 (10)	0.0013 (9)
C11	0.058 (2)	0.071 (3)	0.086 (3)	−0.004 (2)	0.041 (2)	0.003 (2)
N10	0.0509 (15)	0.0483 (15)	0.0315 (12)	0.0179 (12)	0.0171 (11)	0.0057 (10)
C12	0.056 (2)	0.061 (2)	0.0536 (19)	−0.0043 (17)	0.0353 (17)	−0.0044 (16)
C13	0.0442 (18)	0.081 (3)	0.0441 (17)	−0.0077 (16)	0.0286 (15)	−0.0094 (16)
N9	0.0537 (16)	0.0543 (16)	0.0420 (14)	−0.0178 (13)	0.0253 (13)	0.0014 (12)
C14	0.059 (2)	0.085 (3)	0.088 (3)	0.000 (2)	0.040 (2)	0.028 (2)
O13	0.0463 (13)	0.104 (2)	0.0393 (12)	−0.0317 (13)	0.0251 (10)	−0.0199 (12)
O14	0.138 (3)	0.080 (2)	0.077 (2)	−0.014 (2)	0.040 (2)	0.0358 (18)
N8	0.0499 (14)	0.0315 (11)	0.0385 (12)	−0.0079 (10)	0.0315 (11)	−0.0056 (9)
N7	0.0361 (11)	0.0314 (11)	0.0307 (10)	−0.0083 (9)	0.0204 (9)	−0.0060 (9)
C7	0.0385 (15)	0.059 (2)	0.0353 (14)	−0.0051 (14)	0.0171 (12)	0.0006 (13)
C8	0.0480 (16)	0.0519 (18)	0.0325 (14)	−0.0062 (14)	0.0248 (13)	−0.0056 (12)
C9	0.0486 (17)	0.0490 (17)	0.0361 (14)	0.0001 (14)	0.0273 (13)	0.0006 (12)
C10	0.0488 (18)	0.055 (2)	0.0487 (18)	0.0006 (15)	0.0261 (15)	0.0021 (15)

Geometric parameters (Å, º) top

Co1—O5	2.0663 (19)	C13—H13A	0.9700
Co1—O4	2.0680 (19)	C13—H13B	0.9700
Co1—O2	2.075 (2)	N9—C14	1.446 (5)
Co1—O1	2.1004 (19)	N9—H9N1	0.9000
Co1—O6	2.1079 (19)	N9—H9N2	0.9000
Co1—O3	2.116 (2)	C14—H14A	0.9600
O1—C1	1.264 (3)	C14—H14B	0.9600
O2—C2	1.253 (3)	C14—H14C	0.9600
O3—C3	1.254 (3)	O13—H13O	0.9484
O4—C4	1.259 (3)	O13—H13W	0.9606
O5—C5	1.263 (3)	O14—H14O	0.9599
O6—C6	1.262 (3)	O14—H14W	0.9599
O7—C1	1.235 (3)	N8—C9	1.490 (3)
O8—C2	1.245 (3)	N8—C10	1.490 (4)
O9—C3	1.243 (3)	N8—H8NA	0.9000
O10—C4	1.229 (3)	N8—H8NB	0.9000
O11—C5	1.240 (3)	N7—C7	1.480 (4)
O12—C6	1.235 (3)	N7—C8	1.494 (3)
C1—C2	1.555 (3)	N7—H7NA	0.9000
C3—C4	1.557 (3)	N7—H7NB	0.9000
C5—C6	1.550 (3)	C7—H7A	0.9600
C11—N10	1.498 (5)	C7—H7B	0.9600
C11—H11A	0.9600	C7—H7C	0.9600
C11—H11B	0.9600	C8—C9	1.501 (4)
C11—H11C	0.9600	C8—H8C	0.9700
N10—C12	1.458 (4)	C8—H8D	0.9700
N10—H10N	0.9000	C9—H9A	0.9700
N10—H10M	0.9000	C9—H9B	0.9700
C12—C13	1.463 (5)	C10—H10A	0.9600
C12—H12A	0.9700	C10—H10B	0.9600
C12—H12B	0.9700	C10—H10C	0.9600
C13—N9	1.555 (5)

O5—Co1—O4	95.52 (8)	C12—C13—N9	111.9 (3)
O5—Co1—O2	170.01 (8)	C12—C13—H13A	109.2
O4—Co1—O2	91.57 (7)	N9—C13—H13A	109.2
O5—Co1—O1	94.60 (7)	C12—C13—H13B	109.2
O4—Co1—O1	168.55 (7)	N9—C13—H13B	109.2
O2—Co1—O1	79.08 (7)	H13A—C13—H13B	107.9
O5—Co1—O6	79.40 (7)	C14—N9—C13	117.4 (3)
O4—Co1—O6	93.41 (8)	C14—N9—H9N1	107.9
O2—Co1—O6	93.19 (8)	C13—N9—H9N1	107.9
O1—Co1—O6	93.70 (8)	C14—N9—H9N2	107.9
O5—Co1—O3	98.27 (8)	C13—N9—H9N2	107.9
O4—Co1—O3	79.23 (7)	H9N1—N9—H9N2	107.2
O2—Co1—O3	89.95 (9)	N9—C14—H14A	109.5
O1—Co1—O3	94.04 (8)	N9—C14—H14B	109.5
O6—Co1—O3	172.08 (8)	H14A—C14—H14B	109.5
C1—O1—Co1	113.60 (16)	N9—C14—H14C	109.5
C2—O2—Co1	113.38 (16)	H14A—C14—H14C	109.5
C3—O3—Co1	111.60 (16)	H14B—C14—H14C	109.5
C4—O4—Co1	114.24 (16)	H13O—O13—H13W	108.1
C5—O5—Co1	114.15 (15)	H14O—O14—H14W	121.4
C6—O6—Co1	113.20 (15)	C9—N8—C10	109.8 (2)
O7—C1—O1	126.1 (2)	C9—N8—H8NA	109.7
O7—C1—C2	118.8 (2)	C10—N8—H8NA	109.7
O1—C1—C2	115.1 (2)	C9—N8—H8NB	109.7
O8—C2—O2	125.7 (2)	C10—N8—H8NB	109.7
O8—C2—C1	117.5 (2)	H8NA—N8—H8NB	108.2
O2—C2—C1	116.8 (2)	C7—N7—C8	110.2 (2)
O9—C3—O3	125.8 (2)	C7—N7—H7NA	109.6
O9—C3—C4	117.5 (2)	C8—N7—H7NA	109.6
O3—C3—C4	116.7 (2)	C7—N7—H7NB	109.6
O10—C4—O4	125.7 (2)	C8—N7—H7NB	109.6
O10—C4—C3	118.7 (2)	H7NA—N7—H7NB	108.1
O4—C4—C3	115.6 (2)	N7—C7—H7A	109.5
O11—C5—O5	125.7 (2)	N7—C7—H7B	109.5
O11—C5—C6	118.1 (2)	H7A—C7—H7B	109.5
O5—C5—C6	116.2 (2)	N7—C7—H7C	109.5
O12—C6—O6	125.9 (2)	H7A—C7—H7C	109.5
O12—C6—C5	118.0 (2)	H7B—C7—H7C	109.5
O6—C6—C5	116.1 (2)	N7—C8—C9	109.1 (2)
N10—C11—H11A	109.5	N7—C8—H8C	109.9
N10—C11—H11B	109.5	C9—C8—H8C	109.9
H11A—C11—H11B	109.5	N7—C8—H8D	109.9
N10—C11—H11C	109.5	C9—C8—H8D	109.9
H11A—C11—H11C	109.5	H8C—C8—H8D	108.3
H11B—C11—H11C	109.5	N8—C9—C8	109.8 (2)
C12—N10—C11	111.0 (3)	N8—C9—H9A	109.7
C12—N10—H10N	109.4	C8—C9—H9A	109.7
C11—N10—H10N	109.4	N8—C9—H9B	109.7
C12—N10—H10M	109.4	C8—C9—H9B	109.7
C11—N10—H10M	109.4	H9A—C9—H9B	108.2
H10N—N10—H10M	108.0	N8—C10—H10A	109.5
N10—C12—C13	107.1 (3)	N8—C10—H10B	109.5
N10—C12—H12A	110.3	H10A—C10—H10B	109.5
C13—C12—H12A	110.3	N8—C10—H10C	109.5
N10—C12—H12B	110.3	H10A—C10—H10C	109.5
C13—C12—H12B	110.3	H10B—C10—H10C	109.5
H12A—C12—H12B	108.6

O5—Co1—O1—C1	177.89 (18)	Co1—O1—C1—O7	−174.5 (2)
O4—Co1—O1—C1	25.8 (5)	Co1—O1—C1—C2	5.8 (3)
O2—Co1—O1—C1	−9.93 (18)	Co1—O2—C2—O8	164.7 (2)
O6—Co1—O1—C1	−102.47 (19)	Co1—O2—C2—C1	−14.1 (3)
O3—Co1—O1—C1	79.24 (19)	O7—C1—C2—O8	7.1 (4)
O5—Co1—O2—C2	64.5 (5)	O1—C1—C2—O8	−173.2 (2)
O4—Co1—O2—C2	−160.22 (19)	O7—C1—C2—O2	−174.1 (3)
O1—Co1—O2—C2	13.13 (18)	O1—C1—C2—O2	5.7 (4)
O6—Co1—O2—C2	106.28 (19)	Co1—O3—C3—O9	164.8 (3)
O3—Co1—O2—C2	−80.99 (19)	Co1—O3—C3—C4	−15.7 (3)
O5—Co1—O3—C3	108.9 (2)	Co1—O4—C4—O10	−174.0 (3)
O4—Co1—O3—C3	14.76 (19)	Co1—O4—C4—C3	6.7 (3)
O2—Co1—O3—C3	−76.8 (2)	O9—C3—C4—O10	6.8 (4)
O1—Co1—O3—C3	−155.9 (2)	O3—C3—C4—O10	−172.7 (3)
O6—Co1—O3—C3	36.6 (7)	O9—C3—C4—O4	−173.8 (3)
O5—Co1—O4—C4	−108.70 (19)	O3—C3—C4—O4	6.6 (4)
O2—Co1—O4—C4	78.35 (19)	Co1—O5—C5—O11	167.8 (2)
O1—Co1—O4—C4	43.4 (5)	Co1—O5—C5—C6	−10.8 (3)
O6—Co1—O4—C4	171.64 (19)	Co1—O6—C6—O12	−178.4 (2)
O3—Co1—O4—C4	−11.30 (19)	Co1—O6—C6—C5	0.7 (3)
O4—Co1—O5—C5	−83.76 (17)	O11—C5—C6—O12	7.4 (4)
O2—Co1—O5—C5	51.3 (5)	O5—C5—C6—O12	−173.9 (2)
O1—Co1—O5—C5	101.59 (18)	O11—C5—C6—O6	−171.7 (2)
O6—Co1—O5—C5	8.69 (17)	O5—C5—C6—O6	7.0 (3)
O3—Co1—O5—C5	−163.64 (17)	C11—N10—C12—C13	−179.8 (3)
O5—Co1—O6—C6	−4.67 (17)	N10—C12—C13—N9	−172.8 (3)
O4—Co1—O6—C6	90.32 (18)	C12—C13—N9—C14	58.1 (4)
O2—Co1—O6—C6	−177.91 (18)	C7—N7—C8—C9	177.9 (3)
O1—Co1—O6—C6	−98.67 (18)	C10—N8—C9—C8	−176.6 (3)
O3—Co1—O6—C6	68.9 (6)	N7—C8—C9—N8	177.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9N1···O8	0.90	1.86	2.668 (3)	148
O14—H14O···O7	0.96	1.94	2.876 (4)	163
N7—H7NB···O1	0.90	1.90	2.769 (3)	161
O13—H13W···O10	0.96	1.91	2.755 (3)	146
N10—H10M···O11ⁱ	0.90	1.94	2.814 (3)	165
N10—H10N···O9ⁱⁱ	0.90	1.83	2.721 (3)	173
N9—H9N2···O13ⁱⁱⁱ	0.90	1.80	2.679 (3)	163
N8—H8NA···O6^iv	0.90	1.94	2.829 (3)	170
N8—H8NB···O7^v	0.90	2.07	2.916 (3)	156
N8—H8NB···O8^v	0.90	2.25	2.801 (3)	119
N7—H7NA···O12^vi	0.90	1.97	2.751 (3)	144
O13—H13O···O12^vii	0.95	1.75	2.698 (3)	174

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₄N₂)₂[Co(C₂O₄)₃]·2H₂O
M_r	539.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.625 (3), 13.411 (4), 16.996 (2)
β (°)	125.91 (2)
V (Å³)	2330.7 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.50 × 0.48 × 0.26

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.720, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections	9121, 5342, 4178
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.133, 1.05
No. of reflections	5333
No. of parameters	302
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −0.48

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9N1···O8	0.90	1.86	2.668 (3)	147.9
O14—H14O···O7	0.96	1.94	2.876 (4)	163.2
N7—H7NB···O1	0.90	1.90	2.769 (3)	160.5
O13—H13W···O10	0.96	1.91	2.755 (3)	145.8
N10—H10M···O11ⁱ	0.90	1.94	2.814 (3)	164.7
N10—H10N···O9ⁱⁱ	0.90	1.83	2.721 (3)	173.4
N9—H9N2···O13ⁱⁱⁱ	0.90	1.80	2.679 (3)	163.4
N8—H8NA···O6^iv	0.90	1.94	2.829 (3)	169.5
N8—H8NB···O7^v	0.90	2.07	2.916 (3)	155.5
N8—H8NB···O8^v	0.90	2.25	2.801 (3)	118.8
N7—H7NA···O12^vi	0.90	1.97	2.751 (3)	144.2
O13—H13O···O12^vii	0.95	1.75	2.698 (3)	174.1

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

Acknowledgements

The authors thank Professor Amadou Tidiane BA, Minister of Higher Education of Senegal, for his financial support.

References

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