N,N′-Dimethyl­ethylenediammonium dioxalatocuprate(II)

Gaye, P.A.; Sarr, A.D.; Gaye, M.; Sanselme, M.; Agasse, P.V.

doi:10.1107/S1600536811025682

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1046

doi:10.1107/S1600536811025682

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N,N′-Dimethylethylenediammonium dioxalatocuprate(II)

Papa Aly Gaye,^a ^* Aminata Diassé Sarr,^a Mohamed Gaye,^a Morgane Sanselme ^b and Peulon Valérie Agasse ^b

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bSciences et Méthodes Séparatives, UPRES EA 3233 IMR, IRCOF, F-76821, Mont-Saint-Aigan, Université de Rouen Cedex, France
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 20 June 2011; accepted 29 June 2011; online 9 July 2011)

The asymmetric unit of the title salt, (C₄H₁₄N₂)[Cu(C₂O₄)₂], consists of one complex anion and two cationic half-molecules, the other halves being generated by inversion symmetry. The Cu^II atom in the anion is coordinated by two bidentate oxalate ligands in a distorted square-planar geometry. Intermolecular hydrogen bonds, involving the NH groups as donors and O atoms as acceptors, are observed, which lead to the formation of a three-dimensional network structure.

Related literature

For background to decomposition reactions leading to oxalate anions, see: Kelly et al. (2005 ); Diallo et al. (2008 ). For related structures, see: Androš et al. (2010 ); Fan et al. (2001 ); Zhang et al. (2009 ).

Experimental

Crystal data

(C₄H₁₄N₂)[Cu(C₂O₄)₂]
M_r = 329.75
Triclinic, $[P \overline 1]$
a = 5.7734 (5) Å
b = 8.4127 (7) Å
c = 12.5623 (11) Å
α = 90.443 (1)°
β = 100.715 (1)°
γ = 107.188 (1)°
V = 571.46 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
4558 measured reflections
2292 independent reflections
2192 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.07
S = 1.12
2292 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9128 (13)
Cu1—O2	1.9163 (13)
Cu1—O2A	1.9184 (13)
Cu1—O1A	1.9572 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1S—H2S1⋯O3Aⁱ	0.90	2.22	2.939 (2)	137
N1S—H2S2⋯O1Aⁱⁱ	0.90	2.13	3.018 (2)	169
N2S—H4S1⋯O4Aⁱⁱ	0.90	2.15	2.939 (2)	145
N2S—H4S1⋯O3Aⁱⁱ	0.90	2.31	3.004 (2)	134
N2S—H4S2⋯O4ⁱⁱⁱ	0.90	2.11	2.861 (2)	140
N2S—H4S2⋯O3^iv	0.90	2.58	3.131 (2)	120
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y, -z; (iii) x-1, y, z; (iv) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 1999 ); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811025682/wm2502sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025682/wm2502Isup2.hkl

checkCIF report

Comment top

The title salt, (C₄H₁₄N₂)[Cu(C₂O₄)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 copper(II) ions resulting in the formation of the title compound. A similar reaction was found elsewhere (Zhang et al., 2009).

The structure exhibits an ion-pair complex comprising two cationic half-molecules (the other halves being generated by inversion symmetry) and a [Cu(C₂O₄)₂]^2- dianion (Fig. 1). The Cu^II ion is four-coordinated in a slightly distorted square–planar CuO₄ environment, comprising four O donor atoms from two oxalate ligands [Cu–O, 1.9128 (13), 1.9163 (13), 1.9184 (13) and 1.9572 (13) Å]. The O(1)—Cu—O(2 A) and O(2)—Cu—O(1 A) angles are 179.52 (5) and 178.10 (5)°, respectively, which are slightly smaller than those observed in the complex [K₂Cu(ox)₂]^.4H₂O (180 °), where ox is oxalate (Fan et al., 2001). The other two oxygen atoms of each oxalate group are not involved in coordination. The two oxalate anions deviate slightly from planarity, with torsion angles of O(1)—C(1)—C(2)—O(2), O(4)—C(1)—C(2)—O(3), O(1A)—C(1A)—C(2A)—O(2A) and O(4A)—C(1A)—C(2A)—O(3A) -2.5 (2), -3.4 (3), 2.8 (2) and 3.8 (2)°, respectively. These values are similar to those found in [Cu(bpy)(C₂O₄)(H₂O)]^.H₂C₂O₄ (Androš et al., 2010), where bpy is bipyridine.

N—H···O hydrogen-bonding interactions, part of which are bifurcated, between the cations and the complex anions lead to the formation of a three-dimensional network structure (Table 2; Figs. 2, 3).

Related literature top

For background to decomposition reactions leading to oxalate anions, see: Kelly et al. (2005); Diallo et al. (2008). For related structures, see: Androš et al. (2010); Fan et al. (2001); Zhang et al. (2009).

Experimental top

In a 50 ml round bottom flask dimethyl oxalate (2.36 g, 0.020 mol), dissolved in ethanol (10 ml), was reacted with N,N'-dimethyl-1,2-diaminoethane (1.77 g, 0.020 mol) in ethanol (10 ml), to yield immediately a quantitative precipitate. The white solid formed was separated by filtration, washed with methanol and ether and dried under vacuum (yield 3.32 g, 58.5%); m.p.= 513 K. ¹ H 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 copper chloride dihydrate (0.2131 g, 1.25 mmol) was added a methanolic solution (10 ml) of the ligand prepared as described above (0.3554 g, 1.25 mmol). The resulting mixture was heated at 333 K for thirty minutes. The green solution was filtered and then allowed to evaporate slowly in open atmosphere. After one week, blue crystals suitable for X-ray analysis were obtained. The crystals were separated, washed with cold methanol and dried (yield: 65%); Anal. Calc. for (C₄H₁₄N₂)[Cu(C₂O₄)₂](%): C, 29.14; H, 4.28; N, 8.50. Found: C, 29.16; H, 4.26; N, 8.46. Selected IR data (cm^-1, KBr pellet): 3300, 1637, 1600, 1582, 1197, 764.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

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. [Symmetry codes: ) -x + 1, -y + 1, -z; *) -x + 1, -y, -z + 1].
	Fig. 2. Projection of the structure along the b axis showing the anions connected by organics cations. Broken lines stand for hydrogen bonds.
	Fig. 3. Projection of the structure along the a axis showing the anions connected by organics cations. Broken lines stand for hydrogen bonds.

N,N'-Dimethylethylenediammonium dioxalatocuprate(II) top

Crystal data top

(C₄H₁₄N₂)[Cu(C₂O₄)₂]	Z = 2
M_r = 329.75	F(000) = 338
Triclinic, P1	D_x = 1.916 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7734 (5) Å	Cell parameters from 2192 reflections
b = 8.4127 (7) Å	θ = 1.7–26.4°
c = 12.5623 (11) Å	µ = 1.95 mm⁻¹
α = 90.443 (1)°	T = 293 K
β = 100.715 (1)°	Prism, blue
γ = 107.188 (1)°	0.15 × 0.13 × 0.10 mm
V = 571.46 (8) Å³

Data collection top

Bruker SMART CCD diffractometer	R_int = 0.014
Graphite monochromator	θ_max = 26.4°, θ_min = 1.7°
ω scans	h = −7→7
4558 measured reflections	k = −10→10
2292 independent reflections	l = −15→15
2192 reflections with I > 2σ(I)

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.07	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0412P)² + 0.2106P] where P = (F_o² + 2F_c²)/3
2292 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

(C₄H₁₄N₂)[Cu(C₂O₄)₂]	γ = 107.188 (1)°
M_r = 329.75	V = 571.46 (8) Å³
Triclinic, P1	Z = 2
a = 5.7734 (5) Å	Mo Kα radiation
b = 8.4127 (7) Å	µ = 1.95 mm⁻¹
c = 12.5623 (11) Å	T = 293 K
α = 90.443 (1)°	0.15 × 0.13 × 0.10 mm
β = 100.715 (1)°

Data collection top

Bruker SMART CCD diffractometer	2192 reflections with I > 2σ(I)
4558 measured reflections	R_int = 0.014
2292 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.07	H-atom parameters constrained
S = 1.12	Δρ_max = 0.35 e Å⁻³
2292 reflections	Δρ_min = −0.43 e Å⁻³
174 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
Cu1	0.81900 (4)	0.08511 (2)	0.071311 (15)	0.02027 (10)
O1	0.7688 (2)	−0.09898 (16)	0.16179 (10)	0.0236 (3)
O2	0.9414 (3)	0.22323 (16)	0.20393 (11)	0.0273 (3)
O3	0.9874 (3)	0.1983 (2)	0.38225 (12)	0.0400 (4)
O4	0.8221 (3)	−0.14792 (19)	0.33674 (12)	0.0346 (3)
O1A	0.7045 (2)	−0.05261 (16)	−0.06558 (10)	0.0244 (3)
O2A	0.8699 (3)	0.27099 (16)	−0.01838 (11)	0.0274 (3)
O3A	0.7987 (3)	0.32433 (18)	−0.19228 (12)	0.0325 (3)
O4A	0.6466 (2)	−0.01666 (17)	−0.24263 (10)	0.0271 (3)
C1	0.8324 (3)	−0.0538 (2)	0.26338 (15)	0.0230 (4)
C2	0.9307 (3)	0.1394 (2)	0.28879 (15)	0.0249 (4)
C1A	0.7074 (3)	0.0373 (2)	−0.14883 (14)	0.0201 (3)
C2A	0.8000 (3)	0.2289 (2)	−0.11968 (15)	0.0221 (4)
C1S	0.5705 (4)	0.5131 (2)	0.05810 (18)	0.0323 (4)
H1S1	0.7161	0.4764	0.0631	0.039*
H1S2	0.6244	0.6309	0.0809	0.039*
N1S	0.4111 (3)	0.4180 (2)	0.13069 (15)	0.0328 (4)
H2S1	0.2785	0.4547	0.1272	0.039*
H2S2	0.3564	0.3094	0.1074	0.039*
C2S	0.4947 (4)	−0.0903 (3)	0.50540 (16)	0.0302 (4)
H3S1	0.6487	−0.1056	0.4941	0.036*
H3S2	0.4737	−0.1213	0.578	0.036*
N2S	0.2872 (3)	−0.1980 (2)	0.42503 (13)	0.0329 (4)
H4S1	0.313	−0.1731	0.3578	0.039*
H4S2	0.1467	−0.177	0.4324	0.039*
C3S	0.5449 (4)	0.4354 (3)	0.24519 (18)	0.0394 (5)
H1S3	0.6805	0.3899	0.25	0.059*
H1S4	0.434	0.3762	0.2898	0.059*
H1S5	0.6069	0.5512	0.2698	0.059*
C4S	0.2574 (5)	−0.3766 (3)	0.4373 (2)	0.0484 (6)
H2S3	0.4075	−0.3993	0.4303	0.073*
H2S4	0.124	−0.4417	0.382	0.073*
H2S5	0.2213	−0.4051	0.5075	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02469 (14)	0.01821 (14)	0.01732 (14)	0.00556 (9)	0.00424 (9)	0.00003 (9)
O1	0.0270 (7)	0.0220 (6)	0.0214 (6)	0.0065 (5)	0.0054 (5)	0.0008 (5)
O2	0.0344 (7)	0.0231 (6)	0.0228 (7)	0.0070 (6)	0.0046 (5)	−0.0023 (5)
O3	0.0505 (9)	0.0451 (9)	0.0212 (7)	0.0126 (7)	0.0027 (6)	−0.0065 (6)
O4	0.0398 (8)	0.0394 (8)	0.0268 (7)	0.0139 (7)	0.0089 (6)	0.0120 (6)
O1A	0.0326 (7)	0.0193 (6)	0.0194 (6)	0.0060 (5)	0.0034 (5)	−0.0003 (5)
O2A	0.0389 (8)	0.0198 (6)	0.0229 (7)	0.0069 (6)	0.0075 (6)	0.0005 (5)
O3A	0.0419 (8)	0.0299 (7)	0.0280 (7)	0.0139 (6)	0.0071 (6)	0.0104 (6)
O4A	0.0284 (7)	0.0331 (7)	0.0189 (7)	0.0097 (6)	0.0022 (5)	−0.0022 (5)
C1	0.0189 (8)	0.0285 (9)	0.0243 (9)	0.0101 (7)	0.0063 (7)	0.0032 (7)
C2	0.0221 (9)	0.0290 (9)	0.0236 (9)	0.0092 (7)	0.0024 (7)	−0.0032 (7)
C1A	0.0160 (8)	0.0235 (9)	0.0226 (9)	0.0084 (7)	0.0047 (6)	0.0006 (7)
C2A	0.0212 (8)	0.0224 (8)	0.0254 (9)	0.0095 (7)	0.0063 (7)	0.0033 (7)
C1S	0.0270 (10)	0.0234 (9)	0.0457 (12)	0.0029 (8)	0.0135 (9)	−0.0064 (8)
N1S	0.0272 (8)	0.0244 (8)	0.0462 (10)	0.0054 (7)	0.0098 (7)	−0.0023 (7)
C2S	0.0294 (10)	0.0409 (12)	0.0210 (9)	0.0130 (9)	0.0028 (7)	0.0028 (8)
N2S	0.0340 (9)	0.0379 (9)	0.0244 (8)	0.0084 (7)	0.0039 (7)	0.0050 (7)
C3S	0.0414 (12)	0.0311 (11)	0.0445 (13)	0.0124 (9)	0.0032 (10)	−0.0025 (9)
C4S	0.0696 (17)	0.0385 (12)	0.0354 (12)	0.0118 (12)	0.0131 (11)	0.0060 (10)

Geometric parameters (Å, º) top

Cu1—O1	1.9128 (13)	C1S—H1S2	0.97
Cu1—O2	1.9163 (13)	N1S—C3S	1.485 (3)
Cu1—O2A	1.9184 (13)	N1S—H2S1	0.90
Cu1—O1A	1.9572 (13)	N1S—H2S2	0.90
O1—C1	1.282 (2)	C2S—N2S	1.473 (3)
O2—C2	1.284 (2)	C2S—C2Sⁱⁱ	1.511 (4)
O3—C2	1.218 (2)	C2S—H3S1	0.97
O4—C1	1.218 (2)	C2S—H3S2	0.97
O1A—C1A	1.295 (2)	N2S—C4S	1.474 (3)
O2A—C2A	1.275 (2)	N2S—H4S1	0.90
O3A—C2A	1.220 (2)	N2S—H4S2	0.90
O4A—C1A	1.209 (2)	C3S—H1S3	0.96
C1—C2	1.564 (3)	C3S—H1S4	0.96
C1A—C2A	1.558 (2)	C3S—H1S5	0.96
C1S—N1S	1.486 (3)	C4S—H2S3	0.96
C1S—C1Sⁱ	1.513 (4)	C4S—H2S4	0.96
C1S—H1S1	0.97	C4S—H2S5	0.96

O1—Cu1—O2	85.90 (5)	C3S—N1S—H2S1	109.2
O1—Cu1—O2A	179.52 (5)	C1S—N1S—H2S1	109.2
O2—Cu1—O2A	93.63 (6)	C3S—N1S—H2S2	109.2
O1—Cu1—O1A	95.12 (5)	C1S—N1S—H2S2	109.2
O2—Cu1—O1A	178.10 (5)	H2S1—N1S—H2S2	107.9
O2A—Cu1—O1A	85.36 (5)	N2S—C2S—C2Sⁱⁱ	110.15 (19)
C1—O1—Cu1	113.02 (11)	N2S—C2S—H3S1	109.6
C2—O2—Cu1	112.98 (12)	C2Sⁱⁱ—C2S—H3S1	109.6
C1A—O1A—Cu1	111.82 (11)	N2S—C2S—H3S2	109.6
C2A—O2A—Cu1	113.52 (11)	C2Sⁱⁱ—C2S—H3S2	109.6
O4—C1—O1	125.29 (18)	H3S1—C2S—H3S2	108.1
O4—C1—C2	120.57 (17)	C2S—N2S—C4S	112.34 (17)
O1—C1—C2	114.14 (15)	C2S—N2S—H4S1	109.1
O3—C2—O2	125.64 (18)	C4S—N2S—H4S1	109.1
O3—C2—C1	120.45 (17)	C2S—N2S—H4S2	109.1
O2—C2—C1	113.90 (15)	C4S—N2S—H4S2	109.1
O4A—C1A—O1A	125.21 (17)	H4S1—N2S—H4S2	107.9
O4A—C1A—C2A	120.46 (16)	N1S—C3S—H1S3	109.5
O1A—C1A—C2A	114.33 (15)	N1S—C3S—H1S4	109.5
O3A—C2A—O2A	125.78 (17)	H1S3—C3S—H1S4	109.5
O3A—C2A—C1A	119.40 (17)	N1S—C3S—H1S5	109.5
O2A—C2A—C1A	114.82 (15)	H1S3—C3S—H1S5	109.5
N1S—C1S—C1Sⁱ	110.2 (2)	H1S4—C3S—H1S5	109.5
N1S—C1S—H1S1	109.6	N2S—C4S—H2S3	109.5
C1Sⁱ—C1S—H1S1	109.6	N2S—C4S—H2S4	109.5
N1S—C1S—H1S2	109.6	H2S3—C4S—H2S4	109.5
C1Sⁱ—C1S—H1S2	109.6	N2S—C4S—H2S5	109.5
H1S1—C1S—H1S2	108.1	H2S3—C4S—H2S5	109.5
C3S—N1S—C1S	112.06 (16)	H2S4—C4S—H2S5	109.5

O2—Cu1—O1—C1	0.30 (12)	O1—C1—C2—O3	176.97 (17)
O1A—Cu1—O1—C1	178.68 (12)	O4—C1—C2—O2	177.15 (17)
O1—Cu1—O2—C2	−1.77 (13)	O1—C1—C2—O2	−2.5 (2)
O2A—Cu1—O2—C2	178.14 (13)	Cu1—O1A—C1A—O4A	179.71 (14)
O1—Cu1—O1A—C1A	178.09 (11)	Cu1—O1A—C1A—C2A	0.11 (17)
O2A—Cu1—O1A—C1A	−1.83 (12)	Cu1—O2A—C2A—O3A	175.09 (15)
O2—Cu1—O2A—C2A	−178.11 (13)	Cu1—O2A—C2A—C1A	−4.23 (19)
O1A—Cu1—O2A—C2A	3.51 (13)	O4A—C1A—C2A—O3A	3.8 (3)
Cu1—O1—C1—O4	−178.63 (15)	O1A—C1A—C2A—O3A	−176.58 (16)
Cu1—O1—C1—C2	0.99 (18)	O4A—C1A—C2A—O2A	−176.83 (16)
Cu1—O2—C2—O3	−176.78 (17)	O1A—C1A—C2A—O2A	2.8 (2)
Cu1—O2—C2—C1	2.64 (19)	C1Sⁱ—C1S—N1S—C3S	178.0 (2)
O4—C1—C2—O3	−3.4 (3)	C2Sⁱⁱ—C2S—N2S—C4S	−175.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1S—H2S1···O3Aⁱ	0.90	2.22	2.939 (2)	137
N1S—H2S2···O1Aⁱⁱⁱ	0.90	2.13	3.018 (2)	169
N2S—H4S1···O4Aⁱⁱⁱ	0.90	2.15	2.939 (2)	145
N2S—H4S1···O3Aⁱⁱⁱ	0.90	2.31	3.004 (2)	134
N2S—H4S2···O4^iv	0.90	2.11	2.861 (2)	140
N2S—H4S2···O3ⁱⁱ	0.90	2.58	3.131 (2)	120

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₄N₂)[Cu(C₂O₄)₂]
M_r	329.75
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.7734 (5), 8.4127 (7), 12.5623 (11)
α, β, γ (°)	90.443 (1), 100.715 (1), 107.188 (1)
V (Å³)	571.46 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4558, 2292, 2192
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.07, 1.12
No. of reflections	2292
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.43

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 1999), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—O1	1.9128 (13)	Cu1—O2A	1.9184 (13)
Cu1—O2	1.9163 (13)	Cu1—O1A	1.9572 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1S—H2S1···O3Aⁱ	0.90	2.22	2.939 (2)	137
N1S—H2S2···O1Aⁱⁱ	0.90	2.13	3.018 (2)	169
N2S—H4S1···O4Aⁱⁱ	0.90	2.15	2.939 (2)	145
N2S—H4S1···O3Aⁱⁱ	0.90	2.31	3.004 (2)	134
N2S—H4S2···O4ⁱⁱⁱ	0.90	2.11	2.861 (2)	140
N2S—H4S2···O3^iv	0.90	2.58	3.131 (2)	120

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

Acknowledgements

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No.6314PS804).

References

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