N,N'-Dimethyl-ethylenediammonium dioxalatocuprate(II).

The asymmetric unit of the title salt, (C(4)H(14)N(2))[Cu(C(2)O(4))(2)], consists of one complex anion and two cationic half-mol-ecules, 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. Inter-molecular 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 = 329.75

Triclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.07

S = 1.12

2292 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAIn class="Chemical">NT-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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811025682/wm2502sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C4H14N2)[Cu(C2O4)2]	Z = 2
Mr = 329.75	F(000) = 338
Triclinic, P1	Dx = 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

Bruker SMART CCD diffractometer	Rint = 0.014
graphite	θmax = 26.4°, θmin = 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 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(Fo2) + (0.0412P)2 + 0.2106P] where P = (Fo2 + 2Fc2)/3
2292 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O4iv	0.90	2.11	2.861 (2)	140
N2S—H4S2···O3ii	0.90	2.58	3.131 (2)	120

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⋯O3iv	0.90	2.58	3.131 (2)	120

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .