Tetra-kis(aceto-nitrile)copper(I) hydrogen oxalate-oxalic acid-aceto-nitrile (1/0.5/0.5).

In the title compound, [Cu(CH3CN)4](C2HO4)·0.5C2H2O4·0.5CH3CN, the Cu(I) ion is coordinated by the N atoms of four aceto-nitrile ligands in a slightly distorted tetra-hedral environment. The oxalic acid mol-ecule lies across an inversion center. The aceto-nitrile solvent mol-ecule is disordered across an inversion center and was refined with half occupancy. In the crystal, the hydrogen oxalate anions and oxalic acid mol-ecules are linked via O-H⋯O hydrogen bonds, forming chains along [010].

Related literature

For background to tetra­kis­(aceto­nitrile)­copper(I) complexes, see: Morgan (1923 ▶); Heckel (1966 ▶); Kubas et al. (1979 ▶). For details of the affinity of nitrile ligands for CuI ions, see: Cotton et al. (1999 ▶). For the hard–soft acid–base theory, see: Pearson (1968 ▶). For the structure of the closely related tetra­kis­(aceto­nitrile)­copper(I) tetra­fluoro­borate, see: Jones & Crespo (1998 ▶).

Experimental

Crystal data

[Cu(C2H3N)4](C2HO4)·0.5C2H2O4·0.5C2H3N

M = 382.33

Monoclinic,

a = 9.5637 (4) Å

b = 5.5670 (2) Å

c = 32.0682 (12) Å

β = 92.901 (2)°

V = 1705.16 (11) Å3

Z = 4

Cu Kα radiation

μ = 2.15 mm−1

T = 100 K

0.17 × 0.14 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.715, T max = 0.938

8349 measured reflections

2928 independent reflections

2745 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.098

S = 1.12

2928 reflections

236 parameters

18 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.89 e Å−3

Δρmin = −0.50 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: CHEMDRAW (Cambridgesoft, 2003 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813024914/lh5649sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024914/lh5649Isup2.hkl

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

[Cu(C2H3N)4](C2HO4)·0.5C2H2O4·0.5C2H3N	F(000) = 784
Mr = 382.33	Dx = 1.489 Mg m−3
Monoclinic, P21/n	Melting point: not measured K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54184 Å
a = 9.5637 (4) Å	θ = 2.8–66.4°
b = 5.5670 (2) Å	µ = 2.15 mm−1
c = 32.0682 (12) Å	T = 100 K
β = 92.901 (2)°	Plate, colorless
V = 1705.16 (11) Å3	0.17 × 0.14 × 0.03 mm
Z = 4

Bruker APEXII CCD diffractometer	2928 independent reflections
Radiation source: fine-focus sealed tube	2745 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 66.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
Tmin = 0.715, Tmax = 0.938	k = −4→6
8349 measured reflections	l = −37→36

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 atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0394P)2 + 2.6242P] where P = (Fo2 + 2Fc2)/3
2928 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.89 e Å−3
18 restraints	Δρmin = −0.50 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	Occ. (<1)
Cu1	0.00357 (4)	0.91194 (7)	0.139464 (11)	0.02214 (14)
N1	0.1201 (2)	0.6945 (4)	0.10675 (7)	0.0249 (5)
C1	0.1869 (3)	0.5512 (5)	0.09207 (8)	0.0223 (5)
C2	0.2716 (3)	0.3648 (5)	0.07389 (8)	0.0270 (6)
H2A	0.3673	0.3724	0.0863	0.040*
H2B	0.2735	0.3897	0.0437	0.040*
H2C	0.2312	0.2070	0.0794	0.040*
N2	−0.1196 (2)	1.1336 (4)	0.10639 (7)	0.0246 (5)
C3	−0.1829 (3)	1.2842 (5)	0.09054 (7)	0.0221 (5)
C4	−0.2621 (3)	1.4787 (5)	0.07048 (8)	0.0261 (6)
H4A	−0.2024	1.6211	0.0689	0.039*
H4B	−0.3433	1.5164	0.0868	0.039*
H4C	−0.2941	1.4297	0.0422	0.039*
N3	0.1258 (2)	1.1393 (4)	0.17405 (7)	0.0233 (5)
C5	0.1743 (2)	1.2988 (5)	0.19157 (7)	0.0197 (5)
C6	0.2332 (3)	1.5037 (5)	0.21462 (8)	0.0228 (5)
H6A	0.2187	1.6500	0.1979	0.034*
H6B	0.3337	1.4783	0.2204	0.034*
H6C	0.1868	1.5207	0.2410	0.034*
N4	−0.0979 (2)	0.6916 (4)	0.17694 (7)	0.0236 (5)
C7	−0.1385 (3)	0.5341 (5)	0.19555 (8)	0.0209 (5)
C8	−0.1875 (3)	0.3283 (5)	0.21895 (8)	0.0227 (5)
H8A	−0.1808	0.1826	0.2020	0.034*
H8B	−0.2852	0.3540	0.2257	0.034*
H8C	−0.1295	0.3102	0.2448	0.034*
C9	0.5095 (2)	1.0524 (4)	0.17421 (7)	0.0159 (5)
C10	0.5127 (2)	0.7966 (4)	0.15534 (7)	0.0163 (5)
O1	0.53399 (19)	1.2210 (3)	0.14699 (5)	0.0218 (4)
H1	0.533 (3)	1.355 (4)	0.1595 (9)	0.033*
O2	0.48651 (18)	1.0852 (3)	0.21057 (5)	0.0203 (4)
O3	0.48900 (19)	0.7711 (3)	0.11715 (5)	0.0230 (4)
O4	0.53722 (18)	0.6316 (3)	0.18140 (5)	0.0203 (4)
C11	0.4732 (3)	0.9454 (5)	0.02028 (8)	0.0263 (6)
O5	0.5469 (2)	1.0158 (3)	0.05293 (5)	0.0268 (4)
H5	0.519 (3)	0.957 (6)	0.0747 (7)	0.040*
O6	0.3702 (3)	0.8228 (5)	0.02020 (6)	0.0575 (8)
N1S	−0.002 (6)	0.4633 (17)	0.0000 (16)	0.0417 (18)	0.50
C1S	−0.0067 (6)	0.2602 (12)	0.00027 (18)	0.0306 (12)	0.50
C2S	0.011 (3)	0.016 (4)	−0.0032 (11)	0.042 (4)	0.50
H2S1	0.1114	−0.0221	−0.0015	0.064*	0.50
H2S2	−0.0304	−0.0391	−0.0301	0.064*	0.50
H2S3	−0.0347	−0.0653	0.0195	0.064*	0.50

	U11	U22	U33	U12	U13	U23
Cu1	0.0241 (2)	0.0165 (2)	0.0258 (2)	0.00096 (15)	0.00143 (15)	−0.00010 (15)
N1	0.0270 (11)	0.0223 (11)	0.0256 (11)	−0.0008 (10)	0.0035 (9)	−0.0003 (9)
C1	0.0234 (13)	0.0219 (13)	0.0215 (12)	−0.0022 (11)	−0.0010 (10)	0.0013 (11)
C2	0.0266 (14)	0.0234 (14)	0.0308 (14)	0.0039 (11)	0.0001 (11)	−0.0054 (11)
N2	0.0261 (12)	0.0204 (11)	0.0271 (11)	0.0013 (10)	−0.0002 (9)	−0.0005 (9)
C3	0.0218 (12)	0.0233 (13)	0.0213 (12)	−0.0020 (11)	0.0017 (10)	−0.0042 (11)
C4	0.0273 (13)	0.0207 (13)	0.0305 (13)	0.0027 (11)	0.0019 (10)	0.0022 (11)
N3	0.0232 (11)	0.0201 (11)	0.0265 (11)	0.0000 (9)	−0.0004 (9)	0.0006 (10)
C5	0.0174 (12)	0.0210 (13)	0.0207 (12)	0.0041 (11)	0.0020 (9)	0.0044 (11)
C6	0.0211 (12)	0.0204 (13)	0.0269 (13)	0.0009 (10)	0.0014 (10)	−0.0028 (11)
N4	0.0238 (11)	0.0204 (11)	0.0267 (11)	−0.0003 (9)	0.0023 (9)	−0.0007 (10)
C7	0.0185 (12)	0.0203 (13)	0.0238 (12)	0.0022 (11)	0.0001 (9)	−0.0048 (11)
C8	0.0242 (13)	0.0199 (13)	0.0241 (12)	−0.0024 (11)	0.0012 (10)	−0.0002 (10)
C9	0.0142 (11)	0.0134 (11)	0.0198 (12)	0.0006 (9)	−0.0005 (9)	0.0016 (9)
C10	0.0131 (11)	0.0147 (12)	0.0215 (12)	0.0001 (9)	0.0027 (9)	0.0004 (10)
O1	0.0346 (10)	0.0102 (8)	0.0208 (8)	−0.0010 (8)	0.0037 (7)	0.0004 (7)
O2	0.0265 (9)	0.0156 (8)	0.0190 (9)	0.0014 (7)	0.0030 (7)	0.0000 (7)
O3	0.0353 (10)	0.0144 (8)	0.0191 (9)	−0.0016 (8)	−0.0005 (7)	−0.0009 (7)
O4	0.0279 (9)	0.0102 (8)	0.0227 (8)	0.0001 (7)	0.0002 (7)	0.0020 (7)
C11	0.0323 (15)	0.0246 (14)	0.0220 (13)	−0.0025 (12)	0.0013 (11)	0.0012 (11)
O5	0.0361 (11)	0.0260 (10)	0.0184 (9)	−0.0037 (8)	0.0004 (7)	0.0029 (8)
O6	0.0642 (16)	0.0815 (19)	0.0265 (11)	−0.0442 (15)	−0.0011 (10)	0.0054 (12)
N1S	0.048 (3)	0.033 (4)	0.043 (2)	0.009 (14)	−0.002 (2)	0.001 (13)
C1S	0.032 (3)	0.036 (3)	0.024 (2)	0.001 (3)	−0.002 (2)	−0.003 (3)
C2S	0.073 (8)	0.026 (5)	0.029 (8)	−0.019 (6)	0.017 (7)	0.007 (6)

Cu1—N2	1.977 (2)	C7—C8	1.460 (4)
Cu1—N1	1.981 (2)	C8—H8A	0.9800
Cu1—N4	2.002 (2)	C8—H8B	0.9800
Cu1—N3	2.017 (2)	C8—H8C	0.9800
N1—C1	1.139 (3)	C9—O2	1.211 (3)
C1—C2	1.456 (4)	C9—O1	1.311 (3)
C2—H2A	0.9800	C9—C10	1.548 (3)
C2—H2B	0.9800	C10—O3	1.242 (3)
C2—H2C	0.9800	C10—O4	1.256 (3)
N2—C3	1.139 (3)	O1—H1	0.849 (18)
C3—C4	1.452 (4)	C11—O6	1.198 (4)
C4—H4A	0.9800	C11—O5	1.293 (3)
C4—H4B	0.9800	C11—C11i	1.547 (5)
C4—H4C	0.9800	O5—H5	0.829 (18)
N3—C5	1.137 (3)	N1S—C1S	1.132 (12)
C5—C6	1.457 (4)	C1S—C2S	1.38 (3)
C6—H6A	0.9800	C2S—H2S1	0.9800
C6—H6B	0.9800	C2S—H2S2	0.9800
C6—H6C	0.9800	C2S—H2S3	0.9800
N4—C7	1.140 (3)
N2—Cu1—N1	115.66 (9)	H6A—C6—H6C	109.5
N2—Cu1—N4	114.26 (9)	H6B—C6—H6C	109.5
N1—Cu1—N4	104.25 (9)	C7—N4—Cu1	166.9 (2)
N2—Cu1—N3	102.50 (9)	N4—C7—C8	178.4 (3)
N1—Cu1—N3	110.40 (9)	C7—C8—H8A	109.5
N4—Cu1—N3	109.84 (9)	C7—C8—H8B	109.5
C1—N1—Cu1	171.6 (2)	H8A—C8—H8B	109.5
N1—C1—C2	178.9 (3)	C7—C8—H8C	109.5
C1—C2—H2A	109.5	H8A—C8—H8C	109.5
C1—C2—H2B	109.5	H8B—C8—H8C	109.5
H2A—C2—H2B	109.5	O2—C9—O1	125.5 (2)
C1—C2—H2C	109.5	O2—C9—C10	121.6 (2)
H2A—C2—H2C	109.5	O1—C9—C10	112.99 (19)
H2B—C2—H2C	109.5	O3—C10—O4	126.2 (2)
C3—N2—Cu1	171.1 (2)	O3—C10—C9	119.0 (2)
N2—C3—C4	179.2 (3)	O4—C10—C9	114.79 (19)
C3—C4—H4A	109.5	C9—O1—H1	108 (2)
C3—C4—H4B	109.5	O6—C11—O5	126.1 (2)
H4A—C4—H4B	109.5	O6—C11—C11i	122.0 (3)
C3—C4—H4C	109.5	O5—C11—C11i	111.8 (3)
H4A—C4—H4C	109.5	C11—O5—H5	112 (2)
H4B—C4—H4C	109.5	N1S—C1S—C2S	169 (3)
C5—N3—Cu1	166.5 (2)	C1S—C2S—H2S1	109.5
N3—C5—C6	178.5 (3)	C1S—C2S—H2S2	109.5
C5—C6—H6A	109.5	H2S1—C2S—H2S2	109.5
C5—C6—H6B	109.5	C1S—C2S—H2S3	109.5
H6A—C6—H6B	109.5	H2S1—C2S—H2S3	109.5
C5—C6—H6C	109.5	H2S2—C2S—H2S3	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ii	0.85 (2)	1.69 (2)	2.538 (2)	176 (3)
O5—H5···O3	0.83 (2)	1.74 (2)	2.553 (2)	165 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4i	0.85 (2)	1.69 (2)	2.538 (2)	176 (3)
O5—H5⋯O3	0.83 (2)	1.74 (2)	2.553 (2)	165 (4)

Symmetry code: (i) .