catena-Poly[triethyl­ammonium [[tetra-μ-acetato-κ8O:O′-dicuprate(II)]-μ-acetato-κ2O:O′] tetra­hydro­furan monosolvate]

Bugenhagen, B.E.C.; Prosenc, M.H.

doi:10.1107/S1600536812033405

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1142

doi:10.1107/S1600536812033405

Open

access

catena-Poly[triethylammonium [[tetra-μ-acetato-κ⁸O:O′-dicuprate(II)]-μ-acetato-κ²O:O′] tetrahydrofuran monosolvate]

Bernhard E. C. Bugenhagen ^a and Marc H. Prosenc ^b ^*

^aInstitute of Inorganic Chemistry, University of Hamburg, Hamburg, Germany, and ^bInstitute for Physical Chemistry, TU Kaiserslautern, Kaiserslautern, Germany
^*Correspondence e-mail: prosenc@chemie.uni-kl.de

(Received 25 June 2012; accepted 24 July 2012; online 1 August 2012)

In the title compound, {[(C₂H₅)₃NH][Cu₂(CH₃COO)₅]·C₄H₈O}_n, the two different Cu^II atoms are coordinated in a pseudo-square-pyramidal environment by five O atoms from the acetate ligands. Neighbouring pairs of Cu^II atoms are linked by four basally coordinating bridging acetate ligands as in the crystal structure of copper acetate monohydrate. The fifth, apically coordinating ligand links two of the dicopper tetraacetate paddlewheel-units together, thus building a linear coordination polymer which extends along [10-1]. Each apical acetate ligand is linked by an N—H⋯O hydrogen bond to a triethylammonium cation. Weak C—H⋯O hydrogen bonding interactions also occur.

Related literature

For the crystal structure of dicoppertetraacetate dihydrate, see: van Niekerk & Schoening (1953 ); de Meester et al. (1973 ). For copper-based coordination polymers, see: Furukawa et al. (2008 ). The title compound was obtained as a minor byproduct in the synthesis of a copper–salene compound, see: Kleij et al. (2005 ).

Experimental

Crystal data

(C₆H₁₆N)[Cu₂(C₂H₃O₂)₅]·C₄H₈O
M_r = 596.60
Monoclinic, P 2₁ /c
a = 12.1520 (2) Å
b = 12.2726 (2) Å
c = 18.7306 (3) Å
β = 112.956 (1)°
V = 2572.19 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 100 K
0.25 × 0.09 × 0.06 mm

Data collection

Bruker APEX II CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.681, T_max = 0.747
102874 measured reflections
4713 independent reflections
4047 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.062
S = 1.13
4713 reflections
319 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9664 (14)
Cu1—O4	1.9717 (15)
Cu1—O3ⁱ	1.9738 (15)
Cu1—O2	1.9777 (15)
Cu1—O5	2.1216 (13)
Cu2—O7	1.9735 (14)
Cu2—O9	1.9804 (14)
Cu2—O8	1.9806 (14)
Cu2—O10	1.9839 (14)
Cu2—O6	2.1204 (13)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5	0.85 (2)	2.59 (2)	3.212 (2)	130.7 (19)
N1—H1⋯O6	0.85 (2)	1.89 (2)	2.737 (2)	173 (2)
C6—H6C⋯O1	0.98	2.42	3.3238 (18)	153
C13—H13B⋯O3ⁱ	0.99	2.51	3.2956 (19)	137
C15—H15B⋯O10	0.99	2.43	3.3041 (19)	147
Symmetry code: (i) -x+1, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812033405/hp2044sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812033405/hp2044Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812033405/hp2044Isup3.mol

checkCIF report

Comment top

The title compound, catena-poly[[triethylammonium [[tetra-µ-acetato-κ⁸O:O'-dicuprate(II)]-m-acetato-κ²O:O'] tetrahydrofuran monosolvate], was obtained as a minor byproduct in the synthesis of a copper-salene compound (Kleij et al., 2005). The crystal structure consists of dicoppertetraacetate-paddlewheel-units with copper in a pseudo square-pyramidal coordination environment (Fig. 2). These monomeric units are interconnected by bridging, apically coordinating acetato-ligands, thus forming infinite zigzag chains along the [1 0 - 1] plane with an angle of about 165.4 ° with respect to the Cu—Cu bond-vectors (Fig. 3). Additionally, the monomers are skewed in respect to each other as indicated by the torsion-angle O1—Cu1—Cu2—O7 = -39.67 (7)° (see Fig.3, Table 1). One triethylammonium cation per dicoppertetraacetate monomer is present in the crystal structure. A hydrogen-bond between this cation and an oxygen-atom of the bridging acetato-ligand (O6) can be observed (d(N1—H1···O6) = 2.737 (2) Å, Table 2, Fig. 2). Two additional contacts are present between the coordination-chain and the alkyle-residues of the triethylammonium-cations (d(C15—H15B···O10) = 3.3041 (19) Å and d(C13—H13B···O3) = 3.2956 (19) Å, table 2). One short intra-chain contact is found between the methyl group of the bridging acetato-ligand (C6) and oxygen atom O1 of the monomeric unit with a distance of d(C6—H6C···O1) = 3.3238 (18) Å. However, no direct inter-chain contact could be observed. Furthermore, one molecule of tetrahydrofuran per dicoppertetraacetate-unit is present in the crystal structure. In spite of hydrogen-bonds being detected around this solvate-molecule, its orientation could be modeled unequivocally. The Cu—Cu distances in the monomers are d(Cu1—Cu1') = 2.6498 (4) Å and d(Cu2—Cu2') = 2.6542 (4) Å, respectively. This is significantly longer than the distance of 2.616 (1) Å found in dicoppertetraacetate-dihydrate (de Meester et al., 1973). To the contrary, the apical Cu—O bonds in the title-compound are shorter (d(Cu1—O5) = 2.1216 (13) Å and d(Cu2—O6) = 2.1204 (13) Å) than the bond between copper and the aqua-ligand in dicoppertetraacetate-dihydrate (d(Cu—O(H2)) = 2.156 (4) Å). Finally it is to mention that, indicated by the slight differences in the Cu—Cu distances and the Cu—O bond-lengths and the Cu—Cu—O difference of the bond angles to the apically coordinating acetato-ligands mentioned in table 1, two neighbouring monomers exhibit a minor asymmetry. The aforementioned skewing and the position of the triethylammonoium-cation, especially the N—H···O hydrogen bond, are further indicators of this.

Related literature top

For the related structure of dicoppertetraacetate dihydrate, see: van Niekerk & Schoening (1953); de Meester et al. (1973). For copper-based coordination polymers, see: Furukawa et al. (2008). The title compound was obtained as a minor byproduct in the synthesis of a copper–salene compound, see: Kleij et al. (2005).

Computing details top

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

Figures top

	Fig. 1. : Asymmertic unit of he title compound including the triethylammonium-cation and the co-crystallized THF-Molecule. Thermal ellipsoids are drawn at 50% probability.
	Fig. 2. : Two units of dicoppertetraacetate linked by a bridging acetato-ligand. The three hydrogen-bonds between the triethylammonium-cation and the acetato-ligand as well as the short intramolecular contact between H6c and O1 are shown as red dashed lines. The THF-molecule has been omitted for clarity.
	Fig. 3. : Packing of the polymeric chains. The solvate-molecule, the cation and the hydrogen-atoms have been omitted for clarity. No direct inter-chain contact could be observed.

catena-Poly[triethylammonium [[tetra-µ-acetato-κ⁸O:O'-dicuprate(II)]- µ-acetato-κ²O:O'] tetrahydrofuran monosolvate] top

Crystal data top

(C₆H₁₆N)[Cu₂(C₂H₃O₂)₅]·C₄H₈O	F(000) = 1248
M_r = 596.60	D_x = 1.541 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9902 reflections
a = 12.1520 (2) Å	θ = 2.4–34.0°
b = 12.2726 (2) Å	µ = 1.71 mm⁻¹
c = 18.7306 (3) Å	T = 100 K
β = 112.956 (1)°	Block, clear dark blue
V = 2572.19 (7) Å³	0.25 × 0.09 × 0.06 mm
Z = 4

Data collection top

Bruker APEX II CCD area-detector diffractometer	4713 independent reflections
Radiation source: micro-focus	4047 reflections with I > 2σ(I)
Multi-layer optics monochromator	R_int = 0.040
Detector resolution: 8 pixels mm^-1	θ_max = 25.4°, θ_min = 1.8°
ω and ϕ scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −14→14
T_min = 0.681, T_max = 0.747	l = −22→22
102874 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0203P)² + 2.3331P] where P = (F_o² + 2F_c²)/3
4713 reflections	(Δ/σ)_max = 0.004
319 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

(C₆H₁₆N)[Cu₂(C₂H₃O₂)₅]·C₄H₈O	V = 2572.19 (7) Å³
M_r = 596.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1520 (2) Å	µ = 1.71 mm⁻¹
b = 12.2726 (2) Å	T = 100 K
c = 18.7306 (3) Å	0.25 × 0.09 × 0.06 mm
β = 112.956 (1)°

Data collection top

Bruker APEX II CCD area-detector diffractometer	4713 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4047 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.747	R_int = 0.040
102874 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.32 e Å⁻³
4713 reflections	Δρ_min = −0.36 e Å⁻³
319 parameters

Special details top

Experimental. Absorption correction: SADABS-2008/1 (Bruker, 2009) was used for absorption correction. wR2(int) was 0.1027 before and 0.0524 after correction. The Ratio of minimum to maximum transmission is 0.9107. The λ/2 correction factor is 0.0000.

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	0.58451 (2)	0.505128 (19)	0.570813 (12)	0.01381 (7)
Cu2	0.937948 (19)	0.502200 (18)	0.923936 (12)	0.01216 (7)
O1	0.45990 (12)	0.43975 (12)	0.59966 (8)	0.0217 (3)
O2	0.51683 (14)	0.65182 (12)	0.57030 (8)	0.0275 (4)
O3	0.31686 (13)	0.43082 (15)	0.48086 (8)	0.0336 (4)
O4	0.62799 (13)	0.35832 (13)	0.54785 (9)	0.0295 (4)
O5	0.72384 (12)	0.52443 (11)	0.68184 (7)	0.0169 (3)
O6	0.85592 (12)	0.52508 (11)	0.80224 (7)	0.0154 (3)
O7	0.80423 (12)	0.54543 (12)	0.95269 (8)	0.0211 (3)
O8	0.90257 (13)	0.34674 (11)	0.93393 (8)	0.0203 (3)
O9	1.09120 (12)	0.45715 (12)	0.91883 (8)	0.0211 (3)
O10	0.99288 (13)	0.65590 (11)	0.93776 (8)	0.0203 (3)
C1	0.35629 (17)	0.41637 (16)	0.55266 (11)	0.0170 (4)
C2	0.27189 (19)	0.36747 (18)	0.58551 (12)	0.0231 (5)
H2A	0.3171	0.3447	0.6392	0.035*
H2B	0.2317	0.3041	0.5544	0.035*
H2C	0.2121	0.4219	0.5842	0.035*
C3	0.42955 (17)	0.69004 (16)	0.51461 (11)	0.0177 (4)
C4	0.3902 (2)	0.80429 (18)	0.52395 (13)	0.0259 (5)
H4A	0.3487	0.8030	0.5595	0.039*
H4B	0.3360	0.8320	0.4734	0.039*
H4C	0.4603	0.8518	0.5450	0.039*
C5	0.75337 (16)	0.49915 (14)	0.75148 (10)	0.0123 (4)
C6	0.66926 (17)	0.43909 (17)	0.77852 (11)	0.0179 (4)
H6A	0.6513	0.4842	0.8158	0.027*
H6B	0.7064	0.3708	0.8034	0.027*
H6C	0.5951	0.4230	0.7340	0.027*
C7	0.81493 (17)	0.55813 (16)	1.02184 (11)	0.0158 (4)
C8	0.70571 (18)	0.59690 (18)	1.03438 (12)	0.0210 (4)
H8A	0.6998	0.6764	1.0293	0.032*
H8B	0.7125	0.5759	1.0864	0.032*
H8C	0.6340	0.5635	0.9956	0.032*
C9	0.94290 (17)	0.30002 (16)	0.99907 (11)	0.0150 (4)
C10	0.91147 (18)	0.18182 (16)	1.00283 (12)	0.0199 (4)
H10A	0.8507	0.1762	1.0250	0.030*
H10B	0.9832	0.1416	1.0355	0.030*
H10C	0.8801	0.1508	0.9505	0.030*
N1	0.95203 (15)	0.68314 (14)	0.74095 (9)	0.0157 (3)
C11	0.89976 (19)	0.78890 (17)	0.75415 (12)	0.0216 (4)
H11A	0.9146	0.8465	0.7220	0.026*
H11B	0.9409	0.8104	0.8092	0.026*
C12	0.76660 (19)	0.78157 (18)	0.73454 (13)	0.0250 (5)
H12A	0.7520	0.7316	0.7708	0.037*
H12B	0.7260	0.7543	0.6815	0.037*
H12C	0.7357	0.8540	0.7387	0.037*
C13	0.92652 (18)	0.66676 (16)	0.65642 (11)	0.0178 (4)
H13A	0.9663	0.7252	0.6388	0.021*
H13B	0.8394	0.6730	0.6262	0.021*
C14	0.96895 (19)	0.55746 (17)	0.64007 (12)	0.0230 (5)
H14A	0.9390	0.4997	0.6639	0.034*
H14B	1.0565	0.5560	0.6618	0.034*
H14C	0.9388	0.5458	0.5839	0.034*
C15	1.08264 (18)	0.67378 (18)	0.79283 (12)	0.0208 (4)
H15A	1.1132	0.6029	0.7832	0.025*
H15B	1.0912	0.6749	0.8476	0.025*
C16	1.15768 (19)	0.76417 (18)	0.78030 (13)	0.0259 (5)
H16A	1.2415	0.7536	0.8151	0.039*
H16B	1.1296	0.8345	0.7914	0.039*
H16C	1.1506	0.7630	0.7264	0.039*
O11	0.68670 (15)	0.43535 (14)	0.26275 (10)	0.0376 (4)
C17	0.6524 (2)	0.36448 (19)	0.31112 (13)	0.0279 (5)
H17A	0.6561	0.4038	0.3582	0.034*
H17B	0.7072	0.3013	0.3274	0.034*
C18	0.52537 (19)	0.32611 (18)	0.26465 (13)	0.0255 (5)
H18A	0.4663	0.3716	0.2754	0.031*
H18B	0.5146	0.2490	0.2759	0.031*
C19	0.5144 (2)	0.34046 (19)	0.18108 (13)	0.0293 (5)
H19A	0.5431	0.2750	0.1626	0.035*
H19B	0.4308	0.3555	0.1458	0.035*
C20	0.5939 (2)	0.4374 (2)	0.18684 (15)	0.0346 (6)
H20A	0.6284	0.4327	0.1470	0.041*
H20B	0.5476	0.5059	0.1788	0.041*
H1	0.918 (2)	0.632 (2)	0.7560 (13)	0.021 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01246 (12)	0.01771 (13)	0.00901 (12)	−0.00095 (9)	0.00175 (9)	0.00001 (9)
Cu2	0.01315 (12)	0.01314 (12)	0.00850 (12)	−0.00060 (9)	0.00238 (9)	0.00073 (9)
O1	0.0174 (7)	0.0319 (8)	0.0128 (7)	−0.0052 (6)	0.0027 (6)	0.0026 (6)
O2	0.0324 (9)	0.0187 (8)	0.0196 (8)	0.0037 (7)	−0.0027 (7)	−0.0015 (6)
O3	0.0194 (8)	0.0648 (12)	0.0126 (7)	−0.0166 (8)	0.0020 (6)	0.0037 (8)
O4	0.0259 (8)	0.0317 (9)	0.0204 (8)	0.0122 (7)	−0.0022 (6)	−0.0061 (7)
O5	0.0154 (7)	0.0231 (7)	0.0085 (6)	−0.0025 (6)	0.0007 (5)	0.0013 (5)
O6	0.0148 (7)	0.0179 (7)	0.0096 (6)	−0.0037 (5)	0.0007 (5)	0.0013 (5)
O7	0.0167 (7)	0.0308 (8)	0.0147 (7)	0.0024 (6)	0.0050 (6)	−0.0011 (6)
O8	0.0247 (7)	0.0162 (7)	0.0137 (7)	−0.0020 (6)	0.0007 (6)	0.0017 (6)
O9	0.0178 (7)	0.0307 (8)	0.0139 (7)	0.0050 (6)	0.0051 (6)	0.0018 (6)
O10	0.0275 (8)	0.0158 (7)	0.0141 (7)	−0.0045 (6)	0.0043 (6)	0.0002 (6)
C1	0.0183 (10)	0.0164 (10)	0.0170 (10)	0.0010 (8)	0.0076 (8)	−0.0008 (8)
C2	0.0226 (11)	0.0275 (12)	0.0210 (11)	−0.0034 (9)	0.0103 (9)	0.0004 (9)
C3	0.0181 (10)	0.0191 (10)	0.0185 (10)	−0.0008 (8)	0.0101 (8)	0.0024 (8)
C4	0.0281 (12)	0.0214 (11)	0.0282 (12)	0.0028 (9)	0.0109 (10)	−0.0006 (9)
C5	0.0139 (9)	0.0083 (9)	0.0140 (9)	0.0010 (7)	0.0046 (8)	−0.0016 (7)
C6	0.0157 (10)	0.0205 (10)	0.0143 (9)	−0.0019 (8)	0.0024 (8)	0.0008 (8)
C7	0.0188 (10)	0.0113 (9)	0.0176 (10)	−0.0024 (8)	0.0074 (8)	0.0002 (8)
C8	0.0193 (10)	0.0240 (11)	0.0212 (10)	0.0010 (8)	0.0094 (9)	0.0000 (9)
C9	0.0136 (9)	0.0157 (10)	0.0156 (10)	0.0020 (8)	0.0057 (8)	0.0009 (8)
C10	0.0218 (10)	0.0161 (10)	0.0189 (10)	−0.0013 (8)	0.0047 (8)	0.0015 (8)
N1	0.0184 (8)	0.0137 (8)	0.0157 (8)	−0.0030 (7)	0.0073 (7)	−0.0003 (7)
C11	0.0292 (11)	0.0154 (10)	0.0214 (11)	−0.0020 (8)	0.0111 (9)	−0.0018 (8)
C12	0.0281 (12)	0.0214 (11)	0.0290 (12)	0.0048 (9)	0.0149 (10)	0.0011 (9)
C13	0.0208 (10)	0.0182 (10)	0.0132 (9)	−0.0015 (8)	0.0053 (8)	0.0002 (8)
C14	0.0260 (11)	0.0220 (11)	0.0224 (11)	−0.0005 (9)	0.0110 (9)	−0.0035 (9)
C15	0.0193 (10)	0.0253 (11)	0.0159 (10)	−0.0025 (9)	0.0047 (8)	0.0016 (9)
C16	0.0238 (11)	0.0251 (12)	0.0305 (12)	−0.0058 (9)	0.0124 (10)	−0.0032 (10)
O11	0.0344 (9)	0.0347 (10)	0.0437 (10)	−0.0099 (8)	0.0151 (8)	−0.0029 (8)
C17	0.0300 (12)	0.0254 (12)	0.0281 (12)	0.0035 (9)	0.0110 (10)	−0.0050 (10)
C18	0.0254 (12)	0.0222 (11)	0.0295 (12)	0.0057 (9)	0.0114 (10)	0.0024 (9)
C19	0.0284 (12)	0.0298 (12)	0.0281 (12)	0.0012 (10)	0.0091 (10)	0.0000 (10)
C20	0.0373 (14)	0.0307 (13)	0.0414 (14)	0.0035 (11)	0.0216 (12)	0.0080 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.9664 (14)	C9—O10ⁱⁱ	1.258 (2)
Cu1—O4	1.9717 (15)	C9—C10	1.509 (3)
Cu1—O3ⁱ	1.9738 (15)	C10—H10A	0.9800
Cu1—O2	1.9777 (15)	C10—H10B	0.9800
Cu1—O5	2.1216 (13)	C10—H10C	0.9800
Cu1—Cu1ⁱ	2.6498 (4)	N1—C13	1.504 (2)
Cu2—O7	1.9735 (14)	N1—C11	1.507 (3)
Cu2—O9	1.9804 (14)	N1—C15	1.508 (3)
Cu2—O8	1.9806 (14)	N1—H1	0.85 (2)
Cu2—O10	1.9839 (14)	C11—C12	1.516 (3)
Cu2—O6	2.1204 (13)	C11—H11A	0.9900
Cu2—Cu2ⁱⁱ	2.6542 (4)	C11—H11B	0.9900
O1—C1	1.256 (2)	C12—H12A	0.9800
O2—C3	1.253 (2)	C12—H12B	0.9800
O3—C1	1.252 (2)	C12—H12C	0.9800
O3—Cu1ⁱ	1.9739 (15)	C13—C14	1.511 (3)
O4—C3ⁱ	1.254 (2)	C13—H13A	0.9900
O5—C5	1.250 (2)	C13—H13B	0.9900
O6—C5	1.278 (2)	C14—H14A	0.9800
O7—C7	1.260 (2)	C14—H14B	0.9800
O8—C9	1.261 (2)	C14—H14C	0.9800
O9—C7ⁱⁱ	1.258 (2)	C15—C16	1.511 (3)
O10—C9ⁱⁱ	1.258 (2)	C15—H15A	0.9900
C1—C2	1.511 (3)	C15—H15B	0.9900
C2—H2A	0.9800	C16—H16A	0.9800
C2—H2B	0.9800	C16—H16B	0.9800
C2—H2C	0.9800	C16—H16C	0.9800
C3—O4ⁱ	1.254 (2)	O11—C20	1.429 (3)
C3—C4	1.513 (3)	O11—C17	1.430 (3)
C4—H4A	0.9800	C17—C18	1.521 (3)
C4—H4B	0.9800	C17—H17A	0.9900
C4—H4C	0.9800	C17—H17B	0.9900
C5—C6	1.499 (3)	C18—C19	1.529 (3)
C6—H6A	0.9800	C18—H18A	0.9900
C6—H6B	0.9800	C18—H18B	0.9900
C6—H6C	0.9800	C19—C20	1.510 (3)
C7—O9ⁱⁱ	1.258 (2)	C19—H19A	0.9900
C7—C8	1.512 (3)	C19—H19B	0.9900
C8—H8A	0.9800	C20—H20A	0.9900
C8—H8B	0.9800	C20—H20B	0.9900
C8—H8C	0.9800

O1—Cu1—O4	89.30 (7)	O10ⁱⁱ—C9—O8	125.38 (18)
O1—Cu1—O3ⁱ	167.73 (6)	O10ⁱⁱ—C9—C10	116.43 (17)
O4—Cu1—O3ⁱ	89.50 (8)	O8—C9—C10	118.18 (17)
O1—Cu1—O2	90.54 (7)	C9—C10—H10A	109.5
O4—Cu1—O2	167.71 (6)	C9—C10—H10B	109.5
O3ⁱ—Cu1—O2	88.05 (8)	H10A—C10—H10B	109.5
O1—Cu1—O5	100.48 (5)	C9—C10—H10C	109.5
O4—Cu1—O5	97.85 (6)	H10A—C10—H10C	109.5
O3ⁱ—Cu1—O5	91.78 (6)	H10B—C10—H10C	109.5
O2—Cu1—O5	94.27 (6)	C13—N1—C11	111.15 (15)
O1—Cu1—Cu1ⁱ	82.90 (4)	C13—N1—C15	113.66 (15)
O4—Cu1—Cu1ⁱ	84.68 (4)	C11—N1—C15	111.40 (16)
O3ⁱ—Cu1—Cu1ⁱ	84.83 (4)	C13—N1—H1	108.7 (15)
O2—Cu1—Cu1ⁱ	83.10 (4)	C11—N1—H1	106.9 (16)
O5—Cu1—Cu1ⁱ	175.77 (4)	C15—N1—H1	104.5 (15)
O7—Cu2—O9	167.99 (6)	N1—C11—C12	112.80 (17)
O7—Cu2—O8	90.06 (6)	N1—C11—H11A	109.0
O9—Cu2—O8	88.77 (6)	C12—C11—H11A	109.0
O7—Cu2—O10	88.84 (6)	N1—C11—H11B	109.0
O9—Cu2—O10	89.82 (6)	C12—C11—H11B	109.0
O8—Cu2—O10	167.95 (6)	H11A—C11—H11B	107.8
O7—Cu2—O6	99.55 (5)	C11—C12—H12A	109.5
O9—Cu2—O6	92.39 (5)	C11—C12—H12B	109.5
O8—Cu2—O6	101.58 (5)	H12A—C12—H12B	109.5
O10—Cu2—O6	90.44 (5)	C11—C12—H12C	109.5
O7—Cu2—Cu2ⁱⁱ	84.03 (4)	H12A—C12—H12C	109.5
O9—Cu2—Cu2ⁱⁱ	83.96 (4)	H12B—C12—H12C	109.5
O8—Cu2—Cu2ⁱⁱ	86.12 (4)	N1—C13—C14	112.69 (16)
O10—Cu2—Cu2ⁱⁱ	81.83 (4)	N1—C13—H13A	109.1
O6—Cu2—Cu2ⁱⁱ	171.44 (4)	C14—C13—H13A	109.1
C1—O1—Cu1	124.71 (13)	N1—C13—H13B	109.1
C3—O2—Cu1	124.07 (13)	C14—C13—H13B	109.1
C1—O3—Cu1ⁱ	122.14 (13)	H13A—C13—H13B	107.8
C3ⁱ—O4—Cu1	122.47 (13)	C13—C14—H14A	109.5
C5—O5—Cu1	142.18 (12)	C13—C14—H14B	109.5
C5—O6—Cu2	132.82 (12)	H14A—C14—H14B	109.5
C7—O7—Cu2	123.23 (13)	C13—C14—H14C	109.5
C9—O8—Cu2	120.83 (13)	H14A—C14—H14C	109.5
C7ⁱⁱ—O9—Cu2	123.01 (13)	H14B—C14—H14C	109.5
C9ⁱⁱ—O10—Cu2	125.84 (13)	N1—C15—C16	113.03 (17)
O3—C1—O1	125.42 (18)	N1—C15—H15A	109.0
O3—C1—C2	117.23 (18)	C16—C15—H15A	109.0
O1—C1—C2	117.35 (17)	N1—C15—H15B	109.0
C1—C2—H2A	109.5	C16—C15—H15B	109.0
C1—C2—H2B	109.5	H15A—C15—H15B	107.8
H2A—C2—H2B	109.5	C15—C16—H16A	109.5
C1—C2—H2C	109.5	C15—C16—H16B	109.5
H2A—C2—H2C	109.5	H16A—C16—H16B	109.5
H2B—C2—H2C	109.5	C15—C16—H16C	109.5
O2—C3—O4ⁱ	125.63 (19)	H16A—C16—H16C	109.5
O2—C3—C4	116.98 (18)	H16B—C16—H16C	109.5
O4ⁱ—C3—C4	117.39 (18)	C20—O11—C17	109.24 (17)
C3—C4—H4A	109.5	O11—C17—C18	107.89 (18)
C3—C4—H4B	109.5	O11—C17—H17A	110.1
H4A—C4—H4B	109.5	C18—C17—H17A	110.1
C3—C4—H4C	109.5	O11—C17—H17B	110.1
H4A—C4—H4C	109.5	C18—C17—H17B	110.1
H4B—C4—H4C	109.5	H17A—C17—H17B	108.4
O5—C5—O6	120.95 (17)	C17—C18—C19	102.34 (18)
O5—C5—C6	121.24 (16)	C17—C18—H18A	111.3
O6—C5—C6	117.81 (16)	C19—C18—H18A	111.3
C5—C6—H6A	109.5	C17—C18—H18B	111.3
C5—C6—H6B	109.5	C19—C18—H18B	111.3
H6A—C6—H6B	109.5	H18A—C18—H18B	109.2
C5—C6—H6C	109.5	C20—C19—C18	102.71 (19)
H6A—C6—H6C	109.5	C20—C19—H19A	111.2
H6B—C6—H6C	109.5	C18—C19—H19A	111.2
O9ⁱⁱ—C7—O7	125.74 (18)	C20—C19—H19B	111.2
O9ⁱⁱ—C7—C8	117.27 (17)	C18—C19—H19B	111.2
O7—C7—C8	116.98 (17)	H19A—C19—H19B	109.1
C7—C8—H8A	109.5	O11—C20—C19	106.94 (19)
C7—C8—H8B	109.5	O11—C20—H20A	110.3
H8A—C8—H8B	109.5	C19—C20—H20A	110.3
C7—C8—H8C	109.5	O11—C20—H20B	110.3
H8A—C8—H8C	109.5	C19—C20—H20B	110.3
H8B—C8—H8C	109.5	H20A—C20—H20B	108.6

O4—Cu1—O1—C1	−84.84 (17)	O8—Cu2—O9—C7ⁱⁱ	−85.90 (16)
O3ⁱ—Cu1—O1—C1	−0.4 (4)	O10—Cu2—O9—C7ⁱⁱ	82.13 (16)
O2—Cu1—O1—C1	82.87 (17)	O6—Cu2—O9—C7ⁱⁱ	172.55 (16)
O5—Cu1—O1—C1	177.31 (16)	Cu2ⁱⁱ—Cu2—O9—C7ⁱⁱ	0.33 (15)
Cu1ⁱ—Cu1—O1—C1	−0.12 (16)	O7—Cu2—O10—C9ⁱⁱ	83.93 (16)
O1—Cu1—O2—C3	−81.93 (17)	O9—Cu2—O10—C9ⁱⁱ	−84.13 (16)
O4—Cu1—O2—C3	7.2 (4)	O8—Cu2—O10—C9ⁱⁱ	−0.9 (4)
O3ⁱ—Cu1—O2—C3	85.87 (17)	O6—Cu2—O10—C9ⁱⁱ	−176.52 (16)
O5—Cu1—O2—C3	177.52 (17)	Cu2ⁱⁱ—Cu2—O10—C9ⁱⁱ	−0.21 (15)
Cu1ⁱ—Cu1—O2—C3	0.85 (16)	Cu1ⁱ—O3—C1—O1	0.0 (3)
O1—Cu1—O4—C3ⁱ	80.50 (17)	Cu1ⁱ—O3—C1—C2	179.53 (14)
O3ⁱ—Cu1—O4—C3ⁱ	−87.28 (17)	Cu1—O1—C1—O3	0.1 (3)
O2—Cu1—O4—C3ⁱ	−8.8 (4)	Cu1—O1—C1—C2	−179.43 (14)
O5—Cu1—O4—C3ⁱ	−179.01 (16)	Cu1—O2—C3—O4ⁱ	0.8 (3)
Cu1ⁱ—Cu1—O4—C3ⁱ	−2.43 (16)	Cu1—O2—C3—C4	−179.51 (14)
O1—Cu1—O5—C5	10.1 (2)	Cu1—O5—C5—O6	175.75 (13)
O4—Cu1—O5—C5	−80.6 (2)	Cu1—O5—C5—C6	−5.2 (3)
O3ⁱ—Cu1—O5—C5	−170.3 (2)	Cu2—O6—C5—O5	178.19 (12)
O2—Cu1—O5—C5	101.5 (2)	Cu2—O6—C5—C6	−0.9 (3)
Cu1ⁱ—Cu1—O5—C5	153.0 (5)	Cu2—O7—C7—O9ⁱⁱ	−1.9 (3)
O7—Cu2—O6—C5	−45.10 (17)	Cu2—O7—C7—C8	177.02 (13)
O9—Cu2—O6—C5	136.17 (16)	Cu2—O8—C9—O10ⁱⁱ	0.0 (3)
O8—Cu2—O6—C5	46.94 (17)	Cu2—O8—C9—C10	179.31 (13)
O10—Cu2—O6—C5	−133.99 (16)	C13—N1—C11—C12	78.9 (2)
Cu2ⁱⁱ—Cu2—O6—C5	−159.3 (2)	C15—N1—C11—C12	−153.20 (17)
O9—Cu2—O7—C7	3.0 (4)	C11—N1—C13—C14	−175.42 (17)
O8—Cu2—O7—C7	87.31 (16)	C15—N1—C13—C14	57.9 (2)
O10—Cu2—O7—C7	−80.69 (16)	C13—N1—C15—C16	66.7 (2)
O6—Cu2—O7—C7	−170.94 (15)	C11—N1—C15—C16	−59.8 (2)
Cu2ⁱⁱ—Cu2—O7—C7	1.21 (15)	C20—O11—C17—C18	−4.7 (2)
O7—Cu2—O8—C9	−83.88 (15)	O11—C17—C18—C19	23.3 (2)
O9—Cu2—O8—C9	84.17 (15)	C17—C18—C19—C20	−31.8 (2)
O10—Cu2—O8—C9	0.8 (4)	C17—O11—C20—C19	−16.4 (2)
O6—Cu2—O8—C9	176.36 (14)	C18—C19—C20—O11	30.4 (2)
Cu2ⁱⁱ—Cu2—O8—C9	0.14 (14)	O1—Cu1—Cu2—O7	−39.67 (7)
O7—Cu2—O9—C7ⁱⁱ	−1.4 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.85 (2)	2.59 (2)	3.212 (2)	130.7 (19)
N1—H1···O6	0.85 (2)	1.89 (2)	2.737 (2)	173 (2)
C6—H6C···O1	0.98	2.42	3.3238 (18)	153
C13—H13B···O3ⁱ	0.99	2.51	3.2956 (19)	137
C15—H15B···O10	0.99	2.43	3.3041 (19)	147

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	(C₆H₁₆N)[Cu₂(C₂H₃O₂)₅]·C₄H₈O
M_r	596.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.1520 (2), 12.2726 (2), 18.7306 (3)
β (°)	112.956 (1)
V (Å³)	2572.19 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.25 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEX II CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.681, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	102874, 4713, 4047
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.062, 1.13
No. of reflections	4713
No. of parameters	319
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.36

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrik, 2008), SHELXL97 (Sheldrik, 2008), OLEX2 (Dolomanov et al., 2009).

Selected bond lengths (Å) top

Cu1—O1	1.9664 (14)	Cu2—O7	1.9735 (14)
Cu1—O4	1.9717 (15)	Cu2—O9	1.9804 (14)
Cu1—O3ⁱ	1.9738 (15)	Cu2—O8	1.9806 (14)
Cu1—O2	1.9777 (15)	Cu2—O10	1.9839 (14)
Cu1—O5	2.1216 (13)	Cu2—O6	2.1204 (13)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.85 (2)	2.59 (2)	3.212 (2)	130.7 (19)
N1—H1···O6	0.85 (2)	1.89 (2)	2.737 (2)	173 (2)
C6—H6C···O1	0.98	2.42	3.3238 (18)	153
C13—H13B···O3ⁱ	0.99	2.51	3.2956 (19)	137
C15—H15B···O10	0.99	2.43	3.3041 (19)	147

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The DFG is gratefiully acknowledged for financial support (SFB 668 - TP A4).

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Furukawa, H., Kim, J., Ockwig, N. W., O'Keeffe, M. & Yaghi, O. (2008). J. Am. Chem. Soc. 130, 11650–11661. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kleij, A. W., Tooke, D. M., Spek, A. L. & Reek, J. N. H. (2005). Eur. J. Inorg. Chem. 22, 4626–4634. Web of Science CSD CrossRef Google Scholar
Meester, P. de, Fletcher, S. R. & Skapski, A. C. (1973). J. Chem. Soc. Dalton Trans. pp. 2575–2578. Google Scholar
Niekerk, J. N. van & Schoening, F. R. L. (1953). Acta Cryst. 6, 227–232. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1142

doi:10.1107/S1600536812033405

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)