catena-Poly[[tetra­kis(μ2-acetato-κ2O:O′)dicopper(II)(Cu—Cu)]-μ2-acetato-κ2O:O′-[bis­[μ2-3-(dimethyl­amino)propan-1-olato]-κ2N,O:O;κ2O:N,O-bis­[(tetra­hydro­furan-κO)copper(II)]]-μ2-acetato-κ2O:O′]

Shahid, M.; Mazhar, M.; Helliwell, M.; Akhtar, J.; Ahmad, K.

doi:10.1107/S1600536808024148

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1139-m1140

doi:10.1107/S1600536808024148

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catena-Poly[[tetrakis(μ₂-acetato-κ²O:O′)dicopper(II)(Cu—Cu)]-μ₂-acetato-κ²O:O′-[bis[μ₂-3-(dimethylamino)propan-1-olato]-κ²N,O:O;κ²O:N,O-bis[(tetrahydrofuran-κO)copper(II)]]-μ₂-acetato-κ²O:O′]

Muhammad Shahid,^a Muhammad Mazhar,^a ^* Madeleine Helliwell,^b Javeed Akhtar ^b and Kibriya Ahmad ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bThe School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, England
^*Correspondence e-mail: mazhar42pk@yahoo.com

(Received 18 June 2008; accepted 29 July 2008; online 9 August 2008)

The title complex, [Cu₄(C₅H₁₂NO)₂(C₂H₃O₂)₆(C₄H₈O)₂]_n, consists of dinuclear [Cu₂(C₅H₁₂NO)₂(THF)₂] (THF is tetrahydrofuran) and [Cu₂(CH₃COO)₄] units linked through acetate ions, generating parallel one-dimensional polymeric chains propagating in the [1 $[\overline{1}]$ 0] direction. In the first dinuclear unit, Cu^II ions related by inversion symmetry are bridged by two 3-(dimethylamino)propan-1-olate ligands. Likewise, a pair of inversion-related Cu^II ions are bridged by four acetate groups. The crystallographically independent Cu centers are linked to one another by a single bridging acetate group, generating an infinite chain. The distorted square-pyramidal coordination of the first metal center is completed with an apical THF molecule, with a long Cu—O bond length of 2.476 (5) Å. The geometry around the other metal atom is close to octahedral, and the Cu⋯Cu separation in this unit is 2.652 (1) Å. The distance between the metal centers in the first dinuclear unit is considerably longer [3.068 (1) Å], suggesting little or no bonding interaction. The Cu⋯Cu separation between two acetate-bridged independent Cu centers is 4.860 (2) Å. The THF molecule has methylene groups disordered over two positions, with occupancies of 0.608 (13) and 0.392 (13).

Related literature

For related literature, see: Catania et al. (1990 ); El Fallah et al. (2004 ); Li et al. (1994 ); Mazhar et al. (2006 ); Tahir et al. (2007 ); Torres et al. (1996 ); Wang et al. (1993 ); Zhang et al. (2004 ).

Experimental

Crystal data

[Cu₄(C₅H₁₂NO)₂(C₂H₃O₂)₆(C₄H₈O)₂]
M_r = 956.94
Monoclinic, C 2/c
a = 25.686 (5) Å
b = 8.972 (5) Å
c = 18.021 (5) Å
β = 105.782 (5)°
V = 3996 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 100 (2) K
0.23 × 0.10 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
15315 measured reflections
4093 independent reflections
3300 reflections with I > 2σ(I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.156
S = 1.22
4093 reflections
268 parameters
167 restraints
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024148/bh2182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024148/bh2182Isup2.hkl

checkCIF report

Comment top

For the last two decades, there has been a considerable interest in the investigation of Cu^II complexes using carboxylate and aminoalcohol as ligands (Wang et al., 1993; El Fallah et al., 2004; Tahir et al., 2007; Mazhar et al., 2006) due to their potential use as CVD precursors for the deposition of copper and copper(II) oxide with diverse applications. For example, copper oxide is a component of high T_c superconductors (Catania et al., 1990). Being an excellent electrical conductor and good resistor for electromigration, metallic copper may replace aluminum alloys for multi-level metallization applications in Ultra Large Scale Integration (ULSI) technology (Torres et al., 1996; Li et al., 1994).

Herein, we report, the structure of a new polymeric Cu^II complex, (I), in which the molecules are linked into parallel, one dimensional polymeric chains in the [1 -1 0] direction, through acetate and 3-dimethylaminopropan-1-olate (dmap) bridging ligands, with tetrahydrofuran (THF) as an ancillary ligand.

In the title compound (Fig. 1), the environment of Cu1 is distorted square pyramidal, with the ligation set [CuO₄N] consisting of O1, O1ⁱ [symmetry code: (i) 1/2-x, 1/2-y, 1-z] of two bridging-chelating dmap ligands, O2 of the bridging acetate group, O1S of the THF molecule and N1 of one bridging-chelating dmap ligand. The deviation from perfect square pyramidal geometry around Cu1 is evident from the O1—Cu1—O1ⁱ bite angle of 75.99 (18)° (less than 90°) and O1—Cu1—O2 angle, 167.93 (17)° [less than 180°]. Additionally, the Cu—O bond length of Cu1 to the apical O atom, O1S, is 2.476 (5) Å, longer than all other Cu—O bond lengths around Cu1, which are consistent with the sum of the ionic radii, 1.92 Å. The overall geometry around Cu2 is close to octahedral. The equatorial plane is formed by O4, O6, O5ⁱⁱ and O7ⁱⁱ of four bridging acetate groups connecting Cu2 and Cu2ⁱⁱ [symmetry code: (ii) 1-x, -y, 1-z] atoms of two monomers in the polymeric structure, while O atom O3 of the bridging acetate links Cu2 in the axial position in the octahedron. The trans angles in the equatorial plane deviate slightly from ideal value of 180°, and the Cu2—O3 bond length of 2.141 (4) Å is slightly longer than the normal value (1.92 Å), indicating slightly distorted coordination geometry around the Cu2 atom in the complex. All the Cu2—O bond distances in the equatorial plane are in agreement with the bond lengths found in similar complexes (Zhang et al., 2004). The inversion related Cu2 atoms are linked by Cu—Cu bonds of 2.652 (1) Å, completing the octahedral coordination of Cu2. The distance between the inversion related Cu1 atoms is considerably longer, 3.068 (1) Å, suggesting little or no bonding interaction, and the Cu1···Cu2 separation is 4.860 (2) Å.

Related literature top

For related literature, see: Catania et al. (1990); El Fallah et al. (2004); Li et al. (1994); Mazhar et al. (2006); Tahir et al. (2007); Torres et al. (1996); Wang et al. (1993); Zhang et al. (2004).

Experimental top

3-Dimethylamino-1-propanol (0.15 g, 1.25 mmol) was added to a stirred suspension of Cu(CH₃COO)₂.H₂O (0.50 g, 2.50 mmol) in 25 ml of THF. After two hours of stirring, the mixture was vacuum evaporated to dryness and the resulting solid was redissolved in THF to give greenish blue block-shaped crystals, at room temperature, after 10 days.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of (I) showing atom-labeling scheme and displacement ellipsoids at the 50% probability level. H atoms and disordered atoms have been removed for clarity. Symmetry codes: A 1/2-x, 1/2-y, 1-z; B 1-x, -y, 1-z.

catena-Poly[[tetrakis(µ₂-acetato- κ²O:O')dicopper(II)(Cu—Cu)]-µ₂- acetato-κ²O:O'-[bis[µ₂-3-(dimethylamino)propan-1-olato]- κ²N,O:O;κ²O:N,O- bis[(tetrahydrofuran-κO)copper(II)]]-µ₂-acetato- κ²O:O'] top

Crystal data top

[Cu₄(C₅H₁₂NO)₂(C₂H₃O₂)₆(C₄H₈O)₂]	F(000) = 1984
M_r = 956.94	D_x = 1.590 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 2913 reflections
a = 25.686 (5) Å	θ = 2.4–26.4°
b = 8.972 (5) Å	µ = 2.17 mm⁻¹
c = 18.021 (5) Å	T = 100 K
β = 105.782 (5)°	Plate, blue
V = 3996 (3) Å³	0.23 × 0.10 × 0.04 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3300 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.093
Graphite monochromator	θ_max = 26.4°, θ_min = 2.4°
ϕ and ω scans	h = −32→32
15315 measured reflections	k = −11→11
4093 independent reflections	l = −22→21

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0593P)² + 6.3428P] where P = (F_o² + 2F_c²)/3
4093 reflections	(Δ/σ)_max < 0.001
268 parameters	Δρ_max = 1.17 e Å⁻³
167 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

[Cu₄(C₅H₁₂NO)₂(C₂H₃O₂)₆(C₄H₈O)₂]	V = 3996 (3) Å³
M_r = 956.94	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.686 (5) Å	µ = 2.17 mm⁻¹
b = 8.972 (5) Å	T = 100 K
c = 18.021 (5) Å	0.23 × 0.10 × 0.04 mm
β = 105.782 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3300 reflections with I > 2σ(I)
15315 measured reflections	R_int = 0.093
4093 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	167 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.22	Δρ_max = 1.17 e Å⁻³
4093 reflections	Δρ_min = −0.89 e Å⁻³
268 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.30186 (3)	0.30456 (8)	0.55814 (4)	0.0138 (2)
Cu2	0.45657 (3)	0.02909 (8)	0.52386 (4)	0.0172 (2)
O1	0.25020 (14)	0.3612 (4)	0.4632 (2)	0.0151 (8)
O2	0.35126 (14)	0.2046 (5)	0.6459 (2)	0.0176 (9)
O3	0.38789 (15)	0.0922 (5)	0.5624 (2)	0.0185 (9)
O4	0.48175 (19)	−0.1399 (6)	0.5945 (3)	0.0396 (13)
O5	0.55563 (17)	−0.1852 (5)	0.5562 (2)	0.0256 (10)
O6	0.42008 (17)	−0.1147 (6)	0.4445 (3)	0.0351 (12)
O7	0.49313 (17)	−0.1635 (5)	0.4038 (3)	0.0291 (11)
N1	0.35282 (19)	0.4863 (5)	0.5650 (3)	0.0183 (11)
C1	0.3780 (3)	0.5304 (8)	0.6455 (4)	0.0299 (15)
H1A	0.4026	0.6114	0.6466	0.045*
H1B	0.3973	0.4472	0.6734	0.045*
H1C	0.3504	0.5614	0.6689	0.045*
C2	0.3966 (2)	0.4443 (7)	0.5296 (4)	0.0238 (14)
H2A	0.4181	0.5305	0.5265	0.036*
H2B	0.3810	0.4057	0.4787	0.036*
H2C	0.4191	0.3694	0.5606	0.036*
C3	0.3233 (2)	0.6201 (7)	0.5256 (4)	0.0236 (14)
H3A	0.3493	0.6994	0.5275	0.028*
H3B	0.2985	0.6534	0.5542	0.028*
C4	0.2913 (2)	0.5957 (7)	0.4414 (4)	0.0256 (15)
H4A	0.2821	0.6919	0.4168	0.031*
H4B	0.3141	0.5439	0.4148	0.031*
C5	0.2399 (2)	0.5068 (7)	0.4328 (4)	0.0235 (14)
H5A	0.2169	0.5586	0.4591	0.028*
H5B	0.2206	0.5005	0.3786	0.028*
C6	0.3837 (2)	0.1105 (7)	0.6289 (3)	0.0180 (13)
C7	0.4177 (3)	0.0192 (8)	0.6959 (4)	0.0328 (17)
H7A	0.4166	−0.0839	0.6813	0.049*
H7B	0.4035	0.0299	0.7397	0.049*
H7C	0.4544	0.0540	0.7090	0.049*
C8	0.5252 (2)	−0.2083 (7)	0.5982 (4)	0.0209 (13)
C9	0.5405 (3)	−0.3270 (7)	0.6589 (4)	0.0319 (16)
H9A	0.5155	−0.4085	0.6456	0.048*
H9B	0.5394	−0.2866	0.7078	0.048*
H9C	0.5764	−0.3620	0.6623	0.048*
C10	0.4439 (2)	−0.1799 (7)	0.4023 (4)	0.0211 (13)
C11	0.4112 (3)	−0.2912 (7)	0.3460 (4)	0.0311 (16)
H11A	0.3992	−0.3694	0.3738	0.047*
H11B	0.4332	−0.3328	0.3158	0.047*
H11C	0.3804	−0.2424	0.3126	0.047*
O1S	0.25794 (16)	0.4312 (6)	0.6472 (2)	0.0302 (10)
C1S	0.2630 (5)	0.3409 (16)	0.7175 (6)	0.031 (2)	0.608 (13)
H1S1	0.2811	0.3983	0.7628	0.037*	0.608 (13)
H1S2	0.2843	0.2524	0.7159	0.037*	0.608 (13)
C2S	0.2070 (5)	0.2968 (15)	0.7220 (8)	0.035 (2)	0.608 (13)
H2S1	0.1953	0.2038	0.6952	0.042*	0.608 (13)
H2S2	0.2054	0.2885	0.7750	0.042*	0.608 (13)
C3S	0.1749 (4)	0.4257 (14)	0.6819 (6)	0.0286 (18)	0.608 (13)
H3S1	0.1781	0.5108	0.7161	0.034*	0.608 (13)
H3S2	0.1370	0.3998	0.6620	0.034*	0.608 (13)
C4S	0.2002 (2)	0.4563 (8)	0.6182 (4)	0.0272 (12)	0.608 (13)
H4S1	0.1851	0.3906	0.5749	0.033*	0.608 (13)
H4S2	0.1933	0.5585	0.6007	0.033*	0.608 (13)
C1T	0.2742 (8)	0.392 (3)	0.7265 (8)	0.034 (3)	0.392 (13)
H1T1	0.2724	0.4753	0.7599	0.041*	0.392 (13)
H1T2	0.3099	0.3474	0.7417	0.041*	0.392 (13)
C2T	0.2304 (7)	0.281 (2)	0.7224 (11)	0.037 (3)	0.392 (13)
H2T1	0.2230	0.2718	0.7722	0.044*	0.392 (13)
H2T2	0.2410	0.1843	0.7075	0.044*	0.392 (13)
C3T	0.1812 (6)	0.337 (2)	0.6632 (9)	0.030 (2)	0.392 (13)
H3T1	0.1552	0.3768	0.6881	0.036*	0.392 (13)
H3T2	0.1642	0.2560	0.6293	0.036*	0.392 (13)
C4T	0.2002 (2)	0.4563 (8)	0.6182 (4)	0.0272 (12)	0.392 (13)
H4T1	0.1874	0.4401	0.5630	0.033*	0.392 (13)
H4T2	0.1899	0.5551	0.6307	0.033*	0.392 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0061 (3)	0.0192 (4)	0.0153 (4)	0.0016 (3)	0.0012 (3)	−0.0012 (3)
Cu2	0.0079 (3)	0.0222 (4)	0.0218 (4)	0.0048 (3)	0.0045 (3)	0.0020 (3)
O1	0.0100 (18)	0.015 (2)	0.017 (2)	0.0006 (16)	−0.0010 (16)	0.0048 (17)
O2	0.0077 (19)	0.026 (2)	0.017 (2)	0.0038 (16)	0.0001 (16)	−0.0036 (18)
O3	0.0070 (18)	0.032 (3)	0.016 (2)	0.0028 (17)	0.0023 (16)	0.0001 (18)
O4	0.028 (3)	0.043 (3)	0.056 (3)	0.021 (2)	0.026 (3)	0.028 (3)
O5	0.018 (2)	0.035 (3)	0.026 (2)	0.0129 (19)	0.0088 (19)	0.008 (2)
O6	0.013 (2)	0.044 (3)	0.050 (3)	−0.006 (2)	0.010 (2)	−0.022 (3)
O7	0.017 (2)	0.045 (3)	0.025 (2)	−0.003 (2)	0.0047 (19)	−0.010 (2)
N1	0.012 (2)	0.021 (3)	0.024 (3)	−0.002 (2)	0.007 (2)	−0.003 (2)
C1	0.025 (3)	0.035 (4)	0.024 (4)	−0.004 (3)	−0.004 (3)	−0.007 (3)
C2	0.013 (3)	0.024 (4)	0.037 (4)	0.001 (2)	0.011 (3)	−0.002 (3)
C3	0.014 (3)	0.020 (3)	0.035 (4)	0.001 (2)	0.002 (3)	−0.001 (3)
C4	0.016 (3)	0.019 (3)	0.039 (4)	−0.003 (2)	0.002 (3)	0.009 (3)
C5	0.013 (3)	0.027 (4)	0.028 (3)	0.000 (2)	0.001 (3)	0.002 (3)
C6	0.007 (3)	0.022 (3)	0.023 (3)	−0.003 (2)	0.000 (2)	0.001 (3)
C7	0.027 (4)	0.044 (4)	0.027 (4)	0.021 (3)	0.007 (3)	0.010 (3)
C8	0.018 (3)	0.022 (3)	0.020 (3)	−0.001 (2)	0.001 (2)	0.000 (3)
C9	0.027 (4)	0.028 (4)	0.042 (4)	0.010 (3)	0.012 (3)	0.014 (3)
C10	0.018 (3)	0.018 (3)	0.025 (3)	0.003 (2)	0.003 (3)	0.007 (3)
C11	0.030 (4)	0.026 (4)	0.033 (4)	−0.004 (3)	0.001 (3)	−0.002 (3)
O1S	0.0107 (18)	0.057 (3)	0.024 (2)	0.0075 (19)	0.0063 (17)	−0.003 (2)
C1S	0.014 (4)	0.055 (5)	0.021 (4)	0.011 (4)	0.000 (3)	−0.002 (4)
C2S	0.020 (4)	0.049 (5)	0.034 (4)	0.005 (4)	0.006 (4)	0.010 (3)
C3S	0.012 (3)	0.042 (4)	0.032 (4)	0.002 (3)	0.007 (3)	0.002 (4)
C4S	0.011 (2)	0.041 (3)	0.029 (2)	0.008 (2)	0.0047 (19)	0.004 (2)
C1T	0.015 (4)	0.060 (6)	0.023 (4)	0.008 (4)	−0.002 (4)	−0.003 (5)
C2T	0.025 (5)	0.052 (5)	0.030 (5)	0.008 (5)	0.001 (4)	0.008 (4)
C3T	0.015 (4)	0.045 (5)	0.030 (4)	0.004 (4)	0.006 (4)	0.003 (4)
C4T	0.011 (2)	0.041 (3)	0.029 (2)	0.008 (2)	0.0047 (19)	0.004 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.926 (4)	C5—H5B	0.9700
Cu1—O2	1.956 (4)	C6—C7	1.522 (8)
Cu1—O1ⁱ	1.967 (4)	C7—H7A	0.9600
Cu1—N1	2.074 (5)	C7—H7B	0.9600
Cu2—O6	1.965 (5)	C7—H7C	0.9600
Cu2—O4	1.972 (5)	C8—C9	1.501 (8)
Cu2—O5ⁱⁱ	1.974 (4)	C9—H9A	0.9600
Cu2—O7ⁱⁱ	1.977 (4)	C9—H9B	0.9600
Cu2—O3	2.141 (4)	C9—H9C	0.9600
Cu2—Cu2ⁱⁱ	2.6520 (14)	C10—C11	1.506 (9)
O1—C5	1.414 (7)	C11—H11A	0.9600
O1—Cu1ⁱ	1.967 (4)	C11—H11B	0.9600
O2—C6	1.280 (7)	C11—H11C	0.9600
O3—C6	1.243 (7)	O1S—C1T	1.420 (13)
O4—C8	1.260 (7)	O1S—C4S	1.449 (6)
O5—C8	1.244 (7)	O1S—C1S	1.480 (10)
O5—Cu2ⁱⁱ	1.974 (4)	C1S—C2S	1.514 (12)
O6—C10	1.244 (7)	C1S—H1S1	0.9700
O7—C10	1.265 (7)	C1S—H1S2	0.9700
O7—Cu2ⁱⁱ	1.977 (4)	C2S—C3S	1.489 (11)
N1—C1	1.473 (8)	C2S—H2S1	0.9700
N1—C2	1.485 (7)	C2S—H2S2	0.9700
N1—C3	1.492 (8)	C3S—C4S	1.493 (10)
C1—H1A	0.9600	C3S—H3S1	0.9700
C1—H1B	0.9600	C3S—H3S2	0.9700
C1—H1C	0.9600	C4S—H4S1	0.9700
C2—H2A	0.9600	C4S—H4S2	0.9700
C2—H2B	0.9600	C1T—C2T	1.487 (14)
C2—H2C	0.9600	C1T—H1T1	0.9700
C3—C4	1.532 (9)	C1T—H1T2	0.9700
C3—H3A	0.9700	C2T—C3T	1.499 (14)
C3—H3B	0.9700	C2T—H2T1	0.9700
C4—C5	1.514 (8)	C2T—H2T2	0.9700
C4—H4A	0.9700	C3T—H3T1	0.9700
C4—H4B	0.9700	C3T—H3T2	0.9700
C5—H5A	0.9700

O1—Cu1—O2	167.93 (17)	O3—C6—C7	120.8 (5)
O1—Cu1—O1ⁱ	75.99 (18)	O2—C6—C7	115.8 (5)
O2—Cu1—O1ⁱ	93.93 (16)	C6—C7—H7A	109.5
O1—Cu1—N1	96.69 (18)	C6—C7—H7B	109.5
O2—Cu1—N1	93.02 (18)	H7A—C7—H7B	109.5
O1ⁱ—Cu1—N1	172.24 (18)	C6—C7—H7C	109.5
O6—Cu2—O4	88.5 (2)	H7A—C7—H7C	109.5
O6—Cu2—O5ⁱⁱ	89.1 (2)	H7B—C7—H7C	109.5
O4—Cu2—O5ⁱⁱ	167.51 (18)	O5—C8—O4	125.5 (6)
O6—Cu2—O7ⁱⁱ	167.87 (18)	O5—C8—C9	118.6 (5)
O4—Cu2—O7ⁱⁱ	90.1 (2)	O4—C8—C9	115.9 (5)
O5ⁱⁱ—Cu2—O7ⁱⁱ	89.7 (2)	C8—C9—H9A	109.5
O6—Cu2—O3	97.94 (17)	C8—C9—H9B	109.5
O4—Cu2—O3	98.52 (17)	H9A—C9—H9B	109.5
O5ⁱⁱ—Cu2—O3	93.94 (16)	C8—C9—H9C	109.5
O7ⁱⁱ—Cu2—O3	94.19 (17)	H9A—C9—H9C	109.5
O6—Cu2—Cu2ⁱⁱ	84.91 (13)	H9B—C9—H9C	109.5
O4—Cu2—Cu2ⁱⁱ	84.33 (13)	O6—C10—O7	125.9 (6)
O5ⁱⁱ—Cu2—Cu2ⁱⁱ	83.26 (12)	O6—C10—C11	116.5 (5)
O7ⁱⁱ—Cu2—Cu2ⁱⁱ	82.96 (13)	O7—C10—C11	117.6 (6)
O3—Cu2—Cu2ⁱⁱ	176.00 (12)	C10—C11—H11A	109.5
C5—O1—Cu1	126.8 (4)	C10—C11—H11B	109.5
C5—O1—Cu1ⁱ	125.3 (3)	H11A—C11—H11B	109.5
Cu1—O1—Cu1ⁱ	104.01 (18)	C10—C11—H11C	109.5
C6—O2—Cu1	115.5 (4)	H11A—C11—H11C	109.5
C6—O3—Cu2	130.0 (4)	H11B—C11—H11C	109.5
C8—O4—Cu2	122.6 (4)	C1T—O1S—C4S	113.2 (10)
C8—O5—Cu2ⁱⁱ	124.2 (4)	C4S—O1S—C1S	103.7 (6)
C10—O6—Cu2	122.5 (4)	O1S—C1S—C2S	109.0 (8)
C10—O7—Cu2ⁱⁱ	123.7 (4)	O1S—C1S—H1S1	109.9
C1—N1—C2	108.1 (5)	C2S—C1S—H1S1	109.9
C1—N1—C3	106.4 (5)	O1S—C1S—H1S2	109.9
C2—N1—C3	110.3 (5)	C2S—C1S—H1S2	109.9
C1—N1—Cu1	111.7 (4)	H1S1—C1S—H1S2	108.3
C2—N1—Cu1	108.3 (4)	C3S—C2S—C1S	100.4 (9)
C3—N1—Cu1	111.9 (3)	C3S—C2S—H2S1	111.7
N1—C1—H1A	109.5	C1S—C2S—H2S1	111.7
N1—C1—H1B	109.5	C3S—C2S—H2S2	111.7
H1A—C1—H1B	109.5	C1S—C2S—H2S2	111.7
N1—C1—H1C	109.5	H2S1—C2S—H2S2	109.5
H1A—C1—H1C	109.5	C2S—C3S—C4S	102.4 (8)
H1B—C1—H1C	109.5	C2S—C3S—H3S1	111.3
N1—C2—H2A	109.5	C4S—C3S—H3S1	111.3
N1—C2—H2B	109.5	C2S—C3S—H3S2	111.3
H2A—C2—H2B	109.5	C4S—C3S—H3S2	111.3
N1—C2—H2C	109.5	H3S1—C3S—H3S2	109.2
H2A—C2—H2C	109.5	O1S—C4S—C3S	108.2 (6)
H2B—C2—H2C	109.5	O1S—C4S—H4S1	110.1
N1—C3—C4	115.0 (5)	C3S—C4S—H4S1	110.1
N1—C3—H3A	108.5	O1S—C4S—H4S2	110.1
C4—C3—H3A	108.5	C3S—C4S—H4S2	110.1
N1—C3—H3B	108.5	H4S1—C4S—H4S2	108.4
C4—C3—H3B	108.5	O1S—C1T—C2T	96.0 (13)
H3A—C3—H3B	107.5	O1S—C1T—H1T1	112.5
C5—C4—C3	113.2 (5)	C2T—C1T—H1T1	112.5
C5—C4—H4A	108.9	O1S—C1T—H1T2	112.5
C3—C4—H4A	108.9	C2T—C1T—H1T2	112.5
C5—C4—H4B	108.9	H1T1—C1T—H1T2	110.1
C3—C4—H4B	108.9	C1T—C2T—C3T	107.0 (14)
H4A—C4—H4B	107.7	C1T—C2T—H2T1	110.3
O1—C5—C4	112.4 (5)	C3T—C2T—H2T1	110.3
O1—C5—H5A	109.1	C1T—C2T—H2T2	110.3
C4—C5—H5A	109.1	C3T—C2T—H2T2	110.3
O1—C5—H5B	109.1	H2T1—C2T—H2T2	108.6
C4—C5—H5B	109.1	C2T—C3T—H3T1	110.4
H5A—C5—H5B	107.9	C2T—C3T—H3T2	110.4
O3—C6—O2	123.4 (5)	H3T1—C3T—H3T2	108.6

O2—Cu1—O1—C5	−167.5 (7)	C1—N1—C3—C4	−176.8 (5)
O1ⁱ—Cu1—O1—C5	158.4 (5)	C2—N1—C3—C4	66.2 (6)
N1—Cu1—O1—C5	−24.2 (5)	Cu1—N1—C3—C4	−54.5 (6)
O2—Cu1—O1—Cu1ⁱ	34.0 (8)	N1—C3—C4—C5	74.3 (7)
O1ⁱ—Cu1—O1—Cu1ⁱ	0.001 (1)	Cu1—O1—C5—C4	41.8 (7)
N1—Cu1—O1—Cu1ⁱ	177.36 (19)	Cu1ⁱ—O1—C5—C4	−164.1 (4)
O1—Cu1—O2—C6	49.2 (9)	C3—C4—C5—O1	−62.2 (7)
O1ⁱ—Cu1—O2—C6	82.2 (4)	Cu2—O3—C6—O2	148.6 (4)
N1—Cu1—O2—C6	−94.4 (4)	Cu2—O3—C6—C7	−31.7 (8)
O6—Cu2—O3—C6	136.6 (5)	Cu1—O2—C6—O3	6.6 (7)
O4—Cu2—O3—C6	46.9 (6)	Cu1—O2—C6—C7	−173.2 (4)
O5ⁱⁱ—Cu2—O3—C6	−133.8 (5)	Cu2ⁱⁱ—O5—C8—O4	2.4 (9)
O7ⁱⁱ—Cu2—O3—C6	−43.8 (5)	Cu2ⁱⁱ—O5—C8—C9	−177.7 (4)
O6—Cu2—O4—C8	88.2 (6)	Cu2—O4—C8—O5	−4.3 (10)
O5ⁱⁱ—Cu2—O4—C8	9.5 (14)	Cu2—O4—C8—C9	175.8 (5)
O7ⁱⁱ—Cu2—O4—C8	−79.7 (6)	Cu2—O6—C10—O7	−0.3 (9)
O3—Cu2—O4—C8	−174.0 (5)	Cu2—O6—C10—C11	177.8 (4)
Cu2ⁱⁱ—Cu2—O4—C8	3.2 (5)	Cu2ⁱⁱ—O7—C10—O6	0.6 (9)
O4—Cu2—O6—C10	−84.5 (5)	Cu2ⁱⁱ—O7—C10—C11	−177.5 (4)
O5ⁱⁱ—Cu2—O6—C10	83.3 (5)	C1T—O1S—C1S—C2S	127 (4)
O7ⁱⁱ—Cu2—O6—C10	−0.9 (14)	C4S—O1S—C1S—C2S	7.9 (13)
O3—Cu2—O6—C10	177.1 (5)	O1S—C1S—C2S—C3S	−29.8 (14)
Cu2ⁱⁱ—Cu2—O6—C10	0.0 (5)	C1S—C2S—C3S—C4S	38.9 (12)
O1—Cu1—N1—C1	146.9 (4)	C1T—O1S—C4S—C3S	−2.4 (15)
O2—Cu1—N1—C1	−40.3 (4)	C1S—O1S—C4S—C3S	17.8 (10)
O1—Cu1—N1—C2	−94.2 (4)	C2S—C3S—C4S—O1S	−37.0 (11)
O2—Cu1—N1—C2	78.7 (4)	C4S—O1S—C1T—C2T	45.5 (19)
O1—Cu1—N1—C3	27.7 (4)	C1S—O1S—C1T—C2T	−22 (3)
O2—Cu1—N1—C3	−159.5 (4)	O1S—C1T—C2T—C3T	−34 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu₄(C₅H₁₂NO)₂(C₂H₃O₂)₆(C₄H₈O)₂]
M_r	956.94
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	25.686 (5), 8.972 (5), 18.021 (5)
β (°)	105.782 (5)
V (Å³)	3996 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.17
Crystal size (mm)	0.23 × 0.10 × 0.04

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15315, 4093, 3300
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.156, 1.22
No. of reflections	4093
No. of parameters	268
No. of restraints	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −0.89

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

MS is grateful to the Higher Education Commission of Pakistan for financial support for the PhD program.

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