metal-organic compounds
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′]
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
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 [10] direction. In the first dinuclear unit, CuII ions related by inversion symmetry are bridged by two 3-(dimethylamino)propan-1-olate ligands. Likewise, a pair of inversion-related CuII 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
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Data collection: SMART (Bruker, 2001); cell 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
10.1107/S1600536808024148/bh2182sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808024148/bh2182Isup2.hkl
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.
Atoms C1S, C2S and C3S of the THF molecule are disordered over two sites with occupancies constrained to sum to unity, and the highest occupancy fraction refining to a value of 0.608 (13). Distance restraints were applied to the O—C and C—C bond lengths of the disordered THF using the SADI command and restraints were applied to the atomic displacement parameters of this molecule. H atoms were included in calculated positions using the riding model with C—H distances ranging from 0.96 to 0.97 Å and Ueq values 1.2 to 1.5 times those of the parent atoms; the methyl H atoms were calculated so as to maximize the sum of the electron density at the three calculated positions.
Data collection: SMART (Bruker, 2001); cell
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).[Cu4(C5H12NO)2(C2H3O2)6(C4H8O)2] | F(000) = 1984 |
Mr = 956.94 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 3300 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.093 |
Graphite monochromator | θmax = 26.4°, θmin = 2.4° |
ϕ and ω scans | h = −32→32 |
15315 measured reflections | k = −11→11 |
4093 independent reflections | l = −22→21 |
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(Fo2) + (0.0593P)2 + 6.3428P] where P = (Fo2 + 2Fc2)/3 |
4093 reflections | (Δ/σ)max < 0.001 |
268 parameters | Δρmax = 1.17 e Å−3 |
167 restraints | Δρmin = −0.89 e Å−3 |
[Cu4(C5H12NO)2(C2H3O2)6(C4H8O)2] | V = 3996 (3) Å3 |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 3300 reflections with I > 2σ(I) |
15315 measured reflections | Rint = 0.093 |
4093 independent reflections |
R[F2 > 2σ(F2)] = 0.075 | 167 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.22 | Δρmax = 1.17 e Å−3 |
4093 reflections | Δρmin = −0.89 e Å−3 |
268 parameters |
x | y | z | Uiso*/Ueq | 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) |
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) |
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] |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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.
References
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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.
For the last two decades, there has been a considerable interest in the investigation of CuII 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 Tc 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 CuII 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.