metal-organic compounds
Bis{μ-2,2′-[(3-azapentane-1,5-diyl)bis(nitrilomethylidyne)]diphenolato}dicopper(II) dimethyl sulfoxide disolvate
aCentro de Química, Instituto de Ciencias, Universidad Autónoma de Puebla, Edif. 194 Complejo de Ciencias CU, San Manuel, 72570 Puebla, Pue., Mexico, bFacultad de Ciencias Químicas, Universidad Autónoma de Puebla, Edif. 179 Complejo de Ciencias CU, San Manuel, 72570 Puebla, Pue., Mexico, and cDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title compound, [Cu2(C18H19N3O2)2]·2C2H6OS or [Cu2(SalenN3H)2]·2DMSO, where SalenN3H is the multidentate Schiff base 2,2′-[(3-azapentane-1,5-diyl)bis(nitrilomethylidyne)]diphenolate dianion and DMSO is dimethyl sulfoxide, is a solvated dinuclear CuII complex. The neutral complex is built from two Cu(SalenN3H) units related by an inversion center. All heteroatoms in the coordinate the CuII ions, which display highly distorted trigonal bipyramidal geometries. The solvent molecules are located in the structural voids of the complex and are disordered over two positions with occupancies of 0.642 (15) and 0.358 (15). The previously characterized acetone disolvate of the same complex presents identical molecular and crystal structures, and crystallizes with cell parameters very close to those of the DMSO disolvate reported here.
Related literature
The title compound was synthesized by direct synthesis, using metallic copper as starting material (Gutiérrez et al., 2001; Reyes-Ortega et al., 2005). The same dinuclear CuII complex was previously characterized with acetone solvent in place of DMSO (McKenzie & Selvey, 1985).
Experimental
Crystal data
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Refinement
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Data collection: XSCANS (Siemens, 1996); cell XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus.
Supporting information
10.1107/S1600536808008544/si2079sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008544/si2079Isup2.hkl
The title compound was prepared by direct synthesis, mixing equimolecular amounts (0.8 mmol) of elemental copper and neutral Schiff base SalenN3H3 in DMSO (2.4 ml). The mixture was heated at 353 K with magnetic stirring for 5.5 hrs, and then filtered. A crystalline compound, was collected after six days. Yield: 30%.
The
contains one DMSO molecule which is clearly disordered over two positions (Fig. 1, inset). S, O and C atoms were splitted over two sites. Refined occupancies converged to 0.642 (15) and 0.358 (15) for sites A and B, respectively. Geometry was regularized through restraints applied to bond lengths: S—O = 1.475 (20) and S—C = 1.750 (20) Å. Finally, sites in each pair of disordered atoms were restrained, with a standard deviation of 0.04 Å2, to have the same Uij components. All H atoms were placed in idealized positions, and were allowed to ride on their carrier atoms, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.97 (methylene CH2) or 0.96 Å (methyl CH3), and N—H bond length fixed to 0.91 Å. Isotropic displacement parameters for H atoms were calculated as Uiso(H) = xUeq(carrier atom) where x = 1.5 for methyl groups and x = 1.2 otherwise.Data collection: XSCANS (Siemens, 1996); cell
XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).[Cu2(C18H19N3O2)2]·2C2H6OS | F(000) = 940 |
Mr = 902.06 | Dx = 1.480 Mg m−3 |
Monoclinic, P21/c | Melting point: 410 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.817 (3) Å | Cell parameters from 72 reflections |
b = 16.783 (4) Å | θ = 4.8–10.8° |
c = 9.827 (3) Å | µ = 1.21 mm−1 |
β = 106.732 (18)° | T = 298 K |
V = 2024.5 (8) Å3 | Irregular, green |
Z = 2 | 0.16 × 0.16 × 0.12 mm |
Bruker P4 diffractometer | 2191 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.076 |
Graphite monochromator | θmax = 25.1°, θmin = 2.1° |
2θ/ω scans | h = −14→15 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −20→20 |
Tmin = 0.803, Tmax = 0.866 | l = −11→7 |
7380 measured reflections | 1 standard reflections every 48 reflections |
3599 independent reflections | intensity decay: 1% |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0556P)2 + 5.336P] where P = (Fo2 + 2Fc2)/3 |
3599 reflections | (Δ/σ)max < 0.001 |
294 parameters | Δρmax = 0.47 e Å−3 |
30 restraints | Δρmin = −0.82 e Å−3 |
0 constraints |
[Cu2(C18H19N3O2)2]·2C2H6OS | V = 2024.5 (8) Å3 |
Mr = 902.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.817 (3) Å | µ = 1.21 mm−1 |
b = 16.783 (4) Å | T = 298 K |
c = 9.827 (3) Å | 0.16 × 0.16 × 0.12 mm |
β = 106.732 (18)° |
Bruker P4 diffractometer | 2191 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.076 |
Tmin = 0.803, Tmax = 0.866 | 1 standard reflections every 48 reflections |
7380 measured reflections | intensity decay: 1% |
3599 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 30 restraints |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.47 e Å−3 |
3599 reflections | Δρmin = −0.82 e Å−3 |
294 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.59573 (6) | 0.38379 (4) | 0.71636 (8) | 0.0438 (3) | |
O1 | 0.7294 (3) | 0.4094 (3) | 0.8606 (5) | 0.0597 (12) | |
O2 | 0.4577 (3) | 0.3281 (2) | 0.7063 (4) | 0.0487 (11) | |
N1 | 0.6595 (4) | 0.2864 (3) | 0.6677 (5) | 0.0394 (11) | |
N2 | 0.5491 (4) | 0.3917 (3) | 0.4705 (5) | 0.0391 (11) | |
H2B | 0.5898 | 0.4311 | 0.4478 | 0.047* | |
N3 | 0.5343 (4) | 0.4857 (3) | 0.7562 (5) | 0.0386 (11) | |
C1 | 0.8131 (5) | 0.3647 (4) | 0.9119 (6) | 0.0460 (15) | |
C2 | 0.8969 (5) | 0.3907 (4) | 1.0277 (7) | 0.0609 (18) | |
H2A | 0.8908 | 0.4401 | 1.0677 | 0.073* | |
C3 | 0.9878 (6) | 0.3459 (5) | 1.0844 (8) | 0.067 (2) | |
H3A | 1.0419 | 0.3655 | 1.1620 | 0.080* | |
C4 | 1.0014 (5) | 0.2734 (5) | 1.0301 (8) | 0.073 (2) | |
H4A | 1.0636 | 0.2432 | 1.0704 | 0.088* | |
C5 | 0.9219 (5) | 0.2457 (4) | 0.9153 (8) | 0.0605 (18) | |
H5A | 0.9312 | 0.1966 | 0.8763 | 0.073* | |
C6 | 0.8269 (5) | 0.2894 (4) | 0.8548 (6) | 0.0427 (14) | |
C7 | 0.7516 (5) | 0.2566 (3) | 0.7316 (6) | 0.0433 (14) | |
H7A | 0.7715 | 0.2097 | 0.6951 | 0.052* | |
C8 | 0.5930 (5) | 0.2526 (4) | 0.5346 (6) | 0.0476 (15) | |
H8A | 0.5215 | 0.2383 | 0.5420 | 0.057* | |
H8B | 0.6272 | 0.2052 | 0.5104 | 0.057* | |
C9 | 0.5838 (5) | 0.3163 (3) | 0.4234 (6) | 0.0448 (15) | |
H9A | 0.6538 | 0.3233 | 0.4056 | 0.054* | |
H9B | 0.5315 | 0.2998 | 0.3353 | 0.054* | |
C10 | 0.4349 (4) | 0.4115 (3) | 0.4060 (6) | 0.0408 (14) | |
H10A | 0.4141 | 0.4527 | 0.4624 | 0.049* | |
H10B | 0.3910 | 0.3647 | 0.4090 | 0.049* | |
C11 | 0.4088 (5) | 0.4401 (3) | 0.2531 (6) | 0.0423 (14) | |
H11A | 0.4302 | 0.3996 | 0.1959 | 0.051* | |
H11B | 0.3309 | 0.4483 | 0.2153 | 0.051* | |
C12 | 0.4532 (5) | 0.4911 (4) | 0.8083 (6) | 0.0432 (15) | |
H12A | 0.4395 | 0.5411 | 0.8401 | 0.052* | |
C13 | 0.3816 (4) | 0.4273 (4) | 0.8226 (6) | 0.0401 (14) | |
C14 | 0.2997 (5) | 0.4461 (5) | 0.8867 (7) | 0.0600 (19) | |
H14A | 0.2965 | 0.4973 | 0.9215 | 0.072* | |
C15 | 0.2255 (5) | 0.3910 (5) | 0.8987 (8) | 0.0622 (19) | |
H15A | 0.1722 | 0.4041 | 0.9422 | 0.075* | |
C16 | 0.2297 (6) | 0.3161 (5) | 0.8466 (8) | 0.065 (2) | |
H16A | 0.1796 | 0.2782 | 0.8569 | 0.078* | |
C17 | 0.3054 (5) | 0.2953 (4) | 0.7795 (7) | 0.0532 (17) | |
H17A | 0.3031 | 0.2447 | 0.7403 | 0.064* | |
C18 | 0.3875 (5) | 0.3496 (3) | 0.7685 (6) | 0.0415 (14) | |
S1A | 0.8609 (5) | 0.4752 (5) | 0.4851 (8) | 0.068 (2) | 0.642 (15) |
O3A | 0.7492 (8) | 0.4440 (7) | 0.4334 (14) | 0.126 (5) | 0.642 (15) |
C19A | 0.921 (3) | 0.449 (2) | 0.665 (2) | 0.084 (8) | 0.642 (15) |
H19A | 0.9266 | 0.3926 | 0.6738 | 0.126* | 0.642 (15) |
H19B | 0.8767 | 0.4693 | 0.7213 | 0.126* | 0.642 (15) |
H19C | 0.9924 | 0.4727 | 0.6974 | 0.126* | 0.642 (15) |
C20A | 0.845 (2) | 0.5781 (8) | 0.505 (2) | 0.054 (5) | 0.642 (15) |
H20A | 0.8109 | 0.6014 | 0.4137 | 0.081* | 0.642 (15) |
H20B | 0.9154 | 0.6021 | 0.5447 | 0.081* | 0.642 (15) |
H20C | 0.8007 | 0.5871 | 0.5670 | 0.081* | 0.642 (15) |
S1B | 0.8199 (9) | 0.4739 (10) | 0.4918 (19) | 0.082 (4) | 0.358 (15) |
O3B | 0.8755 (13) | 0.4476 (9) | 0.386 (2) | 0.089 (7) | 0.358 (15) |
C19B | 0.901 (5) | 0.431 (4) | 0.650 (6) | 0.12 (2) | 0.358 (15) |
H19D | 0.8815 | 0.3758 | 0.6532 | 0.182* | 0.358 (15) |
H19E | 0.8884 | 0.4584 | 0.7299 | 0.182* | 0.358 (15) |
H19F | 0.9761 | 0.4351 | 0.6538 | 0.182* | 0.358 (15) |
C20B | 0.852 (5) | 0.5716 (17) | 0.550 (5) | 0.107 (18) | 0.358 (15) |
H20D | 0.8245 | 0.6078 | 0.4726 | 0.161* | 0.358 (15) |
H20E | 0.9299 | 0.5772 | 0.5855 | 0.161* | 0.358 (15) |
H20F | 0.8200 | 0.5835 | 0.6249 | 0.161* | 0.358 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0420 (4) | 0.0405 (4) | 0.0467 (5) | 0.0053 (3) | 0.0092 (3) | −0.0004 (4) |
O1 | 0.050 (3) | 0.062 (3) | 0.056 (3) | 0.015 (2) | −0.003 (2) | −0.018 (2) |
O2 | 0.047 (2) | 0.046 (2) | 0.058 (3) | 0.003 (2) | 0.023 (2) | −0.002 (2) |
N1 | 0.042 (3) | 0.036 (3) | 0.039 (3) | 0.005 (2) | 0.010 (2) | 0.005 (2) |
N2 | 0.046 (3) | 0.036 (3) | 0.037 (3) | 0.000 (2) | 0.014 (2) | −0.008 (2) |
N3 | 0.038 (3) | 0.040 (3) | 0.035 (3) | 0.004 (2) | 0.007 (2) | 0.003 (2) |
C1 | 0.045 (3) | 0.063 (4) | 0.031 (3) | 0.005 (3) | 0.012 (3) | −0.001 (3) |
C2 | 0.056 (4) | 0.071 (5) | 0.048 (4) | 0.013 (4) | 0.004 (3) | −0.010 (4) |
C3 | 0.058 (4) | 0.084 (6) | 0.054 (4) | 0.004 (4) | 0.007 (4) | −0.004 (4) |
C4 | 0.048 (4) | 0.094 (6) | 0.066 (5) | 0.029 (4) | −0.001 (4) | 0.010 (5) |
C5 | 0.050 (4) | 0.062 (4) | 0.066 (5) | 0.012 (3) | 0.012 (4) | 0.006 (4) |
C6 | 0.041 (3) | 0.051 (4) | 0.038 (3) | 0.009 (3) | 0.015 (3) | 0.009 (3) |
C7 | 0.047 (3) | 0.031 (3) | 0.053 (4) | 0.005 (3) | 0.017 (3) | 0.006 (3) |
C8 | 0.045 (3) | 0.045 (4) | 0.049 (4) | 0.005 (3) | 0.007 (3) | −0.004 (3) |
C9 | 0.048 (3) | 0.049 (4) | 0.036 (3) | 0.009 (3) | 0.010 (3) | −0.001 (3) |
C10 | 0.040 (3) | 0.033 (3) | 0.049 (4) | 0.000 (2) | 0.011 (3) | −0.003 (3) |
C11 | 0.044 (3) | 0.039 (3) | 0.041 (4) | 0.001 (3) | 0.007 (3) | 0.000 (3) |
C12 | 0.053 (4) | 0.042 (3) | 0.027 (3) | 0.009 (3) | −0.001 (3) | −0.001 (3) |
C13 | 0.034 (3) | 0.057 (4) | 0.029 (3) | 0.008 (3) | 0.008 (2) | 0.007 (3) |
C14 | 0.051 (4) | 0.084 (5) | 0.045 (4) | 0.008 (4) | 0.014 (3) | −0.010 (4) |
C15 | 0.050 (4) | 0.079 (5) | 0.069 (5) | 0.010 (4) | 0.035 (4) | 0.007 (4) |
C16 | 0.055 (4) | 0.077 (5) | 0.064 (5) | −0.006 (4) | 0.020 (4) | 0.021 (4) |
C17 | 0.050 (4) | 0.055 (4) | 0.051 (4) | 0.000 (3) | 0.010 (3) | 0.014 (3) |
C18 | 0.046 (3) | 0.037 (3) | 0.034 (3) | 0.007 (3) | 0.001 (3) | 0.006 (3) |
S1A | 0.046 (3) | 0.070 (3) | 0.085 (4) | −0.009 (3) | 0.014 (3) | 0.012 (2) |
O3A | 0.057 (6) | 0.100 (8) | 0.201 (13) | −0.036 (6) | 0.005 (7) | 0.026 (8) |
C19A | 0.098 (16) | 0.063 (14) | 0.105 (14) | 0.017 (15) | 0.050 (11) | 0.046 (11) |
C20A | 0.056 (8) | 0.052 (7) | 0.044 (12) | 0.003 (6) | −0.002 (8) | 0.028 (6) |
S1B | 0.052 (9) | 0.069 (5) | 0.128 (7) | −0.018 (7) | 0.032 (8) | 0.008 (4) |
O3B | 0.113 (14) | 0.050 (9) | 0.103 (15) | 0.007 (9) | 0.029 (11) | −0.011 (10) |
C19B | 0.12 (3) | 0.11 (4) | 0.16 (4) | −0.05 (2) | 0.07 (3) | 0.04 (3) |
C20B | 0.11 (3) | 0.15 (3) | 0.06 (3) | 0.00 (2) | 0.02 (2) | 0.04 (2) |
Cu1—O1 | 1.932 (4) | C10—H10B | 0.9700 |
Cu1—N1 | 1.948 (5) | C11—N3i | 1.458 (7) |
Cu1—N2 | 2.319 (4) | C11—H11A | 0.9700 |
Cu1—N3 | 1.969 (5) | C11—H11B | 0.9700 |
Cu1—O2 | 1.978 (4) | C12—C13 | 1.444 (8) |
Cu1—Cu1i | 5.7716 (18) | C12—H12A | 0.9300 |
O1—C1 | 1.286 (7) | C13—C14 | 1.407 (8) |
O2—C18 | 1.277 (7) | C13—C18 | 1.418 (8) |
N1—C7 | 1.270 (7) | C14—C15 | 1.357 (9) |
N1—C8 | 1.455 (7) | C14—H14A | 0.9300 |
N2—C10 | 1.456 (7) | C15—C16 | 1.363 (10) |
N2—C9 | 1.460 (7) | C15—H15A | 0.9300 |
N2—H2B | 0.9100 | C16—C17 | 1.367 (9) |
N3—C12 | 1.288 (7) | C16—H16A | 0.9300 |
N3—C11i | 1.458 (7) | C17—C18 | 1.418 (8) |
C1—C2 | 1.392 (8) | C17—H17A | 0.9300 |
C1—C6 | 1.413 (8) | S1A—O3A | 1.471 (10) |
C2—C3 | 1.363 (9) | S1A—C20A | 1.756 (13) |
C2—H2A | 0.9300 | S1A—C19A | 1.766 (15) |
C3—C4 | 1.361 (10) | C19A—H19A | 0.9600 |
C3—H3A | 0.9300 | C19A—H19B | 0.9600 |
C4—C5 | 1.366 (9) | C19A—H19C | 0.9600 |
C4—H4A | 0.9300 | C20A—H20A | 0.9600 |
C5—C6 | 1.400 (8) | C20A—H20B | 0.9600 |
C5—H5A | 0.9300 | C20A—H20C | 0.9600 |
C6—C7 | 1.424 (8) | S1B—O3B | 1.483 (16) |
C7—H7A | 0.9300 | S1B—C20B | 1.75 (2) |
C8—C9 | 1.509 (8) | S1B—C19B | 1.76 (2) |
C8—H8A | 0.9700 | C19B—H19D | 0.9600 |
C8—H8B | 0.9700 | C19B—H19E | 0.9600 |
C9—H9A | 0.9700 | C19B—H19F | 0.9600 |
C9—H9B | 0.9700 | C20B—H20D | 0.9600 |
C10—C11 | 1.521 (8) | C20B—H20E | 0.9600 |
C10—H10A | 0.9700 | C20B—H20F | 0.9600 |
O1—Cu1—O2 | 137.2 (2) | N2—C9—H9A | 109.5 |
O2—Cu1—N2 | 90.92 (17) | C8—C9—H9A | 109.5 |
N2—Cu1—O1 | 131.28 (19) | N2—C9—H9B | 109.5 |
N1—Cu1—N3 | 176.4 (2) | C8—C9—H9B | 109.5 |
O1—Cu1—N1 | 91.16 (18) | H9A—C9—H9B | 108.1 |
O1—Cu1—N3 | 88.98 (18) | N2—C10—C11 | 114.2 (5) |
N1—Cu1—O2 | 91.38 (18) | N2—C10—H10A | 108.7 |
N3—Cu1—O2 | 91.00 (18) | C11—C10—H10A | 108.7 |
N1—Cu1—N2 | 78.03 (17) | N2—C10—H10B | 108.7 |
N3—Cu1—N2 | 99.17 (17) | C11—C10—H10B | 108.7 |
O1—Cu1—Cu1i | 119.32 (15) | H10A—C10—H10B | 107.6 |
N1—Cu1—Cu1i | 120.37 (14) | N3i—C11—C10 | 111.1 (5) |
N3—Cu1—Cu1i | 56.61 (13) | N3i—C11—H11A | 109.4 |
O2—Cu1—Cu1i | 95.61 (12) | C10—C11—H11A | 109.4 |
N2—Cu1—Cu1i | 42.83 (11) | N3i—C11—H11B | 109.4 |
C1—O1—Cu1 | 128.4 (4) | C10—C11—H11B | 109.4 |
C18—O2—Cu1 | 125.9 (4) | H11A—C11—H11B | 108.0 |
C7—N1—C8 | 120.8 (5) | N3—C12—C13 | 126.6 (5) |
C7—N1—Cu1 | 127.3 (4) | N3—C12—H12A | 116.7 |
C8—N1—Cu1 | 111.7 (3) | C13—C12—H12A | 116.7 |
C10—N2—C9 | 114.8 (4) | C14—C13—C18 | 120.1 (6) |
C10—N2—Cu1 | 113.1 (3) | C14—C13—C12 | 117.0 (6) |
C9—N2—Cu1 | 105.7 (3) | C18—C13—C12 | 122.8 (5) |
C10—N2—H2B | 107.7 | C15—C14—C13 | 121.2 (7) |
C9—N2—H2B | 107.7 | C15—C14—H14A | 119.4 |
Cu1—N2—H2B | 107.7 | C13—C14—H14A | 119.4 |
C12—N3—C11i | 116.1 (5) | C14—C15—C16 | 119.4 (6) |
C12—N3—Cu1 | 123.7 (4) | C14—C15—H15A | 120.3 |
C11i—N3—Cu1 | 119.6 (4) | C16—C15—H15A | 120.3 |
O1—C1—C2 | 119.9 (6) | C15—C16—C17 | 121.8 (7) |
O1—C1—C6 | 123.4 (5) | C15—C16—H16A | 119.1 |
C2—C1—C6 | 116.7 (6) | C17—C16—H16A | 119.1 |
C3—C2—C1 | 121.9 (7) | C16—C17—C18 | 121.2 (7) |
C3—C2—H2A | 119.0 | C16—C17—H17A | 119.4 |
C1—C2—H2A | 119.0 | C18—C17—H17A | 119.4 |
C4—C3—C2 | 121.6 (7) | O2—C18—C17 | 119.7 (6) |
C4—C3—H3A | 119.2 | O2—C18—C13 | 124.0 (6) |
C2—C3—H3A | 119.2 | C17—C18—C13 | 116.2 (6) |
C3—C4—C5 | 118.6 (6) | O3A—S1A—C20A | 104.8 (10) |
C3—C4—H4A | 120.7 | O3A—S1A—C19A | 111.1 (14) |
C5—C4—H4A | 120.7 | C20A—S1A—C19A | 99.2 (14) |
C4—C5—C6 | 121.6 (7) | O3B—S1B—C20B | 113 (2) |
C4—C5—H5A | 119.2 | O3B—S1B—C19B | 103 (3) |
C6—C5—H5A | 119.2 | C20B—S1B—C19B | 94 (3) |
C5—C6—C1 | 119.5 (6) | S1B—C19B—H19D | 109.5 |
C5—C6—C7 | 116.8 (6) | S1B—C19B—H19E | 109.5 |
C1—C6—C7 | 123.5 (5) | H19D—C19B—H19E | 109.5 |
N1—C7—C6 | 125.0 (5) | S1B—C19B—H19F | 109.5 |
N1—C7—H7A | 117.5 | H19D—C19B—H19F | 109.5 |
C6—C7—H7A | 117.5 | H19E—C19B—H19F | 109.5 |
N1—C8—C9 | 106.1 (5) | S1B—C20B—H20D | 109.5 |
N1—C8—H8A | 110.5 | S1B—C20B—H20E | 109.5 |
C9—C8—H8A | 110.5 | H20D—C20B—H20E | 109.5 |
N1—C8—H8B | 110.5 | S1B—C20B—H20F | 109.5 |
C9—C8—H8B | 110.5 | H20D—C20B—H20F | 109.5 |
H8A—C8—H8B | 108.7 | H20E—C20B—H20F | 109.5 |
N2—C9—C8 | 110.6 (5) | ||
N1—Cu1—O1—C1 | −11.8 (5) | C6—C1—C2—C3 | −0.4 (10) |
N3—Cu1—O1—C1 | 171.8 (5) | C1—C2—C3—C4 | 0.2 (12) |
O2—Cu1—O1—C1 | 81.5 (6) | C2—C3—C4—C5 | 0.6 (12) |
N2—Cu1—O1—C1 | −86.8 (6) | C3—C4—C5—C6 | −1.2 (11) |
Cu1i—Cu1—O1—C1 | −138.1 (5) | C4—C5—C6—C1 | 1.1 (10) |
O1—Cu1—O2—C18 | 63.5 (5) | C4—C5—C6—C7 | 177.3 (6) |
N1—Cu1—O2—C18 | 156.7 (5) | O1—C1—C6—C5 | 178.3 (6) |
N3—Cu1—O2—C18 | −26.1 (5) | C2—C1—C6—C5 | −0.3 (9) |
N2—Cu1—O2—C18 | −125.3 (4) | O1—C1—C6—C7 | 2.4 (9) |
Cu1i—Cu1—O2—C18 | −82.6 (4) | C2—C1—C6—C7 | −176.2 (6) |
O1—Cu1—N1—C7 | 6.9 (5) | C8—N1—C7—C6 | 174.0 (5) |
O2—Cu1—N1—C7 | −130.3 (5) | Cu1—N1—C7—C6 | 0.6 (9) |
N2—Cu1—N1—C7 | 139.0 (5) | C5—C6—C7—N1 | 176.5 (6) |
Cu1i—Cu1—N1—C7 | 132.3 (5) | C1—C6—C7—N1 | −7.4 (9) |
O1—Cu1—N1—C8 | −167.0 (4) | C7—N1—C8—C9 | −116.1 (6) |
O2—Cu1—N1—C8 | 55.8 (4) | Cu1—N1—C8—C9 | 58.2 (5) |
N2—Cu1—N1—C8 | −34.9 (4) | C10—N2—C9—C8 | −102.8 (6) |
Cu1i—Cu1—N1—C8 | −41.6 (4) | Cu1—N2—C9—C8 | 22.5 (5) |
O1—Cu1—N2—C10 | −146.8 (3) | N1—C8—C9—N2 | −50.9 (6) |
N1—Cu1—N2—C10 | 132.3 (4) | C9—N2—C10—C11 | −75.2 (6) |
N3—Cu1—N2—C10 | −50.0 (4) | Cu1—N2—C10—C11 | 163.4 (4) |
O2—Cu1—N2—C10 | 41.1 (4) | N2—C10—C11—N3i | −63.2 (6) |
Cu1i—Cu1—N2—C10 | −56.2 (3) | C11i—N3—C12—C13 | 177.1 (5) |
O1—Cu1—N2—C9 | 86.8 (4) | Cu1—N3—C12—C13 | −12.0 (8) |
N1—Cu1—N2—C9 | 6.0 (4) | N3—C12—C13—C14 | 178.2 (5) |
N3—Cu1—N2—C9 | −176.4 (3) | N3—C12—C13—C18 | −5.2 (9) |
O2—Cu1—N2—C9 | −85.3 (4) | C18—C13—C14—C15 | 0.2 (9) |
Cu1i—Cu1—N2—C9 | 177.5 (4) | C12—C13—C14—C15 | 176.9 (6) |
O1—Cu1—N3—C12 | −114.8 (5) | C13—C14—C15—C16 | −0.6 (10) |
O2—Cu1—N3—C12 | 22.3 (5) | C14—C15—C16—C17 | −1.4 (11) |
N2—Cu1—N3—C12 | 113.4 (4) | C15—C16—C17—C18 | 3.8 (10) |
Cu1i—Cu1—N3—C12 | 118.4 (5) | Cu1—O2—C18—C17 | −165.4 (4) |
O1—Cu1—N3—C11i | 55.8 (4) | Cu1—O2—C18—C13 | 18.2 (8) |
O2—Cu1—N3—C11i | −167.0 (4) | C16—C17—C18—O2 | 179.4 (6) |
N2—Cu1—N3—C11i | −75.9 (4) | C16—C17—C18—C13 | −3.9 (9) |
Cu1i—Cu1—N3—C11i | −71.0 (4) | C14—C13—C18—O2 | 178.5 (5) |
Cu1—O1—C1—C2 | −172.4 (5) | C12—C13—C18—O2 | 2.0 (8) |
Cu1—O1—C1—C6 | 9.1 (9) | C14—C13—C18—C17 | 2.0 (8) |
O1—C1—C2—C3 | −179.0 (6) | C12—C13—C18—C17 | −174.6 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C18H19N3O2)2]·2C2H6OS |
Mr | 902.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.817 (3), 16.783 (4), 9.827 (3) |
β (°) | 106.732 (18) |
V (Å3) | 2024.5 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.16 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.803, 0.866 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7380, 3599, 2191 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.167, 1.05 |
No. of reflections | 3599 |
No. of parameters | 294 |
No. of restraints | 30 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.82 |
Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Sheldrick, 2008), Mercury (Macrae et al., 2006).
Cu1—O1 | 1.932 (4) | Cu1—N3 | 1.969 (5) |
Cu1—N1 | 1.948 (5) | Cu1—O2 | 1.978 (4) |
Cu1—N2 | 2.319 (4) | ||
O1—Cu1—O2 | 137.2 (2) | N2—Cu1—O1 | 131.28 (19) |
O2—Cu1—N2 | 90.92 (17) | N1—Cu1—N3 | 176.4 (2) |
Acknowledgements
This work was supported by Secretaría de Educación Pública (Sub-Secretaría de Educación Superior) and Vicerectoría de Investigación y Estudios de Posgrado, BUAP (project No. 09/NAT/07).
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.
The title compound was obtained during a general study about direct synthesis in coordination chemistry, i.e. effective synthesis of complexes using zero-valent metals, neutral ligands, and polar solvents as starting materials (Gutiérrez et al., 2001). We expect that new molecular arrangements, as well as new compounds including solvent molecules as ligands, may be achieved using such reactions (Reyes-Ortega et al., 2005). We are also interested in the influence of lattice solvents on magnetic properties of paramagnetic coordination compounds.
The title compound is a dinuclear centrosymmetric CuII complex, formed through coordination of two Schiff base dianions SalenN3H to two CuII ions; the complex is solvated by two DMSO molecules (Fig. 1). In the complex, all heteroatoms of the Schiff base ligands are coordinated to the metallic centers, which present a highly distorted trigonal-bipyramidal geometry. Atoms O1, O2 and N2 form the equatorial plane, while atoms N1 and N3 occupy apical positions, with an angle N1—Cu1—N3 = 176.4 (2)°. DMSO molecules are located in the structural voids of the complex (Fig. 2), and poorly interact with the Schiff bases, as reflected in the disorder found for this molecule (Fig. 1, inset).
The whole complex presents a rigid conformation, as ten coordination bonds are formed. It may thus be expected to be a good candidate for hosting small solvent molecules with a steric volume similar to that of DMSO. This hypothesis is, at least partially, confirmed by the previous X-ray characterization of the acetone disolvate of the same complex (McKenzie & Selvey, 1985). This compound crystallizes in the same space group, with cell parameters very close to those of the title disolvate. The complex conformation is identical, regardless of the solvent inserted in voids. For example, the non-bonding Cu···Cu separation is virtually not modified: 5.7716 (18) Å in the DMSO disolvate, vs. 5.809 Å in the acetone disolvate.