Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056838/hb2633sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056838/hb2633Isup2.hkl |
CCDC reference: 672656
2-Furaldehyde (4 mmol, 384.4 mg) was added dropwise to a dichloromethane (20 ml) solution of diethylenetriamine (2 mmol, 206.4 mg). The mixture was heated under reflux with stirring for 1.5 h. An absolute ethanol solution (5 ml) of cupric chloride dihydrate (3 mmol, 511.4 mg) was then added dropwise, and the mixture was stirred at room temperature for another 15 h. The solution was filtered off, the filterate was kept at room temperature for about 12 days, after which large pale blue blocks of (I) were obtained.
All H-atoms were positioned geometrically and refined using a riding model, with with C—H (methyne) 0.93, C—H = 0.97 (methylene), C—H 0.93 Å (aromatic) and Uiso(H) =1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
[Cu3Cl6(C14H16N3O2)2] | F(000) = 926 |
Mr = 919.92 | Dx = 1.676 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 1576 reflections |
a = 10.9456 (15) Å | θ = 2.9–20.0° |
b = 7.5287 (10) Å | µ = 2.22 mm−1 |
c = 22.248 (2) Å | T = 298 K |
β = 96.048 (2)° | Block, pale blue |
V = 1823.1 (4) Å3 | 0.26 × 0.14 × 0.05 mm |
Z = 2 |
Siemens SMART CCD diffractometer | 3200 independent reflections |
Radiation source: fine-focus sealed tube | 1749 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→13 |
Tmin = 0.597, Tmax = 0.897 | k = −6→8 |
8801 measured reflections | l = −21→26 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0225P)2] where P = (Fo2 + 2Fc2)/3 |
3200 reflections | (Δ/σ)max = 0.002 |
213 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Cu3Cl6(C14H16N3O2)2] | V = 1823.1 (4) Å3 |
Mr = 919.92 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 10.9456 (15) Å | µ = 2.22 mm−1 |
b = 7.5287 (10) Å | T = 298 K |
c = 22.248 (2) Å | 0.26 × 0.14 × 0.05 mm |
β = 96.048 (2)° |
Siemens SMART CCD diffractometer | 3200 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1749 reflections with I > 2σ(I) |
Tmin = 0.597, Tmax = 0.897 | Rint = 0.066 |
8801 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.64 e Å−3 |
3200 reflections | Δρmin = −0.42 e Å−3 |
213 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C13 | 0.4074 (5) | −0.2812 (7) | 0.6330 (2) | 0.0646 (16) | |
H13A | 0.3969 | −0.3504 | 0.6689 | 0.077* | |
H13B | 0.4537 | −0.3517 | 0.6068 | 0.077* | |
Cu1 | 0.45072 (5) | 0.05268 (9) | 0.58051 (3) | 0.0527 (2) | |
Cu2 | 0.2500 | 0.13781 (14) | 0.7500 | 0.0624 (3) | |
Cl1 | 0.42526 (12) | 0.2454 (2) | 0.50298 (6) | 0.0691 (5) | |
Cl2 | 0.32170 (13) | 0.2627 (2) | 0.66945 (6) | 0.0689 (4) | |
Cl3 | 0.07882 (15) | −0.0122 (2) | 0.71301 (7) | 0.0956 (6) | |
C11 | 0.6627 (5) | 0.0402 (8) | 0.6707 (2) | 0.0605 (16) | |
H11A | 0.6451 | 0.0961 | 0.7082 | 0.073* | |
H11B | 0.7511 | 0.0297 | 0.6711 | 0.073* | |
C7 | 0.1142 (5) | −0.1623 (8) | 0.4910 (2) | 0.0537 (15) | |
C2 | 0.7637 (5) | 0.3940 (8) | 0.6357 (3) | 0.0523 (15) | |
O2 | 0.0691 (3) | −0.1249 (5) | 0.43235 (18) | 0.0719 (12) | |
O1 | 0.8276 (4) | 0.3279 (6) | 0.68845 (18) | 0.0753 (12) | |
C6 | 0.2281 (5) | −0.0728 (7) | 0.5094 (2) | 0.0513 (14) | |
H6 | 0.2500 | 0.0148 | 0.4831 | 0.062* | |
C1 | 0.6602 (5) | 0.2975 (8) | 0.6072 (2) | 0.0528 (15) | |
H1 | 0.6204 | 0.3552 | 0.5737 | 0.063* | |
C5 | 0.9170 (6) | 0.4454 (11) | 0.7032 (3) | 0.086 (2) | |
H5 | 0.9746 | 0.4347 | 0.7369 | 0.104* | |
C14 | 0.2835 (5) | −0.2341 (7) | 0.6005 (2) | 0.0596 (15) | |
H14A | 0.2462 | −0.3378 | 0.5802 | 0.071* | |
H14B | 0.2292 | −0.1911 | 0.6291 | 0.071* | |
C3 | 0.8128 (5) | 0.5445 (8) | 0.6198 (2) | 0.0615 (16) | |
H3 | 0.7868 | 0.6141 | 0.5864 | 0.074* | |
C8 | 0.0327 (5) | −0.2627 (8) | 0.5169 (3) | 0.0640 (16) | |
H8 | 0.0412 | −0.3054 | 0.5564 | 0.077* | |
C9 | −0.0679 (6) | −0.2912 (9) | 0.4730 (3) | 0.078 (2) | |
H9 | −0.1392 | −0.3544 | 0.4779 | 0.093* | |
C4 | 0.9142 (6) | 0.5794 (10) | 0.6643 (3) | 0.085 (2) | |
H4 | 0.9673 | 0.6761 | 0.6657 | 0.101* | |
C10 | −0.0405 (6) | −0.2098 (9) | 0.4234 (3) | 0.074 (2) | |
H10 | −0.0904 | −0.2108 | 0.3869 | 0.088* | |
N1 | 0.6121 (3) | 0.1490 (6) | 0.61850 (17) | 0.0478 (11) | |
N3 | 0.3035 (4) | −0.0958 (6) | 0.55647 (19) | 0.0488 (12) | |
N2 | 0.4730 (4) | −0.1175 (6) | 0.64975 (17) | 0.0529 (12) | |
C12 | 0.6046 (5) | −0.1397 (8) | 0.6653 (2) | 0.0672 (17) | |
H12A | 0.6392 | −0.2077 | 0.6341 | 0.081* | |
H12B | 0.6202 | −0.2033 | 0.7032 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C13 | 0.077 (4) | 0.051 (4) | 0.066 (4) | 0.003 (3) | 0.006 (3) | 0.012 (3) |
Cu1 | 0.0446 (4) | 0.0592 (5) | 0.0538 (4) | −0.0022 (4) | 0.0024 (3) | 0.0115 (4) |
Cu2 | 0.0607 (7) | 0.0705 (8) | 0.0559 (6) | 0.000 | 0.0051 (5) | 0.000 |
Cl1 | 0.0545 (9) | 0.0818 (12) | 0.0691 (10) | −0.0113 (8) | −0.0027 (7) | 0.0301 (8) |
Cl2 | 0.0692 (10) | 0.0623 (11) | 0.0764 (10) | −0.0040 (8) | 0.0138 (8) | 0.0099 (8) |
Cl3 | 0.0959 (13) | 0.1257 (18) | 0.0656 (11) | −0.0453 (12) | 0.0108 (9) | −0.0127 (10) |
C11 | 0.055 (4) | 0.067 (5) | 0.057 (4) | 0.002 (3) | −0.005 (3) | 0.013 (3) |
C7 | 0.050 (4) | 0.056 (4) | 0.054 (4) | 0.007 (3) | −0.003 (3) | −0.011 (3) |
C2 | 0.043 (3) | 0.058 (5) | 0.057 (4) | 0.002 (3) | 0.008 (3) | −0.003 (3) |
O2 | 0.057 (3) | 0.088 (3) | 0.069 (3) | 0.002 (2) | −0.003 (2) | −0.007 (2) |
O1 | 0.066 (3) | 0.083 (4) | 0.075 (3) | −0.008 (3) | −0.003 (2) | −0.007 (2) |
C6 | 0.050 (3) | 0.050 (4) | 0.056 (4) | 0.005 (3) | 0.014 (3) | −0.005 (3) |
C1 | 0.045 (4) | 0.065 (5) | 0.049 (3) | 0.015 (3) | 0.010 (3) | 0.002 (3) |
C5 | 0.070 (5) | 0.102 (7) | 0.084 (5) | −0.019 (5) | −0.004 (4) | −0.020 (5) |
C14 | 0.063 (4) | 0.054 (4) | 0.061 (4) | −0.009 (3) | 0.005 (3) | 0.000 (3) |
C3 | 0.058 (4) | 0.056 (4) | 0.073 (4) | −0.001 (4) | 0.014 (3) | 0.002 (3) |
C8 | 0.056 (4) | 0.065 (5) | 0.071 (4) | −0.012 (3) | 0.008 (3) | −0.004 (3) |
C9 | 0.052 (4) | 0.066 (5) | 0.115 (6) | −0.005 (3) | 0.003 (4) | −0.017 (4) |
C4 | 0.064 (4) | 0.075 (6) | 0.117 (6) | −0.029 (4) | 0.023 (4) | −0.033 (5) |
C10 | 0.051 (4) | 0.078 (6) | 0.087 (5) | 0.011 (4) | −0.013 (4) | −0.033 (4) |
N1 | 0.043 (3) | 0.057 (3) | 0.044 (3) | 0.005 (2) | 0.006 (2) | 0.008 (2) |
N3 | 0.049 (3) | 0.048 (3) | 0.052 (3) | −0.001 (2) | 0.013 (2) | 0.001 (2) |
N2 | 0.053 (3) | 0.048 (3) | 0.055 (3) | −0.008 (2) | −0.009 (2) | 0.009 (2) |
C12 | 0.080 (5) | 0.052 (5) | 0.069 (4) | 0.010 (4) | 0.004 (3) | 0.014 (3) |
C13—N2 | 1.455 (6) | O2—C10 | 1.356 (6) |
C13—C14 | 1.510 (6) | O1—C5 | 1.334 (7) |
C13—H13A | 0.9700 | C6—N3 | 1.274 (5) |
C13—H13B | 0.9700 | C6—H6 | 0.9300 |
Cu1—N3 | 1.988 (4) | C1—N1 | 1.273 (6) |
Cu1—N2 | 1.999 (4) | C1—H1 | 0.9300 |
Cu1—N1 | 2.011 (4) | C5—C4 | 1.327 (8) |
Cu1—Cl1 | 2.2489 (15) | C5—H5 | 0.9300 |
Cu1—Cl2 | 2.9998 (16) | C14—N3 | 1.462 (6) |
Cu2—Cl2 | 2.2379 (14) | C14—H14A | 0.9700 |
Cu2—Cl2i | 2.2379 (14) | C14—H14B | 0.9700 |
Cu2—Cl3 | 2.2668 (16) | C3—C4 | 1.432 (7) |
Cu2—Cl3i | 2.2668 (16) | C3—H3 | 0.9300 |
C11—N1 | 1.481 (6) | C8—C9 | 1.409 (7) |
C11—C12 | 1.495 (7) | C8—H8 | 0.9300 |
C11—H11A | 0.9700 | C9—C10 | 1.324 (8) |
C11—H11B | 0.9700 | C9—H9 | 0.9300 |
C7—C8 | 1.344 (7) | C4—H4 | 0.9300 |
C7—O2 | 1.376 (5) | C10—H10 | 0.9300 |
C7—C6 | 1.439 (7) | N2—C12 | 1.455 (6) |
C2—C3 | 1.318 (7) | C12—H12A | 0.9700 |
C2—O1 | 1.393 (6) | C12—H12B | 0.9700 |
C2—C1 | 1.436 (7) | ||
N2—C13—C14 | 108.6 (4) | C2—C1—H1 | 113.6 |
N2—C13—H13A | 110.0 | C4—C5—O1 | 112.2 (6) |
C14—C13—H13A | 110.0 | C4—C5—H5 | 123.9 |
N2—C13—H13B | 110.0 | O1—C5—H5 | 123.9 |
C14—C13—H13B | 110.0 | N3—C14—C13 | 107.3 (4) |
H13A—C13—H13B | 108.4 | N3—C14—H14A | 110.3 |
N3—Cu1—N2 | 82.91 (18) | C13—C14—H14A | 110.3 |
N3—Cu1—N1 | 165.25 (18) | N3—C14—H14B | 110.3 |
N2—Cu1—N1 | 82.92 (17) | C13—C14—H14B | 110.3 |
N3—Cu1—Cl1 | 97.19 (13) | H14A—C14—H14B | 108.5 |
N2—Cu1—Cl1 | 179.66 (14) | C2—C3—C4 | 106.3 (6) |
N1—Cu1—Cl1 | 97.01 (13) | C2—C3—H3 | 126.9 |
N1—Cu1—Cl2 | 89.22 (12) | C4—C3—H3 | 126.9 |
N2—Cu1—Cl2 | 81.79 (13) | C7—C8—C9 | 107.1 (6) |
N3—Cu1—Cl2 | 92.83 (13) | C7—C8—H8 | 126.4 |
Cl1—Cu1—Cl2 | 97.87 (5) | C9—C8—H8 | 126.4 |
Cl2—Cu2—Cl2i | 130.30 (9) | C10—C9—C8 | 106.2 (6) |
Cl2—Cu2—Cl3 | 105.36 (5) | C10—C9—H9 | 126.9 |
Cl2i—Cu2—Cl3 | 98.85 (6) | C8—C9—H9 | 126.9 |
Cl2—Cu2—Cl3i | 98.85 (5) | C5—C4—C3 | 105.9 (6) |
Cl2i—Cu2—Cl3i | 105.36 (5) | C5—C4—H4 | 127.1 |
Cl3—Cu2—Cl3i | 120.23 (11) | C3—C4—H4 | 127.1 |
N1—C11—C12 | 108.5 (4) | C9—C10—O2 | 111.7 (6) |
N1—C11—H11A | 110.0 | C9—C10—H10 | 124.1 |
C12—C11—H11A | 110.0 | O2—C10—H10 | 124.1 |
N1—C11—H11B | 110.0 | C1—N1—C11 | 120.9 (5) |
C12—C11—H11B | 110.0 | C1—N1—Cu1 | 126.7 (4) |
H11A—C11—H11B | 108.4 | C11—N1—Cu1 | 111.7 (3) |
C8—C7—O2 | 109.5 (5) | C6—N3—C14 | 121.2 (4) |
C8—C7—C6 | 137.4 (6) | C6—N3—Cu1 | 125.5 (4) |
O2—C7—C6 | 112.8 (5) | C14—N3—Cu1 | 113.2 (3) |
C3—C2—O1 | 110.5 (5) | C12—N2—C13 | 114.4 (5) |
C3—C2—C1 | 129.9 (6) | C12—N2—Cu1 | 107.1 (3) |
O1—C2—C1 | 119.6 (5) | C13—N2—Cu1 | 109.2 (3) |
C10—O2—C7 | 105.5 (5) | N2—C12—C11 | 108.5 (5) |
C5—O1—C2 | 105.1 (5) | N2—C12—H12A | 110.0 |
N3—C6—C7 | 129.5 (5) | C11—C12—H12A | 110.0 |
N3—C6—H6 | 115.2 | N2—C12—H12B | 110.0 |
C7—C6—H6 | 115.2 | C11—C12—H12B | 110.0 |
N1—C1—C2 | 132.9 (5) | H12A—C12—H12B | 108.4 |
N1—C1—H1 | 113.6 |
Symmetry code: (i) −x+1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cl3ii | 0.93 | 2.80 | 3.669 (7) | 156 |
C10—H10···Cl3iii | 0.93 | 2.80 | 3.451 (8) | 128 |
Symmetry codes: (ii) x+1, y+1, z; (iii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu3Cl6(C14H16N3O2)2] |
Mr | 919.92 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.9456 (15), 7.5287 (10), 22.248 (2) |
β (°) | 96.048 (2) |
V (Å3) | 1823.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.22 |
Crystal size (mm) | 0.26 × 0.14 × 0.05 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.597, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8801, 3200, 1749 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.088, 0.99 |
No. of reflections | 3200 |
No. of parameters | 213 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.42 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Cu1—N3 | 1.988 (4) | Cu1—Cl2 | 2.9998 (16) |
Cu1—N2 | 1.999 (4) | Cu2—Cl2 | 2.2379 (14) |
Cu1—N1 | 2.011 (4) | Cu2—Cl3 | 2.2668 (16) |
Cu1—Cl1 | 2.2489 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cl3i | 0.93 | 2.80 | 3.669 (7) | 156 |
C10—H10···Cl3ii | 0.93 | 2.80 | 3.451 (8) | 128 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y, −z+1. |
Transition metals complexed with multidentate Schiff base ligands result in homo and/or heteronuclear metal complexes with insteresting stereochemistry (e.g. Erxleben et al., 2001). Such species can be used as biological models, catalysis, and molecular ferromagnets (Mukherjee et al., 2002). The Schiff base N,N'-bis(2-furylmethylene)diethylenetriamine is considered to be a good chelating ligand, which can coordinate to transition metals as a tridentate, tetradentate or pentadentate ligand, with consequent variable chemical properties. We report here the synthesis and crystal structure of the title compound, (I), a new copper(II) complex, with a multidentate Schiff base ligand derived from the condensation of 2-furaldehyde and diethylenetriamine.
The complete molecule of (I) (Fig. 1) is generated by 2-fold symmetry. The terminal Cu1 atom is five-coordinated in a distorted square-pyramidal coordination environment consisting of three N atoms of the ligand, one bridging Cl atom and one terminal Cl atom. Cu2 (site symmetry 2) is tetrahedrally coordinated by two bridging Cl atoms and two terminal Cl atoms (Table 1). The two five-membered rings Cu1—N1—C11—C12—N2 and Cu1—N2—C13—C14—N3 form a dihedral angle of 5.7 (3)°, and the dihedral angle between the mean planes of the furan rings is 25.7 (3) °. The Cu1···Cu2 separation is 4.6059 (9) Å.
In the crystal, intermolecular C—H···Cl hydrogen bonds lead to a three-dimensional network (Table 2).