Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040249/su6253sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040249/su6253Isup2.hkl |
CCDC reference: 296677
5-Bromosalicylaldehy (0.1 mmol, 20.1 mg) and N,N'-diethylethane-1,2-diamine (0.1 mmol, 11.6 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To this solution were added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 6.5 mg) and a MeOH solution (3 ml) of Cu(CH3COO)2·H2O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for a further 20 min at room temperature and then filtered. The filtrate was kept in air for 5 d, during which time blue block-shaped crystals of (I) were formed.
The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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.
[Cu(C13H18BrN2O)(NCS)] | F(000) = 844 |
Mr = 419.82 | Dx = 1.726 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3328 reflections |
a = 7.052 (1) Å | θ = 2.4–24.6° |
b = 16.688 (2) Å | µ = 3.96 mm−1 |
c = 13.775 (2) Å | T = 298 K |
β = 94.79 (1)° | Block, blue |
V = 1615.4 (4) Å3 | 0.25 × 0.18 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3564 independent reflections |
Radiation source: fine-focus sealed tube | 2787 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→9 |
Tmin = 0.404, Tmax = 0.510 | k = −21→21 |
11427 measured reflections | l = −16→17 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4325P] where P = (Fo2 + 2Fc2)/3 |
3564 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Cu(C13H18BrN2O)(NCS)] | V = 1615.4 (4) Å3 |
Mr = 419.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.052 (1) Å | µ = 3.96 mm−1 |
b = 16.688 (2) Å | T = 298 K |
c = 13.775 (2) Å | 0.25 × 0.18 × 0.17 mm |
β = 94.79 (1)° |
Bruker SMART CCD area-detector diffractometer | 3564 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2787 reflections with I > 2σ(I) |
Tmin = 0.404, Tmax = 0.510 | Rint = 0.031 |
11427 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.54 e Å−3 |
3564 reflections | Δρmin = −0.41 e Å−3 |
192 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 | ||
Cu1 | 0.24192 (5) | 0.72498 (2) | 1.01867 (3) | 0.03673 (12) | |
Br1 | 0.93758 (5) | 0.40802 (2) | 1.16694 (3) | 0.05364 (13) | |
S1 | −0.29725 (14) | 0.82260 (8) | 1.15452 (8) | 0.0719 (3) | |
O1 | 0.2750 (3) | 0.63306 (12) | 1.09990 (15) | 0.0410 (5) | |
N1 | 0.4757 (4) | 0.70606 (14) | 0.95910 (17) | 0.0352 (5) | |
N2 | 0.2110 (4) | 0.82183 (15) | 0.92092 (18) | 0.0390 (6) | |
N3 | 0.0115 (4) | 0.75086 (19) | 1.0795 (2) | 0.0588 (8) | |
C1 | 0.5849 (4) | 0.59285 (16) | 1.0572 (2) | 0.0324 (6) | |
C2 | 0.4214 (4) | 0.58535 (16) | 1.1096 (2) | 0.0323 (6) | |
C3 | 0.4193 (4) | 0.52132 (18) | 1.1767 (2) | 0.0375 (7) | |
H3 | 0.3135 | 0.5145 | 1.2119 | 0.045* | |
C4 | 0.5687 (4) | 0.46902 (17) | 1.1913 (2) | 0.0382 (7) | |
H4 | 0.5629 | 0.4271 | 1.2355 | 0.046* | |
C5 | 0.7289 (4) | 0.47863 (17) | 1.1403 (2) | 0.0359 (7) | |
C6 | 0.7373 (4) | 0.53849 (17) | 1.0741 (2) | 0.0358 (6) | |
H6 | 0.8445 | 0.5437 | 1.0396 | 0.043* | |
C7 | 0.6001 (4) | 0.65218 (17) | 0.9838 (2) | 0.0348 (6) | |
H7 | 0.7099 | 0.6517 | 0.9508 | 0.042* | |
C8 | 0.5146 (5) | 0.7638 (2) | 0.8834 (3) | 0.0514 (9) | |
H8A | 0.5804 | 0.7376 | 0.8330 | 0.062* | |
H8B | 0.5946 | 0.8067 | 0.9111 | 0.062* | |
C9 | 0.3304 (5) | 0.7965 (2) | 0.8414 (2) | 0.0501 (8) | |
H9A | 0.2633 | 0.7561 | 0.8013 | 0.060* | |
H9B | 0.3531 | 0.8422 | 0.8004 | 0.060* | |
C10 | 0.2880 (6) | 0.8978 (2) | 0.9632 (3) | 0.0696 (12) | |
H10A | 0.4241 | 0.8914 | 0.9776 | 0.083* | |
H10B | 0.2692 | 0.9392 | 0.9139 | 0.083* | |
C11 | 0.2081 (8) | 0.9266 (3) | 1.0516 (4) | 0.1023 (18) | |
H11A | 0.0741 | 0.9358 | 1.0382 | 0.153* | |
H11B | 0.2695 | 0.9757 | 1.0724 | 0.153* | |
H11C | 0.2283 | 0.8871 | 1.1021 | 0.153* | |
C12 | 0.0093 (5) | 0.8275 (2) | 0.8795 (3) | 0.0513 (9) | |
H12A | −0.0680 | 0.8425 | 0.9316 | 0.062* | |
H12B | −0.0314 | 0.7745 | 0.8575 | 0.062* | |
C13 | −0.0328 (5) | 0.8853 (2) | 0.7963 (3) | 0.0573 (10) | |
H13A | −0.0020 | 0.9388 | 0.8179 | 0.086* | |
H13B | −0.1655 | 0.8825 | 0.7743 | 0.086* | |
H13C | 0.0421 | 0.8714 | 0.7437 | 0.086* | |
C14 | −0.1159 (5) | 0.7801 (2) | 1.1115 (2) | 0.0465 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0362 (2) | 0.0425 (2) | 0.0329 (2) | 0.00864 (15) | 0.01138 (15) | 0.00463 (15) |
Br1 | 0.0387 (2) | 0.0456 (2) | 0.0759 (3) | 0.00827 (14) | 0.00099 (17) | 0.00703 (16) |
S1 | 0.0446 (5) | 0.1075 (9) | 0.0651 (7) | 0.0174 (5) | 0.0135 (5) | −0.0313 (6) |
O1 | 0.0387 (12) | 0.0458 (12) | 0.0412 (12) | 0.0094 (9) | 0.0189 (10) | 0.0113 (9) |
N1 | 0.0358 (13) | 0.0378 (12) | 0.0333 (13) | 0.0006 (10) | 0.0106 (11) | 0.0022 (10) |
N2 | 0.0379 (14) | 0.0433 (14) | 0.0358 (14) | 0.0047 (11) | 0.0037 (11) | 0.0045 (11) |
N3 | 0.0573 (19) | 0.0691 (19) | 0.0540 (19) | 0.0265 (16) | 0.0284 (15) | 0.0197 (16) |
C1 | 0.0330 (15) | 0.0321 (14) | 0.0323 (15) | 0.0012 (11) | 0.0030 (12) | −0.0046 (12) |
C2 | 0.0326 (15) | 0.0356 (14) | 0.0291 (15) | −0.0005 (12) | 0.0052 (12) | −0.0038 (12) |
C3 | 0.0373 (16) | 0.0409 (16) | 0.0354 (16) | −0.0037 (13) | 0.0091 (13) | 0.0000 (13) |
C4 | 0.0409 (17) | 0.0346 (15) | 0.0389 (17) | −0.0021 (13) | 0.0018 (14) | 0.0010 (12) |
C5 | 0.0295 (15) | 0.0360 (15) | 0.0414 (17) | 0.0037 (12) | −0.0026 (13) | −0.0063 (13) |
C6 | 0.0284 (14) | 0.0397 (15) | 0.0400 (17) | −0.0002 (12) | 0.0065 (12) | −0.0064 (13) |
C7 | 0.0291 (14) | 0.0386 (15) | 0.0383 (16) | −0.0027 (12) | 0.0115 (12) | −0.0039 (12) |
C8 | 0.052 (2) | 0.0501 (19) | 0.056 (2) | 0.0058 (16) | 0.0244 (17) | 0.0156 (16) |
C9 | 0.050 (2) | 0.060 (2) | 0.0425 (19) | 0.0082 (16) | 0.0150 (16) | 0.0133 (16) |
C10 | 0.068 (3) | 0.064 (2) | 0.073 (3) | 0.007 (2) | −0.011 (2) | −0.009 (2) |
C11 | 0.127 (5) | 0.089 (3) | 0.095 (4) | 0.002 (3) | 0.032 (4) | −0.037 (3) |
C12 | 0.0409 (19) | 0.060 (2) | 0.053 (2) | 0.0056 (16) | 0.0010 (16) | 0.0171 (17) |
C13 | 0.049 (2) | 0.074 (2) | 0.048 (2) | 0.0158 (18) | 0.0028 (17) | 0.0182 (18) |
C14 | 0.0428 (19) | 0.059 (2) | 0.0388 (18) | 0.0077 (16) | 0.0101 (15) | 0.0062 (15) |
Cu1—O1 | 1.902 (2) | C5—C6 | 1.357 (4) |
Cu1—N1 | 1.928 (3) | C6—H6 | 0.9300 |
Cu1—N3 | 1.938 (3) | C7—H7 | 0.9300 |
Cu1—N2 | 2.103 (2) | C8—C9 | 1.482 (5) |
Br1—C5 | 1.897 (3) | C8—H8A | 0.9700 |
S1—C14 | 1.617 (4) | C8—H8B | 0.9700 |
O1—C2 | 1.302 (3) | C9—H9A | 0.9700 |
N1—C7 | 1.282 (4) | C9—H9B | 0.9700 |
N1—C8 | 1.463 (4) | C10—C11 | 1.464 (6) |
N2—C10 | 1.480 (5) | C10—H10A | 0.9700 |
N2—C12 | 1.490 (4) | C10—H10B | 0.9700 |
N2—C9 | 1.497 (4) | C11—H11A | 0.9600 |
N3—C14 | 1.143 (4) | C11—H11B | 0.9600 |
C1—C6 | 1.411 (4) | C11—H11C | 0.9600 |
C1—C2 | 1.416 (4) | C12—C13 | 1.509 (4) |
C1—C7 | 1.426 (4) | C12—H12A | 0.9700 |
C2—C3 | 1.414 (4) | C12—H12B | 0.9700 |
C3—C4 | 1.370 (4) | C13—H13A | 0.9600 |
C3—H3 | 0.9300 | C13—H13B | 0.9600 |
C4—C5 | 1.389 (4) | C13—H13C | 0.9600 |
C4—H4 | 0.9300 | ||
O1—Cu1—N1 | 92.93 (9) | N1—C8—C9 | 108.1 (3) |
O1—Cu1—N3 | 89.52 (11) | N1—C8—H8A | 110.1 |
N1—Cu1—N3 | 176.48 (12) | C9—C8—H8A | 110.1 |
O1—Cu1—N2 | 176.09 (10) | N1—C8—H8B | 110.1 |
N1—Cu1—N2 | 84.27 (10) | C9—C8—H8B | 110.1 |
N3—Cu1—N2 | 93.41 (11) | H8A—C8—H8B | 108.4 |
C2—O1—Cu1 | 127.65 (19) | C8—C9—N2 | 110.3 (3) |
C7—N1—C8 | 119.1 (3) | C8—C9—H9A | 109.6 |
C7—N1—Cu1 | 126.3 (2) | N2—C9—H9A | 109.6 |
C8—N1—Cu1 | 114.43 (19) | C8—C9—H9B | 109.6 |
C10—N2—C12 | 113.8 (3) | N2—C9—H9B | 109.6 |
C10—N2—C9 | 108.6 (3) | H9A—C9—H9B | 108.1 |
C12—N2—C9 | 108.3 (3) | C11—C10—N2 | 117.0 (4) |
C10—N2—Cu1 | 113.0 (2) | C11—C10—H10A | 108.0 |
C12—N2—Cu1 | 109.78 (19) | N2—C10—H10A | 108.0 |
C9—N2—Cu1 | 102.55 (18) | C11—C10—H10B | 108.0 |
C14—N3—Cu1 | 167.6 (3) | N2—C10—H10B | 108.0 |
C6—C1—C2 | 120.0 (3) | H10A—C10—H10B | 107.3 |
C6—C1—C7 | 117.5 (3) | C10—C11—H11A | 109.5 |
C2—C1—C7 | 122.4 (3) | C10—C11—H11B | 109.5 |
O1—C2—C3 | 118.5 (3) | H11A—C11—H11B | 109.5 |
O1—C2—C1 | 124.5 (3) | C10—C11—H11C | 109.5 |
C3—C2—C1 | 117.0 (3) | H11A—C11—H11C | 109.5 |
C4—C3—C2 | 121.9 (3) | H11B—C11—H11C | 109.5 |
C4—C3—H3 | 119.1 | N2—C12—C13 | 116.9 (3) |
C2—C3—H3 | 119.1 | N2—C12—H12A | 108.1 |
C3—C4—C5 | 120.0 (3) | C13—C12—H12A | 108.1 |
C3—C4—H4 | 120.0 | N2—C12—H12B | 108.1 |
C5—C4—H4 | 120.0 | C13—C12—H12B | 108.1 |
C6—C5—C4 | 120.5 (3) | H12A—C12—H12B | 107.3 |
C6—C5—Br1 | 120.7 (2) | C12—C13—H13A | 109.5 |
C4—C5—Br1 | 118.7 (2) | C12—C13—H13B | 109.5 |
C5—C6—C1 | 120.6 (3) | H13A—C13—H13B | 109.5 |
C5—C6—H6 | 119.7 | C12—C13—H13C | 109.5 |
C1—C6—H6 | 119.7 | H13A—C13—H13C | 109.5 |
N1—C7—C1 | 125.8 (3) | H13B—C13—H13C | 109.5 |
N1—C7—H7 | 117.1 | N3—C14—S1 | 178.6 (3) |
C1—C7—H7 | 117.1 |
Experimental details
Crystal data | |
Chemical formula | [Cu(C13H18BrN2O)(NCS)] |
Mr | 419.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.052 (1), 16.688 (2), 13.775 (2) |
β (°) | 94.79 (1) |
V (Å3) | 1615.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.96 |
Crystal size (mm) | 0.25 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.404, 0.510 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11427, 3564, 2787 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.091, 1.03 |
No. of reflections | 3564 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.41 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Cu1—O1 | 1.902 (2) | Cu1—N3 | 1.938 (3) |
Cu1—N1 | 1.928 (3) | Cu1—N2 | 2.103 (2) |
O1—Cu1—N1 | 92.93 (9) | O1—Cu1—N2 | 176.09 (10) |
O1—Cu1—N3 | 89.52 (11) | N1—Cu1—N2 | 84.27 (10) |
N1—Cu1—N3 | 176.48 (12) | N3—Cu1—N2 | 93.41 (11) |
Recently, we have reported a series of Schiff base complexes (You, 2005a,b,c). As an extension of this work on the structural characterization of Schiff base complexes, we describe here the synthesis and structure of the title new copper(II) compound, (I).
The molecular structure of compound (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. Compound (I) is structurally similar to the copper(II) compounds reported recently (You, 2005d,e). The CuII atom is four-coordinated, in a square-planar arrangement, by one O and two N atoms of the Schiff base ligand, and by one N atom of the thiocyanate anion. The values of the trans angles in the CuON3 square plane are 176.48 (12) and 176.09 (10)°, indicating a slightly distorted square-planar coordination. The Cu—O and Cu—N bond lengths (Table 1) are comparable with the corresponding values observed in other Schiff base copper(II) complexes (You & Zhu, 2004) and, as expected, the bond involving amine atom N2 [2.071 (3) Å] is longer than that involving imine atom N1 [1.925 (3) Å] (Mondal et al., 2001).
In the crystal strucrure, the molecules stack along the a axis; the crystal packing is shown in Fig. 2.