Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705773X/su2019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705773X/su2019Isup2.hkl |
CCDC reference: 672676
N-Methyl-1,2-diaminoethane (0.1 mmol, 7.4 mg) and 3-bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) were dissolved in ethanol (10 cm3). The mixture was stirred for 10 min to give a clear yellow solution. To the solution was added an aqueous solution (2 cm3) of ammonium thiocyanate (0.1 mmol, 7.6 mg) and CuCl2.2H2O (0.1 mmol, 17.1 mg), with stirring. The mixture was stirred at room temperature for 1 h and then filtered. After keeping the brown filtrate in air for seven days, blue block-shaped crystals were formed with high yield (73% based on 3-bromo-5-chlorosalicylaldehyde).
The H2 atom was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. The other H atoms were placed in geometrically 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) = 1.2Ueq(C) and 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).
Fig. 1. The structure of the complex, showing the atom-numbering scheme with displacement ellipsoids drawn at the 30% probability level. |
[Cu2(C10H11BrClN2O)2(NCS)2] | F(000) = 1624 |
Mr = 824.38 | Dx = 1.817 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2440 (14) Å | Cell parameters from 1694 reflections |
b = 19.693 (4) Å | θ = 2.4–24.5° |
c = 21.128 (4) Å | µ = 4.41 mm−1 |
β = 90.98 (3)° | T = 298 K |
V = 3013.6 (10) Å3 | Block, blue |
Z = 4 | 0.23 × 0.20 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 3443 independent reflections |
Radiation source: fine-focus sealed tube | 2187 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.430, Tmax = 0.472 | k = −25→25 |
12868 measured reflections | l = −27→27 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0472P)2] where P = (Fo2 + 2Fc2)/3 |
3443 reflections | (Δ/σ)max < 0.001 |
176 parameters | Δρmax = 0.51 e Å−3 |
1 restraint | Δρmin = −0.44 e Å−3 |
[Cu2(C10H11BrClN2O)2(NCS)2] | V = 3013.6 (10) Å3 |
Mr = 824.38 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 7.2440 (14) Å | µ = 4.41 mm−1 |
b = 19.693 (4) Å | T = 298 K |
c = 21.128 (4) Å | 0.23 × 0.20 × 0.20 mm |
β = 90.98 (3)° |
Bruker SMART CCD area-detector diffractometer | 3443 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2187 reflections with I > 2σ(I) |
Tmin = 0.430, Tmax = 0.472 | Rint = 0.064 |
12868 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.51 e Å−3 |
3443 reflections | Δρmin = −0.44 e Å−3 |
176 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 | 0.08641 (8) | 0.23561 (3) | 0.44417 (3) | 0.03910 (18) | |
Br1 | 0.10518 (8) | 0.48082 (3) | 0.42831 (3) | 0.0597 (2) | |
Cl1 | 0.30665 (19) | 0.45169 (8) | 0.17930 (7) | 0.0700 (4) | |
S1 | −0.2341 (2) | 0.28910 (9) | 0.62831 (7) | 0.0673 (4) | |
O1 | 0.1260 (4) | 0.32908 (14) | 0.42352 (13) | 0.0400 (8) | |
N1 | 0.1986 (5) | 0.20430 (18) | 0.36694 (17) | 0.0404 (9) | |
N2 | 0.1020 (6) | 0.13676 (19) | 0.4707 (2) | 0.0489 (10) | |
N3 | −0.0142 (6) | 0.2635 (2) | 0.52432 (18) | 0.0475 (10) | |
C1 | 0.2193 (6) | 0.3142 (2) | 0.3153 (2) | 0.0374 (10) | |
C2 | 0.1652 (6) | 0.3537 (2) | 0.3687 (2) | 0.0363 (10) | |
C3 | 0.1652 (6) | 0.4246 (2) | 0.3588 (2) | 0.0410 (11) | |
C4 | 0.2047 (6) | 0.4542 (3) | 0.3019 (2) | 0.0505 (13) | |
H4 | 0.1992 | 0.5011 | 0.2972 | 0.061* | |
C5 | 0.2524 (6) | 0.4136 (3) | 0.2519 (2) | 0.0495 (13) | |
C6 | 0.2593 (7) | 0.3449 (3) | 0.2576 (2) | 0.0479 (12) | |
H6 | 0.2906 | 0.3183 | 0.2230 | 0.057* | |
C7 | 0.2399 (6) | 0.2413 (2) | 0.3195 (2) | 0.0430 (12) | |
H7 | 0.2877 | 0.2193 | 0.2845 | 0.052* | |
C8 | 0.2424 (8) | 0.1311 (2) | 0.3683 (3) | 0.0628 (15) | |
H8A | 0.3704 | 0.1247 | 0.3812 | 0.075* | |
H8B | 0.2255 | 0.1120 | 0.3263 | 0.075* | |
C9 | 0.1205 (8) | 0.0960 (2) | 0.4131 (2) | 0.0623 (15) | |
H9A | −0.0002 | 0.0891 | 0.3936 | 0.075* | |
H9B | 0.1719 | 0.0519 | 0.4238 | 0.075* | |
C10 | −0.0439 (8) | 0.1095 (3) | 0.5115 (3) | 0.0659 (16) | |
H10A | −0.1620 | 0.1155 | 0.4910 | 0.099* | |
H10B | −0.0421 | 0.1333 | 0.5511 | 0.099* | |
H10C | −0.0224 | 0.0620 | 0.5189 | 0.099* | |
C11 | −0.1063 (6) | 0.2737 (2) | 0.5673 (2) | 0.0447 (12) | |
H2 | 0.211 (4) | 0.132 (3) | 0.491 (2) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0502 (4) | 0.0315 (3) | 0.0357 (3) | −0.0015 (3) | 0.0049 (2) | 0.0000 (2) |
Br1 | 0.0834 (4) | 0.0382 (3) | 0.0574 (4) | 0.0070 (3) | −0.0037 (3) | −0.0075 (2) |
Cl1 | 0.0670 (9) | 0.0903 (11) | 0.0529 (8) | 0.0032 (8) | 0.0099 (7) | 0.0358 (8) |
S1 | 0.0625 (9) | 0.0938 (12) | 0.0463 (8) | 0.0121 (8) | 0.0181 (7) | 0.0091 (8) |
O1 | 0.059 (2) | 0.0303 (17) | 0.0310 (17) | −0.0028 (15) | 0.0085 (15) | 0.0012 (13) |
N1 | 0.047 (2) | 0.032 (2) | 0.043 (2) | −0.0035 (17) | 0.0084 (19) | −0.0033 (18) |
N2 | 0.062 (3) | 0.037 (2) | 0.047 (3) | −0.002 (2) | 0.000 (2) | 0.0011 (19) |
N3 | 0.059 (3) | 0.045 (2) | 0.038 (2) | −0.003 (2) | 0.009 (2) | 0.0016 (19) |
C1 | 0.037 (3) | 0.040 (3) | 0.036 (3) | 0.000 (2) | 0.006 (2) | 0.002 (2) |
C2 | 0.031 (2) | 0.039 (3) | 0.039 (3) | −0.003 (2) | −0.004 (2) | −0.002 (2) |
C3 | 0.042 (3) | 0.039 (3) | 0.042 (3) | 0.002 (2) | −0.002 (2) | −0.003 (2) |
C4 | 0.043 (3) | 0.047 (3) | 0.061 (4) | −0.001 (2) | −0.003 (3) | 0.015 (3) |
C5 | 0.043 (3) | 0.068 (4) | 0.037 (3) | 0.001 (3) | 0.006 (2) | 0.018 (3) |
C6 | 0.044 (3) | 0.061 (4) | 0.039 (3) | 0.000 (2) | 0.008 (2) | 0.000 (2) |
C7 | 0.042 (3) | 0.043 (3) | 0.043 (3) | −0.001 (2) | 0.008 (2) | −0.015 (2) |
C8 | 0.080 (4) | 0.033 (3) | 0.076 (4) | 0.002 (3) | 0.020 (3) | −0.007 (3) |
C9 | 0.093 (4) | 0.036 (3) | 0.058 (4) | 0.003 (3) | −0.001 (3) | −0.003 (3) |
C10 | 0.083 (4) | 0.041 (3) | 0.074 (4) | −0.013 (3) | 0.003 (3) | 0.010 (3) |
C11 | 0.047 (3) | 0.045 (3) | 0.043 (3) | −0.004 (2) | −0.002 (2) | 0.008 (2) |
Cu1—O1 | 1.914 (3) | C1—C7 | 1.445 (6) |
Cu1—N3 | 1.935 (4) | C2—C3 | 1.412 (6) |
Cu1—N1 | 1.936 (4) | C3—C4 | 1.370 (6) |
Cu1—N2 | 2.028 (4) | C4—C5 | 1.374 (7) |
Br1—C3 | 1.896 (4) | C4—H4 | 0.9300 |
Cl1—C5 | 1.758 (5) | C5—C6 | 1.359 (6) |
S1—C11 | 1.628 (5) | C6—H6 | 0.9300 |
O1—C2 | 1.291 (5) | C7—H7 | 0.9300 |
N1—C7 | 1.278 (6) | C8—C9 | 1.478 (7) |
N1—C8 | 1.475 (6) | C8—H8A | 0.9700 |
N2—C9 | 1.464 (6) | C8—H8B | 0.9700 |
N2—C10 | 1.476 (6) | C9—H9A | 0.9700 |
N2—H2 | 0.899 (10) | C9—H9B | 0.9700 |
N3—C11 | 1.154 (6) | C10—H10A | 0.9600 |
C1—C6 | 1.397 (6) | C10—H10B | 0.9600 |
C1—C2 | 1.430 (6) | C10—H10C | 0.9600 |
O1—Cu1—N3 | 89.25 (14) | C6—C5—C4 | 121.4 (4) |
O1—Cu1—N1 | 92.72 (14) | C6—C5—Cl1 | 119.6 (4) |
N3—Cu1—N1 | 176.34 (16) | C4—C5—Cl1 | 119.0 (4) |
O1—Cu1—N2 | 167.94 (16) | C5—C6—C1 | 120.1 (5) |
N3—Cu1—N2 | 92.91 (17) | C5—C6—H6 | 120.0 |
N1—Cu1—N2 | 84.53 (16) | C1—C6—H6 | 120.0 |
C2—O1—Cu1 | 126.9 (3) | N1—C7—C1 | 126.1 (4) |
C7—N1—C8 | 121.3 (4) | N1—C7—H7 | 117.0 |
C7—N1—Cu1 | 125.9 (3) | C1—C7—H7 | 117.0 |
C8—N1—Cu1 | 112.8 (3) | N1—C8—C9 | 109.8 (4) |
C9—N2—C10 | 111.2 (4) | N1—C8—H8A | 109.7 |
C9—N2—Cu1 | 107.6 (3) | C9—C8—H8A | 109.7 |
C10—N2—Cu1 | 118.2 (3) | N1—C8—H8B | 109.7 |
C9—N2—H2 | 104 (3) | C9—C8—H8B | 109.7 |
C10—N2—H2 | 108 (3) | H8A—C8—H8B | 108.2 |
Cu1—N2—H2 | 106 (3) | N2—C9—C8 | 109.9 (4) |
C11—N3—Cu1 | 166.0 (4) | N2—C9—H9A | 109.7 |
C6—C1—C2 | 121.1 (4) | C8—C9—H9A | 109.7 |
C6—C1—C7 | 117.4 (4) | N2—C9—H9B | 109.7 |
C2—C1—C7 | 121.4 (4) | C8—C9—H9B | 109.7 |
O1—C2—C3 | 120.3 (4) | H9A—C9—H9B | 108.2 |
O1—C2—C1 | 124.8 (4) | N2—C10—H10A | 109.5 |
C3—C2—C1 | 114.9 (4) | N2—C10—H10B | 109.5 |
C4—C3—C2 | 123.5 (4) | H10A—C10—H10B | 109.5 |
C4—C3—Br1 | 119.0 (4) | N2—C10—H10C | 109.5 |
C2—C3—Br1 | 117.5 (3) | H10A—C10—H10C | 109.5 |
C3—C4—C5 | 119.1 (5) | H10B—C10—H10C | 109.5 |
C3—C4—H4 | 120.5 | N3—C11—S1 | 179.1 (5) |
C5—C4—H4 | 120.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Br1i | 0.90 (1) | 3.09 (4) | 3.777 (4) | 135 (4) |
N2—H2···O1i | 0.90 (1) | 2.27 (3) | 3.031 (5) | 142 (4) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C10H11BrClN2O)2(NCS)2] |
Mr | 824.38 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.2440 (14), 19.693 (4), 21.128 (4) |
β (°) | 90.98 (3) |
V (Å3) | 3013.6 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.41 |
Crystal size (mm) | 0.23 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.430, 0.472 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12868, 3443, 2187 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.115, 0.99 |
No. of reflections | 3443 |
No. of parameters | 176 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.44 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Cu1—O1 | 1.914 (3) | Cu1—N1 | 1.936 (4) |
Cu1—N3 | 1.935 (4) | Cu1—N2 | 2.028 (4) |
O1—Cu1—N3 | 89.25 (14) | O1—Cu1—N2 | 167.94 (16) |
O1—Cu1—N1 | 92.72 (14) | N3—Cu1—N2 | 92.91 (17) |
N3—Cu1—N1 | 176.34 (16) | N1—Cu1—N2 | 84.53 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Br1i | 0.899 (10) | 3.09 (4) | 3.777 (4) | 135 (4) |
N2—H2···O1i | 0.899 (10) | 2.27 (3) | 3.031 (5) | 142 (4) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
Recently, we has reported the crystal structure of a mononuclear copper(II) complex derived from the Schiff base ligand 1-[3-(cyclohexylamino)propyliminomethyl]-2-naphthol (Zhang, 2004). As an extension of this work on the structural characterization of Schiff base copper(II) compounds, we report on the crystal structure of the new title binuclear complex.
The title compound is a centrosymmetric dithiocyanato-bridged binuclear copper(II) complex, as shown in Fig. 1. The CuII atoms are pentacoordinated by the NNO donor atoms of the Schiff base ligand, 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol (HBCP), and by one N and one S atom, from symmetry related thiocyanate anions, forming a slightly distorted square pyramidal coordination configuration. The Cu···Cu distance is 5.480 (2) Å. The bond lengths and angles (Table 1) are within normal ranges and comparable to the values found in the complex mentioned above.