Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040250/su6254sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040250/su6254Isup2.hkl |
CCDC reference: 296678
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.035
- wR factor = 0.100
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT412_ALERT_2_B Short Intra XH3 .. XHn H9A .. H10A .. 1.74 Ang.
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.66 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.11 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C8 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.51 PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
5-Chlorosalicylaldehy (0.1 mmol, 15.6 mg) and N,N'-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To the above solution was added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 6.5 mg) and an MeOH solution (3 ml) of Cu(CH3COO)2·H2O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for another 20 min at room temperature. The filtrate was kept in air for 9 d, during which time blue block-shaped crystals were formed.
All non-H atoms except C9 and C10 lie in a crystallographic mirror plane. Atom C9 is disordered across the mirror plane and as a result the occupancy factor for the disordered components were fixed at 0.50 each. The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) 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(C11H14ClN2O)(NCS)] | F(000) = 708 |
Mr = 347.31 | Dx = 1.570 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 4650 reflections |
a = 19.172 (2) Å | θ = 2.8–27.2° |
b = 6.764 (1) Å | µ = 1.80 mm−1 |
c = 11.334 (1) Å | T = 298 K |
V = 1469.8 (3) Å3 | Block, blue |
Z = 4 | 0.22 × 0.20 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 1827 independent reflections |
Radiation source: fine-focus sealed tube | 1558 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→24 |
Tmin = 0.692, Tmax = 0.714 | k = −8→8 |
12043 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.053P)2 + 0.9005P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1827 reflections | Δρmax = 0.77 e Å−3 |
117 parameters | Δρmin = −0.60 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (8) |
[Cu(C11H14ClN2O)(NCS)] | V = 1469.8 (3) Å3 |
Mr = 347.31 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 19.172 (2) Å | µ = 1.80 mm−1 |
b = 6.764 (1) Å | T = 298 K |
c = 11.334 (1) Å | 0.22 × 0.20 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 1827 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1558 reflections with I > 2σ(I) |
Tmin = 0.692, Tmax = 0.714 | Rint = 0.026 |
12043 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.77 e Å−3 |
1827 reflections | Δρmin = −0.60 e Å−3 |
117 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 | Occ. (<1) | |
Cu1 | 0.316105 (18) | 0.2500 | 0.13768 (3) | 0.04083 (16) | |
Cl1 | 0.65292 (5) | 0.2500 | −0.15121 (9) | 0.0592 (3) | |
S1 | 0.08076 (5) | 0.2500 | 0.04135 (13) | 0.1106 (7) | |
O1 | 0.35797 (11) | 0.2500 | −0.01487 (19) | 0.0456 (5) | |
N1 | 0.40484 (14) | 0.2500 | 0.2172 (2) | 0.0462 (7) | |
N2 | 0.27443 (15) | 0.2500 | 0.3063 (3) | 0.0615 (9) | |
N3 | 0.22355 (15) | 0.2500 | 0.0701 (3) | 0.0680 (10) | |
C1 | 0.47828 (15) | 0.2500 | 0.0449 (3) | 0.0351 (6) | |
C2 | 0.42428 (15) | 0.2500 | −0.0404 (3) | 0.0363 (6) | |
C3 | 0.44440 (18) | 0.2500 | −0.1602 (3) | 0.0472 (8) | |
H3 | 0.4100 | 0.2500 | −0.2180 | 0.057* | |
C4 | 0.51288 (18) | 0.2500 | −0.1941 (3) | 0.0482 (8) | |
H4 | 0.5245 | 0.2500 | −0.2738 | 0.058* | |
C5 | 0.56501 (16) | 0.2500 | −0.1085 (3) | 0.0426 (7) | |
C6 | 0.54859 (15) | 0.2500 | 0.0085 (3) | 0.0379 (6) | |
H6 | 0.5840 | 0.2500 | 0.0646 | 0.045* | |
C7 | 0.46528 (16) | 0.2500 | 0.1685 (3) | 0.0429 (7) | |
H7 | 0.5039 | 0.2500 | 0.2182 | 0.052* | |
C8 | 0.3988 (2) | 0.2500 | 0.3458 (3) | 0.0844 (18) | |
H8A | 0.4020 | 0.3832 | 0.3745 | 0.101* | 0.50 |
H8B | 0.4367 | 0.1758 | 0.3788 | 0.101* | 0.50 |
C9 | 0.3345 (3) | 0.1673 (11) | 0.3827 (4) | 0.0646 (17) | 0.50 |
H9A | 0.3364 | 0.0261 | 0.3748 | 0.077* | 0.50 |
H9B | 0.3263 | 0.1982 | 0.4642 | 0.077* | 0.50 |
C10 | 0.2307 (2) | 0.0760 (5) | 0.3279 (3) | 0.0935 (13) | |
H10A | 0.2570 | −0.0417 | 0.3119 | 0.140* | |
H10B | 0.1906 | 0.0803 | 0.2772 | 0.140* | |
H10C | 0.2158 | 0.0754 | 0.4088 | 0.140* | |
C11 | 0.16454 (18) | 0.2500 | 0.0584 (3) | 0.0614 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0279 (2) | 0.0560 (3) | 0.0386 (2) | 0.000 | 0.00528 (14) | 0.000 |
Cl1 | 0.0374 (4) | 0.0766 (6) | 0.0636 (6) | 0.000 | 0.0194 (4) | 0.000 |
S1 | 0.0299 (5) | 0.229 (2) | 0.0725 (8) | 0.000 | 0.0026 (5) | 0.000 |
O1 | 0.0290 (10) | 0.0694 (15) | 0.0384 (11) | 0.000 | 0.0023 (9) | 0.000 |
N1 | 0.0354 (13) | 0.0697 (19) | 0.0335 (13) | 0.000 | 0.0039 (11) | 0.000 |
N2 | 0.0365 (14) | 0.102 (3) | 0.0457 (16) | 0.000 | 0.0131 (13) | 0.000 |
N3 | 0.0339 (15) | 0.117 (3) | 0.0533 (19) | 0.000 | 0.0028 (13) | 0.000 |
C1 | 0.0320 (13) | 0.0366 (14) | 0.0366 (14) | 0.000 | 0.0035 (11) | 0.000 |
C2 | 0.0324 (14) | 0.0404 (15) | 0.0360 (15) | 0.000 | 0.0035 (11) | 0.000 |
C3 | 0.0398 (16) | 0.066 (2) | 0.0363 (16) | 0.000 | 0.0020 (13) | 0.000 |
C4 | 0.0489 (18) | 0.060 (2) | 0.0360 (16) | 0.000 | 0.0119 (14) | 0.000 |
C5 | 0.0346 (15) | 0.0452 (17) | 0.0480 (17) | 0.000 | 0.0121 (13) | 0.000 |
C6 | 0.0316 (14) | 0.0397 (16) | 0.0424 (16) | 0.000 | 0.0020 (12) | 0.000 |
C7 | 0.0313 (14) | 0.059 (2) | 0.0385 (15) | 0.000 | −0.0009 (12) | 0.000 |
C8 | 0.049 (2) | 0.169 (6) | 0.0348 (19) | 0.000 | 0.0051 (16) | 0.000 |
C9 | 0.048 (2) | 0.109 (5) | 0.036 (2) | 0.001 (3) | 0.008 (2) | 0.010 (2) |
C10 | 0.122 (3) | 0.068 (2) | 0.090 (2) | 0.016 (2) | 0.061 (2) | 0.0184 (19) |
C11 | 0.0345 (17) | 0.110 (3) | 0.0395 (18) | 0.000 | 0.0062 (14) | 0.000 |
Cu1—O1 | 1.906 (2) | C3—C4 | 1.368 (5) |
Cu1—N1 | 1.925 (3) | C3—H3 | 0.9300 |
Cu1—N3 | 1.932 (3) | C4—C5 | 1.393 (5) |
Cu1—N2 | 2.071 (3) | C4—H4 | 0.9300 |
Cl1—C5 | 1.754 (3) | C5—C6 | 1.363 (5) |
S1—C11 | 1.618 (4) | C6—H6 | 0.9300 |
O1—C2 | 1.304 (4) | C7—H7 | 0.9300 |
N1—C7 | 1.284 (4) | C8—C9 | 1.416 (6) |
N1—C8 | 1.462 (4) | C8—C9i | 1.416 (6) |
N2—C10 | 1.466 (4) | C8—H8A | 0.9601 |
N2—C10i | 1.466 (4) | C8—H8B | 0.9599 |
N2—C9i | 1.546 (6) | C9—C9i | 1.118 (14) |
N2—C9 | 1.546 (6) | C9—H9A | 0.9600 |
N3—C11 | 1.139 (5) | C9—H9B | 0.9600 |
C1—C6 | 1.410 (4) | C10—H10A | 0.9600 |
C1—C2 | 1.417 (4) | C10—H10B | 0.9600 |
C1—C7 | 1.423 (4) | C10—H10C | 0.9600 |
C2—C3 | 1.411 (4) | ||
O1—Cu1—N1 | 93.02 (10) | C4—C5—Cl1 | 119.8 (3) |
O1—Cu1—N3 | 91.56 (12) | C5—C6—C1 | 120.4 (3) |
N1—Cu1—N3 | 175.41 (12) | C5—C6—H6 | 119.8 |
O1—Cu1—N2 | 177.79 (11) | C1—C6—H6 | 119.8 |
N1—Cu1—N2 | 84.76 (12) | N1—C7—C1 | 125.6 (3) |
N3—Cu1—N2 | 90.65 (13) | N1—C7—H7 | 117.2 |
C2—O1—Cu1 | 127.7 (2) | C1—C7—H7 | 117.2 |
C7—N1—C8 | 120.1 (3) | C9—C8—C9i | 46.5 (6) |
C7—N1—Cu1 | 126.6 (2) | C9—C8—N1 | 111.3 (3) |
C8—N1—Cu1 | 113.4 (2) | C9i—C8—N1 | 111.3 (3) |
C10—N2—C10i | 106.8 (3) | C9—C8—H8A | 109.0 |
C10—N2—C9i | 128.5 (4) | C9i—C8—H8A | 65.5 |
C10i—N2—C9i | 92.4 (3) | N1—C8—H8A | 109.4 |
C10—N2—C9 | 92.4 (3) | C9—C8—H8B | 109.7 |
C10i—N2—C9 | 128.5 (4) | C9i—C8—H8B | 138.6 |
C10—N2—Cu1 | 112.0 (2) | N1—C8—H8B | 109.2 |
C10i—N2—Cu1 | 112.0 (2) | H8A—C8—H8B | 108.0 |
C9i—N2—Cu1 | 103.3 (2) | C9i—C9—C8 | 66.8 (3) |
C9—N2—Cu1 | 103.3 (2) | C9i—C9—N2 | 68.8 (3) |
C11—N3—Cu1 | 163.3 (3) | C8—C9—N2 | 109.9 (4) |
C6—C1—C2 | 119.9 (3) | C9i—C9—H9A | 174.2 |
C6—C1—C7 | 117.1 (3) | C8—C9—H9A | 109.4 |
C2—C1—C7 | 123.0 (3) | N2—C9—H9A | 109.6 |
O1—C2—C3 | 118.7 (3) | C9i—C9—H9B | 77.4 |
O1—C2—C1 | 124.1 (3) | C8—C9—H9B | 110.0 |
C3—C2—C1 | 117.2 (3) | N2—C9—H9B | 109.7 |
C4—C3—C2 | 122.2 (3) | H9A—C9—H9B | 108.2 |
C4—C3—H3 | 118.9 | N2—C10—H10A | 109.5 |
C2—C3—H3 | 118.9 | N2—C10—H10B | 109.5 |
C3—C4—C5 | 119.5 (3) | H10A—C10—H10B | 109.5 |
C3—C4—H4 | 120.2 | N2—C10—H10C | 109.5 |
C5—C4—H4 | 120.2 | H10A—C10—H10C | 109.5 |
C6—C5—C4 | 120.8 (3) | H10B—C10—H10C | 109.5 |
C6—C5—Cl1 | 119.4 (3) | N3—C11—S1 | 179.8 (4) |
N1—Cu1—O1—C2 | 0.0 | C3—C4—C5—C6 | 0.0 |
N3—Cu1—O1—C2 | 180.0 | C3—C4—C5—Cl1 | 180.0 |
O1—Cu1—N1—C7 | 0.0 | C4—C5—C6—C1 | 0.0 |
N2—Cu1—N1—C7 | 180.0 | Cl1—C5—C6—C1 | 180.0 |
O1—Cu1—N1—C8 | 180.0 | C2—C1—C6—C5 | 0.0 |
N2—Cu1—N1—C8 | 0.0 | C7—C1—C6—C5 | 180.0 |
N1—Cu1—N2—C10 | −120.0 (2) | C8—N1—C7—C1 | 180.0 |
N3—Cu1—N2—C10 | 60.0 (2) | Cu1—N1—C7—C1 | 0.0 |
N1—Cu1—N2—C10i | 120.0 (2) | C6—C1—C7—N1 | 180.0 |
N3—Cu1—N2—C10i | −60.0 (2) | C2—C1—C7—N1 | 0.0 |
N1—Cu1—N2—C9i | 21.8 (3) | C7—N1—C8—C9 | −154.9 (3) |
N3—Cu1—N2—C9i | −158.2 (3) | Cu1—N1—C8—C9 | 25.1 (3) |
N1—Cu1—N2—C9 | −21.8 (3) | C7—N1—C8—C9i | 154.9 (3) |
N3—Cu1—N2—C9 | 158.2 (3) | Cu1—N1—C8—C9i | −25.1 (3) |
O1—Cu1—N3—C11 | 180.0 | N1—C8—C9—C9i | −99.7 (2) |
N2—Cu1—N3—C11 | 0.0 | C9i—C8—C9—N2 | 55.0 (4) |
Cu1—O1—C2—C3 | 180.0 | N1—C8—C9—N2 | −44.7 (5) |
Cu1—O1—C2—C1 | 0.0 | C10—N2—C9—C9i | −151.5 (2) |
C6—C1—C2—O1 | 180.0 | C10i—N2—C9—C9i | −37.6 (3) |
C7—C1—C2—O1 | 0.0 | Cu1—N2—C9—C9i | 95.25 (11) |
C6—C1—C2—C3 | 0.0 | C10—N2—C9—C8 | 154.7 (4) |
C7—C1—C2—C3 | 180.0 | C10i—N2—C9—C8 | −91.4 (4) |
O1—C2—C3—C4 | 180.0 | C9i—N2—C9—C8 | −53.8 (4) |
C1—C2—C3—C4 | 0.0 | Cu1—N2—C9—C8 | 41.4 (4) |
C2—C3—C4—C5 | 0.0 |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C11H14ClN2O)(NCS)] |
Mr | 347.31 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 298 |
a, b, c (Å) | 19.172 (2), 6.764 (1), 11.334 (1) |
V (Å3) | 1469.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.22 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.692, 0.714 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12043, 1827, 1558 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.100, 1.05 |
No. of reflections | 1827 |
No. of parameters | 117 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.60 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Cu1—O1 | 1.906 (2) | Cu1—N3 | 1.932 (3) |
Cu1—N1 | 1.925 (3) | Cu1—N2 | 2.071 (3) |
O1—Cu1—N1 | 93.02 (10) | O1—Cu1—N2 | 177.79 (11) |
O1—Cu1—N3 | 91.56 (12) | N1—Cu1—N2 | 84.76 (12) |
N1—Cu1—N3 | 175.41 (12) | N3—Cu1—N2 | 90.65 (13) |
Recently, the author has reported on a series of Schiff base complexes (You, 2005a,d,e). As an extension of the work on the structural characterization of Schiff base complexes, the synthesis and structure of a new copper(II) compound, (I), is reported here.
The molecular structure of complex (I), a mononuclear copper(II) compound, 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, 2005b,c). The Cu 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 molecule possesses crystallographic mirror symmetry, with atoms Cu1, Cl1, S1, O1, C1–C8, C11, H3, H4, H6 and H7 lying in the crystallographic mirror plane. The values of the trans angles in the CuON3 square plane are, respectively, 175.41 (12) and 177.79 (11)°, indicating a slightly distorted square-planar coordination. The Cu–O and Cu–N bond lengths (Table 1) are comparable to the corresponding values observed in other Schiff base copper(II) complexes (MacLachlan et al., 1996; Colacio et al., 2000) 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 structure, the molecules stack back-to-back along the b axis and the crystal packing is shown in Fig. 2.