In the structure of the mononuclear title complex, [Cu(C
21H
16NO
2S)
2], the Cu
II atom, which lies on an inversion centre, displays approximately square-planar coordination geometry. The bidentate ligands coordinate through their phenolate O and imine N atoms in a mutually
trans orientation. The structure is stabilized by a three-dimensional network of C—H
O hydrogen bonds.
Supporting information
CCDC reference: 274635
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.034
- wR factor = 0.119
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C21
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9 .. O2 .. 2.73 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 46
C1 -O1 -CU -O1 120.00 10.00 1.555 1.555 1.555 2.565
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 53
C7 -N -CU -N -4.00100.00 1.555 1.555 1.555 2.565
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 54
C8 -N -CU -N 167.00 10.00 1.555 1.555 1.555 2.565
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 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
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
5 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: KappaCCD (Nonius, 1998); cell refinement: DENZO and SCAKEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCAKEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Cu(C21H16NO2S)2] | Z = 1 |
Mr = 756.40 | F(000) = 391 |
Triclinic, P1 | Dx = 1.422 Mg m−3 |
Hall symbol: -P 1 | Melting point: 233 K |
a = 9.172 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.032 (3) Å | Cell parameters from 6926 reflections |
c = 11.106 (3) Å | θ = 2.2–26.0° |
α = 60.825 (2)° | µ = 0.78 mm−1 |
β = 67.219 (2)° | T = 293 K |
γ = 89.136 (3)° | Prism, brown |
V = 883.4 (4) Å3 | 0.3 × 0.1 × 0.1 mm |
Data collection top
KappaCCD diffractometer | 2921 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 26.0°, θmin = 2.2° |
φ scans | h = −11→11 |
6940 measured reflections | k = −13→13 |
3396 independent reflections | l = −11→13 |
Refinement top
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.21 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.2786P] where P = (Fo2 + 2Fc2)/3 |
3396 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2523 (3) | 0.7027 (3) | −0.0563 (3) | 0.0330 (5) | |
C2 | 0.4191 (3) | 0.7658 (3) | −0.1306 (3) | 0.0438 (6) | |
H2 | 0.4939 | 0.7292 | −0.1814 | 0.053* | |
C3 | 0.4719 (3) | 0.8803 (3) | −0.1286 (4) | 0.0487 (7) | |
H3 | 0.5822 | 0.9200 | −0.1780 | 0.058* | |
C4 | 0.3640 (4) | 0.9382 (3) | −0.0541 (4) | 0.0509 (7) | |
H4 | 0.4009 | 1.0174 | −0.0559 | 0.061* | |
C5 | 0.2022 (4) | 0.8765 (3) | 0.0220 (3) | 0.0432 (6) | |
H5 | 0.1296 | 0.9133 | 0.0741 | 0.052* | |
C6 | 0.1435 (3) | 0.7588 (3) | 0.0230 (3) | 0.0321 (5) | |
C8 | −0.2767 (3) | 0.5593 (2) | 0.2080 (3) | 0.0284 (5) | |
C9 | −0.3695 (3) | 0.6583 (3) | 0.1660 (3) | 0.0368 (6) | |
H9 | −0.3201 | 0.7493 | 0.0807 | 0.044* | |
C10 | −0.5363 (3) | 0.6216 (3) | 0.2512 (3) | 0.0402 (6) | |
H10 | −0.5988 | 0.6877 | 0.2221 | 0.048* | |
C11 | −0.6098 (3) | 0.4869 (3) | 0.3793 (3) | 0.0339 (5) | |
C12 | −0.5161 (3) | 0.3890 (3) | 0.4232 (3) | 0.0365 (5) | |
H12 | −0.5651 | 0.2993 | 0.5109 | 0.044* | |
C13 | −0.3506 (3) | 0.4245 (3) | 0.3371 (3) | 0.0347 (5) | |
H13 | −0.2885 | 0.3579 | 0.3656 | 0.042* | |
C14 | −0.8882 (3) | 0.3438 (3) | 0.4245 (3) | 0.0332 (5) | |
C15 | −0.7987 (3) | 0.3604 (3) | 0.2821 (3) | 0.0384 (6) | |
H15 | −0.7021 | 0.4282 | 0.2142 | 0.046* | |
C16 | −0.8525 (3) | 0.2767 (3) | 0.2411 (3) | 0.0392 (6) | |
H16 | −0.7895 | 0.2862 | 0.1470 | 0.047* | |
C17 | −1.0000 (3) | 0.1778 (3) | 0.3384 (3) | 0.0363 (6) | |
C18 | −1.0922 (3) | 0.1675 (3) | 0.4780 (3) | 0.0398 (6) | |
H18 | −1.1928 | 0.1052 | 0.5429 | 0.048* | |
C19 | −1.0369 (3) | 0.2478 (3) | 0.5212 (3) | 0.0389 (6) | |
H19 | −1.0993 | 0.2379 | 0.6156 | 0.047* | |
C20 | −1.0472 (4) | 0.0853 (3) | 0.2911 (3) | 0.0441 (7) | |
C21 | −1.2184 (4) | 0.0012 (4) | 0.3761 (4) | 0.0635 (9) | |
H21A | −1.2302 | −0.0528 | 0.3326 | 0.095* | |
H21B | −1.2914 | 0.0649 | 0.3679 | 0.095* | |
H21C | −1.2429 | −0.0624 | 0.4820 | 0.095* | |
N | −0.1044 (2) | 0.5949 (2) | 0.1184 (2) | 0.0297 (4) | |
O1 | 0.2079 (2) | 0.5977 (2) | −0.0664 (2) | 0.0431 (5) | |
O2 | −0.9483 (3) | 0.0770 (2) | 0.1857 (3) | 0.0601 (6) | |
S | −0.82363 (8) | 0.44069 (8) | 0.48992 (8) | 0.0442 (2) | |
Cu | 0.0000 | 0.5000 | 0.0000 | 0.02865 (15) | |
C7 | −0.0272 (3) | 0.7014 (3) | 0.1053 (3) | 0.0320 (5) | |
H7 | −0.0894 | 0.7450 | 0.1547 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0291 (12) | 0.0352 (12) | 0.0372 (13) | 0.0031 (10) | −0.0142 (11) | −0.0207 (11) |
C2 | 0.0287 (13) | 0.0511 (16) | 0.0523 (16) | 0.0034 (11) | −0.0111 (13) | −0.0322 (14) |
C3 | 0.0349 (14) | 0.0472 (16) | 0.0602 (18) | −0.0036 (12) | −0.0210 (14) | −0.0249 (14) |
C4 | 0.0486 (17) | 0.0421 (15) | 0.074 (2) | 0.0015 (12) | −0.0311 (16) | −0.0348 (15) |
C5 | 0.0451 (16) | 0.0401 (14) | 0.0594 (17) | 0.0086 (12) | −0.0249 (15) | −0.0347 (13) |
C6 | 0.0305 (12) | 0.0336 (12) | 0.0363 (12) | 0.0043 (9) | −0.0147 (11) | −0.0208 (10) |
C8 | 0.0256 (11) | 0.0337 (12) | 0.0301 (11) | 0.0063 (9) | −0.0087 (10) | −0.0221 (10) |
C9 | 0.0352 (13) | 0.0326 (12) | 0.0352 (13) | 0.0095 (10) | −0.0098 (12) | −0.0167 (11) |
C10 | 0.0330 (13) | 0.0436 (14) | 0.0438 (14) | 0.0164 (11) | −0.0140 (12) | −0.0250 (12) |
C11 | 0.0265 (12) | 0.0450 (14) | 0.0375 (13) | 0.0075 (10) | −0.0102 (11) | −0.0294 (12) |
C12 | 0.0333 (13) | 0.0345 (12) | 0.0355 (13) | 0.0020 (10) | −0.0102 (11) | −0.0173 (11) |
C13 | 0.0298 (12) | 0.0327 (12) | 0.0391 (13) | 0.0089 (10) | −0.0145 (11) | −0.0174 (11) |
C14 | 0.0270 (12) | 0.0368 (13) | 0.0373 (13) | 0.0100 (10) | −0.0135 (11) | −0.0207 (11) |
C15 | 0.0303 (13) | 0.0432 (14) | 0.0354 (13) | 0.0034 (10) | −0.0083 (11) | −0.0207 (11) |
C16 | 0.0392 (14) | 0.0449 (14) | 0.0331 (13) | 0.0095 (11) | −0.0140 (12) | −0.0214 (11) |
C17 | 0.0387 (14) | 0.0315 (12) | 0.0413 (14) | 0.0112 (10) | −0.0240 (12) | −0.0158 (11) |
C18 | 0.0303 (13) | 0.0362 (13) | 0.0414 (14) | 0.0037 (10) | −0.0128 (12) | −0.0143 (11) |
C19 | 0.0293 (13) | 0.0435 (14) | 0.0372 (13) | 0.0091 (11) | −0.0088 (12) | −0.0209 (12) |
C20 | 0.0560 (18) | 0.0322 (13) | 0.0471 (16) | 0.0118 (12) | −0.0322 (15) | −0.0154 (12) |
C21 | 0.071 (2) | 0.0485 (18) | 0.069 (2) | −0.0019 (15) | −0.0391 (19) | −0.0221 (16) |
N | 0.0260 (10) | 0.0322 (10) | 0.0318 (10) | 0.0055 (8) | −0.0097 (9) | −0.0196 (8) |
O1 | 0.0259 (9) | 0.0531 (11) | 0.0623 (12) | 0.0044 (8) | −0.0096 (9) | −0.0456 (10) |
O2 | 0.0807 (17) | 0.0511 (13) | 0.0574 (13) | 0.0123 (11) | −0.0325 (14) | −0.0326 (11) |
S | 0.0249 (3) | 0.0648 (5) | 0.0502 (4) | 0.0061 (3) | −0.0059 (3) | −0.0427 (4) |
Cu | 0.0222 (2) | 0.0313 (2) | 0.0364 (3) | 0.00459 (15) | −0.00868 (19) | −0.02337 (19) |
C7 | 0.0331 (13) | 0.0349 (12) | 0.0348 (12) | 0.0080 (10) | −0.0120 (11) | −0.0249 (10) |
Geometric parameters (Å, º) top
C1—O1 | 1.302 (3) | C14—C15 | 1.387 (4) |
C1—C6 | 1.409 (4) | C14—C19 | 1.391 (4) |
C1—C2 | 1.414 (3) | C14—S | 1.769 (3) |
C2—C3 | 1.374 (4) | C15—C16 | 1.379 (4) |
C2—H2 | 0.9300 | C15—H15 | 0.9300 |
C3—C4 | 1.391 (5) | C16—C17 | 1.396 (4) |
C3—H3 | 0.9300 | C16—H16 | 0.9300 |
C4—C5 | 1.371 (4) | C17—C18 | 1.395 (4) |
C4—H4 | 0.9300 | C17—C20 | 1.490 (4) |
C5—C6 | 1.407 (3) | C18—C19 | 1.374 (4) |
C5—H5 | 0.9300 | C18—H18 | 0.9300 |
C6—C7 | 1.430 (3) | C19—H19 | 0.9300 |
C8—C9 | 1.385 (3) | C20—O2 | 1.217 (4) |
C8—C13 | 1.388 (3) | C20—C21 | 1.504 (4) |
C8—N | 1.436 (3) | C21—H21A | 0.9600 |
C9—C10 | 1.387 (4) | C21—H21B | 0.9600 |
C9—H9 | 0.9300 | C21—H21C | 0.9600 |
C10—C11 | 1.384 (4) | N—C7 | 1.297 (3) |
C10—H10 | 0.9300 | N—Cu | 2.019 (2) |
C11—C12 | 1.387 (4) | O1—Cu | 1.8817 (18) |
C11—S | 1.780 (3) | Cu—O1i | 1.8817 (18) |
C12—C13 | 1.379 (3) | Cu—Ni | 2.019 (2) |
C12—H12 | 0.9300 | C7—H7 | 0.9300 |
C13—H13 | 0.9300 | | |
| | | |
O1—C1—C6 | 123.8 (2) | C16—C15—C14 | 120.2 (2) |
O1—C1—C2 | 118.4 (2) | C16—C15—H15 | 119.9 |
C6—C1—C2 | 117.8 (2) | C14—C15—H15 | 119.9 |
C3—C2—C1 | 120.8 (3) | C15—C16—C17 | 121.2 (3) |
C3—C2—H2 | 119.6 | C15—C16—H16 | 119.4 |
C1—C2—H2 | 119.6 | C17—C16—H16 | 119.4 |
C2—C3—C4 | 121.4 (3) | C18—C17—C16 | 117.8 (2) |
C2—C3—H3 | 119.3 | C18—C17—C20 | 123.5 (2) |
C4—C3—H3 | 119.3 | C16—C17—C20 | 118.6 (3) |
C5—C4—C3 | 118.8 (3) | C19—C18—C17 | 121.1 (2) |
C5—C4—H4 | 120.6 | C19—C18—H18 | 119.4 |
C3—C4—H4 | 120.6 | C17—C18—H18 | 119.4 |
C4—C5—C6 | 121.4 (3) | C18—C19—C14 | 120.4 (3) |
C4—C5—H5 | 119.3 | C18—C19—H19 | 119.8 |
C6—C5—H5 | 119.3 | C14—C19—H19 | 119.8 |
C5—C6—C1 | 119.8 (2) | O2—C20—C17 | 120.5 (3) |
C5—C6—C7 | 117.6 (2) | O2—C20—C21 | 120.4 (3) |
C1—C6—C7 | 122.6 (2) | C17—C20—C21 | 119.2 (3) |
C9—C8—C13 | 119.8 (2) | C20—C21—H21A | 109.5 |
C9—C8—N | 120.5 (2) | C20—C21—H21B | 109.5 |
C13—C8—N | 119.7 (2) | H21A—C21—H21B | 109.5 |
C8—C9—C10 | 120.0 (2) | C20—C21—H21C | 109.5 |
C8—C9—H9 | 120.0 | H21A—C21—H21C | 109.5 |
C10—C9—H9 | 120.0 | H21B—C21—H21C | 109.5 |
C11—C10—C9 | 120.0 (2) | C7—N—C8 | 115.35 (19) |
C11—C10—H10 | 120.0 | C7—N—Cu | 123.59 (16) |
C9—C10—H10 | 120.0 | C8—N—Cu | 120.55 (14) |
C10—C11—C12 | 119.9 (2) | C1—O1—Cu | 130.51 (17) |
C10—C11—S | 120.00 (19) | C14—S—C11 | 102.10 (12) |
C12—C11—S | 120.1 (2) | O1—Cu—O1i | 180.00 (15) |
C13—C12—C11 | 120.2 (2) | O1—Cu—N | 91.38 (8) |
C13—C12—H12 | 119.9 | O1i—Cu—N | 88.62 (8) |
C11—C12—H12 | 119.9 | O1—Cu—Ni | 88.62 (8) |
C12—C13—C8 | 120.1 (2) | O1i—Cu—Ni | 91.38 (8) |
C12—C13—H13 | 119.9 | N—Cu—Ni | 180.0 |
C8—C13—H13 | 119.9 | N—C7—C6 | 126.9 (2) |
C15—C14—C19 | 119.2 (2) | N—C7—H7 | 116.6 |
C15—C14—S | 123.2 (2) | C6—C7—H7 | 116.6 |
C19—C14—S | 117.7 (2) | | |
| | | |
O1—C1—C2—C3 | 177.5 (3) | C15—C14—C19—C18 | 1.8 (4) |
C6—C1—C2—C3 | −1.8 (4) | S—C14—C19—C18 | −178.77 (19) |
C1—C2—C3—C4 | −0.1 (5) | C18—C17—C20—O2 | −163.9 (3) |
C2—C3—C4—C5 | 1.8 (5) | C16—C17—C20—O2 | 13.4 (4) |
C3—C4—C5—C6 | −1.5 (5) | C18—C17—C20—C21 | 15.5 (4) |
C4—C5—C6—C1 | −0.3 (4) | C16—C17—C20—C21 | −167.1 (2) |
C4—C5—C6—C7 | −180.0 (3) | C9—C8—N—C7 | 59.5 (3) |
O1—C1—C6—C5 | −177.3 (2) | C13—C8—N—C7 | −120.8 (3) |
C2—C1—C6—C5 | 2.0 (4) | C9—C8—N—Cu | −112.5 (2) |
O1—C1—C6—C7 | 2.4 (4) | C13—C8—N—Cu | 67.1 (3) |
C2—C1—C6—C7 | −178.4 (2) | C6—C1—O1—Cu | 5.6 (4) |
C13—C8—C9—C10 | −1.2 (4) | C2—C1—O1—Cu | −173.65 (19) |
N—C8—C9—C10 | 178.4 (2) | C15—C14—S—C11 | −24.0 (2) |
C8—C9—C10—C11 | 0.9 (4) | C19—C14—S—C11 | 156.7 (2) |
C9—C10—C11—C12 | 0.6 (4) | C10—C11—S—C14 | 100.3 (2) |
C9—C10—C11—S | 179.2 (2) | C12—C11—S—C14 | −81.1 (2) |
C10—C11—C12—C13 | −1.8 (4) | C1—O1—Cu—O1i | 120 (10) |
S—C11—C12—C13 | 179.6 (2) | C1—O1—Cu—N | −10.3 (2) |
C11—C12—C13—C8 | 1.4 (4) | C1—O1—Cu—Ni | 169.7 (2) |
C9—C8—C13—C12 | 0.1 (4) | C7—N—Cu—O1 | 11.1 (2) |
N—C8—C13—C12 | −179.5 (2) | C8—N—Cu—O1 | −177.48 (17) |
C19—C14—C15—C16 | −3.7 (4) | C7—N—Cu—O1i | −168.9 (2) |
S—C14—C15—C16 | 176.9 (2) | C8—N—Cu—O1i | 2.52 (17) |
C14—C15—C16—C17 | 2.4 (4) | C7—N—Cu—Ni | −4 (100) |
C15—C16—C17—C18 | 0.7 (4) | C8—N—Cu—Ni | 167 (10) |
C15—C16—C17—C20 | −176.8 (2) | C8—N—C7—C6 | −179.9 (2) |
C16—C17—C18—C19 | −2.6 (4) | Cu—N—C7—C6 | −8.1 (4) |
C20—C17—C18—C19 | 174.8 (2) | C5—C6—C7—N | 179.2 (2) |
C17—C18—C19—C14 | 1.3 (4) | C1—C6—C7—N | −0.4 (4) |
Symmetry code: (i) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2ii | 0.93 | 2.60 | 3.462 (5) | 154 |
C9—H9···O2iii | 0.93 | 2.73 | 3.550 (3) | 147 |
Symmetry codes: (ii) x+1, y+1, z; (iii) −x−1, −y+1, −z. |
Dihedral angles (°) between the four planes present in (I) topPlanes | P1 | P2 | P3 | P4 |
P1 | 0 | - | - | - |
P2 | 6.21 (7) | 0 | - | - |
P3 | 65.10 (6) | 58.91 (8) | 0 | - |
P4 | 30.13 (7) | 33.78 (9) | 84.12 (8) | 0 |
Notes: P1 = Cu/O1/C1/C6/C7/N, coordination plane containing Cu atom;
P2 = C1–C6, phenyl ring of the iminomethylphenolate;
P3 = C8–C13, phenyl ring (4) of the diphenylsulfane;
P4 = C14–C19, phenyl ring (4') of the diphenylsulfane. |