Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025342/rz2144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025342/rz2144Isup2.hkl |
CCDC reference: 654721
5-Nitrosalicylaldehyde (0.1 mmol, 16.5 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg), and copper acetate monohydrate (0.1 mmol, 20.0 mg) were dissolved in an acetonitrile solution (10 ml). The mixture was stirred at room temperature for 10 min, giving a clear blue solution. Crystals of the title compound were formed by slow evaporation of the solvent over a week at room temperature.
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) = 1.2 or 1.5Ueq(C).
Recently, we have reported a thiocyanate coordinated zinc(II) complex (Ye & You, 2007). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title compound, (I).
The CuII atom in (I) is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff base ligand and one N atom of the thiocyanate ligand defining the basal plane, and the N atom of the acetonitrile group occupying the apical position (Fig. 1). Selected bond distances and angles within the coordination sphere of the metal are given in Table 1. The molecular and crystal structures are stabilized by C—H···N and C—H···O hydrogen bonds (Table 2).
For related literature, see: Ye & You (2007); Hu et al. (2005).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of the title compound, shown with 30% probability displacement ellipsoids. |
[Cu(C12H16N3O3)(NCS)(C2H3N)] | F(000) = 852 |
Mr = 412.95 | Dx = 1.487 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3875 reflections |
a = 12.507 (2) Å | θ = 2.3–24.5° |
b = 11.552 (1) Å | µ = 1.32 mm−1 |
c = 12.787 (2) Å | T = 298 K |
β = 93.543 (1)° | Block, blue |
V = 1844.0 (4) Å3 | 0.23 × 0.21 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4186 independent reflections |
Radiation source: fine-focus sealed tube | 3143 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→16 |
Tmin = 0.745, Tmax = 0.770 | k = −14→14 |
15401 measured reflections | l = −16→16 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.3686P] where P = (Fo2 + 2Fc2)/3 |
4186 reflections | (Δ/σ)max < 0.001 |
229 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Cu(C12H16N3O3)(NCS)(C2H3N)] | V = 1844.0 (4) Å3 |
Mr = 412.95 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.507 (2) Å | µ = 1.32 mm−1 |
b = 11.552 (1) Å | T = 298 K |
c = 12.787 (2) Å | 0.23 × 0.21 × 0.20 mm |
β = 93.543 (1)° |
Bruker SMART CCD area-detector diffractometer | 4186 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3143 reflections with I > 2σ(I) |
Tmin = 0.745, Tmax = 0.770 | Rint = 0.035 |
15401 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.31 e Å−3 |
4186 reflections | Δρmin = −0.25 e Å−3 |
229 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 | 0.21596 (2) | 0.93882 (2) | 0.25457 (2) | 0.04336 (11) | |
S1 | 0.26057 (7) | 0.83713 (8) | −0.09663 (6) | 0.0811 (3) | |
O1 | 0.36548 (13) | 0.89111 (16) | 0.27255 (15) | 0.0596 (5) | |
O2 | 0.68408 (15) | 1.2638 (2) | 0.4508 (2) | 0.0856 (7) | |
O3 | 0.79311 (14) | 1.1489 (2) | 0.38151 (18) | 0.0819 (7) | |
N1 | 0.23620 (14) | 1.03387 (16) | 0.38324 (14) | 0.0414 (4) | |
N2 | 0.06710 (15) | 1.01357 (17) | 0.21204 (15) | 0.0452 (5) | |
N3 | 0.14008 (19) | 0.7828 (2) | 0.3335 (2) | 0.0679 (6) | |
N4 | 0.22514 (18) | 0.8813 (2) | 0.11039 (18) | 0.0656 (6) | |
N5 | 0.70235 (15) | 1.1749 (2) | 0.40349 (17) | 0.0544 (5) | |
C1 | 0.42878 (17) | 1.05305 (18) | 0.37335 (17) | 0.0387 (5) | |
C2 | 0.44268 (19) | 0.95528 (19) | 0.30748 (19) | 0.0448 (5) | |
C3 | 0.5498 (2) | 0.9310 (2) | 0.2819 (2) | 0.0561 (7) | |
H3 | 0.5630 | 0.8650 | 0.2431 | 0.067* | |
C4 | 0.63293 (19) | 1.0008 (2) | 0.31240 (19) | 0.0537 (6) | |
H4 | 0.7016 | 0.9838 | 0.2929 | 0.064* | |
C5 | 0.61515 (17) | 1.0982 (2) | 0.37302 (18) | 0.0437 (5) | |
C6 | 0.51490 (17) | 1.1218 (2) | 0.40523 (17) | 0.0414 (5) | |
H6 | 0.5049 | 1.1847 | 0.4490 | 0.050* | |
C7 | 0.32677 (18) | 1.07729 (19) | 0.41476 (18) | 0.0408 (5) | |
H7 | 0.3266 | 1.1297 | 0.4699 | 0.049* | |
C8 | 0.14448 (19) | 1.0635 (2) | 0.44447 (19) | 0.0508 (6) | |
H8A | 0.1690 | 1.1113 | 0.5035 | 0.061* | |
H8B | 0.1146 | 0.9930 | 0.4719 | 0.061* | |
C9 | 0.05886 (19) | 1.1266 (2) | 0.3807 (2) | 0.0532 (6) | |
H9A | 0.0908 | 1.1918 | 0.3463 | 0.064* | |
H9B | 0.0072 | 1.1570 | 0.4271 | 0.064* | |
C10 | 0.00110 (19) | 1.0514 (2) | 0.2987 (2) | 0.0545 (6) | |
H10A | −0.0255 | 0.9831 | 0.3328 | 0.065* | |
H10B | −0.0604 | 1.0937 | 0.2687 | 0.065* | |
C11 | 0.0905 (2) | 1.1145 (2) | 0.1461 (2) | 0.0619 (7) | |
H11A | 0.0247 | 1.1522 | 0.1234 | 0.093* | |
H11B | 0.1265 | 1.0890 | 0.0860 | 0.093* | |
H11C | 0.1356 | 1.1678 | 0.1860 | 0.093* | |
C12 | −0.0019 (2) | 0.9324 (2) | 0.1481 (2) | 0.0624 (7) | |
H12A | −0.0136 | 0.8636 | 0.1879 | 0.094* | |
H12B | 0.0328 | 0.9124 | 0.0856 | 0.094* | |
H12C | −0.0694 | 0.9687 | 0.1294 | 0.094* | |
C13 | 0.24112 (19) | 0.8638 (2) | 0.0250 (2) | 0.0520 (6) | |
C14 | 0.1136 (2) | 0.7100 (2) | 0.3835 (2) | 0.0528 (6) | |
C15 | 0.0798 (2) | 0.6164 (3) | 0.4485 (2) | 0.0713 (8) | |
H15A | 0.1241 | 0.6145 | 0.5125 | 0.107* | |
H15B | 0.0862 | 0.5444 | 0.4120 | 0.107* | |
H15C | 0.0065 | 0.6281 | 0.4641 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.04219 (18) | 0.04213 (18) | 0.04608 (18) | −0.00245 (12) | 0.00523 (12) | −0.00212 (12) |
S1 | 0.1006 (6) | 0.0958 (6) | 0.0481 (4) | 0.0151 (5) | 0.0143 (4) | 0.0046 (4) |
O1 | 0.0443 (10) | 0.0475 (10) | 0.0868 (13) | 0.0035 (8) | 0.0027 (9) | −0.0201 (9) |
O2 | 0.0455 (11) | 0.0814 (15) | 0.128 (2) | −0.0016 (10) | −0.0067 (11) | −0.0378 (14) |
O3 | 0.0350 (10) | 0.1144 (18) | 0.0968 (16) | 0.0000 (11) | 0.0085 (10) | −0.0257 (14) |
N1 | 0.0392 (10) | 0.0449 (11) | 0.0406 (10) | 0.0004 (8) | 0.0073 (8) | 0.0032 (8) |
N2 | 0.0432 (11) | 0.0459 (11) | 0.0465 (11) | −0.0023 (9) | 0.0029 (9) | 0.0004 (9) |
N3 | 0.0707 (15) | 0.0561 (14) | 0.0764 (16) | −0.0128 (12) | 0.0011 (12) | 0.0113 (13) |
N4 | 0.0653 (15) | 0.0780 (16) | 0.0540 (14) | 0.0053 (13) | 0.0064 (11) | −0.0135 (12) |
N5 | 0.0352 (11) | 0.0694 (15) | 0.0578 (13) | 0.0048 (10) | −0.0037 (9) | −0.0001 (11) |
C1 | 0.0388 (12) | 0.0389 (12) | 0.0383 (11) | 0.0053 (9) | 0.0010 (9) | 0.0066 (9) |
C2 | 0.0447 (13) | 0.0403 (13) | 0.0493 (13) | 0.0073 (10) | 0.0010 (10) | 0.0019 (10) |
C3 | 0.0479 (14) | 0.0573 (16) | 0.0632 (17) | 0.0129 (12) | 0.0046 (12) | −0.0134 (13) |
C4 | 0.0382 (13) | 0.0689 (17) | 0.0543 (15) | 0.0120 (12) | 0.0053 (11) | 0.0003 (13) |
C5 | 0.0350 (12) | 0.0511 (13) | 0.0446 (13) | 0.0048 (10) | −0.0016 (10) | 0.0060 (11) |
C6 | 0.0385 (12) | 0.0442 (13) | 0.0410 (12) | 0.0080 (10) | −0.0009 (9) | 0.0018 (10) |
C7 | 0.0413 (12) | 0.0425 (13) | 0.0386 (12) | 0.0038 (10) | 0.0026 (9) | 0.0014 (9) |
C8 | 0.0416 (13) | 0.0644 (16) | 0.0475 (13) | −0.0065 (12) | 0.0121 (11) | −0.0042 (12) |
C9 | 0.0407 (13) | 0.0600 (16) | 0.0603 (15) | 0.0010 (12) | 0.0144 (11) | −0.0095 (13) |
C10 | 0.0370 (12) | 0.0663 (17) | 0.0607 (16) | −0.0002 (11) | 0.0069 (11) | −0.0048 (13) |
C11 | 0.0709 (18) | 0.0526 (16) | 0.0627 (17) | 0.0043 (14) | 0.0085 (14) | 0.0101 (13) |
C12 | 0.0526 (15) | 0.0692 (18) | 0.0637 (17) | −0.0074 (13) | −0.0101 (13) | −0.0108 (14) |
C13 | 0.0489 (14) | 0.0508 (15) | 0.0563 (16) | 0.0029 (11) | 0.0036 (12) | 0.0008 (12) |
C14 | 0.0508 (14) | 0.0462 (14) | 0.0613 (16) | −0.0044 (12) | 0.0015 (12) | −0.0010 (13) |
C15 | 0.079 (2) | 0.0554 (17) | 0.080 (2) | −0.0118 (16) | 0.0143 (16) | 0.0121 (15) |
Cu1—O1 | 1.950 (2) | C4—C5 | 1.391 (4) |
Cu1—N4 | 1.970 (2) | C4—H4 | 0.9300 |
Cu1—N1 | 1.981 (2) | C5—C6 | 1.371 (3) |
Cu1—N2 | 2.093 (2) | C6—H6 | 0.9300 |
Cu1—N3 | 2.299 (2) | C7—H7 | 0.9300 |
S1—C13 | 1.618 (3) | C8—C9 | 1.495 (3) |
O1—C2 | 1.276 (3) | C8—H8A | 0.9700 |
O2—N5 | 1.220 (3) | C8—H8B | 0.9700 |
O3—N5 | 1.224 (3) | C9—C10 | 1.511 (3) |
N1—C7 | 1.281 (3) | C9—H9A | 0.9700 |
N1—C8 | 1.469 (3) | C9—H9B | 0.9700 |
N2—C11 | 1.479 (3) | C10—H10A | 0.9700 |
N2—C12 | 1.485 (3) | C10—H10B | 0.9700 |
N2—C10 | 1.487 (3) | C11—H11A | 0.9600 |
N3—C14 | 1.119 (3) | C11—H11B | 0.9600 |
N4—C13 | 1.140 (3) | C11—H11C | 0.9600 |
N5—C5 | 1.441 (3) | C12—H12A | 0.9600 |
C1—C6 | 1.379 (3) | C12—H12B | 0.9600 |
C1—C2 | 1.426 (3) | C12—H12C | 0.9600 |
C1—C7 | 1.439 (3) | C14—C15 | 1.443 (4) |
C2—C3 | 1.427 (3) | C15—H15A | 0.9600 |
C3—C4 | 1.354 (4) | C15—H15B | 0.9600 |
C3—H3 | 0.9300 | C15—H15C | 0.9600 |
O1—Cu1—N4 | 84.49 (9) | C1—C6—H6 | 119.7 |
O1—Cu1—N1 | 89.22 (7) | N1—C7—C1 | 126.5 (2) |
N4—Cu1—N1 | 162.26 (9) | N1—C7—H7 | 116.7 |
O1—Cu1—N2 | 168.09 (8) | C1—C7—H7 | 116.7 |
N4—Cu1—N2 | 89.91 (9) | N1—C8—C9 | 112.3 (2) |
N1—Cu1—N2 | 93.04 (7) | N1—C8—H8A | 109.1 |
O1—Cu1—N3 | 98.37 (8) | C9—C8—H8A | 109.1 |
N4—Cu1—N3 | 101.30 (10) | N1—C8—H8B | 109.1 |
N1—Cu1—N3 | 96.01 (8) | C9—C8—H8B | 109.1 |
N2—Cu1—N3 | 93.03 (8) | H8A—C8—H8B | 107.9 |
C2—O1—Cu1 | 125.21 (15) | C8—C9—C10 | 113.2 (2) |
C7—N1—C8 | 116.47 (19) | C8—C9—H9A | 108.9 |
C7—N1—Cu1 | 122.92 (15) | C10—C9—H9A | 108.9 |
C8—N1—Cu1 | 120.52 (15) | C8—C9—H9B | 108.9 |
C11—N2—C12 | 108.2 (2) | C10—C9—H9B | 108.9 |
C11—N2—C10 | 109.4 (2) | H9A—C9—H9B | 107.8 |
C12—N2—C10 | 105.38 (19) | N2—C10—C9 | 115.0 (2) |
C11—N2—Cu1 | 105.60 (15) | N2—C10—H10A | 108.5 |
C12—N2—Cu1 | 111.08 (16) | C9—C10—H10A | 108.5 |
C10—N2—Cu1 | 116.96 (15) | N2—C10—H10B | 108.5 |
C14—N3—Cu1 | 170.0 (2) | C9—C10—H10B | 108.5 |
C13—N4—Cu1 | 168.5 (3) | H10A—C10—H10B | 107.5 |
O2—N5—O3 | 121.7 (2) | N2—C11—H11A | 109.5 |
O2—N5—C5 | 119.4 (2) | N2—C11—H11B | 109.5 |
O3—N5—C5 | 118.9 (2) | H11A—C11—H11B | 109.5 |
C6—C1—C2 | 120.6 (2) | N2—C11—H11C | 109.5 |
C6—C1—C7 | 118.2 (2) | H11A—C11—H11C | 109.5 |
C2—C1—C7 | 121.0 (2) | H11B—C11—H11C | 109.5 |
O1—C2—C1 | 123.3 (2) | N2—C12—H12A | 109.5 |
O1—C2—C3 | 120.4 (2) | N2—C12—H12B | 109.5 |
C1—C2—C3 | 116.2 (2) | H12A—C12—H12B | 109.5 |
C4—C3—C2 | 122.1 (2) | N2—C12—H12C | 109.5 |
C4—C3—H3 | 118.9 | H12A—C12—H12C | 109.5 |
C2—C3—H3 | 118.9 | H12B—C12—H12C | 109.5 |
C3—C4—C5 | 119.7 (2) | N4—C13—S1 | 178.4 (3) |
C3—C4—H4 | 120.1 | N3—C14—C15 | 179.7 (3) |
C5—C4—H4 | 120.1 | C14—C15—H15A | 109.5 |
C6—C5—C4 | 120.6 (2) | C14—C15—H15B | 109.5 |
C6—C5—N5 | 119.2 (2) | H15A—C15—H15B | 109.5 |
C4—C5—N5 | 120.2 (2) | C14—C15—H15C | 109.5 |
C5—C6—C1 | 120.6 (2) | H15A—C15—H15C | 109.5 |
C5—C6—H6 | 119.7 | H15B—C15—H15C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···N4 | 0.96 | 2.43 | 2.969 (3) | 115 |
C10—H10B···O3i | 0.97 | 2.48 | 3.082 (3) | 120 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H16N3O3)(NCS)(C2H3N)] |
Mr | 412.95 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 12.507 (2), 11.552 (1), 12.787 (2) |
β (°) | 93.543 (1) |
V (Å3) | 1844.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.23 × 0.21 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.745, 0.770 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15401, 4186, 3143 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.02 |
No. of reflections | 4186 |
No. of parameters | 229 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.25 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
Cu1—O1 | 1.950 (2) | Cu1—N2 | 2.093 (2) |
Cu1—N4 | 1.970 (2) | Cu1—N3 | 2.299 (2) |
Cu1—N1 | 1.981 (2) | ||
O1—Cu1—N4 | 84.49 (9) | N1—Cu1—N2 | 93.04 (7) |
O1—Cu1—N1 | 89.22 (7) | O1—Cu1—N3 | 98.37 (8) |
N4—Cu1—N1 | 162.26 (9) | N4—Cu1—N3 | 101.30 (10) |
O1—Cu1—N2 | 168.09 (8) | N1—Cu1—N3 | 96.01 (8) |
N4—Cu1—N2 | 89.91 (9) | N2—Cu1—N3 | 93.03 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···N4 | 0.96 | 2.43 | 2.969 (3) | 114.9 |
C10—H10B···O3i | 0.97 | 2.48 | 3.082 (3) | 119.7 |
Symmetry code: (i) x−1, y, z. |
Recently, we have reported a thiocyanate coordinated zinc(II) complex (Ye & You, 2007). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title compound, (I).
The CuII atom in (I) is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff base ligand and one N atom of the thiocyanate ligand defining the basal plane, and the N atom of the acetonitrile group occupying the apical position (Fig. 1). Selected bond distances and angles within the coordination sphere of the metal are given in Table 1. The molecular and crystal structures are stabilized by C—H···N and C—H···O hydrogen bonds (Table 2).