Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041505/sj2338sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041505/sj2338Isup2.hkl |
CCDC reference: 660170
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.072
- wR factor = 0.179
- Data-to-parameter ratio = 18.3
checkCIF/PLATON results
No syntax errors found
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.134 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.13 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C19 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (3) 2.73
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
2-Hydroxy-1-naphthaldehyde (0.1 mmol, 17.0 mg), 2-piperidin-1-ylethylamine (0.1 mmol, 12.7 mg), ammonium thiocyanate (0.1 mmol, 7.5 mg), and Ni(NO3)2·6H2O (0.1 mmol, 29.0 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a red solution. After keeping the solution in air for a week, red block-like crystals were formed.
H atoms were placed in calculated 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).
Nickel(II) complexes with Schiff base ligands have received much attention in recent years (Marganian et al., 1995). Some of the complexes have been found to have pharmacological and antitumor properties (Brückner et al., 2000; Harrop et al., 2003; Ren et al., 2002). Nickel is also present in the active sites of several important classes of metalloproteins, as either a homodinuclear or a heterodinuclear species. As part of our research programme on metal complexes of Schiff base ligands (Diao et al., 2007; Diao, 2007; Li, Huang et al., 2007) we report here the structure of the title compound (I) Fig.1.
The NiII atom in the mononuclear complex is four-coordinate in a square-planar geometry with one phenolate O, one imine N, and one amine N atom of the Schiff base ligand and one terminal N atom of a thiocyanate anion in the coordination sphere (Fig. 1). Bond lengths and angles about the Ni(II) centre are comparable with the values observed in other Schiff base Ni(II) complexes (Arıcı et al., 2005; Li, Jiang et al., 2007; Li, Huang et al., 2007; Usman et al., 2003; Van Hecke et al., 2007).
For the coordination chemistry and biological properties of nickel(II) complexes with Schiff base ligands, see Brückner et al. (2000); Harrop et al. (2003); Marganian et al. (1995); Ren et al. (2002). For related structures, see Arıcı et al. (2005); Diao (2007); Diao et al. (2007); Li, Huang et al. (2007); Li, Jiang et al. (2007); Usman et al. (2003); Van Hecke et al. (2007).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of the complex with displacement parameters drawn at the 30% probability level. |
[Ni(C18H21N2O)(NCS)] | F(000) = 832 |
Mr = 398.16 | Dx = 1.445 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 539 reflections |
a = 11.663 (2) Å | θ = 2.3–24.5° |
b = 12.530 (3) Å | µ = 1.19 mm−1 |
c = 13.484 (3) Å | T = 298 K |
β = 111.77 (3)° | Block, red |
V = 1830.0 (6) Å3 | 0.20 × 0.20 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4144 independent reflections |
Radiation source: fine-focus sealed tube | 2157 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.134 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→15 |
Tmin = 0.797, Tmax = 0.824 | k = −15→16 |
15376 measured reflections | l = −17→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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0415P)2] where P = (Fo2 + 2Fc2)/3 |
4144 reflections | (Δ/σ)max < 0.001 |
226 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Ni(C18H21N2O)(NCS)] | V = 1830.0 (6) Å3 |
Mr = 398.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.663 (2) Å | µ = 1.19 mm−1 |
b = 12.530 (3) Å | T = 298 K |
c = 13.484 (3) Å | 0.20 × 0.20 × 0.17 mm |
β = 111.77 (3)° |
Bruker SMART CCD area-detector diffractometer | 4144 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2157 reflections with I > 2σ(I) |
Tmin = 0.797, Tmax = 0.824 | Rint = 0.134 |
15376 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.36 e Å−3 |
4144 reflections | Δρmin = −0.34 e Å−3 |
226 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 | ||
Ni1 | 0.81734 (6) | 0.61182 (5) | 0.21941 (5) | 0.0371 (2) | |
S1 | 1.23098 (15) | 0.52220 (16) | 0.36976 (15) | 0.0681 (5) | |
O1 | 0.7816 (3) | 0.5295 (3) | 0.0990 (3) | 0.0444 (10) | |
N1 | 0.6722 (4) | 0.6864 (3) | 0.1645 (3) | 0.0389 (11) | |
N2 | 0.8531 (4) | 0.6987 (3) | 0.3496 (3) | 0.0361 (10) | |
N3 | 0.9770 (5) | 0.5519 (4) | 0.2725 (4) | 0.0507 (13) | |
C1 | 0.5878 (4) | 0.6076 (4) | −0.0116 (4) | 0.0335 (12) | |
C2 | 0.6857 (5) | 0.5347 (4) | 0.0089 (4) | 0.0360 (12) | |
C3 | 0.6827 (5) | 0.4611 (5) | −0.0724 (5) | 0.0478 (15) | |
H3 | 0.7444 | 0.4097 | −0.0578 | 0.057* | |
C4 | 0.5922 (5) | 0.4642 (5) | −0.1701 (5) | 0.0476 (15) | |
H4 | 0.5945 | 0.4159 | −0.2217 | 0.057* | |
C5 | 0.4938 (5) | 0.5387 (4) | −0.1970 (4) | 0.0438 (14) | |
C6 | 0.4020 (6) | 0.5438 (5) | −0.3007 (5) | 0.0590 (18) | |
H6 | 0.4058 | 0.4970 | −0.3529 | 0.071* | |
C7 | 0.3085 (7) | 0.6156 (6) | −0.3258 (6) | 0.074 (2) | |
H7 | 0.2492 | 0.6186 | −0.3946 | 0.089* | |
C8 | 0.3022 (6) | 0.6849 (6) | −0.2471 (6) | 0.071 (2) | |
H8 | 0.2371 | 0.7330 | −0.2635 | 0.085* | |
C9 | 0.3904 (5) | 0.6832 (5) | −0.1457 (5) | 0.0532 (16) | |
H9 | 0.3845 | 0.7310 | −0.0950 | 0.064* | |
C10 | 0.4894 (5) | 0.6110 (4) | −0.1168 (4) | 0.0404 (13) | |
C11 | 0.5856 (5) | 0.6796 (4) | 0.0688 (4) | 0.0396 (13) | |
H11 | 0.5181 | 0.7252 | 0.0527 | 0.048* | |
C12 | 0.6534 (5) | 0.7687 (5) | 0.2368 (5) | 0.0501 (16) | |
H12A | 0.5671 | 0.7723 | 0.2280 | 0.060* | |
H12B | 0.6789 | 0.8384 | 0.2211 | 0.060* | |
C13 | 0.7314 (5) | 0.7350 (5) | 0.3487 (5) | 0.0517 (16) | |
H13A | 0.7425 | 0.7945 | 0.3974 | 0.062* | |
H13B | 0.6912 | 0.6775 | 0.3715 | 0.062* | |
C14 | 0.9339 (5) | 0.7901 (4) | 0.3413 (4) | 0.0392 (13) | |
H14A | 1.0082 | 0.7611 | 0.3355 | 0.047* | |
H14B | 0.8903 | 0.8297 | 0.2764 | 0.047* | |
C15 | 0.9699 (5) | 0.8657 (4) | 0.4346 (4) | 0.0470 (15) | |
H15A | 0.8968 | 0.9023 | 0.4349 | 0.056* | |
H15B | 1.0260 | 0.9190 | 0.4262 | 0.056* | |
C16 | 1.0315 (6) | 0.8091 (4) | 0.5405 (4) | 0.0506 (16) | |
H16A | 1.0434 | 0.8589 | 0.5985 | 0.061* | |
H16B | 1.1120 | 0.7831 | 0.5458 | 0.061* | |
C17 | 0.9519 (6) | 0.7147 (5) | 0.5505 (4) | 0.0524 (16) | |
H17A | 0.9968 | 0.6744 | 0.6146 | 0.063* | |
H17B | 0.8768 | 0.7415 | 0.5565 | 0.063* | |
C18 | 0.9195 (6) | 0.6420 (4) | 0.4537 (4) | 0.0483 (15) | |
H18A | 0.9947 | 0.6108 | 0.4519 | 0.058* | |
H18B | 0.8678 | 0.5843 | 0.4612 | 0.058* | |
C19 | 1.0826 (6) | 0.5392 (4) | 0.3121 (4) | 0.0397 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0348 (4) | 0.0382 (4) | 0.0377 (4) | 0.0019 (3) | 0.0127 (3) | −0.0044 (3) |
S1 | 0.0411 (10) | 0.0882 (14) | 0.0700 (12) | 0.0021 (9) | 0.0149 (9) | −0.0089 (10) |
O1 | 0.037 (2) | 0.047 (2) | 0.045 (2) | 0.0026 (18) | 0.0097 (19) | −0.0137 (18) |
N1 | 0.040 (3) | 0.039 (3) | 0.036 (3) | 0.004 (2) | 0.012 (2) | −0.003 (2) |
N2 | 0.037 (3) | 0.037 (3) | 0.040 (3) | −0.002 (2) | 0.020 (2) | −0.004 (2) |
N3 | 0.039 (3) | 0.061 (3) | 0.042 (3) | 0.012 (3) | 0.004 (2) | −0.009 (2) |
C1 | 0.033 (3) | 0.033 (3) | 0.034 (3) | −0.004 (3) | 0.012 (2) | 0.001 (2) |
C2 | 0.036 (3) | 0.036 (3) | 0.039 (3) | −0.005 (3) | 0.017 (3) | −0.004 (2) |
C3 | 0.046 (4) | 0.048 (4) | 0.054 (4) | 0.001 (3) | 0.023 (3) | −0.012 (3) |
C4 | 0.049 (4) | 0.049 (4) | 0.045 (4) | −0.006 (3) | 0.017 (3) | −0.017 (3) |
C5 | 0.051 (4) | 0.040 (3) | 0.042 (3) | −0.012 (3) | 0.019 (3) | −0.002 (3) |
C6 | 0.068 (5) | 0.056 (4) | 0.039 (4) | −0.019 (4) | 0.003 (3) | −0.004 (3) |
C7 | 0.069 (5) | 0.067 (5) | 0.061 (5) | −0.014 (4) | −0.005 (4) | 0.005 (4) |
C8 | 0.065 (5) | 0.062 (5) | 0.063 (5) | 0.004 (4) | −0.003 (4) | 0.007 (4) |
C9 | 0.055 (4) | 0.056 (4) | 0.042 (4) | −0.007 (3) | 0.010 (3) | 0.003 (3) |
C10 | 0.041 (3) | 0.039 (3) | 0.046 (3) | −0.004 (3) | 0.021 (3) | 0.006 (3) |
C11 | 0.039 (3) | 0.038 (3) | 0.043 (3) | 0.003 (3) | 0.015 (3) | 0.003 (3) |
C12 | 0.045 (4) | 0.046 (4) | 0.061 (4) | 0.005 (3) | 0.022 (3) | −0.021 (3) |
C13 | 0.046 (4) | 0.062 (4) | 0.053 (4) | −0.003 (3) | 0.024 (3) | −0.015 (3) |
C14 | 0.043 (3) | 0.039 (3) | 0.039 (3) | −0.006 (3) | 0.018 (3) | −0.002 (3) |
C15 | 0.048 (4) | 0.043 (4) | 0.044 (3) | −0.002 (3) | 0.010 (3) | −0.003 (3) |
C16 | 0.064 (4) | 0.040 (3) | 0.040 (4) | −0.007 (3) | 0.010 (3) | −0.006 (3) |
C17 | 0.072 (4) | 0.050 (4) | 0.038 (3) | −0.002 (3) | 0.023 (3) | −0.004 (3) |
C18 | 0.062 (4) | 0.044 (4) | 0.041 (3) | −0.007 (3) | 0.022 (3) | 0.008 (3) |
C19 | 0.053 (4) | 0.035 (3) | 0.029 (3) | 0.007 (3) | 0.013 (3) | −0.007 (2) |
Ni1—N1 | 1.832 (4) | C7—H7 | 0.9300 |
Ni1—O1 | 1.836 (3) | C8—C9 | 1.373 (8) |
Ni1—N3 | 1.886 (5) | C8—H8 | 0.9300 |
Ni1—N2 | 1.975 (4) | C9—C10 | 1.404 (8) |
S1—C19 | 1.627 (6) | C9—H9 | 0.9300 |
O1—C2 | 1.314 (6) | C11—H11 | 0.9300 |
N1—C11 | 1.314 (6) | C12—C13 | 1.505 (8) |
N1—C12 | 1.489 (6) | C12—H12A | 0.9700 |
N2—C13 | 1.486 (7) | C12—H12B | 0.9700 |
N2—C18 | 1.506 (6) | C13—H13A | 0.9700 |
N2—C14 | 1.513 (6) | C13—H13B | 0.9700 |
N3—C19 | 1.157 (7) | C14—C15 | 1.505 (7) |
C1—C2 | 1.407 (7) | C14—H14A | 0.9700 |
C1—C11 | 1.418 (7) | C14—H14B | 0.9700 |
C1—C10 | 1.457 (7) | C15—C16 | 1.516 (7) |
C2—C3 | 1.423 (7) | C15—H15A | 0.9700 |
C3—C4 | 1.349 (7) | C15—H15B | 0.9700 |
C3—H3 | 0.9300 | C16—C17 | 1.540 (8) |
C4—C5 | 1.418 (8) | C16—H16A | 0.9700 |
C4—H4 | 0.9300 | C16—H16B | 0.9700 |
C5—C6 | 1.412 (8) | C17—C18 | 1.519 (7) |
C5—C10 | 1.425 (7) | C17—H17A | 0.9700 |
C6—C7 | 1.357 (9) | C17—H17B | 0.9700 |
C6—H6 | 0.9300 | C18—H18A | 0.9700 |
C7—C8 | 1.394 (10) | C18—H18B | 0.9700 |
N1—Ni1—O1 | 93.25 (18) | N1—C11—C1 | 124.5 (5) |
N1—Ni1—N3 | 172.3 (2) | N1—C11—H11 | 117.7 |
O1—Ni1—N3 | 88.87 (18) | C1—C11—H11 | 117.7 |
N1—Ni1—N2 | 86.38 (18) | N1—C12—C13 | 106.3 (4) |
O1—Ni1—N2 | 178.83 (17) | N1—C12—H12A | 110.5 |
N3—Ni1—N2 | 91.64 (19) | C13—C12—H12A | 110.5 |
C2—O1—Ni1 | 128.8 (3) | N1—C12—H12B | 110.5 |
C11—N1—C12 | 116.2 (4) | C13—C12—H12B | 110.5 |
C11—N1—Ni1 | 128.5 (4) | H12A—C12—H12B | 108.7 |
C12—N1—Ni1 | 115.3 (3) | N2—C13—C12 | 108.4 (4) |
C13—N2—C18 | 108.1 (4) | N2—C13—H13A | 110.0 |
C13—N2—C14 | 112.8 (4) | C12—C13—H13A | 110.0 |
C18—N2—C14 | 107.9 (4) | N2—C13—H13B | 110.0 |
C13—N2—Ni1 | 106.0 (3) | C12—C13—H13B | 110.0 |
C18—N2—Ni1 | 115.8 (3) | H13A—C13—H13B | 108.4 |
C14—N2—Ni1 | 106.5 (3) | C15—C14—N2 | 113.8 (4) |
C19—N3—Ni1 | 164.1 (5) | C15—C14—H14A | 108.8 |
C2—C1—C11 | 120.4 (5) | N2—C14—H14A | 108.8 |
C2—C1—C10 | 119.9 (5) | C15—C14—H14B | 108.8 |
C11—C1—C10 | 119.7 (5) | N2—C14—H14B | 108.8 |
O1—C2—C1 | 124.4 (5) | H14A—C14—H14B | 107.7 |
O1—C2—C3 | 116.7 (5) | C14—C15—C16 | 112.4 (5) |
C1—C2—C3 | 118.9 (5) | C14—C15—H15A | 109.1 |
C4—C3—C2 | 121.3 (5) | C16—C15—H15A | 109.1 |
C4—C3—H3 | 119.3 | C14—C15—H15B | 109.1 |
C2—C3—H3 | 119.3 | C16—C15—H15B | 109.1 |
C3—C4—C5 | 122.3 (5) | H15A—C15—H15B | 107.9 |
C3—C4—H4 | 118.8 | C15—C16—C17 | 110.6 (5) |
C5—C4—H4 | 118.8 | C15—C16—H16A | 109.5 |
C6—C5—C4 | 121.8 (6) | C17—C16—H16A | 109.5 |
C6—C5—C10 | 119.7 (6) | C15—C16—H16B | 109.5 |
C4—C5—C10 | 118.5 (5) | C17—C16—H16B | 109.5 |
C7—C6—C5 | 121.4 (6) | H16A—C16—H16B | 108.1 |
C7—C6—H6 | 119.3 | C18—C17—C16 | 110.6 (5) |
C5—C6—H6 | 119.3 | C18—C17—H17A | 109.5 |
C6—C7—C8 | 119.1 (6) | C16—C17—H17A | 109.5 |
C6—C7—H7 | 120.4 | C18—C17—H17B | 109.5 |
C8—C7—H7 | 120.4 | C16—C17—H17B | 109.5 |
C9—C8—C7 | 121.2 (7) | H17A—C17—H17B | 108.1 |
C9—C8—H8 | 119.4 | N2—C18—C17 | 113.3 (5) |
C7—C8—H8 | 119.4 | N2—C18—H18A | 108.9 |
C8—C9—C10 | 121.4 (6) | C17—C18—H18A | 108.9 |
C8—C9—H9 | 119.3 | N2—C18—H18B | 108.9 |
C10—C9—H9 | 119.3 | C17—C18—H18B | 108.9 |
C9—C10—C5 | 117.2 (5) | H18A—C18—H18B | 107.7 |
C9—C10—C1 | 123.9 (5) | N3—C19—S1 | 179.0 (5) |
C5—C10—C1 | 118.9 (5) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C18H21N2O)(NCS)] |
Mr | 398.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.663 (2), 12.530 (3), 13.484 (3) |
β (°) | 111.77 (3) |
V (Å3) | 1830.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.20 × 0.20 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.797, 0.824 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15376, 4144, 2157 |
Rint | 0.134 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.179, 0.97 |
No. of reflections | 4144 |
No. of parameters | 226 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.34 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
Nickel(II) complexes with Schiff base ligands have received much attention in recent years (Marganian et al., 1995). Some of the complexes have been found to have pharmacological and antitumor properties (Brückner et al., 2000; Harrop et al., 2003; Ren et al., 2002). Nickel is also present in the active sites of several important classes of metalloproteins, as either a homodinuclear or a heterodinuclear species. As part of our research programme on metal complexes of Schiff base ligands (Diao et al., 2007; Diao, 2007; Li, Huang et al., 2007) we report here the structure of the title compound (I) Fig.1.
The NiII atom in the mononuclear complex is four-coordinate in a square-planar geometry with one phenolate O, one imine N, and one amine N atom of the Schiff base ligand and one terminal N atom of a thiocyanate anion in the coordination sphere (Fig. 1). Bond lengths and angles about the Ni(II) centre are comparable with the values observed in other Schiff base Ni(II) complexes (Arıcı et al., 2005; Li, Jiang et al., 2007; Li, Huang et al., 2007; Usman et al., 2003; Van Hecke et al., 2007).