Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020184/lh6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020184/lh6013Isup2.hkl |
CCDC reference: 202282
4-Piperidylthiosemicarbazide was prepared following a reported procedure (Scovill, 1991). The ligand 2-hydroxy-1-naphthaldehyde 4-piperidylthiosemicarbazone (L) was obtained from a 1:1 molar ratio of 2-hydroxy-1-naphthaldehyde (Aldrich) and 4-piperidylthiosemicarbazide in boiling ethanol containing 2–3 drops of concentrated H2SO4. Compound (I) was prepared from L and nickel(II) nitrate hexahydrate (Aldrich) in a 1:1 molar ratio in a boiling methanol–ammonia solution. Crystals of (I) were obtained by slow evaporation at room temperature of the reaction mixture.
The ammonia H atoms were found in a difference Fourier map and were refined isotropically. The refined N—H distances range from 0.84 (6) to 1.01 (5) Å. H atoms attached to C atoms were included in calculated positions (C—H 0.93–0.97 Å), and refined using a riding model with fixed displacement parameters (Uiso = 1.2Ueq of the atom to which they are bonded).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL/PC (Sheldrick 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999) and Mercury 1.1 (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 and PLATON.
Fig. 1. A view of (I). Displacement ellipsoid drawn at a 30% probability level. | |
Fig. 2. The crystal structure of (I). |
[Ni(C17H17N3OS)(NH3)] | Z = 2 |
Mr = 387.14 | F(000) = 404 |
Triclinic, P1 | Dx = 1.506 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.424 (1) Å | Cell parameters from 39 reflections |
b = 9.482 (1) Å | θ = 2.9–12.5° |
c = 9.668 (1) Å | µ = 1.27 mm−1 |
α = 97.08° | T = 291 K |
β = 93.70° | Laminar, red |
γ = 93.36° | 0.46 × 0.16 × 0.08 mm |
V = 853.61 (16) Å3 |
Siemens P4/PC diffractometer | 2435 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω scans | h = 0→11 |
Absorption correction: analytical based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997) | k = −11→11 |
Tmin = 0.770, Tmax = 0.915 | l = −11→11 |
3219 measured reflections | 3 standard reflections every 97 reflections |
3018 independent reflections | intensity decay: <2% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0584P)2 + 0.0722P] where P = (Fo2 + 2Fc2)/3 |
3018 reflections | (Δ/σ)max = 0.013 |
226 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[Ni(C17H17N3OS)(NH3)] | γ = 93.36° |
Mr = 387.14 | V = 853.61 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.424 (1) Å | Mo Kα radiation |
b = 9.482 (1) Å | µ = 1.27 mm−1 |
c = 9.668 (1) Å | T = 291 K |
α = 97.08° | 0.46 × 0.16 × 0.08 mm |
β = 93.70° |
Siemens P4/PC diffractometer | 2435 reflections with I > 2σ(I) |
Absorption correction: analytical based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997) | Rint = 0.046 |
Tmin = 0.770, Tmax = 0.915 | 3 standard reflections every 97 reflections |
3219 measured reflections | intensity decay: <2% |
3018 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.43 e Å−3 |
3018 reflections | Δρmin = −0.49 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 | 0.20942 (5) | 0.35622 (5) | 0.10346 (5) | 0.03897 (15) | |
S1 | 0.42569 (10) | 0.42316 (10) | 0.17642 (10) | 0.0462 (2) | |
O1 | 0.0236 (3) | 0.3023 (3) | 0.0324 (3) | 0.0484 (6) | |
N1 | 0.2125 (3) | 0.2306 (3) | 0.2343 (3) | 0.0368 (6) | |
N2 | 0.3330 (3) | 0.2189 (3) | 0.3232 (3) | 0.0428 (7) | |
N3 | 0.5641 (3) | 0.3065 (3) | 0.3839 (3) | 0.0457 (7) | |
N4 | 0.2088 (4) | 0.4810 (4) | −0.0394 (4) | 0.0561 (9) | |
H4A | 0.280 (6) | 0.531 (6) | −0.051 (6) | 0.067* | |
H4B | 0.134 (6) | 0.539 (5) | −0.030 (5) | 0.067* | |
H4C | 0.167 (5) | 0.423 (5) | −0.129 (6) | 0.067* | |
C1 | −0.0254 (3) | 0.1153 (4) | 0.1711 (4) | 0.0387 (7) | |
C2 | −0.0573 (4) | 0.1942 (4) | 0.0610 (4) | 0.0453 (8) | |
C3 | −0.1858 (4) | 0.1572 (5) | −0.0270 (4) | 0.0569 (10) | |
H3 | −0.2059 | 0.2076 | −0.1017 | 0.068* | |
C4 | −0.2778 (4) | 0.0503 (5) | −0.0027 (5) | 0.0600 (11) | |
H4 | −0.3595 | 0.0276 | −0.0624 | 0.072* | |
C5 | −0.3524 (4) | −0.1377 (5) | 0.1391 (6) | 0.0702 (14) | |
H5 | −0.4342 | −0.1602 | 0.0795 | 0.084* | |
C6 | −0.3315 (5) | −0.2104 (5) | 0.2496 (7) | 0.0718 (14) | |
H6 | −0.3999 | −0.2793 | 0.2674 | 0.086* | |
C7 | −0.2063 (5) | −0.1812 (5) | 0.3371 (6) | 0.0658 (12) | |
H7 | −0.1907 | −0.2317 | 0.4126 | 0.079* | |
C8 | −0.1063 (4) | −0.0778 (4) | 0.3115 (5) | 0.0519 (9) | |
H8 | −0.0229 | −0.0610 | 0.3696 | 0.062* | |
C9 | −0.1263 (4) | 0.0035 (4) | 0.1997 (4) | 0.0451 (8) | |
C10 | −0.2537 (4) | −0.0288 (4) | 0.1113 (5) | 0.0542 (10) | |
C11 | 0.1077 (3) | 0.1396 (3) | 0.2515 (4) | 0.0393 (7) | |
H11 | 0.1214 | 0.0849 | 0.3241 | 0.047* | |
C12 | 0.4399 (4) | 0.3055 (4) | 0.3029 (3) | 0.0391 (7) | |
C13 | 0.6946 (4) | 0.3812 (5) | 0.3492 (5) | 0.0604 (11) | |
H13A | 0.6705 | 0.4663 | 0.3090 | 0.072* | |
H13B | 0.7402 | 0.3204 | 0.2797 | 0.072* | |
C14 | 0.7960 (5) | 0.4219 (5) | 0.4743 (6) | 0.0711 (13) | |
H14A | 0.7552 | 0.4925 | 0.5386 | 0.085* | |
H14B | 0.8837 | 0.4645 | 0.4457 | 0.085* | |
C15 | 0.8291 (4) | 0.2952 (6) | 0.5482 (5) | 0.0677 (12) | |
H15A | 0.8884 | 0.3268 | 0.6334 | 0.081* | |
H15B | 0.8815 | 0.2300 | 0.4887 | 0.081* | |
C16 | 0.6928 (5) | 0.2193 (5) | 0.5831 (5) | 0.0623 (11) | |
H16A | 0.7156 | 0.1329 | 0.6216 | 0.075* | |
H16B | 0.6487 | 0.2798 | 0.6541 | 0.075* | |
C17 | 0.5886 (4) | 0.1815 (5) | 0.4577 (5) | 0.0560 (10) | |
H17A | 0.6249 | 0.1071 | 0.3942 | 0.067* | |
H17B | 0.4988 | 0.1449 | 0.4874 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0395 (2) | 0.0423 (2) | 0.0379 (2) | 0.00834 (17) | 0.00095 (16) | 0.01443 (17) |
S1 | 0.0437 (5) | 0.0475 (5) | 0.0498 (5) | −0.0040 (4) | −0.0007 (4) | 0.0208 (4) |
O1 | 0.0413 (13) | 0.0589 (15) | 0.0475 (13) | 0.0094 (12) | −0.0071 (11) | 0.0193 (12) |
N1 | 0.0345 (13) | 0.0387 (14) | 0.0378 (14) | 0.0022 (11) | −0.0042 (11) | 0.0101 (11) |
N2 | 0.0331 (14) | 0.0513 (16) | 0.0447 (15) | −0.0065 (12) | −0.0086 (12) | 0.0191 (13) |
N3 | 0.0347 (14) | 0.0514 (17) | 0.0514 (17) | −0.0081 (12) | −0.0042 (12) | 0.0175 (14) |
N4 | 0.0528 (19) | 0.068 (2) | 0.056 (2) | 0.0158 (17) | 0.0102 (16) | 0.0331 (18) |
C1 | 0.0314 (15) | 0.0415 (17) | 0.0419 (17) | 0.0059 (13) | −0.0041 (13) | 0.0019 (14) |
C2 | 0.0376 (17) | 0.053 (2) | 0.0448 (18) | 0.0146 (15) | −0.0035 (14) | 0.0017 (15) |
C3 | 0.048 (2) | 0.067 (3) | 0.054 (2) | 0.0179 (19) | −0.0150 (17) | 0.0005 (18) |
C4 | 0.0391 (19) | 0.066 (3) | 0.067 (3) | 0.0141 (18) | −0.0181 (18) | −0.014 (2) |
C5 | 0.0320 (18) | 0.055 (2) | 0.113 (4) | 0.0024 (17) | −0.005 (2) | −0.023 (3) |
C6 | 0.040 (2) | 0.044 (2) | 0.126 (4) | −0.0103 (17) | 0.016 (2) | −0.009 (3) |
C7 | 0.054 (2) | 0.050 (2) | 0.091 (3) | −0.0106 (19) | 0.010 (2) | 0.004 (2) |
C8 | 0.0410 (19) | 0.0458 (19) | 0.067 (2) | −0.0081 (15) | 0.0010 (17) | 0.0070 (17) |
C9 | 0.0336 (16) | 0.0427 (18) | 0.056 (2) | 0.0048 (14) | −0.0010 (15) | −0.0043 (15) |
C10 | 0.0327 (17) | 0.049 (2) | 0.075 (3) | 0.0056 (15) | −0.0036 (17) | −0.0140 (19) |
C11 | 0.0351 (16) | 0.0392 (17) | 0.0437 (17) | −0.0017 (13) | −0.0049 (14) | 0.0119 (14) |
C12 | 0.0381 (17) | 0.0406 (17) | 0.0392 (16) | 0.0000 (13) | −0.0011 (13) | 0.0111 (13) |
C13 | 0.041 (2) | 0.073 (3) | 0.070 (3) | −0.0117 (19) | −0.0006 (18) | 0.029 (2) |
C14 | 0.043 (2) | 0.074 (3) | 0.093 (3) | −0.014 (2) | −0.014 (2) | 0.018 (3) |
C15 | 0.041 (2) | 0.085 (3) | 0.076 (3) | 0.002 (2) | −0.014 (2) | 0.017 (2) |
C16 | 0.050 (2) | 0.074 (3) | 0.064 (3) | −0.001 (2) | −0.0129 (19) | 0.024 (2) |
C17 | 0.048 (2) | 0.058 (2) | 0.064 (2) | −0.0053 (17) | −0.0090 (18) | 0.0250 (19) |
Ni1—N1 | 1.841 (3) | C5—C10 | 1.411 (7) |
Ni1—O1 | 1.858 (3) | C5—H5 | 0.9300 |
Ni1—N4 | 1.926 (3) | C6—C7 | 1.401 (7) |
Ni1—S1 | 2.1465 (11) | C6—H6 | 0.9300 |
S1—C12 | 1.758 (3) | C7—C8 | 1.375 (6) |
O1—C2 | 1.310 (5) | C7—H7 | 0.9300 |
N1—C11 | 1.305 (4) | C8—C9 | 1.413 (6) |
N1—N2 | 1.397 (4) | C8—H8 | 0.9300 |
N2—C12 | 1.303 (5) | C9—C10 | 1.423 (5) |
N3—C12 | 1.365 (4) | C11—H11 | 0.9300 |
N3—C13 | 1.461 (5) | C13—C14 | 1.488 (6) |
N3—C17 | 1.479 (5) | C13—H13A | 0.9700 |
N4—H4A | 0.84 (6) | C13—H13B | 0.9700 |
N4—H4B | 0.91 (5) | C14—C15 | 1.509 (7) |
N4—H4C | 1.01 (5) | C14—H14A | 0.9700 |
C1—C2 | 1.402 (5) | C14—H14B | 0.9700 |
C1—C11 | 1.424 (5) | C15—C16 | 1.514 (6) |
C1—C9 | 1.446 (5) | C15—H15A | 0.9700 |
C2—C3 | 1.434 (5) | C15—H15B | 0.9700 |
C3—C4 | 1.348 (7) | C16—C17 | 1.504 (6) |
C3—H3 | 0.9300 | C16—H16A | 0.9700 |
C4—C10 | 1.421 (7) | C16—H16B | 0.9700 |
C4—H4 | 0.9300 | C17—H17A | 0.9700 |
C5—C6 | 1.351 (8) | C17—H17B | 0.9700 |
N1—Ni1—O1 | 95.21 (12) | C9—C8—H8 | 119.0 |
N1—Ni1—N4 | 177.42 (16) | C8—C9—C10 | 116.9 (4) |
O1—Ni1—N4 | 84.65 (15) | C8—C9—C1 | 123.8 (3) |
N1—Ni1—S1 | 87.48 (9) | C10—C9—C1 | 119.3 (4) |
O1—Ni1—S1 | 177.17 (9) | C5—C10—C4 | 121.9 (4) |
N4—Ni1—S1 | 92.62 (13) | C5—C10—C9 | 119.4 (4) |
C12—S1—Ni1 | 95.93 (12) | C4—C10—C9 | 118.8 (4) |
C2—O1—Ni1 | 127.1 (2) | N1—C11—C1 | 127.0 (3) |
C11—N1—N2 | 112.4 (3) | N1—C11—H11 | 116.5 |
C11—N1—Ni1 | 125.1 (2) | C1—C11—H11 | 116.5 |
N2—N1—Ni1 | 122.5 (2) | N2—C12—N3 | 119.0 (3) |
C12—N2—N1 | 112.8 (3) | N2—C12—S1 | 121.3 (3) |
C12—N3—C13 | 121.1 (3) | N3—C12—S1 | 119.7 (3) |
C12—N3—C17 | 118.0 (3) | N3—C13—C14 | 111.9 (4) |
C13—N3—C17 | 114.1 (3) | N3—C13—H13A | 109.2 |
Ni1—N4—H4A | 121 (4) | C14—C13—H13A | 109.2 |
Ni1—N4—H4B | 109 (3) | N3—C13—H13B | 109.2 |
H4A—N4—H4B | 108 (5) | C14—C13—H13B | 109.2 |
Ni1—N4—H4C | 107 (3) | H13A—C13—H13B | 107.9 |
H4A—N4—H4C | 112 (5) | C13—C14—C15 | 111.8 (4) |
H4B—N4—H4C | 96 (4) | C13—C14—H14A | 109.2 |
C2—C1—C11 | 120.8 (3) | C15—C14—H14A | 109.2 |
C2—C1—C9 | 119.6 (3) | C13—C14—H14B | 109.2 |
C11—C1—C9 | 119.5 (3) | C15—C14—H14B | 109.2 |
O1—C2—C1 | 123.9 (3) | H14A—C14—H14B | 107.9 |
O1—C2—C3 | 116.7 (3) | C14—C15—C16 | 110.3 (4) |
C1—C2—C3 | 119.4 (4) | C14—C15—H15A | 109.6 |
C4—C3—C2 | 120.9 (4) | C16—C15—H15A | 109.6 |
C4—C3—H3 | 119.6 | C14—C15—H15B | 109.6 |
C2—C3—H3 | 119.6 | C16—C15—H15B | 109.6 |
C3—C4—C10 | 122.0 (3) | H15A—C15—H15B | 108.1 |
C3—C4—H4 | 119.0 | C17—C16—C15 | 112.5 (4) |
C10—C4—H4 | 119.0 | C17—C16—H16A | 109.1 |
C6—C5—C10 | 122.0 (4) | C15—C16—H16A | 109.1 |
C6—C5—H5 | 119.0 | C17—C16—H16B | 109.1 |
C10—C5—H5 | 119.0 | C15—C16—H16B | 109.1 |
C5—C6—C7 | 119.6 (4) | H16A—C16—H16B | 107.8 |
C5—C6—H6 | 120.2 | N3—C17—C16 | 111.5 (3) |
C7—C6—H6 | 120.2 | N3—C17—H17A | 109.3 |
C8—C7—C6 | 120.1 (5) | C16—C17—H17A | 109.3 |
C8—C7—H7 | 120.0 | N3—C17—H17B | 109.3 |
C6—C7—H7 | 120.0 | C16—C17—H17B | 109.3 |
C7—C8—C9 | 122.0 (4) | H17A—C17—H17B | 108.0 |
C7—C8—H8 | 119.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O1i | 0.91 (5) | 2.19 (6) | 3.088 (4) | 170 (5) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C17H17N3OS)(NH3)] |
Mr | 387.14 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 9.424 (1), 9.482 (1), 9.668 (1) |
α, β, γ (°) | 97.08, 93.70, 93.36 |
V (Å3) | 853.61 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.46 × 0.16 × 0.08 |
Data collection | |
Diffractometer | Siemens P4/PC diffractometer |
Absorption correction | Analytical based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997) |
Tmin, Tmax | 0.770, 0.915 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3219, 3018, 2435 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.110, 1.00 |
No. of reflections | 3018 |
No. of parameters | 226 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.49 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL/PC (Sheldrick 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999) and Mercury 1.1 (Bruno et al., 2002), SHELXL97 and PLATON.
Ni1—N1 | 1.841 (3) | O1—C2 | 1.310 (5) |
Ni1—O1 | 1.858 (3) | N1—C11 | 1.305 (4) |
Ni1—N4 | 1.926 (3) | N1—N2 | 1.397 (4) |
Ni1—S1 | 2.1465 (11) | N2—C12 | 1.303 (5) |
S1—C12 | 1.758 (3) | N3—C12 | 1.365 (4) |
N1—Ni1—O1 | 95.21 (12) | N1—Ni1—S1 | 87.48 (9) |
N1—Ni1—N4 | 177.42 (16) | O1—Ni1—S1 | 177.17 (9) |
O1—Ni1—N4 | 84.65 (15) | N4—Ni1—S1 | 92.62 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···O1i | 0.91 (5) | 2.19 (6) | 3.088 (4) | 170 (5) |
Symmetry code: (i) −x, −y+1, −z. |
The Ni atom in the title compound, (I), presents a coordination number of four. The 2-hydroxy-1-naphthaldehyde 4-piperidylthiosemicarbazonate ligand has a charge of 2− and acts as a terdentate ligand, coordinating to the NiII ion via the thiolate S, the azomethine N and the naphthoxy O atom. The ammonia molecule coordinates in the fourth position. The coordination geometry is distorted square planar, as indicated by the distances and angles around the metal ion. The coordinated thiosemicarbazone ligand is almost planar and the angle between the Ni1—S1—N1—N2—C12 and Ni1—O1—N1—C1—C2—C11 chelate rings is 3.9 (1)°. The angle between the Ni1—S1—N1—N2—C12 chelate ring and the mean plane of the naphthalene rings is 9.4 (1)°. The piperidyl ring is in a chair conformation. A self-complimentary intermolecular N—H ··· O hydrogen bond (see Table 2) involving the ammonia H4B atom and the O atom of the coordinated thiosemicarbazone ligand is present in the crystal structure of (I).