Ammine­[2-hydroxy-1-naphth­aldehyde 4-piperidyl­thio­semicarbazonato]­nickel(II)

In the title compound, [Ni(C₁₇H₁₇N₃OS)(NH₃)], the Ni atom is in a distorted square-planar geometry, with the 2-hydroxy-1-naphth­aldehyde 4-piperidyl­thio­semicarbazonate ligand coord­inated in a terdentate manner through the S, N and O atoms. A mol­ecule of ammonia completes the coordination.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.042
• wR factor = 0.110
• Data-to-parameter ratio = 13.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_353  Alert C Long    N-H Bond (0.87A)   N(4)   -   H(4C)  =       1.01 Ang.

PLAT_420  Alert C D-H Without Acceptor       N(4)   -   H(4A)             ?

PLAT_420  Alert C D-H Without Acceptor       N(4)   -   H(4C)             ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

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 Ni^II 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).

S2. Experimental

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.

S3. Refinement

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 (U_iso = 1.2U_eq of the atom to which they are bonded).

Computing details

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.

Figures

	Fig. 1. A view of (I). Displacement ellipsoid drawn at a 30% probability level.
	Fig. 2. The crystal structure of (I).

Ammine[2-hydroxy-1-naphthaldehyde 4-piperidylthiosemicarbazonato]nickel(II)

Crystal data

[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) Å^3

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0584P)^2 + 0.0722P] where P = (Fo^2 + 2Fc^2)/3
3018 reflections	(Δ/σ)max = 0.013
226 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1^i	0.91 (5)	2.19 (6)	3.088 (4)	170 (5)

Symmetry code: (i) −x, −y+1, −z.