Crystal structure of bis­[S-hexyl 3-(4-methyl­benzyl­idene)di­thio­carbazato-κ²N³,S]nickel(II)

In the title complex, [Ni(C₁₅H₂₁N₂S₂)₂], the Ni^II atom exhibits a square-planar coordination geometry and is located on an inversion centre leading to a trans configuration of the N,S-chelating ligands. In the crystal, the complex mol­ecules stack at a distance of 4.6738 (3) Å along the a axis, which exclude any significant inter­actions between the aromatic rings.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.071
• wR factor = 0.218
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

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Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.80 Report
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.626 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         57 Report
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check
PLAT973_ALERT_2_C Check Calcd Positive Residual Density on      Ni       1.06 eA-3

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PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00300 Degree
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
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S1. Structural commentary

The metal is located on a crystallographic inversion centre and the two Schiff bases, in their deprotonated imino thiol­ate form, act as chelating ligands to the metal centre via the azomethine nitro­gen N1 and thiol­ate sulphur S1 atoms in a trans-planar configuration as imposed by the crystal symmetry. The complex has coplanar geometry with the exception of the hexyl chains that pend hedgewise. In the complex, the Ni—S and Ni–N bond distances are of 2.1777 (11) and 1.933 (4) Å, respectively, with a S(2)—Ni—N(2) chelating angle of 86.06 (10)°. These geometrical parameters agree with those reported for similar nickel complexes either when ligands assume a trans (Islam, et al., 2011; Islam, et al., 2014; Zhang, et al., 2004) or a cis configuration (Chan, et al., 2008; Li, et al., 2006). The ligand, recently reported (Howlader, et al., 2015), underwent rotation about the C9—N2 by 180° in order to allow the N,S chelating behavior towards the metal. Upon coordination some salient features are observed with respect to the free ligand, and the most significant are an elongation of the C(9)—S(1) bond length (1.720 (4) Å in NiL₂ that must be compared to 1.670 (3) Å in HL, thus validating the coordination with deprotonated thiol­ate sulphur atom. Correspondingly the N(2)—C(9) bond length, of 1.335 (3) Å, shortens to 1.270 (6) Å in the NiL₂ complex, while the N(1)—N(2) bond length of 1.375 (3) Å in HL is slightly elongated in the complex (1.426 (5) Å, Table 1).

S2. Supra­molecular features

The complexes stack at a distance of 4.6738 (3) Å (axis a), which exclude any significant inter­actions between the aromatic rings.

S3. Synthesis and crystallization

A solution of Ni(CH₃COO)₂.4H₂O (0.06 g, 0.25 mmol, 8 mL methanol) was added to a solution of the ligand, S-hexyl (E)-3-(4-methyl­benzyl­idene)di­thio­carbazate, (0.15 g, 0.5 mmol, 10 mL methanol ). The resulting mixture was stirred at room temperature for four hours. A dark reddish brown precipitate was formed, filtered off, washed with methanol and dried in vacuo over anhydrous CaCl₂. Dark reddish brown single crystals, suitable for X-ray diffraction, of the compound were obtained by slow evaporation from a mixture of chloro­form and aceto­nitrile (1:1) after 7 days. M.P. 374 K.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located geometrically and treated as riding atoms, with C—H = 0.95–0.99 Å, and with Uĩso~(H) = 1.2U~eq~(C) or 1.5U~eq~(C) for methyl H atoms.

Related literature

For the structures of related complexes, see: Chan et al. (2008); Islam et al. (2011, 2014); Li et al. (2006); Zhang et al. (2004). For the ligand, see: Howlader et al. (2015).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures

	Fig. 1. ORTEP drawing (ellipsoid probability at 50%) of the centrosymmetric NiL2 complex.
	Fig. 2. Crystal packing of the complex.

Bis[S-hexyl 3-(4-methylbenzylidene)dithiocarbazato-κ²N³,S]nickel(II)

Crystal data

[Ni(C15H21N2S2)2]	Z = 1
Mr = 645.62	F(000) = 342.00
Triclinic, P1	Dx = 1.355 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54187 Å
a = 4.6738 (3) Å	Cell parameters from 5923 reflections
b = 10.5132 (5) Å	θ = 4.3–68.2°
c = 16.4789 (8) Å	µ = 3.55 mm^−1
α = 86.522 (3)°	T = 173 K
β = 84.850 (3)°	Platelet, brown
γ = 79.057 (3)°	0.37 × 0.08 × 0.02 mm
V = 791.00 (7) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	2029 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.000 pixels mm^-1	Rint = 0.074
ω scans	θmax = 68.2°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −5→5
Tmin = 0.615, Tmax = 0.932	k = −12→12
9100 measured reflections	l = −19→19
2834 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.218	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1314P)^2] where P = (Fo^2 + 2Fc^2)/3
2834 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.98 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni	1.0000	1.0000	1.0000	0.0372 (4)
S1	1.1112 (3)	0.83443 (10)	0.92242 (6)	0.0516 (4)
S2	1.4585 (2)	0.80909 (9)	0.76635 (6)	0.0479 (4)
N1	0.7454 (7)	0.9180 (3)	1.07644 (18)	0.0365 (8)
N2	1.3765 (7)	1.0201 (3)	0.85050 (18)	0.0405 (8)
C1	−0.0675 (10)	0.4837 (4)	1.2473 (3)	0.0514 (11)
H1A	−0.0056	0.4630	1.3025	0.077*
H1B	−0.0491	0.4035	1.2184	0.077*
H1C	−0.2717	0.5288	1.2503	0.077*
C2	0.1222 (9)	0.5695 (4)	1.2022 (2)	0.0420 (10)
C3	0.1476 (9)	0.6854 (4)	1.2321 (3)	0.0489 (11)
H3	0.0431	0.7105	1.2825	0.059*
C4	0.3184 (9)	0.7676 (4)	1.1923 (2)	0.0455 (10)
H4	0.3281	0.8471	1.2154	0.055*
C5	0.4769 (8)	0.7344 (4)	1.1181 (2)	0.0390 (9)
C6	0.4513 (10)	0.6168 (4)	1.0883 (3)	0.0522 (12)
H6	0.5555	0.5913	1.0380	0.063*
C7	0.2807 (10)	0.5349 (4)	1.1288 (2)	0.0511 (11)
H7	0.2718	0.4547	1.1063	0.061*
C8	0.6638 (9)	0.8089 (4)	1.0680 (2)	0.0418 (10)
H8	0.7429	0.7691	1.0186	0.050*
C9	1.3189 (8)	0.9071 (4)	0.8487 (2)	0.0370 (9)
C10	1.6632 (9)	0.9110 (4)	0.7013 (3)	0.0469 (11)
H10A	1.7787	0.9530	0.7355	0.056*
H10B	1.8022	0.8559	0.6632	0.056*
C11	1.4718 (9)	1.0153 (4)	0.6522 (2)	0.0463 (10)
H11A	1.3404	1.0736	0.6903	0.056*
H11B	1.3482	0.9738	0.6203	0.056*
C12	1.6461 (9)	1.0959 (4)	0.5943 (2)	0.0467 (10)
H12A	1.7684	1.1383	0.6262	0.056*
H12B	1.7784	1.0378	0.5563	0.056*
C13	1.4508 (9)	1.1991 (4)	0.5453 (2)	0.0488 (11)
H13A	1.3236	1.1563	0.5154	0.059*
H13B	1.3227	1.2580	0.5837	0.059*
C14	1.6143 (10)	1.2790 (4)	0.4849 (3)	0.0545 (12)
H14A	1.7445	1.2204	0.4468	0.065*
H14B	1.7386	1.3235	0.5147	0.065*
C15	1.4131 (11)	1.3796 (5)	0.4361 (3)	0.0670 (14)
H15A	1.3058	1.3358	0.4015	0.100*
H15B	1.5293	1.4337	0.4019	0.100*
H15C	1.2742	1.4342	0.4735	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0441 (7)	0.0337 (6)	0.0351 (5)	−0.0150 (4)	0.0033 (4)	0.0027 (4)
S1	0.0706 (9)	0.0392 (6)	0.0472 (6)	−0.0254 (6)	0.0172 (6)	−0.0036 (5)
S2	0.0571 (8)	0.0331 (6)	0.0520 (6)	−0.0121 (5)	0.0142 (5)	−0.0052 (4)
N1	0.044 (2)	0.0325 (16)	0.0337 (16)	−0.0097 (15)	0.0010 (14)	−0.0006 (13)
N2	0.045 (2)	0.0378 (18)	0.0370 (17)	−0.0105 (16)	0.0085 (15)	0.0032 (14)
C1	0.047 (3)	0.047 (2)	0.061 (3)	−0.016 (2)	−0.001 (2)	0.013 (2)
C2	0.034 (2)	0.042 (2)	0.050 (2)	−0.0104 (18)	−0.0010 (18)	0.0111 (18)
C3	0.051 (3)	0.044 (2)	0.051 (2)	−0.013 (2)	0.016 (2)	−0.0023 (19)
C4	0.053 (3)	0.034 (2)	0.049 (2)	−0.015 (2)	0.012 (2)	−0.0064 (17)
C5	0.040 (2)	0.039 (2)	0.038 (2)	−0.0142 (18)	0.0024 (18)	0.0049 (16)
C6	0.071 (3)	0.045 (2)	0.044 (2)	−0.027 (2)	0.013 (2)	−0.0083 (19)
C7	0.068 (3)	0.043 (2)	0.048 (2)	−0.027 (2)	0.004 (2)	−0.0037 (18)
C8	0.050 (3)	0.044 (2)	0.0337 (19)	−0.017 (2)	0.0048 (18)	−0.0028 (16)
C9	0.036 (2)	0.037 (2)	0.036 (2)	−0.0065 (18)	0.0024 (17)	0.0012 (16)
C10	0.049 (3)	0.039 (2)	0.050 (2)	−0.010 (2)	0.016 (2)	−0.0037 (18)
C11	0.050 (3)	0.044 (2)	0.045 (2)	−0.014 (2)	0.007 (2)	−0.0020 (18)
C12	0.048 (3)	0.043 (2)	0.049 (2)	−0.016 (2)	0.009 (2)	−0.0037 (18)
C13	0.051 (3)	0.050 (2)	0.047 (2)	−0.017 (2)	0.007 (2)	−0.0016 (19)
C14	0.061 (3)	0.047 (2)	0.056 (3)	−0.019 (2)	0.011 (2)	−0.001 (2)
C15	0.079 (4)	0.061 (3)	0.063 (3)	−0.026 (3)	0.001 (3)	0.007 (2)

Geometric parameters (Å, º)

Ni—N1	1.933 (3)	C6—C7	1.385 (5)
Ni—N1^i	1.933 (3)	C6—H6	0.9500
Ni—S1	2.1775 (10)	C7—H7	0.9500
Ni—S1^i	2.1775 (10)	C8—H8	0.9500
S1—C9	1.720 (4)	C10—C11	1.519 (5)
S2—C9	1.757 (4)	C10—H10A	0.9900
S2—C10	1.811 (4)	C10—H10B	0.9900
N1—C8	1.294 (5)	C11—C12	1.521 (5)
N1—N2^i	1.425 (4)	C11—H11A	0.9900
N2—C9	1.269 (5)	C11—H11B	0.9900
N2—N1^i	1.425 (4)	C12—C13	1.521 (6)
C1—C2	1.501 (5)	C12—H12A	0.9900
C1—H1A	0.9800	C12—H12B	0.9900
C1—H1B	0.9800	C13—C14	1.513 (5)
C1—H1C	0.9800	C13—H13A	0.9900
C2—C3	1.371 (6)	C13—H13B	0.9900
C2—C7	1.391 (6)	C14—C15	1.517 (6)
C3—C4	1.383 (5)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.399 (5)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.387 (5)	C15—H15C	0.9800
C5—C8	1.452 (5)
N1—Ni—N1^i	180.00 (14)	N2—C9—S1	125.9 (3)
N1—Ni—S1	93.96 (9)	N2—C9—S2	120.3 (3)
N1^i—Ni—S1	86.04 (9)	S1—C9—S2	113.9 (2)
N1—Ni—S1^i	86.04 (9)	C11—C10—S2	113.5 (3)
N1^i—Ni—S1^i	93.96 (9)	C11—C10—H10A	108.9
S1—Ni—S1^i	180.0	S2—C10—H10A	108.9
C9—S1—Ni	95.86 (13)	C11—C10—H10B	108.9
C9—S2—C10	103.09 (19)	S2—C10—H10B	108.9
C8—N1—N2^i	113.8 (3)	H10A—C10—H10B	107.7
C8—N1—Ni	126.3 (3)	C10—C11—C12	113.2 (3)
N2^i—N1—Ni	119.9 (2)	C10—C11—H11A	108.9
C9—N2—N1^i	111.9 (3)	C12—C11—H11A	108.9
C2—C1—H1A	109.5	C10—C11—H11B	108.9
C2—C1—H1B	109.5	C12—C11—H11B	108.9
H1A—C1—H1B	109.5	H11A—C11—H11B	107.8
C2—C1—H1C	109.5	C13—C12—C11	112.4 (3)
H1A—C1—H1C	109.5	C13—C12—H12A	109.1
H1B—C1—H1C	109.5	C11—C12—H12A	109.1
C3—C2—C7	117.1 (4)	C13—C12—H12B	109.1
C3—C2—C1	121.3 (4)	C11—C12—H12B	109.1
C7—C2—C1	121.7 (4)	H12A—C12—H12B	107.9
C2—C3—C4	123.0 (4)	C14—C13—C12	114.4 (4)
C2—C3—H3	118.5	C14—C13—H13A	108.7
C4—C3—H3	118.5	C12—C13—H13A	108.7
C3—C4—C5	120.4 (4)	C14—C13—H13B	108.7
C3—C4—H4	119.8	C12—C13—H13B	108.7
C5—C4—H4	119.8	H13A—C13—H13B	107.6
C6—C5—C4	116.3 (3)	C13—C14—C15	113.0 (4)
C6—C5—C8	116.0 (3)	C13—C14—H14A	109.0
C4—C5—C8	127.8 (4)	C15—C14—H14A	109.0
C7—C6—C5	122.9 (4)	C13—C14—H14B	109.0
C7—C6—H6	118.6	C15—C14—H14B	109.0
C5—C6—H6	118.6	H14A—C14—H14B	107.8
C6—C7—C2	120.3 (4)	C14—C15—H15A	109.5
C6—C7—H7	119.9	C14—C15—H15B	109.5
C2—C7—H7	119.9	H15A—C15—H15B	109.5
N1—C8—C5	133.6 (4)	C14—C15—H15C	109.5
N1—C8—H8	113.2	H15A—C15—H15C	109.5
C5—C8—H8	113.2	H15B—C15—H15C	109.5
C7—C2—C3—C4	0.8 (6)	C4—C5—C8—N1	2.7 (8)
C1—C2—C3—C4	−179.6 (4)	N1^i—N2—C9—S1	1.8 (5)
C2—C3—C4—C5	−0.2 (7)	N1^i—N2—C9—S2	−177.5 (2)
C3—C4—C5—C6	0.0 (6)	Ni—S1—C9—N2	2.5 (4)
C3—C4—C5—C8	179.5 (4)	Ni—S1—C9—S2	−178.24 (18)
C4—C5—C6—C7	−0.2 (7)	C10—S2—C9—N2	−0.4 (4)
C8—C5—C6—C7	−179.8 (4)	C10—S2—C9—S1	−179.8 (2)
C5—C6—C7—C2	0.8 (7)	C9—S2—C10—C11	−77.3 (3)
C3—C2—C7—C6	−1.0 (6)	S2—C10—C11—C12	−176.9 (3)
C1—C2—C7—C6	179.3 (4)	C10—C11—C12—C13	179.6 (3)
N2^i—N1—C8—C5	−1.2 (7)	C11—C12—C13—C14	−178.2 (3)
Ni—N1—C8—C5	−179.8 (3)	C12—C13—C14—C15	179.1 (4)
C6—C5—C8—N1	−177.7 (4)

Symmetry code: (i) −x+2, −y+2, −z+2.