Synthesis, crystal structure and Hirshfeld and thermal analysis of bis[benzyl 2-(heptan-4-yl­idene)hydrazine-1-carboxyl­ate-κ2N2,O]bis(thio­cyanato)­nickel(II)

Nithya, P.; Govindarajan, S.; Simpson, J.

doi:10.1107/S2056989020004260

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 76| Part 5| May 2020| Pages 637-641

https://doi.org/10.1107/S2056989020004260

Open

access

Synthesis, crystal structure and Hirshfeld and thermal analysis of bis[benzyl 2-(heptan-4-ylidene)hydrazine-1-carboxylate-κ²N²,O]bis(thiocyanato)nickel(II)

Palanivelu Nithya,^a,^b Subbiah Govindarajan ^a and Jim Simpson ^c ^*

^aDepartment of Chemistry, Bharathiar University, Coimbatore - 641 046, Tamil Nadu, India, ^bDepartment of Chemistry, J. J. College of Arts and Science, Pudukkottai, - 622 422, Tamil Nada, India, and ^cDepartment of Chemistry, University of Otago, PO Box 56, Dunedin 9054, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 16 March 2020; accepted 28 March 2020; online 7 April 2020)

The title centrosymmetric Ni^II complex, [Ni(NCS)₂(C₁₅H₂₂N₂O₂)₂], crystallizes with one half molecule in the asymmetric unit of the monoclinic unit cell. The complex adopts an octahedral coordination geometry with two mutually trans benzyl-2-(heptan-4-ylidene)hydrazine-1-carboxylate ligands in the equatorial plane with the axial positions occupied by N-bound thiocyanato ligands. The overall conformation of the molecule is also affected by two, inversion-related, intramolecular C—H⋯O hydrogen bonds. The crystal structure features N—H⋯S, C—H⋯S and C—H⋯N hydrogen bonds together with C—H⋯π contacts that stack the complexes along the b-axis direction. The packing was further explored by Hirshfeld surface analysis. The thermal properties of the complex were also investigated by simultaneous TGA–DTA analyses.

Keywords: crystal structure; Ni^II complex; benzyl-2-(heptan-4-ylidene)hydrazine-1-carboxylate ligand; thiocyanato ligands; Hirshfeld surface analysis; simultaneous TGA–DTA analyses.

CCDC reference: 1993291

1. Chemical context

Investigations of the Schiff base complexes of benzyl carbazate are scarce except for our own reports (Nithya et al., 2016 , 2017a ,b , 2018a ,b ). These complexes are formed by Schiff base carbazate ligands in their keto form with N,O chelation to give complexes with octahedral geometry. The coordination chemistry of benzyl carbazate Schiff base complexes has gained importance not only from the inorganic point of view, but also because of their biological and thermal properties. In the course of our recent studies on such complexes, we reported the cobalt(II) complex of a Schiff base derived from benzyl carbazate and heptan-4-one with thiocyanates as the charge-compensating ligands (Nithya et al., 2019 ). In this work, we report the synthesis, molecular and crystal structures, Hirshfeld surface analysis and thermal properties of the corresponding nickel complex, bis[benzyl-2-(heptan-4-ylidene)hydrazine-1-carboxylate]bis(thiocyanato)nickel(II), 1.

2. Structural commentary

The title compound, 1, crystallizes in the space group P2₁/c with one half of the complex in the asymmetric unit as the Ni^II cation lies on an inversion centre, Fig. 1. This contrasts with the previously determined Co^II analogue (Nithya et al., 2019) that crystallizes with two unique, centrosymmetric complex molecules in the asymmetric unit. Two inversion-related intramolecular C13—H13A⋯O1 hydrogen bonds, Table 1, influence the conformation of the benzyl-2-(heptan-4-ylidene)hydrazine-1-carboxylate ligands and enclose R₂²(14) ring motifs. Two hydrazine-carboxylate ligands chelate the Ni atom with N1 and O1 donor atoms; these chelating ligands lie trans to one another in the equatorial plane of the slightly distorted octahedral complex. The axial positions are occupied by two thiocyanato ligands bound to the metal through their N3 atoms. The NCS ligands are kinked away from the alkane chains of the other ligands with C16—N3—Ni1 angles of 163.23 (11)°. Bond lengths and angles in the closely related Ni and Co complexes are generally similar, although the Ni1—N1 bond [2.1332 (12) Å] is significantly shorter here than the corresponding Co1—N11 and Co2—N21 vectors [2.206 (5) and 2.248 (6) Å respectively].

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C3–C8 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1ⁱ	0.824 (17)	2.507 (17)	3.2830 (12)	157.3 (16)
C8—H8⋯S1ⁱ	0.95	2.94	3.7080 (16)	139
C10—H10A⋯S1ⁱ	0.99	3.00	3.9059 (14)	154
C10—H10B⋯S1ⁱⁱ	0.99	2.94	3.8464 (15)	153
C13—H13A⋯O1ⁱⁱⁱ	0.99	2.35	3.1783 (18)	141
C2—H2A⋯Cg3^iv	0.99	2.72	3.6041 (17)	149
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (ii) x, y-1, z; (iii) -x+1, -y, -z+2; (iv) -x, -y, -z+2.

Figure 1
The molecular structure of 1 showing the atom numbering with ellipsoids drawn at the 50% probability level. Labelled atoms are related to unlabelled atoms by the symmetry operation −x + 1, −y, −z + 2. Intramolecular hydrogen bonds are shown as dashed black lines.

3. Supramolecular features

In the crystal structure, atom S1 acts as a trifurcated acceptor forming N2—H2N⋯S1 and weaker C8—H8⋯S1 and C10—H10A⋯S1 hydrogen bonds, Table 1, that form chains of complex molecules along the bc diagonal, Fig. 2. Inversion-related pairs of C10—H10B⋯S1 hydrogen bonds link adjacent molecules into rows along the b-axis direction, Fig. 3, while rows also form along a, through C2—H2A⋯Cg3, C—H⋯π contacts, Fig. 4; Cg3 is the centroid of the C3–C8 phenyl ring. These contacts combine to stack molecules of the complex in a regular fashion along the b-axis direction, Fig. 5.

Figure 2
Chains of molecules of 1 along the bc diagonal. Hydrogen bonds are drawn as dashed cyan lines.

Figure 3
Chains of inversion dimers of 1 along b.

Figure 4
Chains of molecules of 1 along a. C—H⋯π contacts are drawn as dashed magenta lines with the centroids (Cg) of the C3–C8 rings shown as magenta spheres.

Figure 5
Overall packing of 1 viewed along the b-axis direction.

4. Hirshfeld surface analysis

Further details of the intermolecular interactions in 1 were obtained using Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) with Hirshfeld surfaces and two-dimensional fingerprint plots generated with CrystalExplorer17 (Turner et al., 2017 ). Hirshfeld surfaces for opposite faces of 1 are shown in Fig. 6(a) and (b). Bold red circles on the Hirshfeld surfaces correspond to the N—H⋯S hydrogen bonds while the weaker C—H⋯S and C—H⋯π contacts appear as faint red circles. Fingerprint plots, Fig. 7, reveal that while H⋯H interactions make the greatest contributions to the surface contacts, as would be expected for a molecule with such a predominance of H atoms, H⋯C/C⋯H and H⋯S/S⋯H contacts are also substantial, Table 2. H⋯N/N⋯H and H⋯O/O⋯H contacts are less significant, with the O⋯C/C⋯O and O⋯S/S⋯O contacts being essentially trivial with contributions of 0.7% and 0.6%, respectively. These are not shown in Fig. 7 but are included in Table 3 for completeness.

Table 2
Percentage contributions to the Hirshfeld surface for 1

Contacts	Included surface area %
H⋯H	55.5
H⋯C/C⋯H	18.8
H⋯S/S⋯H	16.6
H⋯N/N⋯H	4.3
H⋯O/O⋯H	3.2
O⋯C/C⋯O	0.7
O⋯S/S⋯O	0.6

Table 3
Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₁₅H₂₂N₂O2)₂]
M_r	699.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.6406 (3), 10.1280 (3), 15.7458 (4)
β (°)	108.647 (3)
V (Å³)	1910.02 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.66
Crystal size (mm)	0.39 × 0.24 × 0.16

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.772, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12439, 4575, 3961
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.695

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.073, 1.05
No. of reflections	4575
No. of parameters	210
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.39
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), TITAN (Hunter & Simpson, 1999 ), Mercury (Macrae et al., 2020 ), enCIFer (Allen et al., 2004 ), PLATON (Spek, 2020 ) and publCIF (Westrip 2010 ).

Figure 6
Hirshfeld surfaces for opposite faces (a) and (b) of 1 mapped over d_norm in the range −0.3928 to 2.1718 a.u. Cg3 is the centroid of the C3–C8 phenyl ring.

Figure 7
A full two-dimensional fingerprint plot for 1, (a), together with separate principal contact types for the molecule (b)–(f). These were found to be H⋯H, H⋯C/C⋯H, H⋯S/S⋯H, H⋯N/N⋯H and H⋯O/O⋯H contacts.

5. Thermal properties

Fig. 8 shows the thermal decomposition behaviour of 1. Simultaneous TGA–DTA analyses were recorded in air on a Perkin–Elmer SII Thermal Analyser over the temperature range 50–800°C. With the equipment used here, the TGA curve shows the temperature range but not the individual peak temperatures. However, peak temperatures can be seen in the DTA curve. In the first step of decomposition, the weight loss of 74% occurs over the temperature range 115–260°C (TGA). This corresponds to the loss of the Schiff base ligands to form Ni^II thiocyanate as an intermediate. This was marked by both endothermic (170°C) and exothermic peaks (190 and 210°C) in the DTA curve. As the thermal analysis was carried out under a dynamic flowing air atmosphere, the S and N atoms are oxidized to SO₂ and NO₂, while nickel ultimately forms nickel oxide. Similar decomposition processes have been observed in our recent wok on numerous similar complexes, see for example (Nithya et al., 2017a,b, 2018a,b, 2019a,b ).

Figure 8
Simultaneous TGA–DTA analyses for 1. The heavy (darker) lines show the TGA plot with the DTA behaviour shown by the lighter curve.

6. Database survey

As mentioned previously, the most closely related structure to the one reported here is that of the Co^II analogue (Nithya et al. 2019) while we have also reported the structures of 18 other Schiff base complexes of various transition metals with ligands based on benzyl carbazate (Nithya et al. 2016, 2017a,b, 2018a,b). A search in the Cambridge Structural Database (version 5.41, November 2019; Groom et al., 2016 ) for other related transition-metal complexes produced no additional hits. The novelty of the ligands found in these complexes is reinforced by the fact that a search for organic compounds incorporating the PhCH₂OC(O)NHN=C(CH₂)₂ unit produced only two hits. One was our own report of the ligand benzyl 2-cyclopentylidenehydrazinecarboxylate (JENFAM; Nithya et al., 2017a). The other was (2E)-1-ethyl 8-methyl 7-(2-(benzyloxycarbonyl)hydrazono)oct-2-enedioate, (VEWMOA; Gergely et al., 2006 ). In both cases, the bond distances and angles in the structures compare very favourably with those reported here.

7. Synthesis and crystallization

Equimolar amounts of ammonium thiocyanate (0.076 g, 1 mmol) and benzyl carbazate (0.166 g, 1 mmol) were dissolved in methanol (10 mL). Nickel nitrate, Ni(NO₃)₂·6H₂O, (0.146 g, 0.5 mmol) dissolved in 10 mL of doubly distilled water was added to this solution. The resulting blue solution was layered with heptan-4-one (dipropyl ketone) and the solution changed to a green colour. The final solution was left to evaporate at room temperature. After slow evaporation, bluish–green rhombus-shaped crystals suitable for X-ray diffraction analysis were collected, washed with doubly distilled water and air-dried.

Analysis calculated for NiC₃₂H₄₄N₆O₄S₂: Ni, 8.40; C, 54.96; H, 6.30; N, 12.02; S, 9.16%. Found: Ni, 8.25; C, 54.76; H, 6.13; N, 11.80; S, 9.08%; conductance = 14 S cm² mol⁻¹. Yield based on the metal: 80%.

The FT–IR spectrum was recorded on a JASCO-4100 FT–IR spectrophotometer from 4000 to 400 cm⁻¹ using KBr pellets: N—H stretch 3152 cm⁻¹ C=O stretch 1675 cm⁻¹ C=N stretch 1524 cm⁻¹, N—N stretch 1058 cm⁻¹. 2108 cm⁻¹ C≡N stretch of the N-bound thiocyanate ligands.

The electronic absorption spectrum was measured on a JASCO V-630 UV–vis spectrophotometer and recorded in methanol at room temperature: intense bands at 392, 678 and 732 nm were assigned to the ³A_2g → ³T_2g, 3A_2g → ³T_1g(F) and ³A_2g(F) →³T_1g(P) transitions, respectively, supporting the six-coordinate octahedral geometry around the Ni^II cation (Lever, 1984 ).

The ¹H NMR spectrum was recorded on a Bruker AV 400 (400 MHz) spectrometer using tetramethylsilane as an internal reference. Chemical shifts are expressed in parts per million (ppm): 0.84–0.88 and 1.33–2.20 ppm: CH₃ and CH₂ groups, respectively; –OCH₂ proton: 5.08 ppm; aromatic protons multiplets 7.29–7.34 ppm; NH: 9.882 ppm.

Simultaneous TGA–DTA analyses were recorded in air on a PerkinElmer SII Thermal Analyser over the temperature range 50-800°C.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N—H hydrogen atom was located in a difference-Fourier map and its coordinates refined with U_iso(H) = 1.2U_eq(N). All C-bound H atoms were refined using a riding model with d(C—H) = 0.95 Å, U_iso = 1.2U_eq(C) for aromatic 0.99 Å, U_iso = 1.2U_eq(C) for CH₂ and 0.98 Å, U_iso = 1.5U_eq(C) for CH₃ H atoms.

Supporting information

CCDC reference: 1993291

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989020004260/vm2230sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020004260/vm2230Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b) and TITAN (Hunter & Simpson, 1999); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2015b), enCIFer (Allen et al., 2004), PLATON (Spek, 2020) and publCIF (Westrip 2010).

Bis[benzyl 2-(heptan-4-ylidene)hydrazine-1-carboxylate-κ²N²,O]bis(thiocyanato)nickel(II) top

Crystal data top

[Ni(NCS)₂(C₁₅H₂₂N₂O2)₂]	F(000) = 740
M_r = 699.56	D_x = 1.216 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6406 (3) Å	Cell parameters from 6613 reflections
b = 10.1280 (3) Å	θ = 3.6–29.2°
c = 15.7458 (4) Å	µ = 0.66 mm⁻¹
β = 108.647 (3)°	T = 100 K
V = 1910.02 (9) Å³	Rectangular block, blue
Z = 2	0.39 × 0.24 × 0.16 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	4575 independent reflections
Radiation source: Agilent SuperNova (Mo) X-ray Source	3961 reflections with I > 2σ(I)
Detector resolution: 5.1725 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 29.6°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014)	h = −17→17
T_min = 0.772, T_max = 1.000	k = −13→13
12439 measured reflections	l = −21→21

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0259P)² + 0.7321P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4575 reflections	Δρ_max = 0.33 e Å⁻³
210 parameters	Δρ_min = −0.38 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. One reflection with Fo >>> Fc was omitted from the final refinement cycles.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.500000	0.000000	1.000000	0.01311 (7)
O1	0.34390 (7)	0.04585 (10)	1.01346 (6)	0.0166 (2)
C1	0.33197 (11)	−0.01165 (14)	1.07823 (9)	0.0159 (3)
O2	0.25009 (8)	0.01215 (11)	1.11267 (7)	0.0210 (2)
C2	0.16396 (11)	0.10284 (16)	1.06322 (10)	0.0208 (3)
H2A	0.137728	0.078992	0.998872	0.025*
H2B	0.193675	0.194018	1.069115	0.025*
C3	0.06895 (11)	0.09413 (16)	1.10129 (10)	0.0207 (3)
C4	−0.00906 (14)	0.19554 (19)	1.08242 (13)	0.0357 (4)
H4	−0.000374	0.268997	1.047719	0.043*
C5	−0.09990 (15)	0.1901 (2)	1.11410 (14)	0.0428 (5)
H5	−0.153094	0.259680	1.100762	0.051*
C6	−0.11294 (13)	0.0844 (2)	1.16464 (12)	0.0338 (4)
H6	−0.174835	0.081002	1.186420	0.041*
C7	−0.03610 (13)	−0.01634 (18)	1.18350 (11)	0.0277 (4)
H7	−0.044911	−0.089213	1.218626	0.033*
C8	0.05482 (12)	−0.01236 (16)	1.15143 (10)	0.0226 (3)
H8	0.107027	−0.082965	1.164090	0.027*
N2	0.39863 (10)	−0.10797 (13)	1.12383 (8)	0.0187 (3)
H2N	0.3879 (13)	−0.1414 (17)	1.1681 (12)	0.022*
N1	0.48528 (9)	−0.14754 (12)	1.09226 (8)	0.0156 (2)
C9	0.52823 (11)	−0.26137 (15)	1.11779 (9)	0.0170 (3)
C10	0.48835 (12)	−0.35599 (15)	1.17505 (10)	0.0194 (3)
H10A	0.470958	−0.306629	1.223216	0.023*
H10B	0.548117	−0.420395	1.203426	0.023*
C11	0.38364 (14)	−0.42957 (18)	1.11758 (11)	0.0308 (4)
H11A	0.321679	−0.365719	1.094963	0.037*
H11B	0.398761	−0.469318	1.065186	0.037*
C12	0.34816 (16)	−0.53771 (19)	1.17007 (13)	0.0375 (4)
H12A	0.406779	−0.605036	1.188334	0.056*
H12B	0.278687	−0.578254	1.132223	0.056*
H12C	0.336205	−0.499402	1.223428	0.056*
C13	0.62074 (12)	−0.30822 (16)	1.08489 (10)	0.0209 (3)
H13A	0.618840	−0.257813	1.030547	0.025*
H13B	0.608894	−0.402577	1.068126	0.025*
C14	0.73513 (12)	−0.29144 (18)	1.15569 (12)	0.0290 (4)
H14A	0.734359	−0.332963	1.212408	0.035*
H14B	0.751004	−0.196209	1.167194	0.035*
C15	0.82738 (14)	−0.3542 (2)	1.12562 (14)	0.0391 (5)
H15A	0.814383	−0.449445	1.117866	0.059*
H15B	0.899948	−0.338260	1.171121	0.059*
H15C	0.826912	−0.314947	1.068597	0.059*
N3	0.57102 (10)	0.12673 (13)	1.09988 (8)	0.0189 (3)
C16	0.61615 (11)	0.21720 (15)	1.14054 (9)	0.0162 (3)
S1	0.68148 (3)	0.34303 (4)	1.19984 (3)	0.02219 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01222 (12)	0.01537 (14)	0.01307 (13)	−0.00022 (9)	0.00589 (10)	−0.00050 (10)
O1	0.0141 (4)	0.0200 (5)	0.0175 (5)	0.0017 (4)	0.0076 (4)	0.0030 (4)
C1	0.0132 (6)	0.0193 (8)	0.0164 (7)	−0.0004 (5)	0.0066 (5)	−0.0015 (6)
O2	0.0172 (5)	0.0278 (6)	0.0224 (5)	0.0092 (4)	0.0126 (4)	0.0091 (4)
C2	0.0168 (7)	0.0233 (8)	0.0227 (7)	0.0063 (6)	0.0069 (6)	0.0052 (6)
C3	0.0163 (7)	0.0258 (9)	0.0207 (7)	0.0031 (6)	0.0071 (6)	−0.0024 (6)
C4	0.0322 (9)	0.0337 (11)	0.0487 (11)	0.0130 (8)	0.0233 (8)	0.0116 (9)
C5	0.0314 (9)	0.0460 (12)	0.0597 (13)	0.0201 (9)	0.0269 (9)	0.0074 (10)
C6	0.0204 (8)	0.0495 (12)	0.0376 (9)	0.0033 (8)	0.0177 (7)	−0.0030 (9)
C7	0.0189 (7)	0.0404 (11)	0.0251 (8)	−0.0020 (7)	0.0087 (7)	0.0017 (7)
C8	0.0147 (7)	0.0306 (9)	0.0229 (8)	0.0023 (6)	0.0066 (6)	0.0004 (7)
N2	0.0181 (6)	0.0228 (7)	0.0201 (6)	0.0053 (5)	0.0128 (5)	0.0060 (5)
N1	0.0134 (5)	0.0196 (7)	0.0161 (6)	0.0022 (5)	0.0081 (5)	−0.0003 (5)
C9	0.0167 (6)	0.0184 (8)	0.0164 (6)	−0.0002 (6)	0.0060 (5)	−0.0006 (6)
C10	0.0228 (7)	0.0173 (8)	0.0209 (7)	0.0022 (6)	0.0109 (6)	0.0010 (6)
C11	0.0372 (9)	0.0278 (10)	0.0280 (8)	−0.0102 (7)	0.0110 (7)	−0.0019 (7)
C12	0.0428 (10)	0.0303 (10)	0.0407 (10)	−0.0142 (8)	0.0154 (9)	−0.0007 (8)
C13	0.0241 (7)	0.0185 (8)	0.0244 (7)	0.0047 (6)	0.0139 (6)	0.0030 (6)
C14	0.0216 (7)	0.0288 (10)	0.0385 (9)	0.0033 (7)	0.0124 (7)	0.0056 (8)
C15	0.0280 (8)	0.0395 (11)	0.0571 (12)	0.0144 (8)	0.0237 (9)	0.0214 (9)
N3	0.0196 (6)	0.0213 (7)	0.0167 (6)	−0.0013 (5)	0.0072 (5)	−0.0016 (5)
C16	0.0157 (6)	0.0195 (8)	0.0162 (6)	0.0031 (6)	0.0090 (5)	0.0028 (6)
S1	0.02393 (19)	0.0196 (2)	0.0279 (2)	−0.00579 (15)	0.01512 (16)	−0.00852 (16)

Geometric parameters (Å, º) top

Ni1—N3	2.0059 (13)	N2—H2N	0.824 (17)
Ni1—N3ⁱ	2.0059 (12)	N1—C9	1.2829 (19)
Ni1—O1ⁱ	2.1028 (9)	C9—C13	1.4994 (18)
Ni1—O1	2.1028 (9)	C9—C10	1.5086 (19)
Ni1—N1ⁱ	2.1332 (12)	C10—C11	1.536 (2)
Ni1—N1	2.1332 (12)	C10—H10A	0.9900
O1—C1	1.2249 (17)	C10—H10B	0.9900
C1—O2	1.3350 (15)	C11—C12	1.523 (2)
C1—N2	1.3380 (19)	C11—H11A	0.9900
O2—C2	1.4467 (17)	C11—H11B	0.9900
C2—C3	1.5066 (18)	C12—H12A	0.9800
C2—H2A	0.9900	C12—H12B	0.9800
C2—H2B	0.9900	C12—H12C	0.9800
C3—C8	1.381 (2)	C13—C14	1.527 (2)
C3—C4	1.389 (2)	C13—H13A	0.9900
C4—C5	1.392 (2)	C13—H13B	0.9900
C4—H4	0.9500	C14—C15	1.530 (2)
C5—C6	1.375 (3)	C14—H14A	0.9900
C5—H5	0.9500	C14—H14B	0.9900
C6—C7	1.374 (2)	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.396 (2)	C15—H15C	0.9800
C7—H7	0.9500	N3—C16	1.1582 (19)
C8—H8	0.9500	C16—S1	1.6386 (16)
N2—N1	1.3985 (15)

N3—Ni1—N3ⁱ	180.00 (7)	N1—N2—H2N	122.8 (12)
N3—Ni1—O1ⁱ	91.21 (4)	C9—N1—N2	116.57 (11)
N3ⁱ—Ni1—O1ⁱ	88.79 (4)	C9—N1—Ni1	136.26 (9)
N3—Ni1—O1	88.79 (4)	N2—N1—Ni1	106.86 (8)
N3ⁱ—Ni1—O1	91.21 (4)	N1—C9—C13	118.34 (12)
O1ⁱ—Ni1—O1	180.0	N1—C9—C10	124.70 (12)
N3—Ni1—N1ⁱ	88.34 (5)	C13—C9—C10	116.88 (13)
N3ⁱ—Ni1—N1ⁱ	91.66 (5)	C9—C10—C11	110.23 (12)
O1ⁱ—Ni1—N1ⁱ	78.29 (4)	C9—C10—H10A	109.6
O1—Ni1—N1ⁱ	101.71 (4)	C11—C10—H10A	109.6
N3—Ni1—N1	91.66 (5)	C9—C10—H10B	109.6
N3ⁱ—Ni1—N1	88.34 (5)	C11—C10—H10B	109.6
O1ⁱ—Ni1—N1	101.71 (4)	H10A—C10—H10B	108.1
O1—Ni1—N1	78.29 (4)	C12—C11—C10	112.14 (14)
N1ⁱ—Ni1—N1	180.0	C12—C11—H11A	109.2
C1—O1—Ni1	110.38 (9)	C10—C11—H11A	109.2
O1—C1—O2	124.76 (13)	C12—C11—H11B	109.2
O1—C1—N2	124.70 (12)	C10—C11—H11B	109.2
O2—C1—N2	110.53 (12)	H11A—C11—H11B	107.9
C1—O2—C2	116.34 (11)	C11—C12—H12A	109.5
O2—C2—C3	107.88 (12)	C11—C12—H12B	109.5
O2—C2—H2A	110.1	H12A—C12—H12B	109.5
C3—C2—H2A	110.1	C11—C12—H12C	109.5
O2—C2—H2B	110.1	H12A—C12—H12C	109.5
C3—C2—H2B	110.1	H12B—C12—H12C	109.5
H2A—C2—H2B	108.4	C9—C13—C14	111.94 (12)
C8—C3—C4	119.14 (13)	C9—C13—H13A	109.2
C8—C3—C2	122.57 (13)	C14—C13—H13A	109.2
C4—C3—C2	118.26 (14)	C9—C13—H13B	109.2
C3—C4—C5	120.33 (17)	C14—C13—H13B	109.2
C3—C4—H4	119.8	H13A—C13—H13B	107.9
C5—C4—H4	119.8	C13—C14—C15	111.43 (15)
C6—C5—C4	120.24 (16)	C13—C14—H14A	109.3
C6—C5—H5	119.9	C15—C14—H14A	109.3
C4—C5—H5	119.9	C13—C14—H14B	109.3
C7—C6—C5	119.73 (14)	C15—C14—H14B	109.3
C7—C6—H6	120.1	H14A—C14—H14B	108.0
C5—C6—H6	120.1	C14—C15—H15A	109.5
C6—C7—C8	120.48 (16)	C14—C15—H15B	109.5
C6—C7—H7	119.8	H15A—C15—H15B	109.5
C8—C7—H7	119.8	C14—C15—H15C	109.5
C3—C8—C7	120.07 (15)	H15A—C15—H15C	109.5
C3—C8—H8	120.0	H15B—C15—H15C	109.5
C7—C8—H8	120.0	C16—N3—Ni1	163.23 (11)
C1—N2—N1	116.66 (11)	N3—C16—S1	178.75 (14)
C1—N2—H2N	120.5 (12)

Ni1—O1—C1—O2	169.27 (11)	O1—C1—N2—N1	−2.4 (2)
Ni1—O1—C1—N2	−11.39 (18)	O2—C1—N2—N1	177.07 (12)
O1—C1—O2—C2	6.7 (2)	C1—N2—N1—C9	−160.49 (13)
N2—C1—O2—C2	−172.72 (12)	C1—N2—N1—Ni1	14.19 (15)
C1—O2—C2—C3	168.23 (12)	N2—N1—C9—C13	179.49 (12)
O2—C2—C3—C8	−19.5 (2)	Ni1—N1—C9—C13	6.9 (2)
O2—C2—C3—C4	162.63 (15)	N2—N1—C9—C10	3.0 (2)
C8—C3—C4—C5	0.4 (3)	Ni1—N1—C9—C10	−169.67 (10)
C2—C3—C4—C5	178.27 (17)	N1—C9—C10—C11	79.24 (18)
C3—C4—C5—C6	0.2 (3)	C13—C9—C10—C11	−97.34 (15)
C4—C5—C6—C7	−0.3 (3)	C9—C10—C11—C12	173.28 (14)
C5—C6—C7—C8	−0.3 (3)	N1—C9—C13—C14	101.19 (16)
C4—C3—C8—C7	−0.9 (2)	C10—C9—C13—C14	−82.00 (17)
C2—C3—C8—C7	−178.70 (15)	C9—C13—C14—C15	173.33 (13)
C6—C7—C8—C3	0.8 (3)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C8 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1ⁱⁱ	0.824 (17)	2.507 (17)	3.2830 (12)	157.3 (16)
C8—H8···S1ⁱⁱ	0.95	2.94	3.7080 (16)	139
C10—H10A···S1ⁱⁱ	0.99	3.00	3.9059 (14)	154
C10—H10B···S1ⁱⁱⁱ	0.99	2.94	3.8464 (15)	153
C13—H13A···O1ⁱ	0.99	2.35	3.1783 (18)	141
C2—H2A···Cg3^iv	0.99	2.72	3.6041 (17)	149

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y−1/2, −z+5/2; (iii) x, y−1, z; (iv) −x, −y, −z+2.

Percentage contributions to the Hirshfeld surface for 1 top

Contacts	Included surface area %
H···H	55.5
H···C/C···H	18.8
H···S/S···H	16.6
H···N/N···H	4.3
H···O/O···H	3.2
O···C/C···O	0.7
O···S/S···O	0.6

Acknowledgements

We thank the University of Otago for the purchase of the diffractometer and the Chemistry Department, University of Otago for support of the work of JS.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gergely, J., Morgan, J. B. & Overman, L. E. (2006). J. Org. Chem. 71, 9144–9152. CSD CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New Zealand. Google Scholar
Lever, A. B. P. (1984). Inorganic Electronic Spectroscopy, 2nd ed. Amsterdam: Elsevier. Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nithya, P., Govindarajan, S. & Simpson, J. (2019a). IUCrData, 4, x190812. Google Scholar
Nithya, P., Helena, S., Simpson, J., Ilanchelian, M., Muthusankar, A. & Govindarajan, S. (2016). J. Photochem. Photobiol. B, 165, 220–231. Web of Science CSD CrossRef CAS PubMed Google Scholar
Nithya, P., Rajamanikandan, R., Simpson, J., Ilanchelian, M. & Govindarajan, S. (2018b). Polyhedron, 145, 200–217. CSD CrossRef CAS Google Scholar
Nithya, P., Simpson, J. & Govindarajan, S. (2017b). Inorg. Chim. Acta, 467, 180–193. CSD CrossRef CAS Google Scholar
Nithya, P., Simpson, J. & Govindarajan, S. (2018a). Polyhedron, 141, 5–16. CSD CrossRef CAS Google Scholar
Nithya, P., Simpson, J., Helena, S., Rajamanikandan, R. & Govindarajan, S. (2017a). J. Therm. Anal. Calorim. 129, 1001–1019. CSD CrossRef CAS Google Scholar
Nithya, P., Simpson, J. & Govindarajan, S. (2019b). J. Coord. Chem. 72, 1845–1864. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.