Bis{4-methylbenzyl 2-[4-(propan-2-yl)benzyl­idene]hydrazine­carbodi­thio­ato-κ2N2,S}nickel(II): crystal structure and Hirshfeld surface analysis

Yusof, E.N.M.; Ravoof, T.B.S.A.; Tahir, M.I.M.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017002419

research communications

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 397-402

https://doi.org/10.1107/S2056989017002419

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Bis{4-methylbenzyl 2-[4-(propan-2-yl)benzylidene]hydrazinecarbodithioato-κ²N²,S}nickel(II): crystal structure and Hirshfeld surface analysis

Enis Nadia Md Yusof,^a Thahira B. S. A. Ravoof,^a ‡ Mohamed I. M. Tahir,^a Mukesh M. Jotani ^b and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor Darul Ehsan, Malaysia, ^bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and ^cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 February 2017; accepted 13 February 2017; online 17 February 2017)

The complete molecule of the title hydrazine carbodithioate complex, [Ni(C₁₉H₂₁N₂S₂)₂], is generated by the application of a centre of inversion. The Ni^II atom is N,S-chelated by two hydrazinecarbodithioate ligands, which provide a trans-N₂S₂ donor set that defines a distorted square-planar geometry. The conformation of the five-membered chelate ring is an envelope with the Ni^II atom being the flap atom. In the crystal, p-tolyl-C—H⋯π(benzene-ⁱPr), ⁱPr-C—H⋯π(p-tolyl) and π–π interactions [between p-tolyl rings with inter-centroid distance = 3.8051 (12) Å] help to consolidate the three-dimensional architecture. The analysis of the Hirshfeld surface confirms the importance of H-atom contacts in establishing the packing.

Keywords: crystal structure; nickel(II); hydrazine carbodithioate; Hirshfeld surface analysis.

CCDC reference: 1532446

1. Chemical context

Schiff bases derived from S-R-dithiocarbazate (R = methyl/benzyl/methylbenzyl) and heterocyclic aldehydes or ketones have received much attention in recent years owing to their cytotoxicity (Ali et al., 2002 ; Beshir et al., 2008 ; Yusof et al., 2015a ,b ), as well as their specific and selective anti-bacterial and anti-fungal properties (Low et al., 2014 ; Maia et al., 2010 ; Pavan et al., 2010 ).

Schiff bases that react with different metal ions often show different types of coordination modes. Metal complexes are versatile molecules with a wide range of pharmacological properties due to the inherent characteristics of both the central metal atoms and ligands (Meggers, 2009 ). Various transition metal complexes have been reported to induce DNA cleavage by attacking the sugar or base moieties of DNA through the formation of reactive oxygen species (ROS) (Burrows & Muller, 1998 ). A nickel(II) bis-dithiocarbazate complex has been used in the photo-catalytic production of hydrogen as a catalyst (Wise et al., 2015 ). Nickel(II) dithiocarbazate has also been reported to have non-linear optical (NLO) properties (Liu et al., 2016 ) with the potential to be used in signal processing (Bort et al., 2013 ; Hales et al., 2014 ), ultrafast optical communication, data storage, optical limiting (Price et al., 2015 ; Bouit et al., 2007 ), optical switching (Gieseking et al. 2014 ; Thorley et al., 2008 ), logic devices and bio-imaging (Ahn et al., 2012 ; Zhu et al., 2016 ). In line with our interest in evaluating the structures of different isomeric dithiocarbazate Schiff bases and their metal complexes, we report herein the synthesis of the title complex, (I), its X-ray crystal structure determination and a detailed study of the supramolecular association by an analysis of its Hirshfeld surface.

2. Structural commentary

The Ni^II atom in (I), Fig. 1, is located on a crystallographic centre of inversion and is coordinated by two S,N-chelating hydrazinecarbodithioate anions. From symmetry, the resulting N₂S₂ donor set has like atoms trans, and the square-planar coordination geometry is strictly planar. Distortions from the ideal geometry are related to the deviations of angles subtended at nickel by the donor atoms, Table 1. The C1—N1—N2—C2 backbone of the ligand exhibits a twist as seen in the value of the torsion angle, i.e. −165.61 (17)°. Despite being involved in a formal bond to the Ni^II atom, the C1—S1 bond length of 1.7296 (19) Å is still significantly shorter than those formed by the S2 atom, i.e. C1—S2 = 1.7479 (18) Å and C12—S2 = 1.824 (2) Å.

Table 1
Selected bond lengths (Å)

Ni—S1	2.1747 (5)	C1—S2	1.7479 (18)
Ni—N2	1.9137 (15)	C12—S2	1.824 (2)
C1—S1	1.7296 (19)

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The Ni^II atom is situated on a centre of inversion. Unlabelled atoms are related by the symmetry operation (1 − x, 1 − y, 1 − z).

The planarity of the N₂S₂ donor set does not extend to the five-membered chelate ring, which has an envelope conformation with the nickel atom lying 0.465 (2) Å above the least-squares plane through the remaining atoms [r.m.s. deviation = 0.0016 Å]. The sequence of C1=N1, N1—N2 and N2=C2 bond lengths of 1.294 (2), 1.408 (2) and 1.300 (2) Å, respectively, suggests limited conjugation across this residue. Each of the benzene rings of the S- and N-bound substituents is twisted with respect to the least-squares plane through the chelate ring. Thus, a nearly orthogonal relationship exists between the chelate and p-tolyl rings, with the dihedral angle being 89.72 (5)°. Less dramatic is the twist of the ⁱPr-substituted ring with the dihedral angle being 13.83 (9)°. The dihedral angle between the aromatic rings is 84.31 (6)°.

3. Supramolecular features

The two sites potentially available for hydrogen bonding in (I), i.e. the S1 and N1 atoms, are involved in intramolecular interactions, Table 2. The only discernible contacts in the crystal involve π-systems (Spek, 2009 ). Thus, each of the independent rings is involved in C—H⋯π contacts, i.e. p-tolyl-C—H⋯π(ⁱPr-benzene) and ⁱPr-benzene-C—H⋯π(p-tolyl) contacts, Table 2. In addition, centrosymmetrically related p-tolyl rings self-associate via face-to-face, π–π, interactions [inter-centroid distance = 3.8051 (12) Å for symmetry operation −x, −1 − y, 1 − z], indicating the p-tolyl ring participates in two distinct interactions. The result of the supramolecular association is the formation of a three-dimensional architecture, Fig. 2.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the (C3–C8) and (C13–C18) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯S1ⁱ	0.95	2.48	3.0691 (17)	120
C4—H4⋯N1	0.95	2.40	2.865 (2)	110
C17—H17⋯Cg1ⁱⁱ	0.95	2.84	3.761 (2)	164
C11—H11B⋯Cg2ⁱⁱⁱ	0.98	2.96	3.880 (3)	158
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y, -z+1; (iii) $[x, -y-{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The molecular packing in (I)

: a view of the unit-cell contents shown in projection down the b axis. The π–π and C—H⋯π interactions are shown as orange and purple dashed lines, respectively.

4. Analysis of the Hirshfeld surfaces

The Hirshfeld surface analysis for (I) was performed as described in a recent publication of a heavy-atom structure (Mohamad et al., 2017 ). The non-appearance of characteristic red spots on the Hirshfeld surface mapped over d_norm (not shown) clearly indicates the absence of conventional hydrogen bonding in the crystal. The donors and acceptors of C—H⋯π interactions, involving atoms of each of the ⁱPr-benzene and p-tolyl rings, are viewed as blue and light-red regions and correspond to the respective positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (over the range ± 0.025 au), Fig. 3. The acceptors of the C—H⋯π interactions are also viewed as bright-orange spots appearing near ⁱPr-benzene and p-tolyl rings on the Hirshfeld surface mapped over d_e, Fig. 4. The immediate environment about a reference molecule within the Hirshfeld surface mapped with shape-index property is illustrated in Fig. 5. The C—H⋯π and their reciprocal contacts, i.e. π⋯H—C contacts, between ⁱPr–H11B and the p-tolyl ring are represented by red and white dotted lines, respectively in Fig. 5a; the blue dotted lines in Fig. 5a represent π–π stacking between p-tolyl rings at −x, −1 − y, 1 − z. The other C—H⋯π contacts involving p-tolyl-H17 and ⁱPr-benzene rings are illustrated in Fig. 5b.

Figure 3
A view of the Hirshfeld surface for (I)

mapped over the electrostatic potential over the range ±0.025 au.

Figure 4
The view of the Hirshfeld surface mapped over d_e. The bright-orange spots near rings indicate their involvement in C—H⋯π interactions.

Figure 5
Two views (a) and (b) of the Hirshfeld surface mapped with shape-index property about a reference molecule. The C—H⋯π and π⋯H—C interactions in both views are indicated with red and white dotted lines, respectively. The blue dotted lines in (a) indicate π–π stacking between p-tolyl rings.

The overall two-dimensional fingerprint plot and those delineated into H⋯H, C⋯H/H⋯C, S⋯H/H⋯S and N⋯H/H⋯N and C⋯C contacts (McKinnon et al., 2007 ) illustrated in Fig. 6a–f. From the quantitative summary of the relative contributions of the various interatomic contacts given in Table 3, it is important to note the dominant contribution of hydrogen atoms to the Hirshfeld surface, i.e. 95.3%. In the fingerprint plot delineated into H⋯H contacts. Fig. 6b, the points are distributed in the major part of the plot, but they do not make significant contributions to the molecular packing as their interatomic separations are greater than sum of their van der Waals radii, i.e. d_e + d_i > 2.4 Å. The presence of short interatomic C⋯H/H⋯C contacts, see Table 4, and C—H⋯π interactions contribute to the second largest contribution to the Hirshfeld surface, i.e. 22.2%. This is consistent with the fingerprint plot, Fig. 6c, where the short interatomic C⋯H/H⋯C contacts appear as a pair of small peaks at d_e + d_i ∼ 2.8 Å and also as the blue regions around the participating hydrogen atoms, namely H5 and H10B, on the Hirshfeld surface mapped over electrostatic potential, Fig. 3. The involvement of the chelating S1 and N1 atoms in intramolecular interactions, Table 2, prevents them from forming intermolecular S⋯H/H⋯S and N⋯H/H⋯N contacts. However, the symmetrical distribution of points with the usual characteristics in their respective plots, Fig. 6d and e, indicate meaningful contributions to the Hirshfeld surface, Table 3. A small, i.e. 2.1%, but recognizable contribution from C⋯C contacts to the Hirshfeld surface is ascribed to π–π stacking interactions between symmetry-related p-tolyl rings, and appear as an arrow-like distribution of points around d_e = d_i 1.9 Å in Fig. 6f. The other contacts have low percentage contributions to the surface and are likely to have negligible effects on the molecular packing, Table 3.

Table 3
Percentage contribution of the different intermolecular contacts to the Hirshfeld surface in (I)

Contact	% contribution
H⋯H	52.5
C⋯H/H⋯C	22.2
S⋯H/H⋯S	15.3
N⋯H/H⋯N	3.3
C⋯C	2.1
Ni⋯H/H⋯Ni	2.0
S⋯N/N⋯S	1.8
C⋯S/S⋯C	0.4
S⋯S	0.3
C⋯N/N⋯C	0.1

Table 4
Short interatomic contacts in (I)

Contact	distance	symmetry operation
C16⋯H10B	2.84	x, − $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
C19⋯H5	2.88	-x, −1 − y, 1 − z

Figure 6
The two-dimensional fingerprint plots for (I)

: (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) S⋯H/H⋯S, (e) N⋯H/H⋯N and (f) C⋯C interactions.

5. Database survey

There are three closely related nickel(II) dithiocarbazate complexes in the crystallographic literature (Groom et al., 2016 ); these are illustrated in simplified form in Fig. 7. Complex (II) differs from (I) only in the nature of the terminal substituents (Tan et al., 2012 ). Despite there being only small differences in chemical composition, a distinct coordination geometry is observed, with the Ni^II atom located on a twofold rotation axis and the N₂S₂ donor set having cis-dispositions of like atoms. In (III), with a formal link between the two imine functionalities, the cis-N₂S₂ arrangement is imposed by the geometric requirements of the bis(dithiocarbazate) di-anion (Zhou et al., 2002 ). The molecular structure of (IV), again with a cis-N₂S₂ donor set, appears to indicate that steric effects do not preclude a cis-N₂S₂ coordination geometry (Liu et al., 2000 ). With the foregoing in mind, it appears that the molecular structure of (I) is unprecedented, suggesting further systematic investigations in this area are warranted.

Figure 7
Simplified molecular structure diagrams of (I)–(IV). All C atoms, except those of the C—N—N—C backbone, are represented as small black spheres and H atoms have been omitted.

6. Synthesis and crystallization

The S-4-methylbenzyldithiocarbazate (S4MDTC) precursor was synthesized by following a procedure adapted from the literature (Omar et al., 2014 ). The Schiff base was also synthesized using a procedure adapted from the literature (Yusof et al., 2015b) by the reaction of S4MDTC (2.12 g, 0.01 mol), dissolved in hot acetonitrile (100 ml), with an equimolar amount of 4-isopropylbenzaldehyde (1.48 g, 0.01 mol) in absolute ethanol (20 ml). The mixture was then heated at 353 K until half of the mixture solution reduced and allowed to cool to room temperature until a precipitate formed. The compound was recrystallized from ethanol solution and dried over silica gel.

The synthesized Schiff base (0.33 g, 1 mmol) was dissolved in hot acetonitrile (50 ml) and added to nickel(II) acetate tetrahydrate (0.13 g, 0.5 mmol) in an ethanolic solution (30 ml). The mixture was heated and stirred to reduce the volume of the solution. Precipitation occurred once the mixture cooled to room temperature. The precipitate then was filtered and dried over silica gel. The complex was recrystallized from its methanol solution. Brown prismatic crystals were formed from the filtrate after being left to stand for a month. The crystals were filtered and washed with absolute ethanol at room temperature. Yield: 70%. M.p.: 479–480 K. Elemental composition calculated for C₃₈H₄₂N₄NiS₄: C, 61.53; H, 5.71; N, 7.55. Found: C, 61.67; H, 5.87; N, 7.55%. FT–IR (ATR, cm⁻¹): 1589, ν(C=N); 997, ν(N—N); 823, ν(C=S).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C).

Table 5
Experimental details

Crystal data
Chemical formula	[Ni(C₁₉H₂₁N₂S₂)₂]
M_r	741.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.5799 (7), 7.3910 (3), 21.9848 (16)
β (°)	103.033 (7)
V (Å³)	1833.1 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.79
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.895, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8467, 4192, 3393
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.085, 1.02
No. of reflections	4192
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.24
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1532446

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017002419/hb7658sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002419/hb7658Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis{4-methylbenzyl 2-[4-(propan-2-yl)benzylidene]hydrazinecarbodithioato-κ²N²,S}nickel(II): top

Crystal data top

[Ni(C₁₉H₂₁N₂S₂)₂]	F(000) = 780
M_r = 741.70	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 11.5799 (7) Å	Cell parameters from 3077 reflections
b = 7.3910 (3) Å	θ = 2.3–28.7°
c = 21.9848 (16) Å	µ = 0.79 mm⁻¹
β = 103.033 (7)°	T = 100 K
V = 1833.1 (2) Å³	Prism, brown
Z = 2	0.30 × 0.20 × 0.10 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	4192 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3393 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 16.1952 pixels mm^-1	θ_max = 28.6°, θ_min = 2.3°
ω scans	h = −15→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −9→9
T_min = 0.895, T_max = 1.000	l = −27→29
8467 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0367P)² + 0.7493P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4192 reflections	Δρ_max = 0.48 e Å⁻³
217 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
Ni	0.5000	0.5000	0.5000	0.01242 (9)
S1	0.46625 (4)	0.27399 (6)	0.43507 (2)	0.01691 (12)
S2	0.29415 (4)	−0.01653 (6)	0.43496 (2)	0.01892 (12)
N1	0.36782 (13)	0.1991 (2)	0.53197 (7)	0.0153 (3)
N2	0.43911 (13)	0.3485 (2)	0.55606 (7)	0.0141 (3)
C1	0.37730 (16)	0.1603 (2)	0.47593 (9)	0.0150 (4)
C2	0.45497 (16)	0.3715 (2)	0.61599 (9)	0.0156 (4)
H2	0.5057	0.4692	0.6325	0.019*
C3	0.40706 (16)	0.2706 (2)	0.66191 (9)	0.0158 (4)
C4	0.37058 (16)	0.0885 (3)	0.65720 (9)	0.0173 (4)
H4	0.3835	0.0158	0.6237	0.021*
C5	0.31580 (17)	0.0154 (3)	0.70149 (9)	0.0191 (4)
H5	0.2931	−0.1084	0.6981	0.023*
C6	0.29286 (17)	0.1173 (3)	0.75084 (9)	0.0192 (4)
C7	0.33687 (18)	0.2946 (3)	0.75775 (9)	0.0215 (4)
H7	0.3273	0.3649	0.7925	0.026*
C8	0.39416 (17)	0.3687 (3)	0.71472 (9)	0.0197 (4)
H8	0.4252	0.4879	0.7210	0.024*
C9	0.21599 (19)	0.0493 (3)	0.79346 (10)	0.0247 (5)
H9	0.2445	0.1068	0.8353	0.030*
C10	0.0885 (2)	0.1130 (4)	0.76693 (13)	0.0426 (7)
H10A	0.0864	0.2455	0.7655	0.064*
H10B	0.0371	0.0696	0.7937	0.064*
H10C	0.0604	0.0646	0.7247	0.064*
C11	0.2185 (2)	−0.1560 (3)	0.80247 (11)	0.0298 (5)
H11A	0.1814	−0.2148	0.7629	0.045*
H11B	0.1749	−0.1879	0.8343	0.045*
H11C	0.3009	−0.1968	0.8159	0.045*
C12	0.21972 (18)	−0.1039 (3)	0.49369 (9)	0.0202 (4)
H12A	0.2782	−0.1605	0.5283	0.024*
H12B	0.1800	−0.0041	0.5110	0.024*
C13	0.12954 (16)	−0.2422 (3)	0.46281 (9)	0.0167 (4)
C14	0.15875 (17)	−0.4252 (3)	0.46395 (9)	0.0195 (4)
H14	0.2363	−0.4633	0.4841	0.023*
C15	0.07536 (19)	−0.5521 (3)	0.43589 (10)	0.0227 (4)
H15	0.0966	−0.6764	0.4372	0.027*
C16	−0.03838 (18)	−0.5005 (3)	0.40599 (10)	0.0212 (4)
C17	−0.06739 (17)	−0.3171 (3)	0.40435 (10)	0.0230 (4)
H17	−0.1447	−0.2791	0.3838	0.028*
C18	0.01567 (17)	−0.1900 (3)	0.43244 (10)	0.0211 (4)
H18	−0.0054	−0.0656	0.4309	0.025*
C19	−0.1304 (2)	−0.6381 (3)	0.37581 (11)	0.0329 (5)
H19A	−0.1946	−0.6411	0.3982	0.049*
H19B	−0.0936	−0.7580	0.3775	0.049*
H19C	−0.1626	−0.6045	0.3322	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.01367 (16)	0.01287 (16)	0.01220 (17)	−0.00309 (12)	0.00605 (13)	−0.00017 (13)
S1	0.0214 (2)	0.0164 (2)	0.0156 (2)	−0.00518 (18)	0.00956 (19)	−0.00249 (19)
S2	0.0239 (2)	0.0188 (2)	0.0157 (2)	−0.00893 (18)	0.0080 (2)	−0.0039 (2)
N1	0.0169 (8)	0.0147 (7)	0.0157 (8)	−0.0057 (6)	0.0062 (6)	−0.0015 (7)
N2	0.0141 (7)	0.0131 (7)	0.0160 (8)	−0.0033 (6)	0.0054 (6)	−0.0013 (6)
C1	0.0160 (9)	0.0122 (8)	0.0174 (9)	−0.0010 (7)	0.0049 (8)	0.0020 (7)
C2	0.0154 (9)	0.0155 (9)	0.0165 (10)	−0.0035 (7)	0.0049 (8)	0.0003 (8)
C3	0.0146 (9)	0.0205 (9)	0.0127 (9)	−0.0035 (7)	0.0037 (7)	0.0012 (8)
C4	0.0185 (9)	0.0198 (9)	0.0144 (9)	−0.0022 (7)	0.0052 (8)	−0.0012 (8)
C5	0.0202 (9)	0.0200 (9)	0.0169 (10)	−0.0057 (7)	0.0040 (8)	0.0018 (8)
C6	0.0187 (9)	0.0255 (10)	0.0133 (9)	−0.0029 (8)	0.0037 (8)	0.0027 (8)
C7	0.0275 (11)	0.0258 (10)	0.0126 (9)	−0.0035 (8)	0.0074 (8)	−0.0033 (8)
C8	0.0218 (10)	0.0214 (10)	0.0159 (10)	−0.0051 (8)	0.0040 (8)	0.0001 (8)
C9	0.0275 (11)	0.0317 (11)	0.0167 (10)	−0.0059 (9)	0.0089 (9)	0.0021 (9)
C10	0.0313 (13)	0.0582 (17)	0.0461 (16)	0.0062 (11)	0.0250 (12)	0.0199 (14)
C11	0.0330 (12)	0.0345 (12)	0.0240 (11)	−0.0100 (10)	0.0109 (10)	0.0080 (10)
C12	0.0232 (10)	0.0227 (10)	0.0173 (10)	−0.0079 (8)	0.0101 (8)	−0.0014 (8)
C13	0.0170 (9)	0.0199 (9)	0.0156 (9)	−0.0052 (7)	0.0086 (8)	−0.0010 (8)
C14	0.0199 (10)	0.0203 (9)	0.0189 (10)	0.0007 (8)	0.0059 (8)	0.0015 (8)
C15	0.0326 (11)	0.0165 (9)	0.0207 (10)	−0.0021 (8)	0.0094 (9)	0.0000 (8)
C16	0.0260 (10)	0.0230 (10)	0.0159 (10)	−0.0113 (8)	0.0074 (8)	−0.0010 (8)
C17	0.0155 (9)	0.0301 (11)	0.0225 (11)	−0.0019 (8)	0.0025 (8)	0.0032 (9)
C18	0.0222 (10)	0.0174 (9)	0.0251 (11)	−0.0004 (8)	0.0080 (9)	0.0024 (9)
C19	0.0376 (13)	0.0351 (12)	0.0251 (12)	−0.0209 (10)	0.0051 (10)	−0.0034 (10)

Geometric parameters (Å, º) top

Ni—S1	2.1747 (5)	C9—H9	1.0000
Ni—N2	1.9137 (15)	C10—H10A	0.9800
Ni—N2ⁱ	1.9138 (15)	C10—H10B	0.9800
Ni—S1ⁱ	2.1746 (5)	C10—H10C	0.9800
C1—S1	1.7296 (19)	C11—H11A	0.9800
C1—S2	1.7479 (18)	C11—H11B	0.9800
C12—S2	1.824 (2)	C11—H11C	0.9800
N1—C1	1.294 (2)	C12—C13	1.509 (2)
N1—N2	1.408 (2)	C12—H12A	0.9900
N2—C2	1.300 (2)	C12—H12B	0.9900
C2—C3	1.461 (3)	C13—C18	1.391 (3)
C2—H2	0.9500	C13—C14	1.393 (3)
C3—C8	1.405 (3)	C14—C15	1.387 (3)
C3—C4	1.408 (3)	C14—H14	0.9500
C4—C5	1.386 (3)	C15—C16	1.386 (3)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.395 (3)	C16—C17	1.395 (3)
C5—H5	0.9500	C16—C19	1.514 (3)
C6—C7	1.401 (3)	C17—C18	1.386 (3)
C6—C9	1.516 (3)	C17—H17	0.9500
C7—C8	1.385 (3)	C18—H18	0.9500
C7—H7	0.9500	C19—H19A	0.9800
C8—H8	0.9500	C19—H19B	0.9800
C9—C11	1.529 (3)	C19—H19C	0.9800
C9—C10	1.534 (3)

N2—Ni—N2ⁱ	180.00 (7)	C9—C10—H10A	109.5
N2—Ni—S1ⁱ	93.71 (5)	C9—C10—H10B	109.5
N2ⁱ—Ni—S1ⁱ	86.29 (5)	H10A—C10—H10B	109.5
N2—Ni—S1	86.30 (5)	C9—C10—H10C	109.5
N2ⁱ—Ni—S1	93.70 (5)	H10A—C10—H10C	109.5
S1ⁱ—Ni—S1	180.0	H10B—C10—H10C	109.5
C1—S1—Ni	94.14 (6)	C9—C11—H11A	109.5
C1—S2—C12	101.14 (9)	C9—C11—H11B	109.5
C1—N1—N2	111.31 (15)	H11A—C11—H11B	109.5
C2—N2—N1	114.86 (15)	C9—C11—H11C	109.5
C2—N2—Ni	126.01 (13)	H11A—C11—H11C	109.5
N1—N2—Ni	119.11 (12)	H11B—C11—H11C	109.5
N1—C1—S1	125.12 (14)	C13—C12—S2	108.11 (14)
N1—C1—S2	120.09 (14)	C13—C12—H12A	110.1
S1—C1—S2	114.77 (11)	S2—C12—H12A	110.1
N2—C2—C3	130.15 (17)	C13—C12—H12B	110.1
N2—C2—H2	114.9	S2—C12—H12B	110.1
C3—C2—H2	114.9	H12A—C12—H12B	108.4
C8—C3—C4	117.91 (18)	C18—C13—C14	118.53 (17)
C8—C3—C2	115.80 (16)	C18—C13—C12	120.86 (17)
C4—C3—C2	126.26 (18)	C14—C13—C12	120.60 (17)
C5—C4—C3	119.90 (18)	C15—C14—C13	120.43 (18)
C5—C4—H4	120.1	C15—C14—H14	119.8
C3—C4—H4	120.1	C13—C14—H14	119.8
C4—C5—C6	122.24 (18)	C16—C15—C14	121.13 (19)
C4—C5—H5	118.9	C16—C15—H15	119.4
C6—C5—H5	118.9	C14—C15—H15	119.4
C5—C6—C7	117.45 (18)	C15—C16—C17	118.47 (18)
C5—C6—C9	122.87 (18)	C15—C16—C19	121.53 (19)
C7—C6—C9	119.53 (18)	C17—C16—C19	120.00 (19)
C8—C7—C6	120.95 (19)	C18—C17—C16	120.55 (18)
C8—C7—H7	119.5	C18—C17—H17	119.7
C6—C7—H7	119.5	C16—C17—H17	119.7
C7—C8—C3	121.12 (18)	C17—C18—C13	120.87 (18)
C7—C8—H8	119.4	C17—C18—H18	119.6
C3—C8—H8	119.4	C13—C18—H18	119.6
C6—C9—C11	114.35 (18)	C16—C19—H19A	109.5
C6—C9—C10	108.19 (18)	C16—C19—H19B	109.5
C11—C9—C10	110.02 (19)	H19A—C19—H19B	109.5
C6—C9—H9	108.0	C16—C19—H19C	109.5
C11—C9—H9	108.0	H19A—C19—H19C	109.5
C10—C9—H9	108.0	H19B—C19—H19C	109.5

C1—N1—N2—C2	−165.61 (17)	C4—C3—C8—C7	−6.2 (3)
C1—N1—N2—Ni	15.80 (19)	C2—C3—C8—C7	172.25 (17)
N2—N1—C1—S1	0.5 (2)	C5—C6—C9—C11	30.3 (3)
N2—N1—C1—S2	−178.25 (12)	C7—C6—C9—C11	−154.27 (19)
Ni—S1—C1—N1	−12.72 (17)	C5—C6—C9—C10	−92.6 (2)
Ni—S1—C1—S2	166.05 (9)	C7—C6—C9—C10	82.8 (2)
C12—S2—C1—N1	−3.28 (18)	C1—S2—C12—C13	171.91 (13)
C12—S2—C1—S1	177.88 (11)	S2—C12—C13—C18	−86.5 (2)
N1—N2—C2—C3	−2.5 (3)	S2—C12—C13—C14	93.3 (2)
Ni—N2—C2—C3	176.01 (15)	C18—C13—C14—C15	−0.6 (3)
N2—C2—C3—C8	−152.0 (2)	C12—C13—C14—C15	179.55 (19)
N2—C2—C3—C4	26.3 (3)	C13—C14—C15—C16	0.2 (3)
C8—C3—C4—C5	4.7 (3)	C14—C15—C16—C17	0.4 (3)
C2—C3—C4—C5	−173.58 (18)	C14—C15—C16—C19	−179.4 (2)
C3—C4—C5—C6	1.2 (3)	C15—C16—C17—C18	−0.5 (3)
C4—C5—C6—C7	−5.6 (3)	C19—C16—C17—C18	179.2 (2)
C4—C5—C6—C9	169.86 (18)	C16—C17—C18—C13	0.0 (3)
C5—C6—C7—C8	4.1 (3)	C14—C13—C18—C17	0.5 (3)
C9—C6—C7—C8	−171.54 (18)	C12—C13—C18—C17	−179.67 (19)
C6—C7—C8—C3	1.8 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the (C3–C8) and (C13–C18) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···S1ⁱ	0.95	2.48	3.0691 (17)	120
C4—H4···N1	0.95	2.40	2.865 (2)	110
C17—H17···Cg1ⁱⁱ	0.95	2.84	3.761 (2)	164
C11—H11B···Cg2ⁱⁱⁱ	0.98	2.96	3.880 (3)	158

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x, −y−3/2, z−1/2.

Percentage contribution of the different intermolecular contacts to the Hirshfeld surface in (I) top

Contact	% contribution
H···H	52.5
C···H/H···C	22.2
S···H/H···S	15.3
N···H/H···N	3.3
C···C	2.1
Ni···H/H···Ni	2.0
S···N/N···S	1.8
C···S/S···C	0.4
S···S	0.3
C···N/N···C	0.1

Short interatomic contacts in (I) top

Contact	distance	symmetry operation
C16···H10B	2.84	x, -1/2 - y, -1/2 + z
C19···H5	2.88	-x, -1 - y, 1 - z

Footnotes

‡Additional correspondence author, e-mail: thahira@upm.edu.my.

Acknowledgements

We thank the Department of Chemistry, Universiti Putra Malaysia (UPM), for access to facilities. This research was funded by UPM and the Malaysian Government under the Malaysian Fundamental Research Grant Scheme (FRGS No. 01-01-16-1833FR) and Geran Penyelidikan-Inisiatif Putra Siswazah (GP-IPS No. 9504600). ENMY also wishes to acknowledge the MyPhD programme (MyBrain15) for the award of a Malaysian Government Scholarship.

Funding information

Funding for this research was provided by: Malaysian Fundamental Research Grant Scheme (award No. FRGS No. 01-01-16-1833FR); Geran Penyelidikan-Inisiatif Putra Siswazah (award No. GP-IPS No. 9504600).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Ahn, H. Y., Yao, S., Wang, X. & Belfield, K. D. (2012). Appl. Mater. Interfaces, 4, 2847–2854. CrossRef CAS Google Scholar
Ali, M. A., Mirza, A. H., Butcher, R. J., Tarafder, M. T. H., Keat, T. B. & Ali, A. M. (2002). J. Inorg. Biochem. 92, 141–148. CSD CrossRef PubMed Google Scholar
Beshir, A. B., Guchhait, S. K., Gascón, J. A. & Fenteany, G. (2008). Bioorg. Med. Chem. Lett. 18, 498–504. CSD CrossRef PubMed CAS Google Scholar
Bort, G., Gallavardin, T., Ogden, D. & Dalko, P. I. (2013). Angew. Chem. Int. Ed. 52, 4526–4537. CrossRef CAS Google Scholar
Bouit, P. A., Wetzel, G., Berginc, G., Loiseaux, B., Toupet, L., Feneyrou, P., Bretonnière, Y., Kamada, K., Maury, O. & Andraud, C. (2007). Chem. Mater. 19, 5325–5335. CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burrows, C. J. & Muller, J. G. (1998). Chem. Rev. 98, 1109–1152. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gieseking, R. L., Mukhopadhyay, S., Risko, C. & Brédas, J. L. (2014). ACS Photonics, 1, 261–269. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hales, J. M., Barlow, S., Kim, H., Mukhopadhyay, S., Brédas, J. L., Perry, J. W. & Marder, S. R. (2014). Chem. Mater. 26, 549–560. CrossRef CAS Google Scholar
Liu, Z.-H., Duan, C.-Y., Li, J.-H., Liu, Y.-J., Mei, Y.-H. & You, X.-Z. (2000). New J. Chem. 24, 1057–1062. CrossRef CAS Google Scholar
Liu, X., Xiao, Z., Huang, A., Wang, W., Zhang, L., Wang, R. & Sun, D. (2016). New J. Chem. 40, 5957–5965. CSD CrossRef CAS Google Scholar
Low, M. L., Maigre, L., Dorlet, P., Guillot, R., Pagès, J., Crouse, K. A., Policar, C. & Delsuc, N. (2014). Bioconjugate Chem. 25, 2269–2284. CSD CrossRef CAS Google Scholar
Maia, P. I. da S., Fernandes, A. G. de A., Silva, J. J. N., Andricopulo, A. D., Lemos, S. S., Lang, E. S., Abram, U. & Deflon, V. M. (2010). J. Inorg. Biochem. 104, 1276–1282. Web of Science CSD CrossRef CAS PubMed Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Meggers, E. (2009). Chem. Commun. pp. 1001–1010. CrossRef Google Scholar
Mohamad, R., Awang, N., Kamaludin, N. F., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 260–265. CSD CrossRef IUCr Journals Google Scholar
Omar, S. A., Ravoof, T. B., Tahir, M. I. M. & Crouse, K. A. (2014). Transition Met. Chem. 39, 119–126. Web of Science CSD CrossRef CAS Google Scholar
Pavan, F. R., Maia, P. I. da S., Leite, S. R. A., Deflon, V. M., Batista, A. A., Sato, D. N., Franzblau, S. G. & Leite, C. Q. F. (2010). Eur. J. Med. Chem. 45, 1898–1905. Web of Science CrossRef CAS PubMed Google Scholar
Price, R. S., Dubinina, G., Wicks, G., Drobizhev, M., Rebane, A. & Schanze, K. S. (2015). Appl. Mater. Interfaces, 7, 10795–10805. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tan, M.-Y., Ravoof, T. B. S. A., Tahir, M. I. M., Crouse, K. A. & Tiekink, E. R. T. (2012). Acta Cryst. E68, m725–m726. CSD CrossRef IUCr Journals Google Scholar
Thorley, K. J., Hales, J. M., Anderson, H. L. & Perry, J. W. (2008). Angew. Chem. Int. Ed. 47, 7095–7098. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wise, C. F., Liu, D., Mayer, K. J., Crossland, P. M., Hartley, C. L. & McNamara, W. R. (2015). Dalton Trans. 44, 14265–14271. Web of Science CSD CrossRef CAS PubMed Google Scholar
Yusof, E. N. Md., Ravoof, T. B. S. A., Jamsari, J., Tiekink, E. R. T., Veerakumarasivam, A., Crouse, K. A., Tahir, M. I. M. & Ahmad, H. (2015a). Inorg. Chim. Acta, 438, 85–93. CSD CrossRef CAS Google Scholar
Yusof, E. N. Md., Ravoof, T. B. S. A., Tiekink, E. R. T., Veerakumarasivam, A., Crouse, K. A., Tahir, M. M. I. & Ahmad, H. (2015b). Int. J. Mol. Sci. 16, 11034–11054. CAS PubMed Google Scholar
Zhou, J.-H., Wang, Y.-X., Chen, X.-T., Song, Y.-L., Weng, L.-H. & You, X.-Z. (2002). Chin. J. Inorg. Chem. 18, 533–536. CAS Google Scholar
Zhu, Z., Qian, J., Zhao, X., Qin, W., Hu, R., Zhang, H., Li, D., Xu, Z., Tang, B. Z. & He, S. (2016). ACS Nano, 10, 588–597. CrossRef CAS PubMed Google Scholar

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