research communications
Bis{4-methylbenzyl 2-[4-(propan-2-yl)benzylidene]hydrazinecarbodithioato-κ2N2,S}nickel(II): and Hirshfeld surface analysis
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
The complete molecule of the title hydrazine carbodithioate complex, [Ni(C19H21N2S2)2], is generated by the application of a centre of inversion. The NiII 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 NiII 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.
CCDC reference: 1532446
1. Chemical context
S-R-dithiocarbazate (R = methyl/benzyl/methylbenzyl) and heterocyclic or 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).
derived from). 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 and their metal complexes, we report herein the synthesis of the title complex, (I), its X-ray determination and a detailed study of the supramolecular association by an analysis of its Hirshfeld surface.
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, 20092. Structural commentary
The NiII 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 NiII 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.
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The planarity of the N2S2 donor set does not extend to the five-membered chelate ring, which has an 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 −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.
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 dnorm (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 de, 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.
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. de + di > 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 de + di ∼ 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 de = di 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.
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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 NiII 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.
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 . The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C).
details are summarized in Table 5
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Supporting information
CCDC reference: 1532446
https://doi.org/10.1107/S2056989017002419/hb7658sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002419/hb7658Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2011); cell
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).[Ni(C19H21N2S2)2] | F(000) = 780 |
Mr = 741.70 | Dx = 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 |
Agilent Xcalibur Eos Gemini diffractometer | 4192 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3393 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 16.1952 pixels mm-1 | θmax = 28.6°, θmin = 2.3° |
ω scans | h = −15→14 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −9→9 |
Tmin = 0.895, Tmax = 1.000 | l = −27→29 |
8467 measured reflections |
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(Fo2) + (0.0367P)2 + 0.7493P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4192 reflections | Δρmax = 0.48 e Å−3 |
217 parameters | Δρmin = −0.24 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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. |
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 |
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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