[μ2-trans-1,2-Bis­(pyridin-4-yl)ethene-κ2N:N′]bis­{[1,2-bis­(pyridin-4-yl)ethene-κN]bis­[N-(2-hydroxy­eth­yl)-N-iso­propyl­dithio­carbamato-κ2S,S′]cadmium} aceto­nitrile tetra­solvate: crystal structure and Hirshfeld surface analysis

Jotani, M.M.; Poplaukhin, P.; Arman, H.D.; Tiekink, E.R.T.

doi:10.1107/S2056989016010768

research communications

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ISSN: 2056-9890

Volume 72| Part 8| August 2016| Pages 1085-1092

https://doi.org/10.1107/S2056989016010768

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[μ₂-trans-1,2-Bis(pyridin-4-yl)ethene-κ²N:N′]bis{[1,2-bis(pyridin-4-yl)ethene-κN]bis[N-(2-hydroxyethyl)-N-isopropyldithiocarbamato-κ²S,S′]cadmium} acetonitrile tetrasolvate: crystal structure and Hirshfeld surface analysis

Mukesh M. Jotani,^a ‡ Pavel Poplaukhin,^b Hadi D. Arman ^c and Edward R. T. Tiekink ^d ^*

^aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, ^bChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio 43202, USA, ^cDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^dCentre for Crystalline Materials, Faculty 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 28 June 2016; accepted 4 July 2016; online 12 July 2016)

The asymmetric unit of the title compound, [Cd₂(C₁₂H₁₀N₂)₃(C₆H₁₂NOS₂)₄]·4C₂H₃N, comprises a Cd^II atom, two dithiocarbamate (dtc) anions, one and a half trans-1,2-dipyridin-4-ylethylene (bpe) molecules and two acetonitrile solvent molecules. The full binuclear complex is generated by the application of a centre of inversion. The dtc ligands are chelating, one bpe molecule coordinates in a monodentate mode while the other is bidentate bridging. The resulting cis-N₂S₄ coordination geometry is based on an octahedron. Supramolecular layers, sustained by hydroxy-O—H⋯O(hydroxy) and hydroxy-O—H⋯N(bpe) hydrogen bonding, interpenetrate to form a three-dimensional architecture; voids in this arrangement are occupied by the acetonitrile solvent molecules. Additional intermolecular interactions falling within the specified framework have been analysed by Hirshfeld surface analysis, including π–π interactions.

Keywords: crystal structure; dithiocarbamate; 1,2-bis(pyridin-4-yl)ethene; interpenetration; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1489732

1. Chemical context

The recent disclosure of one-dimensional, supramolecular isomers of {Cd[S₂CN(iPr)CH₂CH₂OH]₂}_n notwithstanding (Tan et al., 2013 , 2016 ), the overwhelming majority of binary bis(dialkyldithiocarbamato) compounds of cadmium are usually binuclear with a coordination number of five owing to the presence of equal numbers of chelating and μ₂-tridentate ligands, i.e. are of general formula [Cd(S₂CNR₂)₂]₂ (Tiekink, 2003 ; Tan et al., 2016). However, the dimeric and polymeric aggregates are readily broken down in the presence of bases such as monodentate pyridine, e.g. {Cd[S₂CN(CH₂C(H)Me₂)₂]₂(pyridine)} (Rodina et al., 2011 ) and bidentate 2,2′-bipyridine, e.g. [Cd(S₂CN(Me)iPr)₂(2,2′-bipyridine)] (Wahab et al., 2011 ). Bridging N-donors lead to a greater variety of structures such as the zero-dimensional binuclear compound, [Cd(S₂CNPr₂)₂(2-pyridinealdazine)]₂ (Poplaukhin & Tiekink, 2008 ) and supramolecular chains, e.g. [Cd(S₂CNEt₂)₂(μ₂-1,2-bis(4-pyridyl)ethylene)]_n (Chai et al., 2003 ). The addition of hydrogen-bonding functionality in the dithiocarbamate ligands has greatly enhanced the supramolecular chemistry landscape of related compounds. As a recent exemplar, the formally monomeric compound {Cd[S₂CN(iPr)CH₂CH₂OH]₂}(piperazine) self-assembles into a two-dimensional array via hydroxy-O—H⋯O(hydroxy), hydroxy-O—H⋯N(terminal-piperazine) and coordinating piperazine-N—H⋯O(hydroxy) hydrogen bonds (Safbri et al., 2016 ). As a continuation of investigations in this area, the crystal and molecular structure as well as Hirshfeld surface analysis of the title binuclear compound, {Cd[S₂CN(iPr)CH₂CH₂OH]₂[(4-NC₅H₄)C=C₆H₄N-4)]}₂[(4-NC₅H₄)C=C₆H₄N-4)]·4CH₃CN, (I), featuring both bidentate bridging and monodentate trans-1,2-dipyridin-4-ylethylene ligands is described herein.

2. Structural commentary

The molecular structure of the binuclear title compound, {Cd[S₂CN(iPr)CH₂CH₂OH]₂[(4-NC₅H₄)C=C₆H₄N-4)]}₂[(4-NC₅H₄)C=C₆H₄N-4)]·4CH₃CN, (I), Fig. 1, is situated about a centre of inversion; two acetonitrile molecules of solvation complete the asymmetric unit. Each Cd^II atom is coordinated by two dithiocarbamate ligands and two nitrogen atoms, one derived from a monodentate trans-1,2-dipyridin-4-ylethylene (bispyridylethene; bpe) ligand and another from one end of a bidentate, bridging bpe ligand (located about a centre of inversion). The dithiocarbamate ligands coordinate with significant differences in their Cd—S bond lengths, Table 1. Thus, Δ(Cd—S) = d(Cd—S_long) – d(Cd—S_short) = 0.15 Å for the S1-dithiocarbamate ligand cf. 0.10 Å for the S3-ligand. Nevertheless, there is considerable delocalization of π-electron density in the CdS₂C chelate rings as evidenced by the equivalence of the associated C—S bond lengths, Table 1. The coordination geometry is based on an octahedron. In this description, the more tightly bound S1 and S3 atoms are trans [178.06 (3)°] and the less tightly bound sulfur atoms are trans to nitrogen atoms, Table 1, implying the nitrogen donors are cis. The distortions from the ideal geometry are readily related to the restricted bite angles of the chelating ligands, Table 1. Both bpe ligands exhibit twists as seen in the values of the C14—C15—C18—C18ⁱ and C22—C21—C24—C25 torsion angles of −12.2 (6) and 13.9 (5)° for the bi- and mono-dentate ligands, respectively; symmetry code: (i) 2 − x, −y, 1 − z.

Table 1
Selected geometric parameters (Å, °)

Cd—S1	2.6019 (8)	Cd—N4	2.454 (3)
Cd—S2	2.7457 (8)	C1—S1	1.726 (3)
Cd—S3	2.6043 (8)	C1—S2	1.717 (3)
Cd—S4	2.6967 (8)	C7—S3	1.721 (3)
Cd—N3	2.439 (3)	C7—S4	1.727 (3)

S1—Cd—S2	67.31 (2)	S2—Cd—N4	152.04 (6)
S1—Cd—S3	178.06 (3)	S3—Cd—S4	68.00 (2)
S1—Cd—S4	112.08 (3)	S3—Cd—N3	86.63 (7)
S1—Cd—N3	93.39 (7)	S3—Cd—N4	95.94 (6)
S1—Cd—N4	85.98 (6)	S4—Cd—N3	154.39 (6)
S2—Cd—S3	110.75 (3)	S4—Cd—N4	97.72 (6)
S2—Cd—S4	99.85 (3)	N3—Cd—N4	80.87 (9)
S2—Cd—N3	92.19 (7)

Figure 1
The molecular structure of the binuclear title compound in (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Unlabelled atoms are related by the symmetry operation (2 − x, −y, 1 − z.). The acetonitrile solvent molecules have been omitted for clarity.

3. Supramolecular features

Geometric details of the significant intermolecular interactions are given in Table 2. In the packing, hydroxy-O—H⋯O(hydroxy) hydrogen bonding leads to supramolecular ladders as illustrated in Fig. 2a. These ladders are connected into layers parallel to (101) via hydroxy-O—H⋯N(bpe) hydrogen bonds where the nitrogen atom is derived from the monodentate bpe ligand. Additional ethene-C—H⋯O(hydroxy) interactions are found within this framework, Table 2. As seen from Fig. 2b, this arrangement leads to rectangular channels with Cd⋯Cd separations, which approximate the edges, being 14 and 16 Å. Successive channels are largely occupied by other supramolecular layers, leading to a three-dimensional, concatenated architecture. The smaller voids defined by the interpenetrated structure are occupied by the solvent acetonitrile molecules, Fig. 2c. The N7-acetonitrile molecule is connected to the host framework by pyridyl-C—H⋯N(acetonitrile) interactions whereas the N6-acetonitrile molecule does not form significant interactions in accord with the criteria embodied in PLATON (Spek, 2009 ). This is reflected in the greater displacement ellipsoids for this molecule cf. with the N7-containing molecule. Further analysis of the molecular packing, e.g. pyridyl⋯pyridyl interactions, is given in the following Section.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N5ⁱ	0.83 (4)	1.82 (4)	2.655 (4)	177 (3)
O2—H2O⋯O1ⁱⁱ	0.84 (3)	1.87 (3)	2.689 (3)	165 (5)
C25—H25⋯O2ⁱⁱⁱ	0.95	2.44	3.261 (4)	145
C28—H28⋯N7^iv	0.95	2.56	3.296 (7)	134
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+2, -y+1, -z+2; (iv) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Molecular packing in (I)

: (a) view of the supramolecular ladder sustained by hydroxy-O—H⋯O(hydroxy) hydrogen bonds, shown as orange dashed lines, (b) two-dimensional framework whereby the layers in (a) are connected by hydroxy-O—H⋯N(bpe) hydrogen bonds, shown as blue dashed lines, (c) view of the unit-cell contents shown in projection down the a axis, highlighting the interpenetration of successive supramolecular layers, illustrated in orange and green, with solvent acetonitrile molecules shown in black.

4. Analysis of the Hirshfeld surfaces

Recent Hirshfeld surface analyses of zinc-triad hydroxyethyl-substituted dithiocarbamates has provided key insight into their molecular packing over and beyond hydrogen-bonding considerations. For example, the relatively unusual C—H⋯π(chelate) interactions (Tiekink & Zukerman-Schpector, 2011 ) observed in [Hg(S₂CN(CH₂CH₂OH)₂]_n (Howie et al., 2009 ), are clearly delineated in the Hirshfeld analysis of the molecular packing (Jotani et al., 2016 ). In the present study, using Crystal Explorer 3.1 (Wolff et al., 2012 ), the Hirshfeld surfaces were mapped over d_norm, shape-index, curvedness and electrostatic potential for the asymmetric unit of (I). The electrostatic potentials were calculated using TONTO (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) integrated into Crystal Explorer. Further, the electrostatic potentials were mapped on Hirshfeld surfaces using the STO–3G basis set at Hartree–Fock level of theory over a range ±0.13 au. The contact distances d_i and d_e from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of d_norm. The combination of d_e and d_i in the form of two-dimensional fingerprint plots (McKinnon et al., 2004 ) provides a summary of intermolecular contacts in the crystal.

Two views of Hirshfeld surfaces mapped over d_norm in the −0.2 to 1.8 Å range are shown in Fig. 3. The bright-red spots appearing near pyridyl-N5, hydroxy-O1 and hydrogen atoms H1O and H2O indicate their role as the respective donors and acceptors in the dominant O—H⋯O and O—H⋯N hydrogen bonds; they also appear as blue and red regions, respectively, corresponding to positive and negative electrostatic potentials on the Hirshfeld surface mapped over electrostatic potential, Fig. 4. The light-red spots near ethene-H25, pyridyl-C28 and hydroxy-O2 in Fig. 3 and near acetonitrile-N7, Fig. 5a, indicate their involvement in the intermolecular ethene-C—H⋯O(hydroxy) and pyridyl-C—H⋯N(acetonitrile) interactions. The presence of short intermolecular C⋯C and C⋯H contacts, Table 3, is also evident from the light-red spots appearing near the pyridyl-C16, C19 and C24 and methylene-H3A atoms in Fig. 3. The C18—C18ⁱ link of the bridging bpe ligand can be viewed as a bright-red region around the C18 atom in the d_norm mapped surface, Fig. 3, and as a light-blue region surrounded by a pair of light-red arcs on the surface mapped over electrostatic potential, Fig. 4b; this arises as it is the asymmetric unit that has been investigated not the entire binuclear molecule. With respect to the acetonitrile molecule the d_norm mapped surfaces show only the acetonitrile-N7 to be involved in a significant intermolecular C—H⋯N interaction (Fig. 5a, Table 2), and both acetonitrile molecules had very similar Hirshfeld surfaces mapped over electrostatic potential to that for the N7-molecule illustrated in Fig. 5b.

Table 3
Summary of short interatomic contacts (Å)

Contact	Distance	Symmetry
S1⋯H6A	2.98	2 − x, −y, 2 − z
S4⋯H18	2.97	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
O1⋯H11C	2.64	x, −1 + y, z
O2⋯H30	2.66	2 − x, 1 − y, 2 − z
C1⋯H20	2.83	2 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
C3⋯H2O	2.69 (3)	x, −1 + y, z
C24⋯H3A	2.72	2 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
C28⋯H1O	2.83 (3)	1 + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
C29⋯H1O	2.67 (4)	1 + x, $[{1\over 2}]$ − y, 1 + z
C16⋯C19	3.245 (4)	2 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
C16⋯C20	3.377 (5)	2 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H5A⋯H23	2.31	2 − x, −y, 2 − z

Figure 3
Two views of the Hirshfeld surface mapped over d_norm. The contact points (red) are labelled to indicate the atoms participating in the intermolecular interactions.

Figure 4
Two views of the Hirshfeld surface mapped over the electrostatic potential with positive and negative potential indicated in blue and red, respectively.

Figure 5
A view of the (a) Hirshfeld surface mapped over d_norm and (b) Hirshfeld surface mapped over the electrostatic potential with positive and negative potential indicated in blue and red, respectively, for the N7-acetonitrile molecule.

The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C, N⋯H/H⋯N, C⋯C and S⋯H/H⋯S contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6b-g, respectively; their relative contributions are summarized in Table 4. The H⋯H contacts make the greatest contribution to the Hirshfeld surface, i.e. 51.9% which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule; the single peak at d_e = d_i ∼1.15 Å results from a short intermolecular H⋯H contact between the isopropyl-H5A and pyridyl-H23 atoms, Table 3. In the fingerprint plot delineated into O⋯H/H⋯O contacts, the 6.0% contribution to the Hirshfeld surface arises from the intermolecular O—H⋯O hydrogen bonding and is viewed as a pair of spikes with the tip at d_e + d_i ∼1.8 Å in Fig. 6c. The intermolecular C—H⋯O interactions and short O⋯H/H⋯O contacts, listed in Table 3, are masked by the strong O—H⋯O hydrogen bonding in this plot.

Table 4
Percentage contribution of the different intermolecular contacts to the Hirshfeld surface

Contact	Contribution
H⋯H	51.9
O⋯H/H⋯O	6.0
C⋯H/H⋯C	15.9
N⋯H/H⋯N	10.6
C⋯C	3.1
S⋯H/H⋯S	10.3
C⋯S/S⋯C	0.8
N⋯S/S⋯N	0.7
C⋯N/N⋯C	0.7

Figure 6
Two-dimensional fingerprint plots: (a) overall, and delineated into contributions from different contacts: (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C, (e) N⋯H/H⋯N, (f) C⋯C and (g) S⋯H/H⋯S.

In the absence of C—H⋯π interactions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into C⋯H/H⋯C contacts with 15.9% contribution to the Hirshfeld surface, Fig. 6d, and the pair of thin edges at d_e + d_i ∼2.7 Å result from short interatomic C⋯H/H⋯C contacts, Table 3. A pair of spikes at d_e + d_i ∼1.8 Å correspond to N⋯H/H⋯N contacts, Fig. 6e, confirm the presence of intermolecular O—H⋯N and C—H⋯N interactions. The C⋯C contacts assigned to short interatomic C16⋯C19 and C16⋯C20 contacts listed in Table 3 and π–π stacking interactions within the three-dimensional architecture described in Supramolecular features appear as the two distinct distributions of points in Fig. 6f. The vertex at d_e = d_i = 1.6 Å in the approximately triangular distribution of points in the plot corresponds to short intermolecular C⋯C contacts. The presence of π–π stacking interactions between the centrosymmetrically related N5-pyridyl rings [inter-centroid distance = 3.674 (2) Å, symmetry code: 3 − x, 1 − y, 2 − z] is reflected through the appearance of green points around d_e = d_i ∼1.8 Å, the red and blue triangle pairs on the Hirshfeld surface mapped with shape-index property identified with arrows in the image of Fig. 7, and in the flat region on the Hirshfeld surface mapped over curvedness in Fig. 8. Finally, the S⋯H/H⋯S contacts in the structure with a 10.3% contribution to the surface has a nearly symmetrical distribution of points, Fig. 6g, with the tips at d_e + d_i ∼2.95 Å arising from the short interatomic S⋯H/H⋯S contacts listed in Table 3.

Figure 7
View of Hirshfeld surface mapped with shape-index property. The pairs of red and blue regions, identified with arrows, indicate π–π stacking interactions.

Figure 8
A view of Hirshfeld surface mapped over curvedness for (I)

. The flat regions highlight the involvement of rings in π–π stacking interactions.

An additional descriptor, the enrichment ratio (ER), may be calculated on the basis of Hirshfeld surface analysis (Jelsch et al., 2014 ). This provides further insight into the molecular packing as it indicates the relative propensities to form specific intermolecular interactions. The ER values for (I) are collected in Table 5. The ER value close to but slightly less than unity for H⋯H contacts, i.e. 0.97, is in accord with expectation (Jelsch et al., 2014). The ER value of 1.36 for O⋯H/H⋯O contacts is in the expected 1.2–1.6 range and confirms the involvement of these atoms in the intermolecular O—H⋯O and C—H⋯O interactions. The ER value of 1.20 resulting from the 6% of the surface comprising nitrogen atoms and the 10.6% contribution to the Hirshfeld surface from N⋯H/H⋯N contacts is due to the presence of O—H⋯N hydrogen bonding and the C—H⋯N(acetonitrile) interaction. The high enrichment ratio of 2.23 for the C⋯C contacts reflects the formation of significant π–π stacking interactions and short C⋯C contacts as mentioned above. The ER value close to unity, i.e. 0.92, for C⋯H/H⋯C contacts shows their propensity to form short intermolecular C⋯H/H⋯C contacts. The ER values < 1 related to other contacts and low percentage contribution to the surface do not show any significance in the crystal packing.

Table 5
Enrichment ratios (ER)

Contact	ER
H⋯H	0.97
O⋯H/H⋯O	1.36
N⋯H/H⋯N	1.20
C⋯C	2.23
S⋯H/H⋯S	1.19
C⋯H/H⋯C	0.92
C⋯S/S⋯C	0.58
C⋯N/N⋯C	0.49

5. Database survey

There is a sole example of a cadmium dithiocarbamate coordinated by bpe in the crystallographic literature (Groom et al., 2016 ), namely [Cd(S₂CNEt₂)₂(μ-bpe)]_n, which is a linear coordination polymer with a trans-N₂S₄ donor set (Chai et al., 2003). Reflecting the smaller size of zinc compared to cadmium, the zinc analogues are binuclear zero-dimensional with bpe bridging two five-coordinate (NS₄) zinc atoms (Arman et al., 2009 ). Even in the presence of excess bpe, the [Zn(S₂CNEt₂)₂]₂(μ-bpe) species still forms with non-coordinating bpe included in the structure (Lai & Tiekink, 2003 ). For the analogous xanthate structures, luminescent, zero-dimensional [Zn(S₂COCyEt)₂]₂(μ-bpe) and one-dimensional [Zn(S₂COEt)₂(μ-bpe)]_n are formed with the dimensionality correlated with the steric bulk of the xanthate-bound R groups (Kang et al., 2010 ). With the sterically unencumbered cadmium dithiophosphate analogues, linear coordination polymers are formed regardless of the size of R, i.e. for {Cd[S₂P(OR)₂]₂(μ-bpe)}_n, R = iPr and Cy (Lai & Tiekink, 2004 ).

There are literature precedents for both bidentate, bridging and monodentate bpe ligands in cadmium structures as observed in (I), i.e. [Cd(NO₃)(μ₂-NO₃)(μ-bpe)(bpe)(OH₂)]_n (Dong et al., 1999 ) and [Cd₂(SSO₃)₂(μ-bpe)(bpe)₂(OH₂)₄]_n (Paul et al., 2011 ). Another structure has both bridging and monodentate bpe ligands as well as non-coordinating bpe ligands (and non-coordinating 4,4′-bipyridyl), i.e. [Cd(NO₃)(μ-bpe)(bpe)₂(OH₂)₂]NO₃(bpe)(4,4′-bipyridyl)(H₂O)_4.45 (Lu et al., 2001 ).

6. Synthesis and crystallization

The title compound was isolated regardless of the ratio, i.e. 2:1, 1:1 or 1:2, between the precursor molecules. In a typical experiment, Cd[S₂CN(iPr)CH₂CH₂OH]₂ (190 mg, 0.50 mmol) was dissolved in boiling acetonitrile (30 ml). trans-1,2-Dipyridin-4-ylethylene (47 mg, 0.25 mmol) was added to this solution, which was allowed to slowly cool to room temperature. Yellow prisms precipitated within an hour. The yield was not measured but was close to quantitative based on Cd. M.p. = 463–465 K (uncorrected). IR (neat solid, cm⁻¹): 1607 m, 1449 ms, 1407 s, 1170 s, 1037 s, 968 s, 954 s, 824 s. NMR: ¹H δ (p.p.m.): 8.6 (dd, Ar, 1.46 Hz, 4.68 Hz), 7.6 (dd, Ar, 1.46 Hz, 4.39 Hz), 7.54 (s, –CH=CH–), 5.21 (sept., –CH, 6.72 Hz), 4.82 (t, –OH, 5.56 Hz), 3.76-3.67 (m, –CH₂–CH₂–), 1.18 (d, CH₃, 6.72 Hz). TGA: one sharp step (onset at 497 K, mid-point at 502 K, end-point at 509 K; mass loss 62%) followed by a protracted mass loss totalling 71.5%, assigned to decomposition to CdS (calculated mass loss 69.5%).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The oxygen-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of O—H = 0.84±0.01 Å, and with U_iso(H) set to 1.5U_eq(O).

Table 6
Experimental details

Crystal data
Chemical formula	[Cd₂(C₁₂H₁₀N₂)₃(C₆H₁₂NOS₂)₄]·4C₂H₃N
M_r	1648.84
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	16.884 (2), 14.4021 (15), 17.327 (2)
β (°)	109.112 (3)
V (Å³)	3981.0 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.80
Crystal size (mm)	0.35 × 0.25 × 0.10

Data collection
Diffractometer	AFC12K/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.752, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	36088, 8240, 7736
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.115, 1.13
No. of reflections	8240
No. of parameters	445
No. of restraints	2
Δρ_max, Δρ_min (e Å⁻³)	1.43, −0.81
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1489732

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016010768/hb7594sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016010768/hb7594Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); 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).

[µ₂-trans-1,2-Bis(pyridin-4-yl)ethene-κ²N:N']bis{[1,2-bis(pyridin-4-yl)ethene-κN]bis[N-(2-hydroxyethyl)-N-N-isopropyldithiocarbamato-κ²S,S']cadmium} acetonitrile tetrasolvate: top

Crystal data top

[Cd₂(C₁₂H₁₀N₂)₃(C₆H₁₂NOS₂)₄]·4C₂H₃N	F(000) = 1704
M_r = 1648.84	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.884 (2) Å	Cell parameters from 15613 reflections
b = 14.4021 (15) Å	θ = 2.5–30.5°
c = 17.327 (2) Å	µ = 0.80 mm⁻¹
β = 109.112 (3)°	T = 153 K
V = 3981.0 (8) Å³	Prism, yellow
Z = 2	0.35 × 0.25 × 0.10 mm

Data collection top

AFC12K/SATURN724 diffractometer	8240 independent reflections
Radiation source: fine-focus sealed tube	7736 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 26.5°, θ_min = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −21→19
T_min = 0.752, T_max = 1.000	k = −18→18
36088 measured reflections	l = −21→21

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0538P)² + 4.1818P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.115	(Δ/σ)_max = 0.002
S = 1.13	Δρ_max = 1.43 e Å⁻³
8240 reflections	Δρ_min = −0.81 e Å⁻³
445 parameters

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
Cd	0.86121 (2)	0.27028 (2)	0.77182 (2)	0.02811 (9)
S1	0.91301 (5)	0.14219 (6)	0.88291 (5)	0.0409 (2)
S2	0.74876 (5)	0.12713 (5)	0.75128 (4)	0.03067 (16)
S3	0.80475 (5)	0.39522 (5)	0.65839 (5)	0.03553 (18)
S4	0.77645 (5)	0.40603 (5)	0.81826 (4)	0.03206 (17)
O1	0.65163 (14)	−0.17072 (16)	0.73753 (15)	0.0409 (6)
H1O	0.6124 (19)	−0.142 (3)	0.704 (2)	0.061*
O2	0.70145 (16)	0.70048 (15)	0.85595 (14)	0.0390 (5)
H2O	0.677 (3)	0.738 (2)	0.8189 (19)	0.059*
N1	0.81603 (16)	−0.00780 (17)	0.85909 (15)	0.0320 (5)
N2	0.71824 (16)	0.53113 (17)	0.69907 (15)	0.0315 (5)
N3	0.92734 (16)	0.19783 (18)	0.68118 (16)	0.0338 (6)
N4	1.00214 (16)	0.33683 (17)	0.82938 (15)	0.0309 (5)
N5	1.53044 (18)	0.5788 (2)	1.12686 (18)	0.0427 (7)
N6	0.4531 (4)	0.6223 (6)	0.6589 (4)	0.144 (3)
N7	0.4216 (5)	0.7244 (4)	0.4145 (4)	0.121 (2)
C1	0.82450 (19)	0.07842 (19)	0.83301 (18)	0.0295 (6)
C2	0.7352 (2)	−0.0575 (2)	0.82882 (19)	0.0352 (7)
H2A	0.6892	−0.0117	0.8191	0.042*
H2B	0.7311	−0.1006	0.8719	0.042*
C3	0.7226 (2)	−0.1119 (2)	0.7513 (2)	0.0373 (7)
H3A	0.7136	−0.0688	0.7047	0.045*
H3B	0.7730	−0.1497	0.7564	0.045*
C4	0.8842 (2)	−0.0533 (2)	0.92667 (19)	0.0345 (7)
H4	0.9366	−0.0166	0.9349	0.041*
C5	0.9014 (2)	−0.1517 (2)	0.9049 (2)	0.0408 (7)
H5A	0.9520	−0.1753	0.9465	0.061*
H5B	0.9097	−0.1518	0.8515	0.061*
H5C	0.8537	−0.1915	0.9028	0.061*
C6	0.8641 (3)	−0.0487 (3)	1.0054 (2)	0.0517 (9)
H6A	0.9121	−0.0716	1.0504	0.078*
H6B	0.8149	−0.0872	1.0006	0.078*
H6C	0.8524	0.0158	1.0162	0.078*
C7	0.76189 (18)	0.45215 (19)	0.72260 (18)	0.0283 (6)
C8	0.6803 (2)	0.5800 (2)	0.75284 (19)	0.0338 (7)
H8A	0.6565	0.5338	0.7814	0.041*
H8B	0.6337	0.6194	0.7191	0.041*
C9	0.7430 (2)	0.6407 (2)	0.8161 (2)	0.0361 (7)
H9A	0.7831	0.6006	0.8571	0.043*
H9B	0.7752	0.6784	0.7889	0.043*
C10	0.6999 (2)	0.5689 (2)	0.6145 (2)	0.0426 (8)
H10	0.7369	0.5350	0.5892	0.051*
C11	0.7209 (3)	0.6707 (3)	0.6145 (3)	0.0628 (11)
H11A	0.7093	0.6920	0.5581	0.094*
H11B	0.7803	0.6801	0.6453	0.094*
H11C	0.6866	0.7062	0.6401	0.094*
C12	0.6102 (3)	0.5471 (4)	0.5636 (2)	0.0681 (12)
H12A	0.5997	0.5692	0.5076	0.102*
H12B	0.5719	0.5782	0.5872	0.102*
H12C	0.6012	0.4799	0.5630	0.102*
C13	0.8862 (2)	0.1867 (2)	0.6011 (2)	0.0416 (8)
H13	0.8344	0.2182	0.5779	0.050*
C14	0.9149 (2)	0.1318 (2)	0.5505 (2)	0.0409 (8)
H14	0.8836	0.1268	0.4941	0.049*
C15	0.9902 (2)	0.0840 (2)	0.58273 (19)	0.0338 (7)
C16	1.0352 (2)	0.0992 (2)	0.6648 (2)	0.0351 (7)
H16	1.0886	0.0712	0.6888	0.042*
C17	1.0018 (2)	0.1548 (2)	0.7110 (2)	0.0359 (7)
H17	1.0331	0.1633	0.7671	0.043*
C18	1.0222 (2)	0.0174 (2)	0.53632 (19)	0.0355 (7)
H18	1.0787	−0.0024	0.5596	0.043*
C19	1.0297 (2)	0.4016 (2)	0.78886 (19)	0.0331 (6)
H19	0.9938	0.4200	0.7364	0.040*
C20	1.10796 (19)	0.4431 (2)	0.81939 (19)	0.0338 (6)
H20	1.1244	0.4887	0.7881	0.041*
C21	1.16227 (19)	0.4178 (2)	0.89581 (18)	0.0304 (6)
C22	1.13422 (19)	0.3486 (2)	0.93706 (18)	0.0334 (6)
H22	1.1696	0.3271	0.9887	0.040*
C23	1.0553 (2)	0.3117 (2)	0.90285 (18)	0.0337 (6)
H23	1.0374	0.2658	0.9329	0.040*
C24	1.2428 (2)	0.4655 (2)	0.93038 (19)	0.0337 (6)
H24	1.2517	0.5206	0.9042	0.040*
C25	1.3045 (2)	0.4366 (2)	0.99626 (19)	0.0356 (7)
H25	1.2965	0.3788	1.0190	0.043*
C26	1.38345 (19)	0.4854 (2)	1.03704 (19)	0.0339 (6)
C27	1.4043 (2)	0.5708 (2)	1.0115 (2)	0.0392 (7)
H27	1.3686	0.5987	0.9629	0.047*
C28	1.4775 (2)	0.6149 (3)	1.0576 (2)	0.0440 (8)
H28	1.4908	0.6732	1.0394	0.053*
C29	1.5114 (2)	0.4955 (3)	1.1492 (2)	0.0430 (8)
H29	1.5492	0.4681	1.1970	0.052*
C30	1.4403 (2)	0.4469 (2)	1.1072 (2)	0.0383 (7)
H30	1.4299	0.3875	1.1258	0.046*
C31	0.3930 (3)	0.6527 (4)	0.6166 (3)	0.0811 (16)
C32	0.3169 (3)	0.6944 (4)	0.5636 (3)	0.0715 (13)
H32A	0.3086	0.7549	0.5857	0.107*
H32B	0.2692	0.6539	0.5603	0.107*
H32C	0.3210	0.7027	0.5090	0.107*
C33	0.4380 (4)	0.6986 (4)	0.3603 (3)	0.0757 (14)
C34	0.4564 (4)	0.6632 (6)	0.2899 (4)	0.119 (3)
H34A	0.4786	0.5999	0.3012	0.178*
H34B	0.4980	0.7031	0.2782	0.178*
H34C	0.4049	0.6624	0.2426	0.178*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.02812 (14)	0.02260 (13)	0.03125 (13)	0.00156 (7)	0.00653 (10)	0.00010 (8)
S1	0.0366 (4)	0.0298 (4)	0.0430 (4)	−0.0089 (3)	−0.0052 (4)	0.0069 (3)
S2	0.0283 (4)	0.0252 (3)	0.0334 (4)	0.0014 (3)	0.0032 (3)	0.0011 (3)
S3	0.0419 (5)	0.0318 (4)	0.0335 (4)	0.0103 (3)	0.0132 (3)	0.0037 (3)
S4	0.0373 (4)	0.0265 (3)	0.0312 (4)	0.0030 (3)	0.0096 (3)	0.0016 (3)
O1	0.0307 (12)	0.0283 (11)	0.0510 (14)	−0.0040 (9)	−0.0041 (10)	0.0085 (10)
O2	0.0532 (15)	0.0263 (11)	0.0402 (12)	0.0070 (10)	0.0189 (11)	0.0020 (9)
N1	0.0309 (14)	0.0261 (12)	0.0331 (12)	−0.0038 (10)	0.0025 (11)	0.0019 (10)
N2	0.0324 (14)	0.0270 (12)	0.0335 (12)	0.0059 (10)	0.0086 (11)	0.0034 (10)
N3	0.0322 (14)	0.0327 (13)	0.0352 (13)	0.0048 (11)	0.0094 (11)	−0.0044 (11)
N4	0.0306 (13)	0.0261 (12)	0.0353 (13)	−0.0009 (10)	0.0096 (11)	−0.0012 (10)
N5	0.0317 (15)	0.0477 (16)	0.0436 (15)	−0.0062 (12)	0.0053 (12)	−0.0076 (13)
N6	0.081 (4)	0.252 (8)	0.111 (4)	0.064 (5)	0.049 (3)	0.090 (5)
N7	0.174 (7)	0.100 (4)	0.112 (4)	−0.036 (4)	0.076 (5)	−0.044 (3)
C1	0.0322 (16)	0.0232 (13)	0.0315 (14)	−0.0017 (11)	0.0084 (12)	−0.0016 (11)
C2	0.0311 (16)	0.0319 (15)	0.0394 (16)	−0.0069 (12)	0.0071 (13)	0.0028 (13)
C3	0.0311 (17)	0.0302 (15)	0.0445 (17)	−0.0047 (13)	0.0041 (14)	0.0037 (13)
C4	0.0309 (16)	0.0303 (15)	0.0366 (16)	0.0001 (12)	0.0034 (13)	0.0032 (13)
C5	0.046 (2)	0.0329 (16)	0.0393 (16)	0.0094 (14)	0.0086 (15)	0.0055 (14)
C6	0.055 (2)	0.060 (2)	0.0389 (17)	0.0110 (19)	0.0140 (17)	0.0000 (17)
C7	0.0239 (14)	0.0227 (13)	0.0340 (14)	−0.0010 (11)	0.0035 (12)	−0.0015 (11)
C8	0.0347 (17)	0.0265 (14)	0.0404 (16)	0.0058 (12)	0.0125 (14)	0.0007 (13)
C9	0.0349 (17)	0.0283 (15)	0.0435 (17)	0.0034 (13)	0.0110 (14)	−0.0024 (13)
C10	0.052 (2)	0.0368 (17)	0.0389 (17)	0.0166 (15)	0.0155 (16)	0.0121 (14)
C11	0.091 (3)	0.044 (2)	0.061 (2)	0.011 (2)	0.035 (2)	0.0156 (19)
C12	0.065 (3)	0.083 (3)	0.043 (2)	0.010 (2)	−0.001 (2)	0.007 (2)
C13	0.044 (2)	0.0375 (17)	0.0379 (16)	0.0130 (15)	0.0069 (15)	−0.0028 (14)
C14	0.048 (2)	0.0373 (17)	0.0332 (16)	0.0086 (15)	0.0073 (15)	−0.0029 (13)
C15	0.0381 (17)	0.0267 (14)	0.0390 (16)	0.0030 (12)	0.0157 (14)	0.0035 (13)
C16	0.0289 (16)	0.0320 (15)	0.0438 (17)	0.0026 (12)	0.0111 (14)	−0.0023 (13)
C17	0.0317 (16)	0.0345 (16)	0.0381 (16)	0.0011 (13)	0.0068 (13)	−0.0055 (13)
C18	0.0372 (17)	0.0322 (15)	0.0394 (15)	0.0036 (13)	0.0156 (14)	0.0050 (13)
C19	0.0329 (16)	0.0317 (15)	0.0321 (14)	−0.0006 (12)	0.0072 (13)	0.0017 (12)
C20	0.0324 (16)	0.0313 (15)	0.0367 (15)	−0.0019 (12)	0.0102 (13)	0.0044 (13)
C21	0.0267 (15)	0.0291 (14)	0.0338 (14)	−0.0027 (11)	0.0077 (12)	−0.0039 (12)
C22	0.0300 (16)	0.0342 (15)	0.0311 (14)	−0.0032 (12)	0.0032 (12)	−0.0005 (12)
C23	0.0340 (17)	0.0317 (15)	0.0321 (15)	−0.0030 (12)	0.0066 (13)	0.0032 (12)
C24	0.0340 (17)	0.0304 (15)	0.0369 (15)	−0.0042 (12)	0.0119 (13)	0.0000 (13)
C25	0.0335 (17)	0.0361 (16)	0.0356 (15)	−0.0045 (13)	0.0093 (13)	−0.0001 (13)
C26	0.0298 (16)	0.0357 (15)	0.0360 (15)	−0.0051 (12)	0.0106 (13)	−0.0049 (13)
C27	0.0317 (17)	0.0404 (17)	0.0398 (17)	−0.0012 (14)	0.0039 (14)	0.0015 (14)
C28	0.0363 (19)	0.0414 (18)	0.0506 (19)	−0.0076 (14)	0.0090 (16)	−0.0005 (16)
C29	0.0334 (18)	0.056 (2)	0.0350 (16)	−0.0043 (15)	0.0050 (14)	0.0002 (15)
C30	0.0328 (17)	0.0418 (18)	0.0392 (16)	−0.0061 (14)	0.0106 (14)	0.0020 (14)
C31	0.065 (3)	0.119 (5)	0.070 (3)	0.016 (3)	0.037 (3)	0.033 (3)
C32	0.057 (3)	0.093 (4)	0.060 (3)	−0.002 (3)	0.014 (2)	0.014 (3)
C33	0.084 (4)	0.068 (3)	0.076 (3)	−0.018 (3)	0.028 (3)	−0.015 (3)
C34	0.087 (4)	0.193 (8)	0.085 (4)	−0.049 (5)	0.040 (3)	−0.059 (5)

Geometric parameters (Å, º) top

Cd—S1	2.6019 (8)	C10—C12	1.514 (6)
Cd—S2	2.7457 (8)	C10—H10	1.0000
Cd—S3	2.6043 (8)	C11—H11A	0.9800
Cd—S4	2.6967 (8)	C11—H11B	0.9800
Cd—N3	2.439 (3)	C11—H11C	0.9800
Cd—N4	2.454 (3)	C12—H12A	0.9800
C1—S1	1.726 (3)	C12—H12B	0.9800
C1—S2	1.717 (3)	C12—H12C	0.9800
C7—S3	1.721 (3)	C13—C14	1.381 (5)
C7—S4	1.727 (3)	C13—H13	0.9500
O1—C3	1.422 (4)	C14—C15	1.391 (5)
O1—H1O	0.839 (10)	C14—H14	0.9500
O2—C9	1.425 (4)	C15—C16	1.393 (4)
O2—H2O	0.840 (10)	C15—C18	1.464 (4)
N1—C1	1.345 (4)	C16—C17	1.377 (4)
N1—C2	1.477 (4)	C16—H16	0.9500
N1—C4	1.498 (4)	C17—H17	0.9500
N2—C7	1.344 (4)	C18—C18ⁱ	1.334 (6)
N2—C8	1.472 (4)	C18—H18	0.9500
N2—C10	1.497 (4)	C19—C20	1.388 (4)
N3—C17	1.343 (4)	C19—H19	0.9500
N3—C13	1.343 (4)	C20—C21	1.390 (4)
N4—C19	1.339 (4)	C20—H20	0.9500
N4—C23	1.345 (4)	C21—C22	1.396 (4)
N5—C29	1.333 (5)	C21—C24	1.465 (4)
N5—C28	1.344 (5)	C22—C23	1.375 (4)
N6—C31	1.128 (7)	C22—H22	0.9500
N7—C33	1.126 (7)	C23—H23	0.9500
C2—C3	1.508 (5)	C24—C25	1.335 (4)
C2—H2A	0.9900	C24—H24	0.9500
C2—H2B	0.9900	C25—C26	1.468 (4)
C3—H3A	0.9900	C25—H25	0.9500
C3—H3B	0.9900	C26—C27	1.391 (5)
C4—C6	1.510 (5)	C26—C30	1.393 (5)
C4—C5	1.519 (4)	C27—C28	1.386 (5)
C4—H4	1.0000	C27—H27	0.9500
C5—H5A	0.9800	C28—H28	0.9500
C5—H5B	0.9800	C29—C30	1.375 (5)
C5—H5C	0.9800	C29—H29	0.9500
C6—H6A	0.9800	C30—H30	0.9500
C6—H6B	0.9800	C31—C32	1.443 (7)
C6—H6C	0.9800	C32—H32A	0.9800
C8—C9	1.525 (4)	C32—H32B	0.9800
C8—H8A	0.9900	C32—H32C	0.9800
C8—H8B	0.9900	C33—C34	1.445 (8)
C9—H9A	0.9900	C34—H34A	0.9800
C9—H9B	0.9900	C34—H34B	0.9800
C10—C11	1.510 (5)	C34—H34C	0.9800

S1—Cd—S2	67.31 (2)	C11—C10—C12	113.0 (3)
S1—Cd—S3	178.06 (3)	N2—C10—H10	107.0
S1—Cd—S4	112.08 (3)	C11—C10—H10	107.0
S1—Cd—N3	93.39 (7)	C12—C10—H10	107.0
S1—Cd—N4	85.98 (6)	C10—C11—H11A	109.5
S2—Cd—S3	110.75 (3)	C10—C11—H11B	109.5
S2—Cd—S4	99.85 (3)	H11A—C11—H11B	109.5
S2—Cd—N3	92.19 (7)	C10—C11—H11C	109.5
S2—Cd—N4	152.04 (6)	H11A—C11—H11C	109.5
S3—Cd—S4	68.00 (2)	H11B—C11—H11C	109.5
S3—Cd—N3	86.63 (7)	C10—C12—H12A	109.5
S3—Cd—N4	95.94 (6)	C10—C12—H12B	109.5
S4—Cd—N3	154.39 (6)	H12A—C12—H12B	109.5
S4—Cd—N4	97.72 (6)	C10—C12—H12C	109.5
N3—Cd—N4	80.87 (9)	H12A—C12—H12C	109.5
C1—S1—Cd	88.88 (10)	H12B—C12—H12C	109.5
C1—S2—Cd	84.44 (10)	N3—C13—C14	123.6 (3)
C7—S3—Cd	88.21 (10)	N3—C13—H13	118.2
C7—S4—Cd	85.13 (10)	C14—C13—H13	118.2
C3—O1—H1O	104 (3)	C13—C14—C15	119.5 (3)
C9—O2—H2O	102 (3)	C13—C14—H14	120.2
C1—N1—C2	121.0 (3)	C15—C14—H14	120.2
C1—N1—C4	121.8 (2)	C14—C15—C16	117.0 (3)
C2—N1—C4	116.8 (2)	C14—C15—C18	123.8 (3)
C7—N2—C8	121.5 (3)	C16—C15—C18	119.2 (3)
C7—N2—C10	121.4 (3)	C17—C16—C15	119.6 (3)
C8—N2—C10	116.9 (2)	C17—C16—H16	120.2
C17—N3—C13	116.4 (3)	C15—C16—H16	120.2
C17—N3—Cd	121.2 (2)	N3—C17—C16	123.7 (3)
C13—N3—Cd	121.7 (2)	N3—C17—H17	118.2
C19—N4—C23	116.4 (3)	C16—C17—H17	118.2
C19—N4—Cd	121.1 (2)	C18ⁱ—C18—C15	124.8 (4)
C23—N4—Cd	122.5 (2)	C18ⁱ—C18—H18	117.6
C29—N5—C28	117.0 (3)	C15—C18—H18	117.6
N1—C1—S2	121.5 (2)	N4—C19—C20	123.4 (3)
N1—C1—S1	119.5 (2)	N4—C19—H19	118.3
S2—C1—S1	119.00 (17)	C20—C19—H19	118.3
N1—C2—C3	114.3 (3)	C19—C20—C21	119.9 (3)
N1—C2—H2A	108.7	C19—C20—H20	120.0
C3—C2—H2A	108.7	C21—C20—H20	120.0
N1—C2—H2B	108.7	C20—C21—C22	116.5 (3)
C3—C2—H2B	108.7	C20—C21—C24	120.1 (3)
H2A—C2—H2B	107.6	C22—C21—C24	123.4 (3)
O1—C3—C2	109.0 (3)	C23—C22—C21	119.9 (3)
O1—C3—H3A	109.9	C23—C22—H22	120.1
C2—C3—H3A	109.9	C21—C22—H22	120.1
O1—C3—H3B	109.9	N4—C23—C22	123.8 (3)
C2—C3—H3B	109.9	N4—C23—H23	118.1
H3A—C3—H3B	108.3	C22—C23—H23	118.1
N1—C4—C6	110.1 (3)	C25—C24—C21	124.3 (3)
N1—C4—C5	112.0 (3)	C25—C24—H24	117.8
C6—C4—C5	112.5 (3)	C21—C24—H24	117.8
N1—C4—H4	107.3	C24—C25—C26	126.5 (3)
C6—C4—H4	107.3	C24—C25—H25	116.8
C5—C4—H4	107.3	C26—C25—H25	116.8
C4—C5—H5A	109.5	C27—C26—C30	117.2 (3)
C4—C5—H5B	109.5	C27—C26—C25	123.7 (3)
H5A—C5—H5B	109.5	C30—C26—C25	119.1 (3)
C4—C5—H5C	109.5	C28—C27—C26	119.5 (3)
H5A—C5—H5C	109.5	C28—C27—H27	120.3
H5B—C5—H5C	109.5	C26—C27—H27	120.3
C4—C6—H6A	109.5	N5—C28—C27	123.0 (3)
C4—C6—H6B	109.5	N5—C28—H28	118.5
H6A—C6—H6B	109.5	C27—C28—H28	118.5
C4—C6—H6C	109.5	N5—C29—C30	123.8 (3)
H6A—C6—H6C	109.5	N5—C29—H29	118.1
H6B—C6—H6C	109.5	C30—C29—H29	118.1
N2—C7—S3	120.8 (2)	C29—C30—C26	119.5 (3)
N2—C7—S4	120.5 (2)	C29—C30—H30	120.3
S3—C7—S4	118.65 (16)	C26—C30—H30	120.3
N2—C8—C9	112.6 (3)	N6—C31—C32	178.2 (9)
N2—C8—H8A	109.1	C31—C32—H32A	109.5
C9—C8—H8A	109.1	C31—C32—H32B	109.5
N2—C8—H8B	109.1	H32A—C32—H32B	109.5
C9—C8—H8B	109.1	C31—C32—H32C	109.5
H8A—C8—H8B	107.8	H32A—C32—H32C	109.5
O2—C9—C8	111.0 (3)	H32B—C32—H32C	109.5
O2—C9—H9A	109.4	N7—C33—C34	177.8 (7)
C8—C9—H9A	109.4	C33—C34—H34A	109.5
O2—C9—H9B	109.4	C33—C34—H34B	109.5
C8—C9—H9B	109.4	H34A—C34—H34B	109.5
H9A—C9—H9B	108.0	C33—C34—H34C	109.5
N2—C10—C11	112.3 (3)	H34A—C34—H34C	109.5
N2—C10—C12	110.1 (3)	H34B—C34—H34C	109.5

C2—N1—C1—S2	−11.5 (4)	C13—C14—C15—C16	−3.7 (5)
C4—N1—C1—S2	175.8 (2)	C13—C14—C15—C18	174.0 (3)
C2—N1—C1—S1	168.1 (2)	C14—C15—C16—C17	4.0 (5)
C4—N1—C1—S1	−4.6 (4)	C18—C15—C16—C17	−173.9 (3)
Cd—S2—C1—N1	−174.7 (3)	C13—N3—C17—C16	−2.1 (5)
Cd—S2—C1—S1	5.71 (16)	Cd—N3—C17—C16	168.2 (2)
Cd—S1—C1—N1	174.4 (2)	C15—C16—C17—N3	−1.1 (5)
Cd—S1—C1—S2	−6.00 (17)	C14—C15—C18—C18ⁱ	−12.2 (6)
C1—N1—C2—C3	87.7 (4)	C16—C15—C18—C18ⁱ	165.5 (4)
C4—N1—C2—C3	−99.3 (3)	C23—N4—C19—C20	−0.9 (4)
N1—C2—C3—O1	168.4 (2)	Cd—N4—C19—C20	178.4 (2)
C1—N1—C4—C6	101.6 (3)	N4—C19—C20—C21	0.1 (5)
C2—N1—C4—C6	−71.4 (4)	C19—C20—C21—C22	1.5 (4)
C1—N1—C4—C5	−132.3 (3)	C19—C20—C21—C24	−176.2 (3)
C2—N1—C4—C5	54.6 (4)	C20—C21—C22—C23	−2.2 (4)
C8—N2—C7—S3	179.2 (2)	C24—C21—C22—C23	175.4 (3)
C10—N2—C7—S3	4.5 (4)	C19—N4—C23—C22	0.1 (5)
C8—N2—C7—S4	−1.1 (4)	Cd—N4—C23—C22	−179.2 (2)
C10—N2—C7—S4	−175.8 (2)	C21—C22—C23—N4	1.5 (5)
Cd—S3—C7—N2	−179.5 (2)	C20—C21—C24—C25	−168.5 (3)
Cd—S3—C7—S4	0.81 (16)	C22—C21—C24—C25	13.9 (5)
Cd—S4—C7—N2	179.5 (2)	C21—C24—C25—C26	−174.9 (3)
Cd—S4—C7—S3	−0.78 (15)	C24—C25—C26—C27	0.4 (5)
C7—N2—C8—C9	81.4 (3)	C24—C25—C26—C30	177.9 (3)
C10—N2—C8—C9	−103.6 (3)	C30—C26—C27—C28	−2.4 (5)
N2—C8—C9—O2	168.5 (2)	C25—C26—C27—C28	175.1 (3)
C7—N2—C10—C11	−131.1 (3)	C29—N5—C28—C27	2.3 (5)
C8—N2—C10—C11	53.9 (4)	C26—C27—C28—N5	0.0 (5)
C7—N2—C10—C12	102.0 (4)	C28—N5—C29—C30	−2.2 (5)
C8—N2—C10—C12	−72.9 (4)	N5—C29—C30—C26	−0.2 (5)
C17—N3—C13—C14	2.4 (5)	C27—C26—C30—C29	2.5 (5)
Cd—N3—C13—C14	−167.9 (3)	C25—C26—C30—C29	−175.1 (3)
N3—C13—C14—C15	0.6 (6)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N5ⁱⁱ	0.83 (4)	1.82 (4)	2.655 (4)	177 (3)
O2—H2O···O1ⁱⁱⁱ	0.84 (3)	1.87 (3)	2.689 (3)	165 (5)
C25—H25···O2^iv	0.95	2.44	3.261 (4)	145
C28—H28···N7^v	0.95	2.56	3.296 (7)	134

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

Summary of short interatomic contacts (Å) top

Contact	Distance	Symmetry
S1···H6A	2.98	2 - x, -y, 2 - z
S4···H18	2.97	2 - x, 1/2 + y, 3/2 - z
O1···H11C	2.64	x, -1 + y, z
O2···H30	2.66	2 - x, 1 - y, 2 - z
C1···H20	2.83	2 - x, -1/2 + y, 3/2 - z
C3···H2O	2.69 (3)	x, -1 + y, z
C24···H3A	2.72	2 - x, -1/2 + y, 3/2 - z
C28···H1O	2.83 (3)	1 + x, 1/2 - y, 1/2 + z
C29···H1O	2.67 (4)	1 + x, 1/2 - y, 1 + z
C16···C19	3.245 (4)	2 - x, -1/2 + y, 3/2 - z
C16···C20	3.377 (5)	2 - x, -1/2 + y, 3/2 - z
H5A···H23	2.31	2 - x, -y, 2 - z

Percentage contribution of the different intermolecular contacts to the Hirshfeld surface top

Contact	Contribution
H···H	51.9
O···H/H···O	6.0
C···H/H···C	15.9
N···H/H···N	10.6
C···C	3.1
S···H/H···S	10.3
C···S/S···C	0.8
N···S/S···N	0.7
C···N/N···C	0.7

Enrichment ratios (ER) top

Contact	ER
H···H	0.97
O···H/H···O	1.36
N···H/H···N	1.20
C···C	2.23
S···H/H···S	1.19
C···H/H···C	0.92
C···S/S···C	0.58
C···N/N···C	0.49

Footnotes

‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.

References

Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2009). Acta Cryst. E65, m1472–m1473. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Chai, J., Lai, C. S., Yan, J. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 249–250. Web of Science CSD CrossRef CAS Google Scholar
Dong, Y. B., Layland, R. C., Smith, M. D., Pschirer, N. G., Bunz, U. H. F. & zur Loye, H.-C. (1999). Inorg. Chem. 38, 3056–3060. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals 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
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Howie, R. A., Tiekink, E. R. T., Wardell, J. L. & Wardell, S. M. S. V. (2009). J. Chem. Crystallogr. 39, 293–298. Web of Science CSD CrossRef CAS Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO – A System for Computational Chemistry. Available at: https://hirshfeldsurface.net/ Google Scholar
Jelsch, C., Ejsmont, K. & Huder, L. (2014). IUCrJ, 1, 119–128. Web of Science CrossRef CAS PubMed IUCr Journals Google Scholar
Jotani, M. M., Tan, Y. S. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231. doi: 10.1515/zkri-2016-1943. Google Scholar
Kang, J.-G., Shin, J.-S., Cho, D.-H., Jeong, Y.-K., Park, C., Soh, S. F., Lai, C. S. & Tiekink, E. R. T. (2010). Cryst. Growth Des. 10, 1247–1256. Web of Science CSD CrossRef CAS Google Scholar
Lai, C. S. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 251–252. Web of Science CSD CrossRef CAS Google Scholar
Lai, C. S. & Tiekink, E. R. T. (2004). CrystEngComm, 6, 593–605. Web of Science CSD CrossRef CAS Google Scholar
Lu, J. Y., Runnels, K. A. & Norman, C. (2001). Inorg. Chem. 40, 4516–4517. Web of Science CSD CrossRef PubMed CAS Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
McKinnon, J. J., Spackman, M. A. & Mitchell, A. S. (2004). Acta Cryst. B60, 627–668. Web of Science CrossRef CAS IUCr Journals Google Scholar
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Paul, A. K., Karthik, R. & Natarajan, S. (2011). Cryst. Growth Des. 11, 5741–5749. Web of Science CSD CrossRef CAS Google Scholar
Poplaukhin, P. & Tiekink, E. R. T. (2008). Acta Cryst. E64, m1176. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rodina, T. A., Ivanov, A. V., Gerasimenko, A. V., Ivanov, M. A., Zaeva, A. S., Philippova, T. S. & Antzutkin, O. N. (2011). Inorg. Chim. Acta, 368, 263–270. Web of Science CSD CrossRef CAS Google Scholar
Safbri, S. A. M., Halim, S. N. A., Jotani, M. M. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 158–163. Web of Science CSD CrossRef IUCr Journals 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
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tan, Y. S., Halim, S. N. A. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 113–126. CAS Google Scholar
Tan, Y. S., Sudlow, A. L., Molloy, K. C., Morishima, Y., Fujisawa, K., Jackson, W. J., Henderson, W., Halim, S. N. B. A., Ng, S. W. & Tiekink, E. R. T. (2013). Cryst. Growth Des. 13, 3046–3056. Web of Science CSD CrossRef CAS Google Scholar
Tiekink, E. R. T. (2003). CrystEngComm, 5, 101–113. Web of Science CrossRef CAS Google Scholar
Tiekink, E. R. T. & Zukerman-Schpector, J. (2011). Chem. Commun. 47, 6623–6625. Web of Science CrossRef CAS Google Scholar
Wahab, N. A. A., Baba, I., Mohamed Tahir, M. I. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m551–m552. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. The University of Western Australia. Google Scholar

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