research communications
Bis[N-(2-hydroxyethyl)-N-isopropyldithiocarbamato-κ2S,S′](piperazine-κN)cadmium: and Hirshfeld surface analysis
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and cCentre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The title compound, [Cd(C6H12NOS2)2(C4H10N2)], features a distorted square-pyramidal coordination geometry about the central CdII atom. The dithiocarbamate ligands are chelating, forming similar Cd—S bond lengths and define the approximate basal plane. One of the N atoms of the piperazine molecule, which adopts a chair conformation, occupies the apical site. In the crystal, supramolecular layers propagating in the ac plane are formed via hydroxy-O—H⋯O(hydroxy), hydroxy-O—H⋯N(terminal-piperazine) and coordinated-piperazine-N—H⋯O(hydroxy) hydrogen bonds; the layers also feature methine-C—H⋯S interactions and S⋯S [3.3714 (10) Å] short contacts. The layers stack along the b-axis direction with very weak terminal-piperazine-N—H⋯O(hydroxy) interactions between them. An evaluation of the Hirshfeld surfaces confirms the importance of intermolecular interactions involving oxygen and sulfur atoms.
Keywords: crystal structure; Hirshfeld surface analysis; dithiocarbamate; piperazine; hydrogen bonding.
CCDC reference: 1445316
1. Chemical context
In the solid state, binary bis(dithiocarbamato) compounds of cadmium are usually binuclear with five-coordinate geometries 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). Equally well known is the observation that upon the addition of base, this motif is disrupted, resulting in mononuclear species, such as in the case of the pyridine adduct, {Cd[S2CN(CH2C(H)Me2)2]2(pyridine)} (Rodina et al., 2011). Ditopic donors can give rise to zero- or one-dimensional species. Thus, when the bidentate ligand is capable of chelating, mononuclear species are obtained, e.g. [Cd(S2CN(Me)iPr)2(2,2′-bipyridine)] (Wahab et al., 2011). More variety is found in adducts containing molecules capable of bridging where zero-dimensional binuclear structures, e.g. [Cd(S2CNPr2)2(2-pyridinealdazine)]2 (Poplaukhin & Tiekink, 2008), or supramolecular chains, e.g. [Cd(S2CNEt2)2(μ2-1,2-bis(4-pyridyl)ethylene)]n (Chai et al., 2003), are found. An intriguing structure has been reported where the potentially μ2-bridging ligand, 4-pyridinealdazine, coordinates in the monodentate mode in {Cd[S2CN(Pr)CH2CH2OH]2(4-pyridinealdazine)2} (Broker & Tiekink, 2011). The latter, featuring a dithiocarbamate ligand functionalized with a hydroxyethyl substituent capable of hydrogen bonding, has sparked systematic studies of their wider structural chemistry, revealing hitherto unobserved structural motifs for cadmium dithiocarbamates (Tan et al., 2013, 2016). As a continuation of this work, the title compound was investigated where both the dithiocarbamate ligand and the nitrogen-donor ligand have hydrogen-bonding potential.
2. Structural commentary
The molecular structure of the title compound, {Cd[S2CN(iPr)CH2CH2OH]2[HN(CH2CH2)2NH]}, Fig. 1, comprises a penta-coordinated cadmium atom, being chelated by two dithiocarbamate ligands and connected to a piperazine-N atom, the latter ligand having a chair conformation. The coordination geometry is best described as being distorted square pyramidal with the nitrogen atom in the apical position. This description is quantified by the value of τ, i.e. 0.18, which is closer to the τ value of 0.0 for an ideal square-pyramidal geometry cf. 1.0 for an ideal trigonal bipyramid (Addison et al., 1984). The r.m.s. deviation of the four sulfur atoms is 0.1023 Å, and the cadmium atom lies 0.6570 (4) Å above the plane in the direction of the N3 atom. The distortions from the ideal geometry are related, in part, to the acute chelate angles subtended by the chelating ligands, i.e. 68–69°, and the range of Naxial—Cd—Sbasal angles is 98–116°, Table 1. The dithiocarbamate ligands are coordinating in a slightly asymmetric manner with the difference between the short and long Cd—S bond lengths being ca 0.1 Å for the S1-containing ligand and ca 0.2 Å for the S3-containing ligand, Table 1. The almost symmetric mode of coordination of the dithiocarbamate ligands is reflected in the near equivalence of the associated C—S bond lengths, Table 1, and is consistent with significant delocalization of π-electron density over each four-membered chelate ring.
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The monodentate mode of coordination of the piperazine ligand in the title compound is without precedent in the crystallographic literature of cadmium (Groom & Allen, 2014). However, there are several examples of bridging piperazine, e.g. [CdBr2(μ2-piperazine)]n (Yu et al., 2007), {Cd[1,3-(CO2)2C6H4](μ2-piperazine)(OH2)}n (Gu et al., 2011) and [Cd(SCN)2(μ2-piperazine)]n (Suen & Wang, 2007). In common with the title compound, the piperazine ring adopts a chair conformation in each of these structures.
3. Supramolecular features
In the extended structure, hydroxy-O1—H⋯O2(hydroxy), hydroxy-O2—H⋯N4(terminal-piperazine) and (coordinated-piperazine)-N3—H⋯O1(hydroxy) hydrogen bonds (Table 2) lead to the formation of a supramolecular layer in the ac plane, Fig. 2. Additional stability to the layers are afforded by methine-C—H⋯S1, S3 contacts, Table 2, as well as S2⋯S2i contacts of 3.3714 (10) Å, for (i) 2 − x, 1 − y, 1 − z. Layers thus formed stack along the b axis, with very weak terminal-piperazine-N4—H⋯O2(hydroxy) interactions between them, Table 2 and Fig. 3.
4. Analysis of the Hirshfeld surfaces
The program Crystal Explorer (Wolff et al., 2012) was used to generate Hirshfeld surfaces mapped over dnorm, de and electrostatic potential for the title compound. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) and were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level of theory over a range ±0.14 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (Rohl et al., 2008) provides a summary of intermolecular contacts in the crystal. The relative contributions from various contacts to the Hirshfeld surfaces are tabulated in Table 3.
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The hydrogen-bonding network generated in the crystal through hydroxyl groups located at the edges, piperazine nitrogen-H at the apex and sulfur atoms on the vertices of the distorted square-pyramidal polyhedron can be visualized using Hirshfeld surface analysis. The bright-red spots on the Hirshfeld surface mapped over dnorm, Fig. 4, with labels H1O, H2O and H3N, on the surface represent donors for potential hydrogen bonds, Table 2; the corresponding acceptors on the surfaces appear as bright-red spots at O2, N4 and O1, respectively. The Hirshfeld surface mapped over the electrostatic potential, Fig. 5, represents donors with positive potential (blue regions) and the acceptors with negative potential (red). In addition, the negative potential around the sulfur atoms appear as light-red clouds and the positive potential around piperazine as a light-blue cloud in Fig. 5. The Hirshfeld surfaces mapped over dnorm showing intermolecular O—H⋯O, N—H⋯O and O—H⋯N bonds with symmetry-related molecules are shown in Fig. 6. The pale-red depressions near the atoms H4 and S1, and H10 and S3, Fig. 4, confirm the contribution of these pairs of atoms in the comparatively weak intermolecular C—H⋯S interactions. The pale-red spot near the S2 atom indicates an additional reinforcement to the two-dimensional framework through a non-bonded S⋯S contact.
The overall two-dimensional fingerprint plot, Fig. 7a, and those delineated into H⋯H, S⋯H/H⋯S, O⋯H/H⋯O, C⋯H/H⋯C, N⋯H/H⋯N and S⋯S interactions are illustrated in Fig. 7b–g, respectively. The greatest contribution to the overall Hirshfeld surface, i.e. 67.5%, is due to H⋯H contacts and is reflected in Fig. 4b as widely scattered points with a high concentration in the middle region, shown in green. The contribution from the S⋯H/H⋯S contacts, corresponding to C—H⋯S interactions, is represented by the pair of short spikes in the outer region, at de + di ∼ 2.8 Å, Fig. 7c. In the plots delineated into O⋯H/H⋯O and N⋯H/H⋯N contacts, Fig. 7d and f, the pairs of adjacent peaks have almost same lengths near de + di ∼ 1.8 Å, and clearly indicate the significance of intermolecular hydrogen bonds associated with them in the molecular packing. There is only a very small contribution from C⋯H/H⋯C contacts, i.e. 3.2% (Fig. 7d), and there is no contribution from C⋯C contacts in the structure as the result of the absence of C—H⋯π and π–π stacking interactions. Finally, the presence of S⋯S contacts can also be viewed in the delineated fingerprint plot, Fig. 7g, by the density of points in the de, di region around 1.7–2.4 Å as a broken line segment.
The identified intermolecular interactions were further evaluated by an analysis of the enrichment ratios (ER) that give a quantitative measure of the likelihood of specific intermolecular interactions to occur based on a Hirshfeld surface analysis (Jelsch et al., 2014); ratios are given in Table 4.
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A total of 83.2% of the Hirshfeld surface involves hydrogen atoms and of this, non-bonded H⋯H contacts account for 67.5% of the contacts, which is close to the value of 69.2%, being the value calculated for random contacts so that the corresponding ER value is 0.98, i.e. near unity and in accord with earlier published results (Jelsch et al., 2014). The sulfur atoms comprise 9.7% of the surface and S⋯H/H⋯S contacts provide an overall 17.4% contribution to the surface resulting in an ER of 1.1 which is in the expected range, i.e. 1.0–1.5, for C—H⋯S interactions. The ER value of 1.2 corresponding to O⋯H/H⋯O contacts indicate these show a high propensity to form even though the relative contribution to the overall surface, i.e. 7.9%, is small as is the 4.0% exposure to the surface provided by the hydroxyl oxygen atoms. The other contributions to the surface, i.e. N⋯H/H⋯N and C⋯H/H⋯C, are small and the ER values are not particularly informative although being > 1, indicate a propensity to form as discussed above in Supramolecular features.
5. Database survey
The structural chemistry of cadmium dithiocarbamates where the ligands have been functionalized with one or two hydroxyethyl groups has received some attention in recent years owing to the constant stream of unexpected crystallization outcomes. As mentioned in the Chemical context, [Cd(S2CNR2)2]2 compounds are usually binuclear (Tiekink, 2003). However, recent studies of Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013, 2016) have revealed solvent-dependent and solvent-independent supramolecular molecular isomers, e.g. crystallization from ethanol produced two species [Cd[S2CN(iPr)CH2CH2OH]2·EtOH]x for x = 2 and, unprecedented, n (Tan et al., 2016), with the kinetic, polymeric (x = n) form transforming in solution to the thermodynamic, binuclear form (x = 2). Other recrystallization conditions led to decomposition of the dithiocarbamate ligands and subsequent formation of a and some salts. This behaviour, along with the unexpected structure of {Cd[S2CN(iPr)CH2CH2OH]2(4-pyridinealdazine)2] (Broker & Tiekink, 2011) mentioned in the Chemical context, suggests this is a fertile area of crystallographic research. Finally, it is noted that gold (Jamaludin et al., 2013), zinc (Tan et al., 2015) and bismuth (Ishak et al., 2014) compounds of these ligands display promising potential as anti-cancer agents, and that some gold compounds also exhibit exciting anti-microbial activity (Sim et al., 2014).
The monodentate mode of coordination of the piperazine ligand in the title compound is quite rare, and has not been observed in the structural chemistry of cadmium. However, crystallographically confirmed examples of a monodentate coordination mode for piperazine have been seen in five structures, e.g. as in centrosymmetric, all-trans CoCl2(piperazine)2(MeOH)2 (Suen et al., 2004).
6. Synthesis and crystallization
The reagents Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013; 206 mg, 0.44 mmol) and piperazine (Sigma–Aldrich; 76 mg, 0.43 mmol) were dissolved in chloroform (15 ml) and acetonitrile (5 ml), respectively. The latter solution was added dropwise into the chloroform solution and the resulting mixture was stirred for 1 h at room temperature. Slow evaporation of the clear solution yielded colourless crystals. M.p. 415–417 K. IR (cm−1): ν (O—H) 3281, ν(C—N) 1442, ν (C—O) 1169, ν (C—S) 1029.
7. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.98–1.00 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).
details are summarized in Table 5
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Supporting information
CCDC reference: 1445316
10.1107/S2056989016000165/hb7558sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000165/hb7558Isup2.hkl
In the solid state, binary bis(dithiocarbamato) compounds of cadmium are usually binuclear with five-coordinate geometries 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). Equally well known is the observation that upon the addition of base, this motif is disrupted, resulting in mononuclear species, such as in the case of the pyridine adduct, {Cd[S2CN(CH2C(H)Me2)2]2(pyridine)} (Rodina et al., 2011). Ditopic donors can give rise to zero- or one-dimensional species. Thus, when the bidentate ligand is capable of chelating, mononuclear species are obtained, e.g. [Cd(S2CN(Me)iPr)2(2,2'-bipyridine)] (Wahab et al., 2011). More variety is found in adducts containing molecules capable of bridging where zero-dimensional binuclear structures, e.g. [Cd(S2CNPr2)2(2-pyridinealdazine)]2 (Poplaukhin & Tiekink, 2008), or supramolecular chains, e.g. [Cd(S2CNEt2)2(µ2-1,2-bis(4-pyridyl)ethylene)]n (Chai et al., 2003), are found. An intriguing structure has been reported where the potentially µ2-bridging ligand, 4-pyridinealdazine, coordinates in the monodentate mode in {Cd[S2CN(Pr)CH2CH2OH]2(4-pyridinealdazine)2} (Broker & Tiekink, 2011). The latter, featuring a dithiocarbamate ligand functionalized with a hydroxyethyl substituent capable of hydrogen bonding, has sparked systematic studies of their wider structural chemistry, revealing hitherto unobserved structural motifs for cadmium dithiocarbamates (Tan et al., 2013, 2016). As a continuation of this work, the title compound was investigated where both the dithiocarbamate ligand and the nitrogen-donor ligand have hydrogen-bonding potential.
The molecular structure of the title compound, {Cd[S2CN(iPr)CH2CH2OH]2[HN(CH2CH2)2NH]}, Fig. 1, comprises a penta-coordinated cadmium atom, being chelated by two dithiocarbamate ligands and connected to a piperazine-N atom, the latter with a chair conformation. The coordination geometry is best described as being distorted square pyramidal with the nitrogen atom in the apical position. This description is quantified by the value of τ, i.e. 0.18, which is closer to the τ value of 0.0 for an ideal square-pyramidal geometry cf. 1.0 for an ideal trigonal bipyramid (Addison et al., 1984). The r.m.s. deviation of the four sulfur atoms is 0.1023 Å, and the cadmium atom lies 0.6570 (4) Å above the plane in the direction of the N3 atom. The distortions from the ideal geometry are related, in part, to the acute chelate angles subtended by the chelating ligands, i.e. 68–69°, and the range of Naxial—Cd—Sbasal angles is 98–116°, Table 1. The dithiocarbamate ligands are coordinating in a slightly asymmetric manner with the difference between the short and long Cd—S bond lengths being ca 0.1 Å for the S1-containing ligand and ca 0.2 Å for the S3-containing ligand, Table 1. The almost symmetric mode of coordination of the dithiocarbamate ligands is reflected in the near equivalence of the associated C—S bond lengths, Table 1, and is consistent with significant delocalization of π-electron density over each four-membered chelate ring.
The monodentate mode of coordination of the piperazine ligand in the title compound is without precedent in the crystallographic literature of cadmium (Groom & Allen, 2014). However, there are several examples of bridging piperazine, e.g. [CdBr2(µ2-piperazine)]n (Yu et al., 2007), {Cd[1,3-(CO2)2C6H4](µ2-piperazine)(OH2)}n (Gu et al., 2011) and [Cd(SCN)2(µ2-piperazine)]n (Suen & Wang, 2007). In common with the title compound, the piperazine ring adopts a chair conformation in each of these structures.
In the extended structure, hydroxy-O1—H···O2(hydroxy), hydroxy-O2—H···N4(terminal-piperazine) and (coordinated-piperazine)-N3—H···O1(hydroxy) hydrogen bonds (Table 2) lead to the formation of a supramolecular layer in the ac plane, Fig. 2. Additional stability to the layers are afforded by methine-C—H···S1, S3 contacts, Table 2, as well as S2···S2i contacts of 3.3714 (10) Å, for
(i) 2 - x, 1 - y, 1 - z. Layers thus formed stack along the b axis, with very weak terminal-piperazine-N4—H···O2(hydroxy) interactions between them, Table 2 and Fig. 3.The program Crystal Explorer (Wolff et al., 2012) was used to generate Hirshfeld surfaces mapped over dnorm, de and electrostatic potential for the title compound. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) and were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level of theory over a range ±0.14 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (Rohl et al., 2008) provides a summary of intermolecular contacts in the crystal. The relative contributions from various contacts to the Hirshfeld surfaces are tabulated in Table 3.
The hydrogen-bonding network generated in the crystal through hydroxyl groups located at the edges, piperazine nitrogen-H at the apex and sulfur atoms on the vertices of the distorted square-pyramidal polyhedron can be visualized using Hirshfeld surface analysis. The bright-red spots on the Hirshfeld surface mapped over dnorm, Fig. 4, with labels H1O, H2O and H3N, on the surface represent donors for potential hydrogen bonds, Table 2; the corresponding acceptors on the surfaces appear as bright-red spots at O2, N4 and O1, respectively. The Hirshfeld surface mapped over the electrostatic potential, Fig. 5, represents donors with positive potential (blue regions) and the acceptors with negative potential (red). In addition, the negative potential around the sulfur atoms appear as light-red clouds and the positive potential around piperazine as a light-blue cloud in Fig. 5. The Hirshfeld surfaces mapped over dnorm showing intermolecular O—H···O, N—H···O and O—H···N bonds with symmetry-related molecules are shown in Fig. 6. The pale-red depressions near the atoms H4 and S1, and H10 and S3, Fig. 4, confirm the contribution of these pairs of atoms in the comparatively weak intermolecular C—H···S interactions. The pale-red spot near the S2 atom indicates an additional reinforcement to the two-dimensional framework through a non-bonded S···S contact.
The overall two-dimensional fingerprint plot, Fig. 7a, and those delineated into H···H, S···H/H···S, O···H/H···O, C···H/H···C, N···H/H···N and S···S interactions are illustrated in Fig. 7b--g, respectively. The greatest contribution to the overall Hirshfeld surface, i.e. 67.5%, is due to H···H contacts and is reflected in Fig. 4b as widely scattered points with a high concentration in the middle region, shown in green. The contribution from the S···H/H···S contacts, corresponding to C—H···S interactions, is represented by the pair of short spikes in the outer region, at de + di ~ 2.8 Å, Fig. 7c. In the plots delineated into O···H/H···O and N···H/H···N contacts, Fig. 7d and f, the pairs of adjacent peaks have almost same lengths near de + di ~ 1.8 Å, and clearly indicate the significance of intermolecular hydrogen bonds associated with them in the molecular packing. There is only a very small contribution from C···H/H···C contacts, i.e. 3.2% (Fig. 7d), and there is no contribution from C···C contacts in the structure as the result of the absence of C—H···π and π–π stacking interactions. Finally, the presence of S···S contacts can also be viewed in the delineated fingerprint plot, Fig. 7g, by the density of points in the de, di region around 1.7–2.4 Å as a broken line segment.
The identified intermolecular interactions were further evaluated by an analysis of the enrichment ratios (ER) that give a quantitative measure of the likelihood of specific intermolecular interactions to occur based on a Hirshfeld surface analysis (Jelsch et al., 2014); ratios are given in Table 4.
A total of 83.2% of the Hirshfeld surface involves hydrogen atoms and of this, non-bonded H···H contacts account for 67.5% of the contacts, which is close to the value of 69.2%, being the value calculated for random contacts so that the corresponding ER value is 0.98, i.e. near unity and in accord with earlier published results (Jelsch et al., 2014). The sulfur atoms comprise 9.7% of the surface and S···H/H···S contacts provide an overall 17.4% contribution to the surface resulting in an ER of 1.1 which is in the expected range, i.e. 1.0–1.5, for C—H···S interactions. The ER value of 1.2 corresponding to O···H/H···O contacts indicate these show a high propensity to form even though the relative contribution to the overall surface, i.e. 7.9%, is small as is the 4.0% exposure to the surface provided by the hydroxyl oxygen atoms. The other contributions to the surface, i.e. N···H/H···N and C···H/H···C, are small and the ER values are not particularly informative although being > 1, indicate a propensity to form as discussed above in Supramolecular features.
The structural chemistry of cadmium dithiocarbamates where the ligands have been functionalized with one or two hydroxyethyl groups has received some attention in recent years owing to the constant stream of unexpected crystallization outcomes. As mentioned in the Chemical context, [Cd(S2CNR2)2]2 compounds are usually binuclear (Tiekink, 2003). However, recent studies of Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013, 2016) have revealed solvent-dependent and solvent-independent supramolecular molecular isomers, e.g. crystallization from ethanol produced two species [Cd[S2CN(iPr)CH2CH2OH]2·EtOH]x for x = 2 and, unprecedented, n (Tan et al., 2016), with the kinetic, polymeric (x = n) form transforming in solution to the thermodynamic, binuclear form (x = 2). Other recrystallization conditions led to decomposition of the dithiocarbamate ligands and subsequent formation of a
and some salts. This behaviour, along with unexpected structure of {Cd[S2CN(iPr)CH2CH2OH]2(4-pyridinealdazine)2] (Broker & Tiekink, 2011) mentioned in the Chemical context, suggests this is a fertile area of crystallographic research. Finally, it is noted that gold (Jamaludin et al., 2013), zinc (Tan et al., 2015) and bismuth (Ishak et al., 2014) compounds of these ligands display promising potential as anti-cancer agents, and that some gold compounds also exhibit exciting anti-microbial activity (Sim et al., 2014).The monodentate mode of coordination of the piperazine ligand in the title compound is quite rare, and has not been observed in the structural chemistry of cadmium. However, crystallographically confirmed examples of a monodentate coordination mode for piperazine have been seen in five structures, e.g. as in centrosymmetric, all-trans CoCl2(piperazine)2(MeOH)2 (Suen et al., 2004).
The reagents Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013; 206 mg, 0.44 mmol) and piperazine (Sigma–Aldrich; 76 mg, 0.43 mmol) were dissolved in chloroform (15 ml) and acetonitrile (5 ml), respectively. The latter solution was added dropwise into the chloroform solution and the resulting mixture was stirred for 1 h at room temperature. Slow evaporation of the clear solution yielded colourless crystals. M.p. 415–417 K. IR (cm-1): ν (O—H) 3281, ν(C—N) 1442, ν (C—O) 1169, ν (C—S) 1029.
Crystal data, data collection and structure
details are summarized in Table 5. The carbon-bound H atoms were placed in calculated positions (C—H = 0.98–1.00 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).In the solid state, binary bis(dithiocarbamato) compounds of cadmium are usually binuclear with five-coordinate geometries 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). Equally well known is the observation that upon the addition of base, this motif is disrupted, resulting in mononuclear species, such as in the case of the pyridine adduct, {Cd[S2CN(CH2C(H)Me2)2]2(pyridine)} (Rodina et al., 2011). Ditopic donors can give rise to zero- or one-dimensional species. Thus, when the bidentate ligand is capable of chelating, mononuclear species are obtained, e.g. [Cd(S2CN(Me)iPr)2(2,2'-bipyridine)] (Wahab et al., 2011). More variety is found in adducts containing molecules capable of bridging where zero-dimensional binuclear structures, e.g. [Cd(S2CNPr2)2(2-pyridinealdazine)]2 (Poplaukhin & Tiekink, 2008), or supramolecular chains, e.g. [Cd(S2CNEt2)2(µ2-1,2-bis(4-pyridyl)ethylene)]n (Chai et al., 2003), are found. An intriguing structure has been reported where the potentially µ2-bridging ligand, 4-pyridinealdazine, coordinates in the monodentate mode in {Cd[S2CN(Pr)CH2CH2OH]2(4-pyridinealdazine)2} (Broker & Tiekink, 2011). The latter, featuring a dithiocarbamate ligand functionalized with a hydroxyethyl substituent capable of hydrogen bonding, has sparked systematic studies of their wider structural chemistry, revealing hitherto unobserved structural motifs for cadmium dithiocarbamates (Tan et al., 2013, 2016). As a continuation of this work, the title compound was investigated where both the dithiocarbamate ligand and the nitrogen-donor ligand have hydrogen-bonding potential.
The molecular structure of the title compound, {Cd[S2CN(iPr)CH2CH2OH]2[HN(CH2CH2)2NH]}, Fig. 1, comprises a penta-coordinated cadmium atom, being chelated by two dithiocarbamate ligands and connected to a piperazine-N atom, the latter with a chair conformation. The coordination geometry is best described as being distorted square pyramidal with the nitrogen atom in the apical position. This description is quantified by the value of τ, i.e. 0.18, which is closer to the τ value of 0.0 for an ideal square-pyramidal geometry cf. 1.0 for an ideal trigonal bipyramid (Addison et al., 1984). The r.m.s. deviation of the four sulfur atoms is 0.1023 Å, and the cadmium atom lies 0.6570 (4) Å above the plane in the direction of the N3 atom. The distortions from the ideal geometry are related, in part, to the acute chelate angles subtended by the chelating ligands, i.e. 68–69°, and the range of Naxial—Cd—Sbasal angles is 98–116°, Table 1. The dithiocarbamate ligands are coordinating in a slightly asymmetric manner with the difference between the short and long Cd—S bond lengths being ca 0.1 Å for the S1-containing ligand and ca 0.2 Å for the S3-containing ligand, Table 1. The almost symmetric mode of coordination of the dithiocarbamate ligands is reflected in the near equivalence of the associated C—S bond lengths, Table 1, and is consistent with significant delocalization of π-electron density over each four-membered chelate ring.
The monodentate mode of coordination of the piperazine ligand in the title compound is without precedent in the crystallographic literature of cadmium (Groom & Allen, 2014). However, there are several examples of bridging piperazine, e.g. [CdBr2(µ2-piperazine)]n (Yu et al., 2007), {Cd[1,3-(CO2)2C6H4](µ2-piperazine)(OH2)}n (Gu et al., 2011) and [Cd(SCN)2(µ2-piperazine)]n (Suen & Wang, 2007). In common with the title compound, the piperazine ring adopts a chair conformation in each of these structures.
In the extended structure, hydroxy-O1—H···O2(hydroxy), hydroxy-O2—H···N4(terminal-piperazine) and (coordinated-piperazine)-N3—H···O1(hydroxy) hydrogen bonds (Table 2) lead to the formation of a supramolecular layer in the ac plane, Fig. 2. Additional stability to the layers are afforded by methine-C—H···S1, S3 contacts, Table 2, as well as S2···S2i contacts of 3.3714 (10) Å, for
(i) 2 - x, 1 - y, 1 - z. Layers thus formed stack along the b axis, with very weak terminal-piperazine-N4—H···O2(hydroxy) interactions between them, Table 2 and Fig. 3.The program Crystal Explorer (Wolff et al., 2012) was used to generate Hirshfeld surfaces mapped over dnorm, de and electrostatic potential for the title compound. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) and were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level of theory over a range ±0.14 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (Rohl et al., 2008) provides a summary of intermolecular contacts in the crystal. The relative contributions from various contacts to the Hirshfeld surfaces are tabulated in Table 3.
The hydrogen-bonding network generated in the crystal through hydroxyl groups located at the edges, piperazine nitrogen-H at the apex and sulfur atoms on the vertices of the distorted square-pyramidal polyhedron can be visualized using Hirshfeld surface analysis. The bright-red spots on the Hirshfeld surface mapped over dnorm, Fig. 4, with labels H1O, H2O and H3N, on the surface represent donors for potential hydrogen bonds, Table 2; the corresponding acceptors on the surfaces appear as bright-red spots at O2, N4 and O1, respectively. The Hirshfeld surface mapped over the electrostatic potential, Fig. 5, represents donors with positive potential (blue regions) and the acceptors with negative potential (red). In addition, the negative potential around the sulfur atoms appear as light-red clouds and the positive potential around piperazine as a light-blue cloud in Fig. 5. The Hirshfeld surfaces mapped over dnorm showing intermolecular O—H···O, N—H···O and O—H···N bonds with symmetry-related molecules are shown in Fig. 6. The pale-red depressions near the atoms H4 and S1, and H10 and S3, Fig. 4, confirm the contribution of these pairs of atoms in the comparatively weak intermolecular C—H···S interactions. The pale-red spot near the S2 atom indicates an additional reinforcement to the two-dimensional framework through a non-bonded S···S contact.
The overall two-dimensional fingerprint plot, Fig. 7a, and those delineated into H···H, S···H/H···S, O···H/H···O, C···H/H···C, N···H/H···N and S···S interactions are illustrated in Fig. 7b--g, respectively. The greatest contribution to the overall Hirshfeld surface, i.e. 67.5%, is due to H···H contacts and is reflected in Fig. 4b as widely scattered points with a high concentration in the middle region, shown in green. The contribution from the S···H/H···S contacts, corresponding to C—H···S interactions, is represented by the pair of short spikes in the outer region, at de + di ~ 2.8 Å, Fig. 7c. In the plots delineated into O···H/H···O and N···H/H···N contacts, Fig. 7d and f, the pairs of adjacent peaks have almost same lengths near de + di ~ 1.8 Å, and clearly indicate the significance of intermolecular hydrogen bonds associated with them in the molecular packing. There is only a very small contribution from C···H/H···C contacts, i.e. 3.2% (Fig. 7d), and there is no contribution from C···C contacts in the structure as the result of the absence of C—H···π and π–π stacking interactions. Finally, the presence of S···S contacts can also be viewed in the delineated fingerprint plot, Fig. 7g, by the density of points in the de, di region around 1.7–2.4 Å as a broken line segment.
The identified intermolecular interactions were further evaluated by an analysis of the enrichment ratios (ER) that give a quantitative measure of the likelihood of specific intermolecular interactions to occur based on a Hirshfeld surface analysis (Jelsch et al., 2014); ratios are given in Table 4.
A total of 83.2% of the Hirshfeld surface involves hydrogen atoms and of this, non-bonded H···H contacts account for 67.5% of the contacts, which is close to the value of 69.2%, being the value calculated for random contacts so that the corresponding ER value is 0.98, i.e. near unity and in accord with earlier published results (Jelsch et al., 2014). The sulfur atoms comprise 9.7% of the surface and S···H/H···S contacts provide an overall 17.4% contribution to the surface resulting in an ER of 1.1 which is in the expected range, i.e. 1.0–1.5, for C—H···S interactions. The ER value of 1.2 corresponding to O···H/H···O contacts indicate these show a high propensity to form even though the relative contribution to the overall surface, i.e. 7.9%, is small as is the 4.0% exposure to the surface provided by the hydroxyl oxygen atoms. The other contributions to the surface, i.e. N···H/H···N and C···H/H···C, are small and the ER values are not particularly informative although being > 1, indicate a propensity to form as discussed above in Supramolecular features.
The structural chemistry of cadmium dithiocarbamates where the ligands have been functionalized with one or two hydroxyethyl groups has received some attention in recent years owing to the constant stream of unexpected crystallization outcomes. As mentioned in the Chemical context, [Cd(S2CNR2)2]2 compounds are usually binuclear (Tiekink, 2003). However, recent studies of Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013, 2016) have revealed solvent-dependent and solvent-independent supramolecular molecular isomers, e.g. crystallization from ethanol produced two species [Cd[S2CN(iPr)CH2CH2OH]2·EtOH]x for x = 2 and, unprecedented, n (Tan et al., 2016), with the kinetic, polymeric (x = n) form transforming in solution to the thermodynamic, binuclear form (x = 2). Other recrystallization conditions led to decomposition of the dithiocarbamate ligands and subsequent formation of a
and some salts. This behaviour, along with unexpected structure of {Cd[S2CN(iPr)CH2CH2OH]2(4-pyridinealdazine)2] (Broker & Tiekink, 2011) mentioned in the Chemical context, suggests this is a fertile area of crystallographic research. Finally, it is noted that gold (Jamaludin et al., 2013), zinc (Tan et al., 2015) and bismuth (Ishak et al., 2014) compounds of these ligands display promising potential as anti-cancer agents, and that some gold compounds also exhibit exciting anti-microbial activity (Sim et al., 2014).The monodentate mode of coordination of the piperazine ligand in the title compound is quite rare, and has not been observed in the structural chemistry of cadmium. However, crystallographically confirmed examples of a monodentate coordination mode for piperazine have been seen in five structures, e.g. as in centrosymmetric, all-trans CoCl2(piperazine)2(MeOH)2 (Suen et al., 2004).
For related literature, see: Addison et al. (1984); Broker & Tiekink (2011); Chai et al. (2003); Groom & Allen (2014); Gu et al. (2011); Ishak et al. (2014); Jamaludin et al. (2013); Jayatilaka et al. (2005); Jelsch et al. (2014); Poplaukhin & Tiekink (2008); Rodina et al. (2011); Rohl et al. (2008); Sim et al. (2014); Spackman et al. (2008); Suen & Wang (2007); Suen et al. (2004); Tan et al. (2013); Tan et al. (2015); Tan et al. (2016); Tiekink (2003); Wahab et al. (2011); Wolff et al. (2012); Yu et al. (2007).
The reagents Cd[S2CN(iPr)CH2CH2OH]2 (Tan et al., 2013; 206 mg, 0.44 mmol) and piperazine (Sigma–Aldrich; 76 mg, 0.43 mmol) were dissolved in chloroform (15 ml) and acetonitrile (5 ml), respectively. The latter solution was added dropwise into the chloroform solution and the resulting mixture was stirred for 1 h at room temperature. Slow evaporation of the clear solution yielded colourless crystals. M.p. 415–417 K. IR (cm-1): ν (O—H) 3281, ν(C—N) 1442, ν (C—O) 1169, ν (C—S) 1029.
detailsCrystal data, data collection and structure
details are summarized in Table 5. The carbon-bound H atoms were placed in calculated positions (C—H = 0.98–1.00 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).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: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound, {Cd[S2CN(iPr)CH2CH2OH]2[HN(CH2CH2)2NH]}, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. | |
Fig. 2. A view of the supramolecular layer in the title compound, shown in projection down the b axis. The hydroxy-O1—H···O2(hydroxy) hydrogen bonds are shown as orange dashed lines while both the hydroxy-O2—H···N4(terminal-piperazine) and (coordinated-piperazine)-N3—H···O1(hydroxy) hydrogen bonds are shown as blue dashed lines. The methine-C—H···S and S···S interactions within the layers (see text) are not shown. Only acidic hydrogen atoms are shown. | |
Fig. 3. A view of the unit-cell contents of the title compound shown in projection down the c axis, whereby the supramolecular layers, illustrated in Fig. 2, stack along the b axis. One layer is highlighted in space-filling mode. | |
Fig. 4. Two views of the Hirshfeld surface mapped over dnorm. The contact points (red) are labelled to indicate the atoms participating in the intermolecular interactions. | |
Fig. 5. Two views of the Hirshfeld surface mapped over the electrostatic potential with positive and negative potential indicated in blue and red, respectively. | |
Fig. 6. Hirshfeld surface mapped for a reference molecule over dnorm showing hydrogen bonds with neighbouring molecules. | |
Fig. 7. Two-dimensional fingerprint plots: (a) overall, and delineated into contributions from different contacts: (b) H···H, (c) S···H/H···S, (d) O···H/H···O, (e) C···H/H···C, (f) N···H/H···N and (g) S···S. |
[Cd(C6H12NOS2)2(C4H10N2)] | F(000) = 1144 |
Mr = 555.11 | Dx = 1.594 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.341 (3) Å | Cell parameters from 7141 reflections |
b = 16.9915 (7) Å | θ = 2.3–27.5° |
c = 9.0308 (8) Å | µ = 1.32 mm−1 |
β = 100.620 (16)° | T = 100 K |
V = 2313.7 (5) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.30 × 0.25 mm |
Agilent SuperNova Dual diffractometer with Atlas detector | 5336 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 4483 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.035 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.6° |
ω scan | h = −19→19 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −22→21 |
Tmin = 0.805, Tmax = 1.000 | l = −11→11 |
19918 measured reflections |
Refinement on F2 | 4 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0205P)2 + 0.8997P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.058 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.45 e Å−3 |
5336 reflections | Δρmin = −0.45 e Å−3 |
260 parameters |
[Cd(C6H12NOS2)2(C4H10N2)] | V = 2313.7 (5) Å3 |
Mr = 555.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.341 (3) Å | µ = 1.32 mm−1 |
b = 16.9915 (7) Å | T = 100 K |
c = 9.0308 (8) Å | 0.35 × 0.30 × 0.25 mm |
β = 100.620 (16)° |
Agilent SuperNova Dual diffractometer with Atlas detector | 5336 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 4483 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 1.000 | Rint = 0.035 |
19918 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 260 parameters |
wR(F2) = 0.058 | 4 restraints |
S = 1.03 | Δρmax = 0.45 e Å−3 |
5336 reflections | Δρmin = −0.45 e Å−3 |
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 | ||
Cd | 0.76764 (2) | 0.52627 (2) | 0.47410 (2) | 0.01437 (5) | |
S1 | 0.78258 (4) | 0.56986 (3) | 0.74785 (6) | 0.01975 (12) | |
S2 | 0.93633 (3) | 0.55625 (3) | 0.59115 (6) | 0.01631 (12) | |
S3 | 0.74500 (4) | 0.57217 (3) | 0.20148 (6) | 0.02150 (13) | |
S4 | 0.59316 (3) | 0.56165 (3) | 0.36324 (6) | 0.01639 (12) | |
O1 | 1.18537 (10) | 0.63462 (9) | 0.85852 (17) | 0.0188 (3) | |
H1O | 1.2282 (12) | 0.6228 (14) | 0.923 (2) | 0.028* | |
O2 | 0.33805 (10) | 0.64272 (9) | 0.05591 (18) | 0.0198 (3) | |
H2O | 0.3353 (17) | 0.6586 (14) | 0.1420 (15) | 0.030* | |
N1 | 0.94525 (11) | 0.62212 (10) | 0.86113 (19) | 0.0144 (4) | |
N2 | 0.58291 (11) | 0.62440 (10) | 0.0898 (2) | 0.0146 (4) | |
N3 | 0.76459 (11) | 0.39219 (10) | 0.4310 (2) | 0.0145 (4) | |
H3N | 0.7843 (14) | 0.3924 (13) | 0.3467 (16) | 0.017* | |
N4 | 0.69255 (12) | 0.31320 (10) | 0.6653 (2) | 0.0178 (4) | |
H4N | 0.6902 (15) | 0.2653 (7) | 0.631 (2) | 0.021* | |
C1 | 0.89375 (14) | 0.58600 (11) | 0.7450 (2) | 0.0139 (4) | |
C2 | 1.03323 (13) | 0.65184 (12) | 0.8466 (2) | 0.0161 (4) | |
H2A | 1.0464 | 0.6989 | 0.9115 | 0.019* | |
H2B | 1.0309 | 0.6689 | 0.7411 | 0.019* | |
C3 | 1.10896 (13) | 0.59392 (12) | 0.8877 (3) | 0.0177 (5) | |
H3A | 1.1165 | 0.5789 | 0.9952 | 0.021* | |
H3B | 1.0980 | 0.5458 | 0.8252 | 0.021* | |
C4 | 0.90981 (14) | 0.64845 (13) | 0.9957 (2) | 0.0183 (5) | |
H4 | 0.8542 | 0.6181 | 0.9977 | 0.022* | |
C5 | 0.88517 (16) | 0.73502 (14) | 0.9818 (3) | 0.0277 (6) | |
H5A | 0.8426 | 0.7437 | 0.8881 | 0.042* | |
H5B | 0.9386 | 0.7665 | 0.9806 | 0.042* | |
H5C | 0.8584 | 0.7507 | 1.0678 | 0.042* | |
C6 | 0.97444 (15) | 0.63025 (14) | 1.1409 (3) | 0.0255 (5) | |
H6A | 0.9920 | 0.5748 | 1.1413 | 0.038* | |
H6B | 0.9458 | 0.6407 | 1.2274 | 0.038* | |
H6C | 1.0271 | 0.6636 | 1.1474 | 0.038* | |
C7 | 0.63461 (14) | 0.58907 (11) | 0.2067 (2) | 0.0148 (4) | |
C8 | 0.49551 (13) | 0.65624 (12) | 0.1036 (2) | 0.0156 (4) | |
H8A | 0.4834 | 0.7030 | 0.0377 | 0.019* | |
H8B | 0.4981 | 0.6741 | 0.2087 | 0.019* | |
C9 | 0.41828 (14) | 0.59923 (12) | 0.0634 (3) | 0.0183 (5) | |
H9A | 0.4198 | 0.5741 | −0.0350 | 0.022* | |
H9B | 0.4222 | 0.5575 | 0.1408 | 0.022* | |
C10 | 0.61846 (14) | 0.64931 (12) | −0.0452 (2) | 0.0173 (5) | |
H10 | 0.6722 | 0.6166 | −0.0493 | 0.021* | |
C11 | 0.64800 (16) | 0.73483 (13) | −0.0293 (3) | 0.0253 (5) | |
H11A | 0.6902 | 0.7417 | 0.0654 | 0.038* | |
H11B | 0.5963 | 0.7687 | −0.0292 | 0.038* | |
H11C | 0.6766 | 0.7492 | −0.1140 | 0.038* | |
C12 | 0.55260 (15) | 0.63515 (13) | −0.1906 (3) | 0.0230 (5) | |
H12A | 0.5319 | 0.5805 | −0.1936 | 0.034* | |
H12B | 0.5815 | 0.6451 | −0.2769 | 0.034* | |
H12C | 0.5019 | 0.6707 | −0.1950 | 0.034* | |
C13 | 0.67256 (14) | 0.36241 (12) | 0.4019 (2) | 0.0163 (4) | |
H13A | 0.6711 | 0.3086 | 0.3594 | 0.020* | |
H13B | 0.6349 | 0.3967 | 0.3277 | 0.020* | |
C14 | 0.63728 (14) | 0.36126 (12) | 0.5478 (2) | 0.0173 (5) | |
H14A | 0.6347 | 0.4158 | 0.5851 | 0.021* | |
H14B | 0.5761 | 0.3400 | 0.5281 | 0.021* | |
C15 | 0.78608 (14) | 0.33777 (13) | 0.6863 (2) | 0.0187 (5) | |
H15A | 0.8225 | 0.3006 | 0.7562 | 0.022* | |
H15B | 0.7921 | 0.3905 | 0.7338 | 0.022* | |
C16 | 0.82184 (14) | 0.34096 (12) | 0.5409 (2) | 0.0180 (5) | |
H16A | 0.8831 | 0.3619 | 0.5610 | 0.022* | |
H16B | 0.8234 | 0.2873 | 0.4988 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.01554 (9) | 0.01362 (8) | 0.01268 (9) | −0.00077 (6) | −0.00071 (6) | 0.00017 (6) |
S1 | 0.0124 (3) | 0.0291 (3) | 0.0181 (3) | −0.0043 (2) | 0.0038 (2) | −0.0087 (2) |
S2 | 0.0142 (3) | 0.0209 (3) | 0.0139 (3) | 0.0001 (2) | 0.0027 (2) | −0.0039 (2) |
S3 | 0.0130 (3) | 0.0336 (3) | 0.0182 (3) | 0.0052 (2) | 0.0036 (2) | 0.0104 (2) |
S4 | 0.0155 (3) | 0.0184 (3) | 0.0156 (3) | 0.0017 (2) | 0.0038 (2) | 0.0025 (2) |
O1 | 0.0119 (8) | 0.0277 (8) | 0.0162 (8) | −0.0023 (6) | 0.0008 (6) | 0.0011 (7) |
O2 | 0.0132 (8) | 0.0279 (9) | 0.0177 (8) | 0.0031 (6) | 0.0011 (7) | −0.0014 (7) |
N1 | 0.0130 (9) | 0.0167 (9) | 0.0142 (9) | −0.0016 (7) | 0.0042 (7) | −0.0024 (7) |
N2 | 0.0121 (9) | 0.0155 (9) | 0.0159 (9) | 0.0026 (7) | 0.0014 (7) | 0.0016 (7) |
N3 | 0.0145 (9) | 0.0171 (9) | 0.0123 (9) | 0.0004 (7) | 0.0035 (7) | 0.0018 (7) |
N4 | 0.0212 (10) | 0.0138 (9) | 0.0186 (10) | −0.0017 (7) | 0.0045 (8) | 0.0013 (7) |
C1 | 0.0150 (11) | 0.0109 (10) | 0.0152 (11) | 0.0019 (8) | 0.0015 (8) | 0.0023 (8) |
C2 | 0.0135 (11) | 0.0188 (11) | 0.0161 (11) | −0.0049 (8) | 0.0026 (9) | −0.0011 (9) |
C3 | 0.0134 (11) | 0.0214 (11) | 0.0175 (11) | −0.0026 (8) | 0.0010 (9) | 0.0003 (9) |
C4 | 0.0154 (11) | 0.0246 (12) | 0.0157 (11) | −0.0044 (9) | 0.0050 (9) | −0.0069 (9) |
C5 | 0.0265 (13) | 0.0304 (13) | 0.0271 (14) | 0.0040 (10) | 0.0070 (11) | −0.0108 (11) |
C6 | 0.0230 (13) | 0.0384 (14) | 0.0157 (12) | −0.0078 (10) | 0.0050 (10) | −0.0040 (10) |
C7 | 0.0146 (11) | 0.0122 (10) | 0.0170 (11) | −0.0007 (8) | 0.0014 (9) | −0.0008 (8) |
C8 | 0.0153 (11) | 0.0138 (10) | 0.0176 (11) | 0.0026 (8) | 0.0027 (9) | 0.0011 (8) |
C9 | 0.0151 (11) | 0.0205 (11) | 0.0192 (12) | 0.0026 (8) | 0.0027 (9) | 0.0003 (9) |
C10 | 0.0145 (11) | 0.0220 (11) | 0.0153 (11) | 0.0028 (8) | 0.0026 (9) | 0.0050 (9) |
C11 | 0.0255 (13) | 0.0265 (13) | 0.0231 (13) | −0.0060 (10) | 0.0025 (10) | 0.0072 (10) |
C12 | 0.0210 (12) | 0.0279 (12) | 0.0184 (12) | 0.0024 (9) | −0.0004 (10) | 0.0031 (10) |
C13 | 0.0167 (11) | 0.0151 (10) | 0.0160 (11) | −0.0013 (8) | 0.0000 (9) | −0.0019 (8) |
C14 | 0.0145 (11) | 0.0159 (10) | 0.0209 (12) | −0.0009 (8) | 0.0016 (9) | 0.0000 (9) |
C15 | 0.0181 (11) | 0.0197 (11) | 0.0173 (12) | 0.0040 (9) | 0.0008 (9) | 0.0052 (9) |
C16 | 0.0157 (11) | 0.0175 (11) | 0.0203 (12) | 0.0031 (8) | 0.0023 (9) | 0.0020 (9) |
Cd—S1 | 2.5503 (6) | C4—H4 | 1.0000 |
Cd—S2 | 2.6580 (8) | C5—H5A | 0.9800 |
Cd—S3 | 2.5446 (6) | C5—H5B | 0.9800 |
Cd—S4 | 2.7461 (8) | C5—H5C | 0.9800 |
Cd—N3 | 2.3102 (17) | C6—H6A | 0.9800 |
C1—S1 | 1.732 (2) | C6—H6B | 0.9800 |
C1—S2 | 1.717 (2) | C6—H6C | 0.9800 |
C7—S3 | 1.727 (2) | C8—C9 | 1.522 (3) |
C7—S4 | 1.718 (2) | C8—H8A | 0.9900 |
O1—C3 | 1.427 (2) | C8—H8B | 0.9900 |
O1—H1O | 0.821 (10) | C9—H9A | 0.9900 |
O2—C9 | 1.426 (2) | C9—H9B | 0.9900 |
O2—H2O | 0.831 (10) | C10—C12 | 1.521 (3) |
N1—C1 | 1.340 (3) | C10—C11 | 1.521 (3) |
N1—C2 | 1.470 (3) | C10—H10 | 1.0000 |
N1—C4 | 1.488 (3) | C11—H11A | 0.9800 |
N2—C7 | 1.340 (3) | C11—H11B | 0.9800 |
N2—C8 | 1.472 (3) | C11—H11C | 0.9800 |
N2—C10 | 1.487 (3) | C12—H12A | 0.9800 |
N3—C13 | 1.477 (3) | C12—H12B | 0.9800 |
N3—C16 | 1.481 (3) | C12—H12C | 0.9800 |
N3—H3N | 0.869 (9) | C13—C14 | 1.514 (3) |
N4—C15 | 1.473 (3) | C13—H13A | 0.9900 |
N4—C14 | 1.477 (3) | C13—H13B | 0.9900 |
N4—H4N | 0.868 (9) | C14—H14A | 0.9900 |
C2—C3 | 1.516 (3) | C14—H14B | 0.9900 |
C2—H2A | 0.9900 | C15—C16 | 1.515 (3) |
C2—H2B | 0.9900 | C15—H15A | 0.9900 |
C3—H3A | 0.9900 | C15—H15B | 0.9900 |
C3—H3B | 0.9900 | C16—H16A | 0.9900 |
C4—C5 | 1.518 (3) | C16—H16B | 0.9900 |
C4—C6 | 1.523 (3) | ||
S1—Cd—S2 | 69.63 (2) | C4—C6—H6C | 109.5 |
S1—Cd—S3 | 145.16 (2) | H6A—C6—H6C | 109.5 |
S1—Cd—S4 | 101.38 (2) | H6B—C6—H6C | 109.5 |
S1—Cd—N3 | 116.43 (5) | N2—C7—S4 | 120.98 (16) |
S2—Cd—S3 | 105.98 (2) | N2—C7—S3 | 119.60 (16) |
S2—Cd—S4 | 156.230 (18) | S4—C7—S3 | 119.42 (12) |
S2—Cd—N3 | 104.12 (4) | N2—C8—C9 | 115.29 (17) |
S3—Cd—S4 | 68.29 (2) | N2—C8—H8A | 108.5 |
S3—Cd—N3 | 98.30 (5) | C9—C8—H8A | 108.5 |
S4—Cd—N3 | 99.57 (4) | N2—C8—H8B | 108.5 |
C1—S1—Cd | 86.81 (7) | C9—C8—H8B | 108.5 |
C1—S2—Cd | 83.72 (7) | H8A—C8—H8B | 107.5 |
C7—S3—Cd | 89.09 (8) | O2—C9—C8 | 107.97 (17) |
C7—S4—Cd | 82.85 (7) | O2—C9—H9A | 110.1 |
C3—O1—H1O | 109.0 (18) | C8—C9—H9A | 110.1 |
C9—O2—H2O | 108.4 (18) | O2—C9—H9B | 110.1 |
C1—N1—C2 | 120.42 (18) | C8—C9—H9B | 110.1 |
C1—N1—C4 | 121.68 (17) | H9A—C9—H9B | 108.4 |
C2—N1—C4 | 116.70 (16) | N2—C10—C12 | 112.18 (18) |
C7—N2—C8 | 120.95 (18) | N2—C10—C11 | 110.04 (18) |
C7—N2—C10 | 121.38 (17) | C12—C10—C11 | 111.81 (18) |
C8—N2—C10 | 116.24 (16) | N2—C10—H10 | 107.5 |
C13—N3—C16 | 110.33 (16) | C12—C10—H10 | 107.5 |
C13—N3—Cd | 110.91 (12) | C11—C10—H10 | 107.5 |
C16—N3—Cd | 118.40 (13) | C10—C11—H11A | 109.5 |
C13—N3—H3N | 108.7 (15) | C10—C11—H11B | 109.5 |
C16—N3—H3N | 109.3 (15) | H11A—C11—H11B | 109.5 |
Cd—N3—H3N | 98.3 (15) | C10—C11—H11C | 109.5 |
C15—N4—C14 | 110.64 (16) | H11A—C11—H11C | 109.5 |
C15—N4—H4N | 106.7 (16) | H11B—C11—H11C | 109.5 |
C14—N4—H4N | 106.4 (15) | C10—C12—H12A | 109.5 |
N1—C1—S2 | 120.73 (16) | C10—C12—H12B | 109.5 |
N1—C1—S1 | 120.06 (16) | H12A—C12—H12B | 109.5 |
S2—C1—S1 | 119.20 (12) | C10—C12—H12C | 109.5 |
N1—C2—C3 | 115.48 (17) | H12A—C12—H12C | 109.5 |
N1—C2—H2A | 108.4 | H12B—C12—H12C | 109.5 |
C3—C2—H2A | 108.4 | N3—C13—C14 | 109.43 (17) |
N1—C2—H2B | 108.4 | N3—C13—H13A | 109.8 |
C3—C2—H2B | 108.4 | C14—C13—H13A | 109.8 |
H2A—C2—H2B | 107.5 | N3—C13—H13B | 109.8 |
O1—C3—C2 | 105.00 (16) | C14—C13—H13B | 109.8 |
O1—C3—H3A | 110.7 | H13A—C13—H13B | 108.2 |
C2—C3—H3A | 110.7 | N4—C14—C13 | 112.50 (18) |
O1—C3—H3B | 110.7 | N4—C14—H14A | 109.1 |
C2—C3—H3B | 110.7 | C13—C14—H14A | 109.1 |
H3A—C3—H3B | 108.8 | N4—C14—H14B | 109.1 |
N1—C4—C5 | 110.29 (18) | C13—C14—H14B | 109.1 |
N1—C4—C6 | 111.36 (17) | H14A—C14—H14B | 107.8 |
C5—C4—C6 | 112.35 (18) | N4—C15—C16 | 113.49 (18) |
N1—C4—H4 | 107.5 | N4—C15—H15A | 108.9 |
C5—C4—H4 | 107.5 | C16—C15—H15A | 108.9 |
C6—C4—H4 | 107.5 | N4—C15—H15B | 108.9 |
C4—C5—H5A | 109.5 | C16—C15—H15B | 108.9 |
C4—C5—H5B | 109.5 | H15A—C15—H15B | 107.7 |
H5A—C5—H5B | 109.5 | N3—C16—C15 | 109.71 (17) |
C4—C5—H5C | 109.5 | N3—C16—H16A | 109.7 |
H5A—C5—H5C | 109.5 | C15—C16—H16A | 109.7 |
H5B—C5—H5C | 109.5 | N3—C16—H16B | 109.7 |
C4—C6—H6A | 109.5 | C15—C16—H16B | 109.7 |
C4—C6—H6B | 109.5 | H16A—C16—H16B | 108.2 |
H6A—C6—H6B | 109.5 | ||
C2—N1—C1—S2 | 12.9 (2) | Cd—S4—C7—N2 | −173.40 (17) |
C4—N1—C1—S2 | 179.99 (15) | Cd—S4—C7—S3 | 5.59 (11) |
C2—N1—C1—S1 | −166.32 (14) | Cd—S3—C7—N2 | 173.01 (16) |
C4—N1—C1—S1 | 0.8 (3) | Cd—S3—C7—S4 | −5.99 (11) |
Cd—S2—C1—N1 | −171.64 (16) | C7—N2—C8—C9 | −90.4 (2) |
Cd—S2—C1—S1 | 7.59 (11) | C10—N2—C8—C9 | 103.1 (2) |
Cd—S1—C1—N1 | 171.36 (16) | N2—C8—C9—O2 | −169.59 (17) |
Cd—S1—C1—S2 | −7.88 (11) | C7—N2—C10—C12 | 141.10 (19) |
C1—N1—C2—C3 | −89.4 (2) | C8—N2—C10—C12 | −52.4 (2) |
C4—N1—C2—C3 | 102.9 (2) | C7—N2—C10—C11 | −93.8 (2) |
N1—C2—C3—O1 | 177.54 (16) | C8—N2—C10—C11 | 72.7 (2) |
C1—N1—C4—C5 | −96.9 (2) | C16—N3—C13—C14 | 59.9 (2) |
C2—N1—C4—C5 | 70.7 (2) | Cd—N3—C13—C14 | −73.30 (17) |
C1—N1—C4—C6 | 137.7 (2) | C15—N4—C14—C13 | 52.8 (2) |
C2—N1—C4—C6 | −54.8 (2) | N3—C13—C14—N4 | −57.4 (2) |
C8—N2—C7—S4 | 13.3 (3) | C14—N4—C15—C16 | −51.7 (2) |
C10—N2—C7—S4 | 179.18 (14) | C13—N3—C16—C15 | −58.4 (2) |
C8—N2—C7—S3 | −165.65 (14) | Cd—N3—C16—C15 | 70.83 (19) |
C10—N2—C7—S3 | 0.2 (3) | N4—C15—C16—N3 | 54.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.82 (2) | 1.91 (2) | 2.673 (2) | 155 (2) |
O2—H2O···N4ii | 0.83 (2) | 1.93 (2) | 2.749 (2) | 169 (3) |
N3—H3N···O1iii | 0.87 (2) | 2.05 (2) | 2.894 (2) | 165 (2) |
N4—H4N···O2iv | 0.87 (1) | 2.67 (1) | 3.501 (3) | 162 (1) |
C4—H4···S3v | 1.00 | 2.82 | 3.641 (3) | 140 |
C10—H10···S1vi | 1.00 | 2.83 | 3.659 (3) | 141 |
Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) x, y, z+1; (vi) x, y, z−1. |
Cd—S1 | 2.5503 (6) | C1—S1 | 1.732 (2) |
Cd—S2 | 2.6580 (8) | C1—S2 | 1.717 (2) |
Cd—S3 | 2.5446 (6) | C7—S3 | 1.727 (2) |
Cd—S4 | 2.7461 (8) | C7—S4 | 1.718 (2) |
Cd—N3 | 2.3102 (17) | ||
S1—Cd—S2 | 69.63 (2) | S2—Cd—S4 | 156.230 (18) |
S1—Cd—S3 | 145.16 (2) | S2—Cd—N3 | 104.12 (4) |
S1—Cd—S4 | 101.38 (2) | S3—Cd—S4 | 68.29 (2) |
S1—Cd—N3 | 116.43 (5) | S3—Cd—N3 | 98.30 (5) |
S2—Cd—S3 | 105.98 (2) | S4—Cd—N3 | 99.57 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.819 (19) | 1.910 (19) | 2.673 (2) | 155 (2) |
O2—H2O···N4ii | 0.831 (16) | 1.927 (17) | 2.749 (2) | 169 (3) |
N3—H3N···O1iii | 0.869 (17) | 2.045 (16) | 2.894 (2) | 165 (2) |
N4—H4N···O2iv | 0.869 (13) | 2.666 (14) | 3.501 (3) | 162 (1) |
C4—H4···S3v | 1.00 | 2.82 | 3.641 (3) | 140 |
C10—H10···S1vi | 1.00 | 2.83 | 3.659 (3) | 141 |
Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+1, y−1/2, −z+1/2; (v) x, y, z+1; (vi) x, y, z−1. |
Contact | Contribution |
H···H | 67.5 |
S···H/H···S | 17.4 |
O···H/H···O | 7.9 |
C···H/H···C | 3.2 |
N···H/H···N | 2.3 |
S···S | 1.0 |
Cd···H/H···Cd | 0.6 |
Others | 0.1 |
Experimental details
Crystal data | |
Chemical formula | [Cd(C6H12NOS2)2(C4H10N2)] |
Mr | 555.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 15.341 (3), 16.9915 (7), 9.0308 (8) |
β (°) | 100.620 (16) |
V (Å3) | 2313.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.805, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19918, 5336, 4483 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.058, 1.03 |
No. of reflections | 5336 |
No. of parameters | 260 |
No. of restraints | 4 |
Δρmax, Δρmin (e Å−3) | 0.45, −0.45 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Footnotes
‡Additional correspondence author, e-mail: nadiahhalim@um.edu.my.
Acknowledgements
The University of Malaya's Postgraduate Research Grant Scheme (No. PG097-2014B) is gratefully acknowledged.
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Agilent (2011). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Broker, G. A. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m320–m321. Web of Science CSD CrossRef CAS IUCr Journals 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
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Gu, J.-Z., Lv, D.-Y., Gao, Z.-Q., Liu, J.-Z., Dou, W. & Tang, Y. (2011). J. Solid State Chem. 184, 675–683. Web of Science CSD CrossRef CAS Google Scholar
Ishak, D. H. A., Ooi, K. K., Ang, K. P., Akim, A. Md., Cheah, Y. K., Nordin, N., Halim, S. N. B. A., Seng, H.-L. & Tiekink, E. R. T. (2014). J. Inorg. Biochem. 130, 38–51. Web of Science CrossRef CAS PubMed Google Scholar
Jamaludin, N. S., Goh, Z.-J., Cheah, Y. K., Ang, K.-P., Sim, J. H., Khoo, C. H., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Eur. J. Med. Chem. 67, 127–141. Web of Science CSD CrossRef CAS PubMed 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
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
Rohl, A. L., Moret, M., Kaminsky, W., Claborn, K., McKinnon, J. J. & Kahr, B. (2008). Cryst. Growth Des. 8, 4517–4525. Web of Science CSD 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
Sim, J.-H., Jamaludin, N. S., Khoo, C.-H., Cheah, Y.-K., Halim, S. N. B. A., Seng, H.-L. & Tiekink, E. R. T. (2014). Gold Bull. 47, 225–236. Web of Science CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Suen, M.-C. & Wang, J.-C. (2007). J. Coord. Chem. 60, 2197–2205. Web of Science CSD CrossRef CAS Google Scholar
Suen, M.-C., Wang, Y.-H. & Wang, J.-C. (2004). J. Chin. Chem. Soc. (Taipei), 51, 43–48. CrossRef CAS Google Scholar
Tan, Y. S., Halim, S. N. A. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231 DOI: 10.1515/zkri-2015-1889. Google Scholar
Tan, Y. S., Ooi, K. K., Ang, K. P., Akim, A. Md, Cheah, Y.-K., Halim, S. N. A, Seng, H.-L. & Tiekink, E. R. T. (2015). J. Inorg. Biochem. 150, 48–62. Web of Science CSD CrossRef CAS PubMed 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
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
Yu, J.-H., Ye, L., Bi, M.-H., Hou, Q., Zhang, X. & Xu, J.-Q. (2007). Inorg. Chim. Acta, 360, 1987–1994. Web of Science CSD CrossRef CAS Google Scholar
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