research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1159-1164
doi:10.1107/S2056989015016655

Crystal structures of 5-amino-N-phenyl-3H-1,2,4-di­thia­zol-3-iminium chloride and 5-amino-N-(4-chloro­phen­yl)-3H-1,2,4-di­thia­zol-3-iminium chloride monohydrate

CROSSMARK_Color_square_no_text.svg
Chien Ing Yeo,a Yee Seng Tana and Edward R. T. Tiekinka,b*

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and bCentre for Chemical Crystallography, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edward.tiekink@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 September 2015; accepted 7 September 2015; online 12 September 2015)

The crystal and mol­ecular structures of the title salt, C8H8N3S2+·Cl−, (I), and salt hydrate, C8H7ClN3S2+·Cl−·H2O, (II), are described. The heterocyclic ring in (I) is statistically planar and forms a dihedral angle of 9.05 (12)° with the pendant phenyl ring. The comparable angle in (II) is 15.60 (12)°, indicating a greater twist in this cation. An evaluation of the bond lengths in the H2N—C—N—C—N sequence of each cation indicates significant delocalization of π-electron density over these atoms. The common feature of the crystal packing in (I) and (II) is the formation of charge-assisted amino-N—H⋯Cl− hydrogen bonds, leading to helical chains in (I) and zigzag chains in (II). In (I), these are linked by chains mediated by charge-assisted iminium-N+—H⋯Cl− hydrogen bonds into a three-dimensional architecture. In (II), the chains are linked into a layer by charge-assisted water-O—H⋯Cl− and water-O—H⋯O(water) hydrogen bonds with charge-assisted iminium-N+—H⋯O(water) hydrogen bonds providing the connections between the layers to generate the three-dimensional packing. In (II), the chloride anion and water mol­ecules are resolved into two proximate sites with the major component being present with a site occupancy factor of 0.9327 (18).

CCDC references: 1422604; 1422603

1. Chemical context

The title salts were isolated as a part of a research programme into the crystal engineering aspects and biological potential of phosphanegold(I) carbonimido­thio­ates, i.e. mol­ecules of the general formula R3PAu[SC(OR′)=NR′′]; R, R′, R′′ = aryl and/or alkyl. While earlier work focussed on supra­molecular aggregation patterns (Kuan et al., 2008[Kuan, F. S., Ho, S. Y., Tadbuppa, P. P. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 548-564.]) and solid-state luminescence (Ho et al., 2006[Ho, S. Y., Cheng, E. C.-C., Tiekink, E. R. T. & Yam, V. W.-W. (2006). Inorg. Chem. 45, 8165-8174.]), more recent endeavours have focussed upon biological studies. For example, the Ph3PAu[SC(O–alk­yl)=N(p-tol­yl)] compounds prove to be very potent against Gram-positive bacteria (Yeo, Sim et al., 2013[Yeo, C. I., Sim, J.-H., Khoo, C.-H., Goh, Z.-J., Ang, K.-P., Cheah, Y.-K., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Gold Bull. 46, 145-152.]). In addition, Ph3PAu[SC(O–alk­yl)=N(ar­yl)] com­pounds exhibit significant cytotoxicity and kill cancer cells by initiating a variety of apoptotic pathways (Yeo, Ooi et al., 2013[Yeo, C. I., Ooi, K. K., Akim, A., Ang, K. P., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H. & Tiekink, E. R. T. (2013). J. Inorg. Biochem. 127, 24-38.]; Ooi, Yeo et al., 2015[Ooi, K. K., Yeo, C. I., Ang, K.-P., Akim, A., Cheah, Y., Halim, S. N. A., Seng, H. & Tiekink, E. R. T. (2015). J. Biol. Inorg. Chem. 20, 855-873.]). A focus of recent synthetic efforts has been to increase the functionality of the thio­carbamide mol­ecules in order to produce gold complexes of higher nuclear­ity. During this work bipodal {1,4-[MeOC(=S)N(H)]2C6H4} was synthesized along with its binuclear phosphanegold(I) complexes (Yeo et al., 2015[Yeo, C. I., Khoo, C.-H., Chu, W.-C., Chen, B.-J., Chu, P.-L., Sim, J.-H., Cheah, Y.-K., Ahmad, J., Halim, S. N. A., Seng, H.-L., Ng, S., Otero-de-la-Roza, A. & Tiekink, E. R. T. (2015). RSC Adv. 5, 41401-41411.]). As an expansion of these studies, the 1:2 reactions of thio­urea with aryl­iso­thio­cyanates were undertaken which, rather than yielding bipodal mol­ecules, gave the 1:1 cyclization products, isolated as salts. These and related compounds have been described in the patent literature as having a range of biological properties, e.g. as bactericides, fungicides and plant-growth inhibitors (Röthling et al., 1989[Röthling, T., Hansen, P., Creuzburg, D., Fieseler, C., Stohr, P., Hölzel, H., Steinke, W., Biering, H., Kibbel, H. U., Kranz, L., Luthardt, H., Richter, R. & Vasel, S. (1989). East German Patent DD 267655 A1.]). Herein, the crystal and mol­ecular structures of two examples of these products, i.e. the salt, [C8H8N3S2]Cl (I)[link], and the salt hydrate [C8H7ClN3S2]Cl·H2O (II)[link], are described.

[Scheme 1]

2. Structural commentary

The asymmetric unit of (I)[link], comprising a cation and chloride anion, is shown in Fig. 1[link]. The five-membered 1,2,4-di­thia­zole ring of the cation in (I)[link] is strictly planar with the maximum deviation being less than ±0.003 (2) Å. However, the entire cation is not planar with the dihedral angle between the rings being 9.05 (12)°. Selected geometric parameters are collected in Table 1[link]. While the S—S and S—C bond lengths correspond to single bonds, an evaluation of the C—N bonds, inter­nal and external to the ring, suggest a high level of delocalization of π-electron density across these atoms. The angles subtended at the S atoms are nearly right-angles. The trigonal angles around the C1 atom are all approximately 120° but there is a range of 10° for the angles about the C2 atom, with the widest angle being N2—C2—N3, consistent with double-bond character in the C—N bonds. The widest angle in the mol­ecule is that subtended at the N3 atom, an observation that correlates with the C2=N3 double bond and the presence of the small H atom on the N3 atom.

Table 1
Geometric data (Å, °) for (I)[link] and (II)

Parameter (I) (II)
S1—S2 2.0669 (10) 2.0657 (12)
S1—C1 1.769 (3) 1.749 (3)
S2—C2 1.772 (3) 1.763 (3)
N1—C1 1.309 (3) 1.305 (4)
N2—C1 1.328 (3) 1.337 (4)
N2—C2 1.317 (3) 1.312 (4)
N3—C2 1.328 (3) 1.332 (4)
N3—C3 1.418 (3) 1.424 (4)
     
C1—S1—S2 92.63 (9) 92.68 (11)
C2—S2—S1 92.72 (10) 92.85 (11)
C2—N2—C1 115.1 (2) 115.1 (2)
C2—N3—C3 130.4 (2) 128.0 (3)
N1—C1—N2 122.5 (2) 120.8 (3)
N1—C1—S1 117.8 (2) 119.5 (2)
N2—C1—S1 119.7 (2) 119.8 (2)
N2—C2—N3 125.2 (2) 123.4 (3)
N2—C2—S2 119.8 (2) 119.6 (2)
N3—C2—S2 115.1 (2) 117.0 (2)
[Figure 1]
Figure 1
The asymmetric unit for (I)[link], showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The dashed lines indicate hydrogen bonds.

The asymmetric unit of (II)[link], comprising a cation, a chloride anion and a water mol­ecule of crystallization, is illustrated in Fig. 2[link]. As for (I)[link], the cation is almost planar with the maximum deviation being 0.010 (2) Å for the N2 atom; the r.m.s. deviation for the fitted atoms is 0.010 Å. A greater overall twist in the mol­ecule is evident, as seen in the dihedral angle of 15.60 (12)° formed between the rings. In terms of bond lengths, Table 1[link], the discussion above for (I)[link], holds true for (II)[link]. Similarly, for the bond angles except that the range of angles about the C2 atom is narrower at 6°.

[Figure 2]
Figure 2
The asymmetric unit for (II)[link], showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The dashed lines indicate hydrogen bonds.

Fig. 3[link] presents an overlay diagram of the cations in each of (I)[link] and (II)[link] which highlights the similarity in their mol­ecular structures.

[Figure 3]
Figure 3
Overlay diagram of the cations in (I)[link], red image, and (II)[link], blue image. The cations have been overlapped so that the five-membered rings are coincident.

3. Supra­molecular features

Geometric parameters characterizing the inter­molecular inter­actions operating in the crystal structures of (I)[link] and (II)[link] are collected in Tables 2[link] and 3[link], respectively.

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1N⋯Cl1i 0.87 (2) 2.36 (2) 3.215 (2) 170 (3)
N1—H2N⋯Cl1ii 0.88 (2) 2.29 (2) 3.131 (3) 159 (3)
N3—H3N⋯Cl1 0.88 (2) 2.22 (2) 3.084 (2) 169 (2)
Symmetry codes: (i) [-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]; (ii) [-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1N⋯Cl2i 0.88 (3) 2.30 (3) 3.144 (3) 161 (3)
N1—H2N⋯Cl2 0.88 (2) 2.22 (1) 3.089 (2) 172 (4)
N3—H3N⋯O1W 0.88 (2) 2.06 (2) 2.927 (4) 174 (3)
O1W—H2O⋯O1Wii 0.84 (3) 2.29 (4) 2.884 (4) 128 (3)
O1W—H1O⋯Cl2iii 0.85 (3) 2.16 (3) 3.005 (3) 170 (3)
Symmetry codes: (i) [x, -y+2, z-{\script{1\over 2}}]; (ii) -x+1, -y+1, -z+1; (iii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

The presence of charge-assisted N—H⋯Cl− and N+—H⋯Cl− hydrogen bonds are crucial in establishing the three-dimensional architecture in the crystal structure of (I)[link]. The structure is conveniently described as comprising columns of cations aligned along the a axis connected through hydrogen bonds to rows of chloride ions, also aligned along the a axis. As illustrated in Fig. 4[link], charge-assisted amino-N—H⋯Cl− hydrogen bonds lead to helical chains along [100], being generated by 21 screw symmetry. The chains are linked to neighbouring chains by charge-assisted iminium-N+—H⋯Cl− hydrogen bonds, that in themselves lead to chains aligned along [011]. In this way, a three-dimensional architecture is constructed as shown in projection in Fig. 5[link].

[Figure 4]
Figure 4
Detail of the hydrogen bonding operating in the crystal structure of (I)[link]. The charge-assisted amino-N—H⋯Cl− hydrogen bonds are shown as orange dashed lines and lead to helical chains along [100]. The charge-assisted imino-N+—H⋯Cl− hydrogen bonds are shown as blue dashed lines and lead to chains along [011]. For reasons of clarity, H atoms not involved in hydrogen bonding have been omitted and only one of the chains along [011] is shown.
[Figure 5]
Figure 5
Unit-cell contents for (I)[link] shown in projection down the a axis. The charge-assisted amino-N—H⋯Cl− and imino-N+—H⋯Cl− hydrogen bonds are shown as orange and blue dashed lines, respectively.

A more complicated pattern of hydrogen bonding occurs in the crystal structure of (II)[link]. The amino-H atoms form charge-assisted N—H⋯Cl− hydrogen bonds while the iminium-H atom forms a charge-assisted N+—H⋯O hydrogen bond to the water mol­ecule of crystallization. The water mol­ecule also forms two donor inter­actions, one to another water mol­ecule and the second, charge-assisted, to the chloride anion. Hence, all donor atoms participate in the hydrogen-bonding scheme and each of the chloride and water species forms three hydrogen bonds. A diagram showing the detail of the hydrogen bonding is shown in Fig. 6[link]. The amino-N—H⋯Cl− bridges clearly persist, as for (I)[link], but lead to zigzag chains (glide symmetry) along the c axis. As pairs of water mol­ecules are linked via water-O—H⋯O(water) hydrogen bonds across a centre of inversion and each forms a charge-assisted water-O—H⋯Cl− hydrogen bond, the water mol­ecules form links between the zigzag chains resulting in supra­molecular layers. Finally, the water mol­ecules accept charge-assisted imino-N+—H⋯O(water) hydrogen bonds, providing links between the layers so that a three-dimensional architecture ensues. As seen from Fig. 7[link], globally, the structure may be described as comprising layers of cations parallel to [001] that define rectangular channels parallel to [001] incorporating the anions and inter­nalized water mol­ecules. Not shown in Fig. 5[link], are indications of close Cl1⋯Cl1i contacts of 3.3510 (10) Å which occur within layers rather than between layers; symmetry operation (ii): 1 − x, y, −[{1\over 2}] − z.

[Figure 6]
Figure 6
Detail of the hydrogen bonding operating in the crystal structure of (II)[link]. The charge-assisted amino-N—H⋯Cl− hydrogen bonds are shown as orange dashed lines and lead to zigzag chains along [001]. The charge-assisted imino-N+—H⋯O(water) hydrogen bonds are shown as blue dashed lines and both water-O—H⋯Cl− and water-O—H⋯O(water) hydrogen bonds are shown as brown dashed lines. For reasons of clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 7]
Figure 7
Unit cell contents for (II)[link] shown in projection down the c axis. The charge-assisted amino-N—H⋯Cl− (orange), imino-N+—H⋯Cl− (blue), water-O—H⋯Cl− (brown) and water-O—H⋯O(water) (brown) hydrogen bonds are shown as dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]), revealed there are no direct analogues of (I)[link] and (II)[link] in the crystallographic literature. The structure of a closely related neutral species, i.e. 5-(di­methyl­amino)-3-(phenyl­imino)-1,2,4-di­thia­zole, characterized in its 1:1 co-crystal with 2-(di­methyl­carboxamido-imino)­benzo­thia­zole, (III) in the scheme below, has been reported (Flippen, 1977[Flippen, J. L. (1977). Phosphorus Sulfur Relat. Elem. 3, 185-189.]), along with several benzoyl derivatives, as exemplified by 3-(4-methyl-benzoyl­imino)-5-phenyl­amino-3H-1,2,4-di­thia­zole (IV) (Kleist et al., 1994[Kleist, M., Teller, J., Reinke, H., Dehne, H. & Kopf, J. (1994). Phosphorus Sulfur Silicon Relat. Elem. 97, 149-155.]). An evaluation of the bond lengths in the N—C—N—C—N sequences in these mol­ecules suggests a greater contribution of the canonical structure with formal C=N bonds, i.e. N—C=N—C=N. This difference is traced to the influence of the formal charge on the iminium-N atom.

[Scheme 2]

5. Synthesis and crystallization

Synthesis of (I)[link]. To thio­urea (Merck, 5 mmol, 0.38 g) in aceto­nitrile (20 ml) was added 50% w/v NaOH (10 mmol, 0.40 ml) and phenyl iso­thio­cyanate (Merck, 10 mmol, 1.2 ml). The resulting mixture was stirred for 4 h at 323 K. 5 M HCl (20 mmol, 4.1 ml) was added and the mixture was stirred for another 1 h. The final product was extracted using chloro­form (200 ml). The powder that formed after 2 weeks was re-dissolved in dichoro­methane/aceto­nitrile (1:1 v/v, 200 ml), yielding yellow prisms after 3 weeks. Yield: 0.627 g (51%). M.p. 492–493 K. 1H NMR (400 MHz, DMSO-d6, 298 K): 13.37 (s, br, 1H, NH), 10.73 (s, 1H, NH2), 10.66 (s, br, 1H, NH2), 7.74 (d, 2H, o-Ph-H, J = 7.96 Hz), 7.45 (dd, 2H, m-Ph-H, J = 7.82 Hz, J = 7.82 Hz), 7.27 (t, 1H, p-Ph-H, J = 7.34 Hz). 13C NMR (400 MHz, DMSO-d6, 298 K): 182.9 [SC(=N)N], 176.1 [C(NH2)], 138.5 (Cipso), 129.7 (Cmeta), 126.5 (Cpara) 121.4 (Cortho). IR (cm−1): 3414 (m) (N—H), ν 3007 (m) (C—H), ν 1248 (s) (C—N).

Synthesis of (II)[link]. The p-chloro derivative (II)[link] was prepared as described above but using 4-chloro­phenyl iso­thio­cyanate (Sigma–Aldrich) as the unique reagent. Yellow prismatic crystals were isolated after 4 weeks. Yield: 0.581 g (39%). M.p. 484–485 K. 1H NMR (400 MHz, DMSO-d6, 298 K): 13.51 (s, br, 1H, NH), 10.72 (s, 1H, NH2), 10.41 (s, br, 1H, NH2), 7.77 (d, 2H, m-Ph-H, J = 8.60 Hz), 7.52 (d, 2H, o-Ph-H, J = 8.52 Hz), 3.48 (br, 2H, H2O). 13C NMR (400 MHz, DMSO-d6, 298 K): 183.0 [SC(=N)N], 176.1 [CNH2], 137.4 (Cipso), 130.3 (Cpara), 129.6 (Cmeta), 122.9 (Cortho). IR (cm−1): ν 2965 (br) (O—H), ν 1250 (s) (C—N).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. For (I)[link] and (II)[link], carbon-bound H atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N). For (I)[link], owing to poor agreement, one reflection, i.e. (020), was omitted from the final cycles of refinement. For (II)[link], disorder was noted in the structure, involving the Cl2 anion and water mol­ecule of crystallization so that two proximate positions were resolved for the heteroatoms. The major component refined to a site occupancy factor of 0.9327 (18). The anisotropic displacement parameters for the pair of Cl2 anions and for the water-O atoms were constrained to be equal. Only the water-bound H atoms for the major component were resolved and these were assigned full weight with O—H 0.84±0.01 Å, and with Uiso(H) = 1.5Ueq(O).

Table 4
Experimental details

  (I) (II)
Crystal data
Chemical formula C8H8N3S2+·Cl− C8H7ClN3S2+·Cl−·H2O
Mr 245.74 298.20
Crystal system, space group Orthorhombic, P212121 Monoclinic, C2/c
Temperature (K) 100 100
a, b, c (Å) 6.5702 (4), 10.8637 (7), 14.4964 (10) 17.0581 (7), 14.1660 (7), 10.3215 (4)
α, β, γ (°) 90, 90, 90 90, 101.084 (4), 90
V (Å3) 1034.70 (12) 2447.61 (19)
Z 4 8
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.73 0.85
Crystal size (mm) 0.15 × 0.02 × 0.02 0.20 × 0.10 × 0.05
 
Data collection
Diffractometer Bruker SMART APEX CCD diffractometer Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction Multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.])
Tmin, Tmax 0.898, 1.000 0.748, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 9875, 2378, 2185 19709, 2821, 2142
Rint 0.044 0.064
(sin θ/λ)max (Å−1) 0.650 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.058, 1.07 0.046, 0.102, 1.02
No. of reflections 2378 2821
No. of parameters 136 167
No. of restraints 3 6
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.29, −0.21 0.76, −0.64
Absolute structure Flack x determined using 842 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]). –
Absolute structure parameter 0.08 (5) –
Computer programs: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.]), APEX2 and SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), QMol (Gans & Shalloway, 2001[Gans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, 557-559.]), DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC references: 1422604; 1422603

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S2056989015016655/hb7500sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016655/hb7500Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989015016655/hb7500IIsup3.hkl

Supporting information file. DOI: 10.1107/S2056989015016655/hb7500Isup4.cml

Supporting information file. DOI: 10.1107/S2056989015016655/hb7500IIsup5.cml

checkCIF report


Chemical context top

The title salts were isolated as a part of a research programme into the crystal engineering aspects and biological potential of phosphanegold(I) carbonimido­thio­ates, i.e. molecules of the general formula R3PAu[SC(OR')═NR'']; R, R', R'' = aryl and/or alkyl. While earlier work focussed on supra­molecular aggregation patterns (Kuan et al., 2008) and solid-state luminescence (Ho et al., 2006), more recent endeavours have focussed upon biological studies. For example, the Ph3PAu[SC(O–alkyl)═N(p-tolyl)] compounds prove to be very potent against Gram-positive bacteria (Yeo, Sim et al., 2013). In addition, Ph3PAu[SC(O–alkyl)═N(aryl)] compounds exhibit significant cytotoxicity and kill cancer cells by initiating a variety of apoptotic pathways (Yeo, Ooi et al., 2013; Ooi, Yeo et al., 2015). A focus of recent synthetic efforts has been to increase the functionality of the thio­carbamide molecules in order to produce gold complexes of higher nuclearity. During this work bipodal {1,4-[MeOC(═ S)N(H)]2C6H4} was synthesized along with its binuclear phosphanegold(I)complexes (Yeo et al., 2015). As an expansion of these studies, the 1:2 reactions of thio­urea with aryl­iso­thio­cyanates were undertaken which, rather than yielding bipodal molecules, gave the 1:1 cyclization products, isolated as salts. These and related compounds have been described in the patent literature as having a range of biological properties, e.g. as bactericides, fungicides and plant-growth inhibitors (Röthling et al., 1989). Herein, the crystal and molecular structures of two examples of these products, i.e. the salt, [C8H8N3S2]Cl (I), and the salt hydrate [C8H7ClN3S2]Cl.H2O (II), are described.

Structural commentary top

The asymmetric unit of (I), comprising a cation and chloride anion, is shown in Fig. 1. The five-membered 1,2,4-di­thia­zole ring of the cation in (I) is strictly planar with the maximum deviation being less than ±0.003 (2) Å. However, the entire cation is not planar with the dihedral angle between the rings being 9.05 (12)°. Selected geometric parameters are collected in Table 1. While the S—S and S—C bond lengths correspond to single bonds, an evaluation of the C—N bonds, inter­nal and external to the ring, suggest a high level of delocalization of π-electron density across these atoms. The angles subtended at the S atoms are nearly right-angles. The trigonal angles around the C1 atom are all approximately 120° but there is a range of 10° for the angles about the C2 atom, with the widest angle being N2—C2—N3, consistent with double-bond character in the C—N bonds. The widest angle in the molecule is that subtended at the N3 atom, an observation that correlates with the C2═N3 double bond and the presence of the small H atom on the N3 atom.

The asymmetric unit of (II), comprising a cation, a chloride anion and a water molecule of crystallization, is illustrated in Fig. 2. As for (I), the cation is almost planar with the maximum deviation being 0.010 (2) Å for the N2 atom; the r.m.s. deviation for the fitted atoms is 0.010 Å. A greater overall twist in the molecule is evident, as seen in the dihedral angle of 15.60 (12)° formed between the rings. In terms of bond lengths, Table 1, the discussion above for (I), holds true for (II). Similarly, for the bond angles except that the range of angles about the C2 atom is narrower at 6°.

Fig. 3 presents an overlay diagram of the cations in each of (I) and (II) which highlights the similarity in their molecular structures.

Supra­molecular features top

Geometric parameters characterizing the inter­molecular inter­actions operating in the crystal structures of (I) and (II) are collected in Tables 2 and 3, respectively.

The presence of charge-assisted N—H···Cl- and N+—H···Cl- hydrogen bonds are crucial in establishing the three-dimensional architecture in the crystal structure of (I). The structure is conveniently described as comprising columns of cations aligned along the a axis connected through hydrogen bonds to rows of chloride ions, also aligned along the a axis. As illustrated in Fig. 4, charge-assisted amino-N—H···Cl- hydrogen bonds lead to helical chains along [100], being generated by 21 screw symmetry. The chains are linked to neighbouring chains by charge-assisted iminium-N+—H···Cl- hydrogen bonds, that in themselves lead to chains aligned along [011]. In this way, a three-dimensional architecture is constructed as shown in projection in Fig. 5.

A more complicated pattern of hydrogen bonding occurs in the crystal structure of (II). The amino-H atoms form charge-assisted N—H···Cl- hydrogen bonds while the iminium-H atom forms a charge-assisted N+—H···O hydrogen bond to the water molecule of crystallization. The water molecule also forms two donor inter­actions, one to another water molecule and the second, charge-assisted, to the chloride anion. Hence, all donor atoms participate in the hydrogen-bonding scheme and each of the chloride and water species forms three hydrogen bonds. A diagram showing the detail of the hydrogen bonding is shown in Fig. 6. The amino-N—H···Cl- bridges clearly persist, as for (I), but lead to zigzag chains (glide symmetry) along the c axis. As pairs of water molecules are linked via water-O—H···O(water) hydrogen bonds across a centre of inversion and each forms a charge-assisted water-O—H···Cl- hydrogen bond, the water molecules form links between the zigzag chains resulting in supra­molecular layers. Finally, the water molecules accept charge-assisted iminium-N+—H···O(water) hydrogen bonds, providing links between the layers so that a three-dimensional architecture ensues. As seen from Fig. 7, globally, the structure may be described as comprising layers of cations parallel to [001] that define re­cta­ngular channels parallel to [001] incorporating the anions and inter­nalized water molecules. Not shown in Fig. 5, are indications of close Cl1···Cl1i contacts of 3.3510 (10) Å which occur within layers rather than between layers; symmetry operation (ii): 1 - x, y, -1/2 - z.

Database survey top

A search of the Cambridge Structural Database (Groom & Allen, 2014), revealed there are no direct analogues of (I) and (II) in the crystallographic literature. The structure of a closely related neutral species, i.e. 5-(di­methyl­amino)-3-(phenyl­imino)-1,2,4-di­thia­zole, characterized in its 1:1 co-crystal with 2-(di­methyl­carboxamido-imino)­benzo­thia­zole, (III) in the scheme below, has been reported (Flippen, 1977), along with several benzoyl derivatives, as exemplified by 3-(4-methyl-benzoyl­imino)-5-phenyl­amino-3H-1,2,4-di­thia­zole (IV) (Kleist et al., 1994). An evaluation of the bond lengths in the N—C—N—C—N sequences in these molecules suggests a greater contribution of the canonical structure with formal C═N bonds, i.e. N—C═ N—C═N. This difference is traced to the influence of the formal charge on the iminium-N atom.

Synthesis and crystallization top

Synthesis of (I). To thio­urea (Merck, 5 mmol, 0.38 g) in aceto­nitrile (20 ml) was added 50 % w/v NaOH (10 mmol, 0.40 ml) and phenyl iso­thio­cyanate (Merck, 10 mmol, 1.2 ml). The resulting mixture was stirred for 4 h at 323 K. 5 M HCl (20 mmol, 4.1 ml) was added and the mixture was stirred for another 1 h. The final product was extracted using chloro­form (200 ml). The powder that formed after 2 weeks was re-dissolved in dichoro­methane/aceto­nitrile (1:1 v/v, 200 ml), yielding yellow prisms after 3 weeks. Yield: 0.627 g (51 %). M.p. 492–493 K. 1H NMR (400 MHz, DMSO-d6, 298 K): 13.37 (s, br, 1H, NH), 10.73 (s, 1H, NH2), 10.66 (s, br, 1H, NH2), 7.74 (d, 2H, o-Ph—H, J = 7.96 Hz), 7.45 (dd, 2H, m-Ph—H, J = 7.82 Hz, J = 7.82 Hz), 7.27 (t, 1H, p-Ph—H, J = 7.34 Hz). 13C NMR (400 MHz, DMSO-d6, 298 K): 182.9 [SC(═N)N], 176.1 [C(NH2)], 138.5 (Cipso), 129.7 (Cmeta), 126.5 (Cpara) 121.4 (Cortho). IR (cm-1): 3414 (m) (N—H), ν 3007 (m) (C—H), ν 1248 (s) (C—N).

Synthesis of (II). The p-chloro derivative (II) was prepared as described above but using 4-chloro­phenyl iso­thio­cyanate (Sigma–Aldrich) as the unique reagent. Yellow prismatic crystals were isolated after 4 weeks. Yield: 0.581 g (39 %). M.p. 484–485 K. 1H NMR (400 MHz, DMSO-d6, 298 K): 13.51 (s, br, 1H, NH), 10.72 (s, 1H, NH2), 10.41 (s, br, 1H, NH2), 7.77 (d, 2H, m-Ph—H, J = 8.60 Hz), 7.52 (d, 2H, o-Ph—H, J = 8.52 Hz), 3.48 (br, 2H, H2O). 13C NMR (400 MHz, DMSO-d6, 298 K): 183.0 [SC(═N)N], 176.1 [CNH2], 137.4 (Cipso), 130.3 (Cpara), 129.6 (Cmeta), 122.9 (Cortho). IR (cm-1): ν 2965 (br) (O—H), ν 1250 (s) (C—N).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 4. For (I) and (II), carbon-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N). For (I), owing to poor agreement, one reflection, i.e. (020), was omitted from the final cycles of refinement. For (II), disorder was noted in the structure, involving the Cl2 anion and water molecule of crystallization so that two proximate positions were resolved for the heteroatoms. The major component refined to a site occupancy factor of 0.9327 (18). The anisotropic displacement parameters for the pair of Cl2 anions and for the water-O atoms were constrained to be equal. Only the water-bound H atoms for the major component were resolved and these were assigned full weightwith O—H 0.84±0.01 Å, and with Uiso(H) = 1.5Ueq(O).

Related literature top

For related literature, see:

Computing details top

Data collection: APEX2 (Bruker, 2008) for (I); CrysAlis PRO (Agilent, 2012) for (II). Cell refinement: APEX2 (Bruker, 2008) for (I); CrysAlis PRO (Agilent, 2012) for (II). Data reduction: SAINT (Bruker, 2008) for (I); CrysAlis PRO (Agilent, 2012) for (II). For both compounds, 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), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The asymmetric unit for (I), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. The asymmetric unit for (II), showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The dashed lines indicate hydrogen bonds.
[Figure 3] Fig. 3. Overlay diagram of the cations in (I), red image, and (II), blue image. The cations have been overlapped so that the five-membered rings are coincident.
[Figure 4] Fig. 4. Detail of the hydrogen bonding operating in the crystal structure of (I). The charge-assisted amino-N—H···Cl- hydrogen bonds are shown as orange dashed lines and lead to helical chains along [100]. The charge-assisted imino-N+—H···Cl- hydrogen bonds are shown as blue dashed lines and lead to chains along [011]. For reasons of clarity, H atoms not involved in hydrogen bonding have been omitted and only one of the chains along [011] is shown.
[Figure 5] Fig. 5. Unit-cell contents for (I) shown in projection down the a axis. The charge-assisted amino-N—H···Cl- and imino-N+—H···Cl- hydrogen bonds are shown as orange and blue dashed lines, respectively.
[Figure 6] Fig. 6. Detail of the hydrogen bonding operating in the crystal structure of (II). The charge-assisted amino-N—H···Cl- hydrogen bonds are shown as orange dashed lines and lead to zigzag chains along [001]. The charge-assisted imino-N+—H···O(water) hydrogen bonds are shown as blue dashed lines and both water-O—H···Cl- and water-O—H···O(water) hydrogen bonds are shown as brown dashed lines. For reasons of clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 7] Fig. 7. Unit cell contents for (II) shown in projection down the c axis. The charge-assisted amino-N—H···Cl- (orange), imino-N+—H···Cl- (blue), water-O—H···Cl- (brown) and water-O—H···O(water) (brown) hydrogen bonds are shown as dashed lines.
(I) 5-Amino-N-phenyl-3H-1,2,4-dithiazol-3-iminium chloride top
Crystal data top
C8H8N3S2+·Cl−Dx = 1.578 Mg m−3
Mr = 245.74Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 2635 reflections
a = 6.5702 (4) Åθ = 2.3–27.3°
b = 10.8637 (7) ŵ = 0.73 mm−1
c = 14.4964 (10) ÅT = 100 K
V = 1034.70 (12) Å3Prism, yellow
Z = 40.15 × 0.02 × 0.02 mm
F(000) = 504
Data collection top
Bruker SMART APEX CCD
diffractometer		2378 independent reflections
Radiation source: fine-focus sealed tube2185 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
φ and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.898, Tmax = 1.000k = −14→14
9875 measured reflectionsl = −18→18
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.028 w = 1/[σ2(Fo2) + (0.0242P)2 + 0.0389P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.058(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.29 e Å−3
2378 reflectionsΔρmin = −0.21 e Å−3
136 parametersAbsolute structure: Flack x determined using 842 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
3 restraintsAbsolute structure parameter: 0.08 (5)
Crystal data top
C8H8N3S2+·Cl−V = 1034.70 (12) Å3
Mr = 245.74Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.5702 (4) ŵ = 0.73 mm−1
b = 10.8637 (7) ÅT = 100 K
c = 14.4964 (10) Å0.15 × 0.02 × 0.02 mm
Data collection top
Bruker SMART APEX CCD
diffractometer		2378 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2185 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 1.000Rint = 0.044
9875 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.058Δρmax = 0.29 e Å−3
S = 1.07Δρmin = −0.21 e Å−3
2378 reflectionsAbsolute structure: Flack x determined using 842 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
136 parametersAbsolute structure parameter: 0.08 (5)
3 restraints
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S11.07530 (11)0.36767 (6)0.26929 (5)0.01784 (16)
S20.85079 (11)0.48700 (7)0.22480 (5)0.01919 (17)
N11.0681 (4)0.2920 (2)0.44270 (15)0.0173 (5)
H1N1.027 (4)0.297 (3)0.4995 (11)0.021*
H2N1.182 (3)0.255 (3)0.4263 (19)0.021*
N20.8085 (3)0.4255 (2)0.40293 (14)0.0140 (5)
N30.5664 (4)0.5602 (2)0.33970 (16)0.0175 (5)
H3N0.540 (4)0.605 (2)0.2910 (14)0.021*
C10.9739 (4)0.3609 (2)0.38220 (17)0.0144 (6)
C20.7320 (4)0.4904 (3)0.33453 (18)0.0156 (6)
C30.4216 (4)0.5731 (2)0.41161 (18)0.0153 (6)
C40.4307 (4)0.5100 (2)0.49499 (18)0.0162 (6)
H40.54150.45670.50830.019*
C50.2751 (4)0.5264 (3)0.55831 (19)0.0173 (6)
H50.27800.48170.61460.021*
C60.1161 (4)0.6061 (3)0.54155 (19)0.0194 (6)
H60.01210.61730.58630.023*
C70.1093 (5)0.6702 (3)0.45801 (19)0.0202 (7)
H70.00060.72550.44580.024*
C80.2609 (4)0.6529 (3)0.39322 (19)0.0180 (6)
H80.25540.69560.33610.022*
Cl10.53467 (10)0.70982 (6)0.15949 (4)0.01812 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0186 (4)0.0216 (3)0.0133 (3)0.0037 (3)0.0025 (3)0.0005 (3)
S20.0194 (4)0.0250 (4)0.0132 (3)0.0046 (3)0.0021 (3)0.0022 (3)
N10.0167 (13)0.0221 (12)0.0131 (11)0.0035 (12)0.0024 (10)0.0002 (10)
N20.0144 (13)0.0146 (12)0.0129 (11)−0.0016 (10)−0.0004 (9)−0.0006 (9)
N30.0181 (12)0.0194 (12)0.0151 (11)0.0040 (11)0.0019 (11)0.0045 (10)
C10.0150 (14)0.0150 (13)0.0133 (12)−0.0036 (12)0.0014 (11)−0.0008 (11)
C20.0167 (14)0.0161 (13)0.0138 (12)−0.0033 (12)0.0005 (12)−0.0019 (12)
C30.0134 (14)0.0152 (13)0.0172 (13)−0.0023 (12)0.0017 (12)−0.0031 (11)
C40.0155 (14)0.0155 (13)0.0175 (13)−0.0007 (13)−0.0012 (12)−0.0005 (10)
C50.0184 (15)0.0195 (14)0.0138 (13)−0.0044 (12)−0.0015 (11)−0.0005 (11)
C60.0152 (16)0.0220 (15)0.0210 (15)−0.0017 (12)0.0044 (12)−0.0035 (12)
C70.0166 (18)0.0188 (14)0.0252 (16)0.0036 (12)−0.0012 (12)−0.0039 (12)
C80.0203 (16)0.0162 (14)0.0176 (14)−0.0004 (12)−0.0022 (12)0.0003 (11)
Cl10.0179 (4)0.0221 (3)0.0144 (3)−0.0015 (3)−0.0009 (3)0.0030 (3)
Geometric parameters (Å, º) top
S1—C11.769 (3)C3—C41.391 (4)
S1—S22.0669 (10)C3—C81.392 (4)
S2—C21.772 (3)C4—C51.386 (4)
N1—C11.309 (3)C4—H40.9500
N1—H1N0.869 (13)C5—C61.378 (4)
N1—H2N0.881 (13)C5—H50.9500
N2—C21.317 (3)C6—C71.398 (4)
N2—C11.328 (3)C6—H60.9500
N3—C21.328 (3)C7—C81.382 (4)
N3—C31.418 (3)C7—H70.9500
N3—H3N0.875 (12)C8—H80.9500
C1—S1—S292.63 (9)C8—C3—N3115.5 (2)
C2—S2—S192.72 (10)C5—C4—C3118.7 (3)
C1—N1—H1N117.0 (19)C5—C4—H4120.6
C1—N1—H2N119 (2)C3—C4—H4120.6
H1N—N1—H2N123 (3)C6—C5—C4121.6 (3)
C2—N2—C1115.1 (2)C6—C5—H5119.2
C2—N3—C3130.4 (2)C4—C5—H5119.2
C2—N3—H3N116 (2)C5—C6—C7119.3 (3)
C3—N3—H3N114 (2)C5—C6—H6120.3
N1—C1—N2122.5 (2)C7—C6—H6120.3
N1—C1—S1117.8 (2)C8—C7—C6119.9 (3)
N2—C1—S1119.7 (2)C8—C7—H7120.1
N2—C2—N3125.2 (2)C6—C7—H7120.1
N2—C2—S2119.8 (2)C7—C8—C3120.1 (3)
N3—C2—S2115.1 (2)C7—C8—H8120.0
C4—C3—C8120.4 (3)C3—C8—H8120.0
C4—C3—N3124.1 (2)
C2—N2—C1—N1179.8 (3)C2—N3—C3—C40.2 (4)
C2—N2—C1—S10.4 (3)C2—N3—C3—C8−178.3 (3)
S2—S1—C1—N1−179.9 (2)C8—C3—C4—C51.2 (4)
S2—S1—C1—N2−0.5 (2)N3—C3—C4—C5−177.2 (2)
C1—N2—C2—N3179.2 (2)C3—C4—C5—C6−1.9 (4)
C1—N2—C2—S2−0.1 (3)C4—C5—C6—C71.2 (4)
C3—N3—C2—N2−7.6 (5)C5—C6—C7—C80.2 (4)
C3—N3—C2—S2171.6 (2)C6—C7—C8—C3−0.9 (4)
S1—S2—C2—N2−0.2 (2)C4—C3—C8—C70.2 (4)
S1—S2—C2—N3−179.5 (2)N3—C3—C8—C7178.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl1i0.87 (2)2.36 (2)3.215 (2)170 (3)
N1—H2N···Cl1ii0.88 (2)2.29 (2)3.131 (3)159 (3)
N3—H3N···Cl10.88 (2)2.22 (2)3.084 (2)169 (2)
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+2, y−1/2, −z+1/2.
(II) 5-Amino-N-(4-chlorophenyl)-3H-1,2,4-dithiazol-3-iminium chloride monohydrate top
Crystal data top
C8H7ClN3S2+·Cl−·H2OF(000) = 1216
Mr = 298.20Dx = 1.618 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.0581 (7) ÅCell parameters from 4628 reflections
b = 14.1660 (7) Åθ = 2.4–27.5°
c = 10.3215 (4) ŵ = 0.85 mm−1
β = 101.084 (4)°T = 100 K
V = 2447.61 (19) Å3Prism, yellow
Z = 80.20 × 0.10 × 0.05 mm
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		2821 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2142 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.064
Detector resolution: 10.4041 pixels mm-1θmax = 27.5°, θmin = 2.4°
ω scanh = −22→22
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		k = −18→18
Tmin = 0.748, Tmax = 1.000l = −13→13
19709 measured reflections
Refinement top
Refinement on F26 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0237P)2 + 10.8824P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2821 reflectionsΔρmax = 0.76 e Å−3
167 parametersΔρmin = −0.64 e Å−3
Crystal data top
C8H7ClN3S2+·Cl−·H2OV = 2447.61 (19) Å3
Mr = 298.20Z = 8
Monoclinic, C2/cMo Kα radiation
a = 17.0581 (7) ŵ = 0.85 mm−1
b = 14.1660 (7) ÅT = 100 K
c = 10.3215 (4) Å0.20 × 0.10 × 0.05 mm
β = 101.084 (4)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		2821 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		2142 reflections with I > 2σ(I)
Tmin = 0.748, Tmax = 1.000Rint = 0.064
19709 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0466 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0237P)2 + 10.8824P]
where P = (Fo2 + 2Fc2)/3
2821 reflectionsΔρmax = 0.76 e Å−3
167 parametersΔρmin = −0.64 e Å−3
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.55093 (5)0.90087 (7)−0.09408 (7)0.0413 (2)
Cl20.79427 (5)0.93836 (6)1.03317 (7)0.0315 (2)0.9327 (18)
Cl2'0.8457 (8)0.9762 (9)1.0388 (10)0.0315 (2)0.0673 (18)
S10.70602 (5)0.75085 (6)0.81299 (7)0.02725 (19)
S20.65448 (5)0.65361 (6)0.67312 (7)0.0304 (2)
N10.73581 (17)0.9221 (2)0.7316 (2)0.0307 (6)
H1N0.740 (2)0.9640 (19)0.671 (3)0.037*
H2N0.7550 (19)0.932 (3)0.8156 (13)0.037*
N20.67993 (14)0.81976 (17)0.5669 (2)0.0216 (5)
N30.61963 (15)0.70381 (19)0.4213 (2)0.0253 (6)
H3N0.5993 (18)0.6468 (11)0.415 (3)0.030*
C10.70728 (17)0.8388 (2)0.6944 (3)0.0234 (6)
C20.65147 (16)0.7342 (2)0.5421 (3)0.0222 (6)
C30.60695 (16)0.7557 (2)0.3010 (3)0.0208 (6)
C40.60976 (17)0.8531 (2)0.2941 (3)0.0246 (6)
H40.62300.88950.37260.029*
C50.59310 (17)0.8977 (2)0.1718 (3)0.0258 (6)
H50.59500.96450.16620.031*
C60.57366 (16)0.8435 (2)0.0582 (3)0.0252 (7)
C70.57171 (17)0.7464 (2)0.0638 (3)0.0277 (7)
H70.55930.7103−0.01500.033*
C80.58805 (17)0.7020 (2)0.1854 (3)0.0258 (6)
H80.58640.63510.19040.031*
O1W0.54036 (18)0.5195 (2)0.3920 (3)0.0455 (7)0.9327 (18)
H1O0.5860 (11)0.495 (3)0.419 (4)0.068*
H2O0.5075 (16)0.493 (3)0.430 (4)0.068*
O1W'0.503 (2)0.485 (3)0.336 (4)0.0455 (7)0.0673 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0453 (5)0.0588 (6)0.0198 (4)0.0229 (4)0.0062 (3)0.0110 (4)
Cl20.0394 (5)0.0378 (5)0.0172 (4)0.0038 (4)0.0051 (3)0.0024 (3)
Cl2'0.0394 (5)0.0378 (5)0.0172 (4)0.0038 (4)0.0051 (3)0.0024 (3)
S10.0329 (4)0.0323 (4)0.0169 (4)0.0045 (3)0.0056 (3)0.0028 (3)
S20.0432 (5)0.0290 (4)0.0193 (4)−0.0042 (4)0.0068 (3)0.0052 (3)
N10.0455 (17)0.0270 (15)0.0170 (12)−0.0015 (13)−0.0003 (12)−0.0009 (11)
N20.0220 (12)0.0239 (13)0.0183 (12)0.0001 (10)0.0027 (9)0.0019 (10)
N30.0288 (14)0.0279 (14)0.0191 (12)−0.0079 (11)0.0040 (10)0.0012 (10)
C10.0233 (15)0.0290 (16)0.0183 (13)0.0042 (13)0.0052 (11)0.0025 (12)
C20.0201 (14)0.0293 (17)0.0184 (14)0.0012 (12)0.0070 (11)0.0037 (12)
C30.0175 (13)0.0280 (16)0.0174 (13)−0.0047 (12)0.0045 (10)0.0013 (11)
C40.0228 (15)0.0331 (17)0.0173 (14)0.0008 (13)0.0025 (11)−0.0013 (12)
C50.0221 (15)0.0301 (17)0.0246 (15)0.0049 (13)0.0032 (12)0.0049 (13)
C60.0167 (14)0.0415 (19)0.0171 (13)0.0066 (13)0.0025 (11)0.0053 (13)
C70.0215 (15)0.0423 (19)0.0191 (14)−0.0025 (14)0.0034 (11)−0.0055 (13)
C80.0241 (15)0.0293 (17)0.0240 (15)−0.0074 (13)0.0044 (12)−0.0012 (12)
O1W0.0394 (17)0.0353 (17)0.066 (2)0.0025 (13)0.0211 (15)0.0151 (14)
O1W'0.0394 (17)0.0353 (17)0.066 (2)0.0025 (13)0.0211 (15)0.0151 (14)
Geometric parameters (Å, º) top
Cl1—C61.746 (3)C3—C81.399 (4)
S1—C11.749 (3)C4—C51.390 (4)
S1—S22.0657 (11)C4—H40.9500
S2—C21.763 (3)C5—C61.387 (4)
N1—C11.306 (4)C5—H50.9500
N1—H1N0.876 (10)C6—C71.377 (5)
N1—H2N0.876 (10)C7—C81.384 (4)
N2—C21.312 (4)C7—H70.9500
N2—C11.337 (4)C8—H80.9500
N3—C21.332 (4)O1W—H1O0.850 (10)
N3—C31.423 (4)O1W—H2O0.835 (10)
N3—H3N0.876 (10)O1W'—O1W'i1.75 (9)
C3—C41.384 (4)
C1—S1—S292.68 (11)C8—C3—N3115.8 (3)
C2—S2—S192.84 (11)C3—C4—C5119.8 (3)
C1—N1—H1N119 (2)C3—C4—H4120.1
C1—N1—H2N119 (2)C5—C4—H4120.1
H1N—N1—H2N122 (3)C6—C5—C4119.4 (3)
C2—N2—C1115.1 (2)C6—C5—H5120.3
C2—N3—C3128.0 (3)C4—C5—H5120.3
C2—N3—H3N117 (2)C7—C6—C5121.4 (3)
C3—N3—H3N115 (2)C7—C6—Cl1120.0 (2)
N1—C1—N2120.7 (3)C5—C6—Cl1118.7 (3)
N1—C1—S1119.5 (2)C6—C7—C8119.4 (3)
N2—C1—S1119.8 (2)C6—C7—H7120.3
N2—C2—N3123.4 (3)C8—C7—H7120.3
N2—C2—S2119.6 (2)C7—C8—C3119.9 (3)
N3—C2—S2117.0 (2)C7—C8—H8120.0
C4—C3—C8120.2 (3)C3—C8—H8120.0
C4—C3—N3124.0 (3)H1O—O1W—H2O108.5 (17)
C2—N2—C1—N1−178.8 (3)C2—N3—C3—C8167.1 (3)
C2—N2—C1—S11.9 (4)C8—C3—C4—C50.5 (4)
S2—S1—C1—N1179.7 (2)N3—C3—C4—C5−177.2 (3)
S2—S1—C1—N2−1.0 (2)C3—C4—C5—C60.1 (4)
C1—N2—C2—N3178.0 (3)C4—C5—C6—C7−1.0 (4)
C1—N2—C2—S2−1.9 (3)C4—C5—C6—Cl1178.7 (2)
C3—N3—C2—N2−3.0 (5)C5—C6—C7—C81.2 (4)
C3—N3—C2—S2176.9 (2)Cl1—C6—C7—C8−178.5 (2)
S1—S2—C2—N21.1 (2)C6—C7—C8—C3−0.5 (4)
S1—S2—C2—N3−178.9 (2)C4—C3—C8—C7−0.3 (4)
C2—N3—C3—C4−15.1 (5)N3—C3—C8—C7177.6 (3)
Symmetry code: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl2ii0.88 (3)2.30 (3)3.144 (3)161 (3)
N1—H2N···Cl20.88 (2)2.22 (1)3.089 (2)172 (4)
N3—H3N···O1W0.88 (2)2.06 (2)2.927 (4)174 (3)
O1W—H2O···O1Wiii0.84 (3)2.29 (4)2.884 (4)128 (3)
O1W—H1O···Cl2iv0.85 (3)2.16 (3)3.005 (3)170 (3)
Symmetry codes: (ii) x, −y+2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+3/2.
Geometric data (Å, °) for (I) and (II) top
Parameter(I)(II)
S1—S22.0669 (10)2.0657 (12)
S1—C11.769 (3)1.749 (3)
S2—C21.772 (3)1.763 (3)
N1—C11.309 (3)1.305 (4)
N2—C11.328 (3)1.337 (4)
N2—C21.317 (3)1.312 (4)
N3—C21.328 (3)1.332 (4)
N3—C31.418 (3)1.424 (4)
C1—S1—S292.63 (9)92.68 (11)
C2—S2—S192.72 (10)92.85 (11)
C2—N2—C1115.1 (2)115.1 (2)
C2—N3—C3130.4 (2)128.0 (3)
N1—C1—N2122.5 (2)120.8 (3)
N1—C1—S1117.8 (2)119.5 (2)
N2—C1—S1119.7 (2)119.8 (2)
N2—C2—N3125.2 (2)123.4 (3)
N2—C2—S2119.8 (2)119.6 (2)
N3—C2—S2115.1 (2)117.0 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl1i0.868 (17)2.356 (16)3.215 (2)170 (3)
N1—H2N···Cl1ii0.88 (2)2.29 (2)3.131 (3)159 (3)
N3—H3N···Cl10.88 (2)2.22 (2)3.084 (2)169 (2)
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+2, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl2i0.88 (3)2.30 (3)3.144 (3)161 (3)
N1—H2N···Cl20.877 (16)2.219 (14)3.089 (2)172 (4)
N3—H3N···O1W0.876 (19)2.06 (2)2.927 (4)174 (3)
O1W—H2O···O1Wii0.84 (3)2.29 (4)2.884 (4)128 (3)
O1W—H1O···Cl2iii0.85 (3)2.16 (3)3.005 (3)170 (3)
Symmetry codes: (i) x, −y+2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC8H8N3S2+·Cl−C8H7ClN3S2+·Cl−·H2O
Mr245.74298.20
Crystal system, space groupOrthorhombic, P212121Monoclinic, C2/c
Temperature (K)100100
a, b, c (Å)6.5702 (4), 10.8637 (7), 14.4964 (10)17.0581 (7), 14.1660 (7), 10.3215 (4)
α, β, γ (°)90, 90, 9090, 101.084 (4), 90
V (Å3)1034.70 (12)2447.61 (19)
Z48
Radiation typeMo KαMo Kα
µ (mm−1)0.730.85
Crystal size (mm)0.15 × 0.02 × 0.020.20 × 0.10 × 0.05
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer		Agilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.898, 1.0000.748, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		9875, 2378, 2185 19709, 2821, 2142
Rint0.0440.064
(sin θ/λ)max (Å−1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.058, 1.07 0.046, 0.102, 1.02
No. of reflections23782821
No. of parameters136167
No. of restraints36
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0242P)2 + 0.0389P]
where P = (Fo2 + 2Fc2)/3		 w = 1/[σ2(Fo2) + (0.0237P)2 + 10.8824P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)0.29, −0.210.76, −0.64
Absolute structureFlack x determined using 842 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).?
Absolute structure parameter0.08 (5)?

Computer programs: APEX2 (Bruker, 2008), CrysAlis PRO (Agilent, 2012), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

 

Acknowledgements

This research was supported by the Trans-disciplinary Research Grant Scheme (TR002-2014A) provided by the Ministry of Education, Malaysia. The intensity data set for (II)[link] was provided by the University of Malaya Crystallographic Laboratory.

References

First citationAgilent (2012). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.  Google Scholar
 First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationFlippen, J. L. (1977). Phosphorus Sulfur Relat. Elem. 3, 185–189.  CrossRef CAS Google Scholar
 First citationGans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, 557–559.  Web of Science CrossRef CAS Google Scholar
 First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CSD CrossRef CAS Google Scholar
 First citationHo, S. Y., Cheng, E. C.-C., Tiekink, E. R. T. & Yam, V. W.-W. (2006). Inorg. Chem. 45, 8165–8174.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationKleist, M., Teller, J., Reinke, H., Dehne, H. & Kopf, J. (1994). Phosphorus Sulfur Silicon Relat. Elem. 97, 149–155.  CrossRef CAS Google Scholar
 First citationKuan, F. S., Ho, S. Y., Tadbuppa, P. P. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 548–564.  Web of Science CSD CrossRef CAS Google Scholar
 First citationOoi, K. K., Yeo, C. I., Ang, K.-P., Akim, A., Cheah, Y., Halim, S. N. A., Seng, H. & Tiekink, E. R. T. (2015). J. Biol. Inorg. Chem. 20, 855–873.  CrossRef CAS PubMed Google Scholar
 First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationRöthling, T., Hansen, P., Creuzburg, D., Fieseler, C., Stohr, P., Hölzel, H., Steinke, W., Biering, H., Kibbel, H. U., Kranz, L., Luthardt, H., Richter, R. & Vasel, S. (1989). East German Patent DD 267655 A1.  Google Scholar
 First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationYeo, C. I., Khoo, C.-H., Chu, W.-C., Chen, B.-J., Chu, P.-L., Sim, J.-H., Cheah, Y.-K., Ahmad, J., Halim, S. N. A., Seng, H.-L., Ng, S., Otero-de-la-Roza, A. & Tiekink, E. R. T. (2015). RSC Adv. 5, 41401–41411.  Web of Science CSD CrossRef CAS Google Scholar
 First citationYeo, C. I., Ooi, K. K., Akim, A., Ang, K. P., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H. & Tiekink, E. R. T. (2013). J. Inorg. Biochem. 127, 24–38.  CSD CrossRef CAS PubMed Google Scholar
 First citationYeo, C. I., Sim, J.-H., Khoo, C.-H., Goh, Z.-J., Ang, K.-P., Cheah, Y.-K., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Gold Bull. 46, 145–152.  Web of Science CrossRef CAS Google Scholar

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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1159-1164
doi:10.1107/S2056989015016655
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