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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 294-297
doi:10.1107/S1600536814021138

Crystal structures of the co-crystalline adduct 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine–4-nitro­benzoic acid (1/1) and the salt 2-amino-5-(4-bromo­phen­yl)-1,3,4-thia­diazol-3-ium 2-carb­­oxy-4,6-di­nitro­phenolate

Graham Smitha* and Daniel E. Lynchb

aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and bExilica Limited, The Technocentre, Puma Way, Coventry, CV1 2TT, England
*Correspondence e-mail: g.smith@qut.edu.au

Edited by A. J. Lough, University of Toronto, Canada (Received 17 September 2014; accepted 23 September 2014; online 4 October 2014)

The structures of the 1:1 co-crystalline adduct C8H6BrN3S·C7H5NO4, (I), and the salt C8H7BrN3S+·C7H3N2O7−, (II), obtained from the inter­action of 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine with 4-nitro­benzoic acid and 3,5-di­nitro­salicylic acid, respectively, have been determined. The primary inter-species association in both (I) and (II) is through duplex R22(8) (N—H⋯O/O—H⋯O) or (N—H⋯O/N—H⋯O) hydrogen bonds, respectively, giving heterodimers. In (II), these are close to planar [the dihedral angles between the thia­diazole ring and the two phenyl rings are 2.1 (3) (intra) and 9.8 (2)° (inter)], while in (I) these angles are 22.11 (15) and 26.08 (18)°, respectively. In the crystal of (I), the heterodimers are extended into a chain along b through an amine N—H⋯Nthia­diazole hydrogen bond but in (II), a centrosymmetric cyclic hetero­tetra­mer structure is generated through N—H⋯O hydrogen bonds to phenol and nitro O-atom acceptors and features, together with the primary R22(8) inter­action, conjoined R46(12), R21(6) and S(6) ring motifs. Also present in (I) are π–π inter­actions between thia­diazole rings [minimum ring-centroid separation = 3.4624 (16) Å], as well as short Br⋯Onitro inter­actions in both (I) and (II) [3.296 (3) and 3.104 (3) Å, respectively].

CCDC references: 1025540; 1025541

1. Chemical context

1,3,4-Thia­diazole (TZ) and its derivatives, particularly the 2-amino-substituted analogues (ATZ), which are commonly phenyl-substituted at the 5-site of the thia­diazole ring, exhibit a broad range of biological activities (Jain et al., 2013[Jain, A. K., Sharma, S., Vaidya, A., Ravichandran, V. & Agrawal, R. K. (2013). Chem. Biol. Drug Des. 81, 557-576.]). In the solid state, these 2-amino-1,3,4-thia­diazo­les usually inter­act through duplex N—H⋯N hydrogen bonds, giving a centrosymmetric cyclic R22(8) hydrogen-bonding homodimer motif, which may be discrete e.g. the 5-(3-fluoro­phen­yl)-ATZ deriv­ative (Wang et al., 2009[Wang, Y., Wan, R., Han, F. & Wang, P. (2009). Acta Cryst. E65, o1425.]) or more often is extended into a one-dimensional chain structure through the second 2-amino H-atom by an N—H⋯N4thia­diazole hydrogen bond, e.g. in the 5-(4-bromo­phen­yl)-ATZ derivative (Lynch, 2009a[Lynch, D. E. (2009a). Private communication (refcode: XUVTAK). CCDC, Cambridge, England.]) and the 5-(4-bromo-2-nitro­phen­yl)-ATZ derivative (Zhang et al., 2011[Zhang, J., He, Q., Jiang, Q., Mu, H. & Wan, R. (2011). Acta Cryst. E67, o2255.]).

With an inter­est in the formation of co-crystalline adducts as opposed to proton-transfer salt formation between Lewis bases and aromatic carb­oxy­lic acids, we have looked at some of these 5-phenyl-substituted ATZ analogues and have reported examples of both structure types: one-dimensional chain structures in the 1:1 adduct of 5-(4-meth­oxy­phen­yl)-2-amino-1,3,4-thia­diazol-2-amine with 4-nitro­benzoic acid (Lynch, 2009b[Lynch, D. E. (2009b). Private communication (refcode: XUVQAH). CCDC, Cambridge, England.]) and 5-(4-bromo­phen­yl)-2-amino-1,3,4-thia­diazol-2-amine (BATZ) with 2-(naphthalen-2-yl­oxy)acetic acid (Smith & Lynch, 2013[Smith, G. & Lynch, D. E. (2013). Acta Cryst. C69, 1034-1038.]), as well as the salt of BATZ with 3,5-di­nitro­benzoic acid (Smith & Lynch, 2013[Smith, G. & Lynch, D. E. (2013). Acta Cryst. C69, 1034-1038.]). In this salt structure, the carboxyl­ate group gives the previously mentioned primary cyclic R22(8) association through carboxyl O⋯H—N and amine N—H⋯O hydrogen bonds but instead of forming the chain structure, a centrosymmetric hetero­tetra­mer is formed through a cyclic R42(8) hydrogen-bonding motif.

[Scheme 1]

Herein we report the structures of the 1:1 co-crystalline adduct, C8H6BrN3S·C7H5NO4, (I)[link], and the salt C8H7BrN3S+·C7H3N2O7−, (II)[link], obtained from the inter­action of BATZ with 4-nitro­benzoic acid (PNBA) and 3,5-di­nitro­salicylic acid (DNSA), respectively. The strong acid DNSA (pKa = 2.18) has been employed extensively for the formation of crystalline salts with Lewis bases, forming mainly phenolates (Smith et al., 2007[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2007). Aust. J. Chem. 60, 264-277.]), whereas the weaker acid PNBA (pKa = 3.44) provides examples of both salts (Byriel et al., 1992[Byriel, K. A., Kennard, C. H. L., Lynch, D. E., Smith, G. & Thompson, J. G. (1992). Aust. J. Chem. pp. 969-981.]) and co-crystalline adducts (Aakeröy et al., 2004[Aakeröy, C. B., Desper, J. & Hurley, B. A. (2004). CrystEngComm, 6, 619-624.]).

2. Structural commentary

In the structure of the (1:1) PNBA adduct with BATZ, (I)[link], the primary inter-species R22(8) hydrogen-bonded heterodimer is formed (Fig. 1[link]), in which the 4-bromo­phenyl ring substituent is rotated slightly out of the thia­diazole plane [dihedral angles between the thia­diazole ring and the two benzene rings are 22.11 (15) (intra) and 26.08 (18)° (inter)]. The carb­oxy­lic acid and nitro substituent groups on the PNBA mol­ecule are rotated slightly out of the benzene plane [torsion angles: C2A—C1A—C11A—O11A = −170.2 (3) and C3A— C4A—N4A—O42A = 172.03 (3)°]. This `planar' conformation is found in the parent acid (Bolte, 2009[Bolte, M. (2009). Private communication (refcode NBOAC011). CCDC, Cambridge, England.]) and in its adducts, e.g. with 3-(N,N-di­methyl­amino)­benzoic acid (Aakeröy et al., 2004[Aakeröy, C. B., Desper, J. & Hurley, B. A. (2004). CrystEngComm, 6, 619-624.]).

[Figure 1]
Figure 1
Mol­ecular conformation and atom-numbering scheme for adduct (I)[link], with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

In the DNSA salt (II)[link] (Fig. 2[link]), the primary association is also the expected cyclic R22(8) heterodimer, which is essentially planar [comparative dihedral angles 9.8 (2) (intra) and 2.1 (2)° (inter)]. The DNSA anionic moiety is a phenolate with the anti-related carb­oxy­lic acid H atom forming the common intra­molecular S(6) hydrogen bond which is found in ca. 70% of DNSA salt structures (Smith et al., 2007[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2007). Aust. J. Chem. 60, 264-277.]). The nitro group at C3A in this anion is rotated significantly out of the benzene plane [torsion angle: C2A—C3A—N3A—O32A = −147.8 (4)°] whereas the second nitro group and the carboxyl­ate group lie essentially in the plane [torsion angles: C6A—C5A— N5A—O51A = 179.5 (4) and C2A—C1A— C11A—O11A = −178.0 (4)°].

[Figure 2]
Figure 2
Mol­ecular conformation and atom-numbering scheme for salt (II)[link], with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

3. Supra­molecular features

In (I)[link], the heterodimers are linked through amine N21B—H21B⋯N4Bi hydrogen bonds (Table 1[link]) forming chains which extend along b (Fig. 3[link]). This is similar to the structure of the BATZ adduct with 2-naphthoxyacetic acid (Smith & Lynch, 2013[Smith, G. & Lynch, D. E. (2013). Acta Cryst. C69, 1034-1038.]) and the 5-(4-meth­oxy­phen­yl)thia­diazin-2-amine adduct with 4-NBA (Lynch, 2009b[Lynch, D. E. (2009b). Private communication (refcode: XUVQAH). CCDC, Cambridge, England.]). A weak aromatic C55B—H55B⋯O41Aii hydrogen-bonding association links the chains across c [for symmetry codes, see Table 1[link]] and together with π–π inter­actions between thia­diazole rings [minimum ring-centroid separation = 3.4624 (16) Å], give a two-dimensional supra­molecular structure.

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O11A—H11A⋯N3B 0.90 1.75 2.648 (3) 175
N21B—H21B⋯O12A 0.82 2.04 2.859 (4) 172
N21B—H22B⋯N4Bi 0.92 2.16 3.052 (3) 162
C55B—H55B⋯O41Aii 0.95 2.47 3.302 (4) 146
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [x+1, -y+2, z+{\script{1\over 2}}].
[Figure 3]
Figure 3
A perspective view of the one-dimensional hydrogen-bonded extension in the structure of (I)[link]. Hydrogen bonds are shown as dashed lines.

With (II)[link], a secondary symmetric three-centre hydrogen-bonding inter­action between the second amine-H atom and both the phenolate-O atom (O2B) and the adjacent nitro-O atom (O31A) (Table 2[link]) gives an enlarged centrosymmetric cyclic R64(12) association. This generates a hetero­tetra­mer, which comprises a total of seven conjoined cyclic motifs, the central R64(12) plus two each of R22(8), R12(6) and S(6) motifs (Fig. 4[link]). The hetero­tetra­mers are weakly linked peripherally through both a centrosymmetric cyclic C—H⋯Onitro [C4A—H4A⋯O32Aii] hydrogen-bond pair [graph set R22(10)] and a linear C56B—H56B⋯O51Aiii hydrogen bond, giving a two-dimensional supra­molecular structure (for symmetry codes, see Table 2[link]). Within the cyclic association there is a short O32A⋯O32Aii non-bonding contact [2.835 (4) Å]. However, unlike in the structure of (I)[link], no π–π ring inter­actions are found in (II)[link] [minimum ring-centroid separation = 4.078 (3) Å].

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

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O12A—H12A⋯O2A 0.87 1.57 2.418 (4) 164
N3B—H3B⋯O11A 0.88 1.87 2.744 (4) 172
N21B—H21B⋯O12A 0.88 1.89 2.747 (4) 166
N21B—H22B⋯O2Ai 0.88 2.22 2.897 (4) 134
N21B—H22B⋯O31Ai 0.88 2.19 2.986 (5) 150
C4A—H4A⋯O32Aii 0.95 2.44 3.284 (5) 148
C56B—H56B⋯O51Aiii 0.95 2.44 3.364 (5) 164
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x-1, -y+2, -z; (iii) x+2, y-1, z.
[Figure 4]
Figure 4
A perspective view of the centrosymmetric hydrogen-bonded hetero­tetra­mer units in the unit cell of (II)[link], showing conjoined cyclic R64(12), R22(8), R12(6) and S(6) hydrogen-bonded structural motifs.

In both (I)[link] and (II)[link], short Br⋯Onitro contacts are found: for (I)[link] Br1B⋯O42Aiii = 3.314 (4) Å, and for (II)[link], Br1B⋯ O52Aiv = 3.104 (3) Å [symmetry codes: (iii) x + [{3\over 2}], −y + [{3\over 2}], z + [{1\over 2}]; (iv) −x, −y, −z + 1].

4. Synthesis and crystallization

The title compounds were prepared by the reaction of 1 mmol (260 mg) of 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine with 1 mmol of either 4-nitro­benzoic acid (167 mg) [for (I)] or 3,5-di­nitro­salicylic acid (228 mg) [for (II)] in 20 mL of 50% ethanol–water, with 10 min refluxing. Partial evaporation of the solvent gave colourless needles of (I)[link] or yellow plates of (II)[link] from which specimens were cleaved for the X-ray analyses.

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. Hydrogen atoms potentially involved in hydrogen-bonding inter­actions were located by difference methods but were subsequently included in the refinements with positional parameters fixed and their isotropic displacement parameters riding, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included at calculated positions [C—H = 0.95 Å] and also treated as riding, with Uiso(H) = 1.2Ueq(C).

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C8H6BrN3S·C7H5NO4 C8H7BrN3S+·C7H3N2O7−
Mr 423.25 484.25
Crystal system, space group Monoclinic, C2/c Triclinic, P[\overline{1}]
Temperature (K) 200 200
a, b, c (Å) 8.5205 (6), 12.0394 (7), 31.4321 (18) 5.8017 (3), 10.1903 (5), 15.1592 (9)
α, β, γ (°) 90, 92.982 (6), 90 88.884 (4), 82.438 (5), 85.470 (4)
V (Å3) 3220.0 (3) 885.62 (8)
Z 8 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 2.71 2.49
Crystal size (mm) 0.30 × 0.10 × 0.05 0.25 × 0.20 × 0.18
 
Data collection
Diffractometer Oxford Diffraction Gemini-S CCD detector Oxford Diffraction Gemini-S CCD detector
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]) Multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.])
Tmin, Tmax 0.936, 0.980 0.903, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections 6234, 3164, 2446 5742, 3458, 2479
Rint 0.029 0.045
(sin θ/λ)max (Å−1) 0.617 0.617
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.093, 1.05 0.058, 0.134, 1.08
No. of reflections 3164 3458
No. of parameters 226 263
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.37, −0.30 0.78, −0.82
Computer programs: CrysAlis PRO (Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]), SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC references: 1025540; 1025541

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S1600536814021138/lh5731sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021138/lh5731Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S1600536814021138/lh5731IIsup3.hkl

Supporting information file. DOI: 10.1107/S1600536814021138/lh5731Isup4.cml

Supporting information file. DOI: 10.1107/S1600536814021138/lh5731IIsup5.cml

checkCIF report


Chemical context top

1,3,4-Thia­diazole (TZ) and its derivatives, particularly the 2-amino-substituted analogues (ATZ), which are commonly phenyl-substituted at the 5-site of the thia­diazole ring, exhibit a broad range of biological activities (Jain et al., 2013). In the solid state, these 2-amino-1,3,4-thia­diazo­les usually inter­act through duplex N—H···N hydrogen bonds, giving a centrosymmetric cyclic R22(8) hydrogen-bonding homodimer motif, which may be discrete e.g. the 5-(3-fluoro­phenyl)-ATZ derivative (Wang et al., 2009) or more often is extended into a one-dimensional chain structure through the second 2-amino H-atom by an N—H···N4thia­diazole hydrogen bond, e.g. in the 5-(4-bromo­phenyl)-ATZ derivative (Lynch, 2009a) and the 5-(4-bromo-2-nitro­phenyl)-ATZ derivative (Zhang et al., 2011).

With an inter­est in the formation of co-crystalline adducts as opposed to proton-transfer salt formation between Lewis bases and aromatic carb­oxy­lic acids, we have looked at some of these 5-phenyl-substituted ATZ analogues and have reported examples of both structure types: one-dimensional chain structures in the 1:1 adduct of 5-(4-meth­oxy­phenyl)-2-amino-1,3,4-thia­diazol-2-amine with 4-nitro­benzoic acid (Lynch, 2009b) and 5-(4-bromo­phenyl)-2-amino-1,3,4-thia­diazol-2-amine (BATZ) with 2-(naphthalen-2-yl­oxy)acetic acid (Smith & Lynch, 2013), as well as the salt of BATZ with 3,5-di­nitro­benzoic acid (Smith & Lynch, 2013). In this salt structure, the carboxyl­ate group gives the previously mentioned primary cyclic R22(8) association through carboxyl O···H—N and amine N—H···O hydrogen bonds but instead of forming the chain structure, a centrosymmetric hetero­tetra­mer is formed through a cyclic R24(8) hydrogen-bonding motif.

Herein we report the structures of the 1:1 co-crystalline adduct, C8H6BrN3S·C7H5NO4, (I), and the salt C8H7BrN3S+·C7H3N2O7-, (II), obtained from the inter­action of BATZ with 4-nitro­benzoic acid (PNBA) and 3,5-di­nitro­salicylic acid (DNSA), respectively. The strong acid DNSA (pKa = 2.18) has been employed extensively for the formation of crystalline salts with Lewis bases, forming mainly phenolates (Smith et al., 2007), whereas the weaker acid PNBA (pKa = 3.44) provides examples of both salts (Byriel et al., 1992) and co-crystalline adducts (Aakeröy et al., 2004).

Structural commentary top

In the structure of the (1:1) PNBA adduct with BATZ, (I), the primary inter-species R22(8) hydrogen-bonded heterodimer is formed (Fig. 1), in which the 4-bromo­phenyl ring substituent is rotated slightly out of the thia­diazole plane [dihedral angles between the thia­diazole ring and the two benzene rings are 22.11 (15) (intra) and 26.08 (18)° (inter)]. The carb­oxy­lic acid and nitro substituent groups on the PNBA molecule are rotated slightly out of the benzene plane [torsion angles: C2A—C1A—C11A—O11A = -170.2 (3) and C3A— C4A—N4A—O42A = 172.03 (3)°]. This `planar' conformation is found in the parent acid (Bolte, 2009) and in its adducts, e.g. with 3-(N,N-di­methyl­amino)­benzoic acid (Aakeröy et al., 2004).

In the DNSA salt (II) (Fig. 2), the primary association is also the expected cyclic R22(8) heterodimer, which is essentially planar [comparative dihedral angles 9.8 (2) (intra) and 2.1 (2)° (inter)]. The DNSA anionic moiety is a phenolate with the anti-related carb­oxy­lic acid H atom forming the common intra­molecular S(6) hydrogen bond which is found in ca. 70% of DNSA salt structures (Smith et al., 2007). The nitro group at C3A in this anion are rotated significantly out of the benzene plane [torsion angle: C2A—C3A—N3A— O32A = -147.8 (4)°] whereas the second nitro group and the carboxyl­ate group lie essentially in the plane [torsion angles: C6A—C5A— N5A—O51A = 179.5 (4) and C2A—C1A— C11A—O11A = -178.0 (4)°].

Supra­molecular features top

In (I), the heterodimers are linked through amine N21B—H21B···N4Bi hydrogen bonds (Table 1) forming chains which extend along b (Fig. 3). This is similar to the structure of the BATZ adduct with 2-naphthoxyacetic acid (Smith & Lynch, 2013) and the 5-(4-meth­oxy­phenyl)­thia­diazin-2-amine adduct with 4-NBA (Lynch, 2009b). A weak aromatic C55B—H55B···O41Aii hydrogen-bonding association links the chains across c [for symmetry codes, see Table 1] and together with π–π inter­actions between thia­diazole rings [minimum ring-centroid separation = 3.4624 (16) Å], give a two-dimensional supra­molecular structure.

With (II), a secondary symmetric three-centre hydrogen-bonding inter­action between the second amine-H atom and both the phenolate-O atom (O2B) and the adjacent nitro-O atom (O31A) (Table 2) gives an enlarged centrosymmetric cyclic R46(12) association. This generates a hetero­tetra­mer, which comprises a total of seven conjoined cyclic motifs, the central R46(12) plus two each of R22(8), R21(6) and S(6) motifs (Fig. 4). The hetero­tetra­mers are weakly linked peripherally through both a centrosymmetric cyclic C—H···Onitro [C4A—H4A···O32Aii] hydrogen-bond pair [graph set R22(10)] and a linear C56B—H56B···O51Aiii hydrogen bond, giving a two-dimensional supra­molecular structure (for symmetry codes, see Table 2). Within the cyclic association there is a short O32A···O32Aii non-bonding contact [2.835 (4) Å]. However, unlike in the structure of (I), no π–π ring inter­actions are found in (II) [minimum ring-centroid separation = 4.078 (3) Å].

In both (I) and (II), short Br···Onitro contacts are found: for (I) Br1B···O42Aiii = 3.314 (4) Å, and for (II), Br1B··· O52Aiv = 3.104 (3) Å [symmetry codes: (iii) x + 3/2, -y + 3/2, z + 1/2; (iv) -x, -y, -z + 1].

Synthesis and crystallization top

The title compounds were prepared by the reaction of 1 mmol (260 mg) of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine with 1 mmol of either 4-nitro­benzoic acid (167 mg) [for (I)] or 3,5-di­nitro­salicylic acid (228 mg) [for (II)] in 20 mL of 50% ethanol–water, with 10 min refluxing. Partial evaporation of the solvent gave colourless needles of (I) or yellow plates of (II) from which specimens were cleaved for the X-ray analyses.

Refinement details top

Hydrogen atoms potentially involved in hydrogen-bonding inter­actions were located by difference methods but were subsequently included in the refinements with positional parameters fixed and their isotropic displacement parameters riding, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included at calculated positions [C—H = 0.95 Å] and also treated as riding, with Uiso(H) = 1.2Ueq(C).

Related literature top

For related literature, see: Aakeröy et al. (2004); Bolte (2009); Byriel et al. (1992); Jain et al. (2013); Lynch (2009a, 2009b); Smith & Lynch (2013); Smith et al. (2007); Wang et al. (2009); Zhang et al. (2011).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
Figure 1. Molecular conformation and atom-numbering scheme for adduct (I), with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

Figure 2. Molecular conformation and atom-numbering scheme for salt (II), with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

Figure 3. A perspective view of the one-dimensional hydrogen-bonded extension in the structure of (I). Hydrogen bonds are shown as dashed lines.

Figure 4. A perspective view of the centrosymmetric hydrogen-bonded heterotetramer units in the unit cell of (II), showing conjoined cyclic R46(12), R22(8), R21(6) and S(6) hydrogen-bonded structural motifs.
(I) 5-(4-Bromophenyl)-1,3,4-thiadiazol-2-amine–4-nitrobenzoic acid (1/1) top
Crystal data top
C8H6BrN3S·C7H5NO4F(000) = 1696
Mr = 423.25Dx = 1.754 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1513 reflections
a = 8.5205 (6) Åθ = 3.2–27.5°
b = 12.0394 (7) ŵ = 2.71 mm−1
c = 31.4321 (18) ÅT = 200 K
β = 92.982 (6)°Needle, colourless
V = 3220.0 (3) Å30.30 × 0.10 × 0.05 mm
Z = 8
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer		3164 independent reflections
Radiation source: Enhance (Mo) X-ray source2446 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = −10→10
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		k = −14→13
Tmin = 0.936, Tmax = 0.980l = −37→38
6234 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0387P)2 + 0.5808P]
where P = (Fo2 + 2Fc2)/3
3164 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C8H6BrN3S·C7H5NO4V = 3220.0 (3) Å3
Mr = 423.25Z = 8
Monoclinic, C2/cMo Kα radiation
a = 8.5205 (6) ŵ = 2.71 mm−1
b = 12.0394 (7) ÅT = 200 K
c = 31.4321 (18) Å0.30 × 0.10 × 0.05 mm
β = 92.982 (6)°
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer		3164 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		2446 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.980Rint = 0.029
6234 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.05Δρmax = 0.37 e Å−3
3164 reflectionsΔρmin = −0.30 e Å−3
226 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br1B1.32374 (4)0.82958 (4)0.95135 (1)0.0477 (1)
S1B0.88663 (10)1.17279 (7)0.79873 (3)0.0338 (3)
N3B0.7467 (3)1.0355 (2)0.74804 (8)0.0298 (8)
N4B0.8315 (3)0.9717 (2)0.77756 (8)0.0298 (8)
N21B0.6957 (3)1.2195 (2)0.72930 (9)0.0422 (10)
C2B0.7637 (4)1.1422 (3)0.75456 (10)0.0306 (10)
C5B0.9105 (3)1.0302 (3)0.80565 (9)0.0252 (9)
C51B1.0113 (3)0.9843 (3)0.84056 (9)0.0267 (9)
C52B1.0714 (4)0.8778 (3)0.83755 (10)0.0333 (11)
C53B1.1622 (4)0.8320 (3)0.87055 (10)0.0363 (11)
C54B1.1982 (4)0.8937 (3)0.90645 (10)0.0313 (10)
C55B1.1420 (4)1.0005 (3)0.91008 (10)0.0398 (11)
C56B1.0491 (4)1.0449 (3)0.87727 (10)0.0356 (11)
O11A0.5473 (3)0.94290 (18)0.69115 (7)0.0379 (8)
O12A0.5398 (3)1.1075 (2)0.65888 (8)0.0526 (10)
O41A0.0669 (3)0.8677 (3)0.49887 (8)0.0675 (11)
O42A0.0741 (3)0.7146 (3)0.53310 (9)0.0624 (11)
N4A0.1096 (3)0.8111 (3)0.52893 (9)0.0347 (10)
C1A0.3998 (3)0.9571 (3)0.62604 (9)0.0269 (10)
C2A0.3653 (4)1.0145 (3)0.58884 (10)0.0368 (11)
C3A0.2695 (4)0.9678 (3)0.55671 (10)0.0393 (11)
C4A0.2118 (4)0.8635 (3)0.56300 (10)0.0308 (10)
C5A0.2428 (4)0.8039 (3)0.59996 (10)0.0328 (11)
C6A0.3384 (3)0.8522 (3)0.63168 (10)0.0307 (10)
C11A0.5027 (4)1.0097 (3)0.66014 (10)0.0318 (11)
H21B0.658701.188400.707800.0510*
H22B0.698701.295200.733000.0510*
H52B1.049600.835800.812300.0400*
H53B1.199800.758000.868500.0440*
H55B1.167201.043000.935000.0480*
H56B1.010001.118400.879800.0430*
H2A0.407501.086700.585200.0440*
H3A0.244501.007100.531000.0470*
H5A0.199800.731900.603500.0390*
H6A0.361900.813100.657500.0370*
H11A0.610800.976900.710800.0570*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1B0.0445 (2)0.0621 (3)0.0354 (2)0.0020 (2)−0.0081 (2)0.0168 (2)
S1B0.0460 (5)0.0213 (5)0.0329 (4)−0.0032 (4)−0.0095 (4)−0.0025 (4)
N3B0.0351 (14)0.0206 (15)0.0326 (14)−0.0010 (12)−0.0077 (12)0.0019 (12)
N4B0.0358 (14)0.0205 (15)0.0321 (14)0.0016 (12)−0.0083 (12)0.0009 (12)
N21B0.0622 (19)0.0164 (15)0.0455 (17)−0.0013 (14)−0.0199 (15)0.0008 (13)
C2B0.0353 (18)0.0252 (19)0.0309 (17)−0.0036 (15)−0.0034 (14)0.0005 (14)
C5B0.0299 (16)0.0195 (17)0.0261 (15)−0.0016 (14)0.0006 (13)−0.0016 (13)
C51B0.0285 (16)0.0267 (18)0.0248 (15)−0.0020 (14)0.0004 (12)0.0021 (13)
C52B0.0361 (18)0.032 (2)0.0309 (17)0.0019 (16)−0.0079 (14)−0.0084 (15)
C53B0.0367 (18)0.033 (2)0.0389 (19)0.0090 (16)−0.0015 (15)−0.0009 (16)
C54B0.0277 (16)0.037 (2)0.0290 (17)−0.0009 (16)−0.0006 (13)0.0064 (15)
C55B0.056 (2)0.039 (2)0.0234 (16)−0.0020 (19)−0.0086 (15)−0.0037 (15)
C56B0.052 (2)0.0233 (19)0.0308 (17)0.0017 (17)−0.0039 (15)−0.0038 (14)
O11A0.0489 (14)0.0252 (13)0.0374 (13)−0.0043 (11)−0.0184 (11)−0.0005 (10)
O12A0.0744 (18)0.0289 (16)0.0515 (16)−0.0109 (14)−0.0260 (14)0.0078 (12)
O41A0.082 (2)0.079 (2)0.0387 (15)−0.0277 (18)−0.0246 (15)0.0108 (15)
O42A0.078 (2)0.0484 (19)0.0578 (18)−0.0169 (16)−0.0241 (15)−0.0068 (15)
N4A0.0324 (15)0.040 (2)0.0311 (15)−0.0036 (14)−0.0044 (12)−0.0060 (14)
C1A0.0264 (16)0.0232 (18)0.0309 (17)0.0006 (14)−0.0009 (13)−0.0030 (14)
C2A0.0425 (19)0.030 (2)0.0376 (18)−0.0069 (16)−0.0012 (15)0.0050 (15)
C3A0.048 (2)0.041 (2)0.0282 (17)−0.0064 (18)−0.0053 (15)0.0089 (16)
C4A0.0284 (16)0.035 (2)0.0286 (16)−0.0003 (15)−0.0019 (13)−0.0056 (14)
C5A0.0355 (18)0.024 (2)0.0386 (19)−0.0051 (15)−0.0015 (15)0.0003 (14)
C6A0.0336 (17)0.029 (2)0.0288 (17)0.0015 (15)−0.0058 (14)0.0037 (14)
C11A0.0327 (17)0.026 (2)0.0363 (18)0.0011 (15)−0.0026 (14)−0.0012 (15)
Geometric parameters (Å, º) top
Br1B—C54B1.891 (3)C53B—C54B1.372 (5)
S1B—C2B1.735 (3)C54B—C55B1.379 (5)
S1B—C5B1.741 (4)C55B—C56B1.375 (5)
O11A—C11A1.305 (4)C52B—H52B0.9500
O12A—C11A1.220 (4)C53B—H53B0.9500
O41A—N4A1.206 (4)C55B—H55B0.9500
O42A—N4A1.209 (5)C56B—H56B0.9500
O11A—H11A0.9000C1A—C6A1.382 (5)
N3B—C2B1.308 (4)C1A—C11A1.490 (4)
N3B—N4B1.380 (4)C1A—C2A1.377 (4)
N4B—C5B1.291 (4)C2A—C3A1.384 (5)
N21B—C2B1.336 (4)C3A—C4A1.367 (5)
N21B—H22B0.9200C4A—C5A1.379 (5)
N21B—H21B0.8200C5A—C6A1.383 (5)
N4A—C4A1.485 (4)C2A—H2A0.9500
C5B—C51B1.466 (4)C3A—H3A0.9500
C51B—C56B1.389 (4)C5A—H5A0.9500
C51B—C52B1.386 (5)C6A—H6A0.9500
C52B—C53B1.377 (5)
C2B—S1B—C5B87.27 (15)C52B—C53B—H53B120.00
C11A—O11A—H11A112.00C54B—C53B—H53B120.00
N4B—N3B—C2B113.1 (3)C54B—C55B—H55B120.00
N3B—N4B—C5B113.1 (3)C56B—C55B—H55B120.00
H21B—N21B—H22B124.00C51B—C56B—H56B119.00
C2B—N21B—H21B108.00C55B—C56B—H56B119.00
C2B—N21B—H22B127.00C2A—C1A—C11A119.3 (3)
O42A—N4A—C4A118.1 (3)C6A—C1A—C11A120.6 (3)
O41A—N4A—O42A124.1 (3)C2A—C1A—C6A120.1 (3)
O41A—N4A—C4A117.8 (3)C1A—C2A—C3A120.5 (3)
S1B—C2B—N3B113.0 (2)C2A—C3A—C4A118.1 (3)
S1B—C2B—N21B123.6 (3)N4A—C4A—C3A119.2 (3)
N3B—C2B—N21B123.4 (3)C3A—C4A—C5A123.0 (3)
S1B—C5B—N4B113.5 (2)N4A—C4A—C5A117.8 (3)
N4B—C5B—C51B124.8 (3)C4A—C5A—C6A117.9 (3)
S1B—C5B—C51B121.7 (2)C1A—C6A—C5A120.3 (3)
C52B—C51B—C56B118.2 (3)O11A—C11A—C1A114.4 (3)
C5B—C51B—C56B121.7 (3)O12A—C11A—C1A122.0 (3)
C5B—C51B—C52B120.1 (3)O11A—C11A—O12A123.6 (3)
C51B—C52B—C53B121.0 (3)C1A—C2A—H2A120.00
C52B—C53B—C54B119.7 (3)C3A—C2A—H2A120.00
Br1B—C54B—C55B120.3 (2)C2A—C3A—H3A121.00
Br1B—C54B—C53B119.1 (3)C4A—C3A—H3A121.00
C53B—C54B—C55B120.6 (3)C4A—C5A—H5A121.00
C54B—C55B—C56B119.3 (3)C6A—C5A—H5A121.00
C51B—C56B—C55B121.2 (3)C1A—C6A—H6A120.00
C51B—C52B—H52B119.00C5A—C6A—H6A120.00
C53B—C52B—H52B120.00
C5B—S1B—C2B—N3B0.7 (3)C51B—C52B—C53B—C54B−2.1 (5)
C5B—S1B—C2B—N21B−178.1 (3)C52B—C53B—C54B—Br1B−179.8 (3)
C2B—S1B—C5B—N4B−0.7 (2)C52B—C53B—C54B—C55B1.1 (5)
C2B—S1B—C5B—C51B179.5 (2)C53B—C54B—C55B—C56B0.0 (5)
C2B—N3B—N4B—C5B0.0 (4)Br1B—C54B—C55B—C56B−179.1 (3)
N4B—N3B—C2B—S1B−0.5 (3)C54B—C55B—C56B—C51B−0.2 (5)
N4B—N3B—C2B—N21B178.3 (3)C6A—C1A—C2A—C3A−0.2 (5)
N3B—N4B—C5B—S1B0.5 (3)C11A—C1A—C2A—C3A−179.7 (3)
N3B—N4B—C5B—C51B−179.7 (2)C2A—C1A—C6A—C5A0.4 (4)
O41A—N4A—C4A—C5A171.2 (3)C11A—C1A—C6A—C5A179.9 (3)
O42A—N4A—C4A—C3A172.0 (3)C2A—C1A—C11A—O11A−170.2 (3)
O42A—N4A—C4A—C5A−8.6 (4)C2A—C1A—C11A—O12A10.5 (5)
O41A—N4A—C4A—C3A−8.2 (5)C6A—C1A—C11A—O11A10.3 (4)
N4B—C5B—C51B—C56B−157.4 (3)C6A—C1A—C11A—O12A−169.0 (3)
S1B—C5B—C51B—C52B−157.8 (2)C1A—C2A—C3A—C4A−0.4 (5)
S1B—C5B—C51B—C56B22.4 (4)C2A—C3A—C4A—N4A−179.6 (3)
N4B—C5B—C51B—C52B22.5 (4)C2A—C3A—C4A—C5A1.0 (5)
C56B—C51B—C52B—C53B1.9 (5)N4A—C4A—C5A—C6A179.7 (3)
C5B—C51B—C56B—C55B179.1 (3)C3A—C4A—C5A—C6A−0.8 (5)
C5B—C51B—C52B—C53B−178.0 (3)C4A—C5A—C6A—C1A0.1 (5)
C52B—C51B—C56B—C55B−0.8 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···N3B0.901.752.648 (3)175
N21B—H21B···O12A0.822.042.859 (4)172
N21B—H22B···N4Bi0.922.163.052 (3)162
C55B—H55B···O41Aii0.952.473.302 (4)146
C56B—H56B···S1B0.952.783.166 (3)105
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x+1, −y+2, z+1/2.
(II) 2-Amino-5-(4-bromophenyl)-1,3,4-thiadiazol-3-ium 2-carboxy-4,6-dinitrophenolate top
Crystal data top
C8H7BrN3S+·C7H3N2O7−Z = 2
Mr = 484.25F(000) = 484
Triclinic, P1Dx = 1.816 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8017 (3) ÅCell parameters from 1277 reflections
b = 10.1903 (5) Åθ = 3.6–24.8°
c = 15.1592 (9) ŵ = 2.49 mm−1
α = 88.884 (4)°T = 200 K
β = 82.438 (5)°Block, yellow
γ = 85.470 (4)°0.25 × 0.20 × 0.18 mm
V = 885.62 (8) Å3
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer		3458 independent reflections
Radiation source: Enhance (Mo) X-ray source2479 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = −7→7
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		k = −11→12
Tmin = 0.903, Tmax = 0.980l = −18→9
5742 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0545P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3458 reflectionsΔρmax = 0.78 e Å−3
263 parametersΔρmin = −0.82 e Å−3
0 restraintsExtinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.042 (3)
Crystal data top
C8H7BrN3S+·C7H3N2O7−γ = 85.470 (4)°
Mr = 484.25V = 885.62 (8) Å3
Triclinic, P1Z = 2
a = 5.8017 (3) ÅMo Kα radiation
b = 10.1903 (5) ŵ = 2.49 mm−1
c = 15.1592 (9) ÅT = 200 K
α = 88.884 (4)°0.25 × 0.20 × 0.18 mm
β = 82.438 (5)°
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer		3458 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		2479 reflections with I > 2σ(I)
Tmin = 0.903, Tmax = 0.980Rint = 0.045
5742 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.08Δρmax = 0.78 e Å−3
3458 reflectionsΔρmin = −0.82 e Å−3
263 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O2A0.1351 (5)0.6524 (3)0.0207 (2)0.0330 (9)
O11A−0.0271 (5)0.3833 (3)0.2158 (2)0.0373 (10)
O12A0.2276 (5)0.4583 (3)0.1075 (2)0.0374 (10)
O31A−0.0556 (5)0.8407 (3)−0.0818 (2)0.0360 (10)
O32A−0.2559 (5)0.9897 (3)0.0027 (2)0.0367 (10)
O51A−0.8459 (5)0.8277 (3)0.2177 (2)0.0434 (11)
O52A−0.7757 (5)0.6493 (3)0.2912 (2)0.0447 (11)
N3A−0.1754 (6)0.8761 (4)−0.0119 (2)0.0298 (11)
N5A−0.7202 (6)0.7301 (4)0.2328 (2)0.0314 (12)
C1A−0.1349 (7)0.5803 (4)0.1393 (3)0.0245 (12)
C2A−0.0684 (7)0.6698 (4)0.0697 (3)0.0255 (12)
C3A−0.2287 (7)0.7776 (4)0.0571 (3)0.0256 (12)
C4A−0.4397 (7)0.7983 (4)0.1105 (3)0.0248 (12)
C5A−0.4948 (7)0.7078 (4)0.1777 (3)0.0251 (12)
C6A−0.3473 (7)0.5999 (4)0.1929 (3)0.0274 (12)
C11A0.0285 (7)0.4637 (4)0.1578 (3)0.0294 (14)
Br1B0.60639 (11)−0.41426 (5)0.59418 (3)0.0574 (2)
S1B0.68942 (18)0.05777 (11)0.23777 (7)0.0314 (3)
N3B0.2976 (6)0.1838 (3)0.2484 (2)0.0288 (11)
N4B0.2693 (6)0.0962 (3)0.3171 (2)0.0303 (11)
N21B0.5551 (6)0.2544 (3)0.1290 (2)0.0346 (11)
C2B0.5050 (7)0.1784 (4)0.1978 (3)0.0267 (12)
C5B0.4588 (7)0.0224 (4)0.3197 (3)0.0289 (12)
C51B0.4894 (7)−0.0828 (4)0.3850 (3)0.0289 (12)
C52B0.3110 (8)−0.1094 (5)0.4517 (3)0.0383 (17)
C53B0.3431 (9)−0.2075 (5)0.5136 (3)0.0433 (17)
C54B0.5553 (9)−0.2817 (4)0.5088 (3)0.0368 (14)
C55B0.7313 (9)−0.2594 (5)0.4423 (3)0.0420 (17)
C56B0.6997 (8)−0.1610 (5)0.3807 (3)0.0386 (17)
H4A−0.544100.872400.101400.0300*
H6A−0.390300.539500.239500.0330*
H12A0.221000.529900.075500.0560*
H3B0.183800.241800.237700.0350*
H21B0.449300.313900.113500.0410*
H22B0.694900.246300.098200.0410*
H52B0.16500−0.059300.454600.0460*
H53B0.22040−0.224400.559400.0520*
H55B0.87510−0.311800.438600.0500*
H56B0.82260−0.145900.334600.0460*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O2A0.0266 (15)0.0346 (17)0.0350 (17)0.0035 (14)0.0012 (13)0.0106 (13)
O11A0.0373 (17)0.0299 (17)0.0412 (19)0.0067 (15)−0.0001 (15)0.0131 (14)
O12A0.0308 (17)0.0316 (17)0.047 (2)0.0054 (14)−0.0018 (15)0.0162 (14)
O31A0.0378 (17)0.0395 (18)0.0287 (17)0.0007 (15)−0.0014 (14)0.0122 (14)
O32A0.0308 (16)0.0224 (16)0.054 (2)0.0070 (14)−0.0025 (15)0.0143 (14)
O51A0.0361 (18)0.0377 (19)0.050 (2)0.0159 (16)0.0058 (15)0.0097 (16)
O52A0.0409 (18)0.043 (2)0.044 (2)0.0024 (16)0.0115 (15)0.0174 (16)
N3A0.0237 (19)0.033 (2)0.033 (2)−0.0017 (17)−0.0063 (17)0.0097 (17)
N5A0.030 (2)0.029 (2)0.033 (2)0.0013 (18)0.0012 (17)0.0010 (17)
C1A0.027 (2)0.019 (2)0.028 (2)−0.0007 (18)−0.0072 (18)0.0040 (17)
C2A0.025 (2)0.025 (2)0.026 (2)0.0018 (19)−0.0040 (18)0.0008 (18)
C3A0.027 (2)0.023 (2)0.027 (2)−0.0026 (19)−0.0055 (18)0.0093 (17)
C4A0.024 (2)0.022 (2)0.028 (2)0.0045 (18)−0.0065 (18)0.0022 (17)
C5A0.023 (2)0.026 (2)0.025 (2)0.0037 (18)−0.0018 (17)−0.0022 (17)
C6A0.029 (2)0.025 (2)0.028 (2)−0.0007 (19)−0.0041 (18)0.0049 (18)
C11A0.028 (2)0.026 (2)0.034 (3)0.002 (2)−0.006 (2)0.001 (2)
Br1B0.0977 (5)0.0413 (3)0.0352 (3)−0.0111 (3)−0.0151 (3)0.0174 (2)
S1B0.0254 (6)0.0321 (6)0.0341 (6)0.0043 (5)0.0000 (5)0.0122 (5)
N3B0.0258 (19)0.0265 (19)0.032 (2)0.0067 (16)−0.0026 (16)0.0086 (15)
N4B0.0283 (19)0.033 (2)0.028 (2)0.0002 (17)0.0002 (16)0.0068 (16)
N21B0.0259 (19)0.034 (2)0.041 (2)0.0075 (17)−0.0015 (17)0.0154 (17)
C2B0.026 (2)0.023 (2)0.031 (2)−0.0013 (19)−0.0047 (19)0.0041 (18)
C5B0.031 (2)0.028 (2)0.027 (2)−0.002 (2)−0.0016 (18)0.0031 (18)
C51B0.032 (2)0.031 (2)0.024 (2)−0.007 (2)−0.0022 (18)0.0031 (18)
C52B0.038 (3)0.039 (3)0.036 (3)0.002 (2)−0.001 (2)0.000 (2)
C53B0.048 (3)0.048 (3)0.032 (3)−0.011 (3)0.005 (2)0.007 (2)
C54B0.059 (3)0.028 (2)0.025 (2)−0.009 (2)−0.009 (2)0.0066 (19)
C55B0.047 (3)0.035 (3)0.042 (3)0.006 (2)−0.006 (2)0.013 (2)
C56B0.038 (3)0.041 (3)0.033 (3)0.003 (2)0.004 (2)0.015 (2)
Geometric parameters (Å, º) top
Br1B—C54B1.886 (4)C1A—C6A1.387 (6)
S1B—C5B1.756 (4)C1A—C11A1.506 (6)
S1B—C2B1.720 (4)C1A—C2A1.416 (6)
O2A—C2A1.311 (5)C2A—C3A1.409 (6)
O11A—C11A1.220 (5)C3A—C4A1.380 (6)
O12A—C11A1.296 (5)C4A—C5A1.384 (6)
O31A—N3A1.232 (4)C5A—C6A1.374 (6)
O32A—N3A1.227 (5)C4A—H4A0.9500
O51A—N5A1.222 (5)C6A—H6A0.9500
O52A—N5A1.226 (5)C5B—C51B1.461 (6)
O12A—H12A0.8700C51B—C56B1.398 (6)
N3A—C3A1.456 (6)C51B—C52B1.388 (6)
N5A—C5A1.460 (5)C52B—C53B1.376 (7)
N3B—C2B1.337 (5)C53B—C54B1.387 (7)
N3B—N4B1.360 (4)C54B—C55B1.367 (7)
N4B—C5B1.287 (5)C55B—C56B1.375 (7)
N21B—C2B1.302 (5)C52B—H52B0.9500
N3B—H3B0.8800C53B—H53B0.9500
N21B—H22B0.8800C55B—H55B0.9500
N21B—H21B0.8800C56B—H56B0.9500
C2B—S1B—C5B88.1 (2)O11A—C11A—O12A124.5 (4)
C11A—O12A—H12A104.00O11A—C11A—C1A121.4 (4)
O32A—N3A—C3A117.7 (3)C3A—C4A—H4A121.00
O31A—N3A—O32A123.8 (4)C5A—C4A—H4A121.00
O31A—N3A—C3A118.5 (4)C5A—C6A—H6A120.00
O51A—N5A—C5A118.3 (3)C1A—C6A—H6A120.00
O51A—N5A—O52A123.1 (3)S1B—C2B—N3B109.7 (3)
O52A—N5A—C5A118.5 (4)S1B—C2B—N21B126.3 (3)
N4B—N3B—C2B117.4 (3)N3B—C2B—N21B124.0 (4)
N3B—N4B—C5B110.0 (3)S1B—C5B—N4B114.8 (3)
C2B—N3B—H3B121.00N4B—C5B—C51B124.5 (4)
N4B—N3B—H3B121.00S1B—C5B—C51B120.7 (3)
C2B—N21B—H21B120.00C5B—C51B—C56B120.4 (4)
H21B—N21B—H22B120.00C52B—C51B—C56B118.2 (4)
C2B—N21B—H22B120.00C5B—C51B—C52B121.3 (4)
C2A—C1A—C11A120.1 (4)C51B—C52B—C53B120.8 (4)
C6A—C1A—C11A118.9 (4)C52B—C53B—C54B119.7 (4)
C2A—C1A—C6A121.0 (4)Br1B—C54B—C53B120.6 (4)
C1A—C2A—C3A117.0 (4)C53B—C54B—C55B120.5 (4)
O2A—C2A—C3A122.4 (4)Br1B—C54B—C55B118.9 (4)
O2A—C2A—C1A120.6 (4)C54B—C55B—C56B119.8 (5)
N3A—C3A—C2A121.2 (4)C51B—C56B—C55B121.0 (4)
N3A—C3A—C4A116.4 (4)C51B—C52B—H52B120.00
C2A—C3A—C4A122.4 (4)C53B—C52B—H52B120.00
C3A—C4A—C5A118.0 (4)C52B—C53B—H53B120.00
N5A—C5A—C4A117.3 (4)C54B—C53B—H53B120.00
N5A—C5A—C6A120.2 (4)C54B—C55B—H55B120.00
C4A—C5A—C6A122.4 (4)C56B—C55B—H55B120.00
C1A—C6A—C5A119.2 (4)C51B—C56B—H56B120.00
O12A—C11A—C1A114.2 (4)C55B—C56B—H56B119.00
C2B—S1B—C5B—C51B179.2 (4)C11A—C1A—C6A—C5A178.5 (4)
C2B—S1B—C5B—N4B−1.5 (3)O2A—C2A—C3A—N3A0.1 (6)
C5B—S1B—C2B—N3B1.5 (3)O2A—C2A—C3A—C4A−177.8 (4)
C5B—S1B—C2B—N21B−178.6 (4)C1A—C2A—C3A—C4A1.3 (6)
O32A—N3A—C3A—C2A−147.8 (4)C1A—C2A—C3A—N3A179.2 (4)
O31A—N3A—C3A—C4A−148.7 (4)C2A—C3A—C4A—C5A−1.1 (6)
O32A—N3A—C3A—C4A30.3 (5)N3A—C3A—C4A—C5A−179.0 (4)
O31A—N3A—C3A—C2A33.3 (6)C3A—C4A—C5A—N5A−179.1 (4)
O51A—N5A—C5A—C4A−1.1 (6)C3A—C4A—C5A—C6A0.3 (6)
O51A—N5A—C5A—C6A179.5 (4)C4A—C5A—C6A—C1A0.1 (7)
O52A—N5A—C5A—C4A178.0 (4)N5A—C5A—C6A—C1A179.5 (4)
O52A—N5A—C5A—C6A−1.5 (6)S1B—C5B—C51B—C52B178.1 (4)
N4B—N3B—C2B—N21B178.7 (4)S1B—C5B—C51B—C56B−3.0 (6)
C2B—N3B—N4B—C5B0.3 (5)N4B—C5B—C51B—C52B−1.1 (7)
N4B—N3B—C2B—S1B−1.4 (4)N4B—C5B—C51B—C56B177.8 (4)
N3B—N4B—C5B—C51B−179.8 (4)C5B—C51B—C52B—C53B−179.1 (4)
N3B—N4B—C5B—S1B0.9 (4)C56B—C51B—C52B—C53B2.0 (7)
C6A—C1A—C2A—C3A−0.8 (6)C5B—C51B—C56B—C55B179.3 (4)
C6A—C1A—C2A—O2A178.3 (4)C52B—C51B—C56B—C55B−1.7 (7)
C2A—C1A—C6A—C5A0.2 (6)C51B—C52B—C53B—C54B−0.7 (7)
C11A—C1A—C2A—O2A0.0 (6)C52B—C53B—C54B—Br1B178.7 (4)
C11A—C1A—C2A—C3A−179.1 (4)C52B—C53B—C54B—C55B−1.0 (7)
C2A—C1A—C11A—O11A−178.0 (4)Br1B—C54B—C55B—C56B−178.4 (4)
C2A—C1A—C11A—O12A2.2 (6)C53B—C54B—C55B—C56B1.3 (7)
C6A—C1A—C11A—O11A3.7 (6)C54B—C55B—C56B—C51B0.1 (7)
C6A—C1A—C11A—O12A−176.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12A—H12A···O2A0.871.572.418 (4)164
N3B—H3B···O11A0.881.872.744 (4)172
N21B—H21B···O12A0.881.892.747 (4)166
N21B—H22B···O2Ai0.882.222.897 (4)134
N21B—H22B···O31Ai0.882.192.986 (5)150
C4A—H4A···O32Aii0.952.443.284 (5)148
C56B—H56B···O51Aiii0.952.443.364 (5)164
C56B—H56B···S1B0.952.643.081 (5)109
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x−1, −y+2, −z; (iii) x+2, y−1, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···N3B0.901.752.648 (3)175
N21B—H21B···O12A0.822.042.859 (4)172
N21B—H22B···N4Bi0.922.163.052 (3)162
C55B—H55B···O41Aii0.952.473.302 (4)146
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x+1, −y+2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O12A—H12A···O2A0.871.572.418 (4)164
N3B—H3B···O11A0.881.872.744 (4)172
N21B—H21B···O12A0.881.892.747 (4)166
N21B—H22B···O2Ai0.882.222.897 (4)134
N21B—H22B···O31Ai0.882.192.986 (5)150
C4A—H4A···O32Aii0.952.443.284 (5)148
C56B—H56B···O51Aiii0.952.443.364 (5)164
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x−1, −y+2, −z; (iii) x+2, y−1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC8H6BrN3S·C7H5NO4C8H7BrN3S+·C7H3N2O7−
Mr423.25484.25
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)200200
a, b, c (Å)8.5205 (6), 12.0394 (7), 31.4321 (18)5.8017 (3), 10.1903 (5), 15.1592 (9)
α, β, γ (°)90, 92.982 (6), 9088.884 (4), 82.438 (5), 85.470 (4)
V (Å3)3220.0 (3)885.62 (8)
Z82
Radiation typeMo KαMo Kα
µ (mm−1)2.712.49
Crystal size (mm)0.30 × 0.10 × 0.050.25 × 0.20 × 0.18
Data collection
DiffractometerOxford Diffraction Gemini-S CCD detector
diffractometer		Oxford Diffraction Gemini-S CCD detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)		Multi-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.936, 0.9800.903, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections		6234, 3164, 2446 5742, 3458, 2479
Rint0.0290.045
(sin θ/λ)max (Å−1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.093, 1.05 0.058, 0.134, 1.08
No. of reflections31643458
No. of parameters226263
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.37, −0.300.78, −0.82

Computer programs: CrysAlis PRO (Agilent, 2013), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

 

Acknowledgements

The authors acknowledge financial support from the Science and Engineering Faculty, Queensland University of Technology.

References

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 294-297
doi:10.1107/S1600536814021138
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