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The crystal structures of the anhydrous products from the inter­action of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine with 2-(naphthalen-2-yl­oxy)acetic acid, viz. the 1:1 adduct C8H6BrN3S·C12H10O3, (I), and with 3,5-di­nitro­benzoic acid, viz. the salt 2-amino-5-(4-bromo­phenyl)-1,2,4-thia­diazol-3-ium 3,5-di­nitro­benzoate, C8H7BrN3S+·C7H3N2O6, (II), have been determined. In adduct (I), a heterodimer is formed through a cyclic hydrogen-bonding motif [graph set R22(8)], involving carb­oxy­lic acid–heteroatom O—H...N and amine–carb­oxy­lic acid N—H...O inter­actions. The heterodimers are essentially planar, with a thia­diazole-to-naphthalene ring dihedral angle of 15.9 (2)° and an intra­molecular thia­diazole-to-benzene ring angle of 4.7 (2)°. An amine–heteroatom N—H...N hydrogen bond between the heterodimers generates a one-dimensional chain structure extending down [001]. Also present are weak benzene–benzene and naphthalene–naphthalene π–π stacking inter­actions down the b axis [minimum ring-centroid separation = 3.936 (3) Å]. With salt (II), the cation–anion association is also through a cyclic R22(8) motif but involving duplex N—H...Ocarboxylate hydrogen bonds, giving a heterodimer that is close to planar [dihedral angles between the thia­diazole ring and the two benzene rings = 5.00 (16) (intra) and 7.23 (15)° (inter)]. A secondary centrosymmetric cyclic R_{4}^{2}(8) N—H...Ocarbox­ylate hydrogen-bonding association involving the second amino H atom generates a hetero­tetra­mer. Also present in the crystal structure are weak π–π inter­actions between thia­diazo­lium rings [minimum ring-centroid separation = 3.9466 (18) Å], as well as a short Br...Onitro inter­action [3.314 (4) Å]. The two structures reported here now provide a total of three crystallographically characterized examples of cocrystalline products from the inter­action of 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine with carb­oxy­lic acids, of which only one involves proton transfer.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113019665/fg3301sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113019665/fg3301Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113019665/fg3301IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113019665/fg3301Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113019665/fg3301IIsup5.cml
Supplementary material

CCDC references: 964765; 964766

Introduction top

1,3,4-Thia­diazo­les exhibit a broad range of biological activities (Jain et al., 2013) and numerous crystal structures of these compounds have been reported. The structure count of 1,3,4-thia­dizol-2-amine derivatives alone is currently well over 100. These compounds, like many other 2-amino-N(1)-heterocyclic compounds, inter­associate in the solid state through a centrosymmetric cyclic hydrogen-bonding motif [graph set R22(8); Etter et al., 1990] involving duplex N—H···N hydrogen bonds. In many cases, the second H atom of the 2-amino group forms an inter­molecular hydrogen bond with an N4 heteroatom, giving a polymer extension. This secondary association is still observed in some of the structures of 5-phenyl-1,3,4-thia­diazol-2-amine analogues. Currently, there are 12 known structures of these having variously substituted 5-phenyl rings (Wan et al., 2006, 2009; Guan et al., 2009; Wang, Kong et al., 2009; Wang et al., 2009a,b,c,d; Yin et al., 2008; Lynch, 2009a,b; Zhang et al., 2011). However, there is only one reported structure of a cocrystal of a 5-phenyl-substituted analogue of the parent compound, that being the 1:1 adduct of 5-(4-meth­oxy­phenyl)-1,3,4-thia­diazol-2-amine with 4-nitro­benzoic acid (Lynch, 2009c). In this structure, the carb­oxy­lic acid group forms a cyclic R22(8) association across the N3/N21 site through carb­oxy­lic acid O—H···N and amine N—H···O hydrogen bonds. This association is analogous with the common carb­oxy­lic acid–pyrimidin-2-amine homodimeric motif (Etter & Adsmond, 1990). In the 4-nitro­benzoic acid adduct, the second amino H atom inter­associates with atom N4 of an adjacent molecule, giving a one-dimensional chain structure.

We report here the structures of the 1:1 adduct of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine with 2-(naphthalen-2-yl­oxy)acetic acid, (I) (Fig. 1), and the salt with 3,5-di­nitro­benzoic acid, 2-amino-5-(4-bromo­phenyl)-1,2,4-thia­diazol-3-ium 3,5-di­nitro­benzoate, (II) (Fig. 2). 3,5-Di­nitro­benzoic acid has been employed extensively for the formation of cocrystalline adducts with Lewis bases and some carb­oxy­lic acids (Etter & Frankenbach, 1989; Lynch et al., 1991; Krishnamohan Sharma et al., 1993), and many structures have been reported. In a minority are the structures of proton-transfer salts of this acid, e.g. with organic di­amines (Burchell et al., 2001) or with isonipecotamide (Smith & Wermuth, 2010).

Experimental top

Synthesis and crystallization top

Compounds (I) and (II) were prepared by the reaction of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine (1 mmol, 260 mg) with, respectively, 2-(naphthalen-2-yl­oxy)acetic acid (1 mmol, 200 mg) or 3,5-di­nitro­benzoic acid (1 mmol 210 mg) in ethanol (30 ml), with 10 min of reflux. Partial evaporation of the solvent gave colourless plates of (I) and pale-yellow prisms of (II), from which specimens were cleaved for the X-ray analyses.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms potentially involved in hydrogen-bonding inter­actions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included at calculated positions (aromatic C—H = 0.95 Å) and treated as riding, with Uiso(H) = 1.2Ueq(C). Although not of particular relevance in the achiral structure of (I), the absolute structure Flack parameter (Flack, 1983) was determined as 0.001 (13) (1386 Friedel pairs).

Results and discussion top

The 1:1 adduct of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine with (naphthalen-2-yl­oxy)acetic acid (I) (Fig. 1) is similar in many respects to the 1:1 adduct of the 5-meth­oxy analogue with 4-nitro­benzoic acid (Lynch, 2009c). The presence of the adduct rather than a salt structure is confirmed both on the basis of the located and refined H atom on atom N3B, and by features of the carb­oxy­lic acid group [C—O = 1.313 (7) Å and CO = 1.205 (7) Å]. The dihedral angle between the 4-bromo­phenyl ring and the thia­diazole ring is 4.7 (2)°, while the dihedral angle between the thia­diazole ring and the plane of the naphthalene ring is 15.9 (2)°. These values compare with 25.6 (2) and 32.2 (2)°, respectively, for the corresponding angle in the 5-(4-meth­oxy­phenyl)-1,3,4-thia­diazol-2-amine adduct with 4-nitro­benzoic acid (Lynch, 2009c). In (I), the dihedral angle between the oxyacetic acid group and the naphthalene ring system is 5.7 (2)°, similar to that in the parent acid [3.59 (5)°; Pattabhi et al., 1978; Howie et al., 2001]. Previous cocrystals incorporating 2-(naphthalen-2-yl­oxy)acetic acid include the 1:1 organic salt with 2-thia­zolin-2-amine (Lynch, 2004a) and the 1:1:1 organic salt adduct 2-amino­pyrimidinium 2-(naphthalen-2-yl­oxy)acetate 2-(naphthalen-2-yl­oxy)acetic acid (Lynch, 2004b). The primary inter­molecular association in (I) is also the expected thia­diazole N3/N21···O,O'carboxyl hydrogen-bonded R22(8) motif, giving the heterodimer (Table 2). A secondary association between the second amino H atom and atom N4i of an adjacent molecule (details and symmetry code in Table 2) gives a one-dimensional chain structure which extends along [001] (Fig. 3). Also present in the structure are weak benzene–benzene and naphthalene–naphthalene ππ ring-stacking inter­actions down the short b-axis direction of the cell [minimum ring-centroid separation = 3.936 (3) Å].

The 3,5-di­nitro­benzoate salt, (II) (Fig. 2), is confirmed as such also on the basis of the located and refined H atom on N3B and the carboxyl C—O bond lengths [1.257 (4) and 1.240 (4) Å]. The primary association in this structure is the expected cyclic R22(8) N3/N21···O,O'carboxyl­ate heterodimer motif (Table 3). The difference compared with the adduct motif is in the location of the transferred carb­oxy­lic acid H atom on the hetero N atom, giving duplex N—H···O hydrogen bonds. The dihedral angle between the benzene and thia­diazole rings is 5.00 (16)°, while the angle between the benzoate and thia­diazole rings is 7.23 (15)°. A secondary centrosymmetric cyclic R22(8) N21B—H···Ocarboxyl­ate hydrogen-bonding association involving the second amino H atom generates a hetero­tetra­mer (Fig. 4). Present also are weak ππ inter­actions between thia­diazo­lium rings [minimum ring-centroid separation = 3.936 (3) Å], and a short contact between atom Br1B and nitro atom O31Aii [3.314 (4) Å; symmetry code: (ii) -x, -y, -z + 1]. No associations involving hetero atom N4B are present.

A comparison of the dihedral angles between the two ring systems in the structures of the known 5-phenyl-substituted thia­diazo­les with those of the three known cocrystals [(I) and (II), and including the 4-nitro­benzoic acid adduct (III) (Lynch, 2009c)] (Table 4), indicates that the thia­diazole molecule is generally more planar when it crystallizes with another molecule. This holds true for the 4-meth­oxy derivative (Lynch, 2004a), which is an ethanol solvate with the ethanol O atom associating with atom N4 of the thia­diazole ring through an O—H···N hydrogen bond. Understandably, some of the derivatives listed in Table 4 have large dihedral angles and one, the 4-phen­oxy-substituted analogue (Wan et al., 2009), has a very small angle, because of the influence of their phenyl substitutents (stereochemical as well as associative), but it is inter­esting that all examples having simple unassociative substituent groups have dihedral angles of ca 30° or greater, whereas those which have crystallized with another molecule have dihedral angles of ca 25° or less.

The structures presented here now give a small total of three crystallographically characterized examples of cocrystalline products from the inter­action of 5-(4-bromo­phenyl)-1,3,4-diatriazol-2-amine with carb­oxy­lic acids, of which one, with 3,5-di­nitro­benzoic acid, involves proton transfer. A notable feature is the overall close-to-planar conformational features of the heterodimeric units in these structures compared with the usual conformation of the 5-phenyl-substituted thia­diazo­les themselves.

Related literature top

For related literature, see: Burchell et al. (2001); Etter & Adsmond (1990); Etter & Frankenbach (1989); Etter, MacDonald & Bernstein (1990); Flack (1983); Guan et al. (2009); Howie et al. (2001); Jain et al. (2013); Krishnamohan Sharma, Panneerselvam, Pilati & Desiraju (1993); Lynch (2004a, 2004b, 2009a, 2009b, 2009c); Lynch et al. (1991); Pattabhi et al. (1978); Smith & Wermuth (2010); Wan et al. (2006, 2009); Wang et al. (2009, 2009a, 2009b, 2009c, 2009d); Yin et al. (2008); Zhang et al. (2011).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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
Fig. 1. The molecular conformation and atom-numbering scheme for adduct (I), with inter-species hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. The molecular conformation and atom-numbering scheme for salt (II), with cation–anion hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 3. The one-dimensional hydrogen-bonded chain structure in (I), extending down b. Hydrogen-bonding associations are shown as dashed lines and non-associative H atoms have been omitted. [Symmetry code: (i) -x + 1/2, y, z + 1/2.]

Fig. 4. A perspective view of the centrosymmetric hydrogen-bonded heterotetramer units in the structure of (II), showing conjoined cyclic R22(8) structural motifs. [Symmetry code: (ii) -x + 2, -y + 1, -z + 1.]
(I) 5-(4-Bromophenyl)-1,3,4-thiadiazol-2-amine–2-(naphthalen-2-yloxy)acetic acid (1/1) top
Crystal data top
C8H6BrN3S·C12H10O3F(000) = 928
Mr = 458.33Dx = 1.629 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 1229 reflections
a = 41.357 (2) Åθ = 3.4–28.8°
b = 3.9369 (3) ŵ = 2.34 mm1
c = 11.4761 (5) ÅT = 200 K
V = 1868.53 (19) Å3Plate, colourless
Z = 40.30 × 0.22 × 0.05 mm
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
3309 independent reflections
Radiation source: fine-focus sealed tube2842 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.5°
ω scansh = 2551
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 44
Tmin = 0.900, Tmax = 0.980l = 1411
5208 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)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0169P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3309 reflectionsΔρmax = 0.55 e Å3
262 parametersΔρmin = 0.40 e Å3
1 restraintAbsolute structure: Flack (1983), with 1386 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.001 (13)
Crystal data top
C8H6BrN3S·C12H10O3V = 1868.53 (19) Å3
Mr = 458.33Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 41.357 (2) ŵ = 2.34 mm1
b = 3.9369 (3) ÅT = 200 K
c = 11.4761 (5) Å0.30 × 0.22 × 0.05 mm
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
3309 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2842 reflections with I > 2σ(I)
Tmin = 0.900, Tmax = 0.980Rint = 0.046
5208 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088Δρmax = 0.55 e Å3
S = 1.10Δρmin = 0.40 e Å3
3309 reflectionsAbsolute structure: Flack (1983), with 1386 Friedel pairs
262 parametersAbsolute structure parameter: 0.001 (13)
1 restraint
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
O21A0.37092 (9)0.2424 (9)0.4263 (3)0.0300 (12)
O24A0.30244 (10)0.7191 (10)0.3469 (3)0.0320 (12)
O25A0.31844 (10)0.5208 (10)0.5203 (3)0.0353 (16)
C1A0.40911 (13)0.1450 (11)0.2690 (5)0.0193 (16)
C2A0.40009 (14)0.1199 (13)0.3833 (5)0.0243 (17)
C3A0.41916 (13)0.0339 (14)0.4674 (5)0.0273 (19)
C4A0.44860 (16)0.1617 (14)0.4355 (5)0.0337 (19)
C5A0.49032 (12)0.2669 (11)0.2838 (8)0.0310 (17)
C6A0.50039 (15)0.2460 (13)0.1718 (6)0.0357 (19)
C7A0.47987 (14)0.0992 (13)0.0878 (5)0.0313 (17)
C8A0.45075 (13)0.0257 (13)0.1191 (5)0.0247 (17)
C9A0.43975 (14)0.0112 (13)0.2360 (5)0.0247 (17)
C10A0.45997 (14)0.1417 (12)0.3197 (5)0.0263 (18)
C22A0.35023 (12)0.4127 (13)0.3493 (5)0.0220 (17)
C23A0.32210 (14)0.5544 (13)0.4168 (5)0.0230 (17)
Br1B0.07257 (1)1.78772 (12)0.29602 (7)0.0349 (2)
S1B0.21410 (4)1.2310 (4)0.60715 (11)0.0273 (4)
N3B0.25182 (12)0.9844 (12)0.4541 (3)0.0227 (16)
N4B0.22574 (11)1.1083 (11)0.3930 (4)0.0250 (17)
N21B0.27152 (13)0.9194 (13)0.6446 (4)0.0293 (17)
C2B0.24955 (17)1.0268 (12)0.5671 (5)0.0233 (19)
C5B0.20433 (13)1.2442 (13)0.4602 (4)0.0233 (17)
C51B0.17331 (13)1.3862 (12)0.4192 (5)0.0197 (17)
C52B0.16513 (12)1.3892 (11)0.3010 (6)0.0273 (17)
C53B0.13540 (13)1.5098 (13)0.2642 (5)0.0287 (17)
C54B0.11357 (13)1.6278 (12)0.3446 (5)0.0230 (17)
C55B0.12100 (15)1.6299 (13)0.4620 (5)0.0290 (17)
C56B0.15084 (15)1.5124 (13)0.4977 (5)0.0290 (19)
H1A0.395300.248700.213200.0232*
H3A0.411900.050300.545800.0328*
H4A0.461800.267000.492900.0404*
H5A0.504100.369000.340000.0372*
H6A0.521100.329500.150100.0428*
H7A0.486600.088000.008700.0376*
H8A0.437300.125800.061500.0296*
H21A0.342300.253600.288800.0264*
H22A0.362000.599300.310100.0264*
H24A0.2859 (14)0.823 (13)0.386 (5)0.0384*
H21B0.2885 (14)0.827 (13)0.619 (6)0.0352*
H22B0.2676 (15)1.004 (15)0.719 (5)0.0352*
H52B0.180201.307400.245100.0328*
H53B0.130101.511000.183600.0344*
H55B0.105801.711200.517400.0348*
H56B0.156101.518100.578200.0348*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O21A0.023 (2)0.044 (2)0.023 (2)0.003 (2)0.0010 (17)0.0074 (19)
O24A0.029 (2)0.046 (2)0.021 (2)0.011 (2)0.0013 (18)0.0001 (19)
O25A0.031 (3)0.058 (3)0.017 (2)0.016 (2)0.001 (2)0.004 (2)
C1A0.021 (3)0.019 (2)0.018 (3)0.001 (2)0.003 (2)0.001 (2)
C2A0.023 (3)0.028 (3)0.022 (3)0.005 (3)0.003 (3)0.003 (3)
C3A0.026 (4)0.037 (3)0.019 (3)0.000 (3)0.005 (3)0.005 (3)
C4A0.038 (4)0.035 (3)0.028 (3)0.001 (3)0.009 (3)0.006 (3)
C5A0.026 (3)0.026 (3)0.041 (3)0.006 (2)0.009 (4)0.006 (4)
C6A0.026 (3)0.033 (3)0.048 (4)0.003 (3)0.004 (3)0.019 (3)
C7A0.029 (3)0.037 (3)0.028 (3)0.006 (3)0.006 (3)0.012 (3)
C8A0.019 (3)0.027 (3)0.028 (3)0.003 (3)0.004 (3)0.005 (3)
C9A0.022 (3)0.021 (3)0.031 (3)0.007 (3)0.003 (3)0.001 (2)
C10A0.031 (3)0.021 (2)0.027 (4)0.003 (2)0.005 (3)0.002 (2)
C22A0.017 (3)0.032 (3)0.017 (3)0.003 (3)0.002 (2)0.003 (2)
C23A0.023 (3)0.023 (3)0.023 (3)0.001 (3)0.004 (3)0.001 (3)
Br1B0.0267 (3)0.0408 (3)0.0371 (3)0.0059 (3)0.0002 (4)0.0052 (5)
S1B0.0295 (8)0.0364 (8)0.0161 (6)0.0046 (7)0.0032 (6)0.0022 (7)
N3B0.021 (3)0.038 (3)0.009 (2)0.003 (2)0.001 (2)0.004 (2)
N4B0.020 (3)0.037 (3)0.018 (3)0.001 (2)0.003 (2)0.000 (2)
N21B0.025 (3)0.052 (3)0.011 (3)0.012 (3)0.000 (2)0.005 (2)
C2B0.019 (3)0.029 (3)0.022 (4)0.004 (3)0.006 (3)0.002 (3)
C5B0.024 (3)0.024 (3)0.022 (3)0.002 (3)0.003 (2)0.006 (3)
C51B0.017 (3)0.023 (3)0.019 (3)0.003 (2)0.005 (2)0.001 (2)
C52B0.031 (3)0.030 (3)0.021 (3)0.002 (2)0.014 (4)0.003 (3)
C53B0.029 (3)0.037 (3)0.020 (3)0.001 (3)0.001 (3)0.001 (3)
C54B0.016 (3)0.024 (3)0.029 (3)0.005 (2)0.002 (3)0.005 (2)
C55B0.029 (3)0.035 (3)0.023 (3)0.009 (3)0.005 (3)0.004 (3)
C56B0.038 (4)0.037 (3)0.012 (3)0.006 (3)0.001 (3)0.001 (3)
Geometric parameters (Å, º) top
Br1B—C54B1.893 (5)C8A—C9A1.418 (8)
S1B—C5B1.735 (5)C9A—C10A1.409 (8)
S1B—C2B1.734 (7)C22A—C23A1.505 (8)
O21A—C2A1.390 (7)C1A—H1A0.9500
O21A—C22A1.401 (6)C3A—H3A0.9500
O24A—C23A1.313 (7)C4A—H4A0.9500
O25A—C23A1.205 (7)C5A—H5A0.9500
O24A—H24A0.92 (6)C6A—H6A0.9500
N3B—N4B1.376 (6)C7A—H7A0.9500
N3B—C2B1.311 (7)C8A—H8A0.9500
N4B—C5B1.290 (7)C22A—H22A0.9900
N21B—C2B1.340 (8)C22A—H21A0.9900
N21B—H22B0.93 (6)C5B—C51B1.476 (7)
N21B—H21B0.84 (6)C51B—C56B1.386 (8)
C1A—C2A1.367 (8)C51B—C52B1.398 (9)
C1A—C9A1.424 (8)C52B—C53B1.384 (7)
C2A—C3A1.386 (8)C53B—C54B1.372 (8)
C3A—C4A1.367 (8)C54B—C55B1.382 (8)
C4A—C10A1.412 (8)C55B—C56B1.380 (9)
C5A—C10A1.410 (8)C52B—H52B0.9500
C5A—C6A1.354 (11)C53B—H53B0.9500
C6A—C7A1.408 (9)C55B—H55B0.9500
C7A—C8A1.350 (8)C56B—H56B0.9500
C2B—S1B—C5B87.3 (3)C5A—C6A—H6A120.00
C2A—O21A—C22A118.2 (4)C7A—C6A—H6A120.00
C23A—O24A—H24A113 (4)C6A—C7A—H7A120.00
N4B—N3B—C2B113.8 (5)C8A—C7A—H7A120.00
N3B—N4B—C5B112.4 (4)C7A—C8A—H8A119.00
H21B—N21B—H22B128 (6)C9A—C8A—H8A119.00
C2B—N21B—H22B112 (4)O21A—C22A—H22A110.00
C2B—N21B—H21B118 (5)O21A—C22A—H21A110.00
C2A—C1A—C9A118.1 (5)H21A—C22A—H22A108.00
O21A—C2A—C1A123.5 (5)C23A—C22A—H21A110.00
O21A—C2A—C3A113.5 (5)C23A—C22A—H22A110.00
C1A—C2A—C3A123.0 (5)S1B—C2B—N3B112.4 (5)
C2A—C3A—C4A118.8 (5)N3B—C2B—N21B124.6 (6)
C3A—C4A—C10A121.9 (5)S1B—C2B—N21B122.9 (4)
C6A—C5A—C10A122.0 (6)N4B—C5B—C51B124.3 (5)
C5A—C6A—C7A119.3 (5)S1B—C5B—C51B121.6 (4)
C6A—C7A—C8A120.3 (5)S1B—C5B—N4B114.1 (4)
C7A—C8A—C9A121.6 (5)C5B—C51B—C52B121.5 (5)
C1A—C9A—C8A121.5 (5)C5B—C51B—C56B120.7 (5)
C8A—C9A—C10A118.2 (5)C52B—C51B—C56B117.7 (5)
C1A—C9A—C10A120.3 (5)C51B—C52B—C53B120.9 (5)
C5A—C10A—C9A118.6 (6)C52B—C53B—C54B119.7 (5)
C4A—C10A—C9A117.9 (5)Br1B—C54B—C55B119.0 (4)
C4A—C10A—C5A123.5 (6)Br1B—C54B—C53B120.3 (4)
O21A—C22A—C23A109.0 (5)C53B—C54B—C55B120.8 (5)
O24A—C23A—O25A125.4 (5)C54B—C55B—C56B119.1 (5)
O24A—C23A—C22A110.3 (5)C51B—C56B—C55B121.8 (5)
O25A—C23A—C22A124.3 (5)C51B—C52B—H52B120.00
C2A—C1A—H1A121.00C53B—C52B—H52B120.00
C9A—C1A—H1A121.00C52B—C53B—H53B120.00
C4A—C3A—H3A121.00C54B—C53B—H53B120.00
C2A—C3A—H3A121.00C54B—C55B—H55B121.00
C10A—C4A—H4A119.00C56B—C55B—H55B120.00
C3A—C4A—H4A119.00C51B—C56B—H56B119.00
C6A—C5A—H5A119.00C55B—C56B—H56B119.00
C10A—C5A—H5A119.00
C2B—S1B—C5B—C51B177.5 (4)C5A—C6A—C7A—C8A1.4 (8)
C2B—S1B—C5B—N4B0.1 (4)C6A—C7A—C8A—C9A0.6 (8)
C5B—S1B—C2B—N21B178.5 (5)C7A—C8A—C9A—C10A0.7 (8)
C5B—S1B—C2B—N3B0.1 (4)C7A—C8A—C9A—C1A179.6 (5)
C22A—O21A—C2A—C1A2.6 (7)C1A—C9A—C10A—C5A179.1 (5)
C2A—O21A—C22A—C23A174.0 (4)C8A—C9A—C10A—C4A178.7 (5)
C22A—O21A—C2A—C3A177.9 (4)C1A—C9A—C10A—C4A1.0 (7)
C2B—N3B—N4B—C5B0.5 (6)C8A—C9A—C10A—C5A1.2 (7)
N4B—N3B—C2B—N21B178.2 (5)O21A—C22A—C23A—O25A0.5 (7)
N4B—N3B—C2B—S1B0.4 (6)O21A—C22A—C23A—O24A179.3 (4)
N3B—N4B—C5B—C51B177.6 (5)S1B—C5B—C51B—C52B178.4 (4)
N3B—N4B—C5B—S1B0.4 (6)S1B—C5B—C51B—C56B0.4 (7)
C2A—C1A—C9A—C8A179.6 (5)N4B—C5B—C51B—C52B1.4 (8)
C2A—C1A—C9A—C10A0.1 (7)N4B—C5B—C51B—C56B176.7 (5)
C9A—C1A—C2A—C3A1.0 (8)C5B—C51B—C52B—C53B177.2 (5)
C9A—C1A—C2A—O21A179.6 (5)C56B—C51B—C52B—C53B0.9 (7)
O21A—C2A—C3A—C4A179.4 (5)C5B—C51B—C56B—C55B176.5 (5)
C1A—C2A—C3A—C4A1.1 (8)C52B—C51B—C56B—C55B1.6 (8)
C2A—C3A—C4A—C10A0.1 (8)C51B—C52B—C53B—C54B0.1 (7)
C3A—C4A—C10A—C9A0.9 (8)C52B—C53B—C54B—Br1B179.1 (4)
C3A—C4A—C10A—C5A179.2 (5)C52B—C53B—C54B—C55B0.5 (8)
C10A—C5A—C6A—C7A0.9 (8)Br1B—C54B—C55B—C56B179.8 (4)
C6A—C5A—C10A—C4A179.5 (5)C53B—C54B—C55B—C56B0.2 (8)
C6A—C5A—C10A—C9A0.4 (8)C54B—C55B—C56B—C51B1.3 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21B—H21B···O25A0.84 (6)2.07 (6)2.875 (6)160 (6)
N21B—H22B···N4Bi0.93 (6)2.06 (6)2.948 (7)160 (5)
O24A—H24A···N3B0.92 (6)1.73 (6)2.643 (6)174 (6)
C56B—H56B···S1B0.952.673.106 (6)108
Symmetry code: (i) x+1/2, y, z+1/2.
(II) 2-Amino-5-(4-bromophenyl)-1,2,4-thiadiazol-3-ium 3,5-dinitrobenzoate top
Crystal data top
C8H7BrN3S+·C7H3N2O6F(000) = 936
Mr = 468.25Dx = 1.805 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1748 reflections
a = 7.5815 (6) Åθ = 3.4–27.9°
b = 7.6164 (7) ŵ = 2.56 mm1
c = 29.846 (2) ÅT = 200 K
β = 91.444 (7)°Prism, pale yellow
V = 1722.9 (2) Å30.28 × 0.12 × 0.05 mm
Z = 4
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
3381 independent reflections
Radiation source: Enhance(Mo) X-ray source2601 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = 99
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 59
Tmin = 0.535, Tmax = 0.883l = 3536
7135 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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0326P)2 + 0.6885P]
where P = (Fo2 + 2Fc2)/3
3381 reflections(Δ/σ)max = 0.001
265 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.69 e Å3
Crystal data top
C8H7BrN3S+·C7H3N2O6V = 1722.9 (2) Å3
Mr = 468.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5815 (6) ŵ = 2.56 mm1
b = 7.6164 (7) ÅT = 200 K
c = 29.846 (2) Å0.28 × 0.12 × 0.05 mm
β = 91.444 (7)°
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
3381 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2601 reflections with I > 2σ(I)
Tmin = 0.535, Tmax = 0.883Rint = 0.036
7135 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.37 e Å3
3381 reflectionsΔρmin = 0.69 e Å3
265 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
O21A0.5835 (3)0.4153 (3)0.42266 (8)0.0404 (8)
O22A0.8555 (3)0.5095 (3)0.43875 (8)0.0394 (8)
O31A0.3469 (4)0.4800 (4)0.27142 (10)0.0567 (10)
O32A0.4984 (4)0.5996 (5)0.22060 (10)0.0790 (13)
O51A1.0917 (4)0.7889 (4)0.25291 (10)0.0612 (11)
O52A1.1928 (4)0.7825 (4)0.32083 (10)0.0622 (11)
N3A0.4804 (4)0.5487 (4)0.25863 (10)0.0412 (11)
N5A1.0781 (4)0.7549 (4)0.29270 (11)0.0446 (11)
C1A0.7448 (4)0.5450 (4)0.36485 (11)0.0299 (10)
C2A0.6071 (4)0.5221 (4)0.33442 (11)0.0318 (11)
C3A0.6267 (4)0.5750 (4)0.29078 (11)0.0327 (11)
C4A0.7799 (4)0.6494 (4)0.27589 (12)0.0343 (11)
C5A0.9129 (4)0.6726 (4)0.30725 (11)0.0321 (10)
C6A0.8997 (4)0.6222 (4)0.35105 (11)0.0324 (11)
C11A0.7278 (4)0.4850 (4)0.41273 (11)0.0320 (11)
Br1B0.17691 (5)0.24730 (5)0.64638 (1)0.0501 (2)
S1B0.62338 (11)0.18741 (12)0.58022 (3)0.0366 (3)
N3B0.5522 (4)0.2764 (4)0.50067 (10)0.0327 (9)
N4B0.4070 (3)0.1864 (4)0.51313 (9)0.0314 (9)
N21B0.8267 (5)0.3754 (5)0.52422 (13)0.0531 (14)
C2B0.6792 (5)0.2922 (4)0.53166 (12)0.0358 (11)
C5B0.4237 (4)0.1323 (4)0.55396 (11)0.0277 (10)
C51B0.2849 (4)0.0360 (4)0.57688 (10)0.0258 (10)
C52B0.1319 (4)0.0074 (5)0.55314 (12)0.0371 (11)
C53B0.0046 (4)0.0928 (5)0.57363 (12)0.0384 (11)
C54B0.0127 (4)0.1340 (4)0.61832 (11)0.0319 (11)
C55B0.1645 (4)0.0949 (4)0.64249 (11)0.0341 (11)
C56B0.2997 (4)0.0109 (4)0.62159 (11)0.0332 (11)
H2A0.499700.470300.343500.0380*
H4A0.792700.683000.245500.0410*
H6A0.995400.640000.371700.0390*
H3B0.553 (5)0.326 (5)0.4731 (14)0.057 (12)*
H21B0.845 (6)0.421 (6)0.4980 (17)0.085 (17)*
H22B0.900 (6)0.395 (6)0.5443 (16)0.080 (17)*
H52B0.120800.022200.522300.0450*
H53B0.109000.122800.557100.0460*
H55B0.175500.125700.673300.0410*
H56B0.405200.015400.638100.0400*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O21A0.0348 (13)0.0569 (15)0.0295 (14)0.0106 (12)0.0001 (11)0.0092 (11)
O22A0.0360 (14)0.0536 (15)0.0284 (14)0.0137 (12)0.0028 (11)0.0034 (11)
O31A0.0470 (17)0.0678 (19)0.0544 (18)0.0223 (14)0.0136 (14)0.0138 (15)
O32A0.0526 (19)0.152 (3)0.0318 (17)0.024 (2)0.0123 (14)0.0145 (19)
O51A0.0521 (17)0.090 (2)0.0419 (18)0.0126 (15)0.0095 (14)0.0248 (15)
O52A0.0453 (17)0.097 (2)0.0442 (18)0.0301 (15)0.0017 (14)0.0007 (15)
N3A0.0429 (19)0.0496 (19)0.0309 (18)0.0032 (15)0.0044 (15)0.0003 (14)
N5A0.0366 (18)0.0527 (19)0.045 (2)0.0076 (15)0.0094 (15)0.0052 (16)
C1A0.0330 (18)0.0295 (18)0.0272 (18)0.0018 (15)0.0026 (15)0.0008 (14)
C2A0.0318 (18)0.0316 (19)0.0322 (19)0.0029 (14)0.0034 (16)0.0005 (14)
C3A0.0323 (18)0.0359 (19)0.0295 (19)0.0013 (15)0.0041 (15)0.0019 (15)
C4A0.0375 (19)0.037 (2)0.0285 (19)0.0033 (16)0.0049 (15)0.0025 (15)
C5A0.0296 (17)0.0346 (18)0.0321 (19)0.0017 (15)0.0026 (15)0.0023 (15)
C6A0.0344 (18)0.0346 (19)0.0281 (18)0.0010 (15)0.0003 (15)0.0004 (15)
C11A0.0334 (19)0.0316 (19)0.0312 (19)0.0029 (15)0.0056 (16)0.0013 (15)
Br1B0.0394 (2)0.0639 (3)0.0475 (3)0.0126 (2)0.0129 (2)0.0095 (2)
S1B0.0286 (4)0.0535 (5)0.0276 (5)0.0079 (4)0.0031 (4)0.0071 (4)
N3B0.0296 (15)0.0425 (18)0.0260 (15)0.0070 (13)0.0003 (12)0.0080 (13)
N4B0.0263 (14)0.0393 (15)0.0286 (16)0.0044 (12)0.0017 (12)0.0063 (12)
N21B0.040 (2)0.084 (3)0.035 (2)0.0301 (18)0.0021 (16)0.0129 (19)
C2B0.0330 (19)0.044 (2)0.0303 (19)0.0067 (16)0.0008 (15)0.0031 (15)
C5B0.0236 (16)0.0313 (18)0.0281 (18)0.0015 (14)0.0009 (14)0.0036 (14)
C51B0.0250 (16)0.0276 (17)0.0248 (17)0.0016 (13)0.0018 (14)0.0022 (13)
C52B0.0308 (18)0.054 (2)0.0265 (18)0.0029 (16)0.0004 (15)0.0056 (16)
C53B0.0282 (18)0.057 (2)0.030 (2)0.0067 (16)0.0004 (15)0.0052 (16)
C54B0.0294 (17)0.0326 (19)0.034 (2)0.0003 (15)0.0096 (15)0.0041 (15)
C55B0.0376 (19)0.041 (2)0.0238 (18)0.0001 (16)0.0049 (15)0.0053 (15)
C56B0.0323 (19)0.0379 (19)0.0292 (19)0.0003 (15)0.0035 (15)0.0039 (15)
Geometric parameters (Å, º) top
Br1B—C54B1.890 (3)C1A—C11A1.509 (5)
S1B—C2B1.717 (4)C2A—C3A1.375 (5)
S1B—C5B1.739 (3)C3A—C4A1.376 (4)
O21A—C11A1.258 (4)C4A—C5A1.370 (5)
O22A—C11A1.240 (4)C5A—C6A1.369 (5)
O31A—N3A1.210 (4)C2A—H2A0.9500
O32A—N3A1.210 (4)C4A—H4A0.9500
O51A—N5A1.222 (4)C6A—H6A0.9500
O52A—N5A1.212 (4)C5B—C51B1.466 (4)
N3A—C3A1.462 (4)C51B—C56B1.383 (4)
N5A—C5A1.476 (4)C51B—C52B1.384 (4)
N3B—C2B1.324 (5)C52B—C53B1.378 (5)
N3B—N4B1.357 (4)C53B—C54B1.373 (5)
N4B—C5B1.290 (4)C54B—C55B1.375 (4)
N21B—C2B1.309 (5)C55B—C56B1.372 (4)
N3B—H3B0.91 (4)C52B—H52B0.9500
N21B—H21B0.87 (5)C53B—H53B0.9500
N21B—H22B0.82 (5)C55B—H55B0.9500
C1A—C6A1.385 (4)C56B—H56B0.9500
C1A—C2A1.377 (4)
C2B—S1B—C5B87.83 (17)C1A—C2A—H2A120.00
O31A—N3A—O32A123.3 (3)C3A—C4A—H4A122.00
O31A—N3A—C3A118.6 (3)C5A—C4A—H4A122.00
O32A—N3A—C3A118.0 (3)C5A—C6A—H6A120.00
O51A—N5A—O52A124.0 (3)C1A—C6A—H6A120.00
O51A—N5A—C5A118.0 (3)S1B—C2B—N3B110.9 (3)
O52A—N5A—C5A118.0 (3)S1B—C2B—N21B126.7 (3)
N4B—N3B—C2B115.8 (3)N3B—C2B—N21B122.3 (3)
N3B—N4B—C5B111.1 (3)S1B—C5B—N4B114.4 (2)
N4B—N3B—H3B119 (2)N4B—C5B—C51B123.1 (3)
C2B—N3B—H3B125 (2)S1B—C5B—C51B122.5 (2)
C2B—N21B—H21B120 (3)C5B—C51B—C56B122.5 (3)
C2B—N21B—H22B122 (3)C52B—C51B—C56B118.6 (3)
H21B—N21B—H22B118 (4)C5B—C51B—C52B118.9 (3)
C2A—C1A—C11A120.3 (3)C51B—C52B—C53B121.0 (3)
C6A—C1A—C11A120.2 (3)C52B—C53B—C54B119.0 (3)
C2A—C1A—C6A119.5 (3)Br1B—C54B—C53B118.7 (2)
C1A—C2A—C3A119.3 (3)C53B—C54B—C55B121.2 (3)
N3A—C3A—C2A118.9 (3)Br1B—C54B—C55B120.1 (2)
N3A—C3A—C4A118.5 (3)C54B—C55B—C56B119.2 (3)
C2A—C3A—C4A122.6 (3)C51B—C56B—C55B121.1 (3)
C3A—C4A—C5A116.4 (3)C51B—C52B—H52B119.00
N5A—C5A—C4A118.0 (3)C53B—C52B—H52B120.00
N5A—C5A—C6A118.9 (3)C52B—C53B—H53B121.00
C4A—C5A—C6A123.1 (3)C54B—C53B—H53B120.00
C1A—C6A—C5A119.1 (3)C54B—C55B—H55B120.00
O22A—C11A—C1A117.6 (3)C56B—C55B—H55B120.00
O21A—C11A—C1A116.5 (3)C51B—C56B—H56B120.00
O21A—C11A—O22A125.9 (3)C55B—C56B—H56B119.00
C3A—C2A—H2A120.00
C5B—S1B—C2B—N21B179.9 (4)C11A—C1A—C2A—C3A178.9 (3)
C2B—S1B—C5B—N4B1.0 (3)C1A—C2A—C3A—C4A0.5 (5)
C5B—S1B—C2B—N3B1.1 (3)C1A—C2A—C3A—N3A179.5 (3)
C2B—S1B—C5B—C51B177.7 (3)C2A—C3A—C4A—C5A1.5 (5)
O31A—N3A—C3A—C2A0.5 (5)N3A—C3A—C4A—C5A179.6 (3)
O31A—N3A—C3A—C4A178.5 (3)C3A—C4A—C5A—N5A178.9 (3)
O32A—N3A—C3A—C2A178.4 (3)C3A—C4A—C5A—C6A1.5 (5)
O32A—N3A—C3A—C4A2.7 (5)C4A—C5A—C6A—C1A0.5 (5)
O51A—N5A—C5A—C4A4.1 (5)N5A—C5A—C6A—C1A180.0 (3)
O52A—N5A—C5A—C4A176.8 (3)S1B—C5B—C51B—C52B178.1 (3)
O52A—N5A—C5A—C6A3.6 (5)S1B—C5B—C51B—C56B3.0 (4)
O51A—N5A—C5A—C6A175.5 (3)N4B—C5B—C51B—C52B3.5 (5)
N4B—N3B—C2B—N21B179.9 (3)N4B—C5B—C51B—C56B175.5 (3)
C2B—N3B—N4B—C5B0.3 (4)C5B—C51B—C52B—C53B177.9 (3)
N4B—N3B—C2B—S1B1.0 (4)C56B—C51B—C52B—C53B1.1 (5)
N3B—N4B—C5B—S1B0.6 (4)C5B—C51B—C56B—C55B177.4 (3)
N3B—N4B—C5B—C51B178.0 (3)C52B—C51B—C56B—C55B1.6 (5)
C6A—C1A—C2A—C3A0.6 (5)C51B—C52B—C53B—C54B0.3 (5)
C2A—C1A—C6A—C5A0.6 (5)C52B—C53B—C54B—Br1B178.9 (3)
C11A—C1A—C6A—C5A178.8 (3)C52B—C53B—C54B—C55B1.4 (5)
C2A—C1A—C11A—O21A0.2 (4)Br1B—C54B—C55B—C56B179.3 (2)
C2A—C1A—C11A—O22A179.7 (3)C53B—C54B—C55B—C56B1.0 (5)
C6A—C1A—C11A—O21A179.6 (3)C54B—C55B—C56B—C51B0.5 (5)
C6A—C1A—C11A—O22A0.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···O21A0.91 (4)1.67 (4)2.574 (4)172 (4)
N21B—H21B···O22A0.87 (5)1.90 (5)2.762 (5)173 (5)
N21B—H22B···O22Ai0.82 (5)2.04 (5)2.768 (4)147 (4)
C4A—H4A···O31Aii0.952.543.031 (4)112
C52B—H52B···N4B0.952.532.843 (4)100
C56B—H56B···S1B0.952.753.159 (3)107
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC8H6BrN3S·C12H10O3C8H7BrN3S+·C7H3N2O6
Mr458.33468.25
Crystal system, space groupOrthorhombic, Pca21Monoclinic, P21/c
Temperature (K)200200
a, b, c (Å)41.357 (2), 3.9369 (3), 11.4761 (5)7.5815 (6), 7.6164 (7), 29.846 (2)
α, β, γ (°)90, 90, 9090, 91.444 (7), 90
V3)1868.53 (19)1722.9 (2)
Z44
Radiation typeMo KαMo Kα
µ (mm1)2.342.56
Crystal size (mm)0.30 × 0.22 × 0.050.28 × 0.12 × 0.05
Data collection
DiffractometerOxford Gemini-S CCD area-detector
diffractometer
Oxford Gemini-S CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Multi-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.900, 0.9800.535, 0.883
No. of measured, independent and
observed [I > 2σ(I)] reflections
5208, 3309, 2842 7135, 3381, 2601
Rint0.0460.036
(sin θ/λ)max1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.088, 1.10 0.046, 0.097, 1.07
No. of reflections33093381
No. of parameters262265
No. of restraints10
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.55, 0.400.37, 0.69
Absolute structureFlack (1983), with 1386 Friedel pairs?
Absolute structure parameter0.001 (13)?

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N21B—H21B···O25A0.84 (6)2.07 (6)2.875 (6)160 (6)
N21B—H22B···N4Bi0.93 (6)2.06 (6)2.948 (7)160 (5)
O24A—H24A···N3B0.92 (6)1.73 (6)2.643 (6)174 (6)
Symmetry code: (i) x+1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···O21A0.91 (4)1.67 (4)2.574 (4)172 (4)
N21B—H21B···O22A0.87 (5)1.90 (5)2.762 (5)173 (5)
N21B—H22B···O22Ai0.82 (5)2.04 (5)2.768 (4)147 (4)
Symmetry code: (i) x+2, y+1, z+1.
Dihedral angles between the benzene and thiadiazole rings in the 5-(X-phenyl)-substituted thiadiazol-2-amines and their three known derived adducts or salt structures [(I), (II) and (III)*] top
X substituentDihedral angle (°)N21—H···N4Reference
4-Fluoro30.1 (2)yesa
2-Methyl (A)32.25 (3)yesb
2-Methyl (B)74.50 (3)yesb
2-Fluoro-4-nitro27.1 (2)noc
3-Fluoro37.3 (2)nod
4-Pentyl29.9 (2)noe
2,6-Difluoro35.19 (14)yesf
4-Methoxy14.5 (2)nog
4-Bromo31.4 (6)yesh
2,3,4,5,6-Pentafluoro35.41 (6)yesi
2-Bromo48.35 (3)yesj
4-Methyl31.19 (19)yesk
4-Phenoxy0.99 (16)yesl
4-Bromo-2-nitro40.5 (2)yesm
4-Bromo, (I)4.7 (2)yesn
4-Bromo, (II)5.00 (16)non
4-Methoxy, (III)25.6 (2)yeso
References: (a) Wan et al. (2006); (b) Wang, Kong et al. (2009); (c) Wang et al. (2009a); (d) Wang et al. (2009b); (e) Wang et al. (2009c); (f) Wang et al. (2009d); (g) Lynch (2009a); h Lynch (2009b); (i) Guan et al. (2009); (j) Wan et al. (2009); (k) Wang et al. (2010); (l) Yin et al. (2008); (m) Zhang et al. (2011); (n) this work; (o) Lynch (2009c).

Notes: (*) (III) is 5-(4-methoxyphenyl)-1,3,4-thiadiazol-2-amine–4-nitrobenzoic acid (1/1) (reference m [Reference o in Table?])
 

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