4-({[4-Amino-6-(p-bromo­benz­yl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfan­yl}acet­yl)-3-phenyl­sydnone

Fun, H.-K.; Quah, C.K.; Nithinchandra; Kalluraya, B.

doi:10.1107/S1600536811010798

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o1004

doi:10.1107/S1600536811010798

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4-({[4-Amino-6-(p-bromobenzyl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfanyl}acetyl)-3-phenylsydnone

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Nithinchandra ^b and Balakrishna Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 19 March 2011; accepted 23 March 2011; online 31 March 2011)

In the title compound, C₂₀H₁₅BrN₆O₄S [symstematic name: 4-({[4-amino-6-(p-bromobenzyl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfanyl}acetyl)-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate], the 4,5-dihydro-1,2,4-triazine ring is essentially planar [maximum deviation = 0.020 (1) Å] and is inclined at dihedral angles of 89.06 (9), 82.21 (8) and 83.98 (8)° with respect to the oxadiazol-3-ium, phenyl and benzene rings. The oxadiazol-3-ium ring forms dihedral angles of 52.71 (9) and 8.77 (9)°, respectively, with the phenyl and benzene rings. In the crystal, the molecules are linked via pairs of intermolecular N—H⋯O hydrogen bonds, generating R₂²(10) ring motifs and are further linked via intermolecular N—H⋯N and weak C—H⋯O hydrogen bonds into infinite columns along [100].

Related literature

For general background to and the biological activity of sydnone derivatives, see: Rai et al. (2008); Jyothi et al. (2008 ). For standard bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₀H₁₅BrN₆O₄S
M_r = 515.35
Triclinic, $[P \overline 1]$
a = 6.3842 (3) Å
b = 10.0832 (5) Å
c = 17.1563 (8) Å
α = 104.873 (1)°
β = 93.507 (1)°
γ = 98.189 (1)°
V = 1050.99 (9) Å³
Z = 2
Mo Kα radiation
μ = 2.10 mm⁻¹
T = 100 K
0.32 × 0.26 × 0.06 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.553, T_max = 0.892
21938 measured reflections
6161 independent reflections
5241 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.03
6161 reflections
297 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H1N6⋯N3ⁱ	0.81 (3)	2.47 (3)	2.9835 (19)	123 (2)
N6—H1N6⋯N4ⁱ	0.81 (3)	2.40 (3)	3.050 (2)	138 (3)
N6—H2N6⋯O4ⁱⁱ	0.86 (3)	2.15 (3)	2.989 (2)	164 (2)
C14—H14B⋯O3ⁱⁱⁱ	0.97	2.50	3.416 (2)	157
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z; (iii) -x, -y, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010798/lh5224sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010798/lh5224Isup2.hkl

checkCIF report

Comment top

Sydnones are mesoionic heterocyclic aromatic chemical compounds. The study of sydnones remains as a field of interest because of their electronic structures and varied types of biological activities (Rai et al., 2008). Recently sydnone derivatives were found to exhibit promising antimicrobial properties (Jyothi et al., 2008). Since their discovery, sydnones have shown diverse biological activities and it is thought that the mesoionic nature of the sydnone ring promotes significant interactions with biological systems. Photochemical bromination of 3-aryl-4-acetylsydnone affords 3-aryl-4 bromoacetylsydnones. Condensation of 4-amino-6-(4-bromobenzyl)-3- sulfanyl-1,2,4-triazin-5(4H)-one with 3-aryl-4-bromoacetylsydnones yields S-substituted triazinone derivatives (Jyothi et al., 2008).

The molecular structure is shown in Fig. 1. The 4,5-dihydro-1,2,4-triazine ring (N3-N5/C11-C13) is essentially planar [maximum deviation = 0.020 (1) Å at atom N5] and is inclined at angles of 89.06 (9), 82.21 (8) and 83.98 (8) ° with respect to the oxadiazol-3-ium (O1/N1/N2/C7/C8) phenyl (C1-C6) and benzene (C15-C20) rings. The dihedral angles between oxadiazol-3-ium ring (O1/N1/N2/C7/C8) and the phenyl and benzene rings (C1-C6 and C15-C20) are 52.71 (9) and 8.77 (9)°, respectively. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal (Fig. 2), the molecules are linked via pairs of intermolecular N6–H2N6···O4ⁱⁱ hydrogen bonds (Table 1), generating R₂²(10) ring motifs (Bernstein et al., 1995) and are further linked via intermolecular N6–H1N6···N3ⁱ, N6–H1N6···N4ⁱ and weak C14–H14B···O3ⁱⁱⁱ hydrogen bonds (Table 1) into infinite one-dimensional columns along [100].

Related literature top

For general background to and the biological activity of sydnone derivatives, see: Rai et al. (2008); Jyothi et al. (2008). For standard bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

To a solution of 4-bromoacetyl-3-phenylsydnone (0.01 mol) and 4-amino-6-(4-bromobenzyl)-3-sulfanyl-1,2,4-triazin-5(4H)-one (0.01 mol) in ethanol, catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2 to 3 h. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from 1:2 mixtures of DMF and ethanol by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Part of the crystal structure of the title compound, viewed along the c axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

4-({[4-Amino-6-(p-bromobenzyl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl] sulfanyl}acetyl)-3-phenylsydnone top

Crystal data top

C₂₀H₁₅BrN₆O₄S	Z = 2
M_r = 515.35	F(000) = 520
Triclinic, P1	D_x = 1.628 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3842 (3) Å	Cell parameters from 8506 reflections
b = 10.0832 (5) Å	θ = 2.5–30.1°
c = 17.1563 (8) Å	µ = 2.10 mm⁻¹
α = 104.873 (1)°	T = 100 K
β = 93.507 (1)°	Plate, colourless
γ = 98.189 (1)°	0.32 × 0.26 × 0.06 mm
V = 1050.99 (9) Å³

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	6161 independent reflections
Radiation source: fine-focus sealed tube	5241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 30.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→8
T_min = 0.553, T_max = 0.892	k = −14→14
21938 measured reflections	l = −24→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0469P)² + 0.5765P] where P = (F_o² + 2F_c²)/3
6161 reflections	(Δ/σ)_max = 0.001
297 parameters	Δρ_max = 0.95 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₂₀H₁₅BrN₆O₄S	γ = 98.189 (1)°
M_r = 515.35	V = 1050.99 (9) Å³
Triclinic, P1	Z = 2
a = 6.3842 (3) Å	Mo Kα radiation
b = 10.0832 (5) Å	µ = 2.10 mm⁻¹
c = 17.1563 (8) Å	T = 100 K
α = 104.873 (1)°	0.32 × 0.26 × 0.06 mm
β = 93.507 (1)°

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	6161 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5241 reflections with I > 2σ(I)
T_min = 0.553, T_max = 0.892	R_int = 0.029
21938 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.95 e Å⁻³
6161 reflections	Δρ_min = −0.50 e Å⁻³
297 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

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 > 2sigma(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

	x	y	z	U_iso*/U_eq
Br1	0.14494 (4)	0.177407 (19)	−0.446529 (11)	0.02915 (7)
S1	0.25040 (6)	0.42973 (4)	0.10384 (3)	0.01811 (9)
O1	−0.50655 (19)	0.68942 (12)	0.23590 (8)	0.0188 (2)
O2	−0.2801 (2)	0.71471 (13)	0.14077 (8)	0.0208 (3)
O3	−0.0592 (2)	0.36960 (13)	0.21831 (8)	0.0220 (3)
O4	0.3090 (2)	−0.01318 (13)	−0.08910 (8)	0.0205 (3)
N1	−0.3930 (2)	0.52932 (14)	0.27862 (9)	0.0149 (3)
N2	−0.5387 (2)	0.60958 (15)	0.28897 (9)	0.0186 (3)
N3	−0.0707 (2)	0.26436 (15)	0.00189 (9)	0.0170 (3)
N4	−0.1524 (2)	0.14792 (15)	−0.06048 (9)	0.0181 (3)
N5	0.2602 (2)	0.18642 (14)	0.00230 (9)	0.0143 (3)
N6	0.4749 (2)	0.22357 (17)	0.03542 (11)	0.0206 (3)
C1	−0.2106 (3)	0.44195 (17)	0.37978 (11)	0.0196 (3)
H1A	−0.0839	0.4967	0.3756	0.024*
C2	−0.2207 (3)	0.36200 (19)	0.43441 (11)	0.0238 (4)
H2A	−0.0994	0.3628	0.4675	0.029*
C3	−0.4115 (3)	0.28031 (19)	0.44025 (12)	0.0259 (4)
H3A	−0.4172	0.2280	0.4777	0.031*
C4	−0.5930 (3)	0.2768 (2)	0.39032 (12)	0.0248 (4)
H4A	−0.7196	0.2214	0.3940	0.030*
C5	−0.5857 (3)	0.35610 (18)	0.33486 (11)	0.0200 (3)
H5A	−0.7060	0.3541	0.3009	0.024*
C6	−0.3950 (3)	0.43812 (16)	0.33132 (10)	0.0159 (3)
C7	−0.3307 (3)	0.65627 (16)	0.19113 (10)	0.0158 (3)
C8	−0.2595 (3)	0.54977 (16)	0.22188 (10)	0.0147 (3)
C9	−0.0958 (3)	0.46663 (16)	0.19248 (10)	0.0155 (3)
C10	0.0227 (3)	0.51392 (17)	0.12772 (11)	0.0171 (3)
H10A	0.0694	0.6137	0.1461	0.021*
H10B	−0.0740	0.4948	0.0789	0.021*
C11	0.1283 (2)	0.28045 (16)	0.02926 (10)	0.0140 (3)
C12	−0.0334 (3)	0.05691 (17)	−0.09056 (10)	0.0155 (3)
C13	0.1916 (3)	0.06871 (16)	−0.06161 (10)	0.0150 (3)
C14	−0.1255 (3)	−0.06046 (17)	−0.16342 (11)	0.0186 (3)
H14A	−0.2789	−0.0807	−0.1640	0.022*
H14B	−0.0672	−0.1437	−0.1621	0.022*
C15	−0.0681 (3)	−0.01499 (16)	−0.23796 (10)	0.0169 (3)
C16	−0.1898 (3)	0.07165 (18)	−0.26599 (11)	0.0204 (3)
H16A	−0.3123	0.0922	−0.2421	0.024*
C17	−0.1300 (3)	0.12721 (18)	−0.32900 (11)	0.0229 (4)
H17A	−0.2116	0.1841	−0.3479	0.027*
C18	0.0541 (3)	0.09602 (17)	−0.36308 (11)	0.0204 (3)
C19	0.1758 (3)	0.00851 (18)	−0.33787 (11)	0.0208 (3)
H19A	0.2972	−0.0125	−0.3625	0.025*
C20	0.1132 (3)	−0.04737 (17)	−0.27502 (11)	0.0191 (3)
H20A	0.1929	−0.1067	−0.2577	0.023*
H1N6	0.538 (4)	0.226 (3)	−0.0038 (17)	0.032 (7)*
H2N6	0.512 (4)	0.153 (3)	0.0487 (14)	0.021 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04790 (14)	0.02057 (9)	0.01944 (10)	0.00057 (8)	0.00410 (8)	0.00878 (7)
S1	0.01188 (18)	0.01887 (18)	0.0231 (2)	0.00468 (14)	0.00303 (15)	0.00339 (15)
O1	0.0194 (6)	0.0176 (5)	0.0236 (6)	0.0084 (4)	0.0060 (5)	0.0094 (5)
O2	0.0218 (6)	0.0192 (6)	0.0270 (7)	0.0074 (5)	0.0063 (5)	0.0132 (5)
O3	0.0233 (6)	0.0210 (6)	0.0275 (7)	0.0115 (5)	0.0070 (5)	0.0118 (5)
O4	0.0215 (6)	0.0212 (6)	0.0228 (6)	0.0122 (5)	0.0050 (5)	0.0075 (5)
N1	0.0147 (6)	0.0137 (6)	0.0175 (7)	0.0047 (5)	0.0021 (5)	0.0048 (5)
N2	0.0192 (7)	0.0186 (6)	0.0221 (7)	0.0086 (5)	0.0057 (6)	0.0088 (5)
N3	0.0129 (6)	0.0191 (6)	0.0196 (7)	0.0047 (5)	0.0035 (5)	0.0046 (5)
N4	0.0138 (6)	0.0205 (6)	0.0205 (7)	0.0030 (5)	0.0039 (5)	0.0060 (5)
N5	0.0105 (6)	0.0176 (6)	0.0183 (7)	0.0064 (5)	0.0035 (5)	0.0080 (5)
N6	0.0103 (6)	0.0258 (7)	0.0270 (8)	0.0081 (5)	0.0019 (6)	0.0064 (6)
C1	0.0211 (8)	0.0175 (7)	0.0207 (8)	0.0038 (6)	0.0011 (6)	0.0057 (6)
C2	0.0283 (9)	0.0234 (8)	0.0210 (8)	0.0065 (7)	−0.0025 (7)	0.0080 (7)
C3	0.0376 (11)	0.0219 (8)	0.0211 (9)	0.0050 (7)	0.0044 (8)	0.0106 (7)
C4	0.0277 (9)	0.0236 (8)	0.0236 (9)	−0.0007 (7)	0.0056 (7)	0.0093 (7)
C5	0.0203 (8)	0.0199 (7)	0.0205 (8)	0.0027 (6)	0.0028 (6)	0.0069 (6)
C6	0.0197 (8)	0.0137 (6)	0.0162 (7)	0.0049 (6)	0.0032 (6)	0.0061 (6)
C7	0.0139 (7)	0.0136 (6)	0.0207 (8)	0.0041 (5)	0.0028 (6)	0.0049 (6)
C8	0.0146 (7)	0.0135 (6)	0.0178 (7)	0.0045 (5)	0.0032 (6)	0.0058 (6)
C9	0.0140 (7)	0.0148 (7)	0.0178 (8)	0.0048 (5)	0.0014 (6)	0.0033 (6)
C10	0.0150 (7)	0.0164 (7)	0.0222 (8)	0.0066 (6)	0.0047 (6)	0.0062 (6)
C11	0.0131 (7)	0.0158 (7)	0.0162 (7)	0.0061 (5)	0.0059 (5)	0.0070 (6)
C12	0.0155 (7)	0.0175 (7)	0.0167 (7)	0.0032 (6)	0.0049 (6)	0.0094 (6)
C13	0.0168 (7)	0.0166 (7)	0.0161 (7)	0.0062 (6)	0.0050 (6)	0.0101 (6)
C14	0.0190 (8)	0.0161 (7)	0.0219 (8)	0.0021 (6)	0.0040 (6)	0.0071 (6)
C15	0.0190 (8)	0.0143 (7)	0.0177 (8)	0.0038 (6)	0.0005 (6)	0.0044 (6)
C16	0.0215 (8)	0.0188 (7)	0.0221 (8)	0.0086 (6)	0.0019 (6)	0.0047 (6)
C17	0.0310 (9)	0.0177 (7)	0.0216 (8)	0.0094 (7)	−0.0017 (7)	0.0062 (6)
C18	0.0301 (9)	0.0150 (7)	0.0158 (8)	0.0018 (6)	0.0018 (7)	0.0047 (6)
C19	0.0219 (8)	0.0216 (8)	0.0201 (8)	0.0059 (6)	0.0055 (7)	0.0056 (6)
C20	0.0217 (8)	0.0176 (7)	0.0203 (8)	0.0078 (6)	0.0021 (6)	0.0068 (6)

Geometric parameters (Å, º) top

Br1—C18	1.9049 (18)	C3—H3A	0.9300
S1—C11	1.7508 (17)	C4—C5	1.390 (3)
S1—C10	1.8020 (16)	C4—H4A	0.9300
O1—N2	1.3680 (19)	C5—C6	1.385 (2)
O1—C7	1.429 (2)	C5—H5A	0.9300
O2—C7	1.200 (2)	C7—C8	1.428 (2)
O3—C9	1.218 (2)	C8—C9	1.465 (2)
O4—C13	1.2187 (19)	C9—C10	1.519 (2)
N1—N2	1.3088 (19)	C10—H10A	0.9700
N1—C8	1.368 (2)	C10—H10B	0.9700
N1—C6	1.445 (2)	C12—C13	1.469 (2)
N3—C11	1.300 (2)	C12—C14	1.504 (2)
N3—N4	1.381 (2)	C14—C15	1.514 (2)
N4—C12	1.300 (2)	C14—H14A	0.9700
N5—C11	1.3680 (19)	C14—H14B	0.9700
N5—C13	1.389 (2)	C15—C20	1.393 (2)
N5—N6	1.4112 (19)	C15—C16	1.401 (2)
N6—H1N6	0.81 (3)	C16—C17	1.389 (3)
N6—H2N6	0.86 (3)	C16—H16A	0.9300
C1—C2	1.383 (3)	C17—C18	1.384 (3)
C1—C6	1.389 (2)	C17—H17A	0.9300
C1—H1A	0.9300	C18—C19	1.386 (2)
C2—C3	1.394 (3)	C19—C20	1.393 (3)
C2—H2A	0.9300	C19—H19A	0.9300
C3—C4	1.389 (3)	C20—H20A	0.9300

C11—S1—C10	99.93 (8)	C8—C9—C10	113.52 (13)
N2—O1—C7	110.81 (12)	C9—C10—S1	112.99 (11)
N2—N1—C8	114.46 (14)	C9—C10—H10A	109.0
N2—N1—C6	114.57 (14)	S1—C10—H10A	109.0
C8—N1—C6	130.92 (14)	C9—C10—H10B	109.0
N1—N2—O1	105.56 (13)	S1—C10—H10B	109.0
C11—N3—N4	118.15 (13)	H10A—C10—H10B	107.8
C12—N4—N3	120.73 (14)	N3—C11—N5	124.05 (15)
C11—N5—C13	121.19 (13)	N3—C11—S1	121.47 (12)
C11—N5—N6	116.73 (13)	N5—C11—S1	114.47 (12)
C13—N5—N6	121.61 (13)	N4—C12—C13	123.59 (15)
N5—N6—H1N6	103.2 (19)	N4—C12—C14	118.19 (15)
N5—N6—H2N6	107.7 (15)	C13—C12—C14	118.02 (14)
H1N6—N6—H2N6	103 (2)	O4—C13—N5	122.36 (15)
C2—C1—C6	118.14 (17)	O4—C13—C12	125.46 (16)
C2—C1—H1A	120.9	N5—C13—C12	112.17 (13)
C6—C1—H1A	120.9	C12—C14—C15	107.41 (13)
C1—C2—C3	120.50 (17)	C12—C14—H14A	110.2
C1—C2—H2A	119.8	C15—C14—H14A	110.2
C3—C2—H2A	119.8	C12—C14—H14B	110.2
C4—C3—C2	120.25 (18)	C15—C14—H14B	110.2
C4—C3—H3A	119.9	H14A—C14—H14B	108.5
C2—C3—H3A	119.9	C20—C15—C16	119.23 (16)
C3—C4—C5	120.06 (18)	C20—C15—C14	121.51 (15)
C3—C4—H4A	120.0	C16—C15—C14	119.03 (15)
C5—C4—H4A	120.0	C17—C16—C15	120.87 (17)
C6—C5—C4	118.46 (17)	C17—C16—H16A	119.6
C6—C5—H5A	120.8	C15—C16—H16A	119.6
C4—C5—H5A	120.8	C18—C17—C16	118.47 (16)
C5—C6—C1	122.58 (16)	C18—C17—H17A	120.8
C5—C6—N1	118.14 (15)	C16—C17—H17A	120.8
C1—C6—N1	119.16 (15)	C17—C18—C19	122.11 (17)
O2—C7—C8	136.11 (16)	C17—C18—Br1	119.06 (14)
O2—C7—O1	120.39 (14)	C19—C18—Br1	118.83 (14)
C8—C7—O1	103.49 (14)	C18—C19—C20	118.84 (16)
N1—C8—C7	105.67 (13)	C18—C19—H19A	120.6
N1—C8—C9	126.27 (14)	C20—C19—H19A	120.6
C7—C8—C9	127.67 (15)	C19—C20—C15	120.45 (16)
O3—C9—C8	122.63 (16)	C19—C20—H20A	119.8
O3—C9—C10	123.85 (15)	C15—C20—H20A	119.8

C8—N1—N2—O1	0.65 (18)	N4—N3—C11—N5	−2.7 (2)
C6—N1—N2—O1	178.30 (13)	N4—N3—C11—S1	176.05 (12)
C7—O1—N2—N1	−0.32 (17)	C13—N5—C11—N3	4.4 (2)
C11—N3—N4—C12	0.3 (2)	N6—N5—C11—N3	176.67 (16)
C6—C1—C2—C3	−0.1 (3)	C13—N5—C11—S1	−174.36 (12)
C1—C2—C3—C4	0.9 (3)	N6—N5—C11—S1	−2.14 (19)
C2—C3—C4—C5	−0.7 (3)	C10—S1—C11—N3	6.15 (16)
C3—C4—C5—C6	−0.4 (3)	C10—S1—C11—N5	−175.02 (12)
C4—C5—C6—C1	1.3 (3)	N3—N4—C12—C13	0.4 (2)
C4—C5—C6—N1	−174.73 (16)	N3—N4—C12—C14	−174.35 (15)
C2—C1—C6—C5	−1.1 (3)	C11—N5—C13—O4	176.57 (15)
C2—C1—C6—N1	174.91 (15)	N6—N5—C13—O4	4.7 (2)
N2—N1—C6—C5	51.6 (2)	C11—N5—C13—C12	−3.4 (2)
C8—N1—C6—C5	−131.18 (18)	N6—N5—C13—C12	−175.22 (15)
N2—N1—C6—C1	−124.54 (17)	N4—C12—C13—O4	−178.76 (17)
C8—N1—C6—C1	52.6 (2)	C14—C12—C13—O4	−4.1 (2)
N2—O1—C7—O2	179.06 (15)	N4—C12—C13—N5	1.2 (2)
N2—O1—C7—C8	−0.09 (17)	C14—C12—C13—N5	175.89 (14)
N2—N1—C8—C7	−0.71 (19)	N4—C12—C14—C15	92.39 (18)
C6—N1—C8—C7	−177.89 (16)	C13—C12—C14—C15	−82.61 (17)
N2—N1—C8—C9	−173.89 (15)	C12—C14—C15—C20	93.65 (18)
C6—N1—C8—C9	8.9 (3)	C12—C14—C15—C16	−80.78 (19)
O2—C7—C8—N1	−178.5 (2)	C20—C15—C16—C17	−1.1 (3)
O1—C7—C8—N1	0.44 (17)	C14—C15—C16—C17	173.41 (16)
O2—C7—C8—C9	−5.4 (3)	C15—C16—C17—C18	−0.6 (3)
O1—C7—C8—C9	173.50 (15)	C16—C17—C18—C19	1.9 (3)
N1—C8—C9—O3	−1.7 (3)	C16—C17—C18—Br1	−177.44 (13)
C7—C8—C9—O3	−173.40 (16)	C17—C18—C19—C20	−1.4 (3)
N1—C8—C9—C10	178.64 (15)	Br1—C18—C19—C20	177.91 (13)
C7—C8—C9—C10	6.9 (2)	C18—C19—C20—C15	−0.4 (3)
O3—C9—C10—S1	−9.0 (2)	C16—C15—C20—C19	1.6 (3)
C8—C9—C10—S1	170.66 (11)	C14—C15—C20—C19	−172.79 (16)
C11—S1—C10—C9	87.24 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H1N6···N3ⁱ	0.81 (3)	2.47 (3)	2.9835 (19)	123 (2)
N6—H1N6···N4ⁱ	0.81 (3)	2.40 (3)	3.050 (2)	138 (3)
N6—H2N6···O4ⁱⁱ	0.86 (3)	2.15 (3)	2.989 (2)	164 (2)
C14—H14B···O3ⁱⁱⁱ	0.97	2.50	3.416 (2)	157

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₅BrN₆O₄S
M_r	515.35
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.3842 (3), 10.0832 (5), 17.1563 (8)
α, β, γ (°)	104.873 (1), 93.507 (1), 98.189 (1)
V (Å³)	1050.99 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.10
Crystal size (mm)	0.32 × 0.26 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.553, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	21938, 6161, 5241
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.709

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.03
No. of reflections	6161
No. of parameters	297
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.50

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H1N6···N3ⁱ	0.81 (3)	2.47 (3)	2.9835 (19)	123 (2)
N6—H1N6···N4ⁱ	0.81 (3)	2.40 (3)	3.050 (2)	138 (3)
N6—H2N6···O4ⁱⁱ	0.86 (3)	2.15 (3)	2.989 (2)	164 (2)
C14—H14B···O3ⁱⁱⁱ	0.97	2.50	3.416 (2)	157

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009

§Thomson Reuters ResearcherID: A-5525-2009

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

References

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