4-[(5-Bromo-2-hydroxy­benzyl­idene)amino]-N-(4,6-dimethyl­pyrimidin-2-yl)benzene­sulfonamide–4-bromo-2-[(E)-({4-[(4,6-dimethyl­pyrimidin-2-yl)sulfamo­yl]phen­yl}iminio)meth­yl]phenolate [0.61 (7)/0.39 (7)]

Shad, H.A.; Tahir, M.N.; Chohan, Z.H.

doi:10.1107/S1600536808041214

4-[(5-Bromo-2-hydroxybenzylidene)amino]-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide–4-bromo-2-[(E)-({4-[(4,6-dimethylpyrimidin-2-yl)sulfamoyl]phenyl}iminio)methyl]phenolate [0.61 (7)/0.39 (7)]

H. A. Shad, M. N. Tahir and Z. H. Chohan

The title compound, 0.61C₁₉H₁₇BrN₄O₃S·0.39C₁₉H₁₇BrN₄O₃S, is a Schiff base derived from 5-bromosalicylaldehyde and 4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzenesulfonamide(sulfamethazine) and is isostructural with its chloro analogue. The geometry of the title molecule points to the enol (OH—C=C—C=N) form as the major tautomer, however two electron-density maxima corresponding to the H atoms of the OH and NH groups, found in the region of a strong intramolecular N

O hydrogen bond, do not allow the elimination of the presence of the zwitterionic (O⁻—C=C—C=NH⁺) form in the crystal. Refinement of the occupancies of these H atoms gave a 0.61 (7):0.39 (7) ratio of the enolic and zwitterionic forms. The two benzene rings within the molecule are nearly coplanar and the central benzene ring forms a dihedral angle of 84.1 (1)° with the pyrimidine fragment. An intermolecular N—H

O hydrogen bond links molecules into chains extended along the a axis and a C—H

O link is also present. The H atoms of one of the methyl groups are disordered over two sites with an occupancy ratio of 0.72 (7):0.28 (7).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808041214/gk2160sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808041214/gk2160Isup2.hkl Contains datablock I

CCDC reference: 717306

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.007 Å
R factor = 0.048
wR factor = 0.131
Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT413_ALERT_2_B Short Inter XH3 .. XHn     H18B   ..  H19E    ..       2.09 Ang.

Alert level C
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference N3     --  C15     ..       0.13  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C15    --  C16     ..       0.10  Ang.

Alert level G
PLAT318_ALERT_2_G Check Hybridisation of  N2     in Main Residue .          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

As a result of vital pharmacological effects of sulfonamide and their derivatives, there is a rising attention in synthesizing and biotesting of these derivatives. In the vision of the versatile biological chemistry of sulfonamides, we have synthesized and recently published the crystal structures of several compounds from this group (Chohan et al., 2008a, 2008b; Shad et al., 2008; Tahir et al., 2008). In the same continuation, we herein report the structure of the title compound.

The title compound (I) (Fig. 1) was prepared from sulfamethazine and 5-bromosalicylaldehyde. The crystal of the title compound is isostructural with 4-(5-chloro-2-hydroxybenzylideneamino)-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (II) (Chohan et al., 2008b). In the crystal two tautomers, enolic and zwitterionic, with an approximate ratio of 3:2 coexists, as shown by the refinement of H atom occupancies from the N-H and O-H groups.

We shall restrict discussion to comparison of the bond geometry between (I) and (II). The longest bond in the molecule is C3—Br1, having bond distance 1.890 (5) Å. The bond distances in (I), S1—N2 [1.629 (4) Å] and S1—C11 [1.753 (4) Å] remain equal within experimental errors with those observed in (II). The range of S—O [1.416 (3)–1.431 (3) Å] bond lengths is increased compared to 1.422 (2)–1.4282 (19) Å in (II). The bond angles around the S1-atom are slightly changed. The geometry of intramolecular as well as intermolecular H-bonding is given in Table 1 and shown in Fig 2.

Related literature top

For the crystal structures of similar sulphonamides, see: Chohan et al. (2008a,b); Shad et al. (2008); Tahir et al. (2008).

Experimental top

Sulfamethazine (0.5566 g, 2 mmol) in ethanol (15 ml) was reacted with ethanolic (10 ml) solution of 5-bromosalicylaldehyde (0.4020 g, 2 mmol). The mixture was refluxed for 3 h. The colour of the solution gradually changed from colourless to orange-red. The solution was then cooled to room temperature, filtered and volume reduced to about one-third on rotary evaporator. After 12 days crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003)..

Figures top

	Fig. 1. Molecular structure of the title compound, with the atom numbering scheme. The thermal ellipsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii. The H atoms bonded to O1 and N1 show partial occupancy.
	Fig. 2. Crystal packing of the title compound.

4-[(5-Bromo-2-hydroxybenzylidene)amino]-N-(4,6-dimethylpyrimidin-2- yl)benzenesulfonamide–4-bromo-2-[(E)-({4-[(4,6-dimethylpyrimidin-2- yl)sulfamoyl]phenyl}iminio)methyl]phenolate [61 (7)/39 (7)] top

Crystal data top

0.61C₁₉H₁₇BrN₄O₃S·0.39C₁₉H₁₇BrN₄O₃S	D_x = 1.579 Mg m⁻³
M_r = 461.34	Melting point: 497 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3428 reflections
a = 11.7919 (9) Å	θ = 2.4–25.0°
b = 13.9965 (8) Å	µ = 2.26 mm⁻¹
c = 23.5117 (17) Å	T = 296 K
V = 3880.5 (5) Å³	Prismatic, red
Z = 8	0.20 × 0.16 × 0.14 mm
F(000) = 1872

Data collection top

Bruker KAPPA APEXII CCD diffractometer	3428 independent reflections
Radiation source: fine-focus sealed tube	1961 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
Detector resolution: 7.9 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −16→16
T_min = 0.650, T_max = 0.725	l = −27→26
19597 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.057P)² + 2.1678P] where P = (F_o² + 2F_c²)/3
3428 reflections	(Δ/σ)_max = 0.001
257 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

0.61C₁₉H₁₇BrN₄O₃S·0.39C₁₉H₁₇BrN₄O₃S	V = 3880.5 (5) Å³
M_r = 461.34	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.7919 (9) Å	µ = 2.26 mm⁻¹
b = 13.9965 (8) Å	T = 296 K
c = 23.5117 (17) Å	0.20 × 0.16 × 0.14 mm

Data collection top

Bruker KAPPA APEXII CCD diffractometer	3428 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1961 reflections with I > 2σ(I)
T_min = 0.650, T_max = 0.725	R_int = 0.081
19597 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
3428 reflections	Δρ_min = −0.65 e Å⁻³
257 parameters

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	1.18229 (5)	0.76268 (4)	0.36991 (3)	0.0824 (3)
S1	0.40502 (9)	0.37094 (8)	0.60341 (5)	0.0417 (3)
O1	0.9535 (3)	0.3837 (2)	0.39965 (16)	0.0716 (11)
H1O	0.9124	0.3692	0.4287	0.086*	0.61 (7)
N1	0.8172 (3)	0.4593 (3)	0.46953 (16)	0.0426 (9)
H1N	0.8601	0.3968	0.4558	0.051*	0.39 (7)
O2	0.3377 (3)	0.3110 (2)	0.56749 (13)	0.0560 (9)
O3	0.3565 (2)	0.4558 (2)	0.62541 (13)	0.0511 (8)
N2	0.4430 (3)	0.2997 (2)	0.65478 (15)	0.0452 (10)
H2N	0.4177	0.2421	0.6535	0.068*
N3	0.5374 (3)	0.2497 (3)	0.73414 (17)	0.0472 (10)
N4	0.5447 (3)	0.4138 (2)	0.70529 (16)	0.0458 (9)
C1	0.9643 (4)	0.5482 (3)	0.42496 (19)	0.0440 (11)
C2	1.0200 (4)	0.6363 (3)	0.4176 (2)	0.0493 (12)
H2	0.9966	0.6894	0.4383	0.059*
C3	1.1079 (4)	0.6443 (3)	0.3803 (2)	0.0538 (13)
C4	1.1447 (4)	0.5657 (4)	0.3499 (2)	0.0661 (15)
H4	1.2054	0.5716	0.3249	0.079*
C5	1.0922 (4)	0.4790 (4)	0.3565 (2)	0.0685 (16)
H5	1.1168	0.4269	0.3352	0.082*
C6	1.0036 (4)	0.4677 (3)	0.3942 (2)	0.0532 (13)
C7	0.8679 (4)	0.5393 (3)	0.46274 (19)	0.0450 (11)
H7	0.8424	0.5927	0.4824	0.054*
C8	0.7198 (3)	0.4440 (3)	0.50347 (18)	0.0375 (10)
C9	0.6759 (4)	0.3538 (3)	0.5027 (2)	0.0538 (13)
H9	0.7107	0.3067	0.4809	0.065*
C10	0.5808 (4)	0.3317 (3)	0.5338 (2)	0.0548 (13)
H10	0.5514	0.2701	0.5329	0.066*
C11	0.5290 (3)	0.4005 (3)	0.56628 (17)	0.0359 (10)
C12	0.5738 (4)	0.4917 (3)	0.56843 (19)	0.0430 (11)
H12	0.5405	0.5382	0.5912	0.052*
C13	0.6683 (4)	0.5127 (3)	0.5365 (2)	0.0457 (12)
H13	0.6979	0.5743	0.5372	0.055*
C14	0.5124 (3)	0.3231 (3)	0.70054 (19)	0.0417 (11)
C15	0.6020 (4)	0.2704 (3)	0.7790 (2)	0.0523 (13)
C16	0.6396 (4)	0.3624 (4)	0.7881 (2)	0.0579 (13)
H16	0.6850	0.3764	0.8193	0.069*
C17	0.6095 (4)	0.4328 (3)	0.7507 (2)	0.0501 (12)
C18	0.6482 (5)	0.5342 (4)	0.7575 (3)	0.0784 (17)
H18A	0.6846	0.5550	0.7231	0.118*
H18B	0.7009	0.5382	0.7885	0.118*
H18C	0.5840	0.5743	0.7652	0.118*
C19	0.6307 (5)	0.1897 (4)	0.8188 (2)	0.0797 (18)
H19A	0.5973	0.1316	0.8050	0.120*	0.72 (7)
H19B	0.6015	0.2036	0.8560	0.120*	0.72 (7)
H19C	0.7115	0.1824	0.8208	0.120*	0.72 (7)
H19D	0.6762	0.2134	0.8495	0.120*	0.28 (7)
H19E	0.6720	0.1414	0.7985	0.120*	0.28 (7)
H19F	0.5620	0.1626	0.8337	0.120*	0.28 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0841 (5)	0.0587 (4)	0.1044 (6)	−0.0198 (3)	0.0112 (4)	0.0058 (3)
S1	0.0396 (6)	0.0417 (6)	0.0437 (7)	−0.0038 (5)	−0.0033 (5)	0.0005 (6)
O1	0.086 (3)	0.0396 (19)	0.089 (3)	−0.0101 (18)	0.039 (2)	−0.0107 (19)
N1	0.044 (2)	0.043 (2)	0.041 (2)	0.0041 (18)	0.0030 (19)	0.0006 (18)
O2	0.053 (2)	0.060 (2)	0.056 (2)	−0.0146 (16)	−0.0152 (17)	−0.0017 (17)
O3	0.0480 (18)	0.0495 (19)	0.056 (2)	0.0038 (15)	0.0073 (16)	−0.0015 (16)
N2	0.055 (2)	0.039 (2)	0.042 (2)	−0.0141 (18)	−0.010 (2)	0.0017 (18)
N3	0.047 (2)	0.051 (2)	0.043 (3)	0.0018 (18)	−0.003 (2)	0.000 (2)
N4	0.050 (2)	0.046 (2)	0.042 (3)	−0.0097 (18)	0.001 (2)	−0.0051 (19)
C1	0.042 (3)	0.049 (3)	0.041 (3)	0.005 (2)	−0.006 (2)	0.000 (2)
C2	0.056 (3)	0.038 (3)	0.054 (3)	0.002 (2)	−0.003 (3)	−0.003 (2)
C3	0.043 (3)	0.052 (3)	0.066 (4)	−0.003 (2)	0.002 (3)	0.006 (3)
C4	0.053 (3)	0.060 (3)	0.086 (4)	0.002 (3)	0.028 (3)	−0.002 (3)
C5	0.063 (3)	0.052 (3)	0.091 (5)	0.001 (3)	0.031 (3)	−0.010 (3)
C6	0.056 (3)	0.041 (3)	0.063 (4)	0.003 (2)	0.008 (3)	−0.003 (3)
C7	0.051 (3)	0.041 (3)	0.044 (3)	0.010 (2)	0.000 (2)	−0.002 (2)
C8	0.037 (2)	0.043 (3)	0.033 (3)	0.004 (2)	0.002 (2)	0.001 (2)
C9	0.060 (3)	0.044 (3)	0.058 (3)	0.002 (2)	0.016 (3)	−0.013 (2)
C10	0.059 (3)	0.038 (3)	0.067 (4)	−0.006 (2)	0.011 (3)	−0.011 (2)
C11	0.040 (2)	0.034 (2)	0.034 (3)	0.0019 (19)	−0.004 (2)	−0.0028 (19)
C12	0.050 (3)	0.039 (3)	0.040 (3)	0.005 (2)	0.008 (2)	−0.007 (2)
C13	0.050 (3)	0.035 (2)	0.052 (3)	−0.004 (2)	0.006 (2)	−0.006 (2)
C14	0.041 (3)	0.048 (3)	0.036 (3)	−0.002 (2)	0.004 (2)	−0.001 (2)
C15	0.054 (3)	0.057 (3)	0.046 (3)	0.016 (3)	0.007 (3)	−0.003 (3)
C16	0.046 (3)	0.082 (4)	0.046 (3)	0.008 (3)	−0.009 (2)	−0.016 (3)
C17	0.043 (3)	0.061 (3)	0.046 (3)	−0.005 (2)	0.005 (2)	−0.012 (3)
C18	0.085 (4)	0.070 (4)	0.081 (5)	−0.031 (3)	−0.002 (3)	−0.020 (3)
C19	0.095 (4)	0.083 (4)	0.061 (4)	0.035 (3)	−0.016 (3)	0.002 (3)

Geometric parameters (Å, º) top

Br1—C3	1.890 (5)	C7—H7	0.9300
S1—O3	1.416 (3)	C8—C9	1.365 (6)
S1—O2	1.431 (3)	C8—C13	1.378 (6)
S1—N2	1.629 (4)	C9—C10	1.374 (6)
S1—C11	1.753 (4)	C9—H9	0.9300
O1—C6	1.322 (5)	C10—C11	1.372 (6)
O1—H1O	0.8621	C10—H10	0.9300
N1—C7	1.279 (5)	C11—C12	1.381 (5)
N1—C8	1.414 (5)	C12—C13	1.375 (6)
N1—H1N	1.0611	C12—H12	0.9300
N2—C14	1.391 (5)	C13—H13	0.9300
N2—H2N	0.8600	C15—C16	1.378 (6)
N3—C14	1.329 (5)	C15—C19	1.506 (7)
N3—C15	1.332 (6)	C16—C17	1.368 (6)
N4—C14	1.330 (5)	C16—H16	0.9300
N4—C17	1.339 (6)	C17—C18	1.499 (6)
C1—C2	1.408 (6)	C18—H18A	0.9600
C1—C6	1.416 (6)	C18—H18B	0.9600
C1—C7	1.448 (6)	C18—H18C	0.9600
C2—C3	1.362 (6)	C19—H19A	0.9600
C2—H2	0.9300	C19—H19B	0.9600
C3—C4	1.382 (7)	C19—H19C	0.9600
C4—C5	1.371 (6)	C19—H19D	0.9600
C4—H4	0.9300	C19—H19E	0.9600
C5—C6	1.380 (7)	C19—H19F	0.9600
C5—H5	0.9300

O3—S1—O2	118.9 (2)	C11—C10—C9	120.1 (4)
O3—S1—N2	110.7 (2)	C11—C10—H10	120.0
O2—S1—N2	103.37 (18)	C9—C10—H10	120.0
O3—S1—C11	108.73 (19)	C10—C11—C12	119.9 (4)
O2—S1—C11	107.90 (19)	C10—C11—S1	118.8 (3)
N2—S1—C11	106.54 (18)	C12—C11—S1	121.3 (3)
C6—O1—H1O	122.5	C13—C12—C11	119.2 (4)
C7—N1—C8	125.7 (4)	C13—C12—H12	120.4
C7—N1—H1N	117.4	C11—C12—H12	120.4
C8—N1—H1N	115.7	C12—C13—C8	121.0 (4)
C14—N2—S1	126.3 (3)	C12—C13—H13	119.5
C14—N2—H2N	116.9	C8—C13—H13	119.5
S1—N2—H2N	116.9	N3—C14—N4	128.6 (4)
C14—N3—C15	115.4 (4)	N3—C14—N2	114.1 (4)
C14—N4—C17	114.8 (4)	N4—C14—N2	117.2 (4)
C2—C1—C6	118.8 (4)	N3—C15—C16	120.7 (5)
C2—C1—C7	121.1 (4)	N3—C15—C19	117.2 (5)
C6—C1—C7	120.1 (4)	C16—C15—C19	122.2 (5)
C3—C2—C1	120.4 (4)	C17—C16—C15	119.3 (5)
C3—C2—H2	119.8	C17—C16—H16	120.3
C1—C2—H2	119.8	C15—C16—H16	120.3
C2—C3—C4	120.4 (4)	N4—C17—C16	121.1 (4)
C2—C3—Br1	120.6 (4)	N4—C17—C18	116.6 (5)
C4—C3—Br1	119.0 (4)	C16—C17—C18	122.3 (5)
C5—C4—C3	120.3 (5)	C17—C18—H18A	109.5
C5—C4—H4	119.8	C17—C18—H18B	109.5
C3—C4—H4	119.8	H18A—C18—H18B	109.5
C4—C5—C6	121.1 (5)	C17—C18—H18C	109.5
C4—C5—H5	119.5	H18A—C18—H18C	109.5
C6—C5—H5	119.5	H18B—C18—H18C	109.5
O1—C6—C5	120.2 (4)	C15—C19—H19A	109.5
O1—C6—C1	120.8 (4)	C15—C19—H19B	109.5
C5—C6—C1	119.0 (4)	H19A—C19—H19B	109.5
N1—C7—C1	121.3 (4)	C15—C19—H19C	109.5
N1—C7—H7	119.4	H19A—C19—H19C	109.5
C1—C7—H7	119.4	H19B—C19—H19C	109.5
C9—C8—C13	119.1 (4)	C15—C19—H19D	109.5
C9—C8—N1	116.2 (4)	C15—C19—H19E	109.5
C13—C8—N1	124.7 (4)	H19D—C19—H19E	109.5
C8—C9—C10	120.7 (4)	C15—C19—H19F	109.5
C8—C9—H9	119.6	H19D—C19—H19F	109.5
C10—C9—H9	119.6	H19E—C19—H19F	109.5

O3—S1—N2—C14	−53.3 (4)	O3—S1—C11—C10	−169.9 (4)
O2—S1—N2—C14	178.3 (4)	O2—S1—C11—C10	−39.7 (4)
C11—S1—N2—C14	64.7 (4)	N2—S1—C11—C10	70.8 (4)
C6—C1—C2—C3	1.9 (7)	O3—S1—C11—C12	9.0 (4)
C7—C1—C2—C3	−177.5 (4)	O2—S1—C11—C12	139.2 (3)
C1—C2—C3—C4	−1.1 (7)	N2—S1—C11—C12	−110.4 (4)
C1—C2—C3—Br1	179.6 (3)	C10—C11—C12—C13	1.9 (7)
C2—C3—C4—C5	0.8 (8)	S1—C11—C12—C13	−177.0 (3)
Br1—C3—C4—C5	−179.9 (4)	C11—C12—C13—C8	−1.3 (7)
C3—C4—C5—C6	−1.4 (9)	C9—C8—C13—C12	−0.1 (7)
C4—C5—C6—O1	179.4 (5)	N1—C8—C13—C12	−179.8 (4)
C4—C5—C6—C1	2.2 (8)	C15—N3—C14—N4	1.1 (7)
C2—C1—C6—O1	−179.6 (4)	C15—N3—C14—N2	−178.7 (4)
C7—C1—C6—O1	−0.2 (7)	C17—N4—C14—N3	−1.1 (7)
C2—C1—C6—C5	−2.4 (7)	C17—N4—C14—N2	178.7 (4)
C7—C1—C6—C5	177.0 (5)	S1—N2—C14—N3	−175.0 (3)
C8—N1—C7—C1	−177.3 (4)	S1—N2—C14—N4	5.2 (6)
C2—C1—C7—N1	180.0 (4)	C14—N3—C15—C16	−0.7 (6)
C6—C1—C7—N1	0.6 (7)	C14—N3—C15—C19	179.0 (4)
C7—N1—C8—C9	177.0 (4)	N3—C15—C16—C17	0.4 (7)
C7—N1—C8—C13	−3.2 (7)	C19—C15—C16—C17	−179.3 (5)
C13—C8—C9—C10	0.8 (7)	C14—N4—C17—C16	0.7 (6)
N1—C8—C9—C10	−179.4 (4)	C14—N4—C17—C18	179.7 (4)
C8—C9—C10—C11	−0.3 (7)	C15—C16—C17—N4	−0.4 (7)
C9—C10—C11—C12	−1.1 (7)	C15—C16—C17—C18	−179.4 (5)
C9—C10—C11—S1	177.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	1.06	1.73	2.530 (5)	129
O1—H1O···N1	0.86	1.94	2.530 (5)	124
N2—H2N···O1ⁱ	0.86	2.20	2.871 (4)	135
C9—H9···O2ⁱⁱ	0.93	2.50	3.417 (5)	169

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	0.61C₁₉H₁₇BrN₄O₃S·0.39C₁₉H₁₇BrN₄O₃S
M_r	461.34
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	11.7919 (9), 13.9965 (8), 23.5117 (17)
V (Å³)	3880.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.26
Crystal size (mm)	0.20 × 0.16 × 0.14

Data collection
Diffractometer	Bruker KAPPA APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.650, 0.725
No. of measured, independent and observed [I > 2σ(I)] reflections	19597, 3428, 1961
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.00
No. of reflections	3428
No. of parameters	257
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.65

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003)..