4-[(5-Bromo-2-hydroxy-benzyl-idene)amino]-N-(4,6-dimethyl-pyrimidin-2-yl)benzene-sulfonamide-4-bromo-2-[(E)-({4-[(4,6-dimethyl-pyrimidin-2-yl)sulfamo-yl]phen-yl}iminio)meth-yl]phenolate [0.61 (7)/0.39 (7)].

The title compound, 0.61C(19)H(17)BrN(4)O(3)S·0.39C(19)H(17)BrN(4)O(3)S, is a Schiff base derived from 5-bromo-salicylaldehyde and 4-amino-N-(4,6-dimethyl-2-pyrimidin-yl)benzene-sulfonamide(sulfamethazine) and is isostructural with its chloro analogue. The geometry of the title mol-ecule 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 intra-molecular N⋯H⋯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 mol-ecule are nearly coplanar and the central benzene ring forms a dihedral angle of 84.1 (1)° with the pyrimidine fragment. An inter-molecular N-H⋯O hydrogen bond links mol-ecules 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).

Related literature

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

Experimental

Crystal data

0.61C19H17BrN4O3S·0.39C19H17BrN4O3S

M = 461.34

Orthorhombic,

a = 11.7919 (9) Å

b = 13.9965 (8) Å

c = 23.5117 (17) Å

V = 3880.5 (5) Å3

Z = 8

Mo Kα radiation

μ = 2.26 mm−1

T = 296 (2) K

0.20 × 0.16 × 0.14 mm

Data collection

Bruker KAPPA APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.650, T max = 0.725

19597 measured reflections

3428 independent reflections

1961 reflections with I > 2σ(I)

R int = 0.081

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.131

S = 1.00

3428 reflections

257 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.65 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAIn class="Chemical">NT; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041214/gk2160sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041214/gk2160Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

0.61C19H17BrN4O3S·0.39C19H17BrN4O3S	Dx = 1.579 Mg m−3
Mr = 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

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

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(Fo2) + (0.057P)2 + 2.1678P] where P = (Fo2 + 2Fc2)/3
3428 reflections	(Δ/σ)max = 0.001
257 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.65 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) .