4-[(E)-(5-Bromo-2-hydroxy­phen­yl)methyl­ideneamino]benzene­sulfonamide

Abstract

In the title compound, C₁₃H₁₁ClN₂O₃S, the dihedral angle between the benzene rings is 12.26 (33)° and an intra­molecular O—H⋯N hydrogen bond helps to establish the conformation. In the crystal, N—H⋯O and C—H⋯O inter­actions link the mol­ecules.

Related literature

For a related structure and background discussion, see: Chohan et al. (2009 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

• C₁₃H₁₁BrN₂O₃S

• M _r = 355.21

• Monoclinic,

• a = 6.1224 (15) Å

• b = 4.5263 (13) Å

• c = 23.445 (9) Å

• β = 94.44 (2)°

• V = 647.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 3.34 mm⁻¹

• T = 100 K

• 0.22 × 0.20 × 0.16 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.482, T _max = 0.587

• 3181 measured reflections

• 1653 independent reflections

• 1458 reflections with I > 2σ(I)

• R _int = 0.042

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.087

• S = 1.00

• 1653 reflections

• 188 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.71 e Å⁻³

• Δρ_min = −1.13 e Å⁻³

• Absolute structure: Flack (1983 ▶), 279 Friedal pairs

• Flack parameter: 0.025 (16)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.86	2.583 (7)	146
N2—H21⋯O3i	0.73 (8)	2.26 (7)	2.950 (7)	160 (8)
N2—H22⋯O2ii	0.92 (7)	2.58 (8)	3.325 (7)	139 (6)
C9—H9⋯O2iii	0.93	2.57	3.386 (7)	146

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

As part of our ongoing studies of sulfonamides, we now report the structure of the title compound, (I). The crystal structure of (II) 4-{[(E)-(5-chloro-2-hydroxyphenyl) methylidene]amino}benzenesulfonamide (Chohan et al., 2009) has been reported which differs from (I) due to chloro substitution instead of bromo.

In (I), the benzene rings A (C1—C6) of 5-bromosalicylaldehyde and B (C8—C13) of sulfanilamide are oriented at a dihedral angle of 12.03 (36)°. The Br1 and S1 atoms are at a distance of -0.016 (8) and -0.159 (9) A° from the mean square planes of rings A and B, respectively. There exist two intramolecular H-bonds (Table 1, Fig. 1) forming S(5) and S(6) ring motifs (Bernstein et al., 1995). Three intermolecular H-bondings (Table 1) link the molecules in polymeric nature extending along the b axis (Fig. 2) and forming R₃³(10) and R₂¹(8) ring motifs.

Experimental

Sulfanilamide (0.344 g, 2 mmol) in ethanol (20 ml) was mixed with 5-bromosalicylaldehyde (0.402 g, 2 mmol) in ethanol (10 ml). The resultant mixture was refluxed for 4 h by monitoring through TLC. During refluxing the solution turned from colorless to orange yellow. After completion of reaction, it was cooled to room temperature, filtered and volume reduced to about one-third using rotary evaporator. It was then allowed to stand for 7 days at room temperature. After which a crystallized product was formed that was filtered, washed with ethanol (2 × 5 ml), dried and recrystallized in a mixture of methanol and ethanol (1:1) to afford shiny orange yellow prisms of (I).

Refinement

The coordinates of H-atoms of the NH₂ group were refined. The other H-atoms were positioned geometrically with O—H = 0.82, C—H = 0.93 Å for aromatic H atoms and constrained to ride on their parent atoms, with U_iso(H) = xUeq(C, N, O), where x = 1.2 for all H atoms.

Figures

Fig. 1.

View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radius. The dotted line indicate the intramolecular H-bond.

Fig. 2.

The partial packing of (I) showing how molecules form polymeric chains extending along the crystallographic b axis and ring motifs exist.

Crystal data

C13H11BrN2O3S	F(000) = 356
Mr = 355.21	Dx = 1.821 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1653 reflections
a = 6.1224 (15) Å	θ = 3.3–25.5°
b = 4.5263 (13) Å	µ = 3.34 mm−1
c = 23.445 (9) Å	T = 100 K
β = 94.44 (2)°	Prismatic, yellow
V = 647.8 (3) Å3	0.22 × 0.20 × 0.16 mm
Z = 2

Data collection

Bruker Kappa APEXII CCD diffractometer	1653 independent reflections
Radiation source: fine-focus sealed tube	1458 reflections with I > 2σ(I)
graphite	Rint = 0.042
Detector resolution: 7.80 pixels mm-1	θmax = 25.5°, θmin = 3.3°
ω scans	h = −6→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −2→5
Tmin = 0.482, Tmax = 0.587	l = −28→28
3181 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0554P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
1653 reflections	Δρmax = 0.71 e Å−3
188 parameters	Δρmin = −1.13 e Å−3
1 restraint	Absolute structure: Flack (1983), 279 Friedal pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.025 (16)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.22142 (8)	1.43584 (16)	0.03133 (2)	0.0184 (2)
S1	0.2382 (2)	−0.1521 (3)	0.42877 (6)	0.0131 (4)
O1	0.8682 (5)	0.9320 (15)	0.21201 (14)	0.0184 (11)
O2	0.0460 (7)	−0.3040 (10)	0.40583 (17)	0.0175 (12)
O3	0.4146 (6)	−0.3217 (10)	0.45633 (17)	0.0148 (12)
N1	0.5538 (8)	0.6166 (11)	0.2472 (2)	0.0141 (16)
N2	0.1639 (9)	0.0737 (13)	0.4770 (2)	0.0166 (17)
C1	0.5019 (8)	0.947 (2)	0.16824 (19)	0.0124 (14)
C2	0.7192 (9)	1.0429 (15)	0.1723 (2)	0.0134 (16)
C3	0.7829 (9)	1.2590 (14)	0.1347 (2)	0.0148 (17)
C4	0.6381 (9)	1.3763 (12)	0.0932 (2)	0.0143 (19)
C5	0.4222 (9)	1.2702 (14)	0.0883 (2)	0.0120 (17)
C6	0.3552 (10)	1.0646 (14)	0.1257 (2)	0.0149 (17)
C7	0.4239 (9)	0.7346 (14)	0.2085 (2)	0.0134 (17)
C8	0.4747 (8)	0.4182 (18)	0.2878 (2)	0.0114 (14)
C9	0.6126 (9)	0.3535 (13)	0.3358 (2)	0.0147 (19)
C10	0.5457 (10)	0.1737 (14)	0.3780 (3)	0.0155 (17)
C11	0.3363 (9)	0.0532 (14)	0.3724 (2)	0.0135 (17)
C12	0.1995 (9)	0.1113 (13)	0.3242 (2)	0.0134 (17)
C13	0.2664 (9)	0.2936 (14)	0.2818 (2)	0.0145 (17)
H1	0.81278	0.79686	0.22919	0.0218*
H3	0.92711	1.32519	0.13772	0.0176*
H4	0.68212	1.52308	0.06879	0.0172*
H6	0.21007	1.00207	0.12277	0.0178*
H7	0.27623	0.68391	0.20607	0.0155*
H9	0.75293	0.43345	0.33940	0.0177*
H10	0.63936	0.13250	0.41016	0.0182*
H12	0.06076	0.02660	0.32024	0.0159*
H13	0.17312	0.33314	0.24953	0.0172*
H21	0.258 (12)	0.139 (18)	0.493 (3)	0.0197*
H22	0.062 (11)	0.200 (17)	0.460 (3)	0.0197*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0216 (3)	0.0200 (3)	0.0131 (3)	0.0009 (4)	−0.0012 (2)	0.0024 (3)
S1	0.0143 (7)	0.0109 (8)	0.0142 (7)	−0.0014 (6)	0.0010 (5)	0.0006 (5)
O1	0.0173 (18)	0.019 (2)	0.0186 (18)	−0.009 (3)	0.0003 (14)	0.010 (3)
O2	0.017 (2)	0.017 (2)	0.018 (2)	−0.006 (2)	−0.0015 (17)	0.0027 (19)
O3	0.014 (2)	0.013 (2)	0.017 (2)	0.0027 (18)	−0.0014 (17)	0.0053 (17)
N1	0.013 (2)	0.013 (3)	0.017 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)
N2	0.018 (3)	0.010 (3)	0.022 (3)	−0.001 (3)	0.003 (2)	−0.001 (2)
C1	0.015 (2)	0.010 (3)	0.013 (2)	0.005 (4)	0.0056 (19)	−0.006 (4)
C2	0.017 (3)	0.018 (3)	0.005 (2)	−0.001 (3)	0.000 (2)	−0.003 (2)
C3	0.011 (3)	0.011 (3)	0.023 (3)	−0.002 (3)	0.006 (2)	0.004 (3)
C4	0.020 (3)	0.008 (4)	0.016 (3)	−0.005 (3)	0.009 (2)	0.001 (2)
C5	0.016 (3)	0.010 (3)	0.010 (3)	0.005 (3)	0.002 (2)	−0.006 (2)
C6	0.015 (3)	0.015 (3)	0.015 (3)	−0.001 (3)	0.003 (2)	−0.004 (3)
C7	0.013 (3)	0.008 (3)	0.020 (3)	−0.004 (3)	0.007 (2)	−0.002 (3)
C8	0.017 (2)	0.004 (3)	0.014 (2)	0.002 (3)	0.006 (2)	0.001 (3)
C9	0.009 (3)	0.010 (4)	0.025 (3)	−0.002 (2)	0.001 (2)	−0.002 (2)
C10	0.017 (3)	0.016 (3)	0.013 (3)	0.001 (3)	−0.002 (2)	0.003 (3)
C11	0.017 (3)	0.008 (3)	0.016 (3)	0.001 (3)	0.005 (2)	0.001 (2)
C12	0.012 (3)	0.014 (3)	0.014 (3)	−0.004 (3)	0.000 (2)	−0.001 (3)
C13	0.016 (3)	0.013 (3)	0.014 (3)	0.002 (3)	−0.002 (2)	−0.002 (3)

Geometric parameters (Å, °)

Br1—C5	1.898 (5)	C4—C5	1.403 (8)
S1—O2	1.431 (5)	C5—C6	1.363 (8)
S1—O3	1.437 (4)	C8—C13	1.392 (8)
S1—N2	1.616 (5)	C8—C9	1.385 (7)
S1—C11	1.759 (6)	C9—C10	1.368 (9)
O1—C2	1.349 (7)	C10—C11	1.390 (8)
O1—H1	0.8200	C11—C12	1.379 (7)
N1—C8	1.421 (8)	C12—C13	1.378 (8)
N1—C7	1.276 (7)	C3—H3	0.9300
N2—H21	0.73 (8)	C4—H4	0.9300
N2—H22	0.92 (7)	C6—H6	0.9300
C1—C7	1.454 (9)	C7—H7	0.9300
C1—C6	1.395 (8)	C9—H9	0.9300
C1—C2	1.396 (8)	C10—H10	0.9300
C2—C3	1.393 (8)	C12—H12	0.9300
C3—C4	1.372 (7)	C13—H13	0.9300
O2—S1—O3	118.7 (3)	C9—C8—C13	119.5 (5)
O2—S1—N2	107.4 (3)	N1—C8—C9	117.4 (5)
O2—S1—C11	106.9 (3)	C8—C9—C10	121.0 (5)
O3—S1—N2	105.4 (3)	C9—C10—C11	119.4 (6)
O3—S1—C11	109.4 (3)	S1—C11—C10	120.2 (4)
N2—S1—C11	108.8 (3)	C10—C11—C12	120.0 (5)
C2—O1—H1	109.00	S1—C11—C12	119.7 (4)
C7—N1—C8	121.0 (5)	C11—C12—C13	120.6 (5)
S1—N2—H22	108 (5)	C8—C13—C12	119.4 (5)
S1—N2—H21	111 (6)	C2—C3—H3	119.00
H21—N2—H22	117 (8)	C4—C3—H3	119.00
C2—C1—C6	119.2 (6)	C3—C4—H4	121.00
C2—C1—C7	121.4 (5)	C5—C4—H4	121.00
C6—C1—C7	119.4 (5)	C1—C6—H6	120.00
O1—C2—C1	121.4 (5)	C5—C6—H6	120.00
C1—C2—C3	119.2 (5)	N1—C7—H7	119.00
O1—C2—C3	119.4 (5)	C1—C7—H7	119.00
C2—C3—C4	121.6 (5)	C8—C9—H9	119.00
C3—C4—C5	118.6 (5)	C10—C9—H9	119.00
C4—C5—C6	120.6 (5)	C9—C10—H10	120.00
Br1—C5—C4	118.5 (4)	C11—C10—H10	120.00
Br1—C5—C6	120.8 (4)	C11—C12—H12	120.00
C1—C6—C5	120.7 (6)	C13—C12—H12	120.00
N1—C7—C1	121.4 (5)	C8—C13—H13	120.00
N1—C8—C13	123.1 (5)	C12—C13—H13	120.00
O2—S1—C11—C10	−166.2 (5)	O1—C2—C3—C4	179.3 (5)
O2—S1—C11—C12	18.2 (6)	C1—C2—C3—C4	−1.1 (9)
O3—S1—C11—C10	−36.6 (6)	C2—C3—C4—C5	−1.2 (8)
O3—S1—C11—C12	147.9 (5)	C3—C4—C5—Br1	179.4 (4)
N2—S1—C11—C10	78.1 (6)	C3—C4—C5—C6	3.0 (8)
N2—S1—C11—C12	−97.5 (5)	Br1—C5—C6—C1	−178.8 (5)
C8—N1—C7—C1	177.5 (6)	C4—C5—C6—C1	−2.5 (9)
C7—N1—C8—C9	−165.3 (6)	N1—C8—C9—C10	177.4 (6)
C7—N1—C8—C13	13.4 (10)	C13—C8—C9—C10	−1.3 (10)
C6—C1—C2—O1	−178.8 (6)	N1—C8—C13—C12	−177.7 (6)
C6—C1—C2—C3	1.6 (10)	C9—C8—C13—C12	1.0 (9)
C7—C1—C2—O1	3.2 (10)	C8—C9—C10—C11	0.3 (9)
C7—C1—C2—C3	−176.4 (6)	C9—C10—C11—S1	−174.5 (5)
C2—C1—C6—C5	0.2 (10)	C9—C10—C11—C12	1.1 (9)
C7—C1—C6—C5	178.2 (6)	S1—C11—C12—C13	174.2 (5)
C2—C1—C7—N1	−3.7 (10)	C10—C11—C12—C13	−1.4 (9)
C6—C1—C7—N1	178.3 (6)	C11—C12—C13—C8	0.4 (9)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.583 (7)	146
N2—H21···O3i	0.73 (8)	2.26 (7)	2.950 (7)	160 (8)
N2—H22···O2ii	0.92 (7)	2.58 (8)	3.325 (7)	139 (6)
C9—H9···O2iii	0.93	2.57	3.386 (7)	146

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