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Acta Cryst. (2011). E67, o903    [ doi:10.1107/S1600536811009500 ]

Methyl 2-(4-acetamidobenzenesulfonamido)benzoate

I. U. Khan, S. Sharif, S. Ali, W. Ahmad and E. R. T. Tiekink

Abstract top

The molecule of the title compound, C16H16N2O5S, has the shape of the letter V but with a small twist; the dihedral angle formed between the benzene rings is 79.66 (9)°. The presence of an intramolecular N-H...O hydrogen bond, leading to an S(6) ring, correlates with the near coplanarity of the carboxylate ester group with the benzene ring to which it is connected. The acetamide residue is slightly twisted out of the plane of its benzene ring [C-C-N-C = 13.1 (3)°]. In the crystal, supramolecular chains along the a axis are mediated by N-H...O hydrogen bonds. These are connected into layers via C-H...O interactions.

Comment top

As part of on-going structural studies of sulfonamides (Sharif et al., 2010; Khan et al., 2010), the crystal structure of the title compound, (I), is described. Interest in these derivatives relate to their wide use in the treatment of certain infections caused by Gram-positive and Gram-negative microorganisms, some fungi, and certain protozoa (Korolkovas, 1988; Mandell & Sande, 1992).

The molecule of (I), Fig. 1, has an approximate V-shape with the dihedral angle formed between the benzene rings being 79.66 (9) °. The carboxylate ester substituent is co-planar with the benzene ring to which it is connected [the C1—C2—C7—O3 and torsion angle is 2.9 (2) °] but the acetamide residue is slightly twisted out of the plane [C11—C12—N2—C15 = 13.1 (3) °]. The planarity observed for the carboxylate ester group is readily rationalized in terms of an intramolecular N—H···O hydrogen bond, Table 1, which seals a six-membered ring. The most prominent intermolecular contact in the crystal structure is also of the type N—H···O, Table 1, and this serves to link molecules into a linear supramolecular chain along the a axis, Fig. 3. Chains are linked into layers in the ab plane via C—H···O contacts, Table 1, and these stack along the c axis via inter-digitation of the benzoate ester groups; there is no evidence for significant π-interactions between these, however.

Related literature top

For background to the pharmacological uses of sulfonamides, see: Korolkovas (1988); Mandell & Sande (1992). For related structures, see: Sharif et al. (2010); Khan et al. (2010).

Experimental top

To methyl anthranilate (260 µl, 2 mmol) in water (10 ml) was added p-toluene sulfonyl chloride (380 mg, 2 mmol). With stirring at room temperature, the pH of the solution was maintained with 3% Na2CO3. The progress of the reaction was monitored by TLC. On completion of the reaction, the pH was adjusted to 3 with 3 N HCl. The white precipitates that formed were filtered, washed with distilled water and crystallized from methanol to yield colourless blocks of the title compound.

Refinement top

The C-bound H atoms were geometrically placed (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The N-bound H atoms were refined with the distance restraint N–H = 0.86±0.01 Å, and with Uiso(H) = 1.2Ueq(N). Several low-angle reflections, i.e. (1 0 1), (0 1 0), (0 0 1) and (1 1 0), evidently effected by the beam-stop, were omitted from the final refinement.

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 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 35% probability level.
[Figure 2] Fig. 2. A view of the linear supramolecular chain along the a axis in (I), sustained by N—H···O interactions. These and the intramolecular N—H···O hydrogen bonds which close six-membered rings are shown as orange dashed lines.
[Figure 3] Fig. 3. A view in projection down the b axis of the unit-cell contents for (I). The N—H···O hydrogen bonds and C—H···O contacts are shown as orange and green dashed lines, respectively.
Methyl 2-(4-acetamidobenzenesulfonamido)benzoate top
Crystal data top
C16H16N2O5SZ = 2
Mr = 348.37F(000) = 364
Triclinic, P1Dx = 1.450 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2835 (2) ÅCell parameters from 7451 reflections
b = 9.3722 (3) Åθ = 2.3–28.2°
c = 10.8299 (3) ŵ = 0.23 mm−1
α = 85.537 (1)°T = 293 K
β = 88.614 (1)°Block, colourless
γ = 72.203 (1)°0.20 × 0.18 × 0.09 mm
V = 798.11 (4) Å3
Data collection top
Bruker APEXII CCD
diffractometer		3122 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
graphiteθmax = 27.5°, θmin = 3.4°
φ and ω scansh = −10→10
13593 measured reflectionsk = −12→12
3604 independent reflectionsl = −14→12
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0578P)2 + 0.1747P]
where P = (Fo2 + 2Fc2)/3
3604 reflections(Δ/σ)max = 0.001
225 parametersΔρmax = 0.26 e Å−3
2 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C16H16N2O5Sγ = 72.203 (1)°
Mr = 348.37V = 798.11 (4) Å3
Triclinic, P1Z = 2
a = 8.2835 (2) ÅMo Kα radiation
b = 9.3722 (3) ŵ = 0.23 mm−1
c = 10.8299 (3) ÅT = 293 K
α = 85.537 (1)°0.20 × 0.18 × 0.09 mm
β = 88.614 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		3122 reflections with I > 2σ(I)
13593 measured reflectionsRint = 0.024
3604 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.113Δρmax = 0.26 e Å−3
S = 1.07Δρmin = −0.27 e Å−3
3604 reflectionsAbsolute structure: ?
225 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
S10.42614 (5)0.28976 (4)0.83592 (3)0.04378 (14)
O10.54431 (14)0.14234 (13)0.83938 (11)0.0562 (3)
O20.47186 (15)0.40243 (13)0.89646 (11)0.0544 (3)
O30.30254 (19)0.61672 (14)0.55728 (12)0.0659 (4)
O40.17057 (17)0.62717 (14)0.37946 (11)0.0620 (3)
O5−0.13574 (18)0.09502 (17)1.23293 (14)0.0808 (5)
N10.38913 (18)0.36108 (15)0.69410 (12)0.0477 (3)
H1N0.378 (2)0.4554 (11)0.6809 (18)0.057*
N2−0.21841 (17)0.26393 (16)1.06806 (13)0.0534 (3)
H2N−0.3050 (18)0.3309 (17)1.0351 (17)0.064*
C10.32524 (18)0.30069 (16)0.59818 (13)0.0423 (3)
C20.25586 (17)0.39431 (17)0.49240 (13)0.0414 (3)
C30.1942 (2)0.3327 (2)0.39815 (15)0.0544 (4)
H30.14870.39340.32760.065*
C40.1987 (3)0.1845 (2)0.40639 (18)0.0653 (5)
H40.15690.14530.34240.078*
C50.2660 (3)0.0955 (2)0.51059 (19)0.0678 (5)
H50.2690−0.00480.51720.081*
C60.3289 (3)0.15192 (19)0.60507 (17)0.0608 (5)
H60.37460.08930.67470.073*
C70.24751 (19)0.55468 (18)0.48195 (14)0.0456 (3)
C80.1511 (3)0.7859 (2)0.3623 (2)0.0703 (5)
H8A0.09540.83480.43320.105*
H8B0.08430.82810.28960.105*
H8C0.26070.80030.35260.105*
C90.23368 (18)0.27393 (16)0.89638 (13)0.0423 (3)
C100.2359 (2)0.15891 (17)0.98514 (15)0.0482 (4)
H100.33790.08561.00560.058*
C110.0888 (2)0.15200 (17)1.04354 (15)0.0497 (4)
H110.09150.07501.10380.060*
C12−0.06421 (19)0.26073 (17)1.01202 (14)0.0445 (3)
C13−0.0658 (2)0.37314 (19)0.91947 (16)0.0552 (4)
H13−0.16820.44380.89580.066*
C140.0813 (2)0.38105 (19)0.86290 (15)0.0531 (4)
H140.07900.45780.80240.064*
C15−0.2473 (2)0.18603 (18)1.17324 (16)0.0511 (4)
C16−0.4303 (2)0.2227 (2)1.20973 (19)0.0614 (4)
H16A−0.47550.14701.18370.092*
H16B−0.49250.31881.17080.092*
H16C−0.44010.22581.29810.092*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0411 (2)0.0446 (2)0.0414 (2)−0.00745 (15)−0.01326 (14)0.00368 (15)
O10.0458 (6)0.0516 (6)0.0599 (7)−0.0004 (5)−0.0059 (5)0.0083 (5)
O20.0539 (6)0.0594 (7)0.0508 (6)−0.0184 (5)−0.0218 (5)0.0008 (5)
O30.0896 (9)0.0515 (7)0.0588 (7)−0.0249 (7)−0.0269 (7)0.0045 (6)
O40.0771 (8)0.0539 (7)0.0532 (7)−0.0195 (6)−0.0222 (6)0.0127 (5)
O50.0625 (8)0.0858 (10)0.0740 (9)−0.0021 (7)−0.0046 (7)0.0327 (8)
N10.0589 (8)0.0433 (7)0.0412 (6)−0.0166 (6)−0.0140 (6)0.0035 (5)
N20.0406 (7)0.0577 (8)0.0547 (8)−0.0074 (6)−0.0118 (6)0.0118 (6)
C10.0414 (7)0.0455 (8)0.0390 (7)−0.0120 (6)−0.0037 (6)−0.0021 (6)
C20.0358 (7)0.0489 (8)0.0385 (7)−0.0118 (6)−0.0021 (5)−0.0012 (6)
C30.0578 (9)0.0642 (10)0.0419 (8)−0.0195 (8)−0.0102 (7)−0.0015 (7)
C40.0777 (12)0.0718 (12)0.0552 (10)−0.0325 (10)−0.0098 (9)−0.0160 (9)
C50.0925 (14)0.0533 (10)0.0649 (11)−0.0313 (10)−0.0081 (10)−0.0085 (8)
C60.0831 (13)0.0480 (9)0.0519 (9)−0.0214 (9)−0.0140 (9)0.0021 (7)
C70.0423 (7)0.0508 (8)0.0412 (7)−0.0114 (6)−0.0055 (6)0.0025 (6)
C80.0795 (13)0.0520 (10)0.0739 (12)−0.0156 (9)−0.0132 (10)0.0151 (9)
C90.0414 (7)0.0416 (7)0.0395 (7)−0.0060 (6)−0.0121 (6)−0.0003 (6)
C100.0416 (8)0.0423 (8)0.0523 (8)−0.0018 (6)−0.0128 (6)0.0067 (6)
C110.0490 (8)0.0429 (8)0.0513 (8)−0.0075 (7)−0.0112 (7)0.0086 (6)
C120.0421 (7)0.0464 (8)0.0421 (7)−0.0091 (6)−0.0121 (6)0.0007 (6)
C130.0422 (8)0.0577 (9)0.0530 (9)0.0001 (7)−0.0135 (7)0.0145 (7)
C140.0466 (8)0.0538 (9)0.0482 (8)−0.0035 (7)−0.0124 (7)0.0157 (7)
C150.0518 (9)0.0476 (8)0.0523 (9)−0.0137 (7)−0.0066 (7)0.0011 (7)
C160.0546 (10)0.0624 (11)0.0671 (11)−0.0200 (8)−0.0032 (8)0.0051 (8)
Geometric parameters (Å, °) top
S1—O11.4267 (11)C5—C61.370 (3)
S1—O21.4328 (12)C5—H50.9300
S1—N11.6241 (13)C6—H60.9300
S1—C91.7525 (16)C8—H8A0.9600
O3—C71.2104 (19)C8—H8B0.9600
O4—C71.3237 (18)C8—H8C0.9600
O4—C81.444 (2)C9—C101.383 (2)
O5—C151.208 (2)C9—C141.387 (2)
N1—C11.4074 (19)C10—C111.377 (2)
N1—H1n0.861 (11)C10—H100.9300
N2—C151.361 (2)C11—C121.392 (2)
N2—C121.394 (2)C11—H110.9300
N2—H2n0.859 (16)C12—C131.394 (2)
C1—C61.381 (2)C13—C141.370 (2)
C1—C21.407 (2)C13—H130.9300
C2—C31.391 (2)C14—H140.9300
C2—C71.479 (2)C15—C161.499 (2)
C3—C41.373 (3)C16—H16A0.9600
C3—H30.9300C16—H16B0.9600
C4—C51.371 (3)C16—H16C0.9600
C4—H40.9300
O1—S1—O2117.99 (7)O4—C8—H8A109.5
O1—S1—N1110.76 (7)O4—C8—H8B109.5
O2—S1—N1103.67 (7)H8A—C8—H8B109.5
O1—S1—C9107.67 (7)O4—C8—H8C109.5
O2—S1—C9109.45 (7)H8A—C8—H8C109.5
N1—S1—C9106.78 (7)H8B—C8—H8C109.5
C7—O4—C8116.93 (14)C10—C9—C14119.92 (15)
C1—N1—S1126.68 (11)C10—C9—S1119.16 (11)
C1—N1—H1N113.9 (13)C14—C9—S1120.77 (12)
S1—N1—H1N116.7 (13)C11—C10—C9120.63 (14)
C15—N2—C12128.75 (13)C11—C10—H10119.7
C15—N2—H2N116.5 (14)C9—C10—H10119.7
C12—N2—H2N114.4 (14)C10—C11—C12119.75 (14)
C6—C1—C2119.11 (14)C10—C11—H11120.1
C6—C1—N1121.77 (14)C12—C11—H11120.1
C2—C1—N1119.12 (13)C11—C12—N2123.53 (14)
C3—C2—C1118.39 (14)C11—C12—C13119.09 (15)
C3—C2—C7120.74 (14)N2—C12—C13117.38 (13)
C1—C2—C7120.86 (13)C14—C13—C12120.98 (14)
C4—C3—C2121.80 (16)C14—C13—H13119.5
C4—C3—H3119.1C12—C13—H13119.5
C2—C3—H3119.1C13—C14—C9119.58 (14)
C5—C4—C3118.83 (17)C13—C14—H14120.2
C5—C4—H4120.6C9—C14—H14120.2
C3—C4—H4120.6O5—C15—N2123.33 (16)
C6—C5—C4121.09 (17)O5—C15—C16122.38 (16)
C6—C5—H5119.5N2—C15—C16114.29 (14)
C4—C5—H5119.5C15—C16—H16A109.5
C5—C6—C1120.77 (17)C15—C16—H16B109.5
C5—C6—H6119.6H16A—C16—H16B109.5
C1—C6—H6119.6C15—C16—H16C109.5
O3—C7—O4122.11 (15)H16A—C16—H16C109.5
O3—C7—C2125.32 (14)H16B—C16—H16C109.5
O4—C7—C2112.57 (13)
O1—S1—N1—C158.39 (15)C1—C2—C7—O4−176.68 (13)
O2—S1—N1—C1−174.12 (13)O1—S1—C9—C1030.05 (15)
C9—S1—N1—C1−58.57 (15)O2—S1—C9—C10−99.35 (14)
S1—N1—C1—C6−17.9 (2)N1—S1—C9—C10149.04 (13)
S1—N1—C1—C2162.13 (12)O1—S1—C9—C14−154.60 (13)
C6—C1—C2—C3−0.3 (2)O2—S1—C9—C1475.99 (14)
N1—C1—C2—C3179.62 (14)N1—S1—C9—C14−35.61 (15)
C6—C1—C2—C7179.24 (15)C14—C9—C10—C11−1.9 (2)
N1—C1—C2—C7−0.8 (2)S1—C9—C10—C11173.44 (12)
C1—C2—C3—C40.4 (2)C9—C10—C11—C120.8 (2)
C7—C2—C3—C4−179.21 (16)C10—C11—C12—N2−178.72 (15)
C2—C3—C4—C50.0 (3)C10—C11—C12—C131.4 (2)
C3—C4—C5—C6−0.4 (3)C15—N2—C12—C1113.1 (3)
C4—C5—C6—C10.4 (3)C15—N2—C12—C13−167.05 (17)
C2—C1—C6—C50.0 (3)C11—C12—C13—C14−2.5 (3)
N1—C1—C6—C5180.00 (17)N2—C12—C13—C14177.67 (16)
C8—O4—C7—O3−1.4 (2)C12—C13—C14—C91.3 (3)
C8—O4—C7—C2178.13 (15)C10—C9—C14—C130.9 (3)
C3—C2—C7—O3−177.58 (16)S1—C9—C14—C13−174.40 (13)
C1—C2—C7—O32.9 (2)C12—N2—C15—O5−2.5 (3)
C3—C2—C7—O42.9 (2)C12—N2—C15—C16177.36 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O30.861 (11)1.902 (16)2.6266 (18)140.9 (17)
N2—H2n···O2i0.859 (16)2.311 (17)3.0888 (19)150.7 (15)
C10—H10···O1ii0.932.573.330 (2)140
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O30.861 (11)1.902 (16)2.6266 (18)140.9 (17)
N2—H2n···O2i0.859 (16)2.311 (17)3.0888 (19)150.7 (15)
C10—H10···O1ii0.932.573.330 (2)140
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+2.
references
References top

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Khan, I. U., Ahmad, W., Sharif, S., Ali, S. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o1218.

Korolkovas, A. (1988). Essentials of Medicinal Chemistry, 2nd ed., pp. 699–716. New York: Wiley.

Mandell, G. L. & Sande, M. A. (1992). In Goodman and Gilman, The Pharmacological Basis of Therapeutics 2, edited by A. Gilman, T. W. Rall, A. S. Nies & P. Taylor, 8th ed., pp. 1047–1057. Singapore: McGraw–Hill.

Sharif, S., Iqbal, H., Khan, I. U., John, P. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o1288.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.