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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o955.
Published online 2009 April 2. doi:  10.1107/S1600536809011829
PMCID: PMC2977655

Methyl 5-bromo-2-[meth­yl(methyl­sulfon­yl)amino]benzoate

Abstract

The title compound, C10H12BrNO4S, is an inter­mediate in the synthesis of benzothia­zine. The planar methyl ester group (maximum deviation is 0.0065 Å) is oriented at a dihedral angle of 39.09 (13)° with respect to the aromatic ring. In the crystal structure, weak inter­molecular C—H(...)O inter­actions link the mol­ecules into centrosymmetric dimers, through R 2 2(10) ring motifs.

Related literature

For related structures, see: Arshad et al. (2008 [triangle]); Shafiq et al. (2009 [triangle]); Tahir et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring-motifs, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-0o955-scheme1.jpg

Experimental

Crystal data

  • C10H12BrNO4S
  • M r = 322.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o955-efi1.jpg
  • a = 6.0798 (1) Å
  • b = 10.7853 (3) Å
  • c = 19.5206 (4) Å
  • β = 90.306 (1)°
  • V = 1280.00 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.38 mm−1
  • T = 296 K
  • 0.28 × 0.10 × 0.08 mm

Data collection

  • Bruker Kappa APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.675, T max = 0.766
  • 13682 measured reflections
  • 3170 independent reflections
  • 2215 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.084
  • S = 1.04
  • 3170 reflections
  • 157 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011829/hk2657sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011829/hk2657Isup2.hkl

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

Acknowledgments

MS gratefully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a Scholaship under the Indigenous PhD Program (PIN 042–120567-PS2–276).

supplementary crystallographic information

Comment

We have reported the crystal structures of some benzothiazine derivatives (Shafiq et al., 2009; Tahir et al., 2008; Arshad et al., 2008). The title compound is an intermediate for the synthesis of benzothiazine and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is of course planar. The methyl ester moiety B (O2/C7/O1/C8) is also planar, and they are oriented at a dihedral angle of 39.09 (13)°.

In the crystal structure, weak intermolecular C-H···O interactions link the molecules into centrosymmetric dimers through R22(10) ring motifs (Fig. 2) (Bernstein et al., 1995).

Experimental

For the preparation of the title compound, methyl-2-amino-5-bromobenzoate (1 g, 4 mmol) was added into dichloromethane (10 ml) in a round bottom flask. Then, a solution of methanesulfonyl chloride (0.55 g, 48 mmol) in dichloromethane (10 ml) was added to the mixture in 10-15 min. The mixture was stirred at 333-343 K for 2-3 d. After the completion of reaction, the solvent was evaporated under reduced pressure to get methyl-5-bromo-2-[(methylsulfonyl)amino]benzoate. Methyl-5-bromo-2-[(methylsulfonyl)amino] benzoate (1 g, 33 mmol) was added into dimethylformamide (5 ml), and then to a suspension of NaH (0.15 g, 66 mmol) in dimethylformamide (10 ml). The mixture was stirred at room temperature for 14-16 h, then the title compound was obtained.

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C10H12BrNO4SF(000) = 648
Mr = 322.18Dx = 1.672 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3094 reflections
a = 6.0798 (1) Åθ = 2.1–28.3°
b = 10.7853 (3) ŵ = 3.38 mm1
c = 19.5206 (4) ÅT = 296 K
β = 90.306 (1)°Needle, yellow
V = 1280.00 (5) Å30.28 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer3170 independent reflections
Radiation source: fine-focus sealed tube2215 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 7.40 pixels mm-1θmax = 28.3°, θmin = 2.1°
ω scansh = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −11→14
Tmin = 0.675, Tmax = 0.766l = −26→18
13682 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0383P)2 + 0.314P] where P = (Fo2 + 2Fc2)/3
3170 reflections(Δ/σ)max = 0.001
157 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = −0.43 e Å3

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 (Å2)

xyzUiso*/Ueq
Br10.87436 (5)0.17725 (3)−0.05236 (1)0.0593 (1)
S10.31436 (11)0.27222 (6)0.25490 (3)0.0430 (2)
O10.0398 (3)0.36804 (16)0.10645 (9)0.0480 (6)
O20.3103 (3)0.49394 (17)0.07246 (10)0.0615 (7)
O30.1288 (3)0.2765 (2)0.29944 (10)0.0705 (8)
O40.3995 (4)0.38536 (16)0.22837 (9)0.0626 (8)
N10.2453 (3)0.18507 (17)0.18980 (10)0.0405 (7)
C10.3871 (4)0.2795 (2)0.08386 (11)0.0351 (7)
C20.3870 (4)0.1830 (2)0.13144 (11)0.0361 (7)
C30.5263 (4)0.0825 (2)0.12135 (13)0.0485 (9)
C40.6658 (4)0.0783 (3)0.06623 (13)0.0514 (9)
C50.6714 (4)0.1765 (2)0.02093 (12)0.0400 (8)
C60.5328 (4)0.2764 (2)0.02934 (12)0.0392 (8)
C70.2441 (4)0.3927 (2)0.08770 (11)0.0397 (8)
C8−0.1053 (5)0.4740 (3)0.11019 (16)0.0633 (11)
C90.1119 (5)0.0733 (3)0.20332 (15)0.0638 (11)
C100.5280 (6)0.1954 (3)0.29790 (17)0.0701 (12)
H30.525090.017100.152390.0581*
H40.755810.009650.059480.0616*
H60.536830.34191−0.001590.0470*
H8A−0.034510.539220.135470.0948*
H8B−0.238790.450630.132840.0948*
H8C−0.138920.502470.064730.0948*
H9A0.050010.043440.161090.0955*
H9B−0.004460.093710.234420.0955*
H9C0.203330.010210.223250.0955*
H10A0.655970.193350.269310.1052*
H10B0.483240.112140.308290.1052*
H10C0.561980.238470.339660.1052*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0607 (2)0.0684 (2)0.0489 (2)0.0212 (1)0.0172 (1)−0.0024 (1)
S10.0595 (4)0.0354 (3)0.0342 (3)0.0018 (3)0.0066 (3)−0.0019 (3)
O10.0388 (10)0.0460 (10)0.0593 (11)0.0085 (8)0.0031 (8)−0.0053 (9)
O20.0691 (14)0.0389 (10)0.0769 (13)0.0149 (9)0.0276 (11)0.0158 (10)
O30.0828 (16)0.0770 (14)0.0520 (12)0.0100 (12)0.0257 (11)−0.0111 (11)
O40.1016 (17)0.0352 (10)0.0510 (11)−0.0133 (10)0.0043 (11)−0.0036 (9)
N10.0501 (13)0.0370 (11)0.0343 (10)−0.0033 (9)0.0034 (9)0.0001 (9)
C10.0374 (13)0.0351 (12)0.0327 (11)0.0055 (10)−0.0008 (10)−0.0006 (10)
C20.0418 (14)0.0350 (13)0.0315 (11)0.0009 (10)0.0003 (10)−0.0019 (10)
C30.0645 (18)0.0357 (14)0.0452 (14)0.0104 (12)0.0036 (12)0.0063 (11)
C40.0591 (18)0.0456 (15)0.0495 (15)0.0225 (13)0.0059 (13)−0.0023 (12)
C50.0431 (14)0.0423 (14)0.0346 (12)0.0070 (11)0.0020 (10)−0.0058 (10)
C60.0441 (14)0.0387 (13)0.0347 (12)0.0059 (12)0.0025 (10)0.0032 (10)
C70.0476 (16)0.0397 (14)0.0318 (11)0.0093 (12)0.0045 (10)0.0024 (10)
C80.0525 (19)0.068 (2)0.0695 (19)0.0233 (15)0.0025 (15)−0.0155 (16)
C90.064 (2)0.0674 (19)0.0600 (17)−0.0252 (16)0.0120 (14)−0.0095 (15)
C100.081 (2)0.063 (2)0.066 (2)0.0056 (17)−0.0241 (18)−0.0031 (15)

Geometric parameters (Å, °)

Br1—C51.894 (2)C4—C51.380 (4)
S1—O31.429 (2)C5—C61.378 (3)
S1—O41.424 (2)C3—H30.9300
S1—N11.634 (2)C4—H40.9300
S1—C101.751 (4)C6—H60.9300
O1—C71.324 (3)C8—H8A0.9600
O1—C81.446 (4)C8—H8B0.9600
O2—C71.202 (3)C8—H8C0.9600
N1—C21.432 (3)C9—H9A0.9600
N1—C91.478 (4)C9—H9B0.9600
C1—C21.395 (3)C9—H9C0.9600
C1—C61.389 (3)C10—H10A0.9600
C1—C71.501 (3)C10—H10B0.9600
C2—C31.390 (3)C10—H10C0.9600
C3—C41.374 (4)
Br1···O3i3.3255 (19)C1···H8Bx3.0800
Br1···H4ii3.0200C3···H9C2.9100
Br1···H9Aiii3.2200C3···H9A3.0300
Br1···H10Civ2.9700C4···H9Ax3.0000
S1···O13.4929 (19)C6···H8Bx3.0800
S1···C73.537 (2)C9···H32.7700
O1···S13.4929 (19)C9···H10B3.0700
O1···O43.229 (3)H3···C92.7700
O1···N12.843 (3)H3···H9C2.4000
O2···C6v3.319 (3)H3···O4xii2.7600
O3···Br1vi3.3255 (19)H4···Br1ii3.0200
O4···O13.229 (3)H6···O22.5900
O4···C72.900 (3)H6···O2v2.4300
O4···C10vii3.412 (4)H8A···O22.4800
O4···C13.044 (3)H8A···O3xiii2.9200
O2···H62.5900H8B···C1xi3.0800
O2···H8C2.7400H8B···C6xi3.0800
O2···H8A2.4800H8B···H10Bxiii2.5700
O2···H8Cviii2.8700H8C···O22.7400
O2···H6v2.4300H8C···O2viii2.8700
O3···H8Aix2.9200H9A···C33.0300
O3···H9B2.4800H9A···C4xi3.0000
O4···H3vii2.7600H9A···Br1iii3.2200
O4···H9Cvii2.9200H9B···O32.4800
O4···H10Bvii2.6500H9B···H10Axi2.4300
N1···O12.843 (3)H9C···C32.9100
C1···O43.044 (3)H9C···H32.4000
C6···O2v3.319 (3)H9C···O4xii2.9200
C6···C8x3.441 (4)H10A···H9Bx2.4300
C7···S13.537 (2)H10B···C93.0700
C7···O42.900 (3)H10B···O4xii2.6500
C8···C6xi3.441 (4)H10B···H8Bix2.5700
C10···O4xii3.412 (4)H10C···Br1xiv2.9700
O3—S1—O4118.90 (13)C2—C3—H3119.00
O3—S1—N1106.95 (11)C4—C3—H3119.00
O3—S1—C10108.04 (14)C3—C4—H4120.00
O4—S1—N1107.61 (10)C5—C4—H4120.00
O4—S1—C10108.04 (15)C1—C6—H6120.00
N1—S1—C10106.71 (13)C5—C6—H6120.00
C7—O1—C8115.4 (2)O1—C8—H8A109.00
S1—N1—C2118.33 (15)O1—C8—H8B109.00
S1—N1—C9118.00 (17)O1—C8—H8C109.00
C2—N1—C9117.55 (19)H8A—C8—H8B109.00
C2—C1—C6119.7 (2)H8A—C8—H8C109.00
C2—C1—C7124.8 (2)H8B—C8—H8C109.00
C6—C1—C7115.46 (19)N1—C9—H9A109.00
N1—C2—C1121.4 (2)N1—C9—H9B109.00
N1—C2—C3119.6 (2)N1—C9—H9C109.00
C1—C2—C3119.0 (2)H9A—C9—H9B109.00
C2—C3—C4121.0 (2)H9A—C9—H9C109.00
C3—C4—C5119.6 (3)H9B—C9—H9C109.00
Br1—C5—C4120.37 (18)S1—C10—H10A109.00
Br1—C5—C6119.20 (17)S1—C10—H10B109.00
C4—C5—C6120.4 (2)S1—C10—H10C110.00
C1—C6—C5120.2 (2)H10A—C10—H10B109.00
O1—C7—O2124.5 (2)H10A—C10—H10C109.00
O1—C7—C1113.27 (19)H10B—C10—H10C109.00
O2—C7—C1122.1 (2)
O3—S1—N1—C2169.01 (17)C7—C1—C2—C3179.3 (2)
O3—S1—N1—C9−39.1 (2)C2—C1—C6—C52.2 (3)
O4—S1—N1—C240.2 (2)C7—C1—C6—C5−179.9 (2)
O4—S1—N1—C9−167.94 (19)C2—C1—C7—O1−41.7 (3)
C10—S1—N1—C2−75.6 (2)C2—C1—C7—O2141.0 (2)
C10—S1—N1—C976.3 (2)C6—C1—C7—O1140.6 (2)
C8—O1—C7—O2−2.1 (3)C6—C1—C7—O2−36.8 (3)
C8—O1—C7—C1−179.4 (2)N1—C2—C3—C4−179.4 (2)
S1—N1—C2—C1−77.8 (3)C1—C2—C3—C41.2 (4)
S1—N1—C2—C3102.8 (2)C2—C3—C4—C51.4 (4)
C9—N1—C2—C1130.3 (2)C3—C4—C5—Br1176.30 (19)
C9—N1—C2—C3−49.2 (3)C3—C4—C5—C6−2.3 (4)
C6—C1—C2—N1177.6 (2)Br1—C5—C6—C1−178.13 (18)
C6—C1—C2—C3−3.0 (3)C4—C5—C6—C10.5 (4)
C7—C1—C2—N1−0.2 (4)

Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) −x+2, −y, −z; (iii) −x+1, −y, −z; (iv) x, −y+1/2, z−1/2; (v) −x+1, −y+1, −z; (vi) x−1, −y+1/2, z+1/2; (vii) −x+1, y+1/2, −z+1/2; (viii) −x, −y+1, −z; (ix) −x, y−1/2, −z+1/2; (x) x+1, y, z; (xi) x−1, y, z; (xii) −x+1, y−1/2, −z+1/2; (xiii) −x, y+1/2, −z+1/2; (xiv) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O2v0.932.433.319 (3)159

Symmetry codes: (v) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2657).

References

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  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
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