organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N-(2-Amino-3,5-di­bromo­benz­yl)-N-methyl­cyclo­hexan-1-aminium p-toluene­sulfonate

aDepartment of Pharmaceutical Chemistry, KLEU's College of Pharmacy, Belgaum, India, and bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
*Correspondence e-mail: sudarshan@sscu.iisc.ernet.in

(Received 26 June 2011; accepted 7 July 2011; online 13 July 2011)

The title compound, C14H21Br2N2+·C7H7O3S, features a salt of protonated bromhexine, a pharmaceutical used in the treatment of respiratory disorders, and the p-toluenesulfonate anion. The crystal packing is stabilized by inter­molecular N—H⋯O, N—H⋯Br and C—H⋯O hydrogen bonds.

Related literature

For salts of bromhexine, see: Koo et al. (1984[Koo, C. H., Jung, Y. J. & Lee, S. W. (1984). Arch. Pharm. Res. 7, 115-120.]); Shimizu & Nishigaki (1983[Shimizu, N. & Nishigaki, S. (1983). Acta Cryst. C39, 502-504.]); Shimizu et al. (1983[Shimizu, N. & Nishigaki, S. (1983). Acta Cryst. C39, 502-504.], 1984[Shimizu, N., Nishigaki, S., Nakai, Y. & Osaki, K. (1984). Acta Cryst. C40, 902.]).

[Scheme 1]

Experimental

Crystal data
  • C14H21Br2N2+·C7H7O3S

  • Mr = 548.32

  • Monoclinic, P 21 /c

  • a = 14.008 (5) Å

  • b = 10.404 (5) Å

  • c = 17.157 (5) Å

  • β = 110.148 (5)°

  • V = 2347.4 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.57 mm−1

  • T = 293 K

  • 0.30 × 0.10 × 0.08 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.414, Tmax = 0.764

  • 14496 measured reflections

  • 4608 independent reflections

  • 2343 reflections with I > 2σ(I)

  • Rint = 0.052

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.114

  • S = 1.00

  • 4608 reflections

  • 272 parameters

  • 4 restraints

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

  • Δρmax = 0.78 e Å−3

  • Δρmin = −0.71 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O2i 0.85 (3) 1.93 (4) 2.756 (4) 161 (4)
N2—H2A⋯O1ii 0.85 (3) 2.11 (3) 2.926 (4) 162 (4)
N2—H2B⋯Br1 0.84 (2) 2.67 (3) 3.068 (3) 111 (2)
C7—H7A⋯O2 0.97 2.47 3.257 (5) 138
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x+1, -y+1, -z.

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

There are only three crystal structures on Bromhexine reported in the literature. Analysis of all reported structure of Bromhexine indicates that the N-methyl amino group of Bromhexine is basic in nature and forms a salt with HCl (Koo et al., 1984), salicylic acid (Shimizu et al., 1984) and 1,2-benzisothiazol-3(2H)-one 1,1-dioxide (Shimizu et al., 1983). A similar case is found in the current study where Bromhexine forms a salt with paratoluene sulfonic acid by transfering a proton from sulfonic acid group to N-methyl amino group. The crystal structure is stabilized by N—H···O, N—H···Br and C—H···O intermolecular interactions.

Related literature top

For salts of bromhexine, see: Koo et al. (1984); Shimizu & Nishigaki (1983); Shimizu et al. (1983, 1984).

Experimental top

An equimolar ratio (1:1) of Bromhexine and para-toluene sulfonic acid were dissolved in ethanol and kept for crystallization at room temperature yielding plate shape crystals.

Refinement top

In the absence of significant anomalous dispersion effects, Friedel pairs were merged. H1 was freely refined, but all other H atoms were positioned geometrically and refined using a riding model.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
N-(2-Amino-3,5-dibromobenzyl)-N-methylcyclohexan-1-aminium p-toluenesulfonate top
Crystal data top
C14H21Br2N2+·C7H7O3SF(000) = 1112
Mr = 548.32Dx = 1.551 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2343 reflections
a = 14.008 (5) Åθ = 2.3–26.0°
b = 10.404 (5) ŵ = 3.57 mm1
c = 17.157 (5) ÅT = 293 K
β = 110.148 (5)°Needle, colorless
V = 2347.4 (16) Å30.30 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
4608 independent reflections
Radiation source: fine-focus sealed tube2343 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ϕ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1517
Tmin = 0.414, Tmax = 0.764k = 1112
14496 measured reflectionsl = 2121
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.050P)2]
where P = (Fo2 + 2Fc2)/3
4608 reflections(Δ/σ)max < 0.001
272 parametersΔρmax = 0.78 e Å3
4 restraintsΔρmin = 0.71 e Å3
Crystal data top
C14H21Br2N2+·C7H7O3SV = 2347.4 (16) Å3
Mr = 548.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.008 (5) ŵ = 3.57 mm1
b = 10.404 (5) ÅT = 293 K
c = 17.157 (5) Å0.30 × 0.10 × 0.08 mm
β = 110.148 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
4608 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2343 reflections with I > 2σ(I)
Tmin = 0.414, Tmax = 0.764Rint = 0.052
14496 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0474 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.78 e Å3
4608 reflectionsΔρmin = 0.71 e Å3
272 parameters
Special details top

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 > 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
Br10.06429 (3)0.35949 (7)0.08435 (3)0.0854 (3)
Br20.14386 (4)0.34597 (7)0.25939 (3)0.0893 (3)
N10.5129 (2)0.2898 (3)0.1723 (2)0.0330 (11)
N20.2969 (2)0.3732 (5)0.0301 (2)0.0666 (16)
C10.2959 (3)0.3727 (4)0.1844 (2)0.0411 (14)
C20.1945 (3)0.3605 (4)0.1704 (2)0.0500 (16)
C30.1249 (3)0.3565 (4)0.0899 (3)0.0548 (18)
C40.1613 (3)0.3629 (4)0.0259 (2)0.0466 (14)
C50.2651 (3)0.3701 (4)0.0360 (2)0.0411 (14)
C60.3321 (3)0.3795 (4)0.1181 (2)0.0356 (12)
C70.4449 (3)0.4040 (4)0.1372 (2)0.0406 (14)
C80.6233 (3)0.3192 (4)0.1819 (2)0.0424 (14)
C90.6906 (3)0.2040 (5)0.2153 (3)0.0628 (16)
C100.8014 (3)0.2361 (6)0.2280 (3)0.095 (3)
C110.8394 (3)0.3534 (5)0.2807 (3)0.080 (2)
C120.7710 (3)0.4670 (5)0.2473 (3)0.084 (2)
C130.6605 (3)0.4379 (4)0.2365 (3)0.0639 (18)
C140.4737 (3)0.1716 (4)0.1239 (2)0.0419 (14)
S10.48360 (7)0.75893 (10)0.09405 (5)0.0358 (3)
O10.50153 (19)0.6560 (3)0.04343 (15)0.0440 (10)
O20.48544 (18)0.7100 (3)0.17409 (14)0.0436 (9)
O30.5480 (2)0.8695 (3)0.10102 (18)0.0572 (11)
C150.3570 (3)0.8101 (4)0.0421 (2)0.0317 (11)
C160.2762 (3)0.7309 (4)0.0396 (2)0.0486 (16)
C170.1786 (3)0.7695 (5)0.0001 (3)0.0632 (19)
C180.1571 (3)0.8892 (5)0.0385 (3)0.0596 (19)
C190.2376 (3)0.9666 (5)0.0353 (2)0.0599 (17)
C200.3377 (3)0.9273 (4)0.0037 (2)0.0455 (16)
C210.0474 (3)0.9326 (6)0.0849 (3)0.097 (2)
H10.510 (3)0.283 (4)0.221 (2)0.039 (12)*
H1A0.341450.376560.238560.0493*
H2A0.3594 (16)0.376 (5)0.025 (2)0.1165*
H2B0.257 (2)0.362 (5)0.0791 (13)0.1165*
H30.055500.349540.080030.0656*
H7A0.465720.474320.176550.0483*
H7B0.455100.431130.086570.0483*
H80.625600.338690.126680.0509*
H9A0.684870.177750.267740.0753*
H9B0.668490.132920.176640.0753*
H10A0.808240.249590.174220.1137*
H10B0.843690.163340.253950.1137*
H11A0.842620.335870.337040.0963*
H11B0.907570.373570.282040.0963*
H12A0.794310.538950.285070.1008*
H12B0.775400.491810.194140.1008*
H13A0.654440.423250.290400.0774*
H13B0.618410.511140.211170.0774*
H14A0.517600.100720.148480.0629*
H14B0.406410.153900.123940.0629*
H14C0.471480.183430.067810.0629*
H160.288960.650830.065240.0582*
H170.125430.715100.001110.0757*
H190.224941.047520.059740.0719*
H200.391140.980300.003550.0546*
H21A0.001150.867210.080530.1456*
H21B0.034251.010930.060740.1456*
H21C0.038240.946860.142270.1456*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0448 (3)0.1514 (7)0.0473 (3)0.0073 (3)0.0002 (2)0.0107 (3)
Br20.0855 (4)0.1380 (7)0.0625 (3)0.0055 (4)0.0488 (3)0.0046 (3)
N10.0363 (18)0.030 (2)0.0331 (18)0.0035 (16)0.0126 (15)0.0005 (17)
N20.049 (2)0.114 (4)0.040 (2)0.006 (3)0.0193 (17)0.007 (2)
C10.043 (2)0.039 (3)0.038 (2)0.002 (2)0.0096 (18)0.001 (2)
C20.053 (3)0.061 (3)0.042 (2)0.001 (3)0.024 (2)0.002 (2)
C30.040 (2)0.073 (4)0.053 (3)0.001 (2)0.018 (2)0.006 (3)
C40.035 (2)0.059 (3)0.039 (2)0.005 (2)0.0042 (18)0.001 (2)
C50.038 (2)0.046 (3)0.039 (2)0.006 (2)0.0130 (18)0.002 (2)
C60.039 (2)0.026 (2)0.041 (2)0.001 (2)0.0128 (18)0.001 (2)
C70.039 (2)0.034 (3)0.044 (2)0.001 (2)0.0081 (18)0.004 (2)
C80.032 (2)0.053 (3)0.042 (2)0.004 (2)0.0124 (17)0.003 (2)
C90.045 (2)0.062 (3)0.072 (3)0.009 (3)0.008 (2)0.017 (3)
C100.045 (3)0.124 (6)0.107 (4)0.011 (4)0.016 (3)0.038 (4)
C110.041 (3)0.110 (5)0.080 (4)0.014 (3)0.008 (2)0.016 (4)
C120.046 (3)0.084 (4)0.101 (4)0.016 (3)0.002 (3)0.018 (4)
C130.040 (2)0.039 (3)0.096 (4)0.005 (2)0.002 (2)0.003 (3)
C140.059 (2)0.026 (3)0.042 (2)0.004 (2)0.019 (2)0.008 (2)
S10.0422 (5)0.0333 (7)0.0320 (5)0.0031 (6)0.0131 (4)0.0001 (5)
O10.0552 (16)0.044 (2)0.0405 (15)0.0049 (14)0.0263 (13)0.0070 (14)
O20.0583 (16)0.0459 (19)0.0260 (13)0.0045 (15)0.0137 (12)0.0001 (13)
O30.0478 (16)0.045 (2)0.070 (2)0.0120 (16)0.0089 (14)0.0067 (16)
C150.043 (2)0.028 (2)0.0253 (18)0.002 (2)0.0133 (16)0.0019 (19)
C160.051 (3)0.041 (3)0.051 (2)0.002 (3)0.014 (2)0.012 (2)
C170.045 (3)0.079 (4)0.062 (3)0.005 (3)0.014 (2)0.016 (3)
C180.050 (3)0.078 (4)0.045 (3)0.012 (3)0.009 (2)0.001 (3)
C190.076 (3)0.039 (3)0.052 (3)0.009 (3)0.006 (2)0.003 (2)
C200.053 (3)0.040 (3)0.035 (2)0.005 (2)0.0042 (19)0.001 (2)
C210.059 (3)0.114 (5)0.096 (4)0.027 (3)0.002 (3)0.012 (4)
Geometric parameters (Å, º) top
Br1—C41.912 (4)C7—H7B0.9700
Br2—C21.898 (4)C8—H80.9800
S1—O11.454 (3)C9—H9B0.9700
S1—O21.456 (3)C9—H9A0.9700
S1—O31.441 (3)C10—H10B0.9700
S1—C151.770 (4)C10—H10A0.9700
N1—C71.512 (5)C11—H11A0.9700
N1—C81.529 (5)C11—H11B0.9700
N1—C141.480 (5)C12—H12A0.9700
N2—C51.354 (5)C12—H12B0.9700
N1—H10.85 (3)C13—H13A0.9700
N2—H2B0.84 (2)C13—H13B0.9700
N2—H2A0.85 (3)C14—H14B0.9600
C1—C21.363 (6)C14—H14C0.9600
C1—C61.398 (5)C14—H14A0.9600
C2—C31.390 (6)C15—C161.389 (6)
C3—C41.362 (6)C15—C201.368 (6)
C4—C51.406 (6)C16—C171.361 (6)
C5—C61.401 (5)C17—C181.394 (7)
C6—C71.521 (6)C18—C191.371 (7)
C8—C91.511 (7)C18—C211.535 (7)
C8—C131.529 (6)C19—C201.391 (6)
C9—C101.528 (7)C16—H160.9300
C10—C111.503 (8)C17—H170.9300
C11—C121.505 (7)C19—H190.9300
C12—C131.525 (7)C20—H200.9300
C1—H1A0.9300C21—H21A0.9600
C3—H30.9300C21—H21B0.9600
C7—H7A0.9700C21—H21C0.9600
Br1···N23.068 (3)H1A···H7A2.5400
Br1···Br2i3.880 (2)H1A···O3viii2.6500
Br2···Br1ii3.880 (2)H2A···H7B2.0100
Br1···H2B2.67 (3)H2A···S1iv3.16 (3)
Br2···H19iii3.1200H2A···O1iv2.11 (3)
S1···H14Civ3.1100H2A···C72.64 (3)
S1···H1v3.15 (3)H2B···Br12.67 (3)
S1···H2Aiv3.16 (3)H2B···H12Biv2.4100
O1···C73.312 (5)H3···H17x2.5200
O1···N2iv2.926 (4)H3···H21Ax2.3900
O2···N1v2.756 (4)H7A···H1A2.5400
O2···C14v3.337 (4)H7A···C132.5900
O2···C73.257 (5)H7A···H13B2.0500
O3···C14vi3.376 (5)H7A···O22.4700
O1···H2Aiv2.11 (3)H7B···N22.5000
O1···H8iv2.8500H7B···O12.6000
O1···H7B2.6000H7B···H82.4400
O1···H7Biv2.6600H7B···O1iv2.6600
O1···H14Civ2.6600H7B···H2A2.0100
O2···H13B2.7100H8···H12B2.5700
O2···H162.8100H8···O1iv2.8500
O2···H7A2.4700H8···H7B2.4400
O2···H9Av2.9100H8···H10A2.5800
O2···H1v1.93 (4)H9A···O2viii2.9100
O3···H202.5300H9A···H12.5500
O3···H1Av2.6500H9B···C142.5900
O3···H14Civ2.8700H9B···H14A2.0300
O3···H20vii2.7300H10A···C18iv2.9200
O3···H14Avi2.6200H10A···C17iv3.0700
N1···O2viii2.756 (4)H10A···H82.5800
N2···Br13.068 (3)H11A···C17viii2.9900
N2···O1iv2.926 (4)H12B···H2Biv2.4100
N2···H7B2.5000H12B···H82.5700
C5···C143.470 (6)H13A···H12.4500
C7···O23.257 (5)H13B···H7A2.0500
C7···O13.312 (5)H13B···O22.7100
C14···C20ix3.411 (6)H13B···C72.5800
C14···O2viii3.337 (4)H14A···O3ix2.6200
C14···O3ix3.376 (5)H14A···H9B2.0300
C14···C53.470 (6)H14A···C92.5400
C20···C14vi3.411 (6)H14B···C53.0300
C1···H12.99 (4)H14B···C20ix3.0600
C3···H21Ax2.8900H14B···C62.5600
C5···H162.9600H14C···O3iv2.8700
C5···H14B3.0300H14C···O1iv2.6600
C6···H162.9600H14C···H20ix2.4700
C6···H14B2.5600H14C···S1iv3.1100
C7···H2A2.64 (3)H16···O22.8100
C7···H13B2.5800H16···C52.9600
C9···H14A2.5400H16···C62.9600
C13···H7A2.5900H17···H21A2.4000
C14···H20ix2.8100H17···H3x2.5200
C14···H9B2.5900H19···Br2xi3.1200
C17···H11Av2.9900H20···O32.5300
C17···H10Aiv3.0700H20···C14vi2.8100
C18···H10Aiv2.9200H20···H14Cvi2.4700
C20···H14Bvi3.0600H20···O3vii2.7300
H1···H13A2.4500H21A···H172.4000
H1···S1viii3.15 (3)H21A···C3x2.8900
H1···H9A2.5500H21A···H3x2.3900
H1···C12.99 (4)H21B···H21Bxii2.5900
H1···O2viii1.93 (4)
O2—S1—O3113.17 (17)C8—C9—H9A110.00
O2—S1—C15105.61 (17)C10—C9—H9B109.00
O3—S1—C15106.95 (19)C11—C10—H10A109.00
O1—S1—O3113.92 (18)C11—C10—H10B109.00
O1—S1—C15105.66 (17)C9—C10—H10B109.00
O1—S1—O2110.80 (17)C9—C10—H10A109.00
C8—N1—C14113.1 (3)H10A—C10—H10B108.00
C7—N1—C8111.2 (3)C10—C11—H11B109.00
C7—N1—C14111.6 (3)C10—C11—H11A109.00
C7—N1—H1103 (3)H11A—C11—H11B108.00
C8—N1—H1107 (3)C12—C11—H11A109.00
C14—N1—H1110 (3)C12—C11—H11B109.00
C5—N2—H2A123 (2)C11—C12—H12A109.00
H2A—N2—H2B114 (3)C13—C12—H12A109.00
C5—N2—H2B122 (2)C13—C12—H12B109.00
C2—C1—C6120.6 (3)C11—C12—H12B109.00
Br2—C2—C3117.9 (3)H12A—C12—H12B108.00
Br2—C2—C1121.4 (3)C12—C13—H13A110.00
C1—C2—C3120.7 (4)C12—C13—H13B109.00
C2—C3—C4118.1 (4)C8—C13—H13A110.00
Br1—C4—C3117.4 (3)C8—C13—H13B109.00
C3—C4—C5124.2 (3)H13A—C13—H13B108.00
Br1—C4—C5118.4 (3)H14B—C14—H14C109.00
N2—C5—C4121.5 (3)N1—C14—H14A110.00
N2—C5—C6122.7 (4)N1—C14—H14B109.00
C4—C5—C6115.7 (3)N1—C14—H14C109.00
C1—C6—C5120.6 (4)H14A—C14—H14B109.00
C5—C6—C7121.0 (3)H14A—C14—H14C109.00
C1—C6—C7118.3 (3)S1—C15—C16120.1 (3)
N1—C7—C6114.8 (3)S1—C15—C20120.5 (3)
C9—C8—C13111.8 (3)C16—C15—C20119.4 (4)
N1—C8—C9111.0 (3)C15—C16—C17120.6 (4)
N1—C8—C13110.3 (3)C16—C17—C18121.1 (4)
C8—C9—C10110.6 (4)C17—C18—C19117.7 (4)
C9—C10—C11113.3 (4)C17—C18—C21121.5 (4)
C10—C11—C12111.2 (4)C19—C18—C21120.7 (5)
C11—C12—C13112.1 (4)C18—C19—C20121.7 (4)
C8—C13—C12110.6 (4)C15—C20—C19119.5 (4)
C6—C1—H1A120.00C15—C16—H16120.00
C2—C1—H1A120.00C17—C16—H16120.00
C2—C3—H3121.00C16—C17—H17119.00
C4—C3—H3121.00C18—C17—H17120.00
N1—C7—H7A109.00C18—C19—H19119.00
C6—C7—H7B109.00C20—C19—H19119.00
N1—C7—H7B109.00C15—C20—H20120.00
C6—C7—H7A109.00C19—C20—H20120.00
H7A—C7—H7B108.00C18—C21—H21A109.00
C13—C8—H8108.00C18—C21—H21B109.00
N1—C8—H8108.00C18—C21—H21C110.00
C9—C8—H8108.00H21A—C21—H21B109.00
H9A—C9—H9B108.00H21A—C21—H21C110.00
C8—C9—H9B110.00H21B—C21—H21C110.00
C10—C9—H9A110.00
O2—S1—C15—C1647.4 (3)N2—C5—C6—C1178.4 (4)
O1—S1—C15—C1670.1 (3)N2—C5—C6—C74.7 (7)
O1—S1—C15—C20109.6 (3)C4—C5—C6—C7172.6 (4)
O3—S1—C15—C2012.1 (4)C4—C5—C6—C14.3 (6)
O2—S1—C15—C20133.0 (3)C1—C6—C7—N175.0 (5)
O3—S1—C15—C16168.2 (3)C5—C6—C7—N1108.1 (4)
C8—N1—C7—C6174.7 (3)N1—C8—C9—C10177.7 (3)
C14—N1—C8—C13176.8 (3)C9—C8—C13—C1255.3 (5)
C7—N1—C8—C9178.8 (3)C13—C8—C9—C1054.1 (5)
C7—N1—C8—C1356.7 (4)N1—C8—C13—C12179.3 (3)
C14—N1—C7—C647.3 (4)C8—C9—C10—C1153.7 (5)
C14—N1—C8—C952.3 (4)C9—C10—C11—C1253.7 (6)
C2—C1—C6—C51.9 (6)C10—C11—C12—C1354.2 (5)
C2—C1—C6—C7175.1 (4)C11—C12—C13—C855.1 (5)
C6—C1—C2—C31.0 (6)S1—C15—C16—C17179.8 (3)
C6—C1—C2—Br2178.1 (3)C20—C15—C16—C170.6 (6)
Br2—C2—C3—C4178.0 (3)S1—C15—C20—C19178.7 (3)
C1—C2—C3—C41.1 (6)C16—C15—C20—C191.7 (5)
C2—C3—C4—Br1179.2 (3)C15—C16—C17—C180.2 (7)
C2—C3—C4—C51.7 (6)C16—C17—C18—C190.0 (7)
C3—C4—C5—N2178.4 (4)C16—C17—C18—C21178.6 (4)
Br1—C4—C5—N20.7 (6)C17—C18—C19—C201.1 (6)
Br1—C4—C5—C6176.6 (3)C21—C18—C19—C20177.6 (4)
C3—C4—C5—C64.3 (6)C18—C19—C20—C151.9 (6)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+3/2, z+1/2; (iv) x+1, y+1, z; (v) x+1, y+1/2, z+1/2; (vi) x, y+1, z; (vii) x+1, y+2, z; (viii) x+1, y1/2, z+1/2; (ix) x, y1, z; (x) x, y+1, z; (xi) x, y+3/2, z1/2; (xii) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2viii0.85 (3)1.93 (4)2.756 (4)161 (4)
N2—H2A···O1iv0.85 (3)2.11 (3)2.926 (4)162 (4)
N2—H2B···Br10.84 (2)2.67 (3)3.068 (3)111 (2)
C7—H7A···O20.97002.47003.257 (5)138.00
C20—H20···O30.93002.53002.905 (5)104.00
Symmetry codes: (iv) x+1, y+1, z; (viii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H21Br2N2+·C7H7O3S
Mr548.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)14.008 (5), 10.404 (5), 17.157 (5)
β (°) 110.148 (5)
V3)2347.4 (16)
Z4
Radiation typeMo Kα
µ (mm1)3.57
Crystal size (mm)0.30 × 0.10 × 0.08
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.414, 0.764
No. of measured, independent and
observed [I > 2σ(I)] reflections
14496, 4608, 2343
Rint0.052
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.114, 1.00
No. of reflections4608
No. of parameters272
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.78, 0.71

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.85 (3)1.93 (4)2.756 (4)161 (4)
N2—H2A···O1ii0.85 (3)2.11 (3)2.926 (4)162 (4)
N2—H2B···Br10.84 (2)2.67 (3)3.068 (3)111 (2)
C7—H7A···O20.97002.47003.257 (5)138.00
C20—H20···O30.93002.53002.905 (5)104.00
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+1, z.
 

Acknowledgements

SM would like to thank the CSIR, India, for a research associateship. The authors thanks Professor T. N. Guru Row for scientific discussions.

References

First citationBruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals
First citationKoo, C. H., Jung, Y. J. & Lee, S. W. (1984). Arch. Pharm. Res. 7, 115–120.  CAS
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationShimizu, N. & Nishigaki, S. (1983). Acta Cryst. C39, 502–504.  CSD CrossRef CAS Web of Science IUCr Journals
First citationShimizu, N., Nishigaki, S., Nakai, Y. & Osaki, K. (1984). Acta Cryst. C40, 902.  CSD CrossRef Web of Science IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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