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

Maste, M.M.; Mahapatra, S.; Ramachandran, K.K.; Venugopala, K.N.; Bhat, A.R.

doi:10.1107/S1600536811027358

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2032

doi:10.1107/S1600536811027358

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

Meenaxi M. Maste,^a Sudarshan Mahapatra,^b ^* Krishna Kumar Ramachandran,^b K. N. Venugopala ^b and A. R. Bhat ^a

^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 ); Shimizu & Nishigaki (1983 ); Shimizu et al. (1983, 1984 ).

Experimental

Crystal data

C₁₄H₂₁Br₂N₂⁺·C₇H₇O₃S⁻
M_r = 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 ) T_min = 0.414, T_max = 0.764
14496 measured reflections
4608 independent reflections
2343 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 1998); 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 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811027358/bt5564sup1.cif

Supporting information file. DOI: 10.1107/S1600536811027358/bt5564Isup2.mol

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027358/bt5564Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811027358/bt5564Isup4.cml

checkCIF report

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.

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

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⁺·C₇H₇O₃S⁻	F(000) = 1112
M_r = 548.32	D_x = 1.551 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2343 reflections
a = 14.008 (5) Å	θ = 2.3–26.0°
b = 10.404 (5) Å	µ = 3.57 mm⁻¹
c = 17.157 (5) Å	T = 293 K
β = 110.148 (5)°	Needle, colorless
V = 2347.4 (16) Å³	0.30 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4608 independent reflections
Radiation source: fine-focus sealed tube	2343 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→17
T_min = 0.414, T_max = 0.764	k = −11→12
14496 measured reflections	l = −21→21

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.050P)²] where P = (F_o² + 2F_c²)/3
4608 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.78 e Å⁻³
4 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₁₄H₂₁Br₂N₂⁺·C₇H₇O₃S⁻	V = 2347.4 (16) Å³
M_r = 548.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.008 (5) Å	µ = 3.57 mm⁻¹
b = 10.404 (5) Å	T = 293 K
c = 17.157 (5) Å	0.30 × 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)
T_min = 0.414, T_max = 0.764	R_int = 0.052
14496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	4 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.78 e Å⁻³
4608 reflections	Δρ_min = −0.71 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Br1	0.06429 (3)	0.35949 (7)	−0.08435 (3)	0.0854 (3)
Br2	0.14386 (4)	0.34597 (7)	0.25939 (3)	0.0893 (3)
N1	0.5129 (2)	0.2898 (3)	0.1723 (2)	0.0330 (11)
N2	0.2969 (2)	0.3732 (5)	−0.0301 (2)	0.0666 (16)
C1	0.2959 (3)	0.3727 (4)	0.1844 (2)	0.0411 (14)
C2	0.1945 (3)	0.3605 (4)	0.1704 (2)	0.0500 (16)
C3	0.1249 (3)	0.3565 (4)	0.0899 (3)	0.0548 (18)
C4	0.1613 (3)	0.3629 (4)	0.0259 (2)	0.0466 (14)
C5	0.2651 (3)	0.3701 (4)	0.0360 (2)	0.0411 (14)
C6	0.3321 (3)	0.3795 (4)	0.1181 (2)	0.0356 (12)
C7	0.4449 (3)	0.4040 (4)	0.1372 (2)	0.0406 (14)
C8	0.6233 (3)	0.3192 (4)	0.1819 (2)	0.0424 (14)
C9	0.6906 (3)	0.2040 (5)	0.2153 (3)	0.0628 (16)
C10	0.8014 (3)	0.2361 (6)	0.2280 (3)	0.095 (3)
C11	0.8394 (3)	0.3534 (5)	0.2807 (3)	0.080 (2)
C12	0.7710 (3)	0.4670 (5)	0.2473 (3)	0.084 (2)
C13	0.6605 (3)	0.4379 (4)	0.2365 (3)	0.0639 (18)
C14	0.4737 (3)	0.1716 (4)	0.1239 (2)	0.0419 (14)
S1	0.48360 (7)	0.75893 (10)	0.09405 (5)	0.0358 (3)
O1	0.50153 (19)	0.6560 (3)	0.04343 (15)	0.0440 (10)
O2	0.48544 (18)	0.7100 (3)	0.17409 (14)	0.0436 (9)
O3	0.5480 (2)	0.8695 (3)	0.10102 (18)	0.0572 (11)
C15	0.3570 (3)	0.8101 (4)	0.0421 (2)	0.0317 (11)
C16	0.2762 (3)	0.7309 (4)	0.0396 (2)	0.0486 (16)
C17	0.1786 (3)	0.7695 (5)	0.0001 (3)	0.0632 (19)
C18	0.1571 (3)	0.8892 (5)	−0.0385 (3)	0.0596 (19)
C19	0.2376 (3)	0.9666 (5)	−0.0353 (2)	0.0599 (17)
C20	0.3377 (3)	0.9273 (4)	0.0037 (2)	0.0455 (16)
C21	0.0474 (3)	0.9326 (6)	−0.0849 (3)	0.097 (2)
H1	0.510 (3)	0.283 (4)	0.221 (2)	0.039 (12)*
H1A	0.34145	0.37656	0.23856	0.0493*
H2A	0.3594 (16)	0.376 (5)	−0.025 (2)	0.1165*
H2B	0.257 (2)	0.362 (5)	−0.0791 (13)	0.1165*
H3	0.05550	0.34954	0.08003	0.0656*
H7A	0.46572	0.47432	0.17655	0.0483*
H7B	0.45510	0.43113	0.08657	0.0483*
H8	0.62560	0.33869	0.12668	0.0509*
H9A	0.68487	0.17775	0.26774	0.0753*
H9B	0.66849	0.13292	0.17664	0.0753*
H10A	0.80824	0.24959	0.17422	0.1137*
H10B	0.84369	0.16334	0.25395	0.1137*
H11A	0.84262	0.33587	0.33704	0.0963*
H11B	0.90757	0.37357	0.28204	0.0963*
H12A	0.79431	0.53895	0.28507	0.1008*
H12B	0.77540	0.49181	0.19414	0.1008*
H13A	0.65444	0.42325	0.29040	0.0774*
H13B	0.61841	0.51114	0.21117	0.0774*
H14A	0.51760	0.10072	0.14848	0.0629*
H14B	0.40641	0.15390	0.12394	0.0629*
H14C	0.47148	0.18343	0.06781	0.0629*
H16	0.28896	0.65083	0.06524	0.0582*
H17	0.12543	0.71510	−0.00111	0.0757*
H19	0.22494	1.04752	−0.05974	0.0719*
H20	0.39114	0.98030	0.00355	0.0546*
H21A	0.00115	0.86721	−0.08053	0.1456*
H21B	0.03425	1.01093	−0.06074	0.1456*
H21C	0.03824	0.94686	−0.14227	0.1456*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0448 (3)	0.1514 (7)	0.0473 (3)	0.0073 (3)	−0.0002 (2)	−0.0107 (3)
Br2	0.0855 (4)	0.1380 (7)	0.0625 (3)	0.0055 (4)	0.0488 (3)	−0.0046 (3)
N1	0.0363 (18)	0.030 (2)	0.0331 (18)	−0.0035 (16)	0.0126 (15)	−0.0005 (17)
N2	0.049 (2)	0.114 (4)	0.040 (2)	0.006 (3)	0.0193 (17)	0.007 (2)
C1	0.043 (2)	0.039 (3)	0.038 (2)	0.002 (2)	0.0096 (18)	−0.001 (2)
C2	0.053 (3)	0.061 (3)	0.042 (2)	0.001 (3)	0.024 (2)	−0.002 (2)
C3	0.040 (2)	0.073 (4)	0.053 (3)	−0.001 (2)	0.018 (2)	−0.006 (3)
C4	0.035 (2)	0.059 (3)	0.039 (2)	0.005 (2)	0.0042 (18)	−0.001 (2)
C5	0.038 (2)	0.046 (3)	0.039 (2)	0.006 (2)	0.0130 (18)	−0.002 (2)
C6	0.039 (2)	0.026 (2)	0.041 (2)	0.001 (2)	0.0128 (18)	0.001 (2)
C7	0.039 (2)	0.034 (3)	0.044 (2)	−0.001 (2)	0.0081 (18)	0.004 (2)
C8	0.032 (2)	0.053 (3)	0.042 (2)	−0.004 (2)	0.0124 (17)	0.003 (2)
C9	0.045 (2)	0.062 (3)	0.072 (3)	0.009 (3)	0.008 (2)	−0.017 (3)
C10	0.045 (3)	0.124 (6)	0.107 (4)	0.011 (4)	0.016 (3)	−0.038 (4)
C11	0.041 (3)	0.110 (5)	0.080 (4)	−0.014 (3)	0.008 (2)	−0.016 (4)
C12	0.046 (3)	0.084 (4)	0.101 (4)	−0.016 (3)	−0.002 (3)	0.018 (4)
C13	0.040 (2)	0.039 (3)	0.096 (4)	−0.005 (2)	0.002 (2)	0.003 (3)
C14	0.059 (2)	0.026 (3)	0.042 (2)	−0.004 (2)	0.019 (2)	−0.008 (2)
S1	0.0422 (5)	0.0333 (7)	0.0320 (5)	−0.0031 (6)	0.0131 (4)	0.0001 (5)
O1	0.0552 (16)	0.044 (2)	0.0405 (15)	0.0049 (14)	0.0263 (13)	−0.0070 (14)
O2	0.0583 (16)	0.0459 (19)	0.0260 (13)	0.0045 (15)	0.0137 (12)	0.0001 (13)
O3	0.0478 (16)	0.045 (2)	0.070 (2)	−0.0120 (16)	0.0089 (14)	0.0067 (16)
C15	0.043 (2)	0.028 (2)	0.0253 (18)	−0.002 (2)	0.0133 (16)	−0.0019 (19)
C16	0.051 (3)	0.041 (3)	0.051 (2)	−0.002 (3)	0.014 (2)	0.012 (2)
C17	0.045 (3)	0.079 (4)	0.062 (3)	−0.005 (3)	0.014 (2)	0.016 (3)
C18	0.050 (3)	0.078 (4)	0.045 (3)	0.012 (3)	0.009 (2)	0.001 (3)
C19	0.076 (3)	0.039 (3)	0.052 (3)	0.009 (3)	0.006 (2)	0.003 (2)
C20	0.053 (3)	0.040 (3)	0.035 (2)	−0.005 (2)	0.0042 (19)	−0.001 (2)
C21	0.059 (3)	0.114 (5)	0.096 (4)	0.027 (3)	−0.002 (3)	0.012 (4)

Geometric parameters (Å, º) top

Br1—C4	1.912 (4)	C7—H7B	0.9700
Br2—C2	1.898 (4)	C8—H8	0.9800
S1—O1	1.454 (3)	C9—H9B	0.9700
S1—O2	1.456 (3)	C9—H9A	0.9700
S1—O3	1.441 (3)	C10—H10B	0.9700
S1—C15	1.770 (4)	C10—H10A	0.9700
N1—C7	1.512 (5)	C11—H11A	0.9700
N1—C8	1.529 (5)	C11—H11B	0.9700
N1—C14	1.480 (5)	C12—H12A	0.9700
N2—C5	1.354 (5)	C12—H12B	0.9700
N1—H1	0.85 (3)	C13—H13A	0.9700
N2—H2B	0.84 (2)	C13—H13B	0.9700
N2—H2A	0.85 (3)	C14—H14B	0.9600
C1—C2	1.363 (6)	C14—H14C	0.9600
C1—C6	1.398 (5)	C14—H14A	0.9600
C2—C3	1.390 (6)	C15—C16	1.389 (6)
C3—C4	1.362 (6)	C15—C20	1.368 (6)
C4—C5	1.406 (6)	C16—C17	1.361 (6)
C5—C6	1.401 (5)	C17—C18	1.394 (7)
C6—C7	1.521 (6)	C18—C19	1.371 (7)
C8—C9	1.511 (7)	C18—C21	1.535 (7)
C8—C13	1.529 (6)	C19—C20	1.391 (6)
C9—C10	1.528 (7)	C16—H16	0.9300
C10—C11	1.503 (8)	C17—H17	0.9300
C11—C12	1.505 (7)	C19—H19	0.9300
C12—C13	1.525 (7)	C20—H20	0.9300
C1—H1A	0.9300	C21—H21A	0.9600
C3—H3	0.9300	C21—H21B	0.9600
C7—H7A	0.9700	C21—H21C	0.9600

Br1···N2	3.068 (3)	H1A···H7A	2.5400
Br1···Br2ⁱ	3.880 (2)	H1A···O3^viii	2.6500
Br2···Br1ⁱⁱ	3.880 (2)	H2A···H7B	2.0100
Br1···H2B	2.67 (3)	H2A···S1^iv	3.16 (3)
Br2···H19ⁱⁱⁱ	3.1200	H2A···O1^iv	2.11 (3)
S1···H14C^iv	3.1100	H2A···C7	2.64 (3)
S1···H1^v	3.15 (3)	H2B···Br1	2.67 (3)
S1···H2A^iv	3.16 (3)	H2B···H12B^iv	2.4100
O1···C7	3.312 (5)	H3···H17^x	2.5200
O1···N2^iv	2.926 (4)	H3···H21A^x	2.3900
O2···N1^v	2.756 (4)	H7A···H1A	2.5400
O2···C14^v	3.337 (4)	H7A···C13	2.5900
O2···C7	3.257 (5)	H7A···H13B	2.0500
O3···C14^vi	3.376 (5)	H7A···O2	2.4700
O1···H2A^iv	2.11 (3)	H7B···N2	2.5000
O1···H8^iv	2.8500	H7B···O1	2.6000
O1···H7B	2.6000	H7B···H8	2.4400
O1···H7B^iv	2.6600	H7B···O1^iv	2.6600
O1···H14C^iv	2.6600	H7B···H2A	2.0100
O2···H13B	2.7100	H8···H12B	2.5700
O2···H16	2.8100	H8···O1^iv	2.8500
O2···H7A	2.4700	H8···H7B	2.4400
O2···H9A^v	2.9100	H8···H10A	2.5800
O2···H1^v	1.93 (4)	H9A···O2^viii	2.9100
O3···H20	2.5300	H9A···H1	2.5500
O3···H1A^v	2.6500	H9B···C14	2.5900
O3···H14C^iv	2.8700	H9B···H14A	2.0300
O3···H20^vii	2.7300	H10A···C18^iv	2.9200
O3···H14A^vi	2.6200	H10A···C17^iv	3.0700
N1···O2^viii	2.756 (4)	H10A···H8	2.5800
N2···Br1	3.068 (3)	H11A···C17^viii	2.9900
N2···O1^iv	2.926 (4)	H12B···H2B^iv	2.4100
N2···H7B	2.5000	H12B···H8	2.5700
C5···C14	3.470 (6)	H13A···H1	2.4500
C7···O2	3.257 (5)	H13B···H7A	2.0500
C7···O1	3.312 (5)	H13B···O2	2.7100
C14···C20^ix	3.411 (6)	H13B···C7	2.5800
C14···O2^viii	3.337 (4)	H14A···O3^ix	2.6200
C14···O3^ix	3.376 (5)	H14A···H9B	2.0300
C14···C5	3.470 (6)	H14A···C9	2.5400
C20···C14^vi	3.411 (6)	H14B···C5	3.0300
C1···H1	2.99 (4)	H14B···C20^ix	3.0600
C3···H21A^x	2.8900	H14B···C6	2.5600
C5···H16	2.9600	H14C···O3^iv	2.8700
C5···H14B	3.0300	H14C···O1^iv	2.6600
C6···H16	2.9600	H14C···H20^ix	2.4700
C6···H14B	2.5600	H14C···S1^iv	3.1100
C7···H2A	2.64 (3)	H16···O2	2.8100
C7···H13B	2.5800	H16···C5	2.9600
C9···H14A	2.5400	H16···C6	2.9600
C13···H7A	2.5900	H17···H21A	2.4000
C14···H20^ix	2.8100	H17···H3^x	2.5200
C14···H9B	2.5900	H19···Br2^xi	3.1200
C17···H11A^v	2.9900	H20···O3	2.5300
C17···H10A^iv	3.0700	H20···C14^vi	2.8100
C18···H10A^iv	2.9200	H20···H14C^vi	2.4700
C20···H14B^vi	3.0600	H20···O3^vii	2.7300
H1···H13A	2.4500	H21A···H17	2.4000
H1···S1^viii	3.15 (3)	H21A···C3^x	2.8900
H1···H9A	2.5500	H21A···H3^x	2.3900
H1···C1	2.99 (4)	H21B···H21B^xii	2.5900
H1···O2^viii	1.93 (4)

O2—S1—O3	113.17 (17)	C8—C9—H9A	110.00
O2—S1—C15	105.61 (17)	C10—C9—H9B	109.00
O3—S1—C15	106.95 (19)	C11—C10—H10A	109.00
O1—S1—O3	113.92 (18)	C11—C10—H10B	109.00
O1—S1—C15	105.66 (17)	C9—C10—H10B	109.00
O1—S1—O2	110.80 (17)	C9—C10—H10A	109.00
C8—N1—C14	113.1 (3)	H10A—C10—H10B	108.00
C7—N1—C8	111.2 (3)	C10—C11—H11B	109.00
C7—N1—C14	111.6 (3)	C10—C11—H11A	109.00
C7—N1—H1	103 (3)	H11A—C11—H11B	108.00
C8—N1—H1	107 (3)	C12—C11—H11A	109.00
C14—N1—H1	110 (3)	C12—C11—H11B	109.00
C5—N2—H2A	123 (2)	C11—C12—H12A	109.00
H2A—N2—H2B	114 (3)	C13—C12—H12A	109.00
C5—N2—H2B	122 (2)	C13—C12—H12B	109.00
C2—C1—C6	120.6 (3)	C11—C12—H12B	109.00
Br2—C2—C3	117.9 (3)	H12A—C12—H12B	108.00
Br2—C2—C1	121.4 (3)	C12—C13—H13A	110.00
C1—C2—C3	120.7 (4)	C12—C13—H13B	109.00
C2—C3—C4	118.1 (4)	C8—C13—H13A	110.00
Br1—C4—C3	117.4 (3)	C8—C13—H13B	109.00
C3—C4—C5	124.2 (3)	H13A—C13—H13B	108.00
Br1—C4—C5	118.4 (3)	H14B—C14—H14C	109.00
N2—C5—C4	121.5 (3)	N1—C14—H14A	110.00
N2—C5—C6	122.7 (4)	N1—C14—H14B	109.00
C4—C5—C6	115.7 (3)	N1—C14—H14C	109.00
C1—C6—C5	120.6 (4)	H14A—C14—H14B	109.00
C5—C6—C7	121.0 (3)	H14A—C14—H14C	109.00
C1—C6—C7	118.3 (3)	S1—C15—C16	120.1 (3)
N1—C7—C6	114.8 (3)	S1—C15—C20	120.5 (3)
C9—C8—C13	111.8 (3)	C16—C15—C20	119.4 (4)
N1—C8—C9	111.0 (3)	C15—C16—C17	120.6 (4)
N1—C8—C13	110.3 (3)	C16—C17—C18	121.1 (4)
C8—C9—C10	110.6 (4)	C17—C18—C19	117.7 (4)
C9—C10—C11	113.3 (4)	C17—C18—C21	121.5 (4)
C10—C11—C12	111.2 (4)	C19—C18—C21	120.7 (5)
C11—C12—C13	112.1 (4)	C18—C19—C20	121.7 (4)
C8—C13—C12	110.6 (4)	C15—C20—C19	119.5 (4)
C6—C1—H1A	120.00	C15—C16—H16	120.00
C2—C1—H1A	120.00	C17—C16—H16	120.00
C2—C3—H3	121.00	C16—C17—H17	119.00
C4—C3—H3	121.00	C18—C17—H17	120.00
N1—C7—H7A	109.00	C18—C19—H19	119.00
C6—C7—H7B	109.00	C20—C19—H19	119.00
N1—C7—H7B	109.00	C15—C20—H20	120.00
C6—C7—H7A	109.00	C19—C20—H20	120.00
H7A—C7—H7B	108.00	C18—C21—H21A	109.00
C13—C8—H8	108.00	C18—C21—H21B	109.00
N1—C8—H8	108.00	C18—C21—H21C	110.00
C9—C8—H8	108.00	H21A—C21—H21B	109.00
H9A—C9—H9B	108.00	H21A—C21—H21C	110.00
C8—C9—H9B	110.00	H21B—C21—H21C	110.00
C10—C9—H9A	110.00

O2—S1—C15—C16	−47.4 (3)	N2—C5—C6—C1	−178.4 (4)
O1—S1—C15—C16	70.1 (3)	N2—C5—C6—C7	4.7 (7)
O1—S1—C15—C20	−109.6 (3)	C4—C5—C6—C7	−172.6 (4)
O3—S1—C15—C20	12.1 (4)	C4—C5—C6—C1	4.3 (6)
O2—S1—C15—C20	133.0 (3)	C1—C6—C7—N1	75.0 (5)
O3—S1—C15—C16	−168.2 (3)	C5—C6—C7—N1	−108.1 (4)
C8—N1—C7—C6	174.7 (3)	N1—C8—C9—C10	−177.7 (3)
C14—N1—C8—C13	−176.8 (3)	C9—C8—C13—C12	55.3 (5)
C7—N1—C8—C9	−178.8 (3)	C13—C8—C9—C10	−54.1 (5)
C7—N1—C8—C13	56.7 (4)	N1—C8—C13—C12	179.3 (3)
C14—N1—C7—C6	47.3 (4)	C8—C9—C10—C11	53.7 (5)
C14—N1—C8—C9	−52.3 (4)	C9—C10—C11—C12	−53.7 (6)
C2—C1—C6—C5	−1.9 (6)	C10—C11—C12—C13	54.2 (5)
C2—C1—C6—C7	175.1 (4)	C11—C12—C13—C8	−55.1 (5)
C6—C1—C2—C3	−1.0 (6)	S1—C15—C16—C17	179.8 (3)
C6—C1—C2—Br2	178.1 (3)	C20—C15—C16—C17	−0.6 (6)
Br2—C2—C3—C4	−178.0 (3)	S1—C15—C20—C19	−178.7 (3)
C1—C2—C3—C4	1.1 (6)	C16—C15—C20—C19	1.7 (5)
C2—C3—C4—Br1	−179.2 (3)	C15—C16—C17—C18	−0.2 (7)
C2—C3—C4—C5	1.7 (6)	C16—C17—C18—C19	0.0 (7)
C3—C4—C5—N2	178.4 (4)	C16—C17—C18—C21	178.6 (4)
Br1—C4—C5—N2	−0.7 (6)	C17—C18—C19—C20	1.1 (6)
Br1—C4—C5—C6	176.6 (3)	C21—C18—C19—C20	−177.6 (4)
C3—C4—C5—C6	−4.3 (6)	C18—C19—C20—C15	−1.9 (6)

Symmetry codes: (i) x, −y+1/2, z−1/2; (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, y−1/2, −z+1/2; (ix) x, y−1, z; (x) −x, −y+1, −z; (xi) x, −y+3/2, z−1/2; (xii) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^viii	0.85 (3)	1.93 (4)	2.756 (4)	161 (4)
N2—H2A···O1^iv	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	0.9700	2.4700	3.257 (5)	138.00
C20—H20···O3	0.9300	2.5300	2.905 (5)	104.00

Symmetry codes: (iv) −x+1, −y+1, −z; (viii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₂₁Br₂N₂⁺·C₇H₇O₃S⁻
M_r	548.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.008 (5), 10.404 (5), 17.157 (5)
β (°)	110.148 (5)
V (Å³)	2347.4 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.57
Crystal size (mm)	0.30 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.414, 0.764
No. of measured, independent and observed [I > 2σ(I)] reflections	14496, 4608, 2343
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.114, 1.00
No. of reflections	4608
No. of parameters	272
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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	0.9700	2.4700	3.257 (5)	138.00
C20—H20···O3	0.9300	2.5300	2.905 (5)	104.00

Symmetry codes: (i) −x+1, y−1/2, −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

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

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Volume 67| Part 8| August 2011| Page o2032

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

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

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