N-(2-Bromo-1-phenyl­ethyl)-4-methyl­benzene­sulfonamide

The title compound, C₁₅H₁₆BrNO₂S, was obtained unintentionally in our work on the preparation of vicinal haloamine derivatives. The mol­ecule lies across a crystallographic mirror plane with the NH group disordered across this mirror plane. The dihedral angle between the benzene and phenyl rings is 25.10 (17)°. In the crystal structure, inter­molecular N—H...O hydrogen bonds link the mol­ecules into chains running along the b axis. In addition, C—H...Br hydrogen bonds are observed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.037
• wR factor = 0.097
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.02 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.22 Ratio

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Vicinal haloamine derivates are versatile synthetic intermediates for the synthesis of functional materials and biologically active compounds (Thakur et al., 2003). In our work on the preparation of haloamine derivates we have obtained the title compound, (I).

The molecular structure of (I) is illustrated in Fig.1. The molecule of (I) possesses mirror symmetry, with atoms Br1, S1, C1, C4, C5, C6, C7, C8, C11, H5A and H11 lying on the crystallographic mirror plane. Atom N1 is disordered across the mirror plane. The dihedral angle between the benzene and phenyl rings is 25.10 (17)°.

As shown in Fig.2, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into a chain running along the b axis. In addition, C—H···Br hydrogen bonds are observed.

Related literature

For related literature, see: Thakur et al. (2003).

S2. Experimental

Bromine (21.5 g, 0.134 mol) was added to p-toluenesulfonamide (11.5 g, 0.067 mol) and cooled to 273 K in an ice bath. Sodium hydroxide hydroxide (20%, 5.4 g, 0.135 mol) in water (21.6 ml) was then added dropwise from a separatory funnel. The lower layer containing the reaction product was dissolved in chloroform (70 ml). To the chloroform solution, styrene (13.6 g, 0.131 mol) was added gradually from a separatory funnel. After the addition, the reaction mixture was heated to 318 K for 1 h. The mixture was cooled in an ice bath, then the precipitate was filtered off and washed with ice-cold absolute ethanol (yield 14.8 g, 0.042 mol). Another semi-solid product (3.6 g, 0.01 mol) was obtained by the evaporation of the chloroform solution and it was washed with cold absolute ethanol. The solid product was dissolved in acetone, the solution was evaporated gradually at room temperature to afford single crystals of (I) (m.p. 442–444 K).

S3. Refinement

Atoms Br1, S1, C1, C4, C5, C6, C7, C8, C11, H5A and H11 lie on the mirror plane. Atom N1 is disordered across the mirror plane. H atoms were placed in calculated positions (N—H = 0.87 Å and C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms with U_iso(H) = 1.2–1.5 U_eq(C).

Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Atoms Br1, S1, C1, C4, C5, C6, C7, C8, C11, H5A and H11 lie on the mirror plane. Atom N1 is disordered across the mirror plane. Unlabelled atoms are related to labelled atoms by the symmetry operation (x, 1/2 - y, z). Only one disorder component is shown.
	Fig. 2. Packing diagram of (I), showing hydrogen bonds as dashed lines. Only one disorder component is shown.

N-(2-Bromo-1-phenylethyl)-4-methylbenzenesulfonamide

Crystal data

C15H16BrNO2S	F(000) = 360
Mr = 354.26	Dx = 1.531 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1415 reflections
a = 7.8866 (13) Å	θ = 2.6–23.3°
b = 9.5474 (16) Å	µ = 2.81 mm^−1
c = 10.2881 (16) Å	T = 293 K
β = 97.280 (2)°	Block, colourless
V = 768.4 (2) Å^3	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1873 independent reflections
Radiation source: fine-focus sealed tube	1211 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.50, Tmax = 0.56	k = −12→10
4943 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 0.4403P] where P = (Fo^2 + 2Fc^2)/3
1873 reflections	(Δ/σ)max = 0.001
110 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 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	Occ. (<1)
Br1	0.83529 (7)	0.2500	0.77727 (4)	0.0852 (2)
S1	0.39919 (13)	0.2500	0.45965 (10)	0.0614 (3)
O1	0.3345 (5)	0.1259 (2)	0.5024 (2)	0.1211 (11)
N1	0.5905 (5)	0.1825 (4)	0.5114 (4)	0.0517 (10)	0.50
H1N	0.6121	0.0939	0.5025	0.047 (14)*	0.50
C1	0.3791 (5)	0.2500	0.2874 (3)	0.0509 (9)
C2	0.3740 (4)	0.1250 (3)	0.2209 (3)	0.0626 (7)
H2	0.3767	0.0405	0.2662	0.075*
C3	0.3647 (4)	0.1264 (4)	0.0858 (3)	0.0696 (8)
H3	0.3601	0.0419	0.0406	0.084*
C4	0.3621 (5)	0.2500	0.0166 (4)	0.0640 (11)
C5	0.3536 (7)	0.2500	−0.1320 (4)	0.0944 (17)
H5A	0.4675	0.2500	−0.1557	0.142*
H5B	0.2941	0.3321	−0.1670	0.142*	0.50
H5C	0.2941	0.1679	−0.1670	0.142*	0.50
C6	0.7406 (5)	0.2500	0.4975 (4)	0.0647 (11)
H6	0.7030	0.3453	0.5021	0.078*	0.50
C7	0.8864 (6)	0.2500	0.5997 (4)	0.0940 (17)
H7A	0.9556	0.3319	0.5875	0.113*	0.50
H7B	0.9556	0.1681	0.5875	0.113*	0.50
C8	0.8036 (5)	0.2500	0.3641 (4)	0.0576 (10)
C9	0.8369 (4)	0.1261 (4)	0.3045 (3)	0.0771 (9)
H9	0.8145	0.0414	0.3436	0.093*
C10	0.9037 (4)	0.1267 (5)	0.1866 (3)	0.0924 (11)
H10	0.9256	0.0424	0.1466	0.111*
C11	0.9375 (6)	0.2500	0.1287 (4)	0.0878 (17)
H11	0.9836	0.2500	0.0498	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1040 (4)	0.0977 (4)	0.0524 (3)	0.000	0.0044 (2)	0.000
S1	0.0596 (6)	0.0699 (7)	0.0578 (5)	0.000	0.0197 (5)	0.000
O1	0.243 (3)	0.0521 (14)	0.0787 (15)	−0.0046 (18)	0.0605 (18)	0.0099 (12)
N1	0.064 (3)	0.038 (2)	0.055 (2)	0.003 (2)	0.014 (2)	0.0030 (18)
C1	0.047 (2)	0.048 (2)	0.058 (2)	0.000	0.0100 (16)	0.000
C2	0.0691 (18)	0.0509 (17)	0.0686 (17)	0.0065 (14)	0.0116 (14)	0.0017 (14)
C3	0.0711 (19)	0.068 (2)	0.0700 (18)	0.0048 (16)	0.0116 (15)	−0.0138 (16)
C4	0.049 (2)	0.085 (3)	0.059 (2)	0.000	0.0116 (18)	0.000
C5	0.086 (4)	0.134 (5)	0.065 (3)	0.000	0.014 (2)	0.000
C6	0.059 (3)	0.080 (3)	0.056 (2)	0.000	0.0103 (19)	0.000
C7	0.079 (3)	0.151 (5)	0.052 (2)	0.000	0.010 (2)	0.000
C8	0.050 (2)	0.072 (3)	0.051 (2)	0.000	0.0069 (16)	0.000
C9	0.086 (2)	0.078 (2)	0.0699 (19)	−0.0067 (18)	0.0212 (17)	−0.0076 (17)
C10	0.085 (2)	0.118 (3)	0.078 (2)	0.000 (2)	0.0223 (18)	−0.033 (2)
C11	0.058 (3)	0.155 (6)	0.051 (2)	0.000	0.011 (2)	0.000

Geometric parameters (Å, º)

Br1—C7	1.920 (4)	C5—H5A	0.96
S1—O1^i	1.384 (2)	C5—H5B	0.96
S1—O1	1.384 (2)	C5—H5C	0.96
S1—N1^i	1.665 (4)	C6—N1^i	1.371 (5)
S1—N1	1.665 (4)	C6—C7	1.457 (6)
S1—C1	1.759 (4)	C6—C8	1.518 (5)
N1—N1^i	1.289 (8)	C6—H6	0.96
N1—C6	1.371 (5)	C7—H7A	0.97
N1—H1N	0.87	C7—H7B	0.97
C1—C2	1.374 (3)	C8—C9^i	1.373 (4)
C1—C2^i	1.374 (3)	C8—C9	1.373 (4)
C2—C3	1.382 (4)	C9—C10	1.383 (4)
C2—H2	0.93	C9—H9	0.93
C3—C4	1.377 (4)	C10—C11	1.361 (5)
C3—H3	0.93	C10—H10	0.93
C4—C3^i	1.377 (4)	C11—C10^i	1.361 (5)
C4—C5	1.522 (6)	C11—H11	0.93
O1^i—S1—O1	117.9 (2)	C4—C5—H5C	109.5
O1^i—S1—N1^i	85.6 (2)	H5A—C5—H5C	109.5
O1—S1—N1^i	125.8 (2)	H5B—C5—H5C	109.5
O1^i—S1—N1	125.8 (2)	N1—C6—N1^i	56.1 (4)
O1—S1—N1	85.6 (2)	N1—C6—C7	122.5 (3)
O1^i—S1—C1	109.29 (12)	N1^i—C6—C7	122.5 (3)
O1—S1—C1	109.29 (12)	N1—C6—C8	118.7 (3)
N1^i—S1—C1	106.52 (18)	N1^i—C6—C8	118.7 (3)
N1—S1—C1	106.52 (18)	C7—C6—C8	109.5 (3)
N1^i—N1—C6	61.97 (19)	N1—C6—H6	99.5
N1^i—N1—S1	67.23 (15)	C7—C6—H6	100.6
C6—N1—S1	123.0 (3)	C8—C6—H6	100.6
N1^i—N1—H1N	166.5	C6—C7—Br1	116.4 (3)
C6—N1—H1N	105.3	C6—C7—H7A	108.2
S1—N1—H1N	121.6	Br1—C7—H7A	108.2
C2—C1—C2^i	120.6 (3)	C6—C7—H7B	108.2
C2—C1—S1	119.67 (17)	Br1—C7—H7B	108.2
C2^i—C1—S1	119.67 (17)	H7A—C7—H7B	107.3
C1—C2—C3	119.1 (3)	C9^i—C8—C9	119.0 (4)
C1—C2—H2	120.4	C9^i—C8—C6	120.44 (19)
C3—C2—H2	120.4	C9—C8—C6	120.44 (19)
C4—C3—C2	121.6 (3)	C8—C9—C10	120.2 (4)
C4—C3—H3	119.2	C8—C9—H9	119.9
C2—C3—H3	119.2	C10—C9—H9	119.9
C3^i—C4—C3	117.9 (4)	C11—C10—C9	120.4 (4)
C3^i—C4—C5	121.03 (19)	C11—C10—H10	119.8
C3—C4—C5	121.03 (19)	C9—C10—H10	119.8
C4—C5—H5A	109.3	C10^i—C11—C10	119.8 (4)
C4—C5—H5B	109.5	C10^i—C11—H11	120.1
H5A—C5—H5B	109.5	C10—C11—H11	120.1
O1^i—S1—N1—N1^i	−32.58 (15)	C2—C3—C4—C5	179.4 (3)
O1—S1—N1—N1^i	−154.03 (12)	S1—N1—C6—N1^i	29.8 (4)
C1—S1—N1—N1^i	97.15 (9)	N1^i—N1—C6—C7	109.9 (3)
O1^i—S1—N1—C6	−61.0 (4)	S1—N1—C6—C7	139.6 (3)
O1—S1—N1—C6	177.6 (3)	N1^i—N1—C6—C8	−107.0 (3)
N1^i—S1—N1—C6	−28.4 (4)	S1—N1—C6—C8	−77.2 (3)
C1—S1—N1—C6	68.8 (3)	N1—C6—C7—Br1	−33.9 (3)
O1^i—S1—C1—C2	−156.1 (3)	N1^i—C6—C7—Br1	33.9 (3)
O1—S1—C1—C2	−25.8 (4)	C8—C6—C7—Br1	180.0
N1^i—S1—C1—C2	112.8 (3)	N1—C6—C8—C9^i	124.2 (3)
N1—S1—C1—C2	65.2 (3)	N1^i—C6—C8—C9^i	59.4 (5)
O1^i—S1—C1—C2^i	25.8 (4)	C7—C6—C8—C9^i	−88.2 (3)
O1—S1—C1—C2^i	156.1 (3)	N1—C6—C8—C9	−59.4 (5)
N1^i—S1—C1—C2^i	−65.2 (3)	N1^i—C6—C8—C9	−124.2 (3)
N1—S1—C1—C2^i	−112.8 (3)	C7—C6—C8—C9	88.2 (3)
C2^i—C1—C2—C3	0.4 (6)	C9^i—C8—C9—C10	0.3 (6)
S1—C1—C2—C3	−177.6 (2)	C6—C8—C9—C10	−176.3 (3)
C1—C2—C3—C4	0.6 (5)	C8—C9—C10—C11	0.2 (6)
C2—C3—C4—C3^i	−1.6 (6)	C9—C10—C11—C10^i	−0.7 (7)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^ii	0.87	2.14	3.010 (5)	175
C11—H11···Br1^iii	0.93	2.90	3.603 (4)	134

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