N-Bromo-S-(4-nitro­phen­yl)-S-phenyl­sulfimide

Sheikh, M.C.; Yoshimura, T.; Fujii, T.; Miyatake, R.

doi:10.1107/S2414314616020332

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162033

https://doi.org/10.1107/S2414314616020332

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N-Bromo-S-(4-nitrophenyl)-S-phenylsulfimide

Md. Chanmiya Sheikh,^a Toshiaki Yoshimura,^a ^* Takayoshi Fujii ^a and Ryuta Miyatake ^b

^aDepartment of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan, and ^bCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan
^*Correspondence e-mail: by4ut6@bma.biglobe.ne.jp

Edited by H. Ishida, Okayama University, Japan (Received 30 November 2016; accepted 22 December 2016; online 6 January 2017)

The title compound, C₁₂H₉BrN₂O₂S, the first crystal structure of an N-halosulfimide, adopts a syn conformation about the S=N bond, with a Br—N—S—C(phenyl) torsion angle of −54.64 (17)°. The dihedral angle between between the phenyl and 4-nitrophenyl rings is 65.04 (14)°. In the crystal, molecules are linked by C—H⋯Br, C—H⋯N and C—H⋯O interactions, forming a tape structure along the c axis.

Keywords: crystal structure; N-bromosulfimide; syn conformation.

CCDC reference: 1454896

Structure description

The chemistry of N-halosulfimides (R,R′S=NX) has attracted much attention due to their unique structures and reactivities (Oae & Furukawa, 1983 ; Yoshimura et al., 1977 ; Kumar & Shreeve, 1981 ; Aucott et al., 2004 ). Previously, we have synthesized diaryl(fluoro)-λ⁶-sulfanenitriles by the reaction of S,S-diaryl-N-bromosulfimides with tetrabutylammonium fluoride (Yoshimura et al., 1992 ) and also by the reaction of S,S-diarylsulfimides using Selectfluor^TM, an electrophilic fluorinating reagent, where the reaction proceeds via S,S-diaryl-N-fluorosulfimides as intermediates which undergo 1,2-migration of the F atom (Fujii et al., 2003 ). We have also performed DFT calculations using a model compound, S,S-dimethyl-N-fluorosulfimide, which showed that the syn conformer of N-fluorosulfimide is more stable than the anti one. In order to elucidate the mechanism of this 1,2-migration (retention or inversion), it is important to examine the structures of N-halosulfimides. However, the corresponding N-fluorosulfimides could not be isolated, and similar compounds of N-chlorosulfimides are also unstable for X-ray analysis. The crystal structure of the title compound, N-bromo-S-(4-nitrophenyl)-S-phenylsulfimide, has now been successfully resolved.

The molecular structure of the title compound was found to have a syn conformation, consistent with the prediction of the DFT calculation, as illustrated in Fig. 1. In the crystal, the molecules are linked through weak C3—H2⋯(N=Br) and C5—H3⋯O1 hydrogen bonds, forming a tape along the c axis (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H2⋯Br1ⁱ	0.95	2.86	3.598 (3)	135
C3—H2⋯N1ⁱ	0.95	2.44	3.286 (3)	149
C5—H3⋯O1ⁱⁱ	0.95	2.54	3.435 (3)	158
Symmetry codes: (i) x, y, z-1; (ii) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
A partial packing diagram for the title compound with C—H⋯(N=Br) and C—H⋯O hydrogen bonds shown as blue dashed lines.

Synthesis and crystallization

The title compound was prepared by the method previously reported (Yoshimura et al., 1977) using S-(4-nitrophenyl)-S-phenylsulfimide mono hydrate and N-bromosuccinimide and crystallized from a benzene-hexane (1:1) solution (yield: 95%; m.p. 425–426 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉BrN₂O₂S
M_r	325.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.12236 (10), 18.7734 (3), 7.70271 (10)
β (°)	108.576 (1)
V (Å³)	1250.42 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.02
Crystal size (mm)	0.52 × 0.27 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.226, 0.300
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	14491, 2279, 2124
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.08
No. of reflections	2279
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.40
Computer programs: RAPID-AUTO (Rigaku, 2001 ), SIR92 (Altomare et al., 1994 ), SHELXL97 (Sheldrick, 2008 ), CrystalStructure (Rigaku, 2010 ).

Structural data

CCDC reference: 1454896

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020332/is4014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020332/is4014Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616020332/is4014Isup3.cml

checkCIF report

Computing details top

Cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

N-Bromo-S-(4-nitrophenyl)-S-phenylsulfimide top

Crystal data top

C₁₂H₉BrN₂O₂S	F(000) = 648.00
M_r = 325.18	D_x = 1.727 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 13002 reflections
a = 9.12236 (10) Å	θ = 4.7–68.3°
b = 18.7734 (3) Å	µ = 6.02 mm⁻¹
c = 7.70271 (10) Å	T = 173 K
β = 108.576 (1)°	Block, yellow
V = 1250.42 (3) Å³	0.52 × 0.27 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2124 reflections with F² > 2.0σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.077
ω scans	θ_max = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.226, T_max = 0.300	k = −21→22
14491 measured reflections	l = −9→9
2279 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0602P)² + 0.2679P] where P = (F_o² + 2F_c²)/3
2279 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.83 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.91904 (3)	0.032258 (15)	0.74644 (3)	0.04051 (15)
S1	0.64227 (7)	0.07351 (3)	0.43986 (8)	0.03335 (18)
O1	0.6655 (3)	−0.22788 (11)	0.0004 (3)	0.0550 (6)
O2	0.7188 (3)	−0.15518 (13)	−0.1882 (3)	0.0597 (6)
N1	0.7002 (3)	0.05179 (12)	0.6514 (3)	0.0377 (5)
N2	0.6924 (3)	−0.16817 (13)	−0.0455 (3)	0.0410 (6)
C1	0.6804 (3)	0.00334 (13)	0.2999 (4)	0.0312 (5)
C2	0.6876 (3)	0.01676 (14)	0.1252 (4)	0.0344 (6)
C3	0.6935 (3)	−0.03971 (13)	0.0125 (4)	0.0349 (6)
C4	0.6913 (3)	−0.10794 (14)	0.0781 (4)	0.0336 (6)
C5	0.6850 (3)	−0.12264 (14)	0.2515 (4)	0.0365 (6)
C6	0.6798 (3)	−0.06594 (14)	0.3630 (4)	0.0344 (6)
C7	0.7462 (3)	0.14683 (13)	0.3886 (3)	0.0342 (6)
C8	0.6725 (4)	0.21283 (15)	0.3750 (4)	0.0409 (6)
C9	0.7501 (4)	0.27343 (15)	0.3495 (4)	0.0479 (7)
C10	0.8984 (4)	0.26804 (16)	0.3384 (4)	0.0514 (8)
C11	0.9707 (4)	0.20242 (15)	0.3515 (4)	0.0445 (7)
C12	0.8943 (3)	0.14113 (15)	0.3777 (4)	0.0386 (6)
H1	0.6884	0.0644	0.0837	0.0413*
H2	0.6989	−0.0317	−0.1071	0.0418*
H3	0.6842	−0.1703	0.2924	0.0438*
H4	0.6758	−0.0742	0.4831	0.0413*
H5	0.5709	0.2161	0.3831	0.0490*
H6	0.7016	0.3187	0.3396	0.0575*
H7	0.9511	0.3098	0.3217	0.0617*
H8	1.0720	0.1993	0.3426	0.0534*
H9	0.9433	0.0959	0.3879	0.0464*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0399 (3)	0.0421 (3)	0.0385 (2)	0.00127 (10)	0.01095 (15)	0.00459 (10)
S1	0.0334 (4)	0.0342 (4)	0.0354 (4)	0.0022 (3)	0.0151 (3)	0.0019 (3)
O1	0.0734 (15)	0.0357 (12)	0.0560 (13)	0.0016 (10)	0.0207 (11)	−0.0056 (10)
O2	0.0776 (16)	0.0631 (15)	0.0474 (12)	−0.0027 (12)	0.0324 (11)	−0.0130 (11)
N1	0.0408 (12)	0.0407 (12)	0.0363 (11)	0.0022 (10)	0.0188 (10)	0.0024 (10)
N2	0.0373 (12)	0.0461 (15)	0.0375 (12)	0.0036 (10)	0.0089 (10)	−0.0066 (10)
C1	0.0275 (12)	0.0327 (14)	0.0335 (12)	−0.0007 (10)	0.0098 (10)	−0.0004 (10)
C2	0.0346 (14)	0.0356 (13)	0.0336 (13)	−0.0014 (11)	0.0115 (11)	0.0063 (11)
C3	0.0318 (14)	0.0434 (16)	0.0305 (13)	−0.0026 (10)	0.0115 (11)	0.0019 (11)
C4	0.0286 (12)	0.0382 (14)	0.0331 (12)	−0.0013 (10)	0.0088 (10)	−0.0041 (11)
C5	0.0382 (14)	0.0343 (14)	0.0368 (13)	−0.0001 (11)	0.0118 (11)	0.0034 (11)
C6	0.0356 (13)	0.0381 (14)	0.0315 (12)	−0.0011 (11)	0.0134 (10)	0.0042 (10)
C7	0.0413 (14)	0.0311 (13)	0.0305 (12)	−0.0003 (11)	0.0118 (11)	0.0015 (10)
C8	0.0477 (15)	0.0413 (16)	0.0317 (13)	0.0083 (12)	0.0099 (11)	0.0017 (11)
C9	0.071 (2)	0.0304 (15)	0.0371 (14)	0.0057 (14)	0.0106 (13)	0.0035 (12)
C10	0.070 (2)	0.0410 (17)	0.0407 (15)	−0.0135 (15)	0.0141 (14)	0.0054 (13)
C11	0.0498 (16)	0.0425 (17)	0.0418 (15)	−0.0083 (13)	0.0153 (12)	0.0024 (12)
C12	0.0436 (15)	0.0349 (15)	0.0384 (14)	−0.0010 (11)	0.0145 (12)	0.0032 (11)

Geometric parameters (Å, º) top

Br1—N1	1.930 (3)	C7—C12	1.384 (4)
S1—N1	1.597 (3)	C8—C9	1.387 (5)
S1—C1	1.805 (3)	C9—C10	1.386 (6)
S1—C7	1.786 (3)	C10—C11	1.386 (5)
O1—N2	1.223 (4)	C11—C12	1.393 (5)
O2—N2	1.223 (4)	C2—H1	0.950
N2—C4	1.480 (4)	C3—H2	0.950
C1—C2	1.391 (4)	C5—H3	0.950
C1—C6	1.389 (4)	C6—H4	0.950
C2—C3	1.382 (4)	C8—H5	0.950
C3—C4	1.379 (4)	C9—H6	0.950
C4—C5	1.383 (4)	C10—H7	0.950
C5—C6	1.378 (4)	C11—H8	0.950
C7—C8	1.398 (4)	C12—H9	0.950

N1—S1—C1	111.02 (12)	C9—C10—C11	120.8 (3)
N1—S1—C7	113.30 (11)	C10—C11—C12	119.8 (3)
C1—S1—C7	102.33 (13)	C7—C12—C11	119.2 (3)
Br1—N1—S1	113.69 (15)	C1—C2—H1	120.259
O1—N2—O2	123.9 (3)	C3—C2—H1	120.266
O1—N2—C4	118.1 (3)	C2—C3—H2	120.842
O2—N2—C4	118.0 (3)	C4—C3—H2	120.860
S1—C1—C2	121.54 (19)	C4—C5—H3	121.040
S1—C1—C6	116.8 (2)	C6—C5—H3	121.047
C2—C1—C6	121.0 (3)	C1—C6—H4	119.985
C1—C2—C3	119.5 (3)	C5—C6—H4	119.995
C2—C3—C4	118.3 (3)	C7—C8—H5	120.583
N2—C4—C3	118.0 (3)	C9—C8—H5	120.577
N2—C4—C5	118.7 (3)	C8—C9—H6	119.954
C3—C4—C5	123.3 (3)	C10—C9—H6	119.951
C4—C5—C6	117.9 (3)	C9—C10—H7	119.609
C1—C6—C5	120.0 (3)	C11—C10—H7	119.611
S1—C7—C8	115.0 (3)	C10—C11—H8	120.124
S1—C7—C12	123.5 (2)	C12—C11—H8	120.123
C8—C7—C12	121.3 (3)	C7—C12—H9	120.388
C7—C8—C9	118.8 (3)	C11—C12—H9	120.396
C8—C9—C10	120.1 (3)

N1—S1—C1—C2	−159.09 (16)	C2—C1—C6—C5	−0.6 (4)
N1—S1—C1—C6	30.08 (19)	C6—C1—C2—C3	0.3 (4)
C1—S1—N1—Br1	59.86 (16)	C1—C2—C3—C4	0.3 (4)
N1—S1—C7—C8	−99.02 (16)	C2—C3—C4—N2	178.03 (19)
N1—S1—C7—C12	75.8 (2)	C2—C3—C4—C5	−0.6 (4)
C7—S1—N1—Br1	−54.64 (17)	N2—C4—C5—C6	−178.29 (18)
C1—S1—C7—C8	141.38 (14)	C3—C4—C5—C6	0.4 (4)
C1—S1—C7—C12	−43.80 (19)	C4—C5—C6—C1	0.2 (4)
C7—S1—C1—C2	−37.90 (19)	S1—C7—C8—C9	175.13 (14)
C7—S1—C1—C6	151.26 (15)	S1—C7—C12—C11	−174.89 (15)
O1—N2—C4—C3	−168.46 (19)	C8—C7—C12—C11	−0.4 (4)
O1—N2—C4—C5	10.3 (3)	C12—C7—C8—C9	0.2 (4)
O2—N2—C4—C3	10.9 (3)	C7—C8—C9—C10	−0.2 (4)
O2—N2—C4—C5	−170.3 (2)	C8—C9—C10—C11	0.4 (4)
S1—C1—C2—C3	−170.17 (15)	C9—C10—C11—C12	−0.6 (4)
S1—C1—C6—C5	170.33 (15)	C10—C11—C12—C7	0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···Br1ⁱ	0.95	2.86	3.598 (3)	135
C3—H2···N1ⁱ	0.95	2.44	3.286 (3)	149
C5—H3···O1ⁱⁱ	0.95	2.54	3.435 (3)	158

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

Acknowledgements

The authors are grateful to the Department of Applied Chemistry, Faculty of Engineering, University of Toyama, for the provision of laboratory facilities. They also acknowledge the University of Toyama for providing funds for single-crystal X-ray analyses.

Funding information

Funding for this research was provided by: Grant-in-Aid for Scientific Research on Priority Areas from the Ministry of Education, Science, Sports and Culture, Japan (award Nos. 09239218, 14044032); Japan Society for the Promotion of Science (award No. P11336).

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