2-Methyl-2-(3-nitro­phen­yl)-1,3-dithiane

Mirošová, P.; Nečas, M.; Vícha, R.

doi:10.1107/S1600536812022283

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1827

doi:10.1107/S1600536812022283

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2-Methyl-2-(3-nitrophenyl)-1,3-dithiane

Pavla Mirošová,^a Marek Nečas ^b and Robert Vícha ^a ^*

^aDepartment of Chemistry, Faculty of Technology, Tomas Bata University in Zlin, Nám. T. G. Masaryka 275, Zlín 762 72, Czech Republic, and ^bDepartment of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, Brno-Bohunice 625 00, Czech Republic
^*Correspondence e-mail: rvicha@ft.utb.cz

(Received 17 April 2012; accepted 16 May 2012; online 19 May 2012)

The title compound, C₁₁H₁₃NO₂S₂, contains a 1,3-dithiane ring in an almost ideal chair conformation with the following puckering parameters: Q = 0.7252 (15) Å, θ = 6.71 (13) and φ = 50.4 (11)°. The benzene ring occupies an axial position at the dithiane ring. The nitro group is almost coplanar with the benzene ring [O—N—C—C = −3.2 (2)°]. The molecule has an L-shape with a C—C—C—C torsion angle of −74.15 (17)° for the atoms of the methyl group and the dithiane–benzene linkage. The crystal packing is stabilized only via weak non-specific van der Waals interactions.

Related literature

For the preparation of the title compound, see Vícha et al. (2011 ). For crystallographic data for similar aryl-substituted 1,3-dithianes, see: Fun et al. (2009a ,b ); Samas et al. (2010 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₃NO₂S₂
M_r = 255.36
Orthorhombic, P b c a
a = 13.5388 (3) Å
b = 7.2660 (1) Å
c = 24.1083 (4) Å
V = 2371.60 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 120 K
0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.899, T_max = 1.000
25370 measured reflections
2086 independent reflections
1871 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.074
S = 1.08
2086 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812022283/nk2160sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022283/nk2160Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022283/nk2160Isup3.cml

checkCIF report

Comment top

The six- and five-membered 1,3-disulfur rings are frequently used in organic synthesis as efficient protecting groups for carbonyl moiety. Additionally, these compounds are intermediate stage in the carbonyl-to-methylene transformation process. We have used title compound as a model target for optimization of the selective desulfurization procedure (Vícha et al., 2011). Surprisingly, title compound has not been described in the literature yet (to the best of our knowledge).

The benzene ring (C1–C6) is essentially planar with the maximum deviation from the best plane of 0.0071 (15) Å for C4. The torsion angles C11—C7—C3—C4 and C2—C1—N1—O1 describing mutual orientation of nitro group, benzene ring and dithiane ring are -74.15 (17) and -3.2 (2)°, respectively. The dithiane ring adopts almost ideal chair conformation with the Cremer and Pople puckering parameters Q = 0.7252 (15) Å, θ= 6.71 (13)°, ϕ= 50.4 (11)°. Remarkably, the less bulky methyl substituent occupies the equatorial position at C7. This may be demonstrated by the torsion angle C11—C7—S2—C10 which is of -172.63 (10)°. Furthermore, the C1—C2 edge of the benzene ring is slightly turned over the dithiane ring. The dihedral angle between the benzene best plane (C1–C6) and the imaginary mirror plane of dithiane ring (calculated as the best plane of C3, C7, C9 and C11) is 77.25 (4)°.

Related literature top

For the preparation of the title compound, see Vícha et al. (2011). For crystallographic data for similar aryl-substituted 1,3-dithianes, see: Fun et al. (2009a,b); Samas et al. (2010). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

The title compound was prepared from corresponding 1-(3-nitrophenyl)ethan-1-one and propan-1,3-dithiol as it was published previously (Vícha et al., 2011). The crude material was crystallized from hexane to yield pale yellow crystals (89%). The single-crystal used for data collection was obtained via slow evaporation of chloroform from solution of the title compound at room temperature. NMR, IR and MS spectra are listed in the _exptl_special_details section of the CIF.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top

Fig. 1. The asymmetric unit with atoms represented as 50% probability ellipsoids. H atoms are shown as small spheres at arbitrary radii.

2-Methyl-2-(3-nitrophenyl)-1,3-dithiane top

Crystal data top

C₁₁H₁₃NO₂S₂	D_x = 1.430 Mg m⁻³
M_r = 255.36	Melting point: 350 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 29781 reflections
a = 13.5388 (3) Å	θ = 2.9–27.1°
b = 7.2660 (1) Å	µ = 0.43 mm⁻¹
c = 24.1083 (4) Å	T = 120 K
V = 2371.60 (7) Å³	Block, yellow
Z = 8	0.40 × 0.40 × 0.30 mm
F(000) = 1072

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	2086 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1871 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 8.4353 pixels mm^-1	θ_max = 25.0°, θ_min = 3.3°
ω scan	h = −16→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −8→8
T_min = 0.899, T_max = 1.000	l = −28→28
25370 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0353P)² + 1.7194P] where P = (F_o² + 2F_c²)/3
2086 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₁H₁₃NO₂S₂	V = 2371.60 (7) Å³
M_r = 255.36	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.5388 (3) Å	µ = 0.43 mm⁻¹
b = 7.2660 (1) Å	T = 120 K
c = 24.1083 (4) Å	0.40 × 0.40 × 0.30 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	2086 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1871 reflections with I > 2σ(I)
T_min = 0.899, T_max = 1.000	R_int = 0.016
25370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.08	Δρ_max = 0.38 e Å⁻³
2086 reflections	Δρ_min = −0.19 e Å⁻³
145 parameters

Special details top

Experimental. Spectral properties of title compound: IR (KBr disc): 3075 (w), 2964 (w), 2937 (w), 2897 (w), 2856 (w), 2825 (w),1574 (w), 1524 (s), 1468 (w), 1422 (m), 1346 (s), 1305 (w), 1283 (w), 1274 (w), 1252 (w), 1193 (w), 1166 (w), 1095 (m), 1065 (w), 1048 (w), 997 (w), 929 (w), 903 (m), 895 (m), 870 (w), 805 (s), 761 (w), 738 (s), 688 (s), 626 (s), 564 (w), 540 (w), 486 (w) cm^-1. ¹H NMR (300 MHz; CDCl₃): δ 2.75 (s, 3H); 1.94–2.62 (m, 2H); 2.63–2.82 (m, 4H); 7.57 (t, 1H); 8.13–8.16 (m, 1H); 8.31–8.35 (m, 1H); 8.84–8.85 (m, 1H) ppm. ¹³C NMR (75.5 MHz; CDCl₃): δ 24.5 (CH₂); 28.3 (CH₂); 33.0 (CH₃); 53.3 (C); 122.5 (CH); 123.4 (CH); 129.8 (CH); 134.4 (CH); 147.0 (C);149.0 (C) ppm. MS (EI, 70 eV): 41 (13); 45 (13); 46 (21); 51 (9); 59 (32); 73 (15); 74 (100); 75 (10); 76 (10); 77 (14); 91 (15); 102 (14); 103 (6); 105 (9); 120 (16); 133 (5); 134 (14); 135 (5); 148 (13); 166 (36); 181 (39); 182 (6); 240 (7); 255 (47); 256 (7) m/z (%).

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 > 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
S1	0.42653 (3)	0.06433 (6)	0.318872 (16)	0.02260 (13)
S2	0.34860 (3)	0.31750 (6)	0.406194 (17)	0.02437 (13)
O1	0.78844 (9)	0.06238 (18)	0.31090 (5)	0.0316 (3)
O2	0.88864 (8)	0.19994 (18)	0.36717 (6)	0.0351 (3)
N1	0.80521 (10)	0.15222 (19)	0.35301 (6)	0.0237 (3)
C1	0.72158 (11)	0.2054 (2)	0.38863 (6)	0.0193 (3)
C2	0.62711 (12)	0.1592 (2)	0.37124 (6)	0.0178 (3)
H2A	0.6174	0.0953	0.3373	0.021*
C3	0.54695 (11)	0.2075 (2)	0.40399 (6)	0.0169 (3)
C4	0.56495 (12)	0.3022 (2)	0.45353 (7)	0.0211 (3)
H4A	0.5108	0.3381	0.4761	0.025*
C5	0.66055 (13)	0.3445 (2)	0.47029 (7)	0.0241 (4)
H5A	0.6710	0.4072	0.5044	0.029*
C6	0.74045 (12)	0.2961 (2)	0.43775 (6)	0.0222 (4)
H6A	0.8061	0.3244	0.4488	0.027*
C7	0.44172 (11)	0.1432 (2)	0.39012 (6)	0.0186 (3)
C8	0.44276 (12)	0.2773 (3)	0.28100 (7)	0.0277 (4)
H8A	0.5094	0.3267	0.2890	0.033*
H8B	0.4394	0.2507	0.2408	0.033*
C9	0.36643 (13)	0.4236 (3)	0.29500 (8)	0.0315 (4)
H9A	0.3746	0.5290	0.2694	0.038*
H9B	0.2995	0.3722	0.2892	0.038*
C10	0.37475 (13)	0.4923 (2)	0.35432 (8)	0.0299 (4)
H10A	0.3283	0.5961	0.3595	0.036*
H10B	0.4424	0.5397	0.3604	0.036*
C11	0.41696 (13)	−0.0232 (2)	0.42694 (7)	0.0265 (4)
H11A	0.4648	−0.1218	0.4201	0.040*
H11B	0.3503	−0.0672	0.4182	0.040*
H11C	0.4199	0.0134	0.4660	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0192 (2)	0.0278 (2)	0.0209 (2)	−0.00284 (16)	−0.00093 (15)	−0.00663 (16)
S2	0.0173 (2)	0.0303 (2)	0.0255 (2)	0.00491 (17)	0.00228 (16)	−0.00487 (17)
O1	0.0243 (7)	0.0412 (7)	0.0293 (6)	−0.0001 (6)	0.0060 (5)	−0.0056 (6)
O2	0.0139 (6)	0.0411 (8)	0.0503 (8)	−0.0024 (5)	−0.0002 (6)	0.0003 (6)
N1	0.0170 (7)	0.0241 (7)	0.0299 (8)	0.0003 (6)	0.0011 (6)	0.0070 (6)
C1	0.0177 (8)	0.0162 (7)	0.0239 (8)	0.0014 (6)	0.0012 (6)	0.0044 (6)
C2	0.0191 (8)	0.0168 (7)	0.0176 (7)	0.0003 (6)	−0.0018 (6)	0.0009 (6)
C3	0.0180 (8)	0.0159 (7)	0.0169 (7)	0.0003 (6)	−0.0009 (6)	0.0028 (6)
C4	0.0233 (8)	0.0196 (8)	0.0204 (8)	0.0002 (7)	0.0016 (6)	0.0004 (6)
C5	0.0300 (9)	0.0212 (8)	0.0210 (8)	−0.0035 (7)	−0.0061 (7)	−0.0007 (6)
C6	0.0200 (8)	0.0192 (8)	0.0275 (8)	−0.0044 (7)	−0.0070 (7)	0.0056 (6)
C7	0.0161 (8)	0.0220 (8)	0.0177 (7)	0.0005 (6)	0.0012 (6)	−0.0018 (6)
C8	0.0229 (9)	0.0414 (10)	0.0189 (8)	−0.0022 (8)	−0.0021 (7)	0.0043 (7)
C9	0.0233 (9)	0.0390 (10)	0.0323 (9)	0.0005 (8)	−0.0048 (8)	0.0118 (8)
C10	0.0227 (9)	0.0245 (9)	0.0426 (10)	0.0038 (7)	−0.0017 (8)	0.0016 (8)
C11	0.0205 (8)	0.0296 (9)	0.0294 (9)	−0.0057 (7)	0.0004 (7)	0.0044 (7)

Geometric parameters (Å, º) top

S1—C8	1.8098 (18)	C5—C6	1.382 (2)
S1—C7	1.8224 (15)	C5—H5A	0.9500
S2—C10	1.8171 (19)	C6—H6A	0.9500
S2—C7	1.8285 (16)	C7—C11	1.537 (2)
O1—N1	1.2282 (18)	C8—C9	1.521 (3)
O2—N1	1.2298 (18)	C8—H8A	0.9900
N1—C1	1.473 (2)	C8—H8B	0.9900
C1—C6	1.379 (2)	C9—C10	1.519 (3)
C1—C2	1.387 (2)	C9—H9A	0.9900
C2—C3	1.387 (2)	C9—H9B	0.9900
C2—H2A	0.9500	C10—H10A	0.9900
C3—C4	1.399 (2)	C10—H10B	0.9900
C3—C7	1.536 (2)	C11—H11A	0.9800
C4—C5	1.390 (2)	C11—H11B	0.9800
C4—H4A	0.9500	C11—H11C	0.9800

C8—S1—C7	101.13 (8)	C11—C7—S2	105.78 (11)
C10—S2—C7	101.75 (8)	S1—C7—S2	109.86 (8)
O1—N1—O2	123.30 (14)	C9—C8—S1	113.79 (12)
O1—N1—C1	118.64 (13)	C9—C8—H8A	108.8
O2—N1—C1	118.06 (14)	S1—C8—H8A	108.8
C6—C1—C2	123.08 (15)	C9—C8—H8B	108.8
C6—C1—N1	118.92 (14)	S1—C8—H8B	108.8
C2—C1—N1	117.99 (14)	H8A—C8—H8B	107.7
C1—C2—C3	119.22 (14)	C10—C9—C8	112.84 (14)
C1—C2—H2A	120.4	C10—C9—H9A	109.0
C3—C2—H2A	120.4	C8—C9—H9A	109.0
C2—C3—C4	118.28 (14)	C10—C9—H9B	109.0
C2—C3—C7	121.65 (13)	C8—C9—H9B	109.0
C4—C3—C7	119.78 (14)	H9A—C9—H9B	107.8
C5—C4—C3	121.25 (15)	C9—C10—S2	113.85 (13)
C5—C4—H4A	119.4	C9—C10—H10A	108.8
C3—C4—H4A	119.4	S2—C10—H10A	108.8
C6—C5—C4	120.50 (15)	C9—C10—H10B	108.8
C6—C5—H5A	119.8	S2—C10—H10B	108.8
C4—C5—H5A	119.8	H10A—C10—H10B	107.7
C1—C6—C5	117.65 (15)	C7—C11—H11A	109.5
C1—C6—H6A	121.2	C7—C11—H11B	109.5
C5—C6—H6A	121.2	H11A—C11—H11B	109.5
C3—C7—C11	108.41 (13)	C7—C11—H11C	109.5
C3—C7—S1	113.92 (10)	H11A—C11—H11C	109.5
C11—C7—S1	105.81 (11)	H11B—C11—H11C	109.5
C3—C7—S2	112.50 (11)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₂S₂
M_r	255.36
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	13.5388 (3), 7.2660 (1), 24.1083 (4)
V (Å³)	2371.60 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.899, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25370, 2086, 1871
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.074, 1.08
No. of reflections	2086
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.19

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008.

Acknowledgements

The financial support of this work by the Internal Founding Agency of Tomas Bata University in Zlin project No. IGA/FT/2012/016 is gratefully acknowledged.

References

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