2-(4-Nitro­phen­yl)-1,3-dithiane

Abstract

The nitro group in the title compound, C₁₀H₁₁NO₂S₂, is almost coplanar with the benzene ring, making a dihedral angle of 3.42 (8)°. The 1,3-dithiane ring adopts a chair conformation. The crystal structure is stabilized by inter­molecular C—H⋯O and C—H⋯π [C⋯Cg = 3.4972 (10) Å] inter­actions.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the calculation of ring puckering parameters, see: Cremer & Pople (1975 ▶). For related literature and applications see, for example: Goswami & Maity (2008 ▶); Fun et al. (2009 ▶).

Experimental

Crystal data

• C₁₀H₁₁NO₂S₂

• M _r = 241.32

• Orthorhombic,

• a = 8.7724 (1) Å

• b = 10.2079 (1) Å

• c = 11.9942 (1) Å

• V = 1074.05 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.47 mm⁻¹

• T = 100 (1) K

• 0.46 × 0.22 × 0.08 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.813, T _max = 0.964

• 30643 measured reflections

• 4725 independent reflections

• 4511 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 0.061

• S = 1.06

• 4725 reflections

• 136 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

• Absolute structure: Flack (1983 ▶), 2050 Friedel pairs

• Flack parameter: 0.01 (4)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O2i	0.93	2.59	3.3346 (12)	137
C1—H1A⋯Cg1ii	0.97	2.60	3.4972 (10)	154

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the benzene ring.

supplementary crystallographic information

Comment

Thioacetal protection of carbonyl groups is of paramount importance in synthetic organic chemistry and hence, the development of novel thionation reactions remains of great interest (Goswami & Maity, 2008; Fun et al., 2009). In addition, thioacetals are also utilized as masked acyl anions or masked methylene functions in carbon-carbon bond forming reactions. Herein, we report the synthesis of 2-(4-nitro-phenyl)-[1,3]-dithiane (I) from 4-nitrobenzaldehyde using boron trifluoride etherate catalyst.

Compound (I), Fig. 1, comprises a single molecule in the asymmetric unit. The nitro group is almost coplanar with the benzene ring, making a dihedral angle of 3.42 (8)°. The thiacyclohexane ring adopts a chair conformation with the ring puckering parameters (Cremer & Pople, 1975) of Q = 0.7137 (8) Å, Θ = 173.96 (7)°, and Φ = 135.6 (7)°. The crystal structure is stabilized by intermolecular C—H···O and C—H···π interactions, Table 1.

Experimental

To a stirred dichloromethane (50 mL) solution, maintained at 273 K, of 4-nitrobenzaldehyde (500 mg, 3.31 mmol) and boron trifluoride etherate (0.5 mL) was added dropwise 1,3-propanedithiol (450 mg, 4.1 mmol) over 15 min. The mixture was stirred at room temperature for 4 h and the progress of the reaction monitored by TLC. After completion of the reaction, NaHCO₃ solution was added carefully at room temperature to neutralize the mixture which was then extracted with dichloromethane. The organic layer was dried (anhydrous Na₂SO₄) and the solvent removed under reduced pressure. The crude product was purified by column chromatography using silica gel with 10% ethyl acetate in petroleum ether as eluant to afford (I) (674 mg, 84%) as a colourless crystalline solid along with the other thiane derivatives.

Refinement

All hydrogen atoms were positioned geometrically and refined with a riding model approximation with C—H = 0.93-0.98 Å, and with U_iso (H) = 1.2 U_eq (C).

Figures

Fig. 1.

The molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering.

Crystal data

C10H11NO2S2	F(000) = 504
Mr = 241.32	Dx = 1.492 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9979 reflections
a = 8.7724 (1) Å	θ = 2.6–38.5°
b = 10.2079 (1) Å	µ = 0.47 mm−1
c = 11.9942 (1) Å	T = 100 K
V = 1074.05 (2) Å3	Block, colourless
Z = 4	0.46 × 0.22 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	4725 independent reflections
Radiation source: fine-focus sealed tube	4511 reflections with I > 2σ(I)
graphite	Rint = 0.038
φ and ω scans	θmax = 35.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
Tmin = 0.813, Tmax = 0.964	k = −16→16
30643 measured reflections	l = −18→19

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024	H-atom parameters constrained
wR(F2) = 0.061	w = 1/[σ2(Fo2) + (0.0321P)2 + 0.1305P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
4725 reflections	Δρmax = 0.33 e Å−3
136 parameters	Δρmin = −0.25 e Å−3
0 restraints	Absolute structure: Flack (1983), 2050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (4)

Special details

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.78978 (3)	0.06239 (2)	0.216265 (18)	0.01399 (5)
S2	1.07695 (3)	0.22170 (2)	0.261209 (18)	0.01492 (5)
O1	0.99728 (9)	0.26901 (8)	−0.32568 (6)	0.01819 (14)
O2	1.12536 (10)	0.08795 (8)	−0.33808 (6)	0.02137 (15)
N1	1.05536 (9)	0.17161 (8)	−0.28383 (7)	0.01391 (13)
C1	0.80248 (11)	0.03483 (9)	0.36543 (8)	0.01526 (16)
H1A	0.7009	0.0182	0.3941	0.018*
H1B	0.8631	−0.0431	0.3785	0.018*
C2	0.87227 (11)	0.14837 (10)	0.43022 (8)	0.01481 (15)
H2A	0.8157	0.2276	0.4135	0.018*
H2B	0.8618	0.1312	0.5094	0.018*
C3	1.03975 (11)	0.17104 (11)	0.40367 (8)	0.01636 (17)
H3A	1.0954	0.0907	0.4182	0.020*
H3B	1.0790	0.2376	0.4538	0.020*
C4	0.99151 (10)	0.08515 (9)	0.18616 (7)	0.01235 (15)
H4A	1.0463	0.0046	0.2055	0.015*
C5	1.01013 (10)	0.11049 (9)	0.06296 (7)	0.01189 (14)
C6	1.09657 (10)	0.02450 (9)	−0.00171 (7)	0.01299 (15)
H6A	1.1440	−0.0468	0.0318	0.016*
C7	1.11247 (10)	0.04450 (9)	−0.11583 (8)	0.01293 (15)
H7A	1.1690	−0.0131	−0.1593	0.016*
C8	1.04185 (10)	0.15252 (9)	−0.16301 (7)	0.01169 (14)
C9	0.95653 (11)	0.24152 (9)	−0.10131 (8)	0.01406 (16)
H9A	0.9114	0.3138	−0.1351	0.017*
C10	0.94071 (11)	0.21912 (9)	0.01268 (7)	0.01455 (15)
H10A	0.8836	0.2768	0.0558	0.017*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.01279 (8)	0.01716 (10)	0.01201 (9)	−0.00234 (7)	−0.00105 (7)	−0.00003 (8)
S2	0.01512 (9)	0.01748 (10)	0.01216 (9)	−0.00450 (7)	0.00056 (7)	−0.00083 (7)
O1	0.0228 (3)	0.0179 (3)	0.0138 (3)	0.0016 (3)	−0.0017 (3)	0.0050 (3)
O2	0.0286 (4)	0.0219 (4)	0.0136 (3)	0.0056 (3)	0.0052 (3)	−0.0013 (3)
N1	0.0149 (3)	0.0152 (3)	0.0117 (3)	−0.0013 (3)	0.0008 (3)	0.0010 (3)
C1	0.0167 (4)	0.0169 (4)	0.0121 (4)	−0.0023 (3)	0.0021 (3)	0.0002 (3)
C2	0.0148 (4)	0.0183 (4)	0.0113 (4)	−0.0002 (3)	0.0016 (3)	−0.0019 (3)
C3	0.0147 (4)	0.0236 (4)	0.0108 (4)	−0.0019 (3)	−0.0012 (3)	−0.0010 (3)
C4	0.0133 (3)	0.0137 (4)	0.0100 (3)	0.0006 (3)	−0.0004 (3)	0.0001 (3)
C5	0.0127 (3)	0.0127 (3)	0.0103 (3)	0.0002 (3)	−0.0003 (3)	0.0006 (3)
C6	0.0142 (4)	0.0128 (3)	0.0120 (3)	0.0023 (3)	0.0001 (3)	0.0017 (3)
C7	0.0130 (3)	0.0134 (4)	0.0124 (3)	0.0009 (3)	0.0007 (3)	−0.0006 (3)
C8	0.0130 (3)	0.0131 (4)	0.0090 (3)	−0.0012 (3)	0.0005 (3)	0.0008 (3)
C9	0.0169 (4)	0.0130 (4)	0.0123 (4)	0.0025 (3)	0.0000 (3)	0.0015 (3)
C10	0.0182 (4)	0.0139 (4)	0.0116 (3)	0.0034 (3)	0.0007 (3)	0.0000 (3)

Geometric parameters (Å, °)

S1—C1	1.8145 (9)	C3—H3B	0.9700
S1—C4	1.8210 (9)	C4—C5	1.5090 (12)
S2—C3	1.8148 (10)	C4—H4A	0.9800
S2—C4	1.8208 (9)	C5—C6	1.3953 (13)
O1—N1	1.2248 (10)	C5—C10	1.4016 (13)
O2—N1	1.2368 (11)	C6—C7	1.3910 (13)
N1—C8	1.4670 (11)	C6—H6A	0.9300
C1—C2	1.5238 (13)	C7—C8	1.3855 (12)
C1—H1A	0.9700	C7—H7A	0.9300
C1—H1B	0.9700	C8—C9	1.3905 (13)
C2—C3	1.5210 (13)	C9—C10	1.3930 (13)
C2—H2A	0.9700	C9—H9A	0.9300
C2—H2B	0.9700	C10—H10A	0.9300
C3—H3A	0.9700
C1—S1—C4	98.95 (4)	C5—C4—S1	108.74 (6)
C3—S2—C4	99.98 (4)	S2—C4—S1	113.56 (5)
O1—N1—O2	123.46 (8)	C5—C4—H4A	108.8
O1—N1—C8	118.63 (8)	S2—C4—H4A	108.8
O2—N1—C8	117.91 (8)	S1—C4—H4A	108.8
C2—C1—S1	114.18 (6)	C6—C5—C10	119.65 (8)
C2—C1—H1A	108.7	C6—C5—C4	119.69 (8)
S1—C1—H1A	108.7	C10—C5—C4	120.66 (8)
C2—C1—H1B	108.7	C7—C6—C5	120.61 (8)
S1—C1—H1B	108.7	C7—C6—H6A	119.7
H1A—C1—H1B	107.6	C5—C6—H6A	119.7
C3—C2—C1	113.39 (8)	C8—C7—C6	118.28 (8)
C3—C2—H2A	108.9	C8—C7—H7A	120.9
C1—C2—H2A	108.9	C6—C7—H7A	120.9
C3—C2—H2B	108.9	C7—C8—C9	122.91 (8)
C1—C2—H2B	108.9	C7—C8—N1	118.23 (8)
H2A—C2—H2B	107.7	C9—C8—N1	118.85 (8)
C2—C3—S2	114.47 (6)	C8—C9—C10	117.95 (8)
C2—C3—H3A	108.6	C8—C9—H9A	121.0
S2—C3—H3A	108.6	C10—C9—H9A	121.0
C2—C3—H3B	108.6	C9—C10—C5	120.59 (8)
S2—C3—H3B	108.6	C9—C10—H10A	119.7
H3A—C3—H3B	107.6	C5—C10—H10A	119.7
C5—C4—S2	107.96 (6)
C4—S1—C1—C2	60.04 (8)	C4—C5—C6—C7	178.61 (8)
S1—C1—C2—C3	−66.54 (10)	C5—C6—C7—C8	0.73 (13)
C1—C2—C3—S2	64.81 (10)	C6—C7—C8—C9	0.18 (14)
C4—S2—C3—C2	−57.45 (8)	C6—C7—C8—N1	−178.43 (8)
C3—S2—C4—C5	179.49 (6)	O1—N1—C8—C7	−177.77 (8)
C3—S2—C4—S1	58.85 (6)	O2—N1—C8—C7	2.17 (12)
C1—S1—C4—C5	−179.95 (6)	O1—N1—C8—C9	3.56 (12)
C1—S1—C4—S2	−59.74 (6)	O2—N1—C8—C9	−176.50 (9)
S2—C4—C5—C6	117.37 (8)	C7—C8—C9—C10	−0.79 (14)
S1—C4—C5—C6	−119.01 (8)	N1—C8—C9—C10	177.81 (8)
S2—C4—C5—C10	−63.01 (10)	C8—C9—C10—C5	0.50 (14)
S1—C4—C5—C10	60.60 (10)	C6—C5—C10—C9	0.38 (14)
C10—C5—C6—C7	−1.01 (14)	C4—C5—C10—C9	−179.24 (9)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2i	0.93	2.59	3.3346 (12)	137
C1—H1A···Cg1ii	0.97	2.60	3.4972 (10)	154

Symmetry codes: (i) −x+5/2, −y, z+1/2; (ii) −x+3/2, −y, z+1/2.