2-(4-Nitro­phen­yl)-1,3-dithiane

Fun, H.-K.; Kia, R.; Maity, A.C.; Goswami, S.

doi:10.1107/S1600536809001809

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o348

doi:10.1107/S1600536809001809

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2-(4-Nitrophenyl)-1,3-dithiane

Hoong-Kun Fun,^a ^* Reza Kia,^a Annada C. Maity ^b and Shyamaprosad Goswami ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711 103, India
^*Correspondence e-mail: hkfun@usm.my

(Received 14 January 2009; accepted 14 January 2009; online 17 January 2009)

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, P 2₁ 2₁ 2₁
a = 8.7724 (1) Å
b = 10.2079 (1) Å
c = 11.9942 (1) Å
V = 1074.05 (2) Å³
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[F² > 2σ(F²)] = 0.024
wR(F²) = 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)

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) $[-x+{\script{5\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ . Cg1 is the centroid of the benzene ring.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001809/tk2357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001809/tk2357Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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). Cg1 is the centroid of the benzene ring.

Experimental top

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.

Computing details top

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

Figures top

Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering.

2-(4-Nitrophenyl)-1,3-dithiane top

Crystal data top

C₁₀H₁₁NO₂S₂	F(000) = 504
M_r = 241.32	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0321P)² + 0.1305P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4725 reflections	Δρ_max = 0.33 e Å⁻³
136 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

Crystal data top

C₁₀H₁₁NO₂S₂	V = 1074.05 (2) Å³
M_r = 241.32	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.7724 (1) Å	µ = 0.47 mm⁻¹
b = 10.2079 (1) Å	T = 100 K
c = 11.9942 (1) Å	0.46 × 0.22 × 0.08 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4725 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4511 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.964	R_int = 0.038
30643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.061	Δρ_max = 0.33 e Å⁻³
S = 1.06	Δρ_min = −0.25 e Å⁻³
4725 reflections	Absolute structure: Flack (1983), 2050 Friedel pairs
136 parameters	Absolute structure parameter: 0.01 (4)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₂S₂
M_r	241.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	8.7724 (1), 10.2079 (1), 11.9942 (1)
V (Å³)	1074.05 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.46 × 0.22 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.813, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	30643, 4725, 4511
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.061, 1.06
No. of reflections	4725
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25
Absolute structure	Flack (1983), 2050 Friedel pairs
Absolute structure parameter	0.01 (4)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for Science Fund grant No. 305/PFIZIK/613312. ACM and SG acknowledge the DST (grant No. SR/S1/OC-13/2005), Government of India, for financial support. ACM thanks the UGC, Government of India, for a fellowship. The authors also thank the Universiti Sains Malaysia for Research University Golden Goose grant No. 1001/PFIZIK/811012.

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