Crystal structure of 2-(3-nitro­phen­yl)-1,3-di­thiane

Caracelli, I.; Zukerman-Schpector, J.; Stefani, H.A.; Gozhina, O.; Tiekink, E.R.T.

doi:10.1107/S2056989015002844

organic compounds

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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Pages o181-o182

doi:10.1107/S2056989015002844

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Crystal structure of 2-(3-nitrophenyl)-1,3-dithiane

Ignez Caracelli,^a ^* Julio Zukerman-Schpector,^b Hélio A. Stefani,^c Olga Gozhina ^c and Edward R. T. Tiekink ^d

^aDepartmento de Física, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bDepartmento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^cDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, 05508-900 São Paulo-SP, Brazil, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: julio@power.ufscar.br

Edited by P. C. Healy, Griffith University, Australia (Received 5 February 2015; accepted 10 February 2015; online 13 February 2015)

In the title compound, C₁₀H₁₁NO₂S₂, the 1,3-dithiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the remaining four atoms. The nitrobenzene substituent occupies an equatorial position and forms a dihedral angle of 88.28 (5)° with the least-squares plane through the 1,3-dithiane ring. The nitro group is twisted out of the plane of the benzene ring to which it is connected, forming a dihedral angle of 10.12 (3)°. In the crystal, molecules aggregate into supramolecular zigzag chains (glide symmetry along the c axis) via nitro–benzene N—O⋯π [N—O⋯Cg(benzene) = 3.4279 (18) Å and angle at O = 93.95 (11)°] interactions. The chains pack with no specific intermolecular interactions between them.

Keywords: crystal structure; 1,3-dithiane; conformation; N—O⋯π interactions.

CCDC reference: 1048518

1. Related literature

For background to substituted 1,3-dithianes, see: Ballesteros et al. (2005 ). For nitro–aryl N—O⋯π interactions, see: Huang et al. (2008 ). For the structure of the closely related 3-bromo-substituted compound, see: Zukerman-Schpector et al. (2015 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₁NO₂S₂
M_r = 241.32
Monoclinic, P 2₁ /c
a = 10.8547 (2) Å
b = 13.2655 (3) Å
c = 8.0891 (2) Å
β = 109.087 (1)°
V = 1100.74 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 293 K
0.49 × 0.46 × 0.21 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.687, T_max = 0.745
7241 measured reflections
2035 independent reflections
1799 reflections with I > 2σ(I)
R_int = 0.020

2.3. Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.06
2035 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR2014 (Burla et al., 2015 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1048518

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002844/hg5430sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015002844/hg5430Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015002844/hg5430Isup3.cml

checkCIF report

Related literature top

For background to substituted 1,3-dithianes, see: Ballesteros et al. (2005). For nitro–aryl N—O···π interactions, see: Huang et al. (2008). For the structure of the closely related 3-bromo-substituted compound, see: Zukerman-Schpector et al. (2015).

Experimental top

A solution of 3-nitrobenzaldehyde (0.037 mol, 1 equiv.) in chloroform (20 ml) was combined with an equimolar amount of propane-1,3-dithiol (3.7 ml, 0.037 mol) at room temperature. The solution was stirred for 1 h at this temperature, then cooled to -20 °C after which BF₃ etherate (0.46 ml, 0.0037 mol, 0.1 equiv.) was added drop-wise. The reaction solution was allowed to warm to room temperature and stirred overnight. After this time, the solution was washed three times each with water, 10% aqueous KOH, then water followed by drying over MgSO₄. Evaporation of the solvent furnishes a pure product as colourless crystals in 85% yield. To obtain crystals suitable for X-ray analysis, the product was crystallized from CH₃OH. ¹H NMR (300 MHz, CDCl₃) δ 8.37 (s, 1H), 8.18 (dt, J = 8.3, 2.6 Hz, 1H), 7.83 (ddd, J = 7.2, 3.6, 1.7 Hz, 1H), 7.63–7.48 (m, 1H), 5.26 (s, 1H), 3.10 (ddq, J = 14.4, 12.0, 2.3 Hz, 2H), 2.96 (ddp, J = 13.4, 5.1, 2.7 Hz, 2H), 2.23 (dtq, J = 14.0, 4.6, 2.3 Hz, 1H), 1.98 (dddd, J = 14.3, 12.1, 9.8, 6.0 Hz, 1H). ¹³C NMR (75 MHz, CDCl₃) δ 148.39, 141.18, 133.99, 129.70, 123.36, 123.12, 50.19 (2 x C), 31.75, 24.78. M.pt: 368 K. IR (cm^-1): ν 1525 (N—O); 1348 (N—O); 724 and 687 (C—S),

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. Upper view: detail of the nitro-N—O···π(benzene) interaction. Lower view: the zigzag supramolecular chain along the c axis (glide symmetry) mediated by nitro-N—O···π(benzene) interactions shown as purple dashed lines.
	Fig. 3. A view in projection down the b axis of the unit-cell contents. The nitro-N—O···π(benzene) interactions are shown as purple dashed lines.

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

Crystal data top

C₁₀H₁₁NO₂S₂	F(000) = 504
M_r = 241.32	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8547 (2) Å	Cell parameters from 4425 reflections
b = 13.2655 (3) Å	θ = 2.5–25.4°
c = 8.0891 (2) Å	µ = 0.46 mm⁻¹
β = 109.087 (1)°	T = 293 K
V = 1100.74 (4) Å³	Slab, colourless
Z = 4	0.49 × 0.46 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	1799 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.020
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 25.4°, θ_min = 2.0°
T_min = 0.687, T_max = 0.745	h = −13→12
7241 measured reflections	k = −16→16
2035 independent reflections	l = −8→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0444P)² + 0.3472P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.29 e Å⁻³
2035 reflections	Δρ_min = −0.24 e Å⁻³
137 parameters	Extinction correction: SHELXL2014 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0192 (17)

Crystal data top

C₁₀H₁₁NO₂S₂	V = 1100.74 (4) Å³
M_r = 241.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8547 (2) Å	µ = 0.46 mm⁻¹
b = 13.2655 (3) Å	T = 293 K
c = 8.0891 (2) Å	0.49 × 0.46 × 0.21 mm
β = 109.087 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2035 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1799 reflections with I > 2σ(I)
T_min = 0.687, T_max = 0.745	R_int = 0.020
7241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	Δρ_max = 0.29 e Å⁻³
2035 reflections	Δρ_min = −0.24 e Å⁻³
137 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
S1	0.93087 (4)	0.75719 (3)	0.69969 (5)	0.04460 (16)
S2	0.93019 (4)	0.98623 (3)	0.69835 (6)	0.04646 (16)
O1	0.54267 (18)	0.88063 (13)	0.15045 (19)	0.0830 (5)
O2	0.35484 (16)	0.85594 (14)	0.1765 (2)	0.0917 (6)
N1	0.47188 (18)	0.86855 (11)	0.2380 (2)	0.0608 (5)
C1	0.86732 (14)	0.87164 (10)	0.76325 (19)	0.0340 (3)
H1	0.8887	0.8719	0.8907	0.041*
C2	1.10282 (17)	0.96790 (14)	0.8068 (2)	0.0511 (4)
H2A	1.1494	1.0248	0.7804	0.061*
H2B	1.1198	0.9673	0.9322	0.061*
C3	1.15622 (17)	0.87200 (13)	0.7556 (2)	0.0519 (5)
H3A	1.1364	0.8713	0.6297	0.062*
H3B	1.2503	0.8720	0.8085	0.062*
C4	1.10278 (17)	0.77709 (14)	0.8096 (2)	0.0503 (4)
H4A	1.1185	0.7796	0.9347	0.060*
H4B	1.1503	0.7198	0.7868	0.060*
C5	0.72187 (15)	0.87186 (10)	0.6807 (2)	0.0353 (3)
C6	0.66533 (16)	0.86907 (11)	0.4999 (2)	0.0403 (4)
H6	0.7169	0.8669	0.4280	0.048*
C7	0.53161 (17)	0.86960 (11)	0.4295 (2)	0.0454 (4)
C8	0.45093 (17)	0.87258 (13)	0.5303 (3)	0.0538 (5)
H8	0.3607	0.8722	0.4790	0.065*
C9	0.50821 (18)	0.87617 (13)	0.7092 (3)	0.0539 (5)
H9	0.4561	0.8788	0.7803	0.065*
C10	0.64180 (17)	0.87591 (11)	0.7842 (2)	0.0441 (4)
H10	0.6789	0.8785	0.9053	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0499 (3)	0.0379 (2)	0.0436 (3)	0.00382 (16)	0.01201 (19)	−0.00589 (15)
S2	0.0441 (3)	0.0374 (3)	0.0589 (3)	−0.00061 (16)	0.0181 (2)	0.00780 (17)
O1	0.0889 (12)	0.1119 (14)	0.0382 (8)	0.0027 (9)	0.0071 (8)	0.0037 (7)
O2	0.0563 (9)	0.1212 (14)	0.0696 (10)	0.0056 (9)	−0.0178 (8)	−0.0135 (9)
N1	0.0629 (11)	0.0593 (10)	0.0454 (9)	0.0066 (7)	−0.0023 (8)	−0.0033 (7)
C1	0.0388 (8)	0.0344 (8)	0.0294 (7)	−0.0002 (6)	0.0119 (6)	−0.0002 (5)
C2	0.0416 (9)	0.0581 (11)	0.0532 (10)	−0.0114 (8)	0.0152 (8)	−0.0059 (8)
C3	0.0368 (8)	0.0729 (13)	0.0477 (10)	0.0044 (8)	0.0161 (7)	0.0004 (8)
C4	0.0467 (9)	0.0580 (11)	0.0433 (9)	0.0163 (8)	0.0107 (7)	0.0050 (7)
C5	0.0378 (8)	0.0338 (8)	0.0351 (8)	−0.0015 (6)	0.0128 (6)	0.0003 (5)
C6	0.0426 (9)	0.0438 (9)	0.0355 (8)	0.0009 (6)	0.0140 (7)	0.0009 (6)
C7	0.0456 (9)	0.0417 (9)	0.0408 (9)	−0.0002 (7)	0.0032 (7)	−0.0022 (6)
C8	0.0353 (9)	0.0542 (11)	0.0689 (12)	−0.0036 (7)	0.0131 (8)	−0.0020 (8)
C9	0.0462 (10)	0.0625 (12)	0.0608 (11)	−0.0065 (8)	0.0282 (9)	−0.0023 (8)
C10	0.0472 (9)	0.0490 (9)	0.0403 (9)	−0.0052 (7)	0.0201 (7)	−0.0006 (7)

Geometric parameters (Å, º) top

S1—C4	1.8048 (18)	C3—H3B	0.9700
S1—C1	1.8102 (14)	C4—H4A	0.9700
S2—C2	1.8069 (18)	C4—H4B	0.9700
S2—C1	1.8128 (14)	C5—C6	1.389 (2)
O1—N1	1.214 (2)	C5—C10	1.391 (2)
O2—N1	1.215 (2)	C6—C7	1.375 (2)
N1—C7	1.471 (2)	C6—H6	0.9300
C1—C5	1.500 (2)	C7—C8	1.379 (3)
C1—H1	0.9800	C8—C9	1.377 (3)
C2—C3	1.511 (2)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.377 (3)
C2—H2B	0.9700	C9—H9	0.9300
C3—C4	1.509 (3)	C10—H10	0.9300
C3—H3A	0.9700

C4—S1—C1	99.55 (8)	C3—C4—H4A	108.7
C2—S2—C1	100.11 (8)	S1—C4—H4A	108.7
O1—N1—O2	123.77 (18)	C3—C4—H4B	108.7
O1—N1—C7	117.90 (17)	S1—C4—H4B	108.7
O2—N1—C7	118.32 (19)	H4A—C4—H4B	107.6
C5—C1—S1	108.59 (10)	C6—C5—C10	119.13 (15)
C5—C1—S2	108.10 (10)	C6—C5—C1	120.46 (13)
S1—C1—S2	113.99 (8)	C10—C5—C1	120.41 (14)
C5—C1—H1	108.7	C7—C6—C5	118.65 (15)
S1—C1—H1	108.7	C7—C6—H6	120.7
S2—C1—H1	108.7	C5—C6—H6	120.7
C3—C2—S2	114.22 (12)	C6—C7—C8	122.93 (16)
C3—C2—H2A	108.7	C6—C7—N1	118.60 (16)
S2—C2—H2A	108.7	C8—C7—N1	118.46 (16)
C3—C2—H2B	108.7	C9—C8—C7	117.84 (16)
S2—C2—H2B	108.7	C9—C8—H8	121.1
H2A—C2—H2B	107.6	C7—C8—H8	121.1
C4—C3—C2	113.89 (15)	C10—C9—C8	120.77 (16)
C4—C3—H3A	108.8	C10—C9—H9	119.6
C2—C3—H3A	108.8	C8—C9—H9	119.6
C4—C3—H3B	108.8	C9—C10—C5	120.67 (16)
C2—C3—H3B	108.8	C9—C10—H10	119.7
H3A—C3—H3B	107.7	C5—C10—H10	119.7
C3—C4—S1	114.37 (12)

C4—S1—C1—C5	178.82 (10)	C1—C5—C6—C7	−179.86 (13)
C4—S1—C1—S2	58.27 (10)	C5—C6—C7—C8	−0.1 (2)
C2—S2—C1—C5	−178.78 (10)	C5—C6—C7—N1	178.88 (13)
C2—S2—C1—S1	−57.95 (10)	O1—N1—C7—C6	−9.5 (2)
C1—S2—C2—C3	57.35 (14)	O2—N1—C7—C6	170.67 (16)
S2—C2—C3—C4	−65.25 (19)	O1—N1—C7—C8	169.54 (17)
C2—C3—C4—S1	66.18 (19)	O2—N1—C7—C8	−10.3 (2)
C1—S1—C4—C3	−58.63 (14)	C6—C7—C8—C9	0.7 (2)
S1—C1—C5—C6	−60.31 (15)	N1—C7—C8—C9	−178.35 (15)
S2—C1—C5—C6	63.82 (15)	C7—C8—C9—C10	−0.5 (3)
S1—C1—C5—C10	120.35 (13)	C8—C9—C10—C5	−0.1 (2)
S2—C1—C5—C10	−115.51 (13)	C6—C5—C10—C9	0.6 (2)
C10—C5—C6—C7	−0.5 (2)	C1—C5—C10—C9	179.98 (14)

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₂S₂
M_r	241.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.8547 (2), 13.2655 (3), 8.0891 (2)
β (°)	109.087 (1)
V (Å³)	1100.74 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.49 × 0.46 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.687, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	7241, 2035, 1799
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.06
No. of reflections	2035
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR2014 (Burla et al., 2015), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).

Acknowledgements

We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013-2 to JZS, 306121/2013-2 to IC and 308320/2010-7 to HAS), FAPESP (2012/00424-2 and 2013/2192–2) and CAPES are acknowledged for financial support.

References

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