2-Nitro­benzyl methane­sulfonate

Anuradha, V.; Madan Kumar, S.; Siddaraju, B.P.; Lokanath, N.K.; Nagendra, P.

doi:10.1107/S160053681400899X

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o616

doi:10.1107/S160053681400899X

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2-Nitrobenzyl methanesulfonate

Venkatramu Anuradha,^a S. Madan Kumar,^b B. P. Siddaraju,^c N. K. Lokanath ^b and P. Nagendra ^c ^*

^aDepartment of Physics, Dr M. G. R. Educational and Research Institute, Maduravoyal, Chennai, India, ^bDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Chemistry, BET Academy of Higher Education, Bharathi College, Bharthi Nagara, Mandya 571 422, India
^*Correspondence e-mail: nagendra088@yahoo.co.in

(Received 8 April 2014; accepted 21 April 2014; online 30 April 2014)

In the title compound, C₈H₉NO₅S, the dihedral angle between the benzene ring and the nitro group is 5.86 (15)° and the C—C—O—S group adopts an anti conformation [torsion angle = −168.44 (15)°]. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, generating a three-dimensional network.

CCDC reference: 998614

Related literature

For background to nitrobenzene derivatives, see: Ranu & Banerjee (2005 ); Ballini et al. (2005 ). For a related structure, see: Khan et al. (2008 ).

Experimental

Crystal data

C₈H₉NO₅S
M_r = 231.23
Monoclinic, P 2₁ /c
a = 12.414 (3) Å
b = 7.967 (2) Å
c = 10.994 (3) Å
β = 112.235 (11)°
V = 1006.5 (5) Å³
Z = 4
Cu Kα radiation
μ = 2.94 mm⁻¹
T = 296 K
0.23 × 0.22 × 0.21 mm

Data collection

Bruker X8 Proteum CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.552, T_max = 0.578
6524 measured reflections
1663 independent reflections
1541 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.112
S = 1.08
1663 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.54	3.266 (3)	135
C3—H3⋯O2ⁱⁱ	0.93	2.53	3.335 (3)	145
C7—H7B⋯O4ⁱⁱⁱ	0.97	2.58	3.539 (3)	169
C8—H8A⋯O4ⁱⁱⁱ	0.96	2.42	3.374 (4)	172
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 998614

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681400899X/hb7217sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681400899X/hb7217Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681400899X/hb7217Isup3.cml

checkCIF report

Comment top

Nitroalkenes have been used as substrates for Michael addition reactions (Ranu & Banerjee, 2005) and for the synthesis of many organic molecules (Ballini et al., 2005).

The ORTEP of the title molecule is shown in figure 1. The molecules in the crystal structure are connected with C—H···O hydrogen bonds (Table 1). The C8—H8B···O4 hydrogen bond exhibits ring motifs of the type R²₂(8). The overall geometry of the title compound is similar to the 3,5-dinitrobenzyl methanesulfonate (Khan et al., 2008). Overall packing of the molecule is shown in figure 2.

Related literature top

For background to nitrobenzene derivatives, see: Ranu & Banerjee (2005); Ballini et al. (2005). For a related structure, see: Khan et al. (2008).

Experimental top

Red blocks were obtained from slow evaporation of a solution of ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title molecule, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A viewed along the b axis of the crystal packing of the title compound.

2-Nitrobenzyl methanesulfonate top

Crystal data top

C₈H₉NO₅S	F(000) = 480
M_r = 231.23	D_x = 1.526 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 1663 reflections
a = 12.414 (3) Å	θ = 3.8–64.5°
b = 7.967 (2) Å	µ = 2.94 mm⁻¹
c = 10.994 (3) Å	T = 296 K
β = 112.235 (11)°	Block, red
V = 1006.5 (5) Å³	0.23 × 0.22 × 0.21 mm
Z = 4

Data collection top

Bruker X8 Proteum CCD diffractometer	1663 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1541 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.047
Detector resolution: 10.7 pixels mm^-1	θ_max = 64.5°, θ_min = 3.9°
ϕ and ω scans	h = −14→13
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −8→9
T_min = 0.552, T_max = 0.578	l = −12→9
6524 measured reflections

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0554P)² + 0.5912P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1663 reflections	Δρ_max = 0.41 e Å⁻³
138 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), FC^*=KFC[1+0.001XFC²Λ³/SIN(2Θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0114 (9)

Crystal data top

C₈H₉NO₅S	V = 1006.5 (5) Å³
M_r = 231.23	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.414 (3) Å	µ = 2.94 mm⁻¹
b = 7.967 (2) Å	T = 296 K
c = 10.994 (3) Å	0.23 × 0.22 × 0.21 mm
β = 112.235 (11)°

Data collection top

Bruker X8 Proteum CCD diffractometer	1663 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1541 reflections with I > 2σ(I)
T_min = 0.552, T_max = 0.578	R_int = 0.047
6524 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.08	Δρ_max = 0.41 e Å⁻³
1663 reflections	Δρ_min = −0.32 e Å⁻³
138 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.08637 (5)	0.25179 (7)	0.06271 (5)	0.0405 (2)
O1	0.43500 (18)	0.3906 (3)	0.69206 (16)	0.0672 (7)
O2	0.36003 (19)	0.2381 (2)	0.52088 (19)	0.0601 (7)
O3	0.16548 (14)	0.3941 (2)	0.15092 (14)	0.0458 (5)
O4	0.05351 (17)	0.3133 (3)	−0.06740 (15)	0.0592 (7)
O5	0.14617 (16)	0.0958 (2)	0.09607 (18)	0.0584 (6)
N1	0.38559 (15)	0.3744 (2)	0.57357 (17)	0.0376 (6)
C1	0.35397 (16)	0.5255 (2)	0.49184 (19)	0.0295 (6)
C2	0.3940 (2)	0.6755 (3)	0.5560 (2)	0.0411 (7)
C3	0.3686 (2)	0.8231 (3)	0.4862 (3)	0.0523 (9)
C4	0.3040 (2)	0.8185 (3)	0.3534 (3)	0.0533 (9)
C5	0.2634 (2)	0.6678 (3)	0.2901 (2)	0.0424 (7)
C6	0.28708 (17)	0.5157 (3)	0.35717 (19)	0.0310 (6)
C7	0.2405 (2)	0.3532 (3)	0.2870 (2)	0.0387 (7)
C8	−0.0341 (2)	0.2504 (3)	0.1059 (3)	0.0526 (9)
H2	0.43780	0.67660	0.64580	0.0490*
H3	0.39490	0.92490	0.52830	0.0630*
H4	0.28730	0.91790	0.30560	0.0640*
H5	0.21920	0.66820	0.20030	0.0510*
H7A	0.30420	0.28170	0.28830	0.0460*
H7B	0.19630	0.29430	0.32990	0.0460*
H8A	−0.01050	0.22110	0.19700	0.0790*
H8B	−0.08950	0.16960	0.05320	0.0790*
H8C	−0.06920	0.35980	0.09150	0.0790*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0457 (4)	0.0446 (4)	0.0265 (3)	−0.0009 (2)	0.0083 (3)	−0.0091 (2)
O1	0.0821 (13)	0.0607 (13)	0.0332 (10)	0.0016 (10)	−0.0071 (9)	0.0119 (8)
O2	0.0803 (13)	0.0282 (9)	0.0564 (12)	0.0036 (8)	0.0083 (10)	0.0025 (7)
O3	0.0555 (10)	0.0432 (9)	0.0289 (8)	−0.0069 (7)	0.0050 (7)	−0.0037 (7)
O4	0.0670 (11)	0.0806 (14)	0.0262 (9)	−0.0037 (10)	0.0134 (8)	−0.0061 (8)
O5	0.0595 (11)	0.0463 (11)	0.0559 (11)	0.0051 (8)	0.0065 (9)	−0.0161 (8)
N1	0.0376 (9)	0.0337 (10)	0.0345 (10)	0.0023 (7)	0.0056 (8)	0.0053 (8)
C1	0.0322 (10)	0.0256 (10)	0.0298 (10)	0.0008 (8)	0.0106 (8)	0.0013 (8)
C2	0.0463 (12)	0.0365 (12)	0.0349 (12)	−0.0059 (10)	0.0090 (10)	−0.0070 (9)
C3	0.0668 (16)	0.0272 (12)	0.0591 (16)	−0.0085 (11)	0.0197 (13)	−0.0070 (11)
C4	0.0712 (16)	0.0295 (12)	0.0571 (16)	−0.0019 (11)	0.0220 (13)	0.0121 (11)
C5	0.0531 (13)	0.0382 (13)	0.0325 (11)	−0.0006 (10)	0.0123 (10)	0.0058 (9)
C6	0.0339 (10)	0.0299 (11)	0.0303 (10)	−0.0002 (8)	0.0135 (9)	−0.0014 (8)
C7	0.0465 (12)	0.0361 (12)	0.0279 (11)	−0.0004 (9)	0.0079 (9)	−0.0034 (8)
C8	0.0529 (15)	0.0635 (18)	0.0402 (14)	−0.0060 (11)	0.0163 (12)	−0.0060 (11)

Geometric parameters (Å, º) top

S1—O3	1.5715 (17)	C4—C5	1.384 (3)
S1—O4	1.4181 (18)	C5—C6	1.391 (3)
S1—O5	1.4227 (18)	C6—C7	1.506 (3)
S1—C8	1.732 (3)	C2—H2	0.9300
O1—N1	1.219 (2)	C3—H3	0.9300
O2—N1	1.215 (2)	C4—H4	0.9300
O3—C7	1.469 (3)	C5—H5	0.9300
N1—C1	1.464 (2)	C7—H7A	0.9700
C1—C2	1.381 (3)	C7—H7B	0.9700
C1—C6	1.399 (3)	C8—H8A	0.9600
C2—C3	1.374 (3)	C8—H8B	0.9600
C3—C4	1.375 (4)	C8—H8C	0.9600

O3—S1—O4	104.31 (11)	O3—C7—C6	107.68 (18)
O3—S1—O5	109.14 (10)	C1—C2—H2	120.00
O3—S1—C8	103.78 (11)	C3—C2—H2	120.00
O4—S1—O5	119.00 (13)	C2—C3—H3	120.00
O4—S1—C8	109.28 (14)	C4—C3—H3	120.00
O5—S1—C8	110.13 (12)	C3—C4—H4	120.00
S1—O3—C7	118.41 (14)	C5—C4—H4	120.00
O1—N1—O2	122.6 (2)	C4—C5—H5	119.00
O1—N1—C1	118.59 (18)	C6—C5—H5	119.00
O2—N1—C1	118.77 (17)	O3—C7—H7A	110.00
N1—C1—C2	115.91 (17)	O3—C7—H7B	110.00
N1—C1—C6	121.17 (17)	C6—C7—H7A	110.00
C2—C1—C6	122.93 (18)	C6—C7—H7B	110.00
C1—C2—C3	119.6 (2)	H7A—C7—H7B	108.00
C2—C3—C4	119.3 (2)	S1—C8—H8A	109.00
C3—C4—C5	120.8 (2)	S1—C8—H8B	110.00
C4—C5—C6	121.7 (2)	S1—C8—H8C	110.00
C1—C6—C5	115.73 (19)	H8A—C8—H8B	109.00
C1—C6—C7	123.31 (19)	H8A—C8—H8C	109.00
C5—C6—C7	120.95 (18)	H8B—C8—H8C	109.00

O4—S1—O3—C7	−163.22 (18)	C2—C1—C6—C5	0.5 (3)
O5—S1—O3—C7	−35.1 (2)	C2—C1—C6—C7	−178.4 (2)
C8—S1—O3—C7	82.36 (19)	N1—C1—C6—C7	1.5 (3)
S1—O3—C7—C6	−168.44 (15)	C1—C2—C3—C4	−0.2 (4)
O1—N1—C1—C2	6.4 (3)	C2—C3—C4—C5	0.8 (4)
O2—N1—C1—C2	−174.7 (2)	C3—C4—C5—C6	−0.7 (4)
O2—N1—C1—C6	5.4 (3)	C4—C5—C6—C1	0.1 (4)
O1—N1—C1—C6	−173.6 (2)	C4—C5—C6—C7	179.0 (2)
C6—C1—C2—C3	−0.4 (4)	C1—C6—C7—O3	174.4 (2)
N1—C1—C6—C5	−179.6 (2)	C5—C6—C7—O3	−4.4 (3)
N1—C1—C2—C3	179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.54	3.266 (3)	135
C3—H3···O2ⁱⁱ	0.93	2.53	3.335 (3)	145
C7—H7B···O4ⁱⁱⁱ	0.97	2.58	3.539 (3)	169
C8—H8A···O4ⁱⁱⁱ	0.96	2.42	3.374 (4)	172

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.54	3.266 (3)	135
C3—H3···O2ⁱⁱ	0.93	2.53	3.335 (3)	145
C7—H7B···O4ⁱⁱⁱ	0.97	2.58	3.539 (3)	169
C8—H8A···O4ⁱⁱⁱ	0.96	2.42	3.374 (4)	172

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

Acknowledgements

We are grateful to the IOE, University of Mysore, for providing the single-crystal X-ray diffraction facility. PN thanks the BET Academy of Higher Education for research facilities.

References

Ballini, R., Bosica, G., Fiorini, D., Palmieri, A. & Petrini, M. (2005). Chem. Rev. 105, 933–971. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Khan, G. S., Clark, G. R. & Barker, D. (2008). Acta Cryst. E64, o1470. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ranu, B. C. & Banerjee, S. (2005). Org. Lett. 7, 3049–3052. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar