2-Meth­oxy-5-nitro­benzene-1,3-diyl bis­(benzene­sulfonate)

Xiao, Z.-P.; Fang, R.-Q.; Li, H.-Q.; Zhu, H.-L.

doi:10.1107/S160053680704398X

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2-Methoxy-5-nitrobenzene-1,3-diyl bis(benzenesulfonate)

Z.-P. Xiao, R.-Q. Fang, H.-Q. Li and H.-L. Zhu

In the title molecule, C₁₉H₁₅NO₉S₂, the dihedral angle between the nitro group and the benzene ring to which it is attached is 11.68 (8)°. The N-C bond length of 1.466 (3) Å indicates that no conjugation exists between the nitro group and the benzene ring.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704398X/lh2490sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680704398X/lh2490Isup2.hkl Contains datablock I

CCDC reference: 663761

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.044
wR factor = 0.131
Data-to-parameter ratio = 13.7

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No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

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   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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Comment top

Aromatic nitro compounds are potential intermediates for a variety of fine chemicals. They are easily reduced to the corresponding aromatic amines (Desai et al., 2001). Therefore, aromatic nitro compounds are frequently used in the synthesis of pharmaceuticals (Hoogenraad et al., 2004). We herein reported a crystal structure of 2-methoxy-5-nitrobenzene-1,3-diyl dibenzenesulfonate. As shown in Fig. 1, the nitro group (N1/O1/O2) makes a dihedral angle with the benzene ring (C1—C6) of 11.68 (8) °. In spite of the fact that the nitro group is almost coplanar with the benzene ring, no conjugation is observed as evidenced by the N1—C1 bond length of 1.466 (3) Å. This is an agreement with the standard values of single N—C bond (1.47–1.50 Å) and all other bonds distances are in the the normal ranges (Allen et al., 1987).

Related literature top

For related literature, see: Desai et al. (2001); Hoogenraad et al. (2004).

For bond-length data, see: Allen et al. (1987).

Experimental top

K₂CO₃ was charged into a solution of 2-hydroxy-5-nitrobenzene-1,3-diyl dibenzenesulfonate (4.66 g, 10 mmol) in anhydrous acetone (30 ml) with stirring. CH₃I (0.66 ml, 13 mmol) was added dropwise to the reaction mixture at room temperature. The reaction mixture was then refluxed for 8 h. The residue was filtered and the cake washed with acetone. A shallow yellow solid was given in a yield of 85% after removal of the solvent. Recrystallization from acetone furnished volorless blocks for single-crystal structure determination.

Structure description top

For related literature, see: Desai et al. (2001); Hoogenraad et al. (2004).

For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

2-Methoxy-5-nitrobenzene-1,3-diyl bis(benzenesulfonate) top

Crystal data top

C₁₉H₁₅NO₉S₂	F(000) = 960
M_r = 465.44	D_x = 1.562 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2407 reflections
a = 10.787 (2) Å	θ = 1.3–25.4°
b = 10.895 (2) Å	µ = 0.32 mm⁻¹
c = 16.876 (3) Å	T = 298 K
β = 93.91 (3)°	Block, colorless
V = 1978.7 (6) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3872 independent reflections
Radiation source: fine-focus sealed tube	2898 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = 0→13
T_min = 0.909, T_max = 0.938	k = 0→13
4084 measured reflections	l = −20→20

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0778P)² + 0.2038P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3872 reflections	Δρ_max = 0.40 e Å⁻³
282 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (2)

Crystal data top

C₁₉H₁₅NO₉S₂	V = 1978.7 (6) Å³
M_r = 465.44	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.787 (2) Å	µ = 0.32 mm⁻¹
b = 10.895 (2) Å	T = 298 K
c = 16.876 (3) Å	0.30 × 0.20 × 0.20 mm
β = 93.91 (3)°

Data collection top

Bruker SMART CCD diffractometer	3872 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2898 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.938	R_int = 0.023
4084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.05	Δρ_max = 0.40 e Å⁻³
3872 reflections	Δρ_min = −0.33 e Å⁻³
282 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.

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 > σ(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
S2	−0.23217 (6)	0.74187 (5)	0.01047 (4)	0.03603 (19)
S1	0.37812 (6)	0.76657 (6)	−0.11612 (4)	0.0407 (2)
O3	0.23769 (16)	0.81284 (14)	−0.13794 (10)	0.0410 (4)
O7	−0.09188 (15)	0.68927 (15)	0.02396 (9)	0.0404 (4)
O6	0.10742 (17)	0.85730 (15)	−0.01565 (10)	0.0461 (5)
O9	−0.30660 (17)	0.64741 (17)	−0.02568 (10)	0.0515 (5)
O4	0.39210 (18)	0.64822 (17)	−0.15073 (11)	0.0524 (5)
O8	−0.22762 (19)	0.85748 (16)	−0.02797 (11)	0.0559 (5)
O2	−0.0900 (2)	0.38064 (19)	−0.19229 (12)	0.0659 (6)
O5	0.44911 (18)	0.86750 (18)	−0.14039 (12)	0.0596 (5)
C8	0.3875 (2)	0.7536 (2)	−0.01236 (14)	0.0377 (5)
C3	0.1401 (2)	0.7322 (2)	−0.12367 (14)	0.0354 (5)
C4	0.0728 (2)	0.7565 (2)	−0.05757 (13)	0.0347 (5)
C5	−0.0243 (2)	0.6747 (2)	−0.04417 (13)	0.0355 (5)
C6	−0.0520 (2)	0.5758 (2)	−0.09344 (14)	0.0379 (5)
H6	−0.1144	0.5208	−0.0823	0.046*
N1	−0.0167 (2)	0.4585 (2)	−0.21397 (14)	0.0485 (5)
C14	−0.2601 (2)	0.7581 (2)	0.11059 (14)	0.0367 (5)
C2	0.1108 (2)	0.6383 (2)	−0.17603 (14)	0.0400 (6)
H2	0.1544	0.6276	−0.2212	0.048*
C1	0.0152 (2)	0.5605 (2)	−0.15972 (14)	0.0383 (5)
C13	0.3827 (3)	0.6383 (2)	0.02110 (16)	0.0499 (7)
H13	0.3757	0.5687	−0.0108	0.060*
O1	0.0290 (2)	0.4572 (2)	−0.27821 (13)	0.0733 (7)
C9	0.3998 (3)	0.8590 (3)	0.03325 (17)	0.0517 (7)
H9	0.4035	0.9358	0.0096	0.062*
C15	−0.2564 (3)	0.8751 (2)	0.14369 (16)	0.0486 (6)
H15	−0.2377	0.9433	0.1136	0.058*
C19	−0.2863 (3)	0.6544 (3)	0.15400 (16)	0.0506 (7)
H19	−0.2893	0.5772	0.1305	0.061*
C10	0.4065 (3)	0.8469 (3)	0.11472 (19)	0.0673 (9)
H10	0.4151	0.9161	0.1469	0.081*
C7	0.0787 (3)	0.8778 (3)	0.06494 (15)	0.0518 (7)
H7A	−0.0060	0.9044	0.0661	0.078*
H7B	0.1329	0.9399	0.0882	0.078*
H7C	0.0900	0.8029	0.0945	0.078*
C11	0.4003 (3)	0.7318 (4)	0.14827 (19)	0.0696 (10)
H11	0.4042	0.7244	0.2033	0.084*
C17	−0.3050 (3)	0.7856 (4)	0.26666 (18)	0.0701 (10)
H17	−0.3195	0.7948	0.3200	0.084*
C16	−0.2811 (3)	0.8871 (3)	0.22228 (18)	0.0628 (8)
H16	−0.2816	0.9645	0.2454	0.075*
C18	−0.3080 (3)	0.6690 (3)	0.23317 (17)	0.0653 (9)
H18	−0.3246	0.6009	0.2640	0.078*
C12	0.3885 (3)	0.6280 (3)	0.10238 (18)	0.0689 (9)
H12	0.3844	0.5513	0.1261	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0391 (3)	0.0318 (3)	0.0376 (3)	−0.0018 (2)	0.0057 (2)	0.0007 (2)
S1	0.0459 (4)	0.0375 (4)	0.0401 (4)	−0.0039 (3)	0.0134 (3)	0.0019 (3)
O3	0.0488 (10)	0.0323 (9)	0.0428 (9)	−0.0041 (8)	0.0098 (8)	0.0080 (7)
O7	0.0427 (9)	0.0417 (10)	0.0376 (9)	0.0011 (8)	0.0080 (7)	0.0017 (8)
O6	0.0589 (11)	0.0347 (9)	0.0461 (10)	−0.0088 (8)	0.0137 (8)	−0.0080 (8)
O9	0.0499 (11)	0.0551 (12)	0.0494 (10)	−0.0125 (9)	0.0030 (8)	−0.0120 (9)
O4	0.0617 (12)	0.0487 (11)	0.0481 (10)	0.0066 (9)	0.0134 (9)	−0.0091 (9)
O8	0.0721 (13)	0.0399 (10)	0.0565 (11)	0.0052 (9)	0.0100 (10)	0.0157 (9)
O2	0.0823 (15)	0.0460 (12)	0.0691 (14)	−0.0170 (11)	0.0038 (11)	−0.0126 (10)
O5	0.0583 (12)	0.0552 (12)	0.0678 (12)	−0.0132 (10)	0.0235 (10)	0.0135 (10)
C8	0.0370 (12)	0.0383 (13)	0.0381 (13)	−0.0048 (10)	0.0049 (10)	−0.0025 (10)
C3	0.0409 (13)	0.0303 (12)	0.0351 (12)	−0.0017 (10)	0.0041 (10)	0.0057 (10)
C4	0.0413 (13)	0.0277 (12)	0.0353 (12)	0.0032 (10)	0.0032 (10)	0.0016 (9)
C5	0.0390 (13)	0.0327 (12)	0.0352 (12)	0.0018 (10)	0.0047 (10)	0.0028 (10)
C6	0.0424 (13)	0.0290 (12)	0.0421 (13)	−0.0011 (10)	0.0007 (10)	0.0053 (10)
N1	0.0511 (13)	0.0431 (13)	0.0506 (13)	−0.0002 (11)	−0.0025 (10)	−0.0088 (11)
C14	0.0365 (12)	0.0347 (13)	0.0395 (13)	−0.0006 (10)	0.0063 (10)	−0.0025 (10)
C2	0.0463 (14)	0.0392 (14)	0.0351 (12)	0.0051 (11)	0.0060 (10)	−0.0007 (10)
C1	0.0444 (13)	0.0315 (12)	0.0383 (13)	0.0013 (10)	−0.0024 (10)	−0.0031 (10)
C13	0.0646 (18)	0.0391 (14)	0.0456 (15)	−0.0090 (13)	0.0021 (13)	0.0040 (12)
O1	0.0871 (16)	0.0800 (16)	0.0545 (12)	−0.0138 (13)	0.0181 (11)	−0.0297 (12)
C9	0.0532 (16)	0.0452 (16)	0.0569 (16)	−0.0068 (13)	0.0041 (13)	−0.0136 (13)
C15	0.0517 (16)	0.0411 (15)	0.0532 (15)	−0.0022 (12)	0.0057 (12)	−0.0095 (12)
C19	0.0578 (17)	0.0437 (15)	0.0515 (16)	−0.0002 (13)	0.0131 (13)	0.0071 (12)
C10	0.0559 (18)	0.083 (2)	0.0621 (19)	−0.0016 (17)	−0.0033 (15)	−0.0365 (18)
C7	0.0597 (17)	0.0515 (16)	0.0451 (14)	−0.0122 (14)	0.0096 (12)	−0.0128 (13)
C11	0.0580 (19)	0.109 (3)	0.0413 (16)	−0.0024 (19)	0.0005 (14)	−0.0044 (18)
C17	0.0575 (19)	0.115 (3)	0.0375 (15)	0.0043 (19)	0.0043 (13)	−0.0124 (18)
C16	0.0611 (19)	0.069 (2)	0.0582 (18)	−0.0009 (16)	0.0040 (15)	−0.0286 (16)
C18	0.069 (2)	0.078 (2)	0.0500 (17)	0.0014 (18)	0.0142 (15)	0.0166 (16)
C12	0.083 (2)	0.075 (2)	0.0475 (17)	−0.0125 (19)	0.0011 (16)	0.0149 (16)

Geometric parameters (Å, º) top

S2—O9	1.4175 (18)	C14—C15	1.391 (3)
S2—O8	1.4192 (18)	C2—C1	1.377 (3)
S2—O7	1.6197 (18)	C2—H2	0.9300
S2—C14	1.745 (2)	C13—C12	1.374 (4)
S1—O5	1.4164 (19)	C13—H13	0.9300
S1—O4	1.4278 (19)	C9—C10	1.378 (4)
S1—O3	1.6150 (19)	C9—H9	0.9300
S1—C8	1.753 (2)	C15—C16	1.377 (4)
O3—C3	1.405 (3)	C15—H15	0.9300
O7—C5	1.411 (3)	C19—C18	1.381 (4)
O6—C4	1.345 (3)	C19—H19	0.9300
O6—C7	1.433 (3)	C10—C11	1.380 (5)
O2—N1	1.232 (3)	C10—H10	0.9300
C8—C13	1.379 (3)	C7—H7A	0.9600
C8—C9	1.384 (3)	C7—H7B	0.9600
C3—C2	1.375 (3)	C7—H7C	0.9600
C3—C4	1.397 (3)	C11—C12	1.371 (5)
C4—C5	1.406 (3)	C11—H11	0.9300
C5—C6	1.381 (3)	C17—C16	1.370 (5)
C6—C1	1.384 (3)	C17—C18	1.390 (5)
C6—H6	0.9300	C17—H17	0.9300
N1—O1	1.221 (3)	C16—H16	0.9300
N1—C1	1.466 (3)	C18—H18	0.9300
C14—C19	1.387 (3)	C12—H12	0.9300

O9—S2—O8	118.93 (12)	C2—C1—C6	121.9 (2)
O9—S2—O7	107.45 (11)	C2—C1—N1	119.3 (2)
O8—S2—O7	108.49 (11)	C6—C1—N1	118.9 (2)
O9—S2—C14	111.12 (11)	C12—C13—C8	118.8 (3)
O8—S2—C14	111.47 (12)	C12—C13—H13	120.6
O7—S2—C14	96.97 (10)	C8—C13—H13	120.6
O5—S1—O4	120.56 (12)	C10—C9—C8	118.2 (3)
O5—S1—O3	102.05 (11)	C10—C9—H9	120.9
O4—S1—O3	108.19 (11)	C8—C9—H9	120.9
O5—S1—C8	110.87 (12)	C16—C15—C14	118.1 (3)
O4—S1—C8	109.59 (11)	C16—C15—H15	120.9
O3—S1—C8	104.02 (10)	C14—C15—H15	120.9
C3—O3—S1	117.91 (14)	C18—C19—C14	118.1 (3)
C5—O7—S2	117.04 (14)	C18—C19—H19	120.9
C4—O6—C7	123.80 (19)	C14—C19—H19	120.9
C13—C8—C9	122.2 (2)	C9—C10—C11	119.7 (3)
C13—C8—S1	118.77 (19)	C9—C10—H10	120.2
C9—C8—S1	119.0 (2)	C11—C10—H10	120.2
C2—C3—C4	123.0 (2)	O6—C7—H7A	109.5
C2—C3—O3	119.8 (2)	O6—C7—H7B	109.5
C4—C3—O3	117.1 (2)	H7A—C7—H7B	109.5
O6—C4—C3	115.7 (2)	O6—C7—H7C	109.5
O6—C4—C5	128.0 (2)	H7A—C7—H7C	109.5
C3—C4—C5	116.2 (2)	H7B—C7—H7C	109.5
C6—C5—C4	122.0 (2)	C12—C11—C10	121.5 (3)
C6—C5—O7	118.4 (2)	C12—C11—H11	119.2
C4—C5—O7	119.4 (2)	C10—C11—H11	119.2
C5—C6—C1	118.5 (2)	C16—C17—C18	121.0 (3)
C5—C6—H6	120.7	C16—C17—H17	119.5
C1—C6—H6	120.7	C18—C17—H17	119.5
O1—N1—O2	124.2 (2)	C17—C16—C15	120.4 (3)
O1—N1—C1	118.1 (2)	C17—C16—H16	119.8
O2—N1—C1	117.7 (2)	C15—C16—H16	119.8
C19—C14—C15	122.4 (2)	C19—C18—C17	119.8 (3)
C19—C14—S2	118.91 (19)	C19—C18—H18	120.1
C15—C14—S2	118.67 (19)	C17—C18—H18	120.1
C3—C2—C1	118.2 (2)	C11—C12—C13	119.5 (3)
C3—C2—H2	120.9	C11—C12—H12	120.2
C1—C2—H2	120.9	C13—C12—H12	120.2

Experimental details

Crystal data
Chemical formula	C₁₉H₁₅NO₉S₂
M_r	465.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.787 (2), 10.895 (2), 16.876 (3)
β (°)	93.91 (3)
V (Å³)	1978.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.909, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	4084, 3872, 2898
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.131, 1.05
No. of reflections	3872
No. of parameters	282
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.33

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

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