4-(4-Nitro­benzene­sulfonamido)pyridinium trichloro­acetate

Zhang, P.-W.; Gao, W.-Y.; Zhang, L.; Pu, S.-C.

doi:10.1107/S160053680800069X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o438

doi:10.1107/S160053680800069X

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4-(4-Nitrobenzenesulfonamido)pyridinium trichloroacetate

Peng-Wei Zhang,^a Wen-Yuan Gao,^a ^* Li Zhang ^b and Shou-Cheng Pu ^a

^aSchool of Pharmaceutical Science & Technology, Tianjin University, Tianjin 300072, People's Republic of China, and ^bDepartment of Pharmaceutics, Medical College of Chinese People's Armed Police Force, Tianjin 300162, People's Republic of China
^*Correspondence e-mail: zpw0803@gmail.com

(Received 4 January 2008; accepted 8 January 2008; online 16 January 2008)

In the crystal structure of the title compound, C₁₁H₁₀N₃O₄S·C₂Cl₃O₂, the dihedral angle between the two six-membered rings is 69.2 (1)°. The molecules are connected via intermolecular N—H⋯O hydrogen bonding.

Related literature

For related literature, see: Talley et al. (2000 ); El-Naggar et al. (1981 ).

Experimental

Crystal data

C₁₁H₁₀N₃O₄S·C₂Cl₃O₂
M_r = 442.65
Monoclinic, P 2₁ /c
a = 22.017 (4) Å
b = 6.2187 (12) Å
c = 12.719 (3) Å
β = 97.48 (3)°
V = 1726.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 113 (2) K
0.14 × 0.12 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.910, T_max = 0.973
9585 measured reflections
3017 independent reflections
2440 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.162
S = 1.16
3017 reflections
243 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.897 (10)	1.755 (13)	2.639 (4)	168 (4)
N2—H2⋯O6ⁱⁱ	0.897 (10)	1.825 (15)	2.707 (4)	167 (4)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800069X/nc2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800069X/nc2087Isup2.hkl

checkCIF report

Comment top

Benzenesulfonamides are very important intermediates in the organic synthesis and are widely used for the synthesis of pharmaceutical compounds (Talley et al., 2000). In our ongoing investigations on this topic we characterize the the title compound by single-crystal X-ray diffraction. In its crystal structure the dihedral angle between the phenyl and the pyridinyl ring amount to 69.2 (1)°. The 4-nitro-N-(pyridinium-4-yl)benzenesulfonamide cations and the trichloroacetate anions are connected by intermolecular N—H···O hydrogen bonding between the N—H atoms of the cations and the oxygen atoms of the anions.

Related literature top

For related literature, see: Talley et al. (2000); El-Naggar et al. (1981).

Experimental top

0.5 g(1.8 mmol) of 4-nitro-N-(pyridin-4-yl)benzenesulfonamide was dissolved in a mixture of trichloroacetic acid (2.0 mmol,0.33 g) and ethyl acetate (5 ml). Colorless crystals of the title compound were obtained by slow evaporation of the solvent.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii.

4-(4-Nitrobenzenesulfonamido)pyridinium trichloroacetate top

Crystal data top

C₁₁H₁₀N₃O₄S·C₂Cl₃O₂	F(000) = 896
M_r = 442.65	D_x = 1.703 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.017 (4) Å	Cell parameters from 4622 reflections
b = 6.2187 (12) Å	θ = 1.8–28.1°
c = 12.719 (3) Å	µ = 0.69 mm⁻¹
β = 97.48 (3)°	T = 113 K
V = 1726.6 (6) Å³	Lamellar, colorless
Z = 4	0.14 × 0.12 × 0.04 mm

Data collection top

Rigaku Saturn diffractometer	3017 independent reflections
Radiation source: rotating anode	2440 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.059
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
ω scans	h = −26→26
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −7→7
T_min = 0.910, T_max = 0.973	l = −15→13
9585 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0873P)²] where P = (F_o² + 2F_c²)/3
3017 reflections	(Δ/σ)_max = 0.001
243 parameters	Δρ_max = 0.57 e Å⁻³
2 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₁₁H₁₀N₃O₄S·C₂Cl₃O₂	V = 1726.6 (6) Å³
M_r = 442.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.017 (4) Å	µ = 0.69 mm⁻¹
b = 6.2187 (12) Å	T = 113 K
c = 12.719 (3) Å	0.14 × 0.12 × 0.04 mm
β = 97.48 (3)°

Data collection top

Rigaku Saturn diffractometer	3017 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2440 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.973	R_int = 0.059
9585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	2 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 0.57 e Å⁻³
3017 reflections	Δρ_min = −0.54 e Å⁻³
243 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
S1	0.18257 (4)	1.36555 (14)	0.07245 (7)	0.0191 (3)
O1	0.18542 (11)	1.5313 (4)	0.1516 (2)	0.0249 (6)
O2	0.16464 (11)	1.4166 (4)	−0.03720 (19)	0.0246 (6)
O3	0.04962 (13)	0.5416 (5)	0.2777 (2)	0.0357 (7)
O4	−0.00146 (13)	0.5394 (5)	0.1197 (2)	0.0409 (8)
N1	0.30157 (14)	0.6878 (5)	−0.0407 (3)	0.0231 (7)
N2	0.25080 (13)	1.2586 (5)	0.0880 (2)	0.0193 (7)
N3	0.03717 (14)	0.6156 (5)	0.1877 (3)	0.0248 (7)
C1	0.26602 (16)	1.0661 (5)	0.0425 (3)	0.0182 (8)
C2	0.31203 (16)	0.9400 (6)	0.0978 (3)	0.0219 (8)
H2A	0.3310	0.9837	0.1639	0.026*
C3	0.32893 (16)	0.7525 (6)	0.0544 (3)	0.0241 (8)
H3	0.3597	0.6688	0.0910	0.029*
C4	0.25743 (16)	0.8040 (6)	−0.0958 (3)	0.0225 (8)
H4	0.2395	0.7554	−0.1618	0.027*
C5	0.23811 (16)	0.9937 (6)	−0.0568 (3)	0.0209 (8)
H5	0.2071	1.0732	−0.0954	0.025*
C6	0.13549 (15)	1.1534 (5)	0.1065 (3)	0.0185 (8)
C7	0.09757 (15)	1.0470 (6)	0.0274 (3)	0.0213 (8)
H7	0.0944	1.0934	−0.0426	0.026*
C8	0.06426 (16)	0.8695 (6)	0.0547 (3)	0.0216 (8)
H8	0.0387	0.7945	0.0034	0.026*
C9	0.07022 (15)	0.8085 (6)	0.1592 (3)	0.0209 (8)
C10	0.10690 (16)	0.9146 (6)	0.2399 (3)	0.0219 (8)
H10	0.1088	0.8706	0.3101	0.026*
C11	0.14059 (16)	1.0888 (6)	0.2117 (3)	0.0232 (8)
H11	0.1665	1.1622	0.2632	0.028*
Cl1	0.43685 (4)	0.58693 (15)	0.39003 (8)	0.0283 (3)
Cl2	0.46462 (5)	0.17077 (17)	0.30622 (9)	0.0365 (3)
Cl3	0.41727 (4)	0.20184 (16)	0.50681 (7)	0.0291 (3)
O5	0.31493 (11)	0.1505 (4)	0.33912 (19)	0.0230 (6)
O6	0.33887 (11)	0.4175 (4)	0.2360 (2)	0.0265 (6)
C12	0.41404 (16)	0.3150 (6)	0.3785 (3)	0.0212 (8)
C13	0.34910 (16)	0.2939 (5)	0.3118 (3)	0.0180 (7)
H1	0.3107 (17)	0.568 (4)	−0.075 (3)	0.028 (11)*
H2	0.2756 (17)	1.324 (6)	0.140 (3)	0.047 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0240 (5)	0.0171 (5)	0.0161 (5)	0.0033 (3)	0.0022 (3)	0.0002 (3)
O1	0.0307 (14)	0.0182 (13)	0.0257 (15)	0.0037 (10)	0.0031 (11)	−0.0061 (11)
O2	0.0322 (15)	0.0251 (14)	0.0160 (14)	0.0029 (11)	0.0009 (10)	0.0055 (11)
O3	0.0403 (16)	0.0382 (17)	0.0280 (17)	−0.0053 (13)	0.0023 (12)	0.0112 (14)
O4	0.0468 (18)	0.0483 (19)	0.0276 (17)	−0.0252 (14)	0.0044 (13)	−0.0050 (14)
N1	0.0314 (18)	0.0155 (16)	0.0247 (19)	−0.0008 (13)	0.0120 (13)	−0.0028 (13)
N2	0.0231 (15)	0.0191 (16)	0.0148 (17)	0.0006 (12)	−0.0004 (11)	−0.0027 (13)
N3	0.0277 (18)	0.0256 (17)	0.0220 (19)	0.0001 (13)	0.0067 (13)	−0.0017 (14)
C1	0.0256 (19)	0.0141 (18)	0.017 (2)	−0.0029 (13)	0.0096 (13)	−0.0001 (14)
C2	0.030 (2)	0.0205 (19)	0.015 (2)	0.0007 (14)	0.0023 (14)	0.0000 (15)
C3	0.032 (2)	0.022 (2)	0.019 (2)	0.0021 (15)	0.0053 (15)	0.0035 (16)
C4	0.029 (2)	0.0226 (19)	0.016 (2)	−0.0038 (15)	0.0052 (14)	−0.0004 (15)
C5	0.0251 (19)	0.0208 (19)	0.0166 (19)	0.0009 (14)	0.0016 (14)	0.0026 (15)
C6	0.0191 (18)	0.0209 (19)	0.016 (2)	0.0038 (13)	0.0030 (13)	−0.0014 (14)
C7	0.0237 (19)	0.029 (2)	0.0108 (18)	0.0007 (15)	0.0006 (13)	0.0008 (15)
C8	0.0214 (19)	0.026 (2)	0.016 (2)	0.0010 (14)	0.0002 (14)	−0.0045 (15)
C9	0.0204 (18)	0.0223 (19)	0.021 (2)	0.0028 (14)	0.0071 (14)	−0.0008 (15)
C10	0.026 (2)	0.027 (2)	0.0127 (19)	0.0015 (15)	0.0040 (14)	−0.0007 (15)
C11	0.026 (2)	0.027 (2)	0.017 (2)	0.0007 (15)	0.0013 (14)	−0.0041 (15)
Cl1	0.0313 (5)	0.0241 (5)	0.0291 (6)	−0.0098 (4)	0.0022 (4)	0.0005 (4)
Cl2	0.0349 (6)	0.0404 (6)	0.0364 (7)	0.0111 (4)	0.0135 (4)	−0.0022 (5)
Cl3	0.0325 (5)	0.0345 (6)	0.0187 (5)	−0.0087 (4)	−0.0031 (4)	0.0073 (4)
O5	0.0286 (14)	0.0216 (14)	0.0182 (15)	−0.0052 (10)	0.0010 (10)	0.0034 (10)
O6	0.0330 (15)	0.0242 (14)	0.0209 (15)	−0.0064 (11)	−0.0021 (11)	0.0070 (11)
C12	0.0234 (19)	0.0205 (19)	0.020 (2)	−0.0016 (14)	0.0040 (14)	0.0010 (15)
C13	0.0238 (18)	0.0173 (18)	0.0130 (19)	0.0004 (14)	0.0031 (13)	−0.0033 (14)

Geometric parameters (Å, º) top

S1—O2	1.435 (2)	C4—H4	0.9300
S1—O1	1.436 (3)	C5—H5	0.9300
S1—N2	1.631 (3)	C6—C11	1.388 (5)
S1—C6	1.766 (4)	C6—C7	1.388 (5)
O3—N3	1.231 (4)	C7—C8	1.394 (5)
O4—N3	1.227 (4)	C7—H7	0.9300
N1—C4	1.335 (5)	C8—C9	1.372 (5)
N1—C3	1.341 (5)	C8—H8	0.9300
N1—H1	0.897 (10)	C9—C10	1.387 (5)
N2—C1	1.390 (4)	C10—C11	1.386 (5)
N2—H2	0.897 (10)	C10—H10	0.9300
N3—C9	1.472 (5)	C11—H11	0.9300
C1—C2	1.397 (5)	Cl1—C12	1.765 (4)
C1—C5	1.405 (5)	Cl2—C12	1.777 (4)
C2—C3	1.362 (5)	Cl3—C12	1.770 (4)
C2—H2A	0.9300	O5—C13	1.245 (4)
C3—H3	0.9300	O6—C13	1.231 (4)
C4—C5	1.368 (5)	C12—C13	1.570 (4)

O2—S1—O1	120.25 (15)	C1—C5—H5	120.6
O2—S1—N2	109.93 (16)	C11—C6—C7	121.7 (3)
O1—S1—N2	104.59 (14)	C11—C6—S1	118.4 (3)
O2—S1—C6	107.91 (16)	C7—C6—S1	119.7 (3)
O1—S1—C6	109.75 (17)	C6—C7—C8	118.9 (3)
N2—S1—C6	103.08 (16)	C6—C7—H7	120.5
C4—N1—C3	121.4 (3)	C8—C7—H7	120.5
C4—N1—H1	113 (2)	C9—C8—C7	118.2 (3)
C3—N1—H1	126 (2)	C9—C8—H8	120.9
C1—N2—S1	124.7 (2)	C7—C8—H8	120.9
C1—N2—H2	123 (3)	C8—C9—C10	123.9 (3)
S1—N2—H2	112 (3)	C8—C9—N3	118.4 (3)
O4—N3—O3	124.1 (3)	C10—C9—N3	117.7 (3)
O4—N3—C9	117.4 (3)	C11—C10—C9	117.4 (3)
O3—N3—C9	118.4 (3)	C11—C10—H10	121.3
N2—C1—C2	118.2 (3)	C9—C10—H10	121.3
N2—C1—C5	123.4 (3)	C10—C11—C6	119.8 (3)
C2—C1—C5	118.4 (3)	C10—C11—H11	120.1
C3—C2—C1	119.7 (3)	C6—C11—H11	120.1
C3—C2—H2A	120.2	C13—C12—Cl1	110.7 (2)
C1—C2—H2A	120.2	C13—C12—Cl3	112.9 (3)
N1—C3—C2	120.5 (3)	Cl1—C12—Cl3	109.12 (19)
N1—C3—H3	119.7	C13—C12—Cl2	105.4 (2)
C2—C3—H3	119.7	Cl1—C12—Cl2	109.6 (2)
N1—C4—C5	121.1 (3)	Cl3—C12—Cl2	108.90 (19)
N1—C4—H4	119.5	O6—C13—O5	127.6 (3)
C5—C4—H4	119.5	O6—C13—C12	115.6 (3)
C4—C5—C1	118.8 (3)	O5—C13—C12	116.8 (3)
C4—C5—H5	120.6

O2—S1—N2—C1	−62.4 (3)	S1—C6—C7—C8	175.1 (3)
O1—S1—N2—C1	167.2 (3)	C6—C7—C8—C9	0.4 (5)
C6—S1—N2—C1	52.4 (3)	C7—C8—C9—C10	0.8 (6)
S1—N2—C1—C2	−148.4 (3)	C7—C8—C9—N3	−177.4 (3)
S1—N2—C1—C5	32.5 (5)	O4—N3—C9—C8	−11.3 (5)
N2—C1—C2—C3	−178.7 (3)	O3—N3—C9—C8	169.0 (3)
C5—C1—C2—C3	0.4 (5)	O4—N3—C9—C10	170.3 (3)
C4—N1—C3—C2	0.3 (6)	O3—N3—C9—C10	−9.4 (5)
C1—C2—C3—N1	−0.3 (6)	C8—C9—C10—C11	−1.8 (6)
C3—N1—C4—C5	−0.4 (6)	N3—C9—C10—C11	176.4 (3)
N1—C4—C5—C1	0.6 (6)	C9—C10—C11—C6	1.6 (5)
N2—C1—C5—C4	178.5 (3)	C7—C6—C11—C10	−0.4 (5)
C2—C1—C5—C4	−0.6 (5)	S1—C6—C11—C10	−176.2 (3)
O2—S1—C6—C11	−174.3 (3)	Cl1—C12—C13—O6	37.9 (4)
O1—S1—C6—C11	−41.5 (3)	Cl3—C12—C13—O6	160.6 (3)
N2—S1—C6—C11	69.5 (3)	Cl2—C12—C13—O6	−80.6 (3)
O2—S1—C6—C7	9.9 (3)	Cl1—C12—C13—O5	−144.5 (3)
O1—S1—C6—C7	142.6 (3)	Cl3—C12—C13—O5	−21.8 (4)
N2—S1—C6—C7	−106.4 (3)	Cl2—C12—C13—O5	97.0 (3)
C11—C6—C7—C8	−0.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.90 (1)	1.76 (1)	2.639 (4)	168 (4)
N2—H2···O6ⁱⁱ	0.90 (1)	1.83 (2)	2.707 (4)	167 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₃O₄S·C₂Cl₃O₂
M_r	442.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	22.017 (4), 6.2187 (12), 12.719 (3)
β (°)	97.48 (3)
V (Å³)	1726.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.14 × 0.12 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.910, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	9585, 3017, 2440
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.162, 1.16
No. of reflections	3017
No. of parameters	243
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.54

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.897 (10)	1.755 (13)	2.639 (4)	168 (4)
N2—H2···O6ⁱⁱ	0.897 (10)	1.825 (15)	2.707 (4)	167 (4)

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

References

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Volume 64| Part 2| February 2008| Page o438

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