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In the title compound, C18H14N4O8S2, the conformation observed across the two C—S—N—C linkages is synclinal. In the crystal, a network of intermolecular N—H...O hydrogen bonds and weak C—H...O hydrogen bonds is formed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001775/ci6000sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001775/ci6000Isup2.hkl
Contains datablock I

CCDC reference: 159856

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.100
  • Data-to-parameter ratio = 15.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Bis(4-nitrophenylsulfonyl)-1,4-phenylenediamine and its clathrates with cyclopentanone, cyclohexanone, tetrahydrofuran, N,N-dimethylformamide and pyridine are well documented (Bock et al., 1999). In the structure of bis(4-nitrophenylsulfonyl)-1,3-phenylenediamine, (I), the conformation of the attachment of the 4-nitrophenylsulfonyl substituents to the phenylenediamine moiety is better described by the torsion angles C11—S1—N1—C1 [61.3 (2)°] and C21—S2—N2—C3 [-47.5 (2)°] and they show a (±)-synclinal conformation (Fig. 1). As a result, both the nitrophenyl rings are folded into the same side of the central phenylenediamine moiety, in contrast to the case in bis(4-nitrophenylsulfonyl)-1,4-phenylenediamine (Bock et al., 1999), in which they are arranged on either side to give an extended structure. The distances and angles of (I) are comparable to those observed in the 1,4-phenylenediamine derivative.

In the crystal, each molecule of (I) takes part in eight hydrogen bonds (four independent H bonds, each as acceptor and donor, see Table 2) to five neighboring molecules with a hydrogen-bonded network as a result (Fig. 2). Both amino groups (N1—H1N and N2—H2N), one sulfonyl (O1—S1—-O2) and one nitro (O7—N4—O8) group are involved in the hydrogen bonding. Atom O7 exhibits a bifurcated hydrogen bond.

A weak phenyl–phenyl ring interaction is observed between ring C11—C26 and its inversion related pair at (-1 - x, 1 - y, 2 - z), with a centroid-to-centriod distance of 3.885 (1) Å. The interacting phenyl rings can be arranged in any one of the following ways: (i) parallel-sandwich, (ii) parallel-displaced, (iii) T-shaped and (iv) displaced T-shaped form (Hobza et al., 1994). In this structure, a parallel-displaced geometry is observed for the ring interaction. Using ab initio methods, Hobza et al. (1994) found that the parallel-displaced structure was more stable in the benzene dimer. For that dimer, they obtained a minimum interaction energy of -9.53 kJ mol-1 when the centroid–centroid distance was 3.85 Å and the parallel displacement was 1.6 Å.

Experimental top

Bis(4-nitrophenylsulfonyl)-1,3-phenylenediamine was prepared by a modified synthesis (Shirley et al., 1952) as follows: to 1,3-phenylenediamine (3.24 g, 30 mmol), dissolved in 80 ml hot pyridine, at room temperature, a solution of 1,4-nitrobenzensulfonylchloride (13.3 g, 60 mmol) in 200 ml pyridine was added over 45 min with stirring. After 3 h additional stirring, the reaction mixture was poured into a cold mixture of 1350 ml water and 150 ml concentrated hydrochloric acid. The precipitate was washed with water and n-hexane. Drying in vacuum yielded dark-red (I).3pyridine (19.6 g, 87%). Dissolving this in acetone and precipitating with n-hexane yielded brown (I).2pyridine. Red crystals of (I) without pyridine were obtained by vapor diffusion of n-hexane into a solution of (I).2 pyridine in ethanol.

Refinement top

All H atoms were located from the difference map; the two amino H atoms were freely refined, whereas the others were placed on idealized positions (C—Hphenyl = 0.95 Å) and refined using a riding model.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of (I) viewed along the a axis. Hydrogen bonds are indicated by dashed lines with selected labelled centers for one molecule interacting to five neighboring units (four are shown).
N,N'-m-Phenylenebis(4-nitrobenzenesulfonamide) top
Crystal data top
C18H14N4O8S2F(000) = 984
Mr = 478.45Dx = 1.627 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.8331 (10) ÅCell parameters from 84 reflections
b = 16.4997 (14) Åθ = 10.0–16.5°
c = 17.3290 (13) ŵ = 0.33 mm1
β = 90.216 (8)°T = 150 K
V = 1953.7 (4) Å3Block, red
Z = 40.35 × 0.25 × 0.20 mm
Data collection top
Siemens P4 four-circle
diffractometer
Rint = 0.029
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.4°
Graphite monochromatorh = 09
ω scansk = 021
4837 measured reflectionsl = 2222
4475 independent reflections4 standard reflections every 100 reflections
3740 reflections with I > 2σ(I) intensity decay: <5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w 1/[σ2(Fo2) + (0.0463P)2 + 1.4125P]
where P = (Fo2 + 2Fc2)/3
4475 reflections(Δ/σ)max < 0.001
297 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C18H14N4O8S2V = 1953.7 (4) Å3
Mr = 478.45Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.8331 (10) ŵ = 0.33 mm1
b = 16.4997 (14) ÅT = 150 K
c = 17.3290 (13) Å0.35 × 0.25 × 0.20 mm
β = 90.216 (8)°
Data collection top
Siemens P4 four-circle
diffractometer
Rint = 0.029
4837 measured reflections4 standard reflections every 100 reflections
4475 independent reflections intensity decay: <5%
3740 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.37 e Å3
4475 reflectionsΔρmin = 0.43 e Å3
297 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
xyzUiso*/Ueq
S10.32458 (7)0.25662 (3)0.93385 (2)0.02220 (11)
S20.10600 (6)0.42250 (3)0.68612 (3)0.02294 (11)
O10.1211 (2)0.27413 (9)0.93276 (8)0.0293 (3)
O20.4051 (2)0.20739 (9)0.99392 (8)0.0305 (3)
O30.1297 (2)0.42515 (9)0.76775 (8)0.0333 (3)
O40.2620 (2)0.44533 (9)0.63621 (9)0.0338 (3)
O50.9518 (3)0.55828 (12)0.91301 (11)0.0532 (5)
O60.6896 (3)0.62090 (11)0.87738 (13)0.0567 (5)
O70.7032 (2)0.64062 (11)0.66215 (9)0.0430 (4)
O80.6555 (2)0.61775 (10)0.54221 (9)0.0384 (4)
N10.3843 (2)0.21082 (10)0.85445 (9)0.0229 (3)
H1N0.491 (3)0.1897 (14)0.8601 (13)0.027 (6)*
N20.0493 (2)0.33052 (9)0.66064 (9)0.0215 (3)
H2N0.075 (3)0.3242 (14)0.6136 (15)0.031 (6)*
N30.7767 (3)0.56083 (12)0.90032 (10)0.0371 (4)
N40.6079 (2)0.61198 (10)0.60930 (10)0.0270 (3)
C10.3457 (3)0.24146 (10)0.77878 (10)0.0202 (3)
C20.1641 (3)0.27311 (11)0.75900 (10)0.0204 (3)
H20.06270.27810.79640.025*
C30.1351 (3)0.29713 (10)0.68323 (10)0.0195 (3)
C40.2799 (3)0.28817 (12)0.62786 (10)0.0254 (4)
H40.25720.30460.57610.030*
C50.4570 (3)0.25516 (13)0.64853 (11)0.0305 (4)
H50.55620.24790.61060.037*
C60.4918 (3)0.23262 (12)0.72387 (11)0.0275 (4)
H60.61550.21110.73800.033*
C110.4529 (3)0.34892 (11)0.93101 (10)0.0222 (3)
C120.3584 (3)0.41822 (12)0.90626 (10)0.0248 (4)
H120.22230.41730.89520.030*
C130.4648 (3)0.48886 (12)0.89790 (10)0.0267 (4)
H130.40330.53770.88200.032*
C140.6614 (3)0.48675 (12)0.91315 (10)0.0275 (4)
C150.7572 (3)0.41850 (14)0.93871 (12)0.0306 (4)
H150.89330.41980.94960.037*
C160.6512 (3)0.34837 (13)0.94804 (11)0.0277 (4)
H160.71270.30030.96590.033*
C210.1015 (3)0.48244 (11)0.66381 (10)0.0210 (3)
C220.1549 (3)0.49172 (11)0.58719 (10)0.0234 (4)
H220.07870.46760.54760.028*
C230.3192 (3)0.53609 (11)0.56870 (10)0.0237 (4)
H230.35650.54450.51640.028*
C240.4281 (3)0.56791 (11)0.62844 (10)0.0224 (4)
C250.3780 (3)0.55927 (12)0.70497 (11)0.0264 (4)
H250.45660.58220.74440.032*
C260.2103 (3)0.51636 (12)0.72283 (10)0.0257 (4)
H260.17000.51020.77500.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0242 (2)0.0264 (2)0.0161 (2)0.00276 (17)0.00192 (15)0.00390 (16)
S20.0193 (2)0.0267 (2)0.0228 (2)0.00306 (17)0.00059 (16)0.00095 (17)
O10.0255 (7)0.0382 (8)0.0241 (7)0.0045 (6)0.0015 (5)0.0031 (6)
O20.0388 (8)0.0340 (8)0.0187 (6)0.0037 (6)0.0050 (5)0.0086 (5)
O30.0365 (8)0.0392 (8)0.0240 (7)0.0019 (6)0.0101 (6)0.0062 (6)
O40.0217 (7)0.0358 (8)0.0439 (9)0.0064 (6)0.0056 (6)0.0015 (6)
O50.0449 (10)0.0625 (12)0.0522 (11)0.0282 (9)0.0103 (8)0.0072 (9)
O60.0594 (12)0.0386 (10)0.0720 (13)0.0157 (9)0.0004 (10)0.0150 (9)
O70.0402 (9)0.0529 (10)0.0361 (8)0.0207 (8)0.0018 (7)0.0088 (7)
O80.0438 (9)0.0418 (9)0.0295 (8)0.0106 (7)0.0097 (6)0.0008 (6)
N10.0265 (8)0.0241 (8)0.0182 (7)0.0035 (6)0.0047 (6)0.0026 (6)
N20.0217 (7)0.0253 (8)0.0176 (7)0.0008 (6)0.0047 (6)0.0015 (6)
N30.0434 (11)0.0406 (11)0.0272 (9)0.0173 (9)0.0005 (8)0.0008 (8)
N40.0286 (8)0.0236 (8)0.0287 (8)0.0014 (6)0.0012 (6)0.0015 (6)
C10.0262 (9)0.0174 (8)0.0170 (8)0.0012 (7)0.0035 (6)0.0019 (6)
C20.0223 (8)0.0219 (8)0.0171 (8)0.0011 (7)0.0004 (6)0.0004 (6)
C30.0209 (8)0.0181 (8)0.0194 (8)0.0009 (6)0.0038 (6)0.0010 (6)
C40.0306 (10)0.0287 (9)0.0168 (8)0.0035 (8)0.0006 (7)0.0029 (7)
C50.0301 (10)0.0384 (11)0.0228 (9)0.0086 (8)0.0046 (7)0.0031 (8)
C60.0259 (9)0.0320 (10)0.0245 (9)0.0077 (8)0.0004 (7)0.0041 (8)
C110.0242 (9)0.0268 (9)0.0158 (8)0.0018 (7)0.0007 (6)0.0010 (7)
C120.0224 (9)0.0314 (10)0.0205 (8)0.0002 (7)0.0002 (7)0.0007 (7)
C130.0336 (10)0.0269 (9)0.0196 (8)0.0013 (8)0.0012 (7)0.0008 (7)
C140.0330 (10)0.0331 (10)0.0165 (8)0.0108 (8)0.0030 (7)0.0026 (7)
C150.0228 (9)0.0418 (12)0.0271 (10)0.0054 (8)0.0000 (7)0.0010 (8)
C160.0238 (9)0.0331 (10)0.0261 (9)0.0009 (8)0.0024 (7)0.0006 (8)
C210.0205 (8)0.0205 (8)0.0222 (8)0.0032 (6)0.0010 (6)0.0005 (6)
C220.0241 (9)0.0276 (9)0.0185 (8)0.0022 (7)0.0040 (7)0.0013 (7)
C230.0276 (9)0.0250 (9)0.0185 (8)0.0040 (7)0.0000 (7)0.0000 (7)
C240.0238 (9)0.0194 (8)0.0239 (9)0.0022 (7)0.0003 (7)0.0002 (7)
C250.0291 (10)0.0295 (10)0.0208 (8)0.0004 (8)0.0054 (7)0.0022 (7)
C260.0287 (10)0.0296 (10)0.0186 (8)0.0005 (8)0.0019 (7)0.0002 (7)
Geometric parameters (Å, º) top
S1—O11.4206 (15)C1—C21.390 (2)
S1—O21.4320 (14)C2—C31.386 (2)
S1—N11.621 (2)C3—C41.383 (3)
S1—C111.7577 (19)C4—C51.376 (3)
S2—O31.4238 (14)C5—C61.379 (3)
S2—O41.4260 (15)C11—C121.382 (3)
S2—N21.627 (2)C11—C161.388 (3)
S2—C211.7703 (19)C12—C131.381 (3)
O5—N31.218 (3)C13—C141.371 (3)
O6—N31.223 (3)C14—C151.377 (3)
O7—N41.221 (2)C15—C161.374 (3)
O8—N41.210 (2)C21—C221.384 (2)
N1—C11.431 (2)C21—C261.385 (2)
N2—C31.431 (2)C22—C231.377 (3)
N3—C141.471 (3)C23—C241.381 (3)
N4—C241.464 (2)C24—C251.376 (3)
C1—C61.384 (3)C25—C261.381 (3)
O1—S1—O2120.27 (9)C4—C3—N2118.66 (16)
O1—S1—N1109.10 (9)C2—C3—N2119.88 (16)
O2—S1—N1104.86 (9)C5—C4—C3119.29 (17)
O1—S1—C11108.15 (9)C4—C5—C6120.53 (18)
O2—S1—C11108.59 (9)C5—C6—C1119.73 (18)
N1—S1—C11104.85 (8)C12—C11—C16121.93 (18)
O3—S2—O4120.79 (9)C12—C11—S1119.47 (14)
O3—S2—N2108.92 (9)C16—C11—S1118.40 (15)
O4—S2—N2105.05 (9)C13—C12—C11118.97 (18)
O3—S2—C21106.72 (9)C14—C13—C12118.32 (19)
O4—S2—C21108.66 (9)C13—C14—C15123.40 (19)
N2—S2—C21105.80 (8)C13—C14—N3118.33 (19)
C1—N1—S1124.50 (13)C15—C14—N3118.26 (19)
C3—N2—S2119.59 (12)C16—C15—C14118.39 (18)
O5—N3—O6124.5 (2)C15—C16—C11118.95 (19)
O5—N3—C14118.0 (2)C22—C21—C26121.57 (17)
O6—N3—C14117.49 (19)C22—C21—S2118.64 (14)
O8—N4—O7123.23 (17)C26—C21—S2119.75 (14)
O8—N4—C24118.63 (16)C23—C22—C21119.59 (16)
O7—N4—C24118.14 (16)C22—C23—C24117.96 (17)
C6—C1—C2120.80 (16)C25—C24—C23123.40 (18)
C6—C1—N1117.22 (16)C25—C24—N4118.37 (16)
C2—C1—N1121.79 (16)C23—C24—N4118.22 (16)
C3—C2—C1118.15 (16)C24—C25—C26118.18 (17)
C4—C3—C2121.46 (16)C25—C26—C21119.27 (17)
O1—S1—N1—C154.38 (17)C12—C13—C14—N3176.83 (17)
O2—S1—N1—C1175.56 (15)O5—N3—C14—C13179.05 (19)
C11—S1—N1—C161.3 (2)O6—N3—C14—C130.8 (3)
O3—S2—N2—C366.88 (15)O5—N3—C14—C150.1 (3)
O4—S2—N2—C3162.39 (14)O6—N3—C14—C15179.8 (2)
C21—S2—N2—C347.5 (2)C13—C14—C15—C161.3 (3)
S1—N1—C1—C6138.9 (2)N3—C14—C15—C16177.65 (17)
S1—N1—C1—C246.0 (2)C14—C15—C16—C110.4 (3)
C6—C1—C2—C31.4 (3)C12—C11—C16—C151.1 (3)
N1—C1—C2—C3176.26 (16)S1—C11—C16—C15173.69 (15)
C1—C2—C3—C41.7 (3)O3—S2—C21—C22178.51 (15)
C1—C2—C3—N2179.58 (16)O4—S2—C21—C2246.78 (17)
S2—N2—C3—C4106.8 (2)N2—S2—C21—C2265.6 (2)
S2—N2—C3—C274.5 (2)O3—S2—C21—C263.79 (18)
C2—C3—C4—C50.4 (3)O4—S2—C21—C26135.52 (16)
N2—C3—C4—C5179.15 (18)N2—S2—C21—C26112.12 (16)
C3—C4—C5—C61.2 (3)C26—C21—C22—C230.4 (3)
C4—C5—C6—C11.6 (3)S2—C21—C22—C23178.06 (14)
C2—C1—C6—C50.2 (3)C21—C22—C23—C241.8 (3)
N1—C1—C6—C5174.90 (18)C22—C23—C24—C251.7 (3)
O1—S1—C11—C1218.60 (17)C22—C23—C24—N4177.25 (16)
O2—S1—C11—C12150.65 (15)O8—N4—C24—C25177.91 (18)
N1—S1—C11—C1297.7 (2)O7—N4—C24—C251.5 (3)
O1—S1—C11—C16166.44 (14)O8—N4—C24—C231.1 (3)
O2—S1—C11—C1634.39 (17)O7—N4—C24—C23179.44 (18)
N1—S1—C11—C1677.26 (16)C23—C24—C25—C260.1 (3)
C16—C11—C12—C130.3 (3)N4—C24—C25—C26178.81 (17)
S1—C11—C12—C13174.45 (14)C24—C25—C26—C211.3 (3)
C11—C12—C13—C141.3 (3)C22—C21—C26—C251.2 (3)
C12—C13—C14—C152.1 (3)S2—C21—C26—C25176.44 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.84 (2)2.14 (3)2.974 (2)169 (2)
N1—H1N···O7ii0.81 (2)2.27 (2)3.060 (2)163 (2)
C6—H6···O7ii0.952.433.253 (2)145
C4—H4···O8iii0.952.493.359 (2)152
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x3/2, y1/2, z+3/2; (iii) x1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC18H14N4O8S2
Mr478.45
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)6.8331 (10), 16.4997 (14), 17.3290 (13)
β (°) 90.216 (8)
V3)1953.7 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.35 × 0.25 × 0.20
Data collection
DiffractometerSiemens P4 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4837, 4475, 3740
Rint0.029
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.100, 1.05
No. of reflections4475
No. of parameters297
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.43

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
S1—N11.621 (2)N2—C31.431 (2)
S2—N21.627 (2)N3—C141.471 (3)
N1—C11.431 (2)N4—C241.464 (2)
C11—S1—N1—C161.3 (2)S2—N2—C3—C4106.8 (2)
C21—S2—N2—C347.5 (2)N1—S1—C11—C1297.7 (2)
S1—N1—C1—C6138.9 (2)N2—S2—C21—C2265.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.84 (2)2.14 (3)2.974 (2)169 (2)
N1—H1N···O7ii0.81 (2)2.27 (2)3.060 (2)163 (2)
C6—H6···O7ii0.952.433.253 (2)145
C4—H4···O8iii0.952.493.359 (2)152
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x3/2, y1/2, z+3/2; (iii) x1, y+1, z+1.
 

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