In the title compound, C
18H
14N
4O
8S
2, 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
CCDC reference: 159856
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (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
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.
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.
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.
N,
N'-
m-Phenylenebis(4-nitrobenzenesulfonamide)
top
Crystal data top
C18H14N4O8S2 | F(000) = 984 |
Mr = 478.45 | Dx = 1.627 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8331 (10) Å | Cell parameters from 84 reflections |
b = 16.4997 (14) Å | θ = 10.0–16.5° |
c = 17.3290 (13) Å | µ = 0.33 mm−1 |
β = 90.216 (8)° | T = 150 K |
V = 1953.7 (4) Å3 | Block, red |
Z = 4 | 0.35 × 0.25 × 0.20 mm |
Data collection top
Siemens P4 four-circle diffractometer | Rint = 0.029 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 2.4° |
Graphite monochromator | h = 0→9 |
ω scans | k = 0→21 |
4837 measured reflections | l = −22→22 |
4475 independent reflections | 4 standard reflections every 100 reflections |
3740 reflections with I > 2σ(I) | intensity decay: <5% |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H 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 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
C18H14N4O8S2 | V = 1953.7 (4) Å3 |
Mr = 478.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.8331 (10) Å | µ = 0.33 mm−1 |
b = 16.4997 (14) Å | T = 150 K |
c = 17.3290 (13) Å | 0.35 × 0.25 × 0.20 mm |
β = 90.216 (8)° | |
Data collection top
Siemens P4 four-circle diffractometer | Rint = 0.029 |
4837 measured reflections | 4 standard reflections every 100 reflections |
4475 independent reflections | intensity decay: <5% |
3740 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.37 e Å−3 |
4475 reflections | Δρmin = −0.43 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
S1 | −0.32458 (7) | 0.25662 (3) | 0.93385 (2) | 0.02220 (11) | |
S2 | 0.10600 (6) | 0.42250 (3) | 0.68612 (3) | 0.02294 (11) | |
O1 | −0.1211 (2) | 0.27413 (9) | 0.93276 (8) | 0.0293 (3) | |
O2 | −0.4051 (2) | 0.20739 (9) | 0.99392 (8) | 0.0305 (3) | |
O3 | 0.1297 (2) | 0.42515 (9) | 0.76775 (8) | 0.0333 (3) | |
O4 | 0.2620 (2) | 0.44533 (9) | 0.63621 (9) | 0.0338 (3) | |
O5 | −0.9518 (3) | 0.55828 (12) | 0.91301 (11) | 0.0532 (5) | |
O6 | −0.6896 (3) | 0.62090 (11) | 0.87738 (13) | 0.0567 (5) | |
O7 | −0.7032 (2) | 0.64062 (11) | 0.66215 (9) | 0.0430 (4) | |
O8 | −0.6555 (2) | 0.61775 (10) | 0.54221 (9) | 0.0384 (4) | |
N1 | −0.3843 (2) | 0.21082 (10) | 0.85445 (9) | 0.0229 (3) | |
H1N | −0.491 (3) | 0.1897 (14) | 0.8601 (13) | 0.027 (6)* | |
N2 | 0.0493 (2) | 0.33052 (9) | 0.66064 (9) | 0.0215 (3) | |
H2N | 0.075 (3) | 0.3242 (14) | 0.6136 (15) | 0.031 (6)* | |
N3 | −0.7767 (3) | 0.56083 (12) | 0.90032 (10) | 0.0371 (4) | |
N4 | −0.6079 (2) | 0.61198 (10) | 0.60930 (10) | 0.0270 (3) | |
C1 | −0.3457 (3) | 0.24146 (10) | 0.77878 (10) | 0.0202 (3) | |
C2 | −0.1641 (3) | 0.27311 (11) | 0.75900 (10) | 0.0204 (3) | |
H2 | −0.0627 | 0.2781 | 0.7964 | 0.025* | |
C3 | −0.1351 (3) | 0.29713 (10) | 0.68323 (10) | 0.0195 (3) | |
C4 | −0.2799 (3) | 0.28817 (12) | 0.62786 (10) | 0.0254 (4) | |
H4 | −0.2572 | 0.3046 | 0.5761 | 0.030* | |
C5 | −0.4570 (3) | 0.25516 (13) | 0.64853 (11) | 0.0305 (4) | |
H5 | −0.5562 | 0.2479 | 0.6106 | 0.037* | |
C6 | −0.4918 (3) | 0.23262 (12) | 0.72387 (11) | 0.0275 (4) | |
H6 | −0.6155 | 0.2111 | 0.7380 | 0.033* | |
C11 | −0.4529 (3) | 0.34892 (11) | 0.93101 (10) | 0.0222 (3) | |
C12 | −0.3584 (3) | 0.41822 (12) | 0.90626 (10) | 0.0248 (4) | |
H12 | −0.2223 | 0.4173 | 0.8952 | 0.030* | |
C13 | −0.4648 (3) | 0.48886 (12) | 0.89790 (10) | 0.0267 (4) | |
H13 | −0.4033 | 0.5377 | 0.8820 | 0.032* | |
C14 | −0.6614 (3) | 0.48675 (12) | 0.91315 (10) | 0.0275 (4) | |
C15 | −0.7572 (3) | 0.41850 (14) | 0.93871 (12) | 0.0306 (4) | |
H15 | −0.8933 | 0.4198 | 0.9496 | 0.037* | |
C16 | −0.6512 (3) | 0.34837 (13) | 0.94804 (11) | 0.0277 (4) | |
H16 | −0.7127 | 0.3003 | 0.9659 | 0.033* | |
C21 | −0.1015 (3) | 0.48244 (11) | 0.66381 (10) | 0.0210 (3) | |
C22 | −0.1549 (3) | 0.49172 (11) | 0.58719 (10) | 0.0234 (4) | |
H22 | −0.0787 | 0.4676 | 0.5476 | 0.028* | |
C23 | −0.3192 (3) | 0.53609 (11) | 0.56870 (10) | 0.0237 (4) | |
H23 | −0.3565 | 0.5445 | 0.5164 | 0.028* | |
C24 | −0.4281 (3) | 0.56791 (11) | 0.62844 (10) | 0.0224 (4) | |
C25 | −0.3780 (3) | 0.55927 (12) | 0.70497 (11) | 0.0264 (4) | |
H25 | −0.4566 | 0.5822 | 0.7444 | 0.032* | |
C26 | −0.2103 (3) | 0.51636 (12) | 0.72283 (10) | 0.0257 (4) | |
H26 | −0.1700 | 0.5102 | 0.7750 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0242 (2) | 0.0264 (2) | 0.0161 (2) | 0.00276 (17) | 0.00192 (15) | 0.00390 (16) |
S2 | 0.0193 (2) | 0.0267 (2) | 0.0228 (2) | −0.00306 (17) | −0.00059 (16) | −0.00095 (17) |
O1 | 0.0255 (7) | 0.0382 (8) | 0.0241 (7) | 0.0045 (6) | −0.0015 (5) | 0.0031 (6) |
O2 | 0.0388 (8) | 0.0340 (8) | 0.0187 (6) | 0.0037 (6) | 0.0050 (5) | 0.0086 (5) |
O3 | 0.0365 (8) | 0.0392 (8) | 0.0240 (7) | 0.0019 (6) | −0.0101 (6) | −0.0062 (6) |
O4 | 0.0217 (7) | 0.0358 (8) | 0.0439 (9) | −0.0064 (6) | 0.0056 (6) | 0.0015 (6) |
O5 | 0.0449 (10) | 0.0625 (12) | 0.0522 (11) | 0.0282 (9) | 0.0103 (8) | 0.0072 (9) |
O6 | 0.0594 (12) | 0.0386 (10) | 0.0720 (13) | 0.0157 (9) | −0.0004 (10) | 0.0150 (9) |
O7 | 0.0402 (9) | 0.0529 (10) | 0.0361 (8) | 0.0207 (8) | 0.0018 (7) | −0.0088 (7) |
O8 | 0.0438 (9) | 0.0418 (9) | 0.0295 (8) | 0.0106 (7) | −0.0097 (6) | −0.0008 (6) |
N1 | 0.0265 (8) | 0.0241 (8) | 0.0182 (7) | −0.0035 (6) | 0.0047 (6) | 0.0026 (6) |
N2 | 0.0217 (7) | 0.0253 (8) | 0.0176 (7) | −0.0008 (6) | 0.0047 (6) | −0.0015 (6) |
N3 | 0.0434 (11) | 0.0406 (11) | 0.0272 (9) | 0.0173 (9) | −0.0005 (8) | 0.0008 (8) |
N4 | 0.0286 (8) | 0.0236 (8) | 0.0287 (8) | 0.0014 (6) | −0.0012 (6) | −0.0015 (6) |
C1 | 0.0262 (9) | 0.0174 (8) | 0.0170 (8) | 0.0012 (7) | 0.0035 (6) | 0.0019 (6) |
C2 | 0.0223 (8) | 0.0219 (8) | 0.0171 (8) | 0.0011 (7) | −0.0004 (6) | 0.0004 (6) |
C3 | 0.0209 (8) | 0.0181 (8) | 0.0194 (8) | −0.0009 (6) | 0.0038 (6) | −0.0010 (6) |
C4 | 0.0306 (10) | 0.0287 (9) | 0.0168 (8) | −0.0035 (8) | 0.0006 (7) | 0.0029 (7) |
C5 | 0.0301 (10) | 0.0384 (11) | 0.0228 (9) | −0.0086 (8) | −0.0046 (7) | 0.0031 (8) |
C6 | 0.0259 (9) | 0.0320 (10) | 0.0245 (9) | −0.0077 (8) | 0.0004 (7) | 0.0041 (8) |
C11 | 0.0242 (9) | 0.0268 (9) | 0.0158 (8) | 0.0018 (7) | −0.0007 (6) | −0.0010 (7) |
C12 | 0.0224 (9) | 0.0314 (10) | 0.0205 (8) | 0.0002 (7) | −0.0002 (7) | 0.0007 (7) |
C13 | 0.0336 (10) | 0.0269 (9) | 0.0196 (8) | 0.0013 (8) | −0.0012 (7) | 0.0008 (7) |
C14 | 0.0330 (10) | 0.0331 (10) | 0.0165 (8) | 0.0108 (8) | −0.0030 (7) | −0.0026 (7) |
C15 | 0.0228 (9) | 0.0418 (12) | 0.0271 (10) | 0.0054 (8) | 0.0000 (7) | −0.0010 (8) |
C16 | 0.0238 (9) | 0.0331 (10) | 0.0261 (9) | −0.0009 (8) | 0.0024 (7) | 0.0006 (8) |
C21 | 0.0205 (8) | 0.0205 (8) | 0.0222 (8) | −0.0032 (6) | 0.0010 (6) | 0.0005 (6) |
C22 | 0.0241 (9) | 0.0276 (9) | 0.0185 (8) | −0.0022 (7) | 0.0040 (7) | −0.0013 (7) |
C23 | 0.0276 (9) | 0.0250 (9) | 0.0185 (8) | −0.0040 (7) | 0.0000 (7) | 0.0000 (7) |
C24 | 0.0238 (9) | 0.0194 (8) | 0.0239 (9) | −0.0022 (7) | 0.0003 (7) | −0.0002 (7) |
C25 | 0.0291 (10) | 0.0295 (10) | 0.0208 (8) | 0.0004 (8) | 0.0054 (7) | −0.0022 (7) |
C26 | 0.0287 (10) | 0.0296 (10) | 0.0186 (8) | −0.0005 (8) | 0.0019 (7) | −0.0002 (7) |
Geometric parameters (Å, º) top
S1—O1 | 1.4206 (15) | C1—C2 | 1.390 (2) |
S1—O2 | 1.4320 (14) | C2—C3 | 1.386 (2) |
S1—N1 | 1.621 (2) | C3—C4 | 1.383 (3) |
S1—C11 | 1.7577 (19) | C4—C5 | 1.376 (3) |
S2—O3 | 1.4238 (14) | C5—C6 | 1.379 (3) |
S2—O4 | 1.4260 (15) | C11—C12 | 1.382 (3) |
S2—N2 | 1.627 (2) | C11—C16 | 1.388 (3) |
S2—C21 | 1.7703 (19) | C12—C13 | 1.381 (3) |
O5—N3 | 1.218 (3) | C13—C14 | 1.371 (3) |
O6—N3 | 1.223 (3) | C14—C15 | 1.377 (3) |
O7—N4 | 1.221 (2) | C15—C16 | 1.374 (3) |
O8—N4 | 1.210 (2) | C21—C22 | 1.384 (2) |
N1—C1 | 1.431 (2) | C21—C26 | 1.385 (2) |
N2—C3 | 1.431 (2) | C22—C23 | 1.377 (3) |
N3—C14 | 1.471 (3) | C23—C24 | 1.381 (3) |
N4—C24 | 1.464 (2) | C24—C25 | 1.376 (3) |
C1—C6 | 1.384 (3) | C25—C26 | 1.381 (3) |
| | | |
O1—S1—O2 | 120.27 (9) | C4—C3—N2 | 118.66 (16) |
O1—S1—N1 | 109.10 (9) | C2—C3—N2 | 119.88 (16) |
O2—S1—N1 | 104.86 (9) | C5—C4—C3 | 119.29 (17) |
O1—S1—C11 | 108.15 (9) | C4—C5—C6 | 120.53 (18) |
O2—S1—C11 | 108.59 (9) | C5—C6—C1 | 119.73 (18) |
N1—S1—C11 | 104.85 (8) | C12—C11—C16 | 121.93 (18) |
O3—S2—O4 | 120.79 (9) | C12—C11—S1 | 119.47 (14) |
O3—S2—N2 | 108.92 (9) | C16—C11—S1 | 118.40 (15) |
O4—S2—N2 | 105.05 (9) | C13—C12—C11 | 118.97 (18) |
O3—S2—C21 | 106.72 (9) | C14—C13—C12 | 118.32 (19) |
O4—S2—C21 | 108.66 (9) | C13—C14—C15 | 123.40 (19) |
N2—S2—C21 | 105.80 (8) | C13—C14—N3 | 118.33 (19) |
C1—N1—S1 | 124.50 (13) | C15—C14—N3 | 118.26 (19) |
C3—N2—S2 | 119.59 (12) | C16—C15—C14 | 118.39 (18) |
O5—N3—O6 | 124.5 (2) | C15—C16—C11 | 118.95 (19) |
O5—N3—C14 | 118.0 (2) | C22—C21—C26 | 121.57 (17) |
O6—N3—C14 | 117.49 (19) | C22—C21—S2 | 118.64 (14) |
O8—N4—O7 | 123.23 (17) | C26—C21—S2 | 119.75 (14) |
O8—N4—C24 | 118.63 (16) | C23—C22—C21 | 119.59 (16) |
O7—N4—C24 | 118.14 (16) | C22—C23—C24 | 117.96 (17) |
C6—C1—C2 | 120.80 (16) | C25—C24—C23 | 123.40 (18) |
C6—C1—N1 | 117.22 (16) | C25—C24—N4 | 118.37 (16) |
C2—C1—N1 | 121.79 (16) | C23—C24—N4 | 118.22 (16) |
C3—C2—C1 | 118.15 (16) | C24—C25—C26 | 118.18 (17) |
C4—C3—C2 | 121.46 (16) | C25—C26—C21 | 119.27 (17) |
| | | |
O1—S1—N1—C1 | −54.38 (17) | C12—C13—C14—N3 | −176.83 (17) |
O2—S1—N1—C1 | 175.56 (15) | O5—N3—C14—C13 | 179.05 (19) |
C11—S1—N1—C1 | 61.3 (2) | O6—N3—C14—C13 | −0.8 (3) |
O3—S2—N2—C3 | 66.88 (15) | O5—N3—C14—C15 | 0.1 (3) |
O4—S2—N2—C3 | −162.39 (14) | O6—N3—C14—C15 | −179.8 (2) |
C21—S2—N2—C3 | −47.5 (2) | C13—C14—C15—C16 | −1.3 (3) |
S1—N1—C1—C6 | −138.9 (2) | N3—C14—C15—C16 | 177.65 (17) |
S1—N1—C1—C2 | 46.0 (2) | C14—C15—C16—C11 | −0.4 (3) |
C6—C1—C2—C3 | 1.4 (3) | C12—C11—C16—C15 | 1.1 (3) |
N1—C1—C2—C3 | 176.26 (16) | S1—C11—C16—C15 | −173.69 (15) |
C1—C2—C3—C4 | −1.7 (3) | O3—S2—C21—C22 | 178.51 (15) |
C1—C2—C3—N2 | 179.58 (16) | O4—S2—C21—C22 | 46.78 (17) |
S2—N2—C3—C4 | 106.8 (2) | N2—S2—C21—C22 | −65.6 (2) |
S2—N2—C3—C2 | −74.5 (2) | O3—S2—C21—C26 | −3.79 (18) |
C2—C3—C4—C5 | 0.4 (3) | O4—S2—C21—C26 | −135.52 (16) |
N2—C3—C4—C5 | 179.15 (18) | N2—S2—C21—C26 | 112.12 (16) |
C3—C4—C5—C6 | 1.2 (3) | C26—C21—C22—C23 | 0.4 (3) |
C4—C5—C6—C1 | −1.6 (3) | S2—C21—C22—C23 | 178.06 (14) |
C2—C1—C6—C5 | 0.2 (3) | C21—C22—C23—C24 | −1.8 (3) |
N1—C1—C6—C5 | −174.90 (18) | C22—C23—C24—C25 | 1.7 (3) |
O1—S1—C11—C12 | 18.60 (17) | C22—C23—C24—N4 | −177.25 (16) |
O2—S1—C11—C12 | 150.65 (15) | O8—N4—C24—C25 | −177.91 (18) |
N1—S1—C11—C12 | −97.7 (2) | O7—N4—C24—C25 | 1.5 (3) |
O1—S1—C11—C16 | −166.44 (14) | O8—N4—C24—C23 | 1.1 (3) |
O2—S1—C11—C16 | −34.39 (17) | O7—N4—C24—C23 | −179.44 (18) |
N1—S1—C11—C16 | 77.26 (16) | C23—C24—C25—C26 | −0.1 (3) |
C16—C11—C12—C13 | −0.3 (3) | N4—C24—C25—C26 | 178.81 (17) |
S1—C11—C12—C13 | 174.45 (14) | C24—C25—C26—C21 | −1.3 (3) |
C11—C12—C13—C14 | −1.3 (3) | C22—C21—C26—C25 | 1.2 (3) |
C12—C13—C14—C15 | 2.1 (3) | S2—C21—C26—C25 | −176.44 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2i | 0.84 (2) | 2.14 (3) | 2.974 (2) | 169 (2) |
N1—H1N···O7ii | 0.81 (2) | 2.27 (2) | 3.060 (2) | 163 (2) |
C6—H6···O7ii | 0.95 | 2.43 | 3.253 (2) | 145 |
C4—H4···O8iii | 0.95 | 2.49 | 3.359 (2) | 152 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x−3/2, y−1/2, −z+3/2; (iii) −x−1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C18H14N4O8S2 |
Mr | 478.45 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 6.8331 (10), 16.4997 (14), 17.3290 (13) |
β (°) | 90.216 (8) |
V (Å3) | 1953.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4837, 4475, 3740 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 1.05 |
No. of reflections | 4475 |
No. of parameters | 297 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.43 |
Selected geometric parameters (Å, º) topS1—N1 | 1.621 (2) | N2—C3 | 1.431 (2) |
S2—N2 | 1.627 (2) | N3—C14 | 1.471 (3) |
N1—C1 | 1.431 (2) | N4—C24 | 1.464 (2) |
| | | |
C11—S1—N1—C1 | 61.3 (2) | S2—N2—C3—C4 | 106.8 (2) |
C21—S2—N2—C3 | −47.5 (2) | N1—S1—C11—C12 | −97.7 (2) |
S1—N1—C1—C6 | −138.9 (2) | N2—S2—C21—C22 | −65.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2i | 0.84 (2) | 2.14 (3) | 2.974 (2) | 169 (2) |
N1—H1N···O7ii | 0.81 (2) | 2.27 (2) | 3.060 (2) | 163 (2) |
C6—H6···O7ii | 0.95 | 2.43 | 3.253 (2) | 145 |
C4—H4···O8iii | 0.95 | 2.49 | 3.359 (2) | 152 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x−3/2, y−1/2, −z+3/2; (iii) −x−1, −y+1, −z+1. |
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.