



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811036191/su2300sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536811036191/su2300Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811036191/su2300Isup3.cml |
CCDC reference: 850605
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.058
- wR factor = 0.122
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.964 PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 -- O1 .. 5.4 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N4 -- C24 .. 5.7 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C17 PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C8 -C13 1.37 Ang. PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C14 -C19 1.37 Ang. PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C21 -C26 1.37 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0054 Ang PLAT352_ALERT_3_C Short N-H Bond (0.87A) N1 - H1N ... 0.70 Ang. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 48 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 73 PLAT915_ALERT_3_C Low Friedel Pair Coverage ...................... 87 Perc.
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 28.32 From the CIF: _reflns_number_total 6049 From the CIF: _diffrn_reflns_limit_ max hkl 6. 19. 44. From the CIF: _diffrn_reflns_limit_ min hkl -6. -18. -42. TEST1: Expected hkl limits for theta max Calculated maximum hkl 6. 19. 46. Calculated minimum hkl -6. -19. -46. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.32 From the CIF: _reflns_number_total 6049 Count of symmetry unique reflns 3783 Completeness (_total/calc) 159.90% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2266 Fraction of Friedel pairs measured 0.599 Are heavy atom types Z>Si present yes PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT952_ALERT_5_G Reported and Calculated Lmax Values Differ by .. 2
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 13 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
p-Toluene sulfonyl chloride (2 mmol, 0.3813 g) was added to p-phenylenediamine (1 mmol, 0.108 g) in distilled water (20 ml) in a round-bottom flask (100 ml). The suspension was stirred for 10 h at room temperature while keeping the pH between 8–9 with sodium carbonate solution (3%). The light brown precipitate formed was filtered, washed with distilled water and dried. Light brown needles of (I) were grown from methanol.
The N-bound H-atoms were located in difference Fourier maps and their positions were freely refined with the constraint Uiso(H) = 1.2Ueq(N). The C-bound H-atoms were placed in calculated positions treated as riding atoms: C-H = 0.93 and 0.96 Å for CH and CH3 H-atoms, respectively, with Uiso(H) = k × Ueq(C), where k = 1.5 for CH3 H-atoms and k = 1.2 for all other H-atoms.
As part of our ongoing structural studies of sulfonamides (Khan et al., 2011), the synthesis and structure of the title compound, (I) (Fig. 1), are now described. Related stuctures with different substituents replacing the para-amino group in (I) include 4-methyl-N-(4-nitrophenyl)benzenesulfonamide, (II), (Xing and Zeng, 2005) and 4-methyl-N-(4-methylphenyl)benzenesulfonamide, (III), (Khan et al., 2010). Also worthy of mention is the remarkable sudy of Gelbrich et al. (2007), who made a systematic structural comparison of no fewer than 133 crystal structures of 4,4'-disubstituted benzenesulfonamidobenzenes. However, no compounds with an amino substituent were incorporated into their survey.
There are two independent molecules (A containing S1 and B containing S2) in the asymmetric unit of (I), as shown in Fig. 1. They have similar V-shaped conformations and indeed the dihedral angles between their benzene rings are identical [45.86 (13)°]. Their C—S—N—C torsion angles [67.9 (3)° for A and 70.2 (3)° for B] are also similar. The bond angle sums for N1 and N3 [349.4 and 344.1°, respectively] indicate a clear tendancy towards pyramidal geometry for the nitrogen atoms. Otherwise, their bond lengths and angles are similar to those seen in (II) and (III). Values for the inter-ring dihedral angle and the C—S—N—C torsion angle are 86.1 (1) and 65.85 (13)°, respectively, in (II), and 70.53 (10) and -60.71 (18)°, respectively, in (III), indicating that (I), (II) and (III) have significantly different conformations.
In the crystal of (I), the molecules are linked by N—H···O and N—H···N hydrogen bonds (Table 1). Both the sulfonamide NH groups make intermolecular hydrogen bonds to the sulfonamide O-atom acceptors such that separate [100] C(4) chains of A and B are generated, with adjacent molecules related only by a unit-cell translation. The amine groups each form an N—H···N and an N—H···O link. The former bonds lead to distinctive [100] —N—H···N—H···N— C(2) chains of alternating A and B molecules, and serve to link the C(4) chains into a sheet. The latter bonds generate [001] chains of alternating A and B molecules and overall a three-dimensional array is generated (Fig. 2).
Because of the presence of the —NH2 group, the hydrogen bonding patterns in (I) are not expected to show close similarities to those of the Gelbrich et al. (2007) study. There, the sulfonamide —NH— group was the only possible donor and the structure of (I) does not appear to match any of the groups of structures described by these workers.
For related structures and background to sulfonamides, see: Xing & Zeng (2005); Gelbrich et al. (2007); Khan et al. (2010, 2011).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C13H14N2O2S | F(000) = 1104 |
Mr = 262.32 | Dx = 1.331 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2101 reflections |
a = 5.0598 (3) Å | θ = 2.3–21.0° |
b = 14.7702 (11) Å | µ = 0.24 mm−1 |
c = 35.026 (2) Å | T = 296 K |
V = 2617.7 (3) Å3 | Cut needle, brown |
Z = 8 | 0.41 × 0.35 × 0.20 mm |
Bruker APEXII CCD diffractometer | 6049 independent reflections |
Radiation source: fine-focus sealed tube | 3138 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 28.3°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −6→6 |
Tmin = 0.907, Tmax = 0.953 | k = −18→19 |
14160 measured reflections | l = −42→44 |
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)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0447P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.003 |
6049 reflections | Δρmax = 0.19 e Å−3 |
345 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2266 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (8) |
C13H14N2O2S | V = 2617.7 (3) Å3 |
Mr = 262.32 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.0598 (3) Å | µ = 0.24 mm−1 |
b = 14.7702 (11) Å | T = 296 K |
c = 35.026 (2) Å | 0.41 × 0.35 × 0.20 mm |
Bruker APEXII CCD diffractometer | 6049 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3138 reflections with I > 2σ(I) |
Tmin = 0.907, Tmax = 0.953 | Rint = 0.048 |
14160 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | Δρmax = 0.19 e Å−3 |
S = 0.98 | Δρmin = −0.23 e Å−3 |
6049 reflections | Absolute structure: Flack (1983), 2266 Friedel pairs |
345 parameters | Absolute structure parameter: −0.03 (8) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7219 (6) | 0.5980 (2) | 0.52219 (9) | 0.0461 (9) | |
C2 | 0.5551 (7) | 0.6031 (3) | 0.55343 (11) | 0.0676 (11) | |
H2 | 0.4207 | 0.5608 | 0.5565 | 0.081* | |
C3 | 0.5892 (9) | 0.6712 (3) | 0.57994 (11) | 0.0745 (13) | |
H3 | 0.4774 | 0.6735 | 0.6010 | 0.089* | |
C4 | 0.7816 (9) | 0.7354 (3) | 0.57630 (11) | 0.0650 (11) | |
C5 | 0.9476 (8) | 0.7288 (3) | 0.54593 (11) | 0.0672 (11) | |
H5 | 1.0827 | 0.7710 | 0.5433 | 0.081* | |
C6 | 0.9217 (7) | 0.6609 (3) | 0.51874 (10) | 0.0577 (10) | |
H6 | 1.0386 | 0.6579 | 0.4983 | 0.069* | |
C7 | 0.8067 (12) | 0.8109 (3) | 0.60412 (11) | 0.1064 (17) | |
H7A | 0.7568 | 0.8667 | 0.5921 | 0.160* | |
H7B | 0.9864 | 0.8150 | 0.6127 | 0.160* | |
H7C | 0.6929 | 0.7998 | 0.6256 | 0.160* | |
C8 | 0.7725 (7) | 0.3749 (2) | 0.53228 (10) | 0.0470 (9) | |
C9 | 0.8953 (7) | 0.3861 (3) | 0.56689 (11) | 0.0588 (10) | |
H9 | 1.0308 | 0.4282 | 0.5695 | 0.071* | |
C10 | 0.8171 (9) | 0.3350 (3) | 0.59756 (11) | 0.0667 (11) | |
H10 | 0.9024 | 0.3423 | 0.6209 | 0.080* | |
C11 | 0.6143 (7) | 0.2728 (3) | 0.59452 (11) | 0.0573 (10) | |
C12 | 0.4958 (7) | 0.2624 (3) | 0.55924 (10) | 0.0581 (10) | |
H12 | 0.3598 | 0.2206 | 0.5564 | 0.070* | |
C13 | 0.5747 (7) | 0.3124 (3) | 0.52862 (10) | 0.0521 (9) | |
H13 | 0.4935 | 0.3040 | 0.5051 | 0.062* | |
S1 | 0.67974 (18) | 0.51473 (7) | 0.48702 (3) | 0.0565 (3) | |
N1 | 0.8513 (6) | 0.4261 (2) | 0.49950 (10) | 0.0574 (9) | |
H1N | 0.988 (7) | 0.429 (3) | 0.4975 (11) | 0.069* | |
N2 | 0.5408 (8) | 0.2184 (3) | 0.62512 (10) | 0.0775 (11) | |
H2N | 0.589 (8) | 0.235 (3) | 0.6483 (10) | 0.093* | |
H3N | 0.362 (8) | 0.195 (3) | 0.6230 (10) | 0.093* | |
O1 | 0.7922 (5) | 0.54737 (18) | 0.45226 (7) | 0.0748 (8) | |
O2 | 0.4094 (4) | 0.48778 (19) | 0.48757 (8) | 0.0759 (8) | |
C14 | 0.1982 (6) | 0.7212 (2) | 0.73078 (9) | 0.0433 (8) | |
C15 | 0.0384 (8) | 0.7105 (3) | 0.69949 (11) | 0.0661 (11) | |
H15 | −0.0987 | 0.7509 | 0.6947 | 0.079* | |
C16 | 0.0848 (9) | 0.6391 (3) | 0.67542 (12) | 0.0760 (13) | |
H16 | −0.0247 | 0.6315 | 0.6543 | 0.091* | |
C17 | 0.2854 (9) | 0.5789 (3) | 0.68115 (11) | 0.0652 (11) | |
C18 | 0.4447 (8) | 0.5923 (3) | 0.71206 (11) | 0.0625 (11) | |
H18 | 0.5846 | 0.5527 | 0.7163 | 0.075* | |
C19 | 0.4044 (6) | 0.6623 (2) | 0.73690 (11) | 0.0518 (9) | |
H19 | 0.5157 | 0.6701 | 0.7578 | 0.062* | |
C20 | 0.3247 (11) | 0.4991 (3) | 0.65535 (13) | 0.1056 (17) | |
H20A | 0.4187 | 0.4525 | 0.6688 | 0.158* | |
H20B | 0.4248 | 0.5173 | 0.6334 | 0.158* | |
H20C | 0.1559 | 0.4763 | 0.6473 | 0.158* | |
C21 | 0.2515 (6) | 0.9433 (2) | 0.71400 (10) | 0.0434 (9) | |
C22 | 0.0559 (7) | 1.0077 (3) | 0.71480 (10) | 0.0551 (10) | |
H22 | −0.0298 | 1.0205 | 0.7377 | 0.066* | |
C23 | −0.0137 (7) | 1.0527 (3) | 0.68273 (10) | 0.0581 (10) | |
H23 | −0.1487 | 1.0954 | 0.6838 | 0.070* | |
C24 | 0.1128 (7) | 1.0364 (2) | 0.64826 (10) | 0.0517 (9) | |
C25 | 0.3122 (8) | 0.9737 (3) | 0.64794 (11) | 0.0659 (11) | |
H25 | 0.4034 | 0.9627 | 0.6254 | 0.079* | |
C26 | 0.3792 (7) | 0.9273 (2) | 0.68016 (10) | 0.0563 (10) | |
H26 | 0.5131 | 0.8842 | 0.6792 | 0.068* | |
S2 | 0.14355 (16) | 0.81143 (6) | 0.76258 (3) | 0.0478 (3) | |
N3 | 0.3200 (5) | 0.89631 (19) | 0.74834 (8) | 0.0448 (7) | |
H4N | 0.474 (6) | 0.886 (2) | 0.7494 (9) | 0.054* | |
N4 | 0.0471 (8) | 1.0859 (3) | 0.61552 (10) | 0.0748 (11) | |
H5N | −0.110 (8) | 1.104 (3) | 0.6191 (12) | 0.090* | |
H6N | 0.099 (8) | 1.055 (3) | 0.5963 (11) | 0.090* | |
O3 | −0.1258 (4) | 0.83822 (17) | 0.75914 (7) | 0.0647 (7) | |
O4 | 0.2457 (5) | 0.78643 (19) | 0.79860 (6) | 0.0668 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0446 (19) | 0.049 (2) | 0.045 (2) | 0.0025 (18) | 0.0005 (17) | 0.0031 (17) |
C2 | 0.057 (2) | 0.082 (3) | 0.064 (3) | −0.005 (2) | 0.016 (2) | 0.006 (3) |
C3 | 0.081 (3) | 0.091 (4) | 0.052 (3) | 0.012 (3) | 0.021 (2) | −0.010 (3) |
C4 | 0.081 (3) | 0.062 (3) | 0.053 (3) | 0.016 (3) | −0.001 (2) | 0.004 (2) |
C5 | 0.074 (3) | 0.057 (3) | 0.070 (3) | −0.009 (2) | −0.012 (2) | −0.002 (2) |
C6 | 0.056 (2) | 0.065 (3) | 0.052 (2) | −0.007 (2) | 0.0099 (19) | 0.003 (2) |
C7 | 0.164 (5) | 0.076 (3) | 0.079 (3) | 0.030 (4) | −0.005 (3) | −0.028 (3) |
C8 | 0.042 (2) | 0.048 (2) | 0.051 (2) | 0.0038 (18) | 0.0044 (18) | −0.0066 (19) |
C9 | 0.057 (2) | 0.053 (3) | 0.066 (3) | −0.010 (2) | −0.013 (2) | −0.002 (2) |
C10 | 0.080 (3) | 0.060 (3) | 0.061 (3) | −0.010 (2) | −0.026 (2) | −0.008 (2) |
C11 | 0.065 (3) | 0.046 (2) | 0.061 (3) | 0.002 (2) | −0.010 (2) | −0.003 (2) |
C12 | 0.062 (2) | 0.056 (3) | 0.057 (2) | −0.014 (2) | −0.010 (2) | −0.003 (2) |
C13 | 0.055 (2) | 0.052 (2) | 0.049 (2) | −0.007 (2) | −0.0062 (17) | −0.007 (2) |
S1 | 0.0551 (6) | 0.0642 (7) | 0.0502 (6) | −0.0055 (5) | −0.0044 (5) | −0.0030 (5) |
N1 | 0.0490 (18) | 0.062 (2) | 0.061 (2) | −0.001 (2) | 0.0063 (19) | −0.0103 (17) |
N2 | 0.092 (3) | 0.080 (3) | 0.061 (2) | −0.018 (2) | −0.016 (2) | 0.015 (2) |
O1 | 0.098 (2) | 0.087 (2) | 0.0397 (15) | −0.0100 (18) | 0.0080 (15) | 0.0010 (14) |
O2 | 0.0483 (14) | 0.088 (2) | 0.092 (2) | −0.0104 (15) | −0.0146 (14) | −0.0059 (18) |
C14 | 0.0405 (18) | 0.044 (2) | 0.046 (2) | −0.0038 (17) | 0.0029 (17) | 0.0089 (17) |
C15 | 0.059 (2) | 0.071 (3) | 0.068 (3) | 0.007 (2) | −0.010 (2) | −0.006 (2) |
C16 | 0.084 (3) | 0.079 (3) | 0.065 (3) | −0.008 (3) | −0.017 (2) | −0.006 (3) |
C17 | 0.089 (3) | 0.050 (3) | 0.057 (3) | −0.014 (3) | 0.016 (3) | −0.003 (2) |
C18 | 0.078 (3) | 0.040 (2) | 0.070 (3) | 0.005 (2) | 0.008 (2) | 0.011 (2) |
C19 | 0.052 (2) | 0.044 (2) | 0.059 (2) | −0.0008 (19) | −0.0048 (19) | 0.010 (2) |
C20 | 0.163 (5) | 0.071 (3) | 0.083 (3) | −0.004 (4) | 0.010 (3) | −0.021 (3) |
C21 | 0.0367 (19) | 0.039 (2) | 0.054 (2) | 0.0010 (17) | 0.0005 (17) | −0.0027 (18) |
C22 | 0.062 (2) | 0.058 (3) | 0.046 (2) | 0.021 (2) | 0.0102 (18) | 0.003 (2) |
C23 | 0.060 (2) | 0.055 (3) | 0.059 (3) | 0.021 (2) | 0.003 (2) | 0.002 (2) |
C24 | 0.065 (2) | 0.044 (2) | 0.046 (2) | 0.002 (2) | −0.004 (2) | 0.0006 (19) |
C25 | 0.072 (3) | 0.067 (3) | 0.059 (3) | 0.017 (3) | 0.017 (2) | 0.000 (2) |
C26 | 0.055 (2) | 0.053 (2) | 0.061 (3) | 0.018 (2) | 0.007 (2) | 0.000 (2) |
S2 | 0.0404 (5) | 0.0560 (6) | 0.0469 (6) | 0.0052 (5) | 0.0017 (4) | 0.0051 (5) |
N3 | 0.0351 (14) | 0.0449 (17) | 0.0546 (18) | 0.0059 (15) | −0.0076 (14) | 0.0033 (15) |
N4 | 0.092 (3) | 0.071 (3) | 0.061 (2) | 0.009 (2) | 0.004 (2) | 0.004 (2) |
O3 | 0.0423 (14) | 0.0779 (19) | 0.0739 (17) | 0.0104 (13) | 0.0112 (13) | 0.0022 (15) |
O4 | 0.0828 (19) | 0.077 (2) | 0.0406 (14) | 0.0086 (15) | −0.0042 (13) | 0.0097 (13) |
C1—C6 | 1.378 (4) | C14—C15 | 1.371 (4) |
C1—C2 | 1.384 (4) | C14—C19 | 1.375 (4) |
C1—S1 | 1.754 (4) | C14—S2 | 1.759 (3) |
C2—C3 | 1.380 (5) | C15—C16 | 1.370 (5) |
C2—H2 | 0.9300 | C15—H15 | 0.9300 |
C3—C4 | 1.364 (5) | C16—C17 | 1.365 (6) |
C3—H3 | 0.9300 | C16—H16 | 0.9300 |
C4—C5 | 1.359 (5) | C17—C18 | 1.364 (5) |
C4—C7 | 1.487 (5) | C17—C20 | 1.498 (6) |
C5—C6 | 1.389 (5) | C18—C19 | 1.367 (5) |
C5—H5 | 0.9300 | C18—H18 | 0.9300 |
C6—H6 | 0.9300 | C19—H19 | 0.9300 |
C7—H7A | 0.9600 | C20—H20A | 0.9600 |
C7—H7B | 0.9600 | C20—H20B | 0.9600 |
C7—H7C | 0.9600 | C20—H20C | 0.9600 |
C8—C13 | 1.368 (4) | C21—C26 | 1.371 (4) |
C8—C9 | 1.372 (4) | C21—C22 | 1.373 (4) |
C8—N1 | 1.431 (5) | C21—N3 | 1.431 (4) |
C9—C10 | 1.372 (5) | C22—C23 | 1.352 (4) |
C9—H9 | 0.9300 | C22—H22 | 0.9300 |
C10—C11 | 1.381 (5) | C23—C24 | 1.388 (4) |
C10—H10 | 0.9300 | C23—H23 | 0.9300 |
C11—C12 | 1.382 (4) | C24—C25 | 1.369 (5) |
C11—N2 | 1.391 (5) | C24—N4 | 1.400 (5) |
C12—C13 | 1.362 (4) | C25—C26 | 1.363 (5) |
C12—H12 | 0.9300 | C25—H25 | 0.9300 |
C13—H13 | 0.9300 | C26—H26 | 0.9300 |
S1—O2 | 1.425 (2) | S2—O4 | 1.413 (2) |
S1—O1 | 1.428 (3) | S2—O3 | 1.424 (2) |
S1—N1 | 1.630 (4) | S2—N3 | 1.618 (3) |
N1—H1N | 0.70 (3) | N3—H4N | 0.79 (3) |
N2—H2N | 0.88 (4) | N4—H5N | 0.85 (4) |
N2—H3N | 0.97 (4) | N4—H6N | 0.86 (4) |
C6—C1—C2 | 118.7 (3) | C15—C14—C19 | 120.0 (3) |
C6—C1—S1 | 120.0 (3) | C15—C14—S2 | 120.0 (3) |
C2—C1—S1 | 121.3 (3) | C19—C14—S2 | 120.0 (3) |
C3—C2—C1 | 119.7 (4) | C16—C15—C14 | 118.6 (4) |
C3—C2—H2 | 120.2 | C16—C15—H15 | 120.7 |
C1—C2—H2 | 120.2 | C14—C15—H15 | 120.7 |
C4—C3—C2 | 122.2 (4) | C17—C16—C15 | 122.6 (4) |
C4—C3—H3 | 118.9 | C17—C16—H16 | 118.7 |
C2—C3—H3 | 118.9 | C15—C16—H16 | 118.7 |
C5—C4—C3 | 117.7 (4) | C18—C17—C16 | 117.5 (4) |
C5—C4—C7 | 120.9 (4) | C18—C17—C20 | 121.0 (5) |
C3—C4—C7 | 121.4 (4) | C16—C17—C20 | 121.5 (4) |
C4—C5—C6 | 122.0 (4) | C17—C18—C19 | 121.8 (4) |
C4—C5—H5 | 119.0 | C17—C18—H18 | 119.1 |
C6—C5—H5 | 119.0 | C19—C18—H18 | 119.1 |
C1—C6—C5 | 119.7 (3) | C18—C19—C14 | 119.5 (4) |
C1—C6—H6 | 120.1 | C18—C19—H19 | 120.2 |
C5—C6—H6 | 120.1 | C14—C19—H19 | 120.2 |
C4—C7—H7A | 109.5 | C17—C20—H20A | 109.5 |
C4—C7—H7B | 109.5 | C17—C20—H20B | 109.5 |
H7A—C7—H7B | 109.5 | H20A—C20—H20B | 109.5 |
C4—C7—H7C | 109.5 | C17—C20—H20C | 109.5 |
H7A—C7—H7C | 109.5 | H20A—C20—H20C | 109.5 |
H7B—C7—H7C | 109.5 | H20B—C20—H20C | 109.5 |
C13—C8—C9 | 119.7 (3) | C26—C21—C22 | 118.5 (3) |
C13—C8—N1 | 119.0 (3) | C26—C21—N3 | 121.9 (3) |
C9—C8—N1 | 121.2 (3) | C22—C21—N3 | 119.6 (3) |
C10—C9—C8 | 119.6 (4) | C23—C22—C21 | 120.8 (3) |
C10—C9—H9 | 120.2 | C23—C22—H22 | 119.6 |
C8—C9—H9 | 120.2 | C21—C22—H22 | 119.6 |
C9—C10—C11 | 121.3 (3) | C22—C23—C24 | 121.1 (3) |
C9—C10—H10 | 119.3 | C22—C23—H23 | 119.4 |
C11—C10—H10 | 119.3 | C24—C23—H23 | 119.4 |
C10—C11—C12 | 117.7 (4) | C25—C24—C23 | 117.7 (3) |
C10—C11—N2 | 121.6 (4) | C25—C24—N4 | 121.4 (4) |
C12—C11—N2 | 120.6 (4) | C23—C24—N4 | 120.8 (4) |
C13—C12—C11 | 121.1 (4) | C26—C25—C24 | 121.1 (3) |
C13—C12—H12 | 119.4 | C26—C25—H25 | 119.4 |
C11—C12—H12 | 119.4 | C24—C25—H25 | 119.4 |
C12—C13—C8 | 120.4 (3) | C25—C26—C21 | 120.8 (3) |
C12—C13—H13 | 119.8 | C25—C26—H26 | 119.6 |
C8—C13—H13 | 119.8 | C21—C26—H26 | 119.6 |
O2—S1—O1 | 119.24 (18) | O4—S2—O3 | 119.89 (16) |
O2—S1—N1 | 106.46 (18) | O4—S2—N3 | 106.01 (16) |
O1—S1—N1 | 106.72 (17) | O3—S2—N3 | 106.66 (16) |
O2—S1—C1 | 107.65 (17) | O4—S2—C14 | 108.04 (16) |
O1—S1—C1 | 108.28 (17) | O3—S2—C14 | 107.91 (17) |
N1—S1—C1 | 108.05 (16) | N3—S2—C14 | 107.78 (15) |
C8—N1—S1 | 119.4 (2) | C21—N3—S2 | 120.1 (2) |
C8—N1—H1N | 113 (4) | C21—N3—H4N | 112 (2) |
S1—N1—H1N | 117 (4) | S2—N3—H4N | 112 (3) |
C11—N2—H2N | 119 (3) | C24—N4—H5N | 106 (3) |
C11—N2—H3N | 113 (2) | C24—N4—H6N | 107 (3) |
H2N—N2—H3N | 115 (4) | H5N—N4—H6N | 125 (4) |
C6—C1—C2—C3 | 1.0 (5) | C19—C14—C15—C16 | 1.7 (5) |
S1—C1—C2—C3 | −178.0 (3) | S2—C14—C15—C16 | −179.5 (3) |
C1—C2—C3—C4 | 0.8 (6) | C14—C15—C16—C17 | −0.7 (6) |
C2—C3—C4—C5 | −2.1 (6) | C15—C16—C17—C18 | −0.7 (6) |
C2—C3—C4—C7 | 176.9 (4) | C15—C16—C17—C20 | 177.3 (4) |
C3—C4—C5—C6 | 1.5 (6) | C16—C17—C18—C19 | 1.0 (6) |
C7—C4—C5—C6 | −177.4 (4) | C20—C17—C18—C19 | −177.0 (4) |
C2—C1—C6—C5 | −1.5 (5) | C17—C18—C19—C14 | 0.0 (5) |
S1—C1—C6—C5 | 177.5 (3) | C15—C14—C19—C18 | −1.4 (5) |
C4—C5—C6—C1 | 0.2 (6) | S2—C14—C19—C18 | 179.8 (3) |
C13—C8—C9—C10 | −0.5 (5) | C26—C21—C22—C23 | 1.6 (5) |
N1—C8—C9—C10 | −179.1 (3) | N3—C21—C22—C23 | −179.6 (3) |
C8—C9—C10—C11 | −0.8 (6) | C21—C22—C23—C24 | −1.0 (6) |
C9—C10—C11—C12 | 1.3 (6) | C22—C23—C24—C25 | −0.6 (6) |
C9—C10—C11—N2 | 177.6 (4) | C22—C23—C24—N4 | −177.4 (4) |
C10—C11—C12—C13 | −0.6 (5) | C23—C24—C25—C26 | 1.7 (6) |
N2—C11—C12—C13 | −176.9 (4) | N4—C24—C25—C26 | 178.5 (4) |
C11—C12—C13—C8 | −0.6 (5) | C24—C25—C26—C21 | −1.2 (6) |
C9—C8—C13—C12 | 1.2 (5) | C22—C21—C26—C25 | −0.5 (5) |
N1—C8—C13—C12 | 179.8 (3) | N3—C21—C26—C25 | −179.2 (3) |
C6—C1—S1—O2 | −154.1 (3) | C15—C14—S2—O4 | 154.8 (3) |
C2—C1—S1—O2 | 24.9 (3) | C19—C14—S2—O4 | −26.5 (3) |
C6—C1—S1—O1 | −23.9 (3) | C15—C14—S2—O3 | 23.8 (3) |
C2—C1—S1—O1 | 155.1 (3) | C19—C14—S2—O3 | −157.5 (3) |
C6—C1—S1—N1 | 91.3 (3) | C15—C14—S2—N3 | −91.1 (3) |
C2—C1—S1—N1 | −89.7 (3) | C19—C14—S2—N3 | 87.7 (3) |
C13—C8—N1—S1 | 81.6 (4) | C26—C21—N3—S2 | −100.0 (4) |
C9—C8—N1—S1 | −99.8 (4) | C22—C21—N3—S2 | 81.2 (4) |
O2—S1—N1—C8 | −47.4 (3) | O4—S2—N3—C21 | −174.3 (2) |
O1—S1—N1—C8 | −175.8 (3) | O3—S2—N3—C21 | −45.5 (3) |
C1—S1—N1—C8 | 67.9 (3) | C14—S2—N3—C21 | 70.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.70 (3) | 2.33 (4) | 2.996 (4) | 161 (5) |
N2—H2N···O4ii | 0.88 (4) | 2.18 (4) | 3.052 (4) | 172 (4) |
N2—H3N···N4iii | 0.97 (4) | 2.28 (4) | 3.191 (5) | 155 (4) |
N3—H4N···O3i | 0.79 (3) | 2.17 (3) | 2.957 (3) | 170 (3) |
N4—H5N···N2iv | 0.85 (4) | 2.45 (4) | 3.241 (5) | 155 (4) |
N4—H6N···O1v | 0.86 (4) | 2.47 (4) | 3.323 (5) | 171 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y−1, z; (iv) x−1, y+1, z; (v) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H14N2O2S |
Mr | 262.32 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 5.0598 (3), 14.7702 (11), 35.026 (2) |
V (Å3) | 2617.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.41 × 0.35 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.907, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14160, 6049, 3138 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.122, 0.98 |
No. of reflections | 6049 |
No. of parameters | 345 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.23 |
Absolute structure | Flack (1983), 2266 Friedel pairs |
Absolute structure parameter | −0.03 (8) |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.70 (3) | 2.33 (4) | 2.996 (4) | 161 (5) |
N2—H2N···O4ii | 0.88 (4) | 2.18 (4) | 3.052 (4) | 172 (4) |
N2—H3N···N4iii | 0.97 (4) | 2.28 (4) | 3.191 (5) | 155 (4) |
N3—H4N···O3i | 0.79 (3) | 2.17 (3) | 2.957 (3) | 170 (3) |
N4—H5N···N2iv | 0.85 (4) | 2.45 (4) | 3.241 (5) | 155 (4) |
N4—H6N···O1v | 0.86 (4) | 2.47 (4) | 3.323 (5) | 171 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y−1, z; (iv) x−1, y+1, z; (v) x−1/2, −y+3/2, −z+1. |
As part of our ongoing structural studies of sulfonamides (Khan et al., 2011), the synthesis and structure of the title compound, (I) (Fig. 1), are now described. Related stuctures with different substituents replacing the para-amino group in (I) include 4-methyl-N-(4-nitrophenyl)benzenesulfonamide, (II), (Xing and Zeng, 2005) and 4-methyl-N-(4-methylphenyl)benzenesulfonamide, (III), (Khan et al., 2010). Also worthy of mention is the remarkable sudy of Gelbrich et al. (2007), who made a systematic structural comparison of no fewer than 133 crystal structures of 4,4'-disubstituted benzenesulfonamidobenzenes. However, no compounds with an amino substituent were incorporated into their survey.
There are two independent molecules (A containing S1 and B containing S2) in the asymmetric unit of (I), as shown in Fig. 1. They have similar V-shaped conformations and indeed the dihedral angles between their benzene rings are identical [45.86 (13)°]. Their C—S—N—C torsion angles [67.9 (3)° for A and 70.2 (3)° for B] are also similar. The bond angle sums for N1 and N3 [349.4 and 344.1°, respectively] indicate a clear tendancy towards pyramidal geometry for the nitrogen atoms. Otherwise, their bond lengths and angles are similar to those seen in (II) and (III). Values for the inter-ring dihedral angle and the C—S—N—C torsion angle are 86.1 (1) and 65.85 (13)°, respectively, in (II), and 70.53 (10) and -60.71 (18)°, respectively, in (III), indicating that (I), (II) and (III) have significantly different conformations.
In the crystal of (I), the molecules are linked by N—H···O and N—H···N hydrogen bonds (Table 1). Both the sulfonamide NH groups make intermolecular hydrogen bonds to the sulfonamide O-atom acceptors such that separate [100] C(4) chains of A and B are generated, with adjacent molecules related only by a unit-cell translation. The amine groups each form an N—H···N and an N—H···O link. The former bonds lead to distinctive [100] —N—H···N—H···N— C(2) chains of alternating A and B molecules, and serve to link the C(4) chains into a sheet. The latter bonds generate [001] chains of alternating A and B molecules and overall a three-dimensional array is generated (Fig. 2).
Because of the presence of the —NH2 group, the hydrogen bonding patterns in (I) are not expected to show close similarities to those of the Gelbrich et al. (2007) study. There, the sulfonamide —NH— group was the only possible donor and the structure of (I) does not appear to match any of the groups of structures described by these workers.