Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103025149/bm1545sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025149/bm1545IIsup2.hkl |
CCDC reference: 229114
To a solution of dapsone (1 mmol) in methanol (30 ml) was added a solution of 4-nitrobenzaldehyde (2 mmol) in methanol (10 ml). The mixture was refluxed for 3 h and then cooled, and all the volatiles were removed under vacuum. The resulting solid was recrystallized from toluene. IR (KBr disc, cm−1): ν 3099, 3079, 3061, 2998, 2946, 2885, 1627, 1602, 1579, 1541, 1491, 1412, 1350, 1324, 1296, 1282, 1185, 1151, 1105, 1071, 1005, 954, 854, 748, 735, 706, 683, 663, 642, 633, 584, 560, 503. M.p. 504–506 K. A data set was collected with synchrotron radiation at the Daresbury synchrotron radiation source, station 9.8 (Cernik et al., 1997; Clegg et al., 1998).
Following structure elucidation, refinement was impeded by non-positive definite anisotropic displacement parameters for several atoms. Because of the disorder, all atoms were refined in SHELXL97 with isotropic displacement parameters. The Car—Car bond lengths were restrained to 1.395 Å before each refinement cycle. Atom population parameters of the two molecules were refined and converged to 0.430 (5) and 0.570 (5). The H atoms were initially placed in calculated positions (C—H = 0.95 Å) and thereafter were allowed to ride on their attached atoms with a common isotropic displacement parameter, which refined to 0.026 (2) Å2. The N—O bonds range from 1.103 (11) to 1.362 (17) Å.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97-2 (Sheldrick, 1998); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).
C26H18N4O6S | F(000) = 1064 |
Mr = 514.5 | Dx = 1.551 Mg m−3 |
Monoclinic, Cc | Synchrotron radiation, λ = 0.6934 Å |
Hall symbol: C -2yc | Cell parameters from 1948 reflections |
a = 36.706 (3) Å | θ = 3.3–25.2° |
b = 4.9130 (4) Å | µ = 0.20 mm−1 |
c = 12.364 (5) Å | T = 120 K |
β = 98.808 (4)° | Lozenge, yellow |
V = 2203.4 (9) Å3 | 0.15 × 0.05 × 0.02 mm |
Z = 4 |
Bruker SMART 1K CCD diffractometer | 3069 reflections with I > 2σ(I) |
ω rotation with narrow frames scans | Rint = 0.036 |
Absorption correction: multi-scan SADABS (Bruker, 2000) | θmax = 25.7°, θmin = 3.3° |
Tmin = 0.970, Tmax = 0.996 | h = −45→45 |
9138 measured reflections | k = −5→6 |
4141 independent reflections | l = −15→15 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0612P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.042 | (Δ/σ)max = 0.002 |
wR(F2) = 0.107 | Δρmax = 0.22 e Å−3 |
S = 1.01 | Δρmin = −0.44 e Å−3 |
4141 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
299 parameters | Absolute structure parameter: 0.3 (2) |
50 restraints |
C26H18N4O6S | V = 2203.4 (9) Å3 |
Mr = 514.5 | Z = 4 |
Monoclinic, Cc | Synchrotron radiation, λ = 0.6934 Å |
a = 36.706 (3) Å | µ = 0.20 mm−1 |
b = 4.9130 (4) Å | T = 120 K |
c = 12.364 (5) Å | 0.15 × 0.05 × 0.02 mm |
β = 98.808 (4)° |
Bruker SMART 1K CCD diffractometer | 4141 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 2000) | 3069 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.996 | Rint = 0.036 |
9138 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.107 | Δρmax = 0.22 e Å−3 |
S = 1.01 | Δρmin = −0.44 e Å−3 |
4141 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
299 parameters | Absolute structure parameter: 0.3 (2) |
50 restraints |
Experimental. When there are two overlapping images then the expectation is: a normal (i.e., not racemic) twin, or the wrong space group, or the data have been collected with one axis halved. Data from Professor W. Clegg who commented: the space group is, of course, an ambiguous one, and there may be some pseudo symmetry in this structure, so it does not look trivial. Advice from Simon Parsons taken regarding possible twinning: Clearly a tricky one, I can't see anything that I'd have done differently. There is a possible twin operation about [100], but when I introduce this (with or without the disorder) its scale refines to zero. So I think this is fine as it is. |
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. Cc was the only space group that led to a structure solution with Sir97, no sensible solution was found for C2/c |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.48835 (5) | 1.1073 (4) | 0.36781 (17) | 0.0009 (6)* | 0.430 (5) |
O1 | 0.50208 (17) | 1.2633 (12) | 0.2846 (5) | 0.0099 (16)* | 0.430 (5) |
O2 | 0.47342 (18) | 1.2564 (13) | 0.4571 (5) | 0.0057 (14)* | 0.430 (5) |
O3 | 0.7442 (2) | −0.6570 (15) | 0.6995 (5) | 0.0095 (15)* | 0.430 (5) |
O4 | 0.71713 (18) | −0.7175 (16) | 0.8458 (6) | 0.0067 (13)* | 0.430 (5) |
O5 | 0.2705 (3) | −0.6895 (14) | −0.1624 (5) | 0.0137 (16)* | 0.430 (5) |
O6 | 0.2450 (2) | −0.7028 (19) | −0.0127 (8) | 0.018 (2)* | 0.430 (5) |
N1 | 0.5990 (3) | 0.3283 (18) | 0.5931 (7) | 0.0088 (19)* | 0.430 (5) |
N2 | 0.7188 (4) | −0.624 (2) | 0.7616 (11) | 0.001 (3)* | 0.430 (5) |
N3 | 0.3747 (2) | 0.3041 (19) | 0.1892 (7) | 0.0087 (18)* | 0.430 (5) |
N4 | 0.2690 (3) | −0.623 (2) | −0.0780 (7) | 0.019 (3)* | 0.430 (5) |
C1 | 0.5230 (3) | 0.889 (2) | 0.4347 (7) | 0.010 (2)* | 0.430 (5) |
C2 | 0.5210 (2) | 0.7959 (18) | 0.5387 (7) | 0.010 (2)* | 0.430 (5) |
H2 | 0.5012 | 0.8494 | 0.5752 | 0.0258 (18)* | 0.430 (5) |
C3 | 0.5481 (2) | 0.6235 (17) | 0.5895 (7) | 0.014 (2)* | 0.430 (5) |
H3 | 0.5483 | 0.5769 | 0.6641 | 0.0258 (18)* | 0.430 (5) |
C4 | 0.5753 (2) | 0.5163 (18) | 0.5343 (7) | 0.006 (2)* | 0.430 (5) |
C5 | 0.5785 (2) | 0.6291 (17) | 0.4314 (6) | 0.011 (2)* | 0.430 (5) |
H5 | 0.5990 | 0.5823 | 0.3966 | 0.0258 (18)* | 0.430 (5) |
C6 | 0.5517 (2) | 0.8104 (19) | 0.3799 (8) | 0.010 (2)* | 0.430 (5) |
H6 | 0.5531 | 0.8780 | 0.3087 | 0.0258 (18)* | 0.430 (5) |
C7 | 0.6211 (3) | 0.174 (2) | 0.5431 (9) | 0.010 (2)* | 0.430 (5) |
H7 | 0.6201 | 0.1916 | 0.4662 | 0.0258 (18)* | 0.430 (5) |
C8 | 0.6465 (3) | −0.0207 (19) | 0.6012 (8) | 0.005 (2)* | 0.430 (5) |
C9 | 0.6447 (3) | −0.083 (2) | 0.7099 (9) | 0.015 (3)* | 0.430 (5) |
H9 | 0.6278 | 0.0187 | 0.7447 | 0.0258 (18)* | 0.430 (5) |
C10 | 0.6654 (3) | −0.279 (2) | 0.7722 (12) | 0.020 (4)* | 0.430 (5) |
H10 | 0.6620 | −0.3257 | 0.8445 | 0.0258 (18)* | 0.430 (5) |
C11 | 0.6912 (5) | −0.400 (4) | 0.7194 (12) | 0.016 (5)* | 0.430 (5) |
C12 | 0.6930 (5) | −0.339 (3) | 0.6107 (13) | 0.033 (5)* | 0.430 (5) |
H12 | 0.7113 | −0.4314 | 0.5779 | 0.0258 (18)* | 0.430 (5) |
C13 | 0.6710 (3) | −0.156 (2) | 0.5457 (10) | 0.018 (3)* | 0.430 (5) |
H13 | 0.6724 | −0.1273 | 0.4705 | 0.0258 (18)* | 0.430 (5) |
C14 | 0.4528 (2) | 0.8849 (18) | 0.3096 (6) | 0.002 (2)* | 0.430 (5) |
C15 | 0.4242 (2) | 0.8172 (17) | 0.3677 (7) | 0.004 (2)* | 0.430 (5) |
H15 | 0.4225 | 0.9008 | 0.4360 | 0.0258 (18)* | 0.430 (5) |
C16 | 0.3984 (2) | 0.6258 (16) | 0.3234 (6) | 0.0046 (19)* | 0.430 (5) |
H16 | 0.3786 | 0.5779 | 0.3607 | 0.0258 (18)* | 0.430 (5) |
C17 | 0.4019 (3) | 0.5035 (19) | 0.2230 (7) | 0.007 (2)* | 0.430 (5) |
C18 | 0.4285 (2) | 0.5890 (16) | 0.1599 (6) | 0.010 (2)* | 0.430 (5) |
H18 | 0.4283 | 0.5249 | 0.0873 | 0.0258 (18)* | 0.430 (5) |
C19 | 0.4554 (3) | 0.772 (2) | 0.2081 (7) | 0.012 (2)* | 0.430 (5) |
H19 | 0.4754 | 0.8195 | 0.1713 | 0.0258 (18)* | 0.430 (5) |
C20 | 0.3689 (3) | 0.211 (2) | 0.0922 (8) | 0.010 (2)* | 0.430 (5) |
H20 | 0.3829 | 0.2887 | 0.0413 | 0.0258 (18)* | 0.430 (5) |
C21 | 0.3428 (3) | −0.0037 (19) | 0.0514 (8) | 0.010 (2)* | 0.430 (5) |
C22 | 0.3182 (2) | −0.095 (2) | 0.1187 (8) | 0.011 (2)* | 0.430 (5) |
H22 | 0.3183 | −0.0206 | 0.1897 | 0.0258 (18)* | 0.430 (5) |
C23 | 0.2932 (2) | −0.3004 (18) | 0.0786 (7) | 0.013 (2)* | 0.430 (5) |
H23 | 0.2761 | −0.3684 | 0.1224 | 0.0258 (18)* | 0.430 (5) |
C24 | 0.2936 (4) | −0.404 (3) | −0.0268 (9) | 0.008 (3)* | 0.430 (5) |
C25 | 0.3166 (2) | −0.3103 (15) | −0.0955 (6) | 0.0057 (16)* | 0.430 (5) |
H25 | 0.3164 | −0.3830 | −0.1668 | 0.0258 (18)* | 0.430 (5) |
C26 | 0.3404 (3) | −0.1018 (19) | −0.0546 (8) | 0.012 (2)* | 0.430 (5) |
H26 | 0.3556 | −0.0226 | −0.1015 | 0.0258 (18)* | 0.430 (5) |
S1A | 0.49615 (6) | 1.1094 (5) | 0.32496 (19) | 0.0218 (6)* | 0.570 (5) |
O1A | 0.51043 (19) | 1.2534 (14) | 0.2448 (6) | 0.0282 (16)* | 0.570 (5) |
O2A | 0.48065 (15) | 1.2442 (11) | 0.4150 (5) | 0.0198 (14)* | 0.570 (5) |
O3A | 0.74189 (17) | −0.7026 (12) | 0.7220 (4) | 0.0172 (13)* | 0.570 (5) |
O4A | 0.70790 (14) | −0.7076 (13) | 0.8510 (5) | 0.0184 (13)* | 0.570 (5) |
O5A | 0.2709 (2) | −0.7370 (12) | −0.1443 (5) | 0.0226 (17)* | 0.570 (5) |
O6A | 0.23801 (17) | −0.6636 (15) | −0.0178 (6) | 0.0193 (16)* | 0.570 (5) |
N1A | 0.6112 (2) | 0.3016 (18) | 0.5041 (6) | 0.0242 (18)* | 0.570 (5) |
N2A | 0.7165 (4) | −0.600 (2) | 0.7566 (12) | 0.030 (4)* | 0.570 (5) |
N3A | 0.3844 (3) | 0.3253 (19) | 0.1035 (7) | 0.030 (2)* | 0.570 (5) |
N4A | 0.26429 (17) | −0.6131 (15) | −0.0606 (6) | 0.0032 (16)* | 0.570 (5) |
C1A | 0.5306 (2) | 0.8849 (17) | 0.3881 (6) | 0.019 (2)* | 0.570 (5) |
C2A | 0.5286 (2) | 0.7610 (17) | 0.4883 (6) | 0.019 (2)* | 0.570 (5) |
H2A | 0.5100 | 0.8115 | 0.5298 | 0.0258 (18)* | 0.570 (5) |
C3A | 0.55425 (19) | 0.5632 (14) | 0.5266 (5) | 0.0198 (18)* | 0.570 (5) |
H3A | 0.5517 | 0.4657 | 0.5914 | 0.0258 (18)* | 0.570 (5) |
C4A | 0.5837 (2) | 0.5055 (18) | 0.4714 (6) | 0.019 (2)* | 0.570 (5) |
C5A | 0.5841 (2) | 0.6295 (17) | 0.3696 (7) | 0.028 (2)* | 0.570 (5) |
H5A | 0.6029 | 0.5802 | 0.3281 | 0.0258 (18)* | 0.570 (5) |
C6A | 0.5584 (2) | 0.8201 (18) | 0.3278 (8) | 0.026 (2)* | 0.570 (5) |
H6A | 0.5596 | 0.9054 | 0.2595 | 0.0258 (18)* | 0.570 (5) |
C7A | 0.6139 (3) | 0.204 (2) | 0.5993 (8) | 0.029 (2)* | 0.570 (5) |
H7A | 0.5978 | 0.2663 | 0.6474 | 0.0258 (18)* | 0.570 (5) |
C8A | 0.6421 (2) | −0.0075 (17) | 0.6372 (7) | 0.016 (2)* | 0.570 (5) |
C9A | 0.6425 (2) | −0.1132 (17) | 0.7415 (7) | 0.021 (2)* | 0.570 (5) |
H9A | 0.6253 | −0.0579 | 0.7872 | 0.0258 (18)* | 0.570 (5) |
C10A | 0.6697 (3) | −0.305 (2) | 0.7750 (10) | 0.024 (3)* | 0.570 (5) |
H10A | 0.6723 | −0.3692 | 0.8482 | 0.0258 (18)* | 0.570 (5) |
C11A | 0.6935 (4) | −0.407 (3) | 0.7073 (9) | 0.015 (4)* | 0.570 (5) |
C12A | 0.6924 (3) | −0.313 (2) | 0.6022 (9) | 0.016 (3)* | 0.570 (5) |
H12A | 0.7085 | −0.3774 | 0.5548 | 0.0258 (18)* | 0.570 (5) |
C13A | 0.6657 (2) | −0.1146 (18) | 0.5705 (7) | 0.022 (2)* | 0.570 (5) |
H13A | 0.6635 | −0.0478 | 0.4977 | 0.0258 (18)* | 0.570 (5) |
C14A | 0.4607 (2) | 0.8832 (17) | 0.2627 (6) | 0.0121 (18)* | 0.570 (5) |
C15A | 0.4331 (2) | 0.7988 (18) | 0.3184 (7) | 0.024 (2)* | 0.570 (5) |
H15A | 0.4314 | 0.8691 | 0.3890 | 0.0258 (18)* | 0.570 (5) |
C16A | 0.4075 (2) | 0.6074 (15) | 0.2693 (6) | 0.025 (2)* | 0.570 (5) |
H16A | 0.3889 | 0.5376 | 0.3074 | 0.0258 (18)* | 0.570 (5) |
C17A | 0.4099 (2) | 0.5224 (18) | 0.1636 (6) | 0.022 (2)* | 0.570 (5) |
C18A | 0.43872 (18) | 0.6010 (13) | 0.1085 (6) | 0.0181 (18)* | 0.570 (5) |
H18A | 0.4407 | 0.5286 | 0.0384 | 0.0258 (18)* | 0.570 (5) |
C19A | 0.4641 (2) | 0.7859 (17) | 0.1582 (6) | 0.024 (2)* | 0.570 (5) |
H19A | 0.4837 | 0.8466 | 0.1221 | 0.0258 (18)* | 0.570 (5) |
C20A | 0.3647 (2) | 0.190 (2) | 0.1491 (8) | 0.023 (2)* | 0.570 (5) |
H20A | 0.3651 | 0.2164 | 0.2254 | 0.0258 (18)* | 0.570 (5) |
C21A | 0.3390 (2) | −0.0212 (18) | 0.0904 (7) | 0.018 (2)* | 0.570 (5) |
C22A | 0.3131 (2) | −0.1458 (16) | 0.1459 (7) | 0.0133 (19)* | 0.570 (5) |
H22A | 0.3120 | −0.0921 | 0.2191 | 0.0258 (18)* | 0.570 (5) |
C23A | 0.28862 (16) | −0.3449 (14) | 0.0989 (5) | 0.0086 (13)* | 0.570 (5) |
H23A | 0.2717 | −0.4335 | 0.1381 | 0.0258 (18)* | 0.570 (5) |
C24A | 0.2909 (3) | −0.404 (2) | −0.0090 (6) | 0.008 (2)* | 0.570 (5) |
C25A | 0.3154 (2) | −0.2804 (15) | −0.0688 (6) | 0.0173 (18)* | 0.570 (5) |
H25A | 0.3153 | −0.3275 | −0.1434 | 0.0258 (18)* | 0.570 (5) |
C26A | 0.3401 (3) | −0.0881 (19) | −0.0189 (7) | 0.022 (2)* | 0.570 (5) |
H26A | 0.3574 | −0.0038 | −0.0582 | 0.0258 (18)* | 0.570 (5) |
S1—O1 | 1.435 (7) | S1A—O1A | 1.384 (7) |
S1—O2 | 1.497 (7) | S1A—O2A | 1.482 (7) |
S1—C14 | 1.768 (9) | S1A—C1A | 1.768 (9) |
S1—C1 | 1.770 (10) | S1A—C14A | 1.792 (8) |
O3—N2 | 1.305 (17) | O3A—N2A | 1.194 (17) |
O4—N2 | 1.148 (17) | O4A—N2A | 1.362 (17) |
O5—N4 | 1.103 (11) | O5A—N4A | 1.256 (10) |
O6—N4 | 1.343 (13) | O6A—N4A | 1.195 (8) |
N1—C7 | 1.329 (12) | N1A—C7A | 1.261 (12) |
N1—C4 | 1.395 (13) | N1A—C4A | 1.435 (12) |
N2—C11 | 1.53 (2) | N2A—C11A | 1.351 (15) |
N3—C20 | 1.270 (13) | N3A—C20A | 1.185 (11) |
N3—C17 | 1.416 (13) | N3A—C17A | 1.467 (13) |
N4—C24 | 1.482 (17) | N4A—C24A | 1.494 (12) |
C1—C2 | 1.378 (7) | C1A—C6A | 1.390 (7) |
C1—C6 | 1.389 (7) | C1A—C2A | 1.392 (7) |
C2—C3 | 1.383 (7) | C2A—C3A | 1.384 (7) |
C2—H2 | 0.9500 | C2A—H2A | 0.9500 |
C3—C4 | 1.394 (7) | C3A—C4A | 1.393 (6) |
C3—H3 | 0.9500 | C3A—H3A | 0.9500 |
C4—C5 | 1.409 (7) | C4A—C5A | 1.401 (7) |
C5—C6 | 1.407 (7) | C5A—C6A | 1.373 (7) |
C5—H5 | 0.9500 | C5A—H5A | 0.9500 |
C6—H6 | 0.9500 | C6A—H6A | 0.9500 |
C7—C8 | 1.447 (14) | C7A—C8A | 1.491 (14) |
C7—H7 | 0.9500 | C7A—H7A | 0.9500 |
C8—C13 | 1.382 (8) | C8A—C13A | 1.387 (7) |
C8—C9 | 1.389 (8) | C8A—C9A | 1.389 (7) |
C9—C10 | 1.388 (9) | C9A—C10A | 1.388 (8) |
C9—H9 | 0.9500 | C9A—H9A | 0.9500 |
C10—C11 | 1.364 (9) | C10A—C11A | 1.393 (8) |
C10—H10 | 0.9500 | C10A—H10A | 0.9500 |
C11—C12 | 1.389 (9) | C11A—C12A | 1.375 (8) |
C12—C13 | 1.380 (9) | C12A—C13A | 1.394 (8) |
C12—H12 | 0.9500 | C12A—H12A | 0.9500 |
C13—H13 | 0.9500 | C13A—H13A | 0.9500 |
C14—C19 | 1.388 (7) | C14A—C15A | 1.374 (6) |
C14—C15 | 1.400 (7) | C14A—C19A | 1.402 (7) |
C15—C16 | 1.385 (7) | C15A—C16A | 1.401 (7) |
C15—H15 | 0.9500 | C15A—H15A | 0.9500 |
C16—C17 | 1.403 (7) | C16A—C17A | 1.388 (7) |
C16—H16 | 0.9500 | C16A—H16A | 0.9500 |
C17—C18 | 1.404 (7) | C17A—C18A | 1.398 (7) |
C18—C19 | 1.399 (7) | C18A—C19A | 1.377 (7) |
C18—H18 | 0.9500 | C18A—H18A | 0.9500 |
C19—H19 | 0.9500 | C19A—H19A | 0.9500 |
C20—C21 | 1.464 (15) | C20A—C21A | 1.512 (13) |
C20—H20 | 0.9500 | C20A—H20A | 0.9500 |
C21—C26 | 1.386 (8) | C21A—C22A | 1.397 (7) |
C21—C22 | 1.393 (8) | C21A—C26A | 1.398 (7) |
C22—C23 | 1.401 (8) | C22A—C23A | 1.392 (7) |
C22—H22 | 0.9500 | C22A—H22A | 0.9500 |
C23—C24 | 1.402 (8) | C23A—C24A | 1.381 (7) |
C23—H23 | 0.9500 | C23A—H23A | 0.9500 |
C24—C25 | 1.367 (8) | C24A—C25A | 1.387 (7) |
C25—C26 | 1.388 (8) | C25A—C26A | 1.386 (7) |
C25—H25 | 0.9500 | C25A—H25A | 0.9500 |
C26—H26 | 0.9500 | C26A—H26A | 0.9500 |
O1—S1—O2 | 118.4 (4) | O1A—S1A—O2A | 122.7 (4) |
O1—S1—C14 | 110.9 (4) | O1A—S1A—C1A | 108.1 (4) |
O2—S1—C14 | 105.8 (4) | O2A—S1A—C1A | 106.2 (4) |
O1—S1—C1 | 110.6 (4) | O1A—S1A—C14A | 109.8 (4) |
O2—S1—C1 | 105.7 (4) | O2A—S1A—C14A | 105.2 (3) |
C14—S1—C1 | 104.4 (5) | C1A—S1A—C14A | 103.1 (4) |
C7—N1—C4 | 120.8 (8) | C7A—N1A—C4A | 118.7 (8) |
O4—N2—O3 | 128.8 (11) | O3A—N2A—C11A | 127.0 (14) |
O4—N2—C11 | 118.2 (12) | O3A—N2A—O4A | 116.1 (9) |
O3—N2—C11 | 112.5 (11) | C11A—N2A—O4A | 116.5 (13) |
C20—N3—C17 | 122.4 (8) | C20A—N3A—C17A | 121.1 (9) |
O5—N4—O6 | 127.9 (13) | O6A—N4A—O5A | 122.4 (9) |
O5—N4—C24 | 120.3 (11) | O6A—N4A—C24A | 118.3 (8) |
O6—N4—C24 | 111.6 (8) | O5A—N4A—C24A | 119.2 (6) |
C2—C1—C6 | 121.1 (9) | C6A—C1A—C2A | 121.4 (8) |
C2—C1—S1 | 120.0 (7) | C6A—C1A—S1A | 116.1 (6) |
C6—C1—S1 | 119.0 (6) | C2A—C1A—S1A | 122.3 (6) |
C1—C2—C3 | 119.3 (8) | C3A—C2A—C1A | 119.1 (7) |
C1—C2—H2 | 120.4 | C3A—C2A—H2A | 120.5 |
C3—C2—H2 | 120.4 | C1A—C2A—H2A | 120.5 |
C2—C3—C4 | 121.9 (8) | C2A—C3A—C4A | 120.8 (7) |
C2—C3—H3 | 119.1 | C2A—C3A—H3A | 119.6 |
C4—C3—H3 | 119.1 | C4A—C3A—H3A | 119.6 |
C3—C4—N1 | 115.6 (7) | C3A—C4A—C5A | 118.0 (8) |
C3—C4—C5 | 117.3 (8) | C3A—C4A—N1A | 124.6 (7) |
N1—C4—C5 | 126.8 (7) | C5A—C4A—N1A | 116.9 (6) |
C6—C5—C4 | 120.5 (8) | C6A—C5A—C4A | 122.2 (8) |
C6—C5—H5 | 119.7 | C6A—C5A—H5A | 118.9 |
C4—C5—H5 | 119.7 | C4A—C5A—H5A | 118.9 |
C1—C6—C5 | 119.0 (8) | C5A—C6A—C1A | 118.2 (8) |
C1—C6—H6 | 120.5 | C5A—C6A—H6A | 120.9 |
C5—C6—H6 | 120.5 | C1A—C6A—H6A | 120.9 |
N1—C7—C8 | 122.5 (10) | N1A—C7A—C8A | 120.7 (10) |
N1—C7—H7 | 118.7 | N1A—C7A—H7A | 119.7 |
C8—C7—H7 | 118.7 | C8A—C7A—H7A | 119.7 |
C13—C8—C9 | 120.3 (9) | C13A—C8A—C9A | 119.4 (8) |
C13—C8—C7 | 119.4 (9) | C13A—C8A—C7A | 123.0 (8) |
C9—C8—C7 | 120.2 (9) | C9A—C8A—C7A | 117.5 (7) |
C10—C9—C8 | 125.9 (12) | C10A—C9A—C8A | 115.8 (9) |
C10—C9—H9 | 117.0 | C10A—C9A—H9A | 122.1 |
C8—C9—H9 | 117.0 | C8A—C9A—H9A | 122.1 |
C11—C10—C9 | 113.5 (15) | C9A—C10A—C11A | 123.7 (12) |
C11—C10—H10 | 123.3 | C9A—C10A—H10A | 118.1 |
C9—C10—H10 | 123.3 | C11A—C10A—H10A | 118.1 |
C10—C11—C12 | 120.5 (18) | N2A—C11A—C12A | 126.2 (12) |
C10—C11—N2 | 128.3 (13) | N2A—C11A—C10A | 112.9 (11) |
C12—C11—N2 | 111.0 (12) | C12A—C11A—C10A | 120.9 (13) |
C13—C12—C11 | 126.4 (19) | C11A—C12A—C13A | 114.8 (12) |
C13—C12—H12 | 116.8 | C11A—C12A—H12A | 122.6 |
C11—C12—H12 | 116.8 | C13A—C12A—H12A | 122.6 |
C12—C13—C8 | 113.1 (14) | C8A—C13A—C12A | 125.0 (9) |
C12—C13—H13 | 123.5 | C8A—C13A—H13A | 117.5 |
C8—C13—H13 | 123.5 | C12A—C13A—H13A | 117.5 |
C19—C14—C15 | 122.0 (8) | C15A—C14A—C19A | 122.4 (8) |
C19—C14—S1 | 117.8 (6) | C15A—C14A—S1A | 121.0 (6) |
C15—C14—S1 | 120.2 (6) | C19A—C14A—S1A | 116.5 (5) |
C16—C15—C14 | 118.6 (8) | C14A—C15A—C16A | 119.0 (8) |
C16—C15—H15 | 120.7 | C14A—C15A—H15A | 120.5 |
C14—C15—H15 | 120.7 | C16A—C15A—H15A | 120.5 |
C15—C16—C17 | 119.4 (8) | C17A—C16A—C15A | 118.3 (7) |
C15—C16—H16 | 120.3 | C17A—C16A—H16A | 120.9 |
C17—C16—H16 | 120.3 | C15A—C16A—H16A | 120.9 |
C16—C17—C18 | 122.0 (8) | C16A—C17A—C18A | 122.6 (8) |
C16—C17—N3 | 113.7 (7) | C16A—C17A—N3A | 123.2 (7) |
C18—C17—N3 | 124.2 (7) | C18A—C17A—N3A | 114.0 (6) |
C19—C18—C17 | 117.4 (8) | C19A—C18A—C17A | 118.4 (7) |
C19—C18—H18 | 121.3 | C19A—C18A—H18A | 120.8 |
C17—C18—H18 | 121.3 | C17A—C18A—H18A | 120.8 |
C14—C19—C18 | 120.0 (8) | C18A—C19A—C14A | 119.1 (7) |
C14—C19—H19 | 120.0 | C18A—C19A—H19A | 120.4 |
C18—C19—H19 | 120.0 | C14A—C19A—H19A | 120.4 |
N3—C20—C21 | 126.2 (10) | N3A—C20A—C21A | 122.5 (10) |
N3—C20—H20 | 116.9 | N3A—C20A—H20A | 118.7 |
C21—C20—H20 | 116.9 | C21A—C20A—H20A | 118.7 |
C26—C21—C22 | 119.9 (9) | C22A—C21A—C26A | 119.6 (8) |
C26—C21—C20 | 121.4 (8) | C22A—C21A—C20A | 119.2 (7) |
C22—C21—C20 | 118.5 (8) | C26A—C21A—C20A | 121.1 (7) |
C21—C22—C23 | 118.0 (8) | C23A—C22A—C21A | 123.2 (7) |
C21—C22—H22 | 121.0 | C23A—C22A—H22A | 118.4 |
C23—C22—H22 | 121.0 | C21A—C22A—H22A | 118.4 |
C22—C23—C24 | 119.4 (8) | C24A—C23A—C22A | 114.7 (6) |
C22—C23—H23 | 120.3 | C24A—C23A—H23A | 122.6 |
C24—C23—H23 | 120.3 | C22A—C23A—H23A | 122.6 |
C25—C24—C23 | 123.4 (9) | C23A—C24A—C25A | 124.4 (7) |
C25—C24—N4 | 111.9 (8) | C23A—C24A—N4A | 115.0 (6) |
C23—C24—N4 | 124.6 (8) | C25A—C24A—N4A | 120.6 (7) |
C24—C25—C26 | 115.8 (8) | C26A—C25A—C24A | 119.5 (7) |
C24—C25—H25 | 122.1 | C26A—C25A—H25A | 120.2 |
C26—C25—H25 | 122.1 | C24A—C25A—H25A | 120.2 |
C21—C26—C25 | 123.2 (9) | C25A—C26A—C21A | 118.5 (8) |
C21—C26—H26 | 118.4 | C25A—C26A—H26A | 120.8 |
C25—C26—H26 | 118.4 | C21A—C26A—H26A | 120.8 |
O1—S1—C1—C2 | 157.0 (8) | O1A—S1A—C1A—C6A | −21.5 (9) |
O2—S1—C1—C2 | 27.6 (10) | O2A—S1A—C1A—C6A | −154.9 (7) |
C14—S1—C1—C2 | −83.7 (9) | C14A—S1A—C1A—C6A | 94.7 (8) |
O1—S1—C1—C6 | −24.3 (10) | O1A—S1A—C1A—C2A | 163.8 (8) |
O2—S1—C1—C6 | −153.6 (8) | O2A—S1A—C1A—C2A | 30.4 (9) |
C14—S1—C1—C6 | 95.1 (9) | C14A—S1A—C1A—C2A | −79.9 (8) |
C6—C1—C2—C3 | 0.7 (16) | C6A—C1A—C2A—C3A | −2.0 (14) |
S1—C1—C2—C3 | 179.4 (8) | S1A—C1A—C2A—C3A | 172.4 (7) |
C1—C2—C3—C4 | −7.4 (15) | C1A—C2A—C3A—C4A | 5.9 (13) |
C2—C3—C4—N1 | −175.0 (9) | C2A—C3A—C4A—C5A | −7.4 (13) |
C2—C3—C4—C5 | 11.8 (14) | C2A—C3A—C4A—N1A | −179.0 (8) |
C7—N1—C4—C3 | 166.7 (9) | C7A—N1A—C4A—C3A | −15.0 (14) |
C7—N1—C4—C5 | −20.9 (16) | C7A—N1A—C4A—C5A | 173.3 (9) |
C3—C4—C5—C6 | −9.9 (14) | C3A—C4A—C5A—C6A | 5.3 (14) |
N1—C4—C5—C6 | 177.8 (10) | N1A—C4A—C5A—C6A | 177.6 (8) |
C2—C1—C6—C5 | 1.0 (16) | C4A—C5A—C6A—C1A | −1.7 (15) |
S1—C1—C6—C5 | −177.7 (8) | C2A—C1A—C6A—C5A | 0.0 (14) |
C4—C5—C6—C1 | 3.7 (15) | S1A—C1A—C6A—C5A | −174.8 (7) |
C4—N1—C7—C8 | 179.0 (9) | C4A—N1A—C7A—C8A | −179.8 (8) |
N1—C7—C8—C13 | −174.1 (10) | N1A—C7A—C8A—C13A | −2.2 (14) |
N1—C7—C8—C9 | 10.0 (15) | N1A—C7A—C8A—C9A | −177.5 (9) |
C13—C8—C9—C10 | −1.2 (19) | C13A—C8A—C9A—C10A | 6.1 (13) |
C7—C8—C9—C10 | 174.8 (11) | C7A—C8A—C9A—C10A | −178.4 (9) |
C8—C9—C10—C11 | 5 (2) | C8A—C9A—C10A—C11A | −5.6 (16) |
C9—C10—C11—C12 | −5 (3) | O3A—N2A—C11A—C12A | 7 (2) |
C9—C10—C11—N2 | −179.8 (17) | O4A—N2A—C11A—C12A | −165.8 (13) |
O4—N2—C11—C10 | 4 (3) | O3A—N2A—C11A—C10A | −172.2 (12) |
O3—N2—C11—C10 | −167.6 (17) | O4A—N2A—C11A—C10A | 14.7 (17) |
O4—N2—C11—C12 | −170.8 (14) | C9A—C10A—C11A—N2A | −177.3 (12) |
O3—N2—C11—C12 | 17 (2) | C9A—C10A—C11A—C12A | 3 (2) |
C10—C11—C12—C13 | 1 (3) | N2A—C11A—C12A—C13A | 179.5 (13) |
N2—C11—C12—C13 | 176.7 (15) | C10A—C11A—C12A—C13A | −1.0 (19) |
C11—C12—C13—C8 | 3 (2) | C9A—C8A—C13A—C12A | −4.6 (15) |
C9—C8—C13—C12 | −3.0 (17) | C7A—C8A—C13A—C12A | −179.9 (10) |
C7—C8—C13—C12 | −178.9 (11) | C11A—C12A—C13A—C8A | 1.9 (16) |
O1—S1—C14—C19 | 34.5 (9) | O1A—S1A—C14A—C15A | −154.5 (8) |
O2—S1—C14—C19 | 164.0 (8) | O2A—S1A—C14A—C15A | −20.6 (8) |
C1—S1—C14—C19 | −84.7 (9) | C1A—S1A—C14A—C15A | 90.5 (8) |
O1—S1—C14—C15 | −148.5 (7) | O1A—S1A—C14A—C19A | 29.3 (8) |
O2—S1—C14—C15 | −18.9 (9) | O2A—S1A—C14A—C19A | 163.2 (7) |
C1—S1—C14—C15 | 92.3 (8) | C1A—S1A—C14A—C19A | −85.7 (7) |
C19—C14—C15—C16 | 2.0 (15) | C19A—C14A—C15A—C16A | 0.3 (14) |
S1—C14—C15—C16 | −174.9 (7) | S1A—C14A—C15A—C16A | −175.6 (7) |
C14—C15—C16—C17 | 0.8 (14) | C14A—C15A—C16A—C17A | −3.5 (13) |
C15—C16—C17—C18 | −6.8 (15) | C15A—C16A—C17A—C18A | 5.9 (13) |
C15—C16—C17—N3 | 177.6 (8) | C15A—C16A—C17A—N3A | −179.4 (9) |
C20—N3—C17—C16 | 165.7 (9) | C20A—N3A—C17A—C16A | −14.2 (14) |
C20—N3—C17—C18 | −9.7 (15) | C20A—N3A—C17A—C18A | 160.9 (9) |
C16—C17—C18—C19 | 9.8 (15) | C16A—C17A—C18A—C19A | −4.9 (13) |
N3—C17—C18—C19 | −175.1 (9) | N3A—C17A—C18A—C19A | 179.9 (8) |
C15—C14—C19—C18 | 1.2 (15) | C17A—C18A—C19A—C14A | 1.5 (12) |
S1—C14—C19—C18 | 178.2 (7) | C15A—C14A—C19A—C18A | 0.7 (14) |
C17—C18—C19—C14 | −6.9 (15) | S1A—C14A—C19A—C18A | 176.8 (6) |
C17—N3—C20—C21 | 176.7 (9) | C17A—N3A—C20A—C21A | −177.9 (8) |
N3—C20—C21—C26 | −175.9 (10) | N3A—C20A—C21A—C22A | −171.3 (9) |
N3—C20—C21—C22 | 9.0 (16) | N3A—C20A—C21A—C26A | 6.8 (14) |
C26—C21—C22—C23 | 4.5 (15) | C26A—C21A—C22A—C23A | 2.7 (14) |
C20—C21—C22—C23 | 179.8 (9) | C20A—C21A—C22A—C23A | −179.2 (8) |
C21—C22—C23—C24 | −0.4 (15) | C21A—C22A—C23A—C24A | −2.4 (12) |
C22—C23—C24—C25 | −2.1 (19) | C22A—C23A—C24A—C25A | 0.4 (14) |
C22—C23—C24—N4 | 179.3 (10) | C22A—C23A—C24A—N4A | −178.8 (7) |
O5—N4—C24—C25 | −0.6 (17) | O6A—N4A—C24A—C23A | 18.0 (12) |
O6—N4—C24—C25 | −176.2 (9) | O5A—N4A—C24A—C23A | −159.2 (7) |
O5—N4—C24—C23 | 178.2 (11) | O6A—N4A—C24A—C25A | −161.3 (8) |
O6—N4—C24—C23 | 2.6 (17) | O5A—N4A—C24A—C25A | 21.5 (13) |
C23—C24—C25—C26 | 0.3 (18) | C23A—C24A—C25A—C26A | 1.3 (15) |
N4—C24—C25—C26 | 179.1 (9) | N4A—C24A—C25A—C26A | −179.5 (8) |
C22—C21—C26—C25 | −6.7 (15) | C24A—C25A—C26A—C21A | −1.0 (14) |
C20—C21—C26—C25 | 178.2 (9) | C22A—C21A—C26A—C25A | −0.8 (15) |
C24—C25—C26—C21 | 4.1 (15) | C20A—C21A—C26A—C25A | −178.9 (8) |
Experimental details
Crystal data | |
Chemical formula | C26H18N4O6S |
Mr | 514.5 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 120 |
a, b, c (Å) | 36.706 (3), 4.9130 (4), 12.364 (5) |
β (°) | 98.808 (4) |
V (Å3) | 2203.4 (9) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.6934 Å |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.15 × 0.05 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD diffractometer |
Absorption correction | Multi-scan SADABS (Bruker, 2000) |
Tmin, Tmax | 0.970, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9138, 4141, 3069 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.107, 1.01 |
No. of reflections | 4141 |
No. of parameters | 299 |
No. of restraints | 50 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.44 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.3 (2) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SAINT, SIR97 (Altomare et al., 1999), SHELXL97-2 (Sheldrick, 1998), PLATON (Spek, 2002), WinGX (Farrugia, 1999).
S1—O1 | 1.435 (7) | S1A—O1A | 1.384 (7) |
S1—O2 | 1.497 (7) | S1A—O2A | 1.482 (7) |
S1—C14 | 1.768 (9) | S1A—C1A | 1.768 (9) |
S1—C1 | 1.770 (10) | S1A—C14A | 1.792 (8) |
O3—N2 | 1.305 (17) | O3A—N2A | 1.194 (17) |
O4—N2 | 1.148 (17) | O4A—N2A | 1.362 (17) |
O5—N4 | 1.103 (11) | O5A—N4A | 1.256 (10) |
O6—N4 | 1.343 (13) | O6A—N4A | 1.195 (8) |
O1—S1—O2 | 118.4 (4) | O1A—S1A—O2A | 122.7 (4) |
Atom 1 | Atom 2 | Distance(Å) | Symmetry applied to Atom 2 |
O3 | O5 | 2.937 (10) | 0.5 + x,0.5 + y,1 + z |
O3 | O6 | 2.718 (12) | 0.5 + x,-1.5 − y,0.5 + z |
O4 | N4 | 2.816 (13) | 0.5 + x,-0.5 + y,1 + z |
O3A | O5A | 2.926 (8) | 0.5 + x,0.5 + y,1 + z |
O4A | O6A | 2.885 (9) | 0.5 + x,-0.5 + y,1 + z |
O4A | N4A | 2.959 (9) | 0.5 + x,-0.5 + y,1 + z |
O5A | N2A | 2.815 (15) | -0.5 + x,-0.5 + y,-1 + z |
Dapsone (4-aminophenylsulfone), (I), is an antibiotic that is used with other drugs to treat leprosy. It is also used to help control dermatitis herpetiformis and to prevent pneumocystis carinii pneumonia in people infected with HIV (British National Formulary 45, 2003). The crystal form of (I) has been reported at room temperature by various authors (e.g., Dickinson et al., 1970; Bocelli & Cantoni, 1990; Bertolasi et al., 1993).
4,4'-Sulfonylbis[N-(4-nitrophenylmethylene)benzenamine], (II), has been synthesized from dapsone, and the unusual crystal structure of (II) is now reported. The molecules in the crystal are disordered such that each atom occupies two sites. A plot of a resolved single molecule is shown in Fig.1, and the two overlapping molecules are shown in Fig.2. There is a very small separation between the coordinates for each of the atom pairs but atom positions for the two molecules are resolved.
Essentially, the molecule consists of two planar portions that are inclined to one another by 87.6 (1)° for the minor conformer [population parameter 0.430 (5)] and 87.8 (1)° for the major conformer [population parameter 0.570 (5)]. The disorder prevents a discussion of accurate molecular geometry, but values are similar to those found in other diphenyl sulfones (Sime & Woodhouse, 1974a; Sime & Woodhouse, 1974b; Bertolasi et al., 1993; Glidewell et al., 2001). There are close intermolecular interactions between the O and N atoms of the nitro groups, as shown in Table 2 (Platts et al., 1995) and Fig. 3. While close O···N separations have been observed previously, such as in 1-chloro-3-nitrobenzene (Sharma et al., 1985) and (4,5-spirobi(adamantyl)-N-(3,5- dinitrophenyl)-1,3,2-dioxazolidine (Okada et al., 1992), the close O···O separations in the absence of hydrogen bonding are unusual. The N—O bond lengths indicate that the negative charge distribution between the two O atoms in each nitro group may be unequal. The sixteen O—N—Car—Car torsion angles range from 21.5 (13) to −159.2 (7)° and indicate that some of the nitro groups are twisted slightly from the planes of the aromatic rings. There is some evidence that the molecules A are held together by C—H···O bonding, but the disorder prevents an accurate description of the geometries involved.
The percentage of disordered organic structures in the Cambridge Structural Database (Allen, 2002) rose from 3.9% in 1970 to 15.0% in 1999 (Flippen-Anderson et al., 2001). The April 2003 release of the database contains 49743 structures with some form of disorder out of a total of 296427, i.e. 16.8%. Although whole-molecule disorder is unusual, two crystal structures that exhibit this phenomenon, 2-(2-thienyl)-1-(pyrazinyl)ethene and 2-(2-thienyl)-1-(quinoxalinyl)ethene, have been reported (Ichharam et al., 2001).