Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011301771X/uk3071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011301771X/uk3071Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011301771X/uk3071Isup3.cml |
CCDC reference: 964797
Recently, we have described a novel reference compound, N-tert-butyl-N'-[2-(4-methylphenylamino)-5-nitrobenzenesulfonyl]urea (BM-573), a 5-nitrobenzenesulfonylurea derivative known to be a TXA2 receptor antagonist and a thromboxane synthase inhibitor (Dogné et al., 2004). Such a compound is expected to become the prototype of a new class of antiplatelet agents.
In our study of new TXA2 receptor antagonists and thromboxane synthase inhibitors, we synthesized and crystallized the title compound, (I). This compound may be considered as a structural analogue of BM-573 resulting from the isosteric replacement of its nitro group by a cyano group, and of its –NH– bridge by an –O– bridge. Compound (I) was found to be as potent as this reference compound as a TXA2 receptor antagonist, supporting the view that such structural modifications are tolerated without alteration of the pharmacological profile (Bambi-Nyanguile et al., 2013).
Compound (I) was synthesized in a five-step procedure starting from 4-fluoro-3-nitrobenzonitrile, as previously described by Bambi-Nyanguile et al. (2013). Suitable crystals for X-ray crystallography were grown from a methanol–water mixture (50/50 v/v).
Crystal data, data collection and structure refinement details are summarized in Table 1. All C-bound H atoms were placed in geometrically idealized positions and contrained to ride on their parent atoms, with C—H = 0.93 (aromatic) or 0.96 Å (methyl) and Uiso(H) = kUeq(C), where k = 1.2 for aromatic and 1.5 for methyl H atoms. N-bound H atoms were refined with Uiso(H) = 1.2Ueq(N).
A view of the molecular structures of the two molecules in the asymmetric unit of (I) is shown in Fig. 1. Both molecules show an intramolecular N—H···O hydrogen bond between an N atom of the urea moiety (N13 and N43) and an O atom of the sulfonyl group (O9 and O39), influencing their conformation (Table 2). The angle between the least-squares planes through rings C1–C6 and C19–C24 is 78.9 (2)°, and it is 80.1 (2)° between rings C31–C36 and C49–C54. The similar conformation of both molecules is further reflected by the r.m.s. deviation of 0.054 Å obtained for a least-squares fit of all 27 non-H atoms. Neighbouring molecules form dimers through hydrogen-bond interactions between the remaining N atom (N10 and N40) and the O atom (O12 and O42) of the urea groups (Fig. 2 and Table 2). The crystal packing shows chains of dimers in the b direction, formed by C—H···O interactions between aromatic ring atoms C5, C6, C35 and C36 and O atoms O42, O38, O12 and O8 (Fig. 3 and Table 2).
The occurrence of an intramolecular hydrogen bond in the C—SO2—NH—C(═O)—NH—C fragment was further explored in the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002). A search for this fragment resulted in 79 hits. Only four structures show an intramolecular N—H···O hydrogen bond [CSD refcodes QERXUG (Yagupolskii et al., 2001), TOHBUN (Iwata et al., 1997), TOHBUN01 (Grell et al., 1998) and USOCOV (Gelbrich et al., 2011)]. The C—S—N—C torsion angle has two equally populated preferred regions, +sc and -sc, and has no influence on hydrogen-bond formation (three of the four structures are in the +sc region). The S—N—C—N torsion angle indicates a ±ap conformation, except for the four structures where a ±sp conformation occurs. The N—C—N—C torsion angle has preferred regions ±sp and ±ap (minor and major populations, respectively), and the four structures are all in the +ap region. The equivalent torsion angles for (I) are also given in Table 2 and show -ac, ±sp and -ap conformations. These observations are in agreement with quantum chemical calculations on the model system PhSO2NHC(═O)NHMe (Kasetti et al.,
2010), showing that, in the gas phase, the conformation with an intramolecular hydrogen bond is about 4.12 kcal mol-1 (1 kcal mol-1 = 4.184 kJ mol-1) more stable than the alternative rotamer not showing the intramolecular interaction. In a chloroform medium, the energy difference is reduced to 0.37 kcal mol-1 and in a water medium is even reversed.
In the crystal packing of (I), π–π interactions between the 5-cyanobenzene rings link two molecules into dimers (Fig. 3), with a Cg1···Cg1ii distance of 3.978 (2) Å and a Cg2···Cg2i distance of 3.887 (2) Å [Cg1 and Cg2 are the centroids of the C1–C6 and C31–C36 rings, respectively; symmetry codes: (i) -x + 1, y, -z + 3/2; (ii) -x, y, -z + 3/2]. Furthermore, the packing shows a number of weaker contacts of
C—H···N type [C20—20···N27ii = 3.425 (7) Å and C50—H50···N57i = 3.439 (6) Å].
Despite the fact that methanol was essential as crystallization solvent for obtaining good-quality crystals of (I), no methanol molecules are present in the crystal packing. Also, no voids larger than 18 Å3 are observed in the crystal packing. For the compound TOHBUN, a second polymorph has been found which does not show the intramolecular N—H···O═S interaction (Endo et al., 2003). To date, no second polymorph has been observed for (I).
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
C19H21N3O4S | F(000) = 1632 |
Mr = 387.45 | Dx = 1.229 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6408 (5) Å | Cell parameters from 11196 reflections |
b = 15.8571 (4) Å | θ = 3.3–27.0° |
c = 24.8678 (9) Å | µ = 0.18 mm−1 |
β = 93.534 (4)° | T = 289 K |
V = 4188.0 (3) Å3 | Plate, colourless |
Z = 8 | 0.45 × 0.25 × 0.05 mm |
Agilent SuperNova diffractometer (single source at offset, Eos detector) | 8550 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 5931 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.031 |
Detector resolution: 15.9631 pixels mm-1 | θmax = 26.4°, θmin = 2.7° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = 0→19 |
Tmin = 0.738, Tmax = 1.000 | l = 0→31 |
8550 measured reflections |
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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0449P)2 + 4.7193P] where P = (Fo2 + 2Fc2)/3 |
8548 reflections | (Δ/σ)max < 0.001 |
507 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C19H21N3O4S | V = 4188.0 (3) Å3 |
Mr = 387.45 | Z = 8 |
Monoclinic, P2/c | Mo Kα radiation |
a = 10.6408 (5) Å | µ = 0.18 mm−1 |
b = 15.8571 (4) Å | T = 289 K |
c = 24.8678 (9) Å | 0.45 × 0.25 × 0.05 mm |
β = 93.534 (4)° |
Agilent SuperNova diffractometer (single source at offset, Eos detector) | 8550 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 5931 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 1.000 | Rint = 0.031 |
8550 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.24 e Å−3 |
8548 reflections | Δρmin = −0.26 e Å−3 |
507 parameters |
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 | 0.2478 (4) | 0.34567 (19) | 0.71760 (14) | 0.0644 (9) | |
C2 | 0.1999 (3) | 0.27413 (18) | 0.74231 (13) | 0.0537 (8) | |
C3 | 0.1411 (3) | 0.2811 (2) | 0.78966 (13) | 0.0593 (8) | |
H3 | 0.1117 | 0.2330 | 0.8063 | 0.071* | |
C4 | 0.1256 (4) | 0.3597 (2) | 0.81270 (14) | 0.0673 (9) | |
C5 | 0.1699 (4) | 0.4306 (2) | 0.78713 (16) | 0.0802 (12) | |
H5 | 0.1582 | 0.4836 | 0.8021 | 0.096* | |
C6 | 0.2304 (5) | 0.4241 (2) | 0.74040 (16) | 0.0822 (12) | |
H6 | 0.2597 | 0.4723 | 0.7239 | 0.099* | |
C11 | 0.4395 (4) | 0.15059 (19) | 0.67005 (13) | 0.0560 (8) | |
C14 | 0.4692 (4) | 0.1714 (3) | 0.57238 (13) | 0.0747 (11) | |
C15 | 0.5765 (5) | 0.2355 (3) | 0.58006 (19) | 0.1061 (16) | |
H15A | 0.5425 | 0.2899 | 0.5879 | 0.159* | |
H15B | 0.6210 | 0.2387 | 0.5477 | 0.159* | |
H15C | 0.6334 | 0.2180 | 0.6094 | 0.159* | |
C16 | 0.3760 (5) | 0.2005 (4) | 0.52702 (16) | 0.1179 (19) | |
H16A | 0.3126 | 0.1581 | 0.5203 | 0.177* | |
H16B | 0.4198 | 0.2097 | 0.4949 | 0.177* | |
H16C | 0.3369 | 0.2522 | 0.5373 | 0.177* | |
C17 | 0.5219 (5) | 0.0853 (3) | 0.56087 (17) | 0.1038 (16) | |
H17A | 0.5763 | 0.0674 | 0.5909 | 0.156* | |
H17B | 0.5687 | 0.0880 | 0.5291 | 0.156* | |
H17C | 0.4540 | 0.0458 | 0.5552 | 0.156* | |
C19 | 0.3584 (4) | 0.4019 (2) | 0.64509 (16) | 0.0729 (11) | |
C20 | 0.2939 (5) | 0.4314 (3) | 0.60054 (18) | 0.0884 (13) | |
H20 | 0.2162 | 0.4086 | 0.5891 | 0.106* | |
C21 | 0.3464 (6) | 0.4966 (3) | 0.57221 (19) | 0.1012 (15) | |
H21 | 0.3034 | 0.5171 | 0.5412 | 0.121* | |
C22 | 0.4586 (6) | 0.5312 (3) | 0.5886 (2) | 0.0958 (16) | |
C23 | 0.5211 (5) | 0.5000 (3) | 0.6333 (2) | 0.1036 (16) | |
H23 | 0.5982 | 0.5233 | 0.6450 | 0.124* | |
C24 | 0.4723 (5) | 0.4342 (3) | 0.66215 (18) | 0.0971 (14) | |
H24 | 0.5165 | 0.4125 | 0.6925 | 0.116* | |
C25 | 0.5124 (7) | 0.6055 (3) | 0.5577 (2) | 0.153 (3) | |
H25A | 0.6016 | 0.5982 | 0.5558 | 0.229* | |
H25B | 0.4962 | 0.6572 | 0.5762 | 0.229* | |
H25C | 0.4730 | 0.6074 | 0.5220 | 0.229* | |
C26 | 0.0640 (5) | 0.3668 (3) | 0.86226 (17) | 0.0876 (13) | |
C31 | 0.2504 (4) | 0.84444 (19) | 0.72155 (14) | 0.0615 (9) | |
C32 | 0.3037 (3) | 0.77223 (18) | 0.74597 (13) | 0.0543 (8) | |
C33 | 0.3757 (3) | 0.7775 (2) | 0.79362 (13) | 0.0582 (8) | |
H33 | 0.4087 | 0.7289 | 0.8099 | 0.070* | |
C34 | 0.3993 (3) | 0.8559 (2) | 0.81748 (14) | 0.0633 (9) | |
C35 | 0.3493 (4) | 0.9278 (2) | 0.79213 (16) | 0.0732 (11) | |
H35 | 0.3659 | 0.9804 | 0.8075 | 0.088* | |
C36 | 0.2762 (4) | 0.9227 (2) | 0.74515 (17) | 0.0759 (11) | |
H36 | 0.2437 | 0.9715 | 0.7289 | 0.091* | |
C41 | 0.0426 (4) | 0.6513 (2) | 0.67085 (13) | 0.0603 (9) | |
C44 | −0.0109 (6) | 0.6762 (3) | 0.57342 (16) | 0.1062 (18) | |
C45 | −0.1127 (7) | 0.7391 (4) | 0.5820 (2) | 0.163 (3) | |
H45A | −0.1565 | 0.7235 | 0.6131 | 0.245* | |
H45B | −0.1708 | 0.7403 | 0.5509 | 0.245* | |
H45C | −0.0760 | 0.7940 | 0.5875 | 0.245* | |
C46 | 0.0753 (8) | 0.7068 (4) | 0.52928 (19) | 0.171 (3) | |
H46A | 0.1187 | 0.7571 | 0.5413 | 0.256* | |
H46B | 0.0251 | 0.7185 | 0.4968 | 0.256* | |
H46C | 0.1357 | 0.6637 | 0.5225 | 0.256* | |
C47 | −0.0640 (7) | 0.5897 (3) | 0.5595 (2) | 0.140 (3) | |
H47A | 0.0036 | 0.5516 | 0.5532 | 0.211* | |
H47B | −0.1194 | 0.5935 | 0.5276 | 0.211* | |
H47C | −0.1100 | 0.5692 | 0.5888 | 0.211* | |
C49 | 0.1176 (4) | 0.9018 (2) | 0.64997 (15) | 0.0668 (10) | |
C50 | 0.1664 (4) | 0.9354 (3) | 0.60546 (18) | 0.0840 (12) | |
H50 | 0.2414 | 0.9151 | 0.5932 | 0.101* | |
C51 | 0.1022 (5) | 1.0002 (3) | 0.57886 (18) | 0.0893 (13) | |
H51 | 0.1349 | 1.0231 | 0.5483 | 0.107* | |
C52 | −0.0070 (5) | 1.0316 (3) | 0.59587 (18) | 0.0819 (12) | |
C53 | −0.0529 (5) | 0.9967 (3) | 0.64028 (19) | 0.0944 (14) | |
H53 | −0.1276 | 1.0176 | 0.6527 | 0.113* | |
C54 | 0.0072 (5) | 0.9317 (3) | 0.66756 (17) | 0.0887 (13) | |
H54 | −0.0269 | 0.9083 | 0.6977 | 0.106* | |
C55 | −0.0738 (6) | 1.1053 (3) | 0.5675 (2) | 0.132 (2) | |
H55A | −0.0607 | 1.1554 | 0.5887 | 0.198* | |
H55B | −0.1623 | 1.0936 | 0.5629 | 0.198* | |
H55C | −0.0406 | 1.1135 | 0.5328 | 0.198* | |
C56 | 0.4732 (4) | 0.8609 (3) | 0.86787 (17) | 0.0760 (11) | |
N10 | 0.3536 (3) | 0.14991 (17) | 0.71095 (11) | 0.0560 (7) | |
H10 | 0.389 (3) | 0.140 (2) | 0.7423 (14) | 0.067* | |
N13 | 0.3965 (3) | 0.1687 (2) | 0.62053 (11) | 0.0673 (8) | |
H13 | 0.315 (4) | 0.176 (2) | 0.6176 (15) | 0.081* | |
N27 | 0.0159 (5) | 0.3723 (3) | 0.90141 (17) | 0.1244 (16) | |
N40 | 0.1387 (3) | 0.64971 (18) | 0.71261 (11) | 0.0603 (7) | |
H40 | 0.115 (4) | 0.643 (2) | 0.7430 (15) | 0.072* | |
N43 | 0.0752 (4) | 0.6698 (2) | 0.62208 (12) | 0.0775 (10) | |
H43 | 0.154 (4) | 0.682 (3) | 0.6185 (17) | 0.093* | |
N57 | 0.5319 (4) | 0.8638 (3) | 0.90760 (16) | 0.1037 (13) | |
O8 | 0.1532 (2) | 0.11652 (14) | 0.74811 (11) | 0.0747 (7) | |
O9 | 0.1541 (2) | 0.18033 (15) | 0.65792 (10) | 0.0702 (7) | |
O12 | 0.5490 (2) | 0.13168 (16) | 0.68322 (9) | 0.0673 (6) | |
O18 | 0.3089 (3) | 0.33206 (14) | 0.67201 (11) | 0.0880 (9) | |
O38 | 0.3479 (2) | 0.61399 (14) | 0.75181 (11) | 0.0796 (8) | |
O39 | 0.3266 (3) | 0.67820 (15) | 0.66139 (10) | 0.0789 (8) | |
O42 | −0.0635 (3) | 0.63208 (18) | 0.68313 (10) | 0.0773 (7) | |
O48 | 0.1775 (3) | 0.83257 (14) | 0.67533 (11) | 0.0863 (9) | |
S7 | 0.20576 (8) | 0.17400 (5) | 0.71188 (3) | 0.0562 (2) | |
S37 | 0.28779 (9) | 0.67228 (5) | 0.71509 (4) | 0.0606 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.094 (3) | 0.0373 (16) | 0.064 (2) | 0.0004 (16) | 0.0151 (19) | −0.0012 (14) |
C2 | 0.066 (2) | 0.0366 (16) | 0.0590 (18) | 0.0039 (14) | 0.0043 (16) | −0.0001 (13) |
C3 | 0.071 (2) | 0.0470 (18) | 0.0606 (19) | 0.0046 (16) | 0.0085 (17) | 0.0045 (15) |
C4 | 0.081 (3) | 0.061 (2) | 0.061 (2) | 0.0079 (19) | 0.0134 (18) | −0.0034 (17) |
C5 | 0.117 (4) | 0.048 (2) | 0.077 (3) | 0.006 (2) | 0.018 (2) | −0.0128 (18) |
C6 | 0.129 (4) | 0.0379 (18) | 0.082 (3) | −0.005 (2) | 0.023 (3) | −0.0019 (17) |
C11 | 0.075 (2) | 0.0424 (17) | 0.0503 (18) | 0.0077 (16) | 0.0055 (16) | 0.0007 (13) |
C14 | 0.104 (3) | 0.073 (2) | 0.0478 (18) | 0.020 (2) | 0.0148 (19) | 0.0078 (17) |
C15 | 0.132 (4) | 0.101 (4) | 0.089 (3) | −0.002 (3) | 0.043 (3) | 0.013 (3) |
C16 | 0.152 (5) | 0.149 (5) | 0.053 (2) | 0.041 (4) | 0.008 (3) | 0.025 (3) |
C17 | 0.164 (5) | 0.082 (3) | 0.068 (3) | 0.027 (3) | 0.026 (3) | −0.007 (2) |
C19 | 0.108 (3) | 0.0417 (18) | 0.072 (2) | −0.006 (2) | 0.032 (2) | −0.0029 (17) |
C20 | 0.103 (3) | 0.073 (3) | 0.090 (3) | −0.009 (2) | 0.011 (3) | 0.006 (2) |
C21 | 0.142 (5) | 0.080 (3) | 0.083 (3) | 0.006 (3) | 0.019 (3) | 0.020 (2) |
C22 | 0.147 (5) | 0.062 (3) | 0.084 (3) | −0.016 (3) | 0.050 (3) | −0.004 (2) |
C23 | 0.124 (4) | 0.084 (3) | 0.107 (4) | −0.035 (3) | 0.035 (3) | −0.009 (3) |
C24 | 0.131 (4) | 0.082 (3) | 0.078 (3) | −0.020 (3) | 0.006 (3) | 0.006 (2) |
C25 | 0.240 (8) | 0.082 (3) | 0.148 (5) | −0.021 (4) | 0.103 (5) | 0.022 (3) |
C26 | 0.117 (4) | 0.076 (3) | 0.071 (3) | 0.017 (2) | 0.019 (3) | −0.003 (2) |
C31 | 0.080 (2) | 0.0361 (16) | 0.068 (2) | −0.0042 (15) | 0.0039 (18) | −0.0026 (14) |
C32 | 0.061 (2) | 0.0367 (16) | 0.066 (2) | −0.0069 (14) | 0.0092 (16) | −0.0013 (14) |
C33 | 0.065 (2) | 0.0476 (18) | 0.062 (2) | −0.0081 (15) | 0.0089 (17) | 0.0015 (15) |
C34 | 0.067 (2) | 0.060 (2) | 0.064 (2) | −0.0112 (17) | 0.0098 (17) | −0.0096 (17) |
C35 | 0.091 (3) | 0.047 (2) | 0.082 (3) | −0.0105 (19) | 0.010 (2) | −0.0158 (18) |
C36 | 0.099 (3) | 0.0386 (18) | 0.089 (3) | −0.0014 (18) | 0.000 (2) | −0.0036 (17) |
C41 | 0.083 (3) | 0.0439 (17) | 0.0526 (19) | −0.0032 (17) | −0.0088 (18) | 0.0021 (14) |
C44 | 0.180 (5) | 0.075 (3) | 0.058 (2) | −0.015 (3) | −0.037 (3) | 0.009 (2) |
C45 | 0.222 (8) | 0.115 (5) | 0.138 (5) | 0.019 (5) | −0.113 (5) | 0.004 (4) |
C46 | 0.289 (10) | 0.162 (6) | 0.058 (3) | −0.074 (6) | −0.019 (4) | 0.030 (3) |
C47 | 0.231 (7) | 0.095 (4) | 0.088 (3) | −0.052 (4) | −0.051 (4) | −0.006 (3) |
C49 | 0.086 (3) | 0.0427 (18) | 0.071 (2) | 0.0024 (18) | −0.002 (2) | −0.0031 (16) |
C50 | 0.083 (3) | 0.070 (3) | 0.101 (3) | 0.007 (2) | 0.017 (2) | 0.006 (2) |
C51 | 0.106 (4) | 0.076 (3) | 0.086 (3) | −0.006 (3) | 0.008 (3) | 0.021 (2) |
C52 | 0.100 (3) | 0.063 (2) | 0.080 (3) | 0.009 (2) | −0.016 (2) | −0.004 (2) |
C53 | 0.098 (4) | 0.089 (3) | 0.096 (3) | 0.030 (3) | 0.010 (3) | −0.004 (3) |
C54 | 0.110 (4) | 0.089 (3) | 0.070 (3) | 0.009 (3) | 0.019 (2) | 0.006 (2) |
C55 | 0.169 (6) | 0.092 (4) | 0.127 (4) | 0.036 (4) | −0.050 (4) | 0.011 (3) |
C56 | 0.082 (3) | 0.073 (3) | 0.074 (3) | −0.018 (2) | 0.011 (2) | −0.014 (2) |
N10 | 0.0658 (19) | 0.0546 (16) | 0.0479 (14) | 0.0099 (13) | 0.0044 (13) | 0.0086 (12) |
N13 | 0.077 (2) | 0.079 (2) | 0.0463 (15) | 0.0160 (18) | 0.0039 (15) | 0.0074 (14) |
N27 | 0.173 (5) | 0.120 (3) | 0.086 (3) | 0.025 (3) | 0.049 (3) | −0.004 (2) |
N40 | 0.069 (2) | 0.0571 (16) | 0.0537 (15) | −0.0119 (14) | −0.0035 (14) | 0.0105 (13) |
N43 | 0.105 (3) | 0.075 (2) | 0.0514 (16) | −0.015 (2) | −0.0069 (18) | 0.0089 (15) |
N57 | 0.113 (3) | 0.120 (3) | 0.077 (2) | −0.022 (3) | −0.001 (2) | −0.017 (2) |
O8 | 0.0832 (18) | 0.0418 (12) | 0.1018 (19) | −0.0075 (12) | 0.0271 (15) | 0.0066 (12) |
O9 | 0.0694 (16) | 0.0620 (14) | 0.0769 (16) | 0.0042 (12) | −0.0134 (13) | −0.0130 (12) |
O12 | 0.0685 (17) | 0.0820 (17) | 0.0517 (13) | 0.0163 (13) | 0.0056 (11) | 0.0023 (11) |
O18 | 0.146 (3) | 0.0408 (13) | 0.0827 (17) | −0.0087 (14) | 0.0505 (18) | −0.0032 (12) |
O38 | 0.0821 (19) | 0.0408 (13) | 0.112 (2) | 0.0056 (12) | −0.0226 (16) | 0.0014 (13) |
O39 | 0.093 (2) | 0.0630 (15) | 0.0833 (17) | −0.0063 (14) | 0.0287 (15) | −0.0165 (13) |
O42 | 0.0735 (19) | 0.097 (2) | 0.0598 (15) | −0.0103 (15) | −0.0112 (13) | −0.0004 (13) |
O48 | 0.129 (2) | 0.0411 (13) | 0.0847 (18) | 0.0054 (14) | −0.0274 (17) | −0.0038 (12) |
S7 | 0.0653 (5) | 0.0355 (4) | 0.0679 (5) | −0.0003 (4) | 0.0055 (4) | −0.0005 (3) |
S37 | 0.0706 (6) | 0.0346 (4) | 0.0763 (6) | −0.0013 (4) | 0.0023 (4) | −0.0031 (4) |
C1—C2 | 1.401 (4) | C33—H33 | 0.9300 |
C1—C6 | 1.384 (5) | C33—C34 | 1.394 (4) |
C1—O18 | 1.358 (4) | C34—C35 | 1.392 (5) |
C2—C3 | 1.371 (4) | C34—C56 | 1.440 (5) |
C2—S7 | 1.762 (3) | C35—H35 | 0.9300 |
C3—H3 | 0.9300 | C35—C36 | 1.365 (5) |
C3—C4 | 1.387 (5) | C36—H36 | 0.9300 |
C4—C5 | 1.388 (5) | C41—N40 | 1.412 (4) |
C4—C26 | 1.435 (5) | C41—N43 | 1.315 (5) |
C5—H5 | 0.9300 | C41—O42 | 1.226 (4) |
C5—C6 | 1.367 (5) | C44—C45 | 1.498 (8) |
C6—H6 | 0.9300 | C44—C46 | 1.551 (8) |
C11—N10 | 1.409 (4) | C44—C47 | 1.515 (6) |
C11—N13 | 1.319 (4) | C44—N43 | 1.475 (5) |
C11—O12 | 1.228 (4) | C45—H45A | 0.9600 |
C14—C15 | 1.531 (6) | C45—H45B | 0.9600 |
C14—C16 | 1.527 (6) | C45—H45C | 0.9600 |
C14—C17 | 1.510 (5) | C46—H46A | 0.9600 |
C14—N13 | 1.466 (4) | C46—H46B | 0.9600 |
C15—H15A | 0.9600 | C46—H46C | 0.9600 |
C15—H15B | 0.9600 | C47—H47A | 0.9600 |
C15—H15C | 0.9600 | C47—H47B | 0.9600 |
C16—H16A | 0.9600 | C47—H47C | 0.9600 |
C16—H16B | 0.9600 | C49—C50 | 1.360 (5) |
C16—H16C | 0.9600 | C49—C54 | 1.364 (6) |
C17—H17A | 0.9600 | C49—O48 | 1.400 (4) |
C17—H17B | 0.9600 | C50—H50 | 0.9300 |
C17—H17C | 0.9600 | C50—C51 | 1.380 (6) |
C19—C20 | 1.351 (6) | C51—H51 | 0.9300 |
C19—C24 | 1.359 (6) | C51—C52 | 1.355 (6) |
C19—O18 | 1.412 (4) | C52—C53 | 1.353 (6) |
C20—H20 | 0.9300 | C52—C55 | 1.520 (6) |
C20—C21 | 1.388 (6) | C53—H53 | 0.9300 |
C21—H21 | 0.9300 | C53—C54 | 1.370 (6) |
C21—C22 | 1.354 (7) | C54—H54 | 0.9300 |
C22—C23 | 1.354 (7) | C55—H55A | 0.9600 |
C22—C25 | 1.535 (6) | C55—H55B | 0.9600 |
C23—H23 | 0.9300 | C55—H55C | 0.9600 |
C23—C24 | 1.385 (6) | C56—N57 | 1.137 (5) |
C24—H24 | 0.9300 | N10—H10 | 0.86 (3) |
C25—H25A | 0.9600 | N10—S7 | 1.620 (3) |
C25—H25B | 0.9600 | N13—H13 | 0.88 (4) |
C25—H25C | 0.9600 | N40—H40 | 0.82 (4) |
C26—N27 | 1.131 (5) | N40—S37 | 1.624 (3) |
C31—C32 | 1.400 (4) | N43—H43 | 0.87 (4) |
C31—C36 | 1.392 (4) | O8—S7 | 1.421 (2) |
C31—O48 | 1.359 (4) | O9—S7 | 1.422 (2) |
C32—C33 | 1.373 (4) | O38—S37 | 1.423 (3) |
C32—S37 | 1.765 (3) | O39—S37 | 1.425 (3) |
C6—C1—C2 | 119.1 (3) | C36—C35—C34 | 121.4 (3) |
O18—C1—C2 | 116.3 (3) | C36—C35—H35 | 119.3 |
O18—C1—C6 | 124.6 (3) | C31—C36—H36 | 120.0 |
C1—C2—S7 | 121.2 (2) | C35—C36—C31 | 120.1 (3) |
C3—C2—C1 | 120.6 (3) | C35—C36—H36 | 120.0 |
C3—C2—S7 | 118.1 (2) | N43—C41—N40 | 117.5 (4) |
C2—C3—H3 | 120.0 | O42—C41—N40 | 116.7 (3) |
C2—C3—C4 | 119.9 (3) | O42—C41—N43 | 125.8 (3) |
C4—C3—H3 | 120.0 | C45—C44—C46 | 110.9 (5) |
C3—C4—C5 | 119.1 (3) | C45—C44—C47 | 111.9 (6) |
C3—C4—C26 | 119.9 (3) | C47—C44—C46 | 110.5 (5) |
C5—C4—C26 | 121.0 (3) | N43—C44—C45 | 110.3 (4) |
C4—C5—H5 | 119.4 | N43—C44—C46 | 103.7 (5) |
C6—C5—C4 | 121.3 (3) | N43—C44—C47 | 109.2 (4) |
C6—C5—H5 | 119.4 | C44—C45—H45A | 109.5 |
C1—C6—H6 | 120.0 | C44—C45—H45B | 109.5 |
C5—C6—C1 | 119.9 (3) | C44—C45—H45C | 109.5 |
C5—C6—H6 | 120.0 | H45A—C45—H45B | 109.5 |
N13—C11—N10 | 118.2 (3) | H45A—C45—H45C | 109.5 |
O12—C11—N10 | 116.9 (3) | H45B—C45—H45C | 109.5 |
O12—C11—N13 | 124.9 (3) | C44—C46—H46A | 109.5 |
C16—C14—C15 | 109.7 (4) | C44—C46—H46B | 109.5 |
C17—C14—C15 | 109.9 (4) | C44—C46—H46C | 109.5 |
C17—C14—C16 | 111.4 (4) | H46A—C46—H46B | 109.5 |
N13—C14—C15 | 110.2 (3) | H46A—C46—H46C | 109.5 |
N13—C14—C16 | 105.1 (3) | H46B—C46—H46C | 109.5 |
N13—C14—C17 | 110.4 (3) | C44—C47—H47A | 109.5 |
C14—C15—H15A | 109.5 | C44—C47—H47B | 109.5 |
C14—C15—H15B | 109.5 | C44—C47—H47C | 109.5 |
C14—C15—H15C | 109.5 | H47A—C47—H47B | 109.5 |
H15A—C15—H15B | 109.5 | H47A—C47—H47C | 109.5 |
H15A—C15—H15C | 109.5 | H47B—C47—H47C | 109.5 |
H15B—C15—H15C | 109.5 | C50—C49—C54 | 120.3 (4) |
C14—C16—H16A | 109.5 | C50—C49—O48 | 119.2 (4) |
C14—C16—H16B | 109.5 | C54—C49—O48 | 120.4 (4) |
C14—C16—H16C | 109.5 | C49—C50—H50 | 120.7 |
H16A—C16—H16B | 109.5 | C49—C50—C51 | 118.6 (4) |
H16A—C16—H16C | 109.5 | C51—C50—H50 | 120.7 |
H16B—C16—H16C | 109.5 | C50—C51—H51 | 118.9 |
C14—C17—H17A | 109.5 | C52—C51—C50 | 122.2 (4) |
C14—C17—H17B | 109.5 | C52—C51—H51 | 118.9 |
C14—C17—H17C | 109.5 | C51—C52—C55 | 121.5 (5) |
H17A—C17—H17B | 109.5 | C53—C52—C51 | 117.7 (4) |
H17A—C17—H17C | 109.5 | C53—C52—C55 | 120.8 (5) |
H17B—C17—H17C | 109.5 | C52—C53—H53 | 119.0 |
C20—C19—C24 | 121.6 (4) | C52—C53—C54 | 122.0 (4) |
C20—C19—O18 | 118.4 (4) | C54—C53—H53 | 119.0 |
C24—C19—O18 | 119.9 (4) | C49—C54—C53 | 119.2 (4) |
C19—C20—H20 | 120.8 | C49—C54—H54 | 120.4 |
C19—C20—C21 | 118.4 (5) | C53—C54—H54 | 120.4 |
C21—C20—H20 | 120.8 | C52—C55—H55A | 109.5 |
C20—C21—H21 | 119.2 | C52—C55—H55B | 109.5 |
C22—C21—C20 | 121.6 (5) | C52—C55—H55C | 109.5 |
C22—C21—H21 | 119.2 | H55A—C55—H55B | 109.5 |
C21—C22—C25 | 120.6 (6) | H55A—C55—H55C | 109.5 |
C23—C22—C21 | 118.6 (4) | H55B—C55—H55C | 109.5 |
C23—C22—C25 | 120.8 (6) | N57—C56—C34 | 179.2 (5) |
C22—C23—H23 | 119.3 | C11—N10—H10 | 113 (2) |
C22—C23—C24 | 121.3 (5) | C11—N10—S7 | 133.0 (2) |
C24—C23—H23 | 119.3 | S7—N10—H10 | 114 (2) |
C19—C24—C23 | 118.6 (5) | C11—N13—C14 | 126.8 (3) |
C19—C24—H24 | 120.7 | C11—N13—H13 | 113 (3) |
C23—C24—H24 | 120.7 | C14—N13—H13 | 120 (3) |
C22—C25—H25A | 109.5 | C41—N40—H40 | 116 (3) |
C22—C25—H25B | 109.5 | C41—N40—S37 | 133.3 (3) |
C22—C25—H25C | 109.5 | S37—N40—H40 | 110 (3) |
H25A—C25—H25B | 109.5 | C41—N43—C44 | 125.9 (4) |
H25A—C25—H25C | 109.5 | C41—N43—H43 | 117 (3) |
H25B—C25—H25C | 109.5 | C44—N43—H43 | 117 (3) |
N27—C26—C4 | 179.7 (6) | C1—O18—C19 | 118.9 (3) |
C36—C31—C32 | 118.8 (3) | C31—O48—C49 | 119.5 (3) |
O48—C31—C32 | 116.6 (3) | N10—S7—C2 | 106.20 (16) |
O48—C31—C36 | 124.6 (3) | O8—S7—C2 | 106.26 (15) |
C31—C32—S37 | 121.4 (3) | O8—S7—N10 | 106.17 (15) |
C33—C32—C31 | 120.9 (3) | O8—S7—O9 | 119.96 (16) |
C33—C32—S37 | 117.6 (2) | O9—S7—C2 | 108.65 (15) |
C32—C33—H33 | 120.1 | O9—S7—N10 | 108.80 (15) |
C32—C33—C34 | 119.9 (3) | N40—S37—C32 | 106.37 (16) |
C34—C33—H33 | 120.1 | O38—S37—C32 | 106.07 (16) |
C33—C34—C56 | 119.5 (3) | O38—S37—N40 | 106.30 (16) |
C35—C34—C33 | 118.9 (3) | O38—S37—O39 | 119.96 (18) |
C35—C34—C56 | 121.5 (3) | O39—S37—C32 | 108.84 (15) |
C34—C35—H35 | 119.3 | O39—S37—N40 | 108.53 (16) |
C1—C2—C3—C4 | 1.8 (5) | C33—C32—S37—O39 | −124.6 (3) |
C1—C2—S7—N10 | 65.5 (3) | C33—C34—C35—C36 | 1.2 (6) |
C1—C2—S7—O8 | 178.3 (3) | C34—C35—C36—C31 | 0.0 (6) |
C1—C2—S7—O9 | −51.3 (3) | C36—C31—C32—C33 | 2.9 (5) |
C2—C1—C6—C5 | 1.7 (7) | C36—C31—C32—S37 | −173.8 (3) |
C2—C1—O18—C19 | 179.5 (4) | C36—C31—O48—C49 | −3.4 (6) |
C2—C3—C4—C5 | 0.2 (6) | C41—N40—S37—C32 | 103.0 (3) |
C2—C3—C4—C26 | 180.0 (4) | C41—N40—S37—O38 | −144.3 (3) |
C3—C2—S7—N10 | −117.7 (3) | C41—N40—S37—O39 | −14.0 (4) |
C3—C2—S7—O8 | −5.0 (3) | C45—C44—N43—C41 | 56.5 (6) |
C3—C2—S7—O9 | 125.4 (3) | C46—C44—N43—C41 | 175.3 (4) |
C3—C4—C5—C6 | −1.2 (7) | C47—C44—N43—C41 | −66.9 (6) |
C4—C5—C6—C1 | 0.3 (7) | C49—C50—C51—C52 | 0.4 (7) |
C6—C1—C2—C3 | −2.8 (6) | C50—C49—C54—C53 | −0.9 (7) |
C6—C1—C2—S7 | 173.9 (3) | C50—C49—O48—C31 | 102.8 (4) |
C6—C1—O18—C19 | −0.3 (6) | C50—C51—C52—C53 | −0.4 (7) |
C11—N10—S7—C2 | −102.7 (3) | C50—C51—C52—C55 | 177.5 (4) |
C11—N10—S7—O8 | 144.4 (3) | C51—C52—C53—C54 | −0.3 (7) |
C11—N10—S7—O9 | 14.1 (4) | C52—C53—C54—C49 | 0.9 (7) |
C15—C14—N13—C11 | −58.6 (5) | C54—C49—C50—C51 | 0.3 (6) |
C16—C14—N13—C11 | −176.8 (4) | C54—C49—O48—C31 | −81.6 (5) |
C17—C14—N13—C11 | 63.0 (5) | C55—C52—C53—C54 | −178.2 (4) |
C19—C20—C21—C22 | −0.8 (7) | C56—C34—C35—C36 | −178.1 (4) |
C20—C19—C24—C23 | 1.2 (7) | N10—C11—N13—C14 | −178.9 (3) |
C20—C19—O18—C1 | −101.6 (4) | N13—C11—N10—S7 | −5.2 (5) |
C20—C21—C22—C23 | 0.9 (7) | N40—C41—N43—C44 | −178.8 (4) |
C20—C21—C22—C25 | −177.7 (4) | N43—C41—N40—S37 | 4.5 (5) |
C21—C22—C23—C24 | 0.0 (8) | O12—C11—N10—S7 | 176.9 (3) |
C22—C23—C24—C19 | −1.1 (7) | O12—C11—N13—C14 | −1.1 (6) |
C24—C19—C20—C21 | −0.3 (7) | O18—C1—C2—C3 | 177.4 (3) |
C24—C19—O18—C1 | 82.6 (5) | O18—C1—C2—S7 | −5.9 (5) |
C25—C22—C23—C24 | 178.7 (5) | O18—C1—C6—C5 | −178.5 (4) |
C26—C4—C5—C6 | 179.0 (4) | O18—C19—C20—C21 | −176.1 (4) |
C31—C32—C33—C34 | −1.8 (5) | O18—C19—C24—C23 | 176.9 (4) |
C31—C32—S37—N40 | −64.6 (3) | O42—C41—N40—S37 | −178.0 (3) |
C31—C32—S37—O38 | −177.4 (3) | O42—C41—N43—C44 | 4.0 (6) |
C31—C32—S37—O39 | 52.2 (3) | O48—C31—C32—C33 | −178.1 (3) |
C32—C31—C36—C35 | −2.0 (6) | O48—C31—C32—S37 | 5.2 (5) |
C32—C31—O48—C49 | 177.7 (3) | O48—C31—C36—C35 | 179.1 (4) |
C32—C33—C34—C35 | −0.3 (5) | O48—C49—C50—C51 | 176.0 (4) |
C32—C33—C34—C56 | 179.0 (3) | O48—C49—C54—C53 | −176.6 (4) |
C33—C32—S37—N40 | 118.6 (3) | S7—C2—C3—C4 | −174.9 (3) |
C33—C32—S37—O38 | 5.7 (3) | S37—C32—C33—C34 | 175.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O12i | 0.86 (3) | 1.93 (3) | 2.784 (4) | 171 (3) |
N13—H13···O9 | 0.87 (4) | 2.04 (4) | 2.801 (4) | 145 (3) |
N40—H40···O42ii | 0.82 (4) | 1.96 (4) | 2.774 (4) | 177.0 (15) |
N43—H43···O39 | 0.87 (4) | 2.07 (4) | 2.794 (5) | 141 (4) |
C5—H5···O42ii | 0.93 | 2.60 | 3.484 (4) | 160 |
C6—H6···O38 | 0.93 | 2.52 | 3.266 (4) | 138 |
C35—H35···O12iii | 0.93 | 2.57 | 3.452 (4) | 159 |
C36—H36···O8iv | 0.93 | 2.55 | 3.343 (4) | 144 |
C20—H20···N27ii | 0.93 | 2.56 | 3.425 (7) | 155 |
C50—H50···N57i | 0.93 | 2.55 | 3.439 (6) | 161 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x, y, −z+3/2; (iii) −x+1, y+1, −z+3/2; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C19H21N3O4S |
Mr | 387.45 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 289 |
a, b, c (Å) | 10.6408 (5), 15.8571 (4), 24.8678 (9) |
β (°) | 93.534 (4) |
V (Å3) | 4188.0 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.45 × 0.25 × 0.05 |
Data collection | |
Diffractometer | Agilent SuperNova diffractometer (single source at offset, Eos detector) |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.738, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8550, 8550, 5931 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.174, 1.06 |
No. of reflections | 8548 |
No. of parameters | 507 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.26 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O12i | 0.86 (3) | 1.93 (3) | 2.784 (4) | 171 (3) |
N13—H13···O9 | 0.87 (4) | 2.04 (4) | 2.801 (4) | 145 (3) |
N40—H40···O42ii | 0.82 (4) | 1.96 (4) | 2.774 (4) | 177.0 (15) |
N43—H43···O39 | 0.87 (4) | 2.07 (4) | 2.794 (5) | 141 (4) |
C5—H5···O42ii | 0.93 | 2.60 | 3.484 (4) | 160 |
C6—H6···O38 | 0.93 | 2.52 | 3.266 (4) | 138 |
C35—H35···O12iii | 0.93 | 2.57 | 3.452 (4) | 159 |
C36—H36···O8iv | 0.93 | 2.55 | 3.343 (4) | 144 |
C20—H20···N27ii | 0.93 | 2.56 | 3.425 (7) | 155 |
C50—H50···N57i | 0.93 | 2.55 | 3.439 (6) | 161 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x, y, −z+3/2; (iii) −x+1, y+1, −z+3/2; (iv) x, y+1, z. |
C—S—N—C | S—N—C—N | N—C—N—C | S═O···H—N | |
QERXUG | 85.4 | 11.8 | 178.3 | 2.19 |
TOHBUN | 94.7 | 6.2 | 170.8 | 2.01 |
TOHBUN1 | 94.6 | 6.1 | 170.9 | 2.01 |
USOCOV | -64.3 | -33.0 | 170.5 | 2.15 |
(I), molecule A | -102.7 (3) | -5.2 (5) | -178.9 (4) | 2.04 (4) |
(I), molecule B | -103.0 (3) | 4.5 (5) | -178.8 (4) | 2.07 (4) |
CSD refcodes: QERXUG (Yagupolskii et al., 2001), TOHBUN (Iwata et al., 1997), TOHBUN01 (Grell et al., 1998) and USOCOV (Gelbrich et al., 2011) |