organic compounds
2-(3,4-Dimethyl-5,5-dioxo-2H,4H-pyrazolo[4,3-c][1,2]benzothiazin-2-yl)-N-(3-methoxybenzyl)acetamide
aDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan, bInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, cApplied Chemistry Research Center, PCSIR Laboratories Complex, Lahore 54600, Pakistan, and dDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: matloob_123@yahoo.com
The 21H22N4O4S, contains two molecules (A and B), in which the thiazine rings adopt an S-envelope conformation with the S atoms displaced by 0.621 (2) and 0.697 (2) Å from the mean planes formed by the remaining ring atoms. The dihedral angles between the N-methylacetamide groups and the methoxybenzene rings are 8.67 (10) and 54.49 (6)° in the two molecules and the equivalent torsion angles in the N-methylacetamide chains connecting the ring systems also differ. In the crystal, N—H⋯O hydrogen bonds connect the components into C(4) [100] chains of alternating A and B molecules. The packing is consolidated by weak C—H⋯O interactions, which generate a three-dimensional network.
of the title compound, CRelated literature
For therapeutic applications of benzothiazines, see: Turck et al. (1996); Lombardino et al. (1973); Zinnes et al. (1973). For therapeutic applications of pyrrazoles, see: Silverstein et al. (2000). For the properties and crystal structures of related pyrazolobenzothiazine derivatives, see: Ahmad et al. (2010a,b, 2012; 2011a,b).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812040226/hb6961sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812040226/hb6961Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812040226/hb6961Isup3.cml
3,4-Dimethyl-5,5-dioxidopyrazolo[4,3-c][1,2] benzothiazin-2(4H)-yl acetic acid (1.013 g, 3.3 mmoles) was dissolved in toluene:THF (2:1) and boran–THF complex (1.1 mmoles) was added ton it. The reaction mixture was stirred for a period of 40 minutes and 3-methoxybenzyl amine (0.45 g, 3.3 mmoles) was added to it. The contents of the flask were refluxed for 5 hrs. The solvent was evaporated under vacuum and the title compound as the end product was purified by
Colourless plates were grown from ethyl acetate solution at room temperature by slow evaporation; m.p. 425–426 K.All H atoms were positioned geometrically and refined using a riding model, with N—H = 0.88 Å and C—H = 0.95, 0.98 and 0.99 Å, for aryl, methyl and methylene type H-atoms, respectively. The Uiso(H) were allowed at 1.2Ueq(N/C).
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. | |
Fig. 2. Part of the crystal structure with N—H···O hydrogen bonds shown as dashed lines. H atoms non-participating in hydrogen-bonding are omitted for clarity. | |
Fig. 3. A view of the hydrogen bonding interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. |
C21H22N4O4S | F(000) = 1792 |
Mr = 426.49 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 9915 reflections |
a = 8.6541 (1) Å | θ = 3.4–71.7° |
b = 25.8809 (3) Å | µ = 1.71 mm−1 |
c = 18.3892 (2) Å | T = 173 K |
β = 92.208 (1)° | Plate, colorless |
V = 4115.68 (8) Å3 | 0.14 × 0.12 × 0.02 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | 7975 independent reflections |
Radiation source: fine-focus sealed tube | 6621 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω and ϕ scans | θmax = 72.7°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.796, Tmax = 0.967 | k = −31→32 |
70993 measured reflections | l = −22→22 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0486P)2 + 1.780P] where P = (Fo2 + 2Fc2)/3 |
7975 reflections | (Δ/σ)max = 0.001 |
547 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C21H22N4O4S | V = 4115.68 (8) Å3 |
Mr = 426.49 | Z = 8 |
Monoclinic, P21/c | Cu Kα radiation |
a = 8.6541 (1) Å | µ = 1.71 mm−1 |
b = 25.8809 (3) Å | T = 173 K |
c = 18.3892 (2) Å | 0.14 × 0.12 × 0.02 mm |
β = 92.208 (1)° |
Bruker APEXII CCD diffractometer | 7975 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 6621 reflections with I > 2σ(I) |
Tmin = 0.796, Tmax = 0.967 | Rint = 0.049 |
70993 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.31 e Å−3 |
7975 reflections | Δρmin = −0.37 e Å−3 |
547 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 | ||
S1 | 0.73006 (5) | 0.718057 (16) | 0.68662 (2) | 0.03077 (11) | |
O1 | 0.73608 (18) | 0.75309 (5) | 0.74693 (7) | 0.0448 (3) | |
O2 | 0.58770 (14) | 0.69282 (5) | 0.66768 (8) | 0.0427 (3) | |
O3 | 0.66878 (13) | 0.64371 (5) | 0.36992 (6) | 0.0305 (3) | |
O4 | 1.13937 (15) | 0.51550 (5) | 0.09408 (7) | 0.0442 (3) | |
N1 | 0.78516 (16) | 0.74988 (5) | 0.61494 (7) | 0.0283 (3) | |
N2 | 0.94469 (15) | 0.64777 (5) | 0.50587 (7) | 0.0268 (3) | |
N3 | 0.90464 (15) | 0.68467 (5) | 0.45640 (7) | 0.0258 (3) | |
N4 | 0.83869 (15) | 0.61454 (5) | 0.28889 (7) | 0.0257 (3) | |
H4N | 0.9357 | 0.6140 | 0.2762 | 0.031* | |
C1 | 0.86939 (19) | 0.66886 (6) | 0.70074 (9) | 0.0277 (3) | |
C2 | 0.9089 (2) | 0.65336 (7) | 0.77123 (10) | 0.0379 (4) | |
H2 | 0.8681 | 0.6709 | 0.8116 | 0.045* | |
C3 | 1.0082 (2) | 0.61207 (8) | 0.78196 (11) | 0.0439 (5) | |
H3 | 1.0366 | 0.6012 | 0.8300 | 0.053* | |
C4 | 1.0666 (2) | 0.58638 (7) | 0.72289 (11) | 0.0398 (4) | |
H4 | 1.1326 | 0.5574 | 0.7308 | 0.048* | |
C5 | 1.02988 (19) | 0.60238 (6) | 0.65256 (10) | 0.0310 (4) | |
H5 | 1.0717 | 0.5847 | 0.6126 | 0.037* | |
C6 | 0.93145 (18) | 0.64456 (6) | 0.64015 (9) | 0.0252 (3) | |
C7 | 0.90162 (17) | 0.66776 (6) | 0.56918 (8) | 0.0238 (3) | |
C8 | 0.83336 (18) | 0.71665 (6) | 0.55833 (8) | 0.0242 (3) | |
C9 | 0.83390 (18) | 0.72636 (6) | 0.48488 (8) | 0.0247 (3) | |
C10 | 0.7748 (2) | 0.77070 (7) | 0.44095 (9) | 0.0324 (4) | |
H10A | 0.7004 | 0.7902 | 0.4689 | 0.039* | |
H10B | 0.7238 | 0.7579 | 0.3960 | 0.039* | |
H10C | 0.8612 | 0.7932 | 0.4289 | 0.039* | |
C11 | 0.8664 (2) | 0.79951 (7) | 0.62507 (10) | 0.0343 (4) | |
H11A | 0.8964 | 0.8127 | 0.5777 | 0.041* | |
H11B | 0.9590 | 0.7944 | 0.6566 | 0.041* | |
H11C | 0.7977 | 0.8244 | 0.6477 | 0.041* | |
C12 | 0.93011 (19) | 0.67463 (7) | 0.38043 (8) | 0.0288 (3) | |
H12A | 1.0292 | 0.6560 | 0.3760 | 0.035* | |
H12B | 0.9377 | 0.7078 | 0.3541 | 0.035* | |
C13 | 0.79951 (18) | 0.64258 (6) | 0.34597 (8) | 0.0237 (3) | |
C14 | 0.72376 (19) | 0.58481 (7) | 0.24711 (9) | 0.0303 (4) | |
H14A | 0.6516 | 0.6091 | 0.2218 | 0.036* | |
H14B | 0.6632 | 0.5642 | 0.2813 | 0.036* | |
C15 | 0.78873 (19) | 0.54888 (6) | 0.19144 (8) | 0.0260 (3) | |
C16 | 0.94083 (19) | 0.55117 (6) | 0.16971 (9) | 0.0290 (3) | |
H16 | 1.0103 | 0.5759 | 0.1909 | 0.035* | |
C17 | 0.9909 (2) | 0.51720 (7) | 0.11689 (9) | 0.0315 (4) | |
C18 | 0.8897 (2) | 0.48220 (7) | 0.08388 (9) | 0.0350 (4) | |
H18 | 0.9240 | 0.4596 | 0.0471 | 0.042* | |
C19 | 0.7390 (2) | 0.48049 (7) | 0.10484 (10) | 0.0381 (4) | |
H19 | 0.6688 | 0.4567 | 0.0821 | 0.046* | |
C20 | 0.6881 (2) | 0.51308 (7) | 0.15891 (10) | 0.0339 (4) | |
H20 | 0.5844 | 0.5109 | 0.1737 | 0.041* | |
C21 | 1.2412 (2) | 0.55582 (9) | 0.11614 (13) | 0.0518 (5) | |
H21A | 1.3392 | 0.5519 | 0.0917 | 0.062* | |
H21B | 1.2605 | 0.5542 | 0.1690 | 0.062* | |
H21C | 1.1945 | 0.5892 | 0.1030 | 0.062* | |
S2 | 0.75867 (5) | 0.300172 (18) | 1.06466 (2) | 0.03455 (11) | |
O5 | 0.77325 (18) | 0.27220 (6) | 1.13161 (7) | 0.0496 (4) | |
O6 | 0.88416 (15) | 0.33157 (6) | 1.04272 (7) | 0.0425 (3) | |
O7 | 0.84261 (13) | 0.35681 (5) | 0.74617 (6) | 0.0311 (3) | |
O8 | 0.25890 (16) | 0.51780 (5) | 0.54673 (8) | 0.0489 (4) | |
N5 | 0.72180 (17) | 0.25814 (6) | 0.99927 (7) | 0.0318 (3) | |
N6 | 0.54399 (15) | 0.34265 (5) | 0.86314 (7) | 0.0248 (3) | |
N7 | 0.61082 (15) | 0.30530 (5) | 0.82299 (7) | 0.0240 (3) | |
N8 | 0.64844 (16) | 0.38308 (6) | 0.66855 (8) | 0.0308 (3) | |
H8N | 0.5534 | 0.3765 | 0.6524 | 0.037* | |
C22 | 0.5931 (2) | 0.34022 (7) | 1.06449 (9) | 0.0307 (4) | |
C23 | 0.5371 (2) | 0.35857 (8) | 1.12924 (10) | 0.0404 (4) | |
H23 | 0.5812 | 0.3473 | 1.1746 | 0.048* | |
C24 | 0.4164 (2) | 0.39335 (8) | 1.12678 (11) | 0.0457 (5) | |
H24 | 0.3766 | 0.4060 | 1.1708 | 0.055* | |
C25 | 0.3525 (2) | 0.41003 (7) | 1.06055 (11) | 0.0411 (4) | |
H25 | 0.2717 | 0.4349 | 1.0595 | 0.049* | |
C26 | 0.4056 (2) | 0.39074 (7) | 0.99589 (10) | 0.0328 (4) | |
H26 | 0.3599 | 0.4020 | 0.9508 | 0.039* | |
C27 | 0.52598 (19) | 0.35489 (6) | 0.99667 (9) | 0.0273 (3) | |
C28 | 0.57863 (18) | 0.32881 (6) | 0.93188 (8) | 0.0240 (3) | |
C29 | 0.66903 (18) | 0.28375 (6) | 0.93412 (9) | 0.0256 (3) | |
C30 | 0.68912 (18) | 0.26942 (6) | 0.86324 (9) | 0.0257 (3) | |
C31 | 0.7701 (2) | 0.22448 (7) | 0.83220 (10) | 0.0354 (4) | |
H31A | 0.8316 | 0.2071 | 0.8708 | 0.042* | |
H31B | 0.8385 | 0.2364 | 0.7944 | 0.042* | |
H31C | 0.6939 | 0.2003 | 0.8109 | 0.042* | |
C32 | 0.6376 (3) | 0.21044 (7) | 1.01727 (11) | 0.0452 (5) | |
H32A | 0.6335 | 0.1874 | 0.9749 | 0.054* | |
H32B | 0.5322 | 0.2192 | 1.0305 | 0.054* | |
H32C | 0.6912 | 0.1930 | 1.0583 | 0.054* | |
C33 | 0.60293 (19) | 0.30988 (6) | 0.74456 (8) | 0.0257 (3) | |
H33A | 0.4954 | 0.3177 | 0.7278 | 0.031* | |
H33B | 0.6333 | 0.2767 | 0.7225 | 0.031* | |
C34 | 0.71003 (17) | 0.35267 (6) | 0.72004 (8) | 0.0236 (3) | |
C35 | 0.7295 (2) | 0.42690 (8) | 0.63715 (11) | 0.0396 (4) | |
H35A | 0.7603 | 0.4179 | 0.5874 | 0.048* | |
H35B | 0.8246 | 0.4343 | 0.6670 | 0.048* | |
C36 | 0.6281 (2) | 0.47419 (7) | 0.63410 (10) | 0.0354 (4) | |
C37 | 0.4907 (2) | 0.47291 (7) | 0.59220 (9) | 0.0326 (4) | |
H37 | 0.4611 | 0.4421 | 0.5672 | 0.039* | |
C38 | 0.3965 (2) | 0.51621 (7) | 0.58663 (10) | 0.0387 (4) | |
C39 | 0.4419 (3) | 0.56167 (8) | 0.62194 (13) | 0.0509 (5) | |
H39 | 0.3795 | 0.5918 | 0.6172 | 0.061* | |
C40 | 0.5767 (3) | 0.56283 (8) | 0.66352 (13) | 0.0565 (6) | |
H40 | 0.6066 | 0.5938 | 0.6879 | 0.068* | |
C41 | 0.6705 (3) | 0.51915 (9) | 0.67061 (12) | 0.0496 (5) | |
H41 | 0.7628 | 0.5202 | 0.7002 | 0.059* | |
C42 | 0.2039 (2) | 0.47010 (9) | 0.51694 (13) | 0.0520 (5) | |
H42A | 0.1065 | 0.4760 | 0.4893 | 0.062* | |
H42B | 0.1867 | 0.4456 | 0.5565 | 0.062* | |
H42C | 0.2807 | 0.4559 | 0.4846 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0327 (2) | 0.0311 (2) | 0.0291 (2) | 0.00564 (16) | 0.00925 (17) | −0.00061 (15) |
O1 | 0.0658 (9) | 0.0403 (7) | 0.0290 (6) | 0.0125 (7) | 0.0132 (6) | −0.0043 (5) |
O2 | 0.0280 (6) | 0.0434 (8) | 0.0573 (8) | 0.0044 (6) | 0.0111 (6) | 0.0064 (6) |
O3 | 0.0220 (6) | 0.0431 (7) | 0.0266 (6) | −0.0017 (5) | 0.0033 (5) | −0.0041 (5) |
O4 | 0.0383 (7) | 0.0459 (8) | 0.0493 (8) | −0.0035 (6) | 0.0146 (6) | −0.0187 (6) |
N1 | 0.0340 (8) | 0.0260 (7) | 0.0250 (7) | 0.0039 (6) | 0.0045 (6) | −0.0037 (5) |
N2 | 0.0250 (7) | 0.0284 (7) | 0.0267 (7) | 0.0026 (5) | −0.0011 (6) | −0.0039 (5) |
N3 | 0.0229 (7) | 0.0314 (7) | 0.0229 (6) | 0.0013 (5) | 0.0001 (5) | −0.0040 (5) |
N4 | 0.0201 (6) | 0.0330 (7) | 0.0242 (6) | −0.0010 (5) | 0.0029 (5) | −0.0037 (5) |
C1 | 0.0274 (8) | 0.0274 (8) | 0.0285 (8) | −0.0017 (6) | 0.0026 (7) | 0.0018 (6) |
C2 | 0.0462 (11) | 0.0396 (10) | 0.0281 (9) | −0.0011 (8) | 0.0040 (8) | 0.0022 (7) |
C3 | 0.0519 (12) | 0.0451 (11) | 0.0342 (10) | 0.0007 (9) | −0.0046 (9) | 0.0124 (8) |
C4 | 0.0384 (10) | 0.0344 (10) | 0.0461 (11) | 0.0049 (8) | −0.0058 (9) | 0.0098 (8) |
C5 | 0.0269 (8) | 0.0289 (8) | 0.0372 (9) | 0.0005 (7) | 0.0003 (7) | −0.0003 (7) |
C6 | 0.0217 (7) | 0.0251 (8) | 0.0287 (8) | −0.0034 (6) | −0.0013 (6) | −0.0008 (6) |
C7 | 0.0192 (7) | 0.0260 (8) | 0.0262 (8) | 0.0000 (6) | −0.0009 (6) | −0.0041 (6) |
C8 | 0.0220 (7) | 0.0263 (8) | 0.0243 (7) | 0.0021 (6) | 0.0001 (6) | −0.0032 (6) |
C9 | 0.0199 (7) | 0.0285 (8) | 0.0256 (8) | 0.0005 (6) | −0.0005 (6) | −0.0037 (6) |
C10 | 0.0324 (9) | 0.0363 (9) | 0.0286 (8) | 0.0050 (7) | 0.0009 (7) | 0.0023 (7) |
C11 | 0.0415 (10) | 0.0282 (8) | 0.0332 (9) | −0.0004 (7) | 0.0007 (8) | −0.0053 (7) |
C12 | 0.0243 (8) | 0.0378 (9) | 0.0244 (8) | −0.0029 (7) | 0.0034 (7) | −0.0061 (7) |
C13 | 0.0214 (7) | 0.0286 (8) | 0.0209 (7) | 0.0018 (6) | 0.0001 (6) | 0.0031 (6) |
C14 | 0.0234 (8) | 0.0382 (9) | 0.0292 (8) | −0.0033 (7) | 0.0004 (7) | −0.0069 (7) |
C15 | 0.0283 (8) | 0.0270 (8) | 0.0225 (7) | 0.0001 (6) | −0.0016 (7) | 0.0009 (6) |
C16 | 0.0288 (8) | 0.0305 (8) | 0.0277 (8) | −0.0035 (7) | 0.0003 (7) | −0.0043 (6) |
C17 | 0.0340 (9) | 0.0322 (9) | 0.0286 (8) | −0.0001 (7) | 0.0048 (7) | −0.0016 (7) |
C18 | 0.0464 (11) | 0.0294 (9) | 0.0293 (9) | −0.0002 (8) | 0.0014 (8) | −0.0062 (7) |
C19 | 0.0430 (10) | 0.0327 (9) | 0.0381 (10) | −0.0089 (8) | −0.0053 (8) | −0.0071 (7) |
C20 | 0.0290 (9) | 0.0364 (9) | 0.0361 (9) | −0.0053 (7) | −0.0015 (8) | −0.0017 (7) |
C21 | 0.0338 (10) | 0.0597 (13) | 0.0632 (14) | −0.0082 (9) | 0.0192 (10) | −0.0177 (11) |
S2 | 0.0328 (2) | 0.0449 (3) | 0.0257 (2) | −0.00011 (18) | −0.00307 (17) | 0.00447 (17) |
O5 | 0.0581 (9) | 0.0620 (9) | 0.0283 (7) | 0.0026 (7) | −0.0064 (6) | 0.0098 (6) |
O6 | 0.0301 (7) | 0.0562 (8) | 0.0409 (7) | −0.0053 (6) | −0.0041 (6) | 0.0006 (6) |
O7 | 0.0211 (6) | 0.0437 (7) | 0.0284 (6) | −0.0027 (5) | 0.0003 (5) | −0.0008 (5) |
O8 | 0.0414 (8) | 0.0413 (8) | 0.0641 (9) | 0.0124 (6) | 0.0046 (7) | 0.0058 (7) |
N5 | 0.0333 (8) | 0.0337 (8) | 0.0283 (7) | 0.0045 (6) | −0.0008 (6) | 0.0066 (6) |
N6 | 0.0235 (7) | 0.0260 (7) | 0.0252 (7) | 0.0017 (5) | 0.0032 (5) | −0.0012 (5) |
N7 | 0.0223 (6) | 0.0269 (7) | 0.0230 (6) | 0.0019 (5) | 0.0027 (5) | −0.0013 (5) |
N8 | 0.0217 (7) | 0.0377 (8) | 0.0327 (7) | −0.0052 (6) | −0.0018 (6) | 0.0060 (6) |
C22 | 0.0307 (9) | 0.0338 (9) | 0.0278 (8) | −0.0063 (7) | 0.0047 (7) | −0.0002 (7) |
C23 | 0.0463 (11) | 0.0487 (11) | 0.0267 (9) | −0.0112 (9) | 0.0074 (8) | −0.0039 (8) |
C24 | 0.0496 (12) | 0.0515 (12) | 0.0374 (10) | −0.0103 (10) | 0.0204 (9) | −0.0148 (9) |
C25 | 0.0376 (10) | 0.0367 (10) | 0.0501 (11) | −0.0014 (8) | 0.0144 (9) | −0.0108 (8) |
C26 | 0.0308 (9) | 0.0309 (9) | 0.0371 (9) | −0.0012 (7) | 0.0066 (8) | −0.0020 (7) |
C27 | 0.0267 (8) | 0.0278 (8) | 0.0278 (8) | −0.0052 (6) | 0.0069 (7) | 0.0001 (6) |
C28 | 0.0213 (7) | 0.0270 (8) | 0.0239 (8) | −0.0017 (6) | 0.0029 (6) | 0.0018 (6) |
C29 | 0.0225 (8) | 0.0282 (8) | 0.0262 (8) | 0.0019 (6) | 0.0006 (6) | 0.0037 (6) |
C30 | 0.0192 (7) | 0.0272 (8) | 0.0307 (8) | 0.0012 (6) | 0.0011 (6) | −0.0001 (6) |
C31 | 0.0305 (9) | 0.0364 (9) | 0.0392 (9) | 0.0102 (7) | −0.0003 (8) | −0.0047 (7) |
C32 | 0.0568 (13) | 0.0354 (10) | 0.0434 (11) | −0.0003 (9) | 0.0001 (10) | 0.0115 (8) |
C33 | 0.0247 (8) | 0.0304 (8) | 0.0219 (7) | −0.0012 (6) | −0.0003 (6) | −0.0024 (6) |
C34 | 0.0206 (7) | 0.0314 (8) | 0.0191 (7) | 0.0004 (6) | 0.0036 (6) | −0.0055 (6) |
C35 | 0.0276 (9) | 0.0452 (11) | 0.0460 (11) | −0.0052 (8) | 0.0027 (8) | 0.0148 (8) |
C36 | 0.0342 (9) | 0.0364 (9) | 0.0361 (9) | −0.0084 (7) | 0.0065 (8) | 0.0056 (7) |
C37 | 0.0343 (9) | 0.0298 (9) | 0.0343 (9) | −0.0024 (7) | 0.0076 (8) | 0.0021 (7) |
C38 | 0.0377 (10) | 0.0360 (10) | 0.0431 (10) | 0.0017 (8) | 0.0120 (8) | 0.0041 (8) |
C39 | 0.0550 (13) | 0.0318 (10) | 0.0672 (14) | 0.0017 (9) | 0.0199 (11) | −0.0030 (9) |
C40 | 0.0708 (16) | 0.0388 (11) | 0.0610 (14) | −0.0169 (11) | 0.0181 (12) | −0.0129 (10) |
C41 | 0.0510 (12) | 0.0506 (12) | 0.0471 (11) | −0.0193 (10) | 0.0016 (10) | −0.0020 (9) |
C42 | 0.0365 (11) | 0.0541 (13) | 0.0649 (14) | 0.0035 (9) | −0.0064 (10) | 0.0050 (11) |
S1—O2 | 1.4257 (14) | S2—O6 | 1.4270 (14) |
S1—O1 | 1.4319 (13) | S2—O5 | 1.4296 (13) |
S1—N1 | 1.6406 (14) | S2—N5 | 1.6436 (15) |
S1—C1 | 1.7659 (17) | S2—C22 | 1.7684 (18) |
O3—C13 | 1.2302 (19) | O7—C34 | 1.2314 (19) |
O4—C17 | 1.367 (2) | O8—C38 | 1.375 (3) |
O4—C21 | 1.415 (2) | O8—C42 | 1.425 (3) |
N1—C8 | 1.4250 (19) | N5—C29 | 1.429 (2) |
N1—C11 | 1.473 (2) | N5—C32 | 1.478 (2) |
N2—C7 | 1.340 (2) | N6—C28 | 1.337 (2) |
N2—N3 | 1.3547 (19) | N6—N7 | 1.3592 (18) |
N3—C9 | 1.356 (2) | N7—C30 | 1.353 (2) |
N3—C12 | 1.4462 (19) | N7—C33 | 1.4461 (19) |
N4—C13 | 1.331 (2) | N8—C34 | 1.327 (2) |
N4—C14 | 1.453 (2) | N8—C35 | 1.464 (2) |
N4—H4N | 0.8800 | N8—H8N | 0.8800 |
C1—C2 | 1.387 (2) | C22—C23 | 1.387 (2) |
C1—C6 | 1.404 (2) | C22—C27 | 1.408 (2) |
C2—C3 | 1.381 (3) | C23—C24 | 1.378 (3) |
C2—H2 | 0.9500 | C23—H23 | 0.9500 |
C3—C4 | 1.385 (3) | C24—C25 | 1.387 (3) |
C3—H3 | 0.9500 | C24—H24 | 0.9500 |
C4—C5 | 1.383 (3) | C25—C26 | 1.384 (2) |
C4—H4 | 0.9500 | C25—H25 | 0.9500 |
C5—C6 | 1.398 (2) | C26—C27 | 1.395 (2) |
C5—H5 | 0.9500 | C26—H26 | 0.9500 |
C6—C7 | 1.451 (2) | C27—C28 | 1.457 (2) |
C7—C8 | 1.407 (2) | C28—C29 | 1.404 (2) |
C8—C9 | 1.374 (2) | C29—C30 | 1.373 (2) |
C9—C10 | 1.483 (2) | C30—C31 | 1.483 (2) |
C10—H10A | 0.9800 | C31—H31A | 0.9800 |
C10—H10B | 0.9800 | C31—H31B | 0.9800 |
C10—H10C | 0.9800 | C31—H31C | 0.9800 |
C11—H11A | 0.9800 | C32—H32A | 0.9800 |
C11—H11B | 0.9800 | C32—H32B | 0.9800 |
C11—H11C | 0.9800 | C32—H32C | 0.9800 |
C12—C13 | 1.521 (2) | C33—C34 | 1.524 (2) |
C12—H12A | 0.9900 | C33—H33A | 0.9900 |
C12—H12B | 0.9900 | C33—H33B | 0.9900 |
C14—C15 | 1.508 (2) | C35—C36 | 1.506 (3) |
C14—H14A | 0.9900 | C35—H35A | 0.9900 |
C14—H14B | 0.9900 | C35—H35B | 0.9900 |
C15—C20 | 1.391 (2) | C36—C41 | 1.386 (3) |
C15—C16 | 1.391 (2) | C36—C37 | 1.392 (3) |
C16—C17 | 1.392 (2) | C37—C38 | 1.387 (3) |
C16—H16 | 0.9500 | C37—H37 | 0.9500 |
C17—C18 | 1.384 (2) | C38—C39 | 1.393 (3) |
C18—C19 | 1.375 (3) | C39—C40 | 1.370 (4) |
C18—H18 | 0.9500 | C39—H39 | 0.9500 |
C19—C20 | 1.388 (3) | C40—C41 | 1.395 (3) |
C19—H19 | 0.9500 | C40—H40 | 0.9500 |
C20—H20 | 0.9500 | C41—H41 | 0.9500 |
C21—H21A | 0.9800 | C42—H42A | 0.9800 |
C21—H21B | 0.9800 | C42—H42B | 0.9800 |
C21—H21C | 0.9800 | C42—H42C | 0.9800 |
O2—S1—O1 | 118.99 (9) | O6—S2—O5 | 119.27 (9) |
O2—S1—N1 | 107.99 (8) | O6—S2—N5 | 107.37 (8) |
O1—S1—N1 | 107.54 (8) | O5—S2—N5 | 107.64 (8) |
O2—S1—C1 | 106.52 (8) | O6—S2—C22 | 106.94 (8) |
O1—S1—C1 | 109.78 (8) | O5—S2—C22 | 110.05 (9) |
N1—S1—C1 | 105.20 (7) | N5—S2—C22 | 104.61 (8) |
C17—O4—C21 | 118.06 (14) | C38—O8—C42 | 116.66 (15) |
C8—N1—C11 | 117.85 (13) | C29—N5—C32 | 115.53 (14) |
C8—N1—S1 | 112.72 (11) | C29—N5—S2 | 110.68 (11) |
C11—N1—S1 | 119.23 (11) | C32—N5—S2 | 118.20 (12) |
C7—N2—N3 | 103.82 (12) | C28—N6—N7 | 103.79 (12) |
N2—N3—C9 | 114.16 (12) | C30—N7—N6 | 113.93 (12) |
N2—N3—C12 | 118.52 (13) | C30—N7—C33 | 127.25 (13) |
C9—N3—C12 | 127.16 (14) | N6—N7—C33 | 118.60 (12) |
C13—N4—C14 | 121.04 (13) | C34—N8—C35 | 123.75 (14) |
C13—N4—H4N | 119.5 | C34—N8—H8N | 118.1 |
C14—N4—H4N | 119.5 | C35—N8—H8N | 118.1 |
C2—C1—C6 | 121.61 (16) | C23—C22—C27 | 121.50 (17) |
C2—C1—S1 | 119.22 (13) | C23—C22—S2 | 120.63 (15) |
C6—C1—S1 | 119.08 (12) | C27—C22—S2 | 117.79 (12) |
C3—C2—C1 | 119.14 (17) | C24—C23—C22 | 119.02 (18) |
C3—C2—H2 | 120.4 | C24—C23—H23 | 120.5 |
C1—C2—H2 | 120.4 | C22—C23—H23 | 120.5 |
C2—C3—C4 | 120.21 (17) | C23—C24—C25 | 120.53 (17) |
C2—C3—H3 | 119.9 | C23—C24—H24 | 119.7 |
C4—C3—H3 | 119.9 | C25—C24—H24 | 119.7 |
C5—C4—C3 | 120.80 (17) | C26—C25—C24 | 120.52 (19) |
C5—C4—H4 | 119.6 | C26—C25—H25 | 119.7 |
C3—C4—H4 | 119.6 | C24—C25—H25 | 119.7 |
C4—C5—C6 | 120.19 (16) | C25—C26—C27 | 120.24 (18) |
C4—C5—H5 | 119.9 | C25—C26—H26 | 119.9 |
C6—C5—H5 | 119.9 | C27—C26—H26 | 119.9 |
C5—C6—C1 | 117.99 (15) | C26—C27—C22 | 118.10 (15) |
C5—C6—C7 | 123.80 (15) | C26—C27—C28 | 123.83 (15) |
C1—C6—C7 | 117.92 (14) | C22—C27—C28 | 117.91 (15) |
N2—C7—C8 | 110.69 (14) | N6—C28—C29 | 110.78 (14) |
N2—C7—C6 | 125.17 (14) | N6—C28—C27 | 125.66 (14) |
C8—C7—C6 | 123.98 (14) | C29—C28—C27 | 123.52 (14) |
C9—C8—C7 | 106.65 (13) | C30—C29—C28 | 106.71 (14) |
C9—C8—N1 | 128.31 (14) | C30—C29—N5 | 128.52 (15) |
C7—C8—N1 | 124.90 (14) | C28—C29—N5 | 124.72 (14) |
N3—C9—C8 | 104.64 (14) | N7—C30—C29 | 104.76 (13) |
N3—C9—C10 | 123.84 (14) | N7—C30—C31 | 124.18 (15) |
C8—C9—C10 | 131.52 (15) | C29—C30—C31 | 131.01 (15) |
C9—C10—H10A | 109.5 | C30—C31—H31A | 109.5 |
C9—C10—H10B | 109.5 | C30—C31—H31B | 109.5 |
H10A—C10—H10B | 109.5 | H31A—C31—H31B | 109.5 |
C9—C10—H10C | 109.5 | C30—C31—H31C | 109.5 |
H10A—C10—H10C | 109.5 | H31A—C31—H31C | 109.5 |
H10B—C10—H10C | 109.5 | H31B—C31—H31C | 109.5 |
N1—C11—H11A | 109.5 | N5—C32—H32A | 109.5 |
N1—C11—H11B | 109.5 | N5—C32—H32B | 109.5 |
H11A—C11—H11B | 109.5 | H32A—C32—H32B | 109.5 |
N1—C11—H11C | 109.5 | N5—C32—H32C | 109.5 |
H11A—C11—H11C | 109.5 | H32A—C32—H32C | 109.5 |
H11B—C11—H11C | 109.5 | H32B—C32—H32C | 109.5 |
N3—C12—C13 | 111.23 (13) | N7—C33—C34 | 110.42 (13) |
N3—C12—H12A | 109.4 | N7—C33—H33A | 109.6 |
C13—C12—H12A | 109.4 | C34—C33—H33A | 109.6 |
N3—C12—H12B | 109.4 | N7—C33—H33B | 109.6 |
C13—C12—H12B | 109.4 | C34—C33—H33B | 109.6 |
H12A—C12—H12B | 108.0 | H33A—C33—H33B | 108.1 |
O3—C13—N4 | 124.14 (15) | O7—C34—N8 | 124.70 (15) |
O3—C13—C12 | 121.12 (14) | O7—C34—C33 | 121.08 (14) |
N4—C13—C12 | 114.73 (13) | N8—C34—C33 | 114.21 (13) |
N4—C14—C15 | 114.83 (13) | N8—C35—C36 | 110.90 (14) |
N4—C14—H14A | 108.6 | N8—C35—H35A | 109.5 |
C15—C14—H14A | 108.6 | C36—C35—H35A | 109.5 |
N4—C14—H14B | 108.6 | N8—C35—H35B | 109.5 |
C15—C14—H14B | 108.6 | C36—C35—H35B | 109.5 |
H14A—C14—H14B | 107.5 | H35A—C35—H35B | 108.0 |
C20—C15—C16 | 119.23 (15) | C41—C36—C37 | 119.54 (19) |
C20—C15—C14 | 117.34 (15) | C41—C36—C35 | 121.41 (19) |
C16—C15—C14 | 123.39 (15) | C37—C36—C35 | 119.03 (17) |
C15—C16—C17 | 119.81 (16) | C38—C37—C36 | 120.55 (17) |
C15—C16—H16 | 120.1 | C38—C37—H37 | 119.7 |
C17—C16—H16 | 120.1 | C36—C37—H37 | 119.7 |
O4—C17—C18 | 115.50 (15) | O8—C38—C37 | 123.90 (18) |
O4—C17—C16 | 123.79 (16) | O8—C38—C39 | 116.50 (18) |
C18—C17—C16 | 120.71 (16) | C37—C38—C39 | 119.6 (2) |
C19—C18—C17 | 119.30 (16) | C40—C39—C38 | 119.8 (2) |
C19—C18—H18 | 120.4 | C40—C39—H39 | 120.1 |
C17—C18—H18 | 120.4 | C38—C39—H39 | 120.1 |
C18—C19—C20 | 120.76 (17) | C39—C40—C41 | 121.0 (2) |
C18—C19—H19 | 119.6 | C39—C40—H40 | 119.5 |
C20—C19—H19 | 119.6 | C41—C40—H40 | 119.5 |
C19—C20—C15 | 120.16 (17) | C36—C41—C40 | 119.5 (2) |
C19—C20—H20 | 119.9 | C36—C41—H41 | 120.2 |
C15—C20—H20 | 119.9 | C40—C41—H41 | 120.2 |
O4—C21—H21A | 109.5 | O8—C42—H42A | 109.5 |
O4—C21—H21B | 109.5 | O8—C42—H42B | 109.5 |
H21A—C21—H21B | 109.5 | H42A—C42—H42B | 109.5 |
O4—C21—H21C | 109.5 | O8—C42—H42C | 109.5 |
H21A—C21—H21C | 109.5 | H42A—C42—H42C | 109.5 |
H21B—C21—H21C | 109.5 | H42B—C42—H42C | 109.5 |
O2—S1—N1—C8 | −70.02 (13) | O6—S2—N5—C29 | −64.49 (13) |
O1—S1—N1—C8 | 160.41 (12) | O5—S2—N5—C29 | 165.94 (12) |
C1—S1—N1—C8 | 43.43 (13) | C22—S2—N5—C29 | 48.89 (13) |
O2—S1—N1—C11 | 145.41 (13) | O6—S2—N5—C32 | 159.02 (14) |
O1—S1—N1—C11 | 15.84 (15) | O5—S2—N5—C32 | 29.45 (16) |
C1—S1—N1—C11 | −101.13 (14) | C22—S2—N5—C32 | −87.59 (14) |
C7—N2—N3—C9 | −1.96 (17) | C28—N6—N7—C30 | −1.62 (17) |
C7—N2—N3—C12 | −177.68 (13) | C28—N6—N7—C33 | −176.66 (13) |
O2—S1—C1—C2 | −99.39 (15) | O6—S2—C22—C23 | −103.66 (15) |
O1—S1—C1—C2 | 30.69 (17) | O5—S2—C22—C23 | 27.27 (18) |
N1—S1—C1—C2 | 146.13 (14) | N5—S2—C22—C23 | 142.65 (15) |
O2—S1—C1—C6 | 77.32 (14) | O6—S2—C22—C27 | 73.01 (15) |
O1—S1—C1—C6 | −152.60 (13) | O5—S2—C22—C27 | −156.06 (13) |
N1—S1—C1—C6 | −37.16 (15) | N5—S2—C22—C27 | −40.69 (15) |
C6—C1—C2—C3 | −1.9 (3) | C27—C22—C23—C24 | −2.3 (3) |
S1—C1—C2—C3 | 174.73 (15) | S2—C22—C23—C24 | 174.25 (15) |
C1—C2—C3—C4 | −0.4 (3) | C22—C23—C24—C25 | −0.4 (3) |
C2—C3—C4—C5 | 1.7 (3) | C23—C24—C25—C26 | 2.1 (3) |
C3—C4—C5—C6 | −0.7 (3) | C24—C25—C26—C27 | −1.1 (3) |
C4—C5—C6—C1 | −1.5 (2) | C25—C26—C27—C22 | −1.5 (2) |
C4—C5—C6—C7 | 172.30 (16) | C25—C26—C27—C28 | 173.67 (16) |
C2—C1—C6—C5 | 2.8 (2) | C23—C22—C27—C26 | 3.2 (2) |
S1—C1—C6—C5 | −173.81 (12) | S2—C22—C27—C26 | −173.39 (12) |
C2—C1—C6—C7 | −171.34 (15) | C23—C22—C27—C28 | −172.24 (16) |
S1—C1—C6—C7 | 12.0 (2) | S2—C22—C27—C28 | 11.1 (2) |
N3—N2—C7—C8 | 0.75 (17) | N7—N6—C28—C29 | 1.21 (17) |
N3—N2—C7—C6 | −174.70 (14) | N7—N6—C28—C27 | −176.35 (15) |
C5—C6—C7—N2 | 10.3 (2) | C26—C27—C28—N6 | 14.7 (3) |
C1—C6—C7—N2 | −175.85 (15) | C22—C27—C28—N6 | −170.05 (15) |
C5—C6—C7—C8 | −164.52 (16) | C26—C27—C28—C29 | −162.53 (16) |
C1—C6—C7—C8 | 9.3 (2) | C22—C27—C28—C29 | 12.7 (2) |
N2—C7—C8—C9 | 0.62 (18) | N6—C28—C29—C30 | −0.46 (18) |
C6—C7—C8—C9 | 176.14 (14) | C27—C28—C29—C30 | 177.17 (15) |
N2—C7—C8—N1 | −175.25 (15) | N6—C28—C29—N5 | −178.22 (15) |
C6—C7—C8—N1 | 0.3 (3) | C27—C28—C29—N5 | −0.6 (3) |
C11—N1—C8—C9 | −60.2 (2) | C32—N5—C29—C30 | −73.5 (2) |
S1—N1—C8—C9 | 154.68 (14) | S2—N5—C29—C30 | 148.71 (15) |
C11—N1—C8—C7 | 114.74 (18) | C32—N5—C29—C28 | 103.7 (2) |
S1—N1—C8—C7 | −30.4 (2) | S2—N5—C29—C28 | −34.0 (2) |
N2—N3—C9—C8 | 2.36 (18) | N6—N7—C30—C29 | 1.36 (18) |
C12—N3—C9—C8 | 177.63 (14) | C33—N7—C30—C29 | 175.89 (14) |
N2—N3—C9—C10 | −177.77 (15) | N6—N7—C30—C31 | 179.17 (15) |
C12—N3—C9—C10 | −2.5 (3) | C33—N7—C30—C31 | −6.3 (3) |
C7—C8—C9—N3 | −1.71 (17) | C28—C29—C30—N7 | −0.52 (17) |
N1—C8—C9—N3 | 173.98 (15) | N5—C29—C30—N7 | 177.14 (16) |
C7—C8—C9—C10 | 178.43 (17) | C28—C29—C30—C31 | −178.12 (17) |
N1—C8—C9—C10 | −5.9 (3) | N5—C29—C30—C31 | −0.5 (3) |
N2—N3—C12—C13 | 82.23 (17) | C30—N7—C33—C34 | −101.77 (18) |
C9—N3—C12—C13 | −92.87 (19) | N6—N7—C33—C34 | 72.54 (17) |
C14—N4—C13—O3 | 3.8 (2) | C35—N8—C34—O7 | −1.8 (3) |
C14—N4—C13—C12 | −175.58 (14) | C35—N8—C34—C33 | 179.52 (15) |
N3—C12—C13—O3 | 26.5 (2) | N7—C33—C34—O7 | 44.81 (19) |
N3—C12—C13—N4 | −154.08 (14) | N7—C33—C34—N8 | −136.44 (14) |
C13—N4—C14—C15 | −171.18 (14) | C34—N8—C35—C36 | −132.81 (17) |
N4—C14—C15—C20 | 169.04 (15) | N8—C35—C36—C41 | 119.73 (19) |
N4—C14—C15—C16 | −13.3 (2) | N8—C35—C36—C37 | −61.8 (2) |
C20—C15—C16—C17 | −1.1 (3) | C41—C36—C37—C38 | 0.2 (3) |
C14—C15—C16—C17 | −178.74 (16) | C35—C36—C37—C38 | −178.29 (16) |
C21—O4—C17—C18 | 169.25 (18) | C42—O8—C38—C37 | 7.5 (3) |
C21—O4—C17—C16 | −10.9 (3) | C42—O8—C38—C39 | −173.53 (18) |
C15—C16—C17—O4 | −177.66 (16) | C36—C37—C38—O8 | −179.58 (16) |
C15—C16—C17—C18 | 2.1 (3) | C36—C37—C38—C39 | 1.5 (3) |
O4—C17—C18—C19 | 178.50 (17) | O8—C38—C39—C40 | 179.12 (18) |
C16—C17—C18—C19 | −1.3 (3) | C37—C38—C39—C40 | −1.9 (3) |
C17—C18—C19—C20 | −0.5 (3) | C38—C39—C40—C41 | 0.6 (3) |
C18—C19—C20—C15 | 1.5 (3) | C37—C36—C41—C40 | −1.4 (3) |
C16—C15—C20—C19 | −0.7 (3) | C35—C36—C41—C40 | 176.98 (18) |
C14—C15—C20—C19 | 177.06 (16) | C39—C40—C41—C36 | 1.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4N···O7i | 0.88 | 2.12 | 2.9511 (17) | 158 |
N8—H8N···O3ii | 0.88 | 2.02 | 2.8928 (18) | 171 |
C10—H10C···O6iii | 0.98 | 2.45 | 3.349 (2) | 152 |
C12—H12A···O7i | 0.99 | 2.56 | 3.2099 (19) | 123 |
C14—H14A···N6ii | 0.99 | 2.58 | 3.556 (2) | 168 |
C16—H16···O7i | 0.95 | 2.43 | 3.369 (2) | 172 |
C25—H25···O4iv | 0.95 | 2.47 | 3.365 (2) | 156 |
C31—H31C···O2v | 0.98 | 2.49 | 3.203 (2) | 129 |
C33—H33A···O3ii | 0.99 | 2.46 | 3.320 (2) | 145 |
C33—H33B···O5vi | 0.99 | 2.45 | 3.352 (2) | 151 |
C40—H40···O2 | 0.95 | 2.59 | 3.367 (3) | 139 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, y+1/2, −z+3/2; (iv) x−1, y, z+1; (v) −x+1, y−1/2, −z+3/2; (vi) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C21H22N4O4S |
Mr | 426.49 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.6541 (1), 25.8809 (3), 18.3892 (2) |
β (°) | 92.208 (1) |
V (Å3) | 4115.68 (8) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.14 × 0.12 × 0.02 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.796, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 70993, 7975, 6621 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.098, 1.02 |
No. of reflections | 7975 |
No. of parameters | 547 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.37 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4N···O7i | 0.88 | 2.12 | 2.9511 (17) | 157.9 |
N8—H8N···O3ii | 0.88 | 2.02 | 2.8928 (18) | 171 |
C10—H10C···O6iii | 0.98 | 2.45 | 3.349 (2) | 152 |
C12—H12A···O7i | 0.99 | 2.56 | 3.2099 (19) | 123 |
C14—H14A···N6ii | 0.99 | 2.58 | 3.556 (2) | 168 |
C16—H16···O7i | 0.95 | 2.43 | 3.369 (2) | 172 |
C25—H25···O4iv | 0.95 | 2.47 | 3.365 (2) | 156 |
C31—H31C···O2v | 0.98 | 2.49 | 3.203 (2) | 129 |
C33—H33A···O3ii | 0.99 | 2.46 | 3.320 (2) | 145 |
C33—H33B···O5vi | 0.99 | 2.45 | 3.352 (2) | 151 |
C40—H40···O2 | 0.95 | 2.59 | 3.367 (3) | 139 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, y+1/2, −z+3/2; (iv) x−1, y, z+1; (v) −x+1, y−1/2, −z+3/2; (vi) x, −y+1/2, z−1/2. |
Acknowledgements
The authors are grateful to the Higher Education Commission, Pakistan, and the Institute of Chemistry, University of the Punjab, Lahore, Pakistan, for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
1,2-Benzothiazines are the core nuclei for their potent anti-inflammatory and analgesic drugs, known as oxicams (Turck et al., 1996; Lombardino et al., 1973; Zinnes et al., 1973). On the other hand, celecoxib, a pyrazole compound is an anti-inflammatory drug and a selective inhibitor of cox-2 enzyme (Silverstein et al., 2000). These structural and bioactivity features have led us to the synthesis of new carboxamides based on pyrazolobenzothiazines, which are structural hybrids of both of these medicinally important heterocycles (Ahmad et al., 2010a; 2010b, 2012). We report the synthesis and crystal structure of the title compound in this article.
The asymmetric unit of the title compound contains two independent conformers (Fig. 1). In both molecules, the heterocyclic thiazine rings adopt S-envelope conformations with atoms S1 and S2 displaced by 0.621 (2) and 0.697 (2) Å, respectively, from the mean planes formed by the remaining ring atoms (rmsd 0.0469 and 0.0608 Å, respectively). In both molecules, the atoms N1–N3/C1/C6–C9 and N5–N6/C22/C27–C30 of the thiazine and pyrrazole rings are individually close to coplanar (rmsd 0.0392 and 0.0548 Å) and form dihedral angles 14.01 (7) and 15.69 (8)° with the mean-planes of the benzene rings (C1–C6) and (C22–C27), respectively. The N-methylacetamide groups (O3/N4/C12–C14) and (O7/N8/C33–C35)) are individually almost planar (rmsd 0.0229 and 0.0047 Å, respectively) and their mean-planes are oriented at drastically different angles, 8.67 (10) and 54.49 (6)°, with respect to the benzene rings (C15–C20) and (C36–C41), respectively. The conformational differences in the two molecules are more pronounced from a comparison of torsion angles involving the N-methylacetamide chain connecting the methoxy benzene and pyrrazole rings, e.g., in one molecule the torsion angles, N2/N3–C12/C13, N3/C12–C13/N4, C12/C13–N4/C14, C13/N4–C14/C15 and N4/C14–C15/C16 are: 82.23 (17), -154.08 (14), -175.58 (14), -171.18 (14) and -13.3 (2)°, respectively. The corresponnding torsion angles in the second molecule are: 72.54 (17), -136.44 (14), 179.52 (15), -132.81 (17) and -61.8 (2)°, respectively. The bond distances and angles in both molecules of the title compound agree very well with the corresponding bond distances and angles reported in closely related compounds (Ahmad et al., 2010b; Ahmad et al., 2011a; Ahmad et al., 2011b).
The crystal structure features intermolecular hydrogen bonding interactions N4—H4N···O7 and N8—H8N···O3 resulting in chains of molecules extended along [100] (Fig. 2 & Tab. 1). The crystal structure is further consolidated by weak C—H···O hydrogen bonds, which result in a 3-D network (Fig. 3 & Tab. 1).
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