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N′-(2-Chlorobenzylidene)-2-(3,4-dimethyl-5,5-dioxo-2H,4H-pyrazolo[4,3-c][1,2]benzothiazin-2-yl)acetohydrazide
aInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, cDepartment of Chemistry, University of Baluchistan, Quetta 6700, Pakistan, bApplied Chemistry Research Centre, PCSIR Laboratories Complex, Lahore 54600, Pakistan, dDepartment of Chemistry, Gomal University, Dera Ismail Khan, Pakistan, and eDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: drhamidlatif@yahoo.com
The 20H18ClN5O3S, contains two independent molecules with significantly different conformations of the heterocyclic thiazine rings. In both molecules, the thiazine rings adopt half-chair conformations, with the S atoms displaced by 0.382 (3) and 0.533 (3) Å and N atoms −0.351 and −0.275 Å, respectively, from the planes formed by the remaining ring atoms. The is stabilized by weak intermolecular N—H⋯O and C—H⋯O interactions.
of the title compound, CRelated literature
For related structures, see: Ahmad et al. (2008, 2009
, 2011
); Siddiqui et al. (2008
). For puckering parameters, see: Cremer & Pople (1975
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997
); data reduction: SCALEPACK (Otwinowski & Minor, 1997
); 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
https://doi.org/10.1107/S160053681005227X/jh2243sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681005227X/jh2243Isup2.hkl
A mixture of 2-(3,4-dimethyl-5,5-dioxidopyrazolo[4,3-c][1,2]benzothiazin- 2(4H)-yl)acetohydrazide (1.0 g, 3.12 mmol) and 2-chlorobenzaldehyde (0.44 g, 3.12 mmol) were dissolved in ethanol (50 ml) followed by the addition of 2 drops of glacial acetic acid. The mixture was subjected to reflux for 4 - 5 h. The completion of reaction was monitored with the help of thin layer
(TLC). The precipitates formed were collected and washed with methanol (yield = 77%). The crystals of (I) suitable for crystallographic analysis were grown from its solution in dimethylamide at room temperature by slow evaporation.All the H atoms were discernible in the difference
However, they were positioned at the idealized positions and refined by the riding-model approximation using constraints: N—H = 0.88 Å, C—H = 0.98, 0.99 and 0.95 Å for methyl, methylene and aryl H-atoms, respectively, and Uiso(H) = 1.2Ueq(parent atoms). The methyl groups were allowed to rotate about their axes during the refinement.In continuation to our research exploring potential biologically active derivatives of benzothiazines (Ahmad et al., 2008; 2009), we have devised the fusion of the pyrazole moiety with 1,2-benzothiazine nucleus in an attempt to synthesize novel bioactive molecules. In this paper, we report the synthesis and
of the title compound, (I).In the structure of the title compound, there are two independent molecules (molecule a and molecule b) in an θ = 60.0 (4) and 63.4 (2)° and φ = 27.8 (3) and 20.0 (2)°, respectively. Similar conformations of the corresponding rings have been reported in some closely related molecules (Siddiqui et al., 2008; Ahmad et al., 2011).
with significantly different conformations of the heterocyclic thiazine rings (Figs. 1 and 2). In both molecules, the thiazine rings adopt half-chair conformations. In molecule a, S1 and N1 atoms are displaced by 0.382 (3) and -0.351 (3) Å, respectively, from the plane formed by the remaining ring atoms(C5–C8). In molecule b, S2 and N6 atoms are displaced by 0.533 (3) and -0.275 (3) Å, respectively, from the plane formed by the remaining ring atoms(C25–C28). The methyl groups attached to N1 and N6 are displaced by significantly different distances from the basal planes of the thiazine rings in the two molecules; 1.802 (4) and 1.694 (4) Å, respectively. The pertinent puckering parameters (Cremer & Pople, 1975) in molecules a and b are: Q = 0.475 (2) and 0.532 (4) Å,The mean-planes defined by the pyrazolo and benzene rings of the benzothiazin fragment are inclined with respt to each other at 12.55 (7) and 18.04 (8)°, in the molecules a and b, respectively. The chlorophenyl-methylidene-acetohydrazide moieties in the two molecules display identical conformation. In the molecules labeled as a, intermolecular hydrogen bonds N4—H04···O3 result in the formation of dimmers and C18—H18···O1 link the molecules into chains. Similarly, the molecules b also exhibit intermolecular hydrogen bonds N9—H09···O6 resulting in the formation of dimmers while C38—H38···O4 link the molecules into chains. The molecules a and b are connected via C29—H29B···O2 hydrogen bonds further stabilizing the
(Tab. 1).For related structures, see: Ahmad et al. (2008, 2009, 2011); Siddiqui et al. (2008). For puckering parameters, see: Cremer & Pople (1975).
Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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).C20H18ClN5O3S | Z = 4 |
Mr = 443.90 | F(000) = 920 |
Triclinic, P1 | Dx = 1.455 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4881 (2) Å | Cell parameters from 8973 reflections |
b = 12.7518 (3) Å | θ = 1.0–27.5° |
c = 15.5690 (4) Å | µ = 0.33 mm−1 |
α = 71.2778 (11)° | T = 173 K |
β = 78.6837 (13)° | Block, colorless |
γ = 70.4911 (12)° | 0.20 × 0.18 × 0.16 mm |
V = 2025.92 (8) Å3 |
Nonius KappaCCD diffractometer | 7106 independent reflections |
Radiation source: fine-focus sealed tube | 5649 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω and φ scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −13→13 |
Tmin = 0.938, Tmax = 0.950 | k = −15→15 |
13799 measured reflections | l = −18→18 |
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: difference Fourier map |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.760P] where P = (Fo2 + 2Fc2)/3 |
7106 reflections | (Δ/σ)max = 0.001 |
545 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C20H18ClN5O3S | γ = 70.4911 (12)° |
Mr = 443.90 | V = 2025.92 (8) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.4881 (2) Å | Mo Kα radiation |
b = 12.7518 (3) Å | µ = 0.33 mm−1 |
c = 15.5690 (4) Å | T = 173 K |
α = 71.2778 (11)° | 0.20 × 0.18 × 0.16 mm |
β = 78.6837 (13)° |
Nonius KappaCCD diffractometer | 7106 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 5649 reflections with I > 2σ(I) |
Tmin = 0.938, Tmax = 0.950 | Rint = 0.024 |
13799 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.25 e Å−3 |
7106 reflections | Δρmin = −0.39 e Å−3 |
545 parameters |
Experimental. Colorless crystals; mp 482 - 484 K. IR (KBr) cm-1: 3478, 1699, 1595, 1340, 1155. 1H-NMR (DMSO– d6) (400 MHz) δ 2.32 (3H, s, CCH3), 2.98 (3H, s, NCH3), 5.52 (2H, s, NCH2), 7.63–7.69 (2H, m, ArH), 7.76–7.80 (2H, q, J = 17.9, 7.6 Hz, ArH), 7.86 (1H, d, J = 7.80 Hz, ArH), 7.93 (1H, d, J = 7.7 Hz, ArH), 8.08 (1H, d, J = 8.2 Hz, ArH), 8.16 (1H, d, J = 8.0 Hz, ArH), 8.46 (1H, s, N═CH), 12.09 (1H, br s, NH). 13C NMR: 8.5, 38.9, 51.3, 121.4, 122.4, 123.1, 124.6, 124.7, 124.9, 126.2, 126.4, 127.5, 127.7, 127.8, 128.1, 130.6, 132.9, 134.2, 136.2, 136.8, 166.3. MS m/z: 444.0(M+). |
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 | ||
Cl1 | 0.25790 (5) | 0.47702 (5) | −0.33819 (4) | 0.03347 (14) | |
Cl2 | −0.26345 (5) | −0.48073 (5) | 0.84350 (4) | 0.03564 (15) | |
S1 | −0.50025 (5) | 0.25138 (5) | 0.37138 (3) | 0.03121 (15) | |
S2 | 0.50831 (4) | −0.18110 (4) | 0.15070 (3) | 0.02402 (13) | |
O1 | −0.61045 (14) | 0.22302 (16) | 0.41864 (11) | 0.0472 (4) | |
O2 | −0.48908 (16) | 0.36345 (13) | 0.35969 (11) | 0.0462 (4) | |
O3 | −0.11061 (14) | 0.42389 (13) | 0.08697 (10) | 0.0364 (4) | |
O4 | 0.61488 (12) | −0.22162 (13) | 0.09197 (10) | 0.0330 (3) | |
O5 | 0.50899 (13) | −0.10151 (12) | 0.19769 (10) | 0.0305 (3) | |
O6 | 0.10093 (14) | −0.41879 (13) | 0.41403 (10) | 0.0336 (4) | |
N1 | −0.48174 (14) | 0.23141 (14) | 0.26951 (11) | 0.0256 (4) | |
N2 | −0.14910 (15) | 0.17558 (14) | 0.21567 (11) | 0.0257 (4) | |
N3 | −0.19344 (14) | 0.23215 (14) | 0.13286 (11) | 0.0235 (4) | |
N4 | 0.00120 (15) | 0.38951 (15) | −0.04161 (11) | 0.0271 (4) | |
H04 | 0.0281 | 0.4500 | −0.0526 | 0.033* | |
N5 | 0.03678 (15) | 0.32466 (14) | −0.10331 (11) | 0.0247 (4) | |
N6 | 0.47766 (14) | −0.29427 (14) | 0.22751 (11) | 0.0232 (4) | |
N7 | 0.15457 (14) | −0.16124 (14) | 0.29530 (11) | 0.0240 (4) | |
N8 | 0.19665 (14) | −0.23898 (14) | 0.37419 (11) | 0.0226 (4) | |
N9 | −0.00865 (15) | −0.38815 (15) | 0.54391 (11) | 0.0264 (4) | |
H09 | −0.0389 | −0.4461 | 0.5523 | 0.032* | |
N10 | −0.04085 (14) | −0.32727 (14) | 0.60840 (11) | 0.0235 (4) | |
C1 | −0.15139 (19) | 0.05007 (17) | 0.41734 (14) | 0.0271 (4) | |
H1 | −0.0729 | 0.0304 | 0.3834 | 0.033* | |
C2 | −0.1625 (2) | 0.00523 (19) | 0.51109 (14) | 0.0317 (5) | |
H2 | −0.0914 | −0.0450 | 0.5409 | 0.038* | |
C3 | −0.2761 (2) | 0.03255 (19) | 0.56234 (15) | 0.0339 (5) | |
H3 | −0.2822 | 0.0019 | 0.6268 | 0.041* | |
C4 | −0.3804 (2) | 0.10447 (18) | 0.51930 (14) | 0.0318 (5) | |
H4 | −0.4588 | 0.1226 | 0.5537 | 0.038* | |
C5 | −0.36949 (18) | 0.14994 (17) | 0.42513 (13) | 0.0259 (4) | |
C6 | −0.25467 (17) | 0.12395 (16) | 0.37233 (13) | 0.0234 (4) | |
C7 | −0.25122 (17) | 0.17367 (16) | 0.27358 (13) | 0.0214 (4) | |
C8 | −0.35875 (17) | 0.22887 (17) | 0.22753 (13) | 0.0226 (4) | |
C9 | −0.5213 (2) | 0.1342 (2) | 0.26466 (16) | 0.0358 (5) | |
H9A | −0.5154 | 0.1350 | 0.2008 | 0.043* | |
H9B | −0.6074 | 0.1426 | 0.2917 | 0.043* | |
H9C | −0.4674 | 0.0607 | 0.2983 | 0.043* | |
C10 | −0.31995 (17) | 0.26745 (17) | 0.13709 (13) | 0.0237 (4) | |
C11 | −0.3911 (2) | 0.3342 (2) | 0.05664 (14) | 0.0342 (5) | |
H11A | −0.4802 | 0.3497 | 0.0762 | 0.041* | |
H11B | −0.3686 | 0.2891 | 0.0122 | 0.041* | |
H11C | −0.3713 | 0.4076 | 0.0286 | 0.041* | |
C12 | −0.10719 (18) | 0.25138 (18) | 0.05219 (13) | 0.0264 (4) | |
H12A | −0.1446 | 0.2551 | −0.0012 | 0.032* | |
H12B | −0.0307 | 0.1852 | 0.0593 | 0.032* | |
C13 | −0.07352 (18) | 0.36260 (18) | 0.03483 (13) | 0.0256 (4) | |
C14 | 0.10219 (17) | 0.36567 (18) | −0.17459 (13) | 0.0257 (4) | |
H14 | 0.1229 | 0.4339 | −0.1801 | 0.031* | |
C15 | 0.14552 (17) | 0.30888 (17) | −0.24767 (13) | 0.0239 (4) | |
C16 | 0.21805 (17) | 0.35203 (18) | −0.32574 (14) | 0.0262 (4) | |
C17 | 0.25943 (19) | 0.2978 (2) | −0.39504 (15) | 0.0339 (5) | |
H17 | 0.3080 | 0.3289 | −0.4479 | 0.041* | |
C18 | 0.2294 (2) | 0.1983 (2) | −0.38658 (15) | 0.0375 (5) | |
H18 | 0.2584 | 0.1601 | −0.4334 | 0.045* | |
C19 | 0.1572 (2) | 0.1542 (2) | −0.31005 (15) | 0.0355 (5) | |
H19 | 0.1366 | 0.0859 | −0.3044 | 0.043* | |
C20 | 0.11527 (19) | 0.20949 (19) | −0.24212 (14) | 0.0300 (5) | |
H20 | 0.0646 | 0.1793 | −0.1904 | 0.036* | |
C21 | 0.15474 (18) | −0.05797 (17) | 0.08887 (14) | 0.0264 (4) | |
H21 | 0.0741 | −0.0537 | 0.1200 | 0.032* | |
C22 | 0.16845 (19) | −0.00809 (18) | −0.00436 (14) | 0.0301 (5) | |
H22 | 0.0967 | 0.0316 | −0.0362 | 0.036* | |
C23 | 0.28514 (19) | −0.01504 (18) | −0.05205 (14) | 0.0300 (5) | |
H23 | 0.2931 | 0.0184 | −0.1161 | 0.036* | |
C24 | 0.38999 (19) | −0.07118 (17) | −0.00546 (13) | 0.0262 (4) | |
H24 | 0.4703 | −0.0775 | −0.0375 | 0.031* | |
C25 | 0.37652 (17) | −0.11814 (16) | 0.08832 (13) | 0.0223 (4) | |
C26 | 0.25873 (17) | −0.11432 (16) | 0.13714 (13) | 0.0227 (4) | |
C27 | 0.25414 (17) | −0.17512 (16) | 0.23418 (13) | 0.0215 (4) | |
C28 | 0.35753 (17) | −0.25970 (17) | 0.27479 (13) | 0.0223 (4) | |
C29 | 0.5033 (2) | −0.39860 (18) | 0.19582 (15) | 0.0322 (5) | |
H29A | 0.4899 | −0.4631 | 0.2476 | 0.039* | |
H29B | 0.5895 | −0.4193 | 0.1689 | 0.039* | |
H29C | 0.4473 | −0.3823 | 0.1500 | 0.039* | |
C30 | 0.31849 (17) | −0.30032 (16) | 0.36504 (13) | 0.0225 (4) | |
C31 | 0.38679 (19) | −0.39090 (18) | 0.44001 (14) | 0.0311 (5) | |
H31A | 0.4756 | −0.4133 | 0.4194 | 0.037* | |
H31B | 0.3560 | −0.4587 | 0.4575 | 0.037* | |
H31C | 0.3739 | −0.3605 | 0.4926 | 0.037* | |
C32 | 0.11075 (18) | −0.25551 (17) | 0.45531 (13) | 0.0252 (4) | |
H32A | 0.0379 | −0.1858 | 0.4501 | 0.030* | |
H32B | 0.1516 | −0.2658 | 0.5091 | 0.030* | |
C33 | 0.06770 (17) | −0.36078 (17) | 0.46880 (13) | 0.0242 (4) | |
C34 | −0.10689 (17) | −0.36873 (17) | 0.67866 (13) | 0.0245 (4) | |
H34 | −0.1301 | −0.4350 | 0.6822 | 0.029* | |
C35 | −0.14732 (17) | −0.31510 (17) | 0.75402 (13) | 0.0227 (4) | |
C36 | −0.21890 (17) | −0.35873 (18) | 0.83283 (14) | 0.0262 (4) | |
C37 | −0.25619 (18) | −0.3068 (2) | 0.90357 (14) | 0.0316 (5) | |
H37 | −0.3026 | −0.3390 | 0.9573 | 0.038* | |
C38 | −0.22519 (19) | −0.2081 (2) | 0.89518 (15) | 0.0339 (5) | |
H38 | −0.2522 | −0.1710 | 0.9426 | 0.041* | |
C39 | −0.15498 (19) | −0.16290 (19) | 0.81798 (15) | 0.0318 (5) | |
H39 | −0.1339 | −0.0949 | 0.8125 | 0.038* | |
C40 | −0.11553 (18) | −0.21659 (18) | 0.74900 (14) | 0.0272 (4) | |
H40 | −0.0656 | −0.1859 | 0.6969 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0357 (3) | 0.0364 (3) | 0.0268 (3) | −0.0187 (2) | 0.0064 (2) | −0.0037 (2) |
Cl2 | 0.0393 (3) | 0.0396 (3) | 0.0294 (3) | −0.0234 (2) | 0.0074 (2) | −0.0053 (2) |
S1 | 0.0320 (3) | 0.0300 (3) | 0.0205 (3) | −0.0019 (2) | 0.0051 (2) | −0.0043 (2) |
S2 | 0.0226 (2) | 0.0284 (3) | 0.0189 (3) | −0.0114 (2) | 0.00193 (19) | −0.0018 (2) |
O1 | 0.0310 (8) | 0.0627 (11) | 0.0270 (9) | −0.0042 (8) | 0.0108 (7) | −0.0027 (8) |
O2 | 0.0704 (11) | 0.0260 (8) | 0.0323 (9) | −0.0015 (8) | −0.0032 (8) | −0.0091 (7) |
O3 | 0.0515 (9) | 0.0381 (9) | 0.0277 (8) | −0.0269 (7) | 0.0168 (7) | −0.0175 (7) |
O4 | 0.0253 (7) | 0.0407 (9) | 0.0231 (8) | −0.0080 (6) | 0.0070 (6) | −0.0029 (7) |
O5 | 0.0337 (8) | 0.0335 (8) | 0.0287 (8) | −0.0181 (6) | −0.0019 (6) | −0.0066 (7) |
O6 | 0.0458 (9) | 0.0357 (8) | 0.0272 (8) | −0.0248 (7) | 0.0162 (7) | −0.0172 (7) |
N1 | 0.0224 (8) | 0.0312 (9) | 0.0190 (9) | −0.0097 (7) | 0.0034 (7) | −0.0027 (7) |
N2 | 0.0277 (9) | 0.0294 (9) | 0.0206 (9) | −0.0130 (7) | 0.0013 (7) | −0.0048 (7) |
N3 | 0.0270 (8) | 0.0282 (9) | 0.0162 (8) | −0.0137 (7) | 0.0040 (7) | −0.0049 (7) |
N4 | 0.0356 (9) | 0.0314 (10) | 0.0209 (9) | −0.0203 (8) | 0.0084 (7) | −0.0114 (8) |
N5 | 0.0273 (8) | 0.0280 (9) | 0.0207 (9) | −0.0103 (7) | 0.0029 (7) | −0.0100 (7) |
N6 | 0.0234 (8) | 0.0243 (9) | 0.0179 (8) | −0.0083 (7) | 0.0015 (7) | −0.0014 (7) |
N7 | 0.0257 (8) | 0.0247 (9) | 0.0198 (9) | −0.0113 (7) | 0.0006 (7) | −0.0012 (7) |
N8 | 0.0269 (8) | 0.0238 (9) | 0.0172 (8) | −0.0128 (7) | 0.0039 (7) | −0.0039 (7) |
N9 | 0.0338 (9) | 0.0304 (9) | 0.0218 (9) | −0.0191 (8) | 0.0094 (7) | −0.0133 (8) |
N10 | 0.0256 (8) | 0.0270 (9) | 0.0196 (9) | −0.0102 (7) | 0.0037 (7) | −0.0094 (7) |
C1 | 0.0289 (10) | 0.0294 (11) | 0.0258 (11) | −0.0132 (9) | −0.0026 (8) | −0.0064 (9) |
C2 | 0.0347 (11) | 0.0344 (12) | 0.0267 (12) | −0.0134 (9) | −0.0100 (9) | −0.0016 (10) |
C3 | 0.0451 (13) | 0.0373 (13) | 0.0197 (11) | −0.0202 (10) | −0.0026 (9) | −0.0003 (9) |
C4 | 0.0370 (12) | 0.0323 (12) | 0.0217 (11) | −0.0115 (9) | 0.0030 (9) | −0.0034 (9) |
C5 | 0.0313 (11) | 0.0246 (11) | 0.0202 (11) | −0.0106 (8) | 0.0017 (8) | −0.0038 (9) |
C6 | 0.0289 (10) | 0.0221 (10) | 0.0218 (10) | −0.0132 (8) | −0.0003 (8) | −0.0050 (8) |
C7 | 0.0246 (10) | 0.0222 (10) | 0.0187 (10) | −0.0110 (8) | 0.0019 (8) | −0.0055 (8) |
C8 | 0.0229 (10) | 0.0250 (10) | 0.0197 (10) | −0.0096 (8) | 0.0026 (8) | −0.0060 (8) |
C9 | 0.0299 (11) | 0.0446 (14) | 0.0354 (13) | −0.0199 (10) | 0.0006 (10) | −0.0073 (11) |
C10 | 0.0267 (10) | 0.0251 (10) | 0.0205 (10) | −0.0115 (8) | 0.0010 (8) | −0.0060 (8) |
C11 | 0.0361 (12) | 0.0405 (13) | 0.0215 (11) | −0.0138 (10) | −0.0023 (9) | −0.0001 (10) |
C12 | 0.0308 (10) | 0.0299 (11) | 0.0210 (11) | −0.0167 (9) | 0.0093 (8) | −0.0093 (9) |
C13 | 0.0277 (10) | 0.0305 (11) | 0.0202 (10) | −0.0140 (9) | 0.0048 (8) | −0.0074 (9) |
C14 | 0.0263 (10) | 0.0313 (11) | 0.0216 (11) | −0.0148 (9) | 0.0048 (8) | −0.0079 (9) |
C15 | 0.0240 (10) | 0.0287 (11) | 0.0180 (10) | −0.0081 (8) | −0.0003 (8) | −0.0055 (8) |
C16 | 0.0241 (10) | 0.0322 (11) | 0.0208 (10) | −0.0097 (8) | 0.0006 (8) | −0.0052 (9) |
C17 | 0.0326 (11) | 0.0463 (14) | 0.0213 (11) | −0.0135 (10) | 0.0074 (9) | −0.0109 (10) |
C18 | 0.0384 (12) | 0.0500 (15) | 0.0286 (12) | −0.0148 (11) | 0.0080 (10) | −0.0218 (11) |
C19 | 0.0415 (12) | 0.0390 (13) | 0.0314 (12) | −0.0148 (10) | 0.0017 (10) | −0.0169 (10) |
C20 | 0.0334 (11) | 0.0360 (12) | 0.0226 (11) | −0.0170 (9) | 0.0061 (9) | −0.0088 (9) |
C21 | 0.0264 (10) | 0.0281 (11) | 0.0258 (11) | −0.0138 (8) | −0.0021 (8) | −0.0033 (9) |
C22 | 0.0327 (11) | 0.0336 (12) | 0.0246 (11) | −0.0143 (9) | −0.0088 (9) | −0.0005 (9) |
C23 | 0.0386 (12) | 0.0335 (12) | 0.0187 (10) | −0.0171 (9) | −0.0024 (9) | −0.0018 (9) |
C24 | 0.0315 (10) | 0.0271 (11) | 0.0200 (10) | −0.0136 (9) | 0.0012 (8) | −0.0033 (9) |
C25 | 0.0266 (10) | 0.0212 (10) | 0.0189 (10) | −0.0103 (8) | −0.0004 (8) | −0.0027 (8) |
C26 | 0.0281 (10) | 0.0219 (10) | 0.0192 (10) | −0.0125 (8) | 0.0012 (8) | −0.0037 (8) |
C27 | 0.0232 (9) | 0.0227 (10) | 0.0189 (10) | −0.0116 (8) | 0.0013 (8) | −0.0030 (8) |
C28 | 0.0224 (9) | 0.0261 (10) | 0.0178 (10) | −0.0111 (8) | 0.0015 (8) | −0.0031 (8) |
C29 | 0.0386 (12) | 0.0261 (11) | 0.0296 (12) | −0.0097 (9) | 0.0006 (9) | −0.0066 (9) |
C30 | 0.0250 (10) | 0.0239 (10) | 0.0199 (10) | −0.0115 (8) | 0.0016 (8) | −0.0057 (8) |
C31 | 0.0331 (11) | 0.0323 (12) | 0.0201 (11) | −0.0096 (9) | 0.0011 (9) | 0.0008 (9) |
C32 | 0.0301 (10) | 0.0269 (11) | 0.0197 (10) | −0.0145 (8) | 0.0084 (8) | −0.0080 (9) |
C33 | 0.0255 (10) | 0.0277 (11) | 0.0201 (10) | −0.0122 (8) | 0.0044 (8) | −0.0066 (9) |
C34 | 0.0267 (10) | 0.0280 (11) | 0.0217 (10) | −0.0141 (8) | 0.0042 (8) | −0.0083 (9) |
C35 | 0.0208 (9) | 0.0285 (11) | 0.0174 (10) | −0.0079 (8) | 0.0012 (8) | −0.0055 (8) |
C36 | 0.0222 (10) | 0.0335 (12) | 0.0219 (11) | −0.0097 (8) | 0.0003 (8) | −0.0062 (9) |
C37 | 0.0269 (10) | 0.0478 (14) | 0.0185 (11) | −0.0136 (10) | 0.0051 (8) | −0.0086 (10) |
C38 | 0.0294 (11) | 0.0512 (14) | 0.0263 (12) | −0.0114 (10) | 0.0033 (9) | −0.0215 (11) |
C39 | 0.0320 (11) | 0.0368 (12) | 0.0314 (12) | −0.0124 (9) | 0.0006 (9) | −0.0155 (10) |
C40 | 0.0273 (10) | 0.0329 (11) | 0.0234 (11) | −0.0131 (9) | 0.0030 (8) | −0.0094 (9) |
Cl1—C16 | 1.744 (2) | C11—H11C | 0.9800 |
Cl2—C36 | 1.744 (2) | C12—C13 | 1.521 (3) |
S1—O2 | 1.4276 (17) | C12—H12A | 0.9900 |
S1—O1 | 1.4298 (17) | C12—H12B | 0.9900 |
S1—N1 | 1.6481 (17) | C14—C15 | 1.460 (3) |
S1—C5 | 1.769 (2) | C14—H14 | 0.9500 |
S2—O4 | 1.4295 (14) | C15—C20 | 1.395 (3) |
S2—O5 | 1.4315 (15) | C15—C16 | 1.398 (3) |
S2—N6 | 1.6440 (16) | C16—C17 | 1.388 (3) |
S2—C25 | 1.7734 (19) | C17—C18 | 1.384 (3) |
O3—C13 | 1.225 (2) | C17—H17 | 0.9500 |
O6—C33 | 1.228 (2) | C18—C19 | 1.384 (3) |
N1—C8 | 1.430 (2) | C18—H18 | 0.9500 |
N1—C9 | 1.483 (3) | C19—C20 | 1.378 (3) |
N2—C7 | 1.334 (2) | C19—H19 | 0.9500 |
N2—N3 | 1.363 (2) | C20—H20 | 0.9500 |
N3—C10 | 1.365 (2) | C21—C22 | 1.386 (3) |
N3—C12 | 1.448 (2) | C21—C26 | 1.393 (3) |
N4—C13 | 1.343 (2) | C21—H21 | 0.9500 |
N4—N5 | 1.380 (2) | C22—C23 | 1.389 (3) |
N4—H04 | 0.8800 | C22—H22 | 0.9500 |
N5—C14 | 1.278 (2) | C23—C24 | 1.387 (3) |
N6—C28 | 1.430 (2) | C23—H23 | 0.9500 |
N6—C29 | 1.484 (3) | C24—C25 | 1.388 (3) |
N7—C27 | 1.338 (2) | C24—H24 | 0.9500 |
N7—N8 | 1.362 (2) | C25—C26 | 1.410 (3) |
N8—C30 | 1.361 (2) | C26—C27 | 1.460 (3) |
N8—C32 | 1.446 (2) | C27—C28 | 1.405 (3) |
N9—C33 | 1.341 (2) | C28—C30 | 1.373 (3) |
N9—N10 | 1.382 (2) | C29—H29A | 0.9800 |
N9—H09 | 0.8800 | C29—H29B | 0.9800 |
N10—C34 | 1.274 (2) | C29—H29C | 0.9800 |
C1—C2 | 1.383 (3) | C30—C31 | 1.483 (3) |
C1—C6 | 1.394 (3) | C31—H31A | 0.9800 |
C1—H1 | 0.9500 | C31—H31B | 0.9800 |
C2—C3 | 1.388 (3) | C31—H31C | 0.9800 |
C2—H2 | 0.9500 | C32—C33 | 1.521 (3) |
C3—C4 | 1.383 (3) | C32—H32A | 0.9900 |
C3—H3 | 0.9500 | C32—H32B | 0.9900 |
C4—C5 | 1.390 (3) | C34—C35 | 1.466 (3) |
C4—H4 | 0.9500 | C34—H34 | 0.9500 |
C5—C6 | 1.408 (3) | C35—C40 | 1.396 (3) |
C6—C7 | 1.461 (3) | C35—C36 | 1.401 (3) |
C7—C8 | 1.407 (3) | C36—C37 | 1.388 (3) |
C8—C10 | 1.371 (3) | C37—C38 | 1.381 (3) |
C9—H9A | 0.9800 | C37—H37 | 0.9500 |
C9—H9B | 0.9800 | C38—C39 | 1.383 (3) |
C9—H9C | 0.9800 | C38—H38 | 0.9500 |
C10—C11 | 1.488 (3) | C39—C40 | 1.379 (3) |
C11—H11A | 0.9800 | C39—H39 | 0.9500 |
C11—H11B | 0.9800 | C40—H40 | 0.9500 |
O2—S1—O1 | 119.67 (11) | C20—C15—C14 | 120.97 (18) |
O2—S1—N1 | 107.75 (9) | C16—C15—C14 | 121.48 (18) |
O1—S1—N1 | 107.62 (10) | C17—C16—C15 | 121.44 (19) |
O2—S1—C5 | 106.56 (10) | C17—C16—Cl1 | 118.40 (16) |
O1—S1—C5 | 109.55 (10) | C15—C16—Cl1 | 120.16 (15) |
N1—S1—C5 | 104.71 (9) | C18—C17—C16 | 119.5 (2) |
O4—S2—O5 | 119.73 (9) | C18—C17—H17 | 120.3 |
O4—S2—N6 | 108.16 (9) | C16—C17—H17 | 120.3 |
O5—S2—N6 | 107.65 (8) | C17—C18—C19 | 120.1 (2) |
O4—S2—C25 | 109.04 (9) | C17—C18—H18 | 119.9 |
O5—S2—C25 | 107.54 (9) | C19—C18—H18 | 119.9 |
N6—S2—C25 | 103.53 (8) | C20—C19—C18 | 120.0 (2) |
C8—N1—C9 | 113.18 (16) | C20—C19—H19 | 120.0 |
C8—N1—S1 | 110.51 (12) | C18—C19—H19 | 120.0 |
C9—N1—S1 | 115.83 (13) | C19—C20—C15 | 121.4 (2) |
C7—N2—N3 | 103.85 (15) | C19—C20—H20 | 119.3 |
N2—N3—C10 | 113.56 (15) | C15—C20—H20 | 119.3 |
N2—N3—C12 | 119.49 (15) | C22—C21—C26 | 120.25 (18) |
C10—N3—C12 | 126.94 (17) | C22—C21—H21 | 119.9 |
C13—N4—N5 | 121.66 (16) | C26—C21—H21 | 119.9 |
C13—N4—H04 | 119.2 | C21—C22—C23 | 121.22 (19) |
N5—N4—H04 | 119.2 | C21—C22—H22 | 119.4 |
C14—N5—N4 | 113.66 (16) | C23—C22—H22 | 119.4 |
C28—N6—C29 | 115.32 (15) | C24—C23—C22 | 119.52 (19) |
C28—N6—S2 | 109.81 (12) | C24—C23—H23 | 120.2 |
C29—N6—S2 | 115.80 (13) | C22—C23—H23 | 120.2 |
C27—N7—N8 | 103.62 (15) | C23—C24—C25 | 119.43 (19) |
C30—N8—N7 | 113.79 (15) | C23—C24—H24 | 120.3 |
C30—N8—C32 | 126.45 (17) | C25—C24—H24 | 120.3 |
N7—N8—C32 | 119.58 (15) | C24—C25—C26 | 121.56 (17) |
C33—N9—N10 | 121.36 (16) | C24—C25—S2 | 120.38 (15) |
C33—N9—H09 | 119.3 | C26—C25—S2 | 118.03 (14) |
N10—N9—H09 | 119.3 | C21—C26—C25 | 117.97 (17) |
C34—N10—N9 | 113.79 (16) | C21—C26—C27 | 124.23 (17) |
C2—C1—C6 | 120.39 (19) | C25—C26—C27 | 117.72 (17) |
C2—C1—H1 | 119.8 | N7—C27—C28 | 111.17 (16) |
C6—C1—H1 | 119.8 | N7—C27—C26 | 126.21 (17) |
C1—C2—C3 | 121.03 (19) | C28—C27—C26 | 122.61 (17) |
C1—C2—H2 | 119.5 | C30—C28—C27 | 106.59 (16) |
C3—C2—H2 | 119.5 | C30—C28—N6 | 128.76 (17) |
C4—C3—C2 | 119.8 (2) | C27—C28—N6 | 124.65 (17) |
C4—C3—H3 | 120.1 | N6—C29—H29A | 109.5 |
C2—C3—H3 | 120.1 | N6—C29—H29B | 109.5 |
C3—C4—C5 | 119.4 (2) | H29A—C29—H29B | 109.5 |
C3—C4—H4 | 120.3 | N6—C29—H29C | 109.5 |
C5—C4—H4 | 120.3 | H29A—C29—H29C | 109.5 |
C4—C5—C6 | 121.53 (19) | H29B—C29—H29C | 109.5 |
C4—C5—S1 | 119.17 (15) | N8—C30—C28 | 104.83 (16) |
C6—C5—S1 | 119.13 (15) | N8—C30—C31 | 124.68 (17) |
C1—C6—C5 | 117.93 (18) | C28—C30—C31 | 130.49 (17) |
C1—C6—C7 | 123.84 (18) | C30—C31—H31A | 109.5 |
C5—C6—C7 | 118.22 (17) | C30—C31—H31B | 109.5 |
N2—C7—C8 | 111.11 (16) | H31A—C31—H31B | 109.5 |
N2—C7—C6 | 125.81 (17) | C30—C31—H31C | 109.5 |
C8—C7—C6 | 123.06 (16) | H31A—C31—H31C | 109.5 |
C10—C8—C7 | 106.71 (16) | H31B—C31—H31C | 109.5 |
C10—C8—N1 | 128.69 (17) | N8—C32—C33 | 111.10 (15) |
C7—C8—N1 | 124.34 (17) | N8—C32—H32A | 109.4 |
N1—C9—H9A | 109.5 | C33—C32—H32A | 109.4 |
N1—C9—H9B | 109.5 | N8—C32—H32B | 109.4 |
H9A—C9—H9B | 109.5 | C33—C32—H32B | 109.4 |
N1—C9—H9C | 109.5 | H32A—C32—H32B | 108.0 |
H9A—C9—H9C | 109.5 | O6—C33—N9 | 121.04 (18) |
H9B—C9—H9C | 109.5 | O6—C33—C32 | 122.09 (17) |
N3—C10—C8 | 104.75 (17) | N9—C33—C32 | 116.87 (16) |
N3—C10—C11 | 124.02 (17) | N10—C34—C35 | 120.56 (18) |
C8—C10—C11 | 131.22 (18) | N10—C34—H34 | 119.7 |
C10—C11—H11A | 109.5 | C35—C34—H34 | 119.7 |
C10—C11—H11B | 109.5 | C40—C35—C36 | 117.36 (18) |
H11A—C11—H11B | 109.5 | C40—C35—C34 | 120.32 (18) |
C10—C11—H11C | 109.5 | C36—C35—C34 | 122.32 (18) |
H11A—C11—H11C | 109.5 | C37—C36—C35 | 121.51 (19) |
H11B—C11—H11C | 109.5 | C37—C36—Cl2 | 118.54 (16) |
N3—C12—C13 | 112.17 (16) | C35—C36—Cl2 | 119.96 (15) |
N3—C12—H12A | 109.2 | C38—C37—C36 | 119.40 (19) |
C13—C12—H12A | 109.2 | C38—C37—H37 | 120.3 |
N3—C12—H12B | 109.2 | C36—C37—H37 | 120.3 |
C13—C12—H12B | 109.2 | C37—C38—C39 | 120.28 (19) |
H12A—C12—H12B | 107.9 | C37—C38—H38 | 119.9 |
O3—C13—N4 | 121.57 (18) | C39—C38—H38 | 119.9 |
O3—C13—C12 | 122.80 (17) | C40—C39—C38 | 120.0 (2) |
N4—C13—C12 | 115.63 (17) | C40—C39—H39 | 120.0 |
N5—C14—C15 | 120.76 (18) | C38—C39—H39 | 120.0 |
N5—C14—H14 | 119.6 | C39—C40—C35 | 121.42 (19) |
C15—C14—H14 | 119.6 | C39—C40—H40 | 119.3 |
C20—C15—C16 | 117.54 (18) | C35—C40—H40 | 119.3 |
O2—S1—N1—C8 | 64.64 (15) | C20—C15—C16—Cl1 | 179.16 (15) |
O1—S1—N1—C8 | −165.04 (13) | C14—C15—C16—Cl1 | −0.5 (3) |
C5—S1—N1—C8 | −48.53 (15) | C15—C16—C17—C18 | −0.6 (3) |
O2—S1—N1—C9 | −164.98 (14) | Cl1—C16—C17—C18 | 179.75 (17) |
O1—S1—N1—C9 | −34.66 (17) | C16—C17—C18—C19 | 0.9 (3) |
C5—S1—N1—C9 | 81.85 (15) | C17—C18—C19—C20 | −0.1 (3) |
C7—N2—N3—C10 | 1.0 (2) | C18—C19—C20—C15 | −1.1 (3) |
C7—N2—N3—C12 | 179.57 (16) | C16—C15—C20—C19 | 1.3 (3) |
C13—N4—N5—C14 | 176.32 (19) | C14—C15—C20—C19 | −179.00 (19) |
O4—S2—N6—C28 | −167.43 (12) | C26—C21—C22—C23 | 1.4 (3) |
O5—S2—N6—C28 | 61.86 (14) | C21—C22—C23—C24 | −1.1 (3) |
C25—S2—N6—C28 | −51.83 (14) | C22—C23—C24—C25 | −0.9 (3) |
O4—S2—N6—C29 | −34.67 (16) | C23—C24—C25—C26 | 2.6 (3) |
O5—S2—N6—C29 | −165.37 (13) | C23—C24—C25—S2 | −175.41 (15) |
C25—S2—N6—C29 | 80.94 (15) | O4—S2—C25—C24 | −26.45 (19) |
C27—N7—N8—C30 | 0.4 (2) | O5—S2—C25—C24 | 104.80 (16) |
C27—N7—N8—C32 | −175.10 (15) | N6—S2—C25—C24 | −141.43 (16) |
C33—N9—N10—C34 | −175.35 (18) | O4—S2—C25—C26 | 155.45 (15) |
C6—C1—C2—C3 | 0.0 (3) | O5—S2—C25—C26 | −73.30 (16) |
C1—C2—C3—C4 | 0.8 (3) | N6—S2—C25—C26 | 40.48 (17) |
C2—C3—C4—C5 | −1.0 (3) | C22—C21—C26—C25 | 0.3 (3) |
C3—C4—C5—C6 | 0.4 (3) | C22—C21—C26—C27 | −176.28 (18) |
C3—C4—C5—S1 | −174.74 (16) | C24—C25—C26—C21 | −2.3 (3) |
O2—S1—C5—C4 | 95.97 (18) | S2—C25—C26—C21 | 175.79 (14) |
O1—S1—C5—C4 | −34.8 (2) | C24—C25—C26—C27 | 174.49 (17) |
N1—S1—C5—C4 | −150.01 (16) | S2—C25—C26—C27 | −7.4 (2) |
O2—S1—C5—C6 | −79.25 (17) | N8—N7—C27—C28 | −0.7 (2) |
O1—S1—C5—C6 | 149.94 (16) | N8—N7—C27—C26 | 178.13 (17) |
N1—S1—C5—C6 | 34.76 (18) | C21—C26—C27—N7 | −19.1 (3) |
C2—C1—C6—C5 | −0.6 (3) | C25—C26—C27—N7 | 164.35 (18) |
C2—C1—C6—C7 | −179.12 (18) | C21—C26—C27—C28 | 159.56 (19) |
C4—C5—C6—C1 | 0.4 (3) | C25—C26—C27—C28 | −17.0 (3) |
S1—C5—C6—C1 | 175.55 (14) | N7—C27—C28—C30 | 0.7 (2) |
C4—C5—C6—C7 | 179.03 (18) | C26—C27—C28—C30 | −178.12 (17) |
S1—C5—C6—C7 | −5.9 (2) | N7—C27—C28—N6 | −179.99 (16) |
N3—N2—C7—C8 | −0.2 (2) | C26—C27—C28—N6 | 1.2 (3) |
N3—N2—C7—C6 | −178.90 (17) | C29—N6—C28—C30 | 83.4 (2) |
C1—C6—C7—N2 | −14.4 (3) | S2—N6—C28—C30 | −143.56 (18) |
C5—C6—C7—N2 | 167.13 (18) | C29—N6—C28—C27 | −95.7 (2) |
C1—C6—C7—C8 | 167.05 (18) | S2—N6—C28—C27 | 37.3 (2) |
C5—C6—C7—C8 | −11.5 (3) | N7—N8—C30—C28 | 0.0 (2) |
N2—C7—C8—C10 | −0.7 (2) | C32—N8—C30—C28 | 175.16 (17) |
C6—C7—C8—C10 | 178.07 (17) | N7—N8—C30—C31 | −179.45 (17) |
N2—C7—C8—N1 | 173.85 (17) | C32—N8—C30—C31 | −4.3 (3) |
C6—C7—C8—N1 | −7.4 (3) | C27—C28—C30—N8 | −0.4 (2) |
C9—N1—C8—C10 | 82.0 (2) | N6—C28—C30—N8 | −179.69 (18) |
S1—N1—C8—C10 | −146.19 (18) | C27—C28—C30—C31 | 179.02 (19) |
C9—N1—C8—C7 | −91.3 (2) | N6—C28—C30—C31 | −0.2 (3) |
S1—N1—C8—C7 | 40.5 (2) | C30—N8—C32—C33 | −76.9 (2) |
N2—N3—C10—C8 | −1.5 (2) | N7—N8—C32—C33 | 97.98 (19) |
C12—N3—C10—C8 | −179.88 (17) | N10—N9—C33—O6 | 176.29 (17) |
N2—N3—C10—C11 | 177.98 (18) | N10—N9—C33—C32 | −3.5 (3) |
C12—N3—C10—C11 | −0.4 (3) | N8—C32—C33—O6 | −2.4 (3) |
C7—C8—C10—N3 | 1.2 (2) | N8—C32—C33—N9 | 177.41 (17) |
N1—C8—C10—N3 | −172.99 (18) | N9—N10—C34—C35 | 179.12 (16) |
C7—C8—C10—C11 | −178.1 (2) | N10—C34—C35—C40 | 1.0 (3) |
N1—C8—C10—C11 | 7.6 (4) | N10—C34—C35—C36 | −179.33 (19) |
N2—N3—C12—C13 | −87.3 (2) | C40—C35—C36—C37 | −0.5 (3) |
C10—N3—C12—C13 | 91.0 (2) | C34—C35—C36—C37 | 179.91 (18) |
N5—N4—C13—O3 | −175.86 (18) | C40—C35—C36—Cl2 | 179.38 (14) |
N5—N4—C13—C12 | 4.7 (3) | C34—C35—C36—Cl2 | −0.3 (3) |
N3—C12—C13—O3 | 3.9 (3) | C35—C36—C37—C38 | 1.9 (3) |
N3—C12—C13—N4 | −176.66 (17) | Cl2—C36—C37—C38 | −177.96 (16) |
N4—N5—C14—C15 | −178.77 (16) | C36—C37—C38—C39 | −1.6 (3) |
N5—C14—C15—C20 | 0.9 (3) | C37—C38—C39—C40 | −0.1 (3) |
N5—C14—C15—C16 | −179.43 (19) | C38—C39—C40—C35 | 1.5 (3) |
C20—C15—C16—C17 | −0.5 (3) | C36—C35—C40—C39 | −1.3 (3) |
C14—C15—C16—C17 | 179.85 (18) | C34—C35—C40—C39 | 178.39 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Cl1 | 0.95 | 2.64 | 3.048 (2) | 106 |
C34—H34···Cl2 | 0.95 | 2.67 | 3.068 (2) | 106 |
N4—H04···O3i | 0.88 | 2.01 | 2.883 (2) | 172 |
N9—H09···O6ii | 0.88 | 1.96 | 2.837 (2) | 173 |
C18—H18···O1iii | 0.95 | 2.55 | 3.204 (3) | 127 |
C29—H29A···O2iv | 0.98 | 2.31 | 3.266 (3) | 165 |
C38—H38···O4v | 0.95 | 2.54 | 3.233 (2) | 130 |
C9—H9B···O1 | 0.98 | 2.49 | 2.843 (3) | 101 |
C29—H29B···O4 | 0.98 | 2.51 | 2.851 (3) | 100 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y−1, −z+1; (iii) x+1, y, z−1; (iv) x+1, y−1, z; (v) x−1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C20H18ClN5O3S |
Mr | 443.90 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 11.4881 (2), 12.7518 (3), 15.5690 (4) |
α, β, γ (°) | 71.2778 (11), 78.6837 (13), 70.4911 (12) |
V (Å3) | 2025.92 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.20 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.938, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13799, 7106, 5649 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.106, 1.00 |
No. of reflections | 7106 |
No. of parameters | 545 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.39 |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), 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—H04···O3i | 0.88 | 2.01 | 2.883 (2) | 172.0 |
N9—H09···O6ii | 0.88 | 1.96 | 2.837 (2) | 173.2 |
C18—H18···O1iii | 0.95 | 2.55 | 3.204 (3) | 126.6 |
C29—H29A···O2iv | 0.98 | 2.31 | 3.266 (3) | 165.4 |
C38—H38···O4v | 0.95 | 2.54 | 3.233 (2) | 129.9 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y−1, −z+1; (iii) x+1, y, z−1; (iv) x+1, y−1, z; (v) x−1, y, z+1. |
Acknowledgements
The authors are grateful to the Higher Education Commission, Pakistan and the Institute of Chemistry, University of the Punjab, Lahore, Pakistan for financial assistance.
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.
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In continuation to our research exploring potential biologically active derivatives of benzothiazines (Ahmad et al., 2008; 2009), we have devised the fusion of the pyrazole moiety with 1,2-benzothiazine nucleus in an attempt to synthesize novel bioactive molecules. In this paper, we report the synthesis and crystal structure of the title compound, (I).
In the structure of the title compound, there are two independent molecules (molecule a and molecule b) in an asymmetric unit with significantly different conformations of the heterocyclic thiazine rings (Figs. 1 and 2). In both molecules, the thiazine rings adopt half-chair conformations. In molecule a, S1 and N1 atoms are displaced by 0.382 (3) and -0.351 (3) Å, respectively, from the plane formed by the remaining ring atoms(C5–C8). In molecule b, S2 and N6 atoms are displaced by 0.533 (3) and -0.275 (3) Å, respectively, from the plane formed by the remaining ring atoms(C25–C28). The methyl groups attached to N1 and N6 are displaced by significantly different distances from the basal planes of the thiazine rings in the two molecules; 1.802 (4) and 1.694 (4) Å, respectively. The pertinent puckering parameters (Cremer & Pople, 1975) in molecules a and b are: Q = 0.475 (2) and 0.532 (4) Å, θ = 60.0 (4) and 63.4 (2)° and φ = 27.8 (3) and 20.0 (2)°, respectively. Similar conformations of the corresponding rings have been reported in some closely related molecules (Siddiqui et al., 2008; Ahmad et al., 2011).
The mean-planes defined by the pyrazolo and benzene rings of the benzothiazin fragment are inclined with respt to each other at 12.55 (7) and 18.04 (8)°, in the molecules a and b, respectively. The chlorophenyl-methylidene-acetohydrazide moieties in the two molecules display identical conformation. In the molecules labeled as a, intermolecular hydrogen bonds N4—H04···O3 result in the formation of dimmers and C18—H18···O1 link the molecules into chains. Similarly, the molecules b also exhibit intermolecular hydrogen bonds N9—H09···O6 resulting in the formation of dimmers while C38—H38···O4 link the molecules into chains. The molecules a and b are connected via C29—H29B···O2 hydrogen bonds further stabilizing the crystal structure (Tab. 1).