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The polar hydrochlorothiazide polymorph (I) (systematic name: 6-chloro-1,1-dioxo-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide, C7H8ClN3O4S2) and, recently designed by us, the polar 2-aminopyridine hydrochlorothiazide water <1/1/1> (C7H8ClN3O4S2·C5H6N2·H2O), (II), have been investigated. The crystal structures of both materials were determined using the single-crystal X-ray diffraction technique. The intermolecular interactions in (I) and (II) were studied in detail via topological electron-density analysis. The obtained results showed hydrogen bonds with a character intermediate between closed-shell and shared-shell in both crystal structures. The most important hydrogen bonds in (I) are formed between sulfonamide groups, whereas in (II), water molecules play a crucial role as they interconnect 2-aminopyridine and hydrochlorothiazide molecules. Calculations of the optical properties revealed that both materials exhibit large linear birefringence, twice that of calcite. The theoretically predicted second harmonic generation efficiency is four times and five times larger than that of KH2PO4 for (I) and (II), respectively. The information gathered on intermolecular interactions and structure–property correlations was used to identify the best strategies for the future design of new functional materials of this kind.
Keywords: crystal engineering; electron density; hydrochlorothiazide; linear birefringence; second-harmonic generation.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520621009914/rm5053sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S2052520621009914/rm5053Isup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S2052520621009914/rm5053IIsup3.hkl |
 | Chemical Markup Language (CML) file https://doi.org/10.1107/S2052520621009914/rm5053Isup4.cml |
| Chemical Markup Language (CML) file https://doi.org/10.1107/S2052520621009914/rm5053IIsup5.cml |
 | Zip compressed file https://doi.org/10.1107/S2052520621009914/rm5053sup6.zip |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S2052520621009914/rm5053sup7.pdf |
CCDC references: 2091059; 2091060
Computing details top
For both structures, data collection: CrysAlis PRO 1.171.40.14e (Rigaku Oxford Diffraction, 2018); cell refinement: CrysAlis PRO 1.171.40.14e (Rigaku Oxford Diffraction, 2018); data reduction: CrysAlis PRO 1.171.40.14e (Rigaku Oxford Diffraction, 2018); program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2014). Program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2018) for (I); SHELXL2018/3 (Sheldrick, 2018) for (II). Molecular graphics: Mercury (Macrae et al., 2008) for (I); Mercury (Macrae, 2008) for (II).
6-Chloro-1,1-dioxo-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide (I) top
Crystal data top
| C7H8ClN3O4S2 | F(000) = 304 |
| Mr = 297.73 | Dx = 1.712 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.3288 (1) Å | Cell parameters from 63951 reflections |
| b = 8.5032 (1) Å | θ = 3.0–47.6° |
| c = 9.9467 (1) Å | µ = 0.70 mm−1 |
| β = 111.290 (1)° | T = 100 K |
| V = 577.56 (1) Å3 | Block, colourless |
| Z = 2 | 0.30 × 0.27 × 0.08 mm |
Data collection top
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 9760 reflections with I > 2σ(I) |
| Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | Rint = 0.061 |
| Mirror monochromator | θmax = 47.8°, θmin = 3.0° |
| Absorption correction: multi-scan CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −15→15 |
| Tmin = 0.537, Tmax = 1.000 | k = −17→17 |
| 86128 measured reflections | l = −20→20 |
| 10895 independent reflections |
Refinement top
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.048P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
| S = 1.04 | Δρmax = 0.55 e Å−3 |
| 10895 reflections | Δρmin = −0.55 e Å−3 |
| 166 parameters | Absolute structure: Flack x determined using 4113 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
| 5 restraints | Absolute structure parameter: −0.019 (18) |
| Primary atom site location: difference Fourier map |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| S2 | 0.45382 (4) | 0.49237 (3) | 0.81106 (2) | 0.00980 (4) | |
| S1 | 0.34696 (4) | 0.51684 (3) | 0.24339 (2) | 0.01015 (4) | |
| Cl6 | 0.00600 (5) | 0.62732 (6) | 0.72581 (3) | 0.02632 (8) | |
| O2A | 0.64184 (13) | 0.45609 (11) | 0.80294 (9) | 0.01331 (12) | |
| O1B | 0.54785 (13) | 0.56380 (13) | 0.29022 (9) | 0.01736 (16) | |
| O2B | 0.35807 (14) | 0.37394 (11) | 0.86484 (9) | 0.01563 (14) | |
| O1A | 0.29479 (15) | 0.36109 (11) | 0.18533 (9) | 0.01541 (13) | |
| N2A | 0.48276 (15) | 0.64057 (12) | 0.91511 (9) | 0.01395 (14) | |
| H2A1 | 0.391 (3) | 0.656 (3) | 0.952 (2) | 0.017* | |
| H2A2 | 0.541 (3) | 0.720 (2) | 0.893 (2) | 0.017* | |
| N1 | −0.05419 (14) | 0.63716 (16) | 0.20505 (9) | 0.01679 (17) | |
| H1 | −0.168 (2) | 0.680 (3) | 0.188 (2) | 0.020* | |
| C4 | 0.37362 (14) | 0.51809 (13) | 0.52346 (9) | 0.01051 (13) | |
| H4 | 0.504314 | 0.482682 | 0.545947 | 0.013* | |
| N2 | 0.21595 (14) | 0.64052 (12) | 0.11967 (9) | 0.01223 (12) | |
| H2 | 0.258 (3) | 0.7358 (16) | 0.145 (2) | 0.015* | |
| C5 | 0.30188 (15) | 0.54103 (13) | 0.63368 (9) | 0.01094 (14) | |
| C1 | 0.25559 (15) | 0.54656 (12) | 0.38073 (9) | 0.01044 (13) | |
| C7 | −0.00735 (16) | 0.63072 (17) | 0.45601 (11) | 0.01598 (18) | |
| H7 | −0.135238 | 0.671901 | 0.434965 | 0.019* | |
| C3 | 0.00539 (16) | 0.61488 (15) | 0.08221 (10) | 0.01414 (16) | |
| H3A | −0.068154 | 0.688869 | 0.004592 | 0.017* | |
| H3B | −0.028148 | 0.506619 | 0.044771 | 0.017* | |
| C6 | 0.10856 (16) | 0.59750 (16) | 0.59649 (11) | 0.01448 (17) | |
| C2 | 0.06223 (15) | 0.60408 (14) | 0.34252 (10) | 0.01235 (15) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S2 | 0.01079 (8) | 0.01038 (9) | 0.00765 (7) | −0.00104 (7) | 0.00268 (6) | 0.00072 (6) |
| S1 | 0.00923 (8) | 0.01334 (10) | 0.00801 (7) | 0.00108 (7) | 0.00328 (6) | 0.00025 (6) |
| Cl6 | 0.01638 (12) | 0.0517 (2) | 0.01393 (9) | 0.00819 (14) | 0.00916 (9) | −0.00041 (12) |
| O2A | 0.0110 (3) | 0.0160 (3) | 0.0118 (2) | 0.0024 (2) | 0.0028 (2) | 0.0019 (2) |
| O1B | 0.0089 (3) | 0.0292 (5) | 0.0138 (3) | −0.0009 (3) | 0.0039 (2) | 0.0013 (3) |
| O2B | 0.0196 (4) | 0.0133 (3) | 0.0143 (3) | −0.0052 (3) | 0.0065 (3) | 0.0021 (2) |
| O1A | 0.0206 (4) | 0.0126 (3) | 0.0150 (3) | 0.0016 (3) | 0.0089 (3) | −0.0014 (2) |
| N2A | 0.0178 (4) | 0.0132 (3) | 0.0120 (3) | −0.0038 (3) | 0.0067 (3) | −0.0027 (3) |
| N1 | 0.0105 (3) | 0.0278 (5) | 0.0101 (3) | 0.0068 (3) | 0.0014 (2) | 0.0019 (3) |
| C4 | 0.0095 (3) | 0.0136 (4) | 0.0082 (2) | 0.0016 (3) | 0.0029 (2) | 0.0003 (2) |
| N2 | 0.0128 (3) | 0.0133 (3) | 0.0095 (2) | −0.0001 (3) | 0.0028 (2) | 0.0011 (2) |
| C5 | 0.0093 (3) | 0.0148 (4) | 0.0084 (3) | 0.0011 (3) | 0.0028 (2) | 0.0001 (2) |
| C1 | 0.0088 (3) | 0.0142 (4) | 0.0079 (3) | 0.0019 (3) | 0.0026 (2) | 0.0000 (2) |
| C7 | 0.0097 (3) | 0.0264 (5) | 0.0114 (3) | 0.0049 (4) | 0.0033 (3) | −0.0007 (3) |
| C3 | 0.0116 (4) | 0.0193 (4) | 0.0091 (3) | 0.0013 (3) | 0.0009 (3) | −0.0002 (3) |
| C6 | 0.0103 (3) | 0.0239 (5) | 0.0105 (3) | 0.0027 (3) | 0.0053 (3) | −0.0006 (3) |
| C2 | 0.0084 (3) | 0.0182 (4) | 0.0094 (3) | 0.0027 (3) | 0.0019 (2) | 0.0001 (3) |
Geometric parameters (Å, º) top
| S2—O2B | 1.4371 (9) | N1—H1 | 0.869 (12) |
| S2—O2A | 1.4427 (9) | C4—C1 | 1.3895 (12) |
| S2—N2A | 1.5952 (10) | C4—C5 | 1.3910 (12) |
| S2—C5 | 1.7600 (9) | C4—H4 | 0.9500 |
| S1—O1B | 1.4304 (9) | N2—C3 | 1.4664 (14) |
| S1—O1A | 1.4399 (10) | N2—H2 | 0.871 (12) |
| S1—N2 | 1.6383 (9) | C5—C6 | 1.4121 (15) |
| S1—C1 | 1.7444 (9) | C1—C2 | 1.4145 (14) |
| Cl6—C6 | 1.7280 (10) | C7—C6 | 1.3755 (15) |
| N2A—H2A1 | 0.886 (12) | C7—C2 | 1.4155 (14) |
| N2A—H2A2 | 0.871 (12) | C7—H7 | 0.9500 |
| N1—C2 | 1.3526 (13) | C3—H3A | 0.9900 |
| N1—C3 | 1.4516 (14) | C3—H3B | 0.9900 |
| O2B—S2—O2A | 118.45 (6) | S1—N2—H2 | 109.4 (14) |
| O2B—S2—N2A | 106.26 (5) | C4—C5—C6 | 118.14 (8) |
| O2A—S2—N2A | 107.49 (5) | C4—C5—S2 | 118.33 (7) |
| O2B—S2—C5 | 108.73 (5) | C6—C5—S2 | 123.50 (7) |
| O2A—S2—C5 | 105.29 (5) | C4—C1—C2 | 121.74 (8) |
| N2A—S2—C5 | 110.57 (5) | C4—C1—S1 | 120.09 (7) |
| O1B—S1—O1A | 118.65 (6) | C2—C1—S1 | 118.14 (7) |
| O1B—S1—N2 | 108.58 (5) | C6—C7—C2 | 120.59 (10) |
| O1A—S1—N2 | 106.94 (5) | C6—C7—H7 | 119.7 |
| O1B—S1—C1 | 110.30 (5) | C2—C7—H7 | 119.7 |
| O1A—S1—C1 | 109.02 (5) | N1—C3—N2 | 112.16 (8) |
| N2—S1—C1 | 102.02 (5) | N1—C3—H3A | 109.2 |
| S2—N2A—H2A1 | 116.5 (16) | N2—C3—H3A | 109.2 |
| S2—N2A—H2A2 | 114.6 (15) | N1—C3—H3B | 109.2 |
| H2A1—N2A—H2A2 | 120 (2) | N2—C3—H3B | 109.2 |
| C2—N1—C3 | 123.48 (9) | H3A—C3—H3B | 107.9 |
| C2—N1—H1 | 119.6 (15) | C7—C6—C5 | 121.79 (9) |
| C3—N1—H1 | 116.8 (15) | C7—C6—Cl6 | 116.80 (8) |
| C1—C4—C5 | 120.50 (9) | C5—C6—Cl6 | 121.41 (8) |
| C1—C4—H4 | 119.7 | N1—C2—C1 | 123.11 (9) |
| C5—C4—H4 | 119.7 | N1—C2—C7 | 119.69 (9) |
| C3—N2—S1 | 111.79 (7) | C1—C2—C7 | 117.18 (9) |
| C3—N2—H2 | 116.4 (15) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2A—H2A1···N2i | 0.89 (1) | 2.45 (1) | 3.2943 (13) | 160 (2) |
| N2A—H2A2···O1Aii | 0.87 (1) | 2.04 (1) | 2.8905 (13) | 164 (2) |
| N1—H1···O2Biii | 0.87 (1) | 2.10 (2) | 2.8935 (14) | 152 (2) |
| N2—H2···O2Aii | 0.87 (1) | 2.01 (1) | 2.8804 (13) | 178 (2) |
| C7—H7···O1Biv | 0.95 | 2.43 | 3.1251 (14) | 130 |
| C3—H3A···O1Av | 0.99 | 2.49 | 3.4717 (14) | 172 |
| Symmetry codes: (i) x, y, z+1; (ii) −x+1, y+1/2, −z+1; (iii) −x, y+1/2, −z+1; (iv) x−1, y, z; (v) −x, y+1/2, −z. |
6-Chloro-1,1-dioxo-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide
pyridin-2-amine monosolvate monohydrate (II) top
Crystal data top
| C7H8ClN3O4S2·C5H6N2·H2O | Dx = 1.628 Mg m−3 |
| Mr = 409.87 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pna21 | Cell parameters from 25539 reflections |
| a = 31.6312 (6) Å | θ = 2.6–48.2° |
| b = 7.3092 (1) Å | µ = 0.51 mm−1 |
| c = 7.2332 (1) Å | T = 100 K |
| V = 1672.31 (5) Å3 | Plate, colourless |
| Z = 4 | 0.30 × 0.30 × 0.30 mm |
| F(000) = 848 |
Data collection top
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 15872 independent reflections |
| Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 12319 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.045 |
| Detector resolution: 10.0000 pixels mm-1 | θmax = 48.6°, θmin = 2.6° |
| Absorption correction: multi-scan CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −66→66 |
| Tmin = 0.644, Tmax = 1.000 | k = −15→15 |
| 78875 measured reflections | l = −14→15 |
Refinement top
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0433P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.083 | (Δ/σ)max = 0.008 |
| S = 1.00 | Δρmax = 0.64 e Å−3 |
| 15872 reflections | Δρmin = −0.29 e Å−3 |
| 308 parameters | Absolute structure: Flack x determined using 4462 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
| 247 restraints | Absolute structure parameter: −0.006 (14) |
| Primary atom site location: difference Fourier map |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| S2 | 0.27228 (2) | 0.62876 (3) | 0.71947 (4) | 0.01239 (4) | |
| S1 | 0.43378 (2) | 0.65095 (4) | 0.97138 (4) | 0.01624 (4) | |
| Cl6 | 0.30819 (2) | 0.76429 (4) | 0.31624 (4) | 0.02185 (5) | |
| O2A | 0.25597 (3) | 0.51402 (11) | 0.57498 (12) | 0.01813 (13) | |
| O1W | 0.51342 (3) | 0.76765 (13) | 0.28502 (13) | 0.02053 (15) | |
| H1W1 | 0.53983 (10) | 0.781 (3) | 0.269 (2) | 0.025* | |
| H1W2 | 0.5024 (4) | 0.814 (3) | 0.1889 (16) | 0.025* | |
| O2B | 0.27051 (3) | 0.56628 (12) | 0.90776 (11) | 0.01636 (12) | |
| O1B | 0.42331 (3) | 0.49194 (13) | 1.07812 (13) | 0.02196 (15) | |
| O1A | 0.43835 (3) | 0.82305 (13) | 1.06767 (14) | 0.02101 (15) | |
| N2A | 0.24600 (3) | 0.81661 (12) | 0.71273 (14) | 0.01531 (12) | |
| H2A2 | 0.2491 (6) | 0.881 (3) | 0.800 (3) | 0.018* | |
| H2A1 | 0.2423 (6) | 0.867 (3) | 0.606 (3) | 0.018* | |
| N1 | 0.45560 (4) | 0.76147 (18) | 0.58304 (17) | 0.0248 (2) | |
| H1 | 0.4642 (7) | 0.786 (3) | 0.473 (2) | 0.030* | |
| N2 | 0.47843 (3) | 0.61303 (15) | 0.86543 (15) | 0.01971 (16) | |
| H2 | 0.4779 (6) | 0.4990 (18) | 0.824 (3) | 0.024* | |
| C5 | 0.32634 (3) | 0.67104 (14) | 0.67439 (14) | 0.01329 (13) | |
| C6 | 0.34195 (3) | 0.72646 (14) | 0.50071 (14) | 0.01550 (15) | |
| C7 | 0.38433 (4) | 0.75663 (15) | 0.47146 (16) | 0.01855 (17) | |
| H7 | 0.393856 | 0.792993 | 0.352441 | 0.022* | |
| C4 | 0.35499 (3) | 0.64753 (13) | 0.81795 (14) | 0.01388 (14) | |
| H4 | 0.345250 | 0.609219 | 0.935993 | 0.017* | |
| C2 | 0.41385 (4) | 0.73428 (16) | 0.61581 (16) | 0.01765 (17) | |
| C1 | 0.39793 (3) | 0.67976 (14) | 0.79000 (14) | 0.01531 (15) | |
| C3 | 0.48746 (4) | 0.75361 (17) | 0.7265 (2) | 0.0229 (2) | |
| H31 | 0.489236 | 0.874295 | 0.788162 | 0.027* | |
| H32 | 0.515279 | 0.727992 | 0.669362 | 0.027* | |
| N1B | 0.59542 (9) | 0.811 (2) | 0.2236 (7) | 0.0192 (3) | 0.832 (3) |
| C6B | 0.62184 (6) | 0.8570 (2) | 0.3624 (3) | 0.0215 (3) | 0.832 (3) |
| H6B | 0.609979 | 0.886510 | 0.479307 | 0.026* | 0.832 (3) |
| C5B | 0.66513 (5) | 0.8633 (2) | 0.3433 (3) | 0.0275 (4) | 0.832 (3) |
| H5B | 0.682868 | 0.894923 | 0.444407 | 0.033* | 0.832 (3) |
| C4B | 0.68196 (6) | 0.8218 (2) | 0.1703 (4) | 0.0288 (4) | 0.832 (3) |
| H4B | 0.711684 | 0.825721 | 0.152097 | 0.035* | 0.832 (3) |
| C3B | 0.65588 (7) | 0.7751 (2) | 0.0259 (3) | 0.0267 (4) | 0.832 (3) |
| H3B | 0.667136 | 0.747635 | −0.092615 | 0.032* | 0.832 (3) |
| C2B | 0.61203 (7) | 0.7692 (3) | 0.0584 (3) | 0.0209 (3) | 0.832 (3) |
| N2B | 0.58380 (6) | 0.7274 (2) | −0.0794 (2) | 0.0312 (3) | 0.832 (3) |
| H2B1 | 0.5943 (9) | 0.666 (3) | −0.175 (3) | 0.037* | 0.832 (3) |
| H2B2 | 0.5577 (5) | 0.684 (4) | −0.066 (5) | 0.037* | 0.832 (3) |
| N1C | 0.5983 (4) | 0.816 (10) | 0.225 (3) | 0.0192 (3) | 0.168 (3) |
| C6C | 0.5994 (3) | 0.770 (2) | 0.0426 (17) | 0.030 (2) | 0.168 (3) |
| H6C | 0.573570 | 0.747478 | −0.020451 | 0.036* | 0.168 (3) |
| C5C | 0.6367 (3) | 0.7565 (11) | −0.0526 (14) | 0.034 (2) | 0.168 (3) |
| H5C | 0.637279 | 0.722035 | −0.179262 | 0.041* | 0.168 (3) |
| C4C | 0.6736 (3) | 0.7945 (11) | 0.0429 (14) | 0.0303 (19) | 0.168 (3) |
| H4C | 0.699807 | 0.790857 | −0.021288 | 0.036* | 0.168 (3) |
| C3C | 0.6735 (3) | 0.8370 (12) | 0.2263 (14) | 0.0283 (19) | 0.168 (3) |
| H3C | 0.699104 | 0.860061 | 0.290732 | 0.034* | 0.168 (3) |
| C2C | 0.6352 (2) | 0.8454 (9) | 0.3151 (11) | 0.0219 (14) | 0.168 (3) |
| N2C | 0.6322 (2) | 0.8840 (11) | 0.4986 (10) | 0.0303 (16) | 0.168 (3) |
| H2C1 | 0.607801 | 0.888325 | 0.552450 | 0.036* | 0.168 |
| H2C2 | 0.654691 | 0.903872 | 0.563190 | 0.036* | 0.168 |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S2 | 0.01581 (8) | 0.01094 (7) | 0.01043 (8) | −0.00048 (6) | −0.00097 (7) | 0.00039 (7) |
| S1 | 0.01394 (9) | 0.01778 (9) | 0.01701 (10) | 0.00222 (7) | 0.00028 (8) | 0.00026 (8) |
| Cl6 | 0.02555 (11) | 0.02805 (13) | 0.01194 (9) | 0.00441 (9) | −0.00029 (8) | 0.00444 (9) |
| O2A | 0.0229 (3) | 0.0155 (3) | 0.0160 (3) | −0.0015 (2) | −0.0032 (3) | −0.0038 (3) |
| O1W | 0.0164 (3) | 0.0245 (4) | 0.0207 (4) | −0.0016 (3) | 0.0022 (3) | 0.0020 (3) |
| O2B | 0.0187 (3) | 0.0177 (3) | 0.0126 (3) | −0.0020 (2) | −0.0006 (2) | 0.0052 (2) |
| O1B | 0.0208 (3) | 0.0239 (4) | 0.0213 (4) | 0.0009 (3) | −0.0016 (3) | 0.0064 (3) |
| O1A | 0.0191 (3) | 0.0214 (4) | 0.0225 (4) | 0.0033 (3) | −0.0007 (3) | −0.0051 (3) |
| N2A | 0.0186 (3) | 0.0138 (3) | 0.0135 (3) | 0.0024 (2) | −0.0004 (3) | 0.0001 (3) |
| N1 | 0.0175 (4) | 0.0329 (5) | 0.0238 (5) | 0.0041 (3) | 0.0086 (3) | 0.0065 (4) |
| N2 | 0.0147 (3) | 0.0198 (4) | 0.0246 (4) | 0.0038 (3) | 0.0029 (3) | −0.0011 (3) |
| C5 | 0.0160 (3) | 0.0130 (3) | 0.0110 (3) | 0.0011 (3) | 0.0008 (2) | 0.0005 (3) |
| C6 | 0.0202 (4) | 0.0151 (3) | 0.0111 (3) | 0.0035 (3) | 0.0021 (3) | 0.0016 (3) |
| C7 | 0.0207 (4) | 0.0203 (4) | 0.0146 (4) | 0.0047 (3) | 0.0056 (3) | 0.0031 (3) |
| C4 | 0.0160 (3) | 0.0141 (3) | 0.0116 (3) | 0.0013 (3) | 0.0011 (3) | 0.0005 (3) |
| C2 | 0.0177 (4) | 0.0183 (4) | 0.0169 (4) | 0.0037 (3) | 0.0054 (3) | 0.0020 (3) |
| C1 | 0.0149 (3) | 0.0165 (4) | 0.0145 (4) | 0.0025 (3) | 0.0017 (3) | 0.0009 (3) |
| C3 | 0.0164 (4) | 0.0238 (5) | 0.0284 (5) | 0.0018 (3) | 0.0062 (4) | 0.0008 (4) |
| N1B | 0.0158 (5) | 0.0209 (10) | 0.0211 (4) | −0.0006 (11) | 0.0018 (5) | −0.0011 (4) |
| C6B | 0.0199 (6) | 0.0180 (6) | 0.0266 (7) | −0.0001 (5) | −0.0022 (5) | −0.0014 (5) |
| C5B | 0.0187 (6) | 0.0171 (6) | 0.0467 (11) | −0.0010 (4) | −0.0062 (6) | −0.0034 (6) |
| C4B | 0.0182 (7) | 0.0142 (6) | 0.0540 (14) | −0.0003 (5) | 0.0080 (7) | −0.0011 (7) |
| C3B | 0.0252 (8) | 0.0167 (6) | 0.0384 (10) | 0.0021 (5) | 0.0136 (7) | 0.0015 (6) |
| C2B | 0.0232 (8) | 0.0168 (6) | 0.0226 (7) | 0.0044 (7) | 0.0046 (6) | 0.0011 (5) |
| N2B | 0.0366 (8) | 0.0347 (8) | 0.0224 (6) | 0.0066 (6) | −0.0021 (5) | −0.0049 (5) |
| N1C | 0.0158 (5) | 0.0209 (10) | 0.0211 (4) | −0.0006 (11) | 0.0018 (5) | −0.0011 (4) |
| C6C | 0.028 (5) | 0.028 (4) | 0.035 (5) | 0.008 (5) | 0.010 (4) | −0.002 (4) |
| C5C | 0.046 (5) | 0.018 (3) | 0.039 (5) | 0.005 (3) | 0.015 (4) | 0.000 (3) |
| C4C | 0.020 (3) | 0.016 (3) | 0.055 (6) | −0.001 (2) | 0.008 (3) | 0.007 (3) |
| C3C | 0.019 (3) | 0.016 (3) | 0.050 (6) | 0.004 (2) | 0.014 (3) | −0.006 (3) |
| C2C | 0.017 (3) | 0.014 (2) | 0.035 (4) | 0.0034 (19) | 0.014 (3) | 0.000 (2) |
| N2C | 0.031 (3) | 0.029 (3) | 0.030 (4) | 0.002 (3) | −0.006 (3) | −0.003 (3) |
Geometric parameters (Å, º) top
| S2—O2A | 1.4360 (8) | C3—H32 | 0.9900 |
| S2—O2B | 1.4376 (8) | N1B—C2B | 1.341 (4) |
| S2—N2A | 1.6058 (9) | N1B—C6B | 1.349 (3) |
| S2—C5 | 1.7679 (10) | C6B—C5B | 1.377 (2) |
| S1—O1B | 1.4340 (10) | C6B—H6B | 0.9500 |
| S1—O1A | 1.4451 (10) | C5B—C4B | 1.393 (3) |
| S1—N2 | 1.6306 (10) | C5B—H5B | 0.9500 |
| S1—C1 | 1.7469 (11) | C4B—C3B | 1.374 (3) |
| Cl6—C6 | 1.7311 (11) | C4B—H4B | 0.9500 |
| O1W—H1W1 | 0.8495 (14) | C3B—C2B | 1.407 (3) |
| O1W—H1W2 | 0.8493 (14) | C3B—H3B | 0.9500 |
| N2A—H2A2 | 0.80 (2) | C2B—N2B | 1.373 (3) |
| N2A—H2A1 | 0.86 (2) | N2B—H2B1 | 0.890 (13) |
| N1—C2 | 1.3561 (16) | N2B—H2B2 | 0.890 (13) |
| N1—C3 | 1.4478 (19) | N1C—C2C | 1.353 (12) |
| N1—H1 | 0.859 (12) | N1C—C6C | 1.362 (14) |
| N2—C3 | 1.4654 (17) | C6C—C5C | 1.371 (10) |
| N2—H2 | 0.886 (12) | C6C—H6C | 0.9500 |
| C5—C4 | 1.3890 (14) | C5C—C4C | 1.384 (11) |
| C5—C6 | 1.4093 (14) | C5C—H5C | 0.9500 |
| C6—C7 | 1.3751 (15) | C4C—C3C | 1.362 (10) |
| C7—C2 | 1.4102 (17) | C4C—H4C | 0.9500 |
| C7—H7 | 0.9500 | C3C—C2C | 1.373 (9) |
| C4—C1 | 1.3930 (14) | C3C—H3C | 0.9500 |
| C4—H4 | 0.9500 | C2C—N2C | 1.361 (9) |
| C2—C1 | 1.4143 (15) | N2C—H2C1 | 0.8651 |
| C3—H31 | 0.9900 | N2C—H2C2 | 0.8634 |
| O2A—S2—O2B | 119.34 (5) | N2—C3—H31 | 109.1 |
| O2A—S2—N2A | 106.94 (5) | N1—C3—H32 | 109.1 |
| O2B—S2—N2A | 106.27 (5) | N2—C3—H32 | 109.1 |
| O2A—S2—C5 | 108.39 (5) | H31—C3—H32 | 107.8 |
| O2B—S2—C5 | 105.54 (5) | C2B—N1B—C6B | 118.5 (2) |
| N2A—S2—C5 | 110.22 (5) | N1B—C6B—C5B | 123.4 (2) |
| O1B—S1—O1A | 117.98 (6) | N1B—C6B—H6B | 118.3 |
| O1B—S1—N2 | 108.37 (6) | C5B—C6B—H6B | 118.3 |
| O1A—S1—N2 | 106.72 (6) | C6B—C5B—C4B | 117.54 (17) |
| O1B—S1—C1 | 110.62 (5) | C6B—C5B—H5B | 121.2 |
| O1A—S1—C1 | 108.78 (5) | C4B—C5B—H5B | 121.2 |
| N2—S1—C1 | 103.29 (5) | C3B—C4B—C5B | 120.50 (16) |
| H1W1—O1W—H1W2 | 104.2 (2) | C3B—C4B—H4B | 119.8 |
| S2—N2A—H2A2 | 114.6 (14) | C5B—C4B—H4B | 119.8 |
| S2—N2A—H2A1 | 117.5 (14) | C4B—C3B—C2B | 118.20 (18) |
| H2A2—N2A—H2A1 | 118.4 (19) | C4B—C3B—H3B | 120.9 |
| C2—N1—C3 | 123.14 (11) | C2B—C3B—H3B | 120.9 |
| C2—N1—H1 | 120.0 (15) | N1B—C2B—N2B | 116.3 (2) |
| C3—N1—H1 | 116.9 (15) | N1B—C2B—C3B | 121.9 (2) |
| C3—N2—S1 | 111.84 (8) | N2B—C2B—C3B | 121.8 (2) |
| C3—N2—H2 | 115.5 (15) | C2B—N2B—H2B1 | 116 (2) |
| S1—N2—H2 | 107.7 (13) | C2B—N2B—H2B2 | 127 (2) |
| C4—C5—C6 | 118.25 (9) | H2B1—N2B—H2B2 | 105 (3) |
| C4—C5—S2 | 118.14 (7) | C2C—N1C—C6C | 118.9 (12) |
| C6—C5—S2 | 123.61 (8) | N1C—C6C—C5C | 121.8 (11) |
| C7—C6—C5 | 121.66 (10) | N1C—C6C—H6C | 119.1 |
| C7—C6—Cl6 | 117.20 (8) | C5C—C6C—H6C | 119.1 |
| C5—C6—Cl6 | 121.13 (8) | C6C—C5C—C4C | 117.4 (9) |
| C6—C7—C2 | 120.87 (10) | C6C—C5C—H5C | 121.3 |
| C6—C7—H7 | 119.6 | C4C—C5C—H5C | 121.3 |
| C2—C7—H7 | 119.6 | C3C—C4C—C5C | 122.0 (8) |
| C5—C4—C1 | 120.45 (9) | C3C—C4C—H4C | 119.0 |
| C5—C4—H4 | 119.8 | C5C—C4C—H4C | 119.0 |
| C1—C4—H4 | 119.8 | C4C—C3C—C2C | 117.9 (8) |
| N1—C2—C7 | 119.89 (10) | C4C—C3C—H3C | 121.0 |
| N1—C2—C1 | 122.95 (11) | C2C—C3C—H3C | 121.0 |
| C7—C2—C1 | 117.15 (10) | N1C—C2C—N2C | 116.3 (9) |
| C4—C1—C2 | 121.61 (10) | N1C—C2C—C3C | 121.9 (10) |
| C4—C1—S1 | 120.23 (8) | N2C—C2C—C3C | 121.8 (8) |
| C2—C1—S1 | 118.15 (8) | C2C—N2C—H2C1 | 120.6 |
| N1—C3—N2 | 112.55 (10) | C2C—N2C—H2C2 | 120.4 |
| N1—C3—H31 | 109.1 | H2C1—N2C—H2C2 | 119.0 |
| O1B—S1—N2—C3 | 169.19 (9) | C7—C2—C1—S1 | 179.98 (8) |
| O1A—S1—N2—C3 | −62.79 (11) | O1B—S1—C1—C4 | 40.21 (10) |
| C1—S1—N2—C3 | 51.82 (10) | O1A—S1—C1—C4 | −90.89 (10) |
| O2A—S2—C5—C4 | −131.79 (8) | N2—S1—C1—C4 | 155.99 (9) |
| O2B—S2—C5—C4 | −2.86 (9) | O1B—S1—C1—C2 | −139.14 (9) |
| N2A—S2—C5—C4 | 111.50 (8) | O1A—S1—C1—C2 | 89.76 (10) |
| O2A—S2—C5—C6 | 47.93 (10) | N2—S1—C1—C2 | −23.36 (10) |
| O2B—S2—C5—C6 | 176.86 (9) | C2—N1—C3—N2 | 36.43 (17) |
| N2A—S2—C5—C6 | −68.79 (10) | S1—N2—C3—N1 | −61.00 (12) |
| C4—C5—C6—C7 | 0.18 (15) | C2B—N1B—C6B—C5B | 0.0 (15) |
| S2—C5—C6—C7 | −179.54 (8) | N1B—C6B—C5B—C4B | 0.8 (8) |
| C4—C5—C6—Cl6 | −178.38 (8) | C6B—C5B—C4B—C3B | −0.5 (3) |
| S2—C5—C6—Cl6 | 1.90 (13) | C5B—C4B—C3B—C2B | −0.5 (3) |
| C5—C6—C7—C2 | −0.48 (16) | C6B—N1B—C2B—N2B | −178.5 (8) |
| Cl6—C6—C7—C2 | 178.13 (9) | C6B—N1B—C2B—C3B | −1.0 (15) |
| C6—C5—C4—C1 | 0.54 (15) | C4B—C3B—C2B—N1B | 1.3 (8) |
| S2—C5—C4—C1 | −179.73 (8) | C4B—C3B—C2B—N2B | 178.68 (19) |
| C3—N1—C2—C7 | 175.60 (11) | C2C—N1C—C6C—C5C | −1 (8) |
| C3—N1—C2—C1 | −5.8 (2) | N1C—C6C—C5C—C4C | −1 (4) |
| C6—C7—C2—N1 | 178.78 (11) | C6C—C5C—C4C—C3C | 2.6 (15) |
| C6—C7—C2—C1 | 0.08 (16) | C5C—C4C—C3C—C2C | −1.4 (13) |
| C5—C4—C1—C2 | −0.96 (16) | C6C—N1C—C2C—N2C | −178 (4) |
| C5—C4—C1—S1 | 179.71 (8) | C6C—N1C—C2C—C3C | 2 (8) |
| N1—C2—C1—C4 | −178.02 (11) | C4C—C3C—C2C—N1C | −1 (4) |
| C7—C2—C1—C4 | 0.64 (16) | C4C—C3C—C2C—N2C | 178.9 (8) |
| N1—C2—C1—S1 | 1.32 (16) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W1···N1Ba | 0.85 (1) | 1.80 (1) | 2.651 (3) | 177 (2) |
| O1W—H1W2···O1Ai | 0.85 (1) | 2.21 (1) | 2.8764 (13) | 136 (1) |
| N2A—H2A2···O2Aii | 0.80 (2) | 2.22 (2) | 2.9919 (13) | 164.5 (19) |
| N2A—H2A1···O2Biii | 0.86 (2) | 2.09 (2) | 2.9101 (12) | 160.1 (19) |
| N1—H1···O1W | 0.86 (1) | 2.07 (2) | 2.8273 (14) | 146 (2) |
| N2—H2···O1Wiv | 0.89 (1) | 1.99 (1) | 2.8542 (14) | 165 (2) |
| C7—H7···O1Ai | 0.95 | 2.50 | 3.4184 (15) | 162 |
| C5Ba—H5Ba···O2Av | 0.95 | 2.58 | 3.4448 (18) | 151 |
| N2Ba—H2B1a···O1Bvi | 0.89 (1) | 2.20 (2) | 2.9592 (19) | 143 (3) |
| N2Ba—H2B2a···N2i | 0.89 (1) | 2.61 (2) | 3.459 (2) | 161 (3) |
| C5Cb—H5Cb···N2Cbi | 0.95 | 2.62 | 3.380 (12) | 138 |
| N2Cb—H2C1b···O1Avii | 0.87 | 2.57 | 3.133 (7) | 124 |
| Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y+1/2, z+1/2; (iii) −x+1/2, y+1/2, z−1/2; (iv) −x+1, −y+1, z+1/2; (v) x+1/2, −y+3/2, z; (vi) −x+1, −y+1, z−3/2; (vii) −x+1, −y+2, z−1/2. |
