Acta Cryst. (2007). E63, o3685 [ doi:10.1107/S1600536807034137 ]
In the title compound [systematic name: 6-chloro-3-(dichloromethyl)-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide], C8H8Cl3N3O4S2, N-H
O and N-HN interactions combine to create a three-dimensional hydrogen-bonded network.
The compound was sourced from Sigma-Aldrich and a single-crystal sample was recrystallized from a saturated acetonitrile solution by isothermal solvent evaporation at room temperature.
The positions of all the H atoms were obtained from the use of difference Fourier maps. In the final refinement, all H atoms were constrained to geometrically sensible positions with a riding model [C—H = 0.95–1.00Å and Uiso(H) = 1.2Ueq(C)], except for H5, which was allowed to refine freely, and H7 and H8, which were allowed to refine subject to a distance restraint [N—H = 0.88 (1)Å and Uiso(H) = 1.2Ueq(N)]. The highest density peak in the final differnce Fourier is 1.07Å from atom Cl3.
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2007).
![[Figure 1]](./lh2457fig1thm.gif)
| Fig. 1. The molecular structure showing 50% probablility displacement ellipsoids. |
![[Figure 2]](./lh2457fig2thm.gif)
| Fig. 2. The R22(16) hydrogen-bond motif in the crystal structure. Hydrogen bonds are indicated by dashed lines. |
| C8H8Cl3N3O4S2 | F000 = 768 |
| Mr = 380.64 | Dx = 1.853 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 10438 reflections |
| a = 8.7881 (2) Å | θ = 2.4–28.5º |
| b = 9.7924 (2) Å | µ = 0.99 mm−1 |
| c = 15.8527 (3) Å | T = 150 (2) K |
| V = 1364.23 (5) Å3 | Block, colourless |
| Z = 4 | 0.18 × 0.09 × 0.08 mm |
| Oxford Diffraction Gemini diffractometer | 2426 independent reflections |
| Radiation source: Enhance (Mo) X-ray Source | 2345 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.030 |
| T = 150(2) K | θmax = 28.5º |
| ω and π scans | θmin = 2.4º |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | h = −11→11 |
| Tmin = 0.930, Tmax = 1.000 | k = −12→12 |
| 16293 measured reflections | l = −20→21 |
| Refinement on F2 | Hydrogen site location: difference Fourier map |
| 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) + (0.0406P)2 + 1.852P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.079 | (Δ/σ)max < 0.001 |
| S = 1.06 | Δρmax = 1.09 e Å−3 |
| 2426 reflections | Δρmin = −0.43 e Å−3 |
| 190 parameters | Extinction correction: none |
| 2 restraints | Absolute structure: Flack (1983), 1013 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.02 (9) |
| Secondary atom site location: structure-invariant direct methods |
| C8H8Cl3N3O4S2 | V = 1364.23 (5) Å3 |
| Mr = 380.64 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα |
| a = 8.7881 (2) Å | µ = 0.99 mm−1 |
| b = 9.7924 (2) Å | T = 150 (2) K |
| c = 15.8527 (3) Å | 0.18 × 0.09 × 0.08 mm |
| Oxford Diffraction Gemini diffractometer | 2426 independent reflections |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2345 reflections with I > 2σ(I) |
| Tmin = 0.930, Tmax = 1.000 | Rint = 0.030 |
| 16293 measured reflections |
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.079 | Δρmax = 1.09 e Å−3 |
| S = 1.06 | Δρmin = −0.43 e Å−3 |
| 2426 reflections | Absolute structure: Flack (1983), 1013 Friedel pairs |
| 190 parameters | Flack parameter: −0.02 (9) |
| 2 restraints |
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 > 2sigma(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 | 0.14654 (10) | 0.06986 (8) | 0.09856 (5) | 0.01639 (18) | |
| Cl1 | 0.16750 (10) | 0.70063 (8) | 0.14482 (5) | 0.0227 (2) | |
| S2 | 0.10072 (9) | 0.57477 (8) | −0.04076 (5) | 0.01492 (18) | |
| Cl3 | 0.22251 (13) | −0.16217 (10) | 0.34050 (6) | 0.0351 (3) | |
| Cl2 | 0.46909 (11) | 0.03493 (14) | 0.33187 (7) | 0.0439 (3) | |
| O3 | −0.0121 (3) | 0.6738 (2) | −0.02101 (14) | 0.0219 (5) | |
| O4 | 0.0781 (3) | 0.4843 (2) | −0.11050 (14) | 0.0208 (5) | |
| O2 | 0.2201 (3) | 0.0264 (2) | 0.02376 (15) | 0.0268 (6) | |
| O1 | −0.0074 (3) | 0.0296 (3) | 0.11374 (16) | 0.0265 (6) | |
| N3 | 0.2576 (3) | 0.6584 (3) | −0.05901 (17) | 0.0173 (6) | |
| H7 | 0.276 (4) | 0.716 (3) | −0.0177 (16) | 0.021* | |
| H8 | 0.339 (3) | 0.608 (3) | −0.067 (2) | 0.021* | |
| C6 | 0.1876 (4) | 0.3021 (3) | 0.19017 (19) | 0.0152 (7) | |
| C5 | 0.1573 (4) | 0.2474 (3) | 0.1092 (2) | 0.0154 (7) | |
| C2 | 0.1626 (4) | 0.5259 (3) | 0.1290 (2) | 0.0156 (7) | |
| N1 | 0.2182 (4) | 0.2223 (3) | 0.25852 (17) | 0.0199 (6) | |
| H3 | 0.2533 | 0.2612 | 0.3047 | 0.024* | |
| C3 | 0.1318 (4) | 0.4710 (3) | 0.0488 (2) | 0.0147 (7) | |
| C4 | 0.1312 (4) | 0.3306 (3) | 0.0401 (2) | 0.0152 (6) | |
| H2 | 0.1127 | 0.2909 | −0.0137 | 0.018* | |
| C7 | 0.1953 (4) | 0.0768 (4) | 0.25786 (19) | 0.0180 (7) | |
| H4 | 0.0835 | 0.0595 | 0.2626 | 0.022* | |
| N2 | 0.2475 (4) | 0.0172 (3) | 0.17859 (17) | 0.0195 (6) | |
| H5 | 0.350 (5) | 0.023 (4) | 0.174 (2) | 0.023* | |
| C1 | 0.1896 (4) | 0.4449 (3) | 0.1979 (2) | 0.0174 (7) | |
| H1 | 0.2098 | 0.4857 | 0.2511 | 0.021* | |
| C8 | 0.2723 (4) | 0.0121 (4) | 0.3342 (2) | 0.0232 (8) | |
| H6 | 0.2325 | 0.0585 | 0.3859 | 0.028* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0245 (4) | 0.0128 (4) | 0.0119 (4) | −0.0004 (3) | −0.0028 (3) | −0.0011 (3) |
| Cl1 | 0.0364 (5) | 0.0130 (4) | 0.0188 (4) | −0.0022 (3) | 0.0006 (4) | −0.0032 (3) |
| S2 | 0.0146 (4) | 0.0154 (4) | 0.0147 (4) | 0.0011 (3) | −0.0014 (3) | 0.0012 (3) |
| Cl3 | 0.0606 (7) | 0.0201 (4) | 0.0247 (5) | −0.0014 (4) | −0.0097 (5) | 0.0023 (4) |
| Cl2 | 0.0219 (5) | 0.0729 (8) | 0.0369 (6) | −0.0006 (5) | −0.0066 (4) | 0.0091 (5) |
| O3 | 0.0193 (12) | 0.0203 (12) | 0.0261 (13) | 0.0043 (10) | −0.0020 (10) | 0.0001 (10) |
| O4 | 0.0275 (13) | 0.0194 (12) | 0.0156 (12) | 0.0013 (10) | −0.0049 (10) | 0.0012 (10) |
| O2 | 0.0429 (15) | 0.0216 (12) | 0.0158 (12) | 0.0063 (12) | −0.0006 (12) | −0.0049 (10) |
| O1 | 0.0265 (14) | 0.0222 (13) | 0.0309 (14) | −0.0077 (11) | −0.0065 (11) | 0.0008 (11) |
| N3 | 0.0178 (15) | 0.0175 (14) | 0.0165 (14) | 0.0002 (12) | 0.0020 (12) | 0.0003 (12) |
| C6 | 0.0165 (17) | 0.0169 (16) | 0.0121 (15) | −0.0005 (14) | 0.0008 (12) | 0.0008 (13) |
| C5 | 0.0173 (16) | 0.0142 (16) | 0.0147 (16) | −0.0031 (13) | 0.0023 (13) | 0.0003 (13) |
| C2 | 0.0146 (16) | 0.0140 (15) | 0.0183 (16) | −0.0022 (13) | 0.0045 (13) | −0.0039 (13) |
| N1 | 0.0323 (16) | 0.0167 (14) | 0.0106 (13) | −0.0011 (13) | −0.0017 (12) | −0.0002 (11) |
| C3 | 0.0141 (16) | 0.0154 (15) | 0.0146 (16) | −0.0013 (13) | 0.0009 (13) | 0.0022 (13) |
| C4 | 0.0167 (16) | 0.0168 (15) | 0.0122 (14) | −0.0005 (13) | −0.0002 (13) | −0.0019 (14) |
| C7 | 0.0223 (16) | 0.0184 (16) | 0.0134 (15) | 0.0004 (14) | 0.0001 (13) | −0.0007 (14) |
| N2 | 0.0241 (16) | 0.0206 (14) | 0.0137 (14) | 0.0017 (13) | −0.0006 (12) | 0.0004 (11) |
| C1 | 0.0204 (17) | 0.0178 (17) | 0.0141 (15) | −0.0013 (14) | 0.0005 (13) | −0.0030 (14) |
| C8 | 0.033 (2) | 0.0216 (17) | 0.0151 (17) | −0.0007 (16) | −0.0071 (16) | 0.0023 (14) |
| S1—O2 | 1.416 (3) | C6—C5 | 1.416 (4) |
| S1—O1 | 1.429 (3) | C5—C4 | 1.385 (4) |
| S1—N2 | 1.632 (3) | C2—C1 | 1.371 (5) |
| S1—C5 | 1.749 (3) | C2—C3 | 1.406 (5) |
| Cl1—C2 | 1.730 (3) | N1—C7 | 1.439 (5) |
| S2—O3 | 1.422 (2) | N1—H3 | 0.8800 |
| S2—O4 | 1.430 (2) | C3—C4 | 1.382 (4) |
| S2—N3 | 1.630 (3) | C4—H2 | 0.9500 |
| S2—C3 | 1.767 (3) | C7—N2 | 1.460 (4) |
| Cl3—C8 | 1.765 (4) | C7—C8 | 1.525 (5) |
| Cl2—C8 | 1.744 (4) | C7—H4 | 1.0000 |
| N3—H7 | 0.877 (10) | N2—H5 | 0.91 (4) |
| N3—H8 | 0.876 (10) | C1—H1 | 0.9500 |
| C6—N1 | 1.362 (4) | C8—H6 | 1.0000 |
| C6—C1 | 1.405 (5) | ||
| O2—S1—O1 | 119.33 (17) | C7—N1—H3 | 118.9 |
| O2—S1—N2 | 107.96 (15) | C4—C3—C2 | 118.1 (3) |
| O1—S1—N2 | 107.23 (16) | C4—C3—S2 | 119.4 (3) |
| O2—S1—C5 | 110.78 (15) | C2—C3—S2 | 122.4 (2) |
| O1—S1—C5 | 108.02 (15) | C3—C4—C5 | 120.3 (3) |
| N2—S1—C5 | 102.10 (16) | C3—C4—H2 | 119.8 |
| O3—S2—O4 | 119.70 (14) | C5—C4—H2 | 119.8 |
| O3—S2—N3 | 106.65 (15) | N1—C7—N2 | 111.0 (3) |
| O4—S2—N3 | 106.95 (15) | N1—C7—C8 | 110.1 (3) |
| O3—S2—C3 | 108.84 (15) | N2—C7—C8 | 112.2 (3) |
| O4—S2—C3 | 106.65 (14) | N1—C7—H4 | 107.8 |
| N3—S2—C3 | 107.51 (14) | N2—C7—H4 | 107.8 |
| S2—N3—H7 | 110 (3) | C8—C7—H4 | 107.8 |
| S2—N3—H8 | 116 (3) | C7—N2—S1 | 111.9 (2) |
| H7—N3—H8 | 109 (4) | C7—N2—H5 | 111 (2) |
| N1—C6—C1 | 119.9 (3) | S1—N2—H5 | 117 (2) |
| N1—C6—C5 | 122.8 (3) | C2—C1—C6 | 120.3 (3) |
| C1—C6—C5 | 117.3 (3) | C2—C1—H1 | 119.9 |
| C4—C5—C6 | 121.8 (3) | C6—C1—H1 | 119.9 |
| C4—C5—S1 | 119.9 (2) | C7—C8—Cl2 | 111.7 (3) |
| C6—C5—S1 | 118.3 (2) | C7—C8—Cl3 | 109.7 (2) |
| C1—C2—C3 | 122.2 (3) | Cl2—C8—Cl3 | 111.8 (2) |
| C1—C2—Cl1 | 116.9 (2) | C7—C8—H6 | 107.8 |
| C3—C2—Cl1 | 120.9 (3) | Cl2—C8—H6 | 107.8 |
| C6—N1—C7 | 122.3 (3) | Cl3—C8—H6 | 107.8 |
| C6—N1—H3 | 118.9 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3···N3i | 0.88 | 2.30 | 3.127 (4) | 156 |
| N2—H5···O4ii | 0.91 (4) | 2.24 (4) | 3.099 (4) | 157 (3) |
| N3—H7···O3iii | 0.88 (3) | 2.24 (3) | 2.899 (4) | 132 (3) |
| N3—H8···O1ii | 0.88 (3) | 2.05 (3) | 2.900 (4) | 164 (3) |
| Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x+1/2, −y+1/2, −z; (iii) x+1/2, −y+3/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3···N3i | 0.88 | 2.30 | 3.127 (4) | 156 |
| N2—H5···O4ii | 0.91 (4) | 2.24 (4) | 3.099 (4) | 157 (3) |
| N3—H7···O3iii | 0.88 (3) | 2.24 (3) | 2.899 (4) | 132 (3) |
| N3—H8···O1ii | 0.88 (3) | 2.05 (3) | 2.900 (4) | 164 (3) |
| Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x+1/2, −y+1/2, −z; (iii) x+1/2, −y+3/2, −z. |
The authors thank the Basic Technology programme of the UK Research Councils for funding this work under the project Control and Prediction of the Organic Solid State (URL: http://www.cposs.org.uk).
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Trichlormethiazide (TCMT) is a thiazide diuretic used in in the treatment of hypertension and here we report the single-crystal structure at 150 K (Fig. 1). This work forms part of a wider investigation that couples automated parallel crystallization (Florence et al., 2006) with crystal structure prediction methodology to investigate the basic science underlying solid-state diversity in a range of thiazide diuretic compounds (Johnston et al., 2007; Fernandes et al., 2007).
Molecules crystallize in orthorhombic space group P212121 with one molecule in the asymmetric unit. One N—H···N and three N—H···O intermolecular interactions combine to create a three-dimensional hydrogen-bonded network. The N—H···N contact links molecules to form an infinite hydrogen bonded chain along [001]. Contacts N2—H5···O4 and N3—H8···O1 combine to form an R22(16) (Etter, 1990) motif (Fig. 2) that stacks along the direction [100] with adjacent stacks connected via N3—H7···O3.