organic compounds
7-[(3-Chloro-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepin-11-yl)amino]heptanoic acid S,S-dioxide hydrochloride
aLatvian Institute of Organic Synthesis, Aizkraukles Street 21, Riga, LV-1006, Latvia, and bUniversity of Latvia, Department of Chemistry, Kr. Valdemara Street 48, Riga, LV-1013, Latvia
*Correspondence e-mail: alvis.zvirgzdins@lais.lv
In the title compound, C21H26ClN2O4S.Cl, also known as tianeptine hydrochloride, the seven-membered ring adopts a boat conformation. The dihedral angle between the mean planes of the benzene rings is 44.44 (7)°. There is an intramolecular hydrogen bond formed via S= O⋯H—N. In the crystal, molecules are connected via pairs of N—H.·O, N—H⋯Cl and O—H⋯Cl hydrogen bonds, forming inversion dimers, which are consolidated by C—H⋯O interactions. The dimers are linked by C—H⋯O and C—H⋯Cl interactions, forming a two-dimensional network lying parallel to (011).
Related literature
For general information about tianeptine and its preparation, see: Guzman et al. (2010). For related structures, see: Orola et al. (2012).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: COLLECT (Hooft, 1998); cell HKL 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: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010).
Supporting information
Tianeptine sodium salt (0.5 g;1.09 mmol) was dissolved in 20 ml deionized water in a Erlenmeyer flask and added ~3 mmol of hydrochloric acid. Mixture were stirred for 6 h. After 6 h suspension was filtered and washed with cold water. The product was dried and recrystallized from water by slow evaporation at room temperature.
All hydrogen atoms were positioned geometrically with C—H distances ranging from 0.93 to 0.97 Å and refined as riding on their parent atoms with Uiso(H) = 1.5 Ueq(C) for methyl groups and Uiso(H) = 1.2 Ueq(C) for others.
Data collection: COLLECT (Hooft, 1998); cell
HKL 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: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound showing 50% probability ellipsoids and hydrogen atoms are shown as small spheres of arbitrary radii. | |
Fig. 2. Packing diagram of the title compound viewed along the c axis. Blue lines indicate hydrogen bonds. |
C21H26ClN2O4S+·Cl− | Z = 2 |
Mr = 473.40 | F(000) = 496 |
Triclinic, P1 | Dx = 1.380 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5439 (2) Å | Cell parameters from 6759 reflections |
b = 10.0910 (2) Å | θ = 1.0–27.1° |
c = 13.1802 (3) Å | µ = 0.41 mm−1 |
α = 104.4000 (12)° | T = 190 K |
β = 101.538 (1)° | Plate, colourless |
γ = 105.0180 (11)° | 0.24 × 0.20 × 0.14 mm |
V = 1139.04 (4) Å3 |
Nonius KappaCCD diffractometer | 4015 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.1°, θmin = 3.1° |
CCD scans | h = −11→12 |
7552 measured reflections | k = −12→12 |
4985 independent reflections | l = −16→16 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0363P)2 + 0.641P] where P = (Fo2 + 2Fc2)/3 |
4985 reflections | (Δ/σ)max = 0.018 |
273 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C21H26ClN2O4S+·Cl− | γ = 105.0180 (11)° |
Mr = 473.40 | V = 1139.04 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5439 (2) Å | Mo Kα radiation |
b = 10.0910 (2) Å | µ = 0.41 mm−1 |
c = 13.1802 (3) Å | T = 190 K |
α = 104.4000 (12)° | 0.24 × 0.20 × 0.14 mm |
β = 101.538 (1)° |
Nonius KappaCCD diffractometer | 4015 reflections with I > 2σ(I) |
7552 measured reflections | Rint = 0.021 |
4985 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.76 e Å−3 |
4985 reflections | Δρmin = −0.34 e Å−3 |
273 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 | ||
Cl1 | 0.48761 (6) | 0.92769 (6) | 0.32682 (5) | 0.03721 (15) | |
S1 | 1.08561 (5) | 1.04778 (5) | 0.36222 (4) | 0.02568 (12) | |
Cl2 | 0.77093 (5) | 0.48993 (5) | −0.09234 (4) | 0.03147 (13) | |
O2 | 1.17517 (14) | 0.95570 (14) | 0.37600 (11) | 0.0274 (3) | |
N2 | 1.04759 (17) | 0.69630 (16) | 0.20172 (13) | 0.0218 (3) | |
H3A | 1.1139 | 0.6682 | 0.1689 | 0.026* | |
H3B | 1.0994 | 0.7516 | 0.2708 | 0.026* | |
O4 | 0.57739 (17) | 0.42297 (18) | 0.67606 (12) | 0.0375 (4) | |
H6 | 0.6331 | 0.4443 | 0.7378 | 0.056* | |
O1 | 1.08744 (17) | 1.15746 (16) | 0.45495 (12) | 0.0371 (4) | |
O3 | 0.76590 (16) | 0.35639 (18) | 0.62834 (12) | 0.0382 (4) | |
N1 | 1.13800 (18) | 1.12491 (17) | 0.27471 (14) | 0.0281 (4) | |
C5 | 0.7141 (2) | 0.7622 (2) | 0.13441 (16) | 0.0264 (4) | |
H2 | 0.6903 | 0.6926 | 0.0667 | 0.032* | |
C4 | 0.5978 (2) | 0.7900 (2) | 0.17507 (17) | 0.0288 (4) | |
H3 | 0.4974 | 0.7398 | 0.1352 | 0.035* | |
C6 | 0.8655 (2) | 0.83537 (19) | 0.19193 (15) | 0.0212 (4) | |
C2 | 0.7818 (2) | 0.9710 (2) | 0.33545 (16) | 0.0265 (4) | |
H5 | 0.8047 | 1.0416 | 0.4025 | 0.032* | |
C18 | 0.7174 (2) | 0.4501 (2) | 0.40383 (16) | 0.0266 (4) | |
H6A | 0.6521 | 0.5092 | 0.4011 | 0.032* | |
H6B | 0.7988 | 0.4970 | 0.4713 | 0.032* | |
C7 | 0.9826 (2) | 0.7887 (2) | 0.14329 (15) | 0.0216 (4) | |
H7 | 0.9253 | 0.7226 | 0.0698 | 0.026* | |
C3 | 0.6328 (2) | 0.8933 (2) | 0.27553 (17) | 0.0272 (4) | |
C21 | 0.6408 (2) | 0.3647 (2) | 0.60345 (16) | 0.0261 (4) | |
C20 | 0.5396 (2) | 0.3075 (2) | 0.48869 (16) | 0.0282 (4) | |
H10A | 0.4775 | 0.3685 | 0.4796 | 0.034* | |
H10B | 0.4726 | 0.2109 | 0.4761 | 0.034* | |
C16 | 0.8769 (2) | 0.5855 (2) | 0.30509 (16) | 0.0268 (4) | |
H11A | 0.8158 | 0.6486 | 0.3035 | 0.032* | |
H11B | 0.9622 | 0.6312 | 0.3702 | 0.032* | |
C1 | 0.8963 (2) | 0.9404 (2) | 0.29264 (15) | 0.0228 (4) | |
C15 | 0.9334 (2) | 0.5636 (2) | 0.20475 (16) | 0.0249 (4) | |
H13A | 0.9785 | 0.4873 | 0.2007 | 0.030* | |
H13B | 0.8475 | 0.5310 | 0.1405 | 0.030* | |
C13 | 1.1778 (2) | 1.0475 (2) | 0.18368 (16) | 0.0273 (4) | |
C19 | 0.6274 (2) | 0.3021 (2) | 0.40408 (16) | 0.0291 (4) | |
H15A | 0.6963 | 0.2486 | 0.4177 | 0.035* | |
H15B | 0.5570 | 0.2497 | 0.3322 | 0.035* | |
C8 | 1.1112 (2) | 0.8998 (2) | 0.12618 (15) | 0.0244 (4) | |
C17 | 0.7835 (3) | 0.4409 (2) | 0.30818 (18) | 0.0338 (5) | |
H17A | 0.7014 | 0.3949 | 0.2411 | 0.041* | |
H17B | 0.8465 | 0.3796 | 0.3104 | 0.041* | |
C9 | 1.1641 (2) | 0.8421 (3) | 0.03912 (17) | 0.0338 (5) | |
H18 | 1.1217 | 0.7438 | 0.0004 | 0.041* | |
C14 | 1.0767 (3) | 1.2418 (2) | 0.2609 (2) | 0.0444 (6) | |
H19A | 1.1297 | 1.2932 | 0.2203 | 0.067* | |
H19B | 1.0895 | 1.3074 | 0.3313 | 0.067* | |
H19C | 0.9710 | 1.2007 | 0.2221 | 0.067* | |
C12 | 1.2910 (2) | 1.1316 (3) | 0.1514 (2) | 0.0381 (5) | |
H20 | 1.3341 | 1.2301 | 0.1891 | 0.046* | |
C10 | 1.2774 (3) | 0.9263 (3) | 0.0089 (2) | 0.0437 (6) | |
H21 | 1.3110 | 0.8851 | −0.0489 | 0.052* | |
C11 | 1.3399 (3) | 1.0725 (3) | 0.0656 (2) | 0.0437 (6) | |
H22 | 1.4151 | 1.1306 | 0.0455 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0319 (3) | 0.0313 (3) | 0.0597 (4) | 0.0146 (2) | 0.0278 (3) | 0.0173 (3) |
S1 | 0.0248 (2) | 0.0244 (2) | 0.0245 (2) | 0.00797 (19) | 0.00501 (19) | 0.0035 (2) |
Cl2 | 0.0313 (3) | 0.0342 (3) | 0.0234 (2) | 0.0100 (2) | 0.0077 (2) | 0.0005 (2) |
O2 | 0.0264 (7) | 0.0312 (7) | 0.0254 (7) | 0.0130 (6) | 0.0048 (6) | 0.0086 (6) |
N2 | 0.0221 (8) | 0.0241 (8) | 0.0221 (8) | 0.0099 (6) | 0.0091 (6) | 0.0075 (7) |
O4 | 0.0396 (9) | 0.0494 (9) | 0.0282 (8) | 0.0243 (8) | 0.0087 (7) | 0.0107 (7) |
O1 | 0.0359 (8) | 0.0334 (8) | 0.0324 (8) | 0.0106 (7) | 0.0060 (6) | −0.0025 (7) |
O3 | 0.0293 (8) | 0.0611 (10) | 0.0343 (8) | 0.0210 (7) | 0.0112 (6) | 0.0242 (8) |
N1 | 0.0265 (8) | 0.0238 (8) | 0.0337 (9) | 0.0080 (7) | 0.0070 (7) | 0.0102 (7) |
C5 | 0.0272 (10) | 0.0288 (10) | 0.0235 (10) | 0.0096 (8) | 0.0062 (8) | 0.0091 (8) |
C4 | 0.0223 (10) | 0.0304 (11) | 0.0353 (11) | 0.0078 (8) | 0.0088 (8) | 0.0132 (9) |
C6 | 0.0222 (9) | 0.0227 (9) | 0.0225 (9) | 0.0088 (7) | 0.0083 (7) | 0.0108 (8) |
C2 | 0.0321 (10) | 0.0236 (10) | 0.0290 (10) | 0.0129 (8) | 0.0132 (8) | 0.0096 (8) |
C18 | 0.0287 (10) | 0.0273 (10) | 0.0288 (10) | 0.0114 (8) | 0.0123 (8) | 0.0119 (9) |
C7 | 0.0234 (9) | 0.0242 (9) | 0.0180 (9) | 0.0085 (7) | 0.0065 (7) | 0.0068 (8) |
C3 | 0.0277 (10) | 0.0262 (10) | 0.0398 (11) | 0.0140 (8) | 0.0192 (9) | 0.0179 (9) |
C21 | 0.0273 (10) | 0.0261 (10) | 0.0300 (10) | 0.0086 (8) | 0.0106 (8) | 0.0160 (9) |
C20 | 0.0254 (10) | 0.0293 (10) | 0.0291 (10) | 0.0047 (8) | 0.0082 (8) | 0.0119 (9) |
C16 | 0.0299 (10) | 0.0284 (10) | 0.0264 (10) | 0.0109 (8) | 0.0135 (8) | 0.0103 (9) |
C1 | 0.0230 (9) | 0.0219 (9) | 0.0249 (9) | 0.0086 (7) | 0.0072 (7) | 0.0086 (8) |
C15 | 0.0274 (10) | 0.0221 (9) | 0.0271 (10) | 0.0081 (8) | 0.0112 (8) | 0.0083 (8) |
C13 | 0.0233 (10) | 0.0323 (11) | 0.0311 (10) | 0.0111 (8) | 0.0076 (8) | 0.0163 (9) |
C19 | 0.0324 (11) | 0.0262 (10) | 0.0272 (10) | 0.0064 (8) | 0.0107 (8) | 0.0074 (9) |
C8 | 0.0227 (9) | 0.0314 (10) | 0.0235 (9) | 0.0114 (8) | 0.0072 (8) | 0.0133 (8) |
C17 | 0.0452 (12) | 0.0280 (11) | 0.0340 (11) | 0.0132 (9) | 0.0209 (10) | 0.0105 (9) |
C9 | 0.0341 (11) | 0.0434 (12) | 0.0309 (11) | 0.0161 (10) | 0.0141 (9) | 0.0162 (10) |
C14 | 0.0553 (15) | 0.0302 (12) | 0.0531 (15) | 0.0198 (11) | 0.0141 (12) | 0.0171 (11) |
C12 | 0.0286 (11) | 0.0400 (13) | 0.0507 (14) | 0.0077 (9) | 0.0107 (10) | 0.0270 (12) |
C10 | 0.0401 (13) | 0.0665 (17) | 0.0386 (13) | 0.0212 (12) | 0.0233 (11) | 0.0272 (13) |
C11 | 0.0323 (12) | 0.0622 (17) | 0.0528 (15) | 0.0146 (11) | 0.0216 (11) | 0.0391 (14) |
Cl1—C3 | 1.7332 (19) | C7—H7 | 0.9800 |
S1—O1 | 1.4240 (15) | C21—C20 | 1.499 (3) |
S1—O2 | 1.4354 (14) | C20—C19 | 1.522 (3) |
S1—N1 | 1.6315 (17) | C20—H10A | 0.9700 |
S1—C1 | 1.7629 (19) | C20—H10B | 0.9700 |
N2—C15 | 1.507 (2) | C16—C15 | 1.513 (3) |
N2—C7 | 1.521 (2) | C16—C17 | 1.515 (3) |
N2—H3A | 0.9000 | C16—H11A | 0.9700 |
N2—H3B | 0.9000 | C16—H11B | 0.9700 |
O4—C21 | 1.328 (2) | C15—H13A | 0.9700 |
O4—H6 | 0.8200 | C15—H13B | 0.9700 |
O3—C21 | 1.204 (2) | C13—C8 | 1.397 (3) |
N1—C13 | 1.436 (3) | C13—C12 | 1.400 (3) |
N1—C14 | 1.480 (3) | C19—H15A | 0.9700 |
C5—C4 | 1.387 (3) | C19—H15B | 0.9700 |
C5—C6 | 1.392 (3) | C8—C9 | 1.401 (3) |
C5—H2 | 0.9300 | C17—H17A | 0.9700 |
C4—C3 | 1.381 (3) | C17—H17B | 0.9700 |
C4—H3 | 0.9300 | C9—C10 | 1.384 (3) |
C6—C1 | 1.398 (3) | C9—H18 | 0.9300 |
C6—C7 | 1.513 (2) | C14—H19A | 0.9600 |
C2—C3 | 1.388 (3) | C14—H19B | 0.9600 |
C2—C1 | 1.393 (3) | C14—H19C | 0.9600 |
C2—H5 | 0.9300 | C12—C11 | 1.369 (3) |
C18—C17 | 1.512 (3) | C12—H20 | 0.9300 |
C18—C19 | 1.518 (3) | C10—C11 | 1.381 (4) |
C18—H6A | 0.9700 | C10—H21 | 0.9300 |
C18—H6B | 0.9700 | C11—H22 | 0.9300 |
C7—C8 | 1.529 (2) | ||
O1—S1—O2 | 119.59 (9) | C15—C16—C17 | 109.79 (16) |
O1—S1—N1 | 108.15 (9) | C15—C16—H11A | 109.7 |
O2—S1—N1 | 106.88 (8) | C17—C16—H11A | 109.7 |
O1—S1—C1 | 108.63 (9) | C15—C16—H11B | 109.7 |
O2—S1—C1 | 109.38 (8) | C17—C16—H11B | 109.7 |
N1—S1—C1 | 102.91 (8) | H11A—C16—H11B | 108.2 |
C15—N2—C7 | 115.42 (14) | C2—C1—C6 | 122.19 (17) |
C15—N2—H3A | 108.4 | C2—C1—S1 | 118.86 (15) |
C7—N2—H3A | 108.4 | C6—C1—S1 | 118.74 (14) |
C15—N2—H3B | 108.4 | N2—C15—C16 | 114.61 (16) |
C7—N2—H3B | 108.4 | N2—C15—H13A | 108.6 |
H3A—N2—H3B | 107.5 | C16—C15—H13A | 108.6 |
C21—O4—H6 | 109.5 | N2—C15—H13B | 108.6 |
C13—N1—C14 | 117.16 (17) | C16—C15—H13B | 108.6 |
C13—N1—S1 | 120.96 (13) | H13A—C15—H13B | 107.6 |
C14—N1—S1 | 115.98 (15) | C8—C13—C12 | 119.4 (2) |
C4—C5—C6 | 121.92 (19) | C8—C13—N1 | 125.42 (17) |
C4—C5—H2 | 119.0 | C12—C13—N1 | 115.16 (19) |
C6—C5—H2 | 119.0 | C18—C19—C20 | 113.90 (17) |
C3—C4—C5 | 119.18 (18) | C18—C19—H15A | 108.8 |
C3—C4—H3 | 120.4 | C20—C19—H15A | 108.8 |
C5—C4—H3 | 120.4 | C18—C19—H15B | 108.8 |
C5—C6—C1 | 117.17 (17) | C20—C19—H15B | 108.8 |
C5—C6—C7 | 117.27 (17) | H15A—C19—H15B | 107.7 |
C1—C6—C7 | 125.46 (16) | C13—C8—C9 | 117.75 (18) |
C3—C2—C1 | 118.31 (18) | C13—C8—C7 | 128.70 (17) |
C3—C2—H5 | 120.8 | C9—C8—C7 | 113.54 (18) |
C1—C2—H5 | 120.8 | C18—C17—C16 | 114.47 (17) |
C17—C18—C19 | 112.27 (17) | C18—C17—H17A | 108.6 |
C17—C18—H6A | 109.2 | C16—C17—H17A | 108.6 |
C19—C18—H6A | 109.2 | C18—C17—H17B | 108.6 |
C17—C18—H6B | 109.2 | C16—C17—H17B | 108.6 |
C19—C18—H6B | 109.2 | H17A—C17—H17B | 107.6 |
H6A—C18—H6B | 107.9 | C10—C9—C8 | 122.2 (2) |
C6—C7—N2 | 111.23 (14) | C10—C9—H18 | 118.9 |
C6—C7—C8 | 120.45 (16) | C8—C9—H18 | 118.9 |
N2—C7—C8 | 109.32 (14) | N1—C14—H19A | 109.5 |
C6—C7—H7 | 104.8 | N1—C14—H19B | 109.5 |
N2—C7—H7 | 104.8 | H19A—C14—H19B | 109.5 |
C8—C7—H7 | 104.8 | N1—C14—H19C | 109.5 |
C4—C3—C2 | 121.21 (18) | H19A—C14—H19C | 109.5 |
C4—C3—Cl1 | 119.27 (15) | H19B—C14—H19C | 109.5 |
C2—C3—Cl1 | 119.51 (16) | C11—C12—C13 | 121.6 (2) |
O3—C21—O4 | 122.96 (19) | C11—C12—H20 | 119.2 |
O3—C21—C20 | 123.80 (19) | C13—C12—H20 | 119.2 |
O4—C21—C20 | 113.22 (17) | C11—C10—C9 | 119.1 (2) |
C21—C20—C19 | 112.61 (16) | C11—C10—H21 | 120.4 |
C21—C20—H10A | 109.1 | C9—C10—H21 | 120.4 |
C19—C20—H10A | 109.1 | C12—C11—C10 | 119.9 (2) |
C21—C20—H10B | 109.1 | C12—C11—H22 | 120.0 |
C19—C20—H10B | 109.1 | C10—C11—H22 | 120.0 |
H10A—C20—H10B | 107.8 | ||
O1—S1—N1—C13 | 166.82 (14) | N1—S1—C1—C2 | −116.33 (15) |
O2—S1—N1—C13 | 36.83 (17) | O1—S1—C1—C6 | 173.00 (14) |
C1—S1—N1—C13 | −78.34 (16) | O2—S1—C1—C6 | −54.86 (16) |
O1—S1—N1—C14 | −41.01 (17) | N1—S1—C1—C6 | 58.50 (16) |
O2—S1—N1—C14 | −170.99 (15) | C7—N2—C15—C16 | −92.52 (19) |
C1—S1—N1—C14 | 73.83 (17) | C17—C16—C15—N2 | −170.85 (16) |
C6—C5—C4—C3 | 0.0 (3) | C14—N1—C13—C8 | −117.4 (2) |
C4—C5—C6—C1 | −0.8 (3) | S1—N1—C13—C8 | 34.5 (3) |
C4—C5—C6—C7 | 175.82 (17) | C14—N1—C13—C12 | 61.3 (2) |
C5—C6—C7—N2 | −102.80 (18) | S1—N1—C13—C12 | −146.80 (15) |
C1—C6—C7—N2 | 73.5 (2) | C17—C18—C19—C20 | −171.27 (17) |
C5—C6—C7—C8 | 127.40 (18) | C21—C20—C19—C18 | −68.0 (2) |
C1—C6—C7—C8 | −56.3 (2) | C12—C13—C8—C9 | 1.3 (3) |
C15—N2—C7—C6 | 56.1 (2) | N1—C13—C8—C9 | 179.94 (17) |
C15—N2—C7—C8 | −168.43 (15) | C12—C13—C8—C7 | −177.35 (18) |
C5—C4—C3—C2 | 1.0 (3) | N1—C13—C8—C7 | 1.3 (3) |
C5—C4—C3—Cl1 | −179.69 (14) | C6—C7—C8—C13 | 27.4 (3) |
C1—C2—C3—C4 | −1.2 (3) | N2—C7—C8—C13 | −103.2 (2) |
C1—C2—C3—Cl1 | 179.56 (13) | C6—C7—C8—C9 | −151.28 (17) |
O3—C21—C20—C19 | −26.4 (3) | N2—C7—C8—C9 | 78.08 (19) |
O4—C21—C20—C19 | 155.14 (17) | C19—C18—C17—C16 | −178.95 (17) |
C3—C2—C1—C6 | 0.3 (3) | C15—C16—C17—C18 | −178.47 (17) |
C3—C2—C1—S1 | 174.95 (13) | C13—C8—C9—C10 | −0.6 (3) |
C5—C6—C1—C2 | 0.7 (3) | C7—C8—C9—C10 | 178.25 (19) |
C7—C6—C1—C2 | −175.65 (17) | C8—C13—C12—C11 | −0.9 (3) |
C5—C6—C1—S1 | −174.00 (13) | N1—C13—C12—C11 | −179.73 (19) |
C7—C6—C1—S1 | 9.7 (2) | C8—C9—C10—C11 | −0.5 (3) |
O1—S1—C1—C2 | −1.84 (17) | C13—C12—C11—C10 | −0.2 (3) |
O2—S1—C1—C2 | 130.31 (15) | C9—C10—C11—C12 | 0.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H3A···Cl2i | 0.90 | 2.31 | 3.154 (2) | 157 |
N2—H3B···O3ii | 0.90 | 2.32 | 2.821 (2) | 115 |
C16—H11B···O3ii | 0.97 | 2.56 | 3.201 (2) | 124 |
O4—H6···Cl2iii | 0.82 | 2.22 | 3.043 (2) | 176 |
C4—H3···Cl2iv | 0.93 | 2.82 | 3.651 (2) | 150 |
C18—H6A···O4v | 0.97 | 2.56 | 3.467 (2) | 157 |
C7—H7···Cl2 | 0.98 | 2.59 | 3.534 (2) | 162 |
N2—H3B···S1 | 0.90 | 2.98 | 3.533 (2) | 121 |
N2—H3B···O2 | 0.90 | 2.02 | 2.802 (2) | 144 |
C2—H5···O1 | 0.93 | 2.52 | 2.894 (2) | 104 |
C14—H19B···O1 | 0.96 | 2.48 | 2.881 (3) | 105 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+1, −y+1, −z; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C21H26ClN2O4S+·Cl− |
Mr | 473.40 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 190 |
a, b, c (Å) | 9.5439 (2), 10.0910 (2), 13.1802 (3) |
α, β, γ (°) | 104.4000 (12), 101.538 (1), 105.0180 (11) |
V (Å3) | 1139.04 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.24 × 0.20 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7552, 4985, 4015 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.100, 1.03 |
No. of reflections | 4985 |
No. of parameters | 273 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.34 |
Computer programs: COLLECT (Hooft, 1998), HKL DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H3A···Cl2i | 0.90 | 2.31 | 3.154 (2) | 156.7 |
N2—H3B···O3ii | 0.90 | 2.32 | 2.821 (2) | 115.2 |
C16—H11B···O3ii | 0.97 | 2.56 | 3.201 (2) | 123.5 |
O4—H6···Cl2iii | 0.82 | 2.22 | 3.043 (2) | 175.7 |
C4—H3···Cl2iv | 0.93 | 2.82 | 3.651 (2) | 149.6 |
C18—H6A···O4v | 0.97 | 2.56 | 3.467 (2) | 156.6 |
C7—H7···Cl2 | 0.98 | 2.59 | 3.534 (2) | 162.2 |
N2—H3B···O2 | 0.90 | 2.02 | 2.802 (2) | 144.0 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+1, −y+1, −z; (v) −x+1, −y+1, −z+1. |
Acknowledgements
This work was supported by the European Regional Development Fund (No. 2011/0014/2DP/2.1.1.1.0/10/APIA/VIAA/092).
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.
Tianeptine salts are of wide interest since they are crystalline. Although the synthesis of the title compound, tianeptine hydrochloride, has been described (Guzman et al., 2010) we describe in this article an improved method of its synthesis and its crystal structure.
In the title compound (Fig. 1), the seven-membered ring adopts a boat conformation with the values of torsion angles: C1—S1—N1—C13 = -78.4 (2) and C1—C6—C7—C8 = -56.3 (3)°. The dihedral angle between the mean planes of the two benzene rings (C1–C6 and C8–C13) is 44.44 (7)°. There is an intramolecular hydrogen bond in the title molecule which is formed via S1═O2···H3B—N2 that stabilizes the molecular structure. In the crystal, the molecules are connected via hydrogen bonds between carboxyl and amine groups and chloride anion, O4—H6···Cl2, N2—H3A···Cl2 and N2—H3B···O3. The crystal structure is further consolidated by intermolecular interactions, C18—H6A···O4, C4—H3···Cl2, C16—H11B···O3 and C7—H7···Cl2 (Table 1 and Fig. 2). The supramolecular structure of tianeptine hydrochloride consists of parallel oriented tricyclic fragment and parallel oriented carbon atom chains (heptanoic acid). Carbon atom chains are linked with hydrogen bonds via chloride anion, amine and carboxylgroup. The torsion angle C8—C7—N2—C15 is -168.4 (2)° so that the carbon atom chain C15—C20 is almost parallel to the benzene ring C8—C13.
The crystal structures of tianeptine polymorphs have been reported recently (Orola et al., 2012). The title structure is more similar with polymorph A structure in which tianeptine molecules are linked via hydrogen bonds between amine and carboxyl groups. The tianeptine molecules in the structure of tianeptine polymorph B are in a zwiterrion form.