7-[(3-Chloro-6-methyl-6,11-dihydro­dibenzo[c,f][1,2]thia­zepin-11-yl)amino]­hepta­noic acid S,S-dioxide hydro­chloride

Mishnev, A.; Zvirgzdins, A.; Actins, A.; Delina, M.

doi:10.1107/S1600536812042432

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3136

doi:10.1107/S1600536812042432

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7-[(3-Chloro-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepin-11-yl)amino]heptanoic acid S,S-dioxide hydrochloride

Anatoly Mishnev,^a Alvis Zvirgzdins,^b ^* Andris Actins ^b and Mara Delina ^b

^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

(Received 31 August 2012; accepted 10 October 2012; online 13 October 2012)

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

C₂₁H₂₆ClN₂O₄S⁺·Cl⁻
M_r = 473.40
Triclinic, $[P \overline 1]$
a = 9.5439 (2) Å
b = 10.0910 (2) Å
c = 13.1802 (3) Å
α = 104.000 (1)°
β = 101.538 (1)°
γ = 105.018 (1)°
V = 1139.04 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 190 K
0.24 × 0.20 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
7552 measured reflections
4985 independent reflections
4015 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.03
4985 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Cl2^iv	0.93	2.82	3.651 (2)	150
C18—H6A⋯O4^v	0.97	2.56	3.467 (2)	157
C7—H7⋯Cl2	0.98	2.59	3.534 (2)	162
N2—H3B⋯O2	0.90	2.02	2.802 (2)	144
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.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: 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

Crystal structure: contains datablock global. DOI: 10.1107/S1600536812042432/pv2586sup1.cif

checkCIF report

Comment top

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.

Related literature top

For general information about tianeptine and its preparation, see: Guzman et al. (2010). For related structures, see: Orola et al. (2012).

Experimental top

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.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: 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).

Figures top

	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.

7-[(3-Chloro-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepin- 11-yl)amino]heptanoic acid S,S-dioxide hydrochloride top

Crystal data top

C₂₁H₂₆ClN₂O₄S⁺·Cl⁻	Z = 2
M_r = 473.40	F(000) = 496
Triclinic, P1	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	4015 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 27.1°, θ_min = 3.1°
CCD scans	h = −11→12
7552 measured reflections	k = −12→12
4985 independent reflections	l = −16→16

Refinement top

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(F_o²) + (0.0363P)² + 0.641P] where P = (F_o² + 2F_c²)/3
4985 reflections	(Δ/σ)_max = 0.018
273 parameters	Δρ_max = 0.76 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₁H₂₆ClN₂O₄S⁺·Cl⁻	γ = 105.0180 (11)°
M_r = 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)°

Data collection top

Nonius KappaCCD diffractometer	4015 reflections with I > 2σ(I)
7552 measured reflections	R_int = 0.021
4985 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	Δρ_max = 0.76 e Å⁻³
4985 reflections	Δρ_min = −0.34 e Å⁻³
273 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cl2^iv	0.93	2.82	3.651 (2)	150
C18—H6A···O4^v	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⁻
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···Cl2^iv	0.93	2.82	3.651 (2)	149.6
C18—H6A···O4^v	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

Guzman, H., Popov, A., Rammeloo, T. J. L., Remenar, J., Saoud, J. B. & Tawa, M. (2010). US Patent No. 20,100,112,051 A1 20100506. Google Scholar
Hooft, R. (1998). COLLECT. Nonius B V, Delft, The Netherlands. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Orola, L., Veidis, M. V., Sarcevica, I., Actins, A., Belyakov, S. & Platonenko, A. (2012). Int. J. Pharm. 432, 50–56. Web of Science CrossRef CAS PubMed Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

7-[(3-Chloro-6-methyl-6,11-di­hydro­dibenzo[c,f][1,2]thia­zepin-11-yl)amino]­hepta­noic acid S,S-dioxide hydro­chloride

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

7-[(3-Chloro-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepin-11-yl)amino]heptanoic acid S,S-dioxide hydrochloride