(R)-[1-(2-Chloro­phen­yl)-2-meth­oxy-2-oxoeth­yl][2-(thio­phen-2-yl)eth­yl]ammonium (+)-camphor-10-sulfonate acetone monosolvate

Liang, Y.-S.; Mu, S.; Liu, Y.; Liu, D.-K.

doi:10.1107/S160053681004523X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3117

https://doi.org/10.1107/S160053681004523X

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(R)-[1-(2-Chlorophenyl)-2-methoxy-2-oxoethyl][2-(thiophen-2-yl)ethyl]ammonium (+)-camphor-10-sulfonate acetone monosolvate

Yan-Shu Liang,^a Shuai Mu,^b Ying Liu ^c ^* and Deng-Ke Liu ^c

^aTianjin University of Commerce, Tianjin 300134, People's Republic of China, ^bSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China, and ^cTianjin Institute of Pharmaceutical Research, Tianjin 300193, People's Republic of China
^*Correspondence e-mail: liudk@tjipr.com

(Received 9 October 2010; accepted 4 November 2010; online 10 November 2010)

The title compound, C₁₅H₁₇ClNO₂S⁺·C₁₀H₁₅O₄S⁻·C₃H₆O, was synthesized by N-alkylation of α-amino-(2-chlorophenyl)acetate with 2-thienylethyl p-toluenesulfonate, followed by reaction with (+)-camphor-10-sulfonic acid. In the crystal, the cations and anions are linked through N—H⋯O hydrogen bonds. The thiophene ring of the cation was found to be disordered over two sites, with refined occupancies of 0.798 (4) and 0.202 (4).

Related literature

For background to the antiplatelet agent clopidogrel, see: Kang et al. (2007 ). For the preparation of the title compound, an intermediate of clopidogrel, see: Descamps & Radisson (1992 ). For a database of bond lengths and angles, see: Bruno et al. (2004 ).

Experimental

Crystal data

C₁₅H₁₇ClNO₂S⁺·C₁₀H₁₅O₄S⁻·C₃H₆O
M_r = 600.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.101 (3) Å
b = 14.209 (4) Å
c = 18.325 (5) Å
V = 3150.7 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 294 K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART-CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.912, T_max = 0.943
18154 measured reflections
6435 independent reflections
4010 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.096
S = 0.99
6435 reflections
402 parameters
70 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 2828 Friedel pairs
Flack parameter: −0.04 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.93 (3)	1.82 (3)	2.729 (3)	164 (3)
N1—H1A⋯O5ⁱ	0.88 (3)	2.63 (2)	3.180 (3)	121.1 (19)
N1—H1A⋯O4ⁱ	0.88 (3)	1.99 (3)	2.856 (3)	169 (2)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681004523X/bh2318sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004523X/bh2318Isup2.hkl

checkCIF report

Comment top

Clopidogrel treatment is associated with a reduction in thrombotic complications in coronary stent placement, improved outcome after acute coronary syndromes, and decreased mortality in patients with coronary artery disease (Kang et al., 2007). Now, we present the crystal structure of the title compound, (I), an intermediate of Clopidogrel (Fig. 1, Table 1).

All bond lengths and angles in (I) are within normal ranges (Bruno et al., 2004). In the cation, C5 to C9, N1, O1 and O2 are almost coplanar (r.m.s. deviation 0.0363 Å and maximum deviation 0.0610 (2) Å). In the anion, the dihedral angles formed between C17 to C20 plane and C17/C20/C21 plane, C17/C20/C21 plane and C17/C20/C24/C25 plane are 54.45 (2)° and 54.47 (3)°, respectively. The crystal is stabilized by N—H···O hydrogen bonds between the cations and the anions, which link the molecules into sheets in the bc plane (Fig. 2, Table 2).

Related literature top

For background to the antiplatelet agent clopidogrel, see: Kang et al. (2007). For the preparation of the title compound, an intermediate of clopidogrel, see: Descamps & Radisson (1992). For a database of bond lengths and angles, see: Bruno et al. (2004).

Experimental top

(I) was prepared according to the method of Descamps & Radisson (1992). 12.5 g of methyl alpha-amino(2-chlorophenyl)acetate was released from its hydrochloride by reaction with 9 g of NaHCO₃ in the presence of 200 ml of CH₂Cl₂ and 65 ml of water. The resulting amine was dissolved in 65 ml of acetonitrile; 6.2 g of NaHCO₃ and 15.6 g of 2-thienylethyl-para-toluenesulfonate were then introduced; the mixture was kept at 353 K for 22 h and the volatile products were then evaporated off under reduced pressure. The residue was dissolved in 200 ml of ethyl acetate and 65 ml of water; the organic phase was separated off. After the usual treatments the aminoester was obtained and dissolved in 70 ml of acetone, then 8.7 g of (+)-10-camphorsulfonic acid was introduced. The mixture was stirred at room temperature for 12 h to get precipitate, and 11 g of camphorsulfonate was thus obtained. The camphorsulfonate was suspended in 50 ml of refluxing acetone and 25 ml of methyl ethyl ketone to obtain complete dissolution. The mixture was standing under 298 K, then white crystals were grown slowly. The crystals were washed with cold acetone, yield 6.8 g, m.p. 368 K.

Structure description top

For background to the antiplatelet agent clopidogrel, see: Kang et al. (2007). For the preparation of the title compound, an intermediate of clopidogrel, see: Descamps & Radisson (1992). For a database of bond lengths and angles, see: Bruno et al. (2004).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram for (I) with hydrogen bonds drawn as dashed lines.

(R)-[1-(2-Chlorophenyl)-2-methoxy-2-oxoethyl][2-(thiophen-2- yl)ethyl]ammonium (+)-camphor-10-sulfonate acetone monosolvate top

Crystal data top

C₁₅H₁₇ClNO₂S⁺·C₁₀H₁₅O₄S⁻·C₃H₆O	D_x = 1.265 Mg m⁻³
M_r = 600.16	Melting point: 368 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4370 reflections
a = 12.101 (3) Å	θ = 2.2–23.4°
b = 14.209 (4) Å	µ = 0.30 mm⁻¹
c = 18.325 (5) Å	T = 294 K
V = 3150.7 (14) Å³	Block, colourless
Z = 4	0.26 × 0.24 × 0.20 mm
F(000) = 1272

Data collection top

Bruker SMART-CCD area-detector diffractometer	6435 independent reflections
Radiation source: fine-focus sealed tube	4010 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 26.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→15
T_min = 0.912, T_max = 0.943	k = −17→17
18154 measured reflections	l = −13→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0457P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.003
6435 reflections	Δρ_max = 0.17 e Å⁻³
402 parameters	Δρ_min = −0.18 e Å⁻³
70 restraints	Absolute structure: Flack (1983), 2828 Friedel pairs
0 constraints	Absolute structure parameter: −0.04 (6)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₅H₁₇ClNO₂S⁺·C₁₀H₁₅O₄S⁻·C₃H₆O	V = 3150.7 (14) Å³
M_r = 600.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.101 (3) Å	µ = 0.30 mm⁻¹
b = 14.209 (4) Å	T = 294 K
c = 18.325 (5) Å	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker SMART-CCD area-detector diffractometer	6435 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4010 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.943	R_int = 0.039
18154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	Δρ_max = 0.17 e Å⁻³
S = 0.99	Δρ_min = −0.18 e Å⁻³
6435 reflections	Absolute structure: Flack (1983), 2828 Friedel pairs
402 parameters	Absolute structure parameter: −0.04 (6)
70 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.41386 (6)	0.37358 (5)	0.48307 (4)	0.0722 (2)
S2	0.77423 (6)	0.77371 (5)	0.58832 (4)	0.04884 (18)
O1	0.60127 (19)	0.69806 (14)	0.40519 (11)	0.0766 (6)
O2	0.62818 (19)	0.55299 (14)	0.36419 (11)	0.0779 (7)
O3	0.65698 (14)	0.75282 (13)	0.58489 (10)	0.0617 (5)
O4	0.83735 (15)	0.72491 (13)	0.53212 (9)	0.0610 (5)
O5	0.79800 (15)	0.87314 (12)	0.58933 (11)	0.0653 (5)
O6	0.6787 (2)	0.60281 (18)	0.75506 (17)	0.1049 (9)
N1	0.4941 (2)	0.64436 (14)	0.52533 (12)	0.0421 (5)
S1	0.40689 (11)	0.62354 (14)	0.78089 (8)	0.0841 (6)	0.798 (4)
C1	0.2895 (5)	0.5925 (5)	0.8266 (3)	0.0692 (18)	0.798 (4)
H1	0.2888	0.5652	0.8727	0.083*	0.798 (4)
C2	0.1991 (5)	0.6124 (5)	0.7880 (3)	0.0622 (16)	0.798 (4)
H2	0.1275	0.6025	0.8047	0.075*	0.798 (4)
C3	0.2257 (5)	0.6518 (10)	0.7158 (5)	0.0578 (19)	0.798 (4)
H3	0.1731	0.6706	0.6819	0.069*	0.798 (4)
C4	0.3347 (2)	0.65728 (18)	0.70495 (14)	0.0510 (7)	0.798 (4)
S1'	0.1970 (7)	0.6383 (13)	0.7155 (7)	0.082 (3)	0.202 (4)
C1'	0.2174 (16)	0.594 (2)	0.8011 (11)	0.058 (8)	0.202 (4)
H1'	0.1667	0.5567	0.8258	0.069*	0.202 (4)
C2'	0.3154 (17)	0.6201 (16)	0.8281 (7)	0.050 (6)	0.202 (4)
H2'	0.3368	0.6123	0.8765	0.060*	0.202 (4)
C3'	0.3863 (12)	0.6634 (16)	0.7701 (6)	0.077 (8)	0.202 (4)
H3'	0.4553	0.6904	0.7777	0.092*	0.202 (4)
C4'	0.3347 (2)	0.65728 (18)	0.70495 (14)	0.0510 (7)	0.202 (4)
C5	0.3906 (2)	0.69093 (18)	0.63647 (15)	0.0569 (7)
H5A	0.4520	0.7316	0.6494	0.068*
H5B	0.3387	0.7276	0.6079	0.068*
C6	0.4329 (2)	0.60951 (17)	0.59081 (14)	0.0534 (7)
H6A	0.4816	0.5707	0.6202	0.064*
H6B	0.3712	0.5709	0.5752	0.064*
C7	0.5266 (2)	0.56885 (16)	0.47250 (14)	0.0444 (6)
H7	0.4588	0.5425	0.4517	0.053*
C8	0.5905 (2)	0.61535 (19)	0.41131 (14)	0.0496 (6)
C9	0.6918 (3)	0.5885 (2)	0.30261 (18)	0.0890 (12)
H9A	0.6464	0.6296	0.2738	0.133*
H9B	0.7162	0.5367	0.2731	0.133*
H9C	0.7548	0.6226	0.3203	0.133*
C10	0.5895 (2)	0.48914 (16)	0.50914 (14)	0.0430 (6)
C11	0.6942 (2)	0.50530 (19)	0.53687 (16)	0.0614 (8)
H11	0.7251	0.5650	0.5332	0.074*
C12	0.7536 (3)	0.4337 (2)	0.56997 (18)	0.0763 (10)
H12	0.8237	0.4456	0.5886	0.092*
C13	0.7088 (3)	0.3454 (2)	0.5751 (2)	0.0829 (10)
H13	0.7489	0.2975	0.5974	0.100*
C14	0.6057 (3)	0.3269 (2)	0.54794 (18)	0.0684 (9)
H14	0.5760	0.2666	0.5513	0.082*
C15	0.5459 (2)	0.39861 (18)	0.51539 (14)	0.0506 (7)
C16	0.8220 (2)	0.7252 (2)	0.67130 (14)	0.0610 (7)
H16A	0.8147	0.6573	0.6679	0.073*
H16B	0.9004	0.7388	0.6750	0.073*
C17	0.7675 (2)	0.75628 (18)	0.74299 (13)	0.0502 (7)
C18	0.6771 (3)	0.8337 (2)	0.74243 (16)	0.0683 (9)
H18A	0.6980	0.8854	0.7107	0.082*
H18B	0.6068	0.8084	0.7262	0.082*
C19	0.6703 (3)	0.8666 (3)	0.82296 (18)	0.0803 (10)
H19A	0.6923	0.9319	0.8279	0.096*
H19B	0.5963	0.8587	0.8423	0.096*
C20	0.7528 (3)	0.8007 (3)	0.86121 (17)	0.0772 (10)
H20	0.7777	0.8227	0.9092	0.093*
C21	0.8457 (2)	0.7907 (2)	0.80388 (15)	0.0661 (8)
C22	0.9343 (3)	0.7182 (3)	0.8242 (2)	0.1106 (14)
H22A	0.9014	0.6568	0.8268	0.166*
H22B	0.9657	0.7341	0.8707	0.166*
H22C	0.9913	0.7182	0.7877	0.166*
C23	0.9031 (3)	0.8840 (3)	0.7847 (2)	0.1080 (13)
H23A	0.9479	0.9039	0.8250	0.162*
H23B	0.8483	0.9311	0.7746	0.162*
H23C	0.9488	0.8753	0.7424	0.162*
C24	0.7097 (3)	0.6759 (3)	0.7821 (2)	0.0713 (8)
C25	0.7012 (3)	0.7047 (3)	0.86146 (19)	0.0928 (11)
H25A	0.6247	0.7072	0.8773	0.111*
H25B	0.7417	0.6617	0.8927	0.111*
O7	0.5385 (3)	1.09004 (19)	0.51597 (19)	0.1357 (12)
C26	0.5766 (4)	0.9442 (3)	0.4603 (2)	0.1191 (15)
H26A	0.5182	0.9098	0.4369	0.179*
H26B	0.6277	0.9008	0.4821	0.179*
H26C	0.6145	0.9819	0.4248	0.179*
C27	0.5296 (3)	1.0056 (2)	0.5173 (2)	0.0789 (10)
C28	0.4691 (3)	0.9580 (3)	0.5765 (2)	0.0971 (12)
H28A	0.4356	1.0042	0.6077	0.146*
H28B	0.5195	0.9202	0.6045	0.146*
H28C	0.4127	0.9184	0.5560	0.146*
H1A	0.451 (2)	0.6847 (18)	0.5023 (14)	0.051 (8)*
H1B	0.558 (3)	0.676 (2)	0.5390 (16)	0.074 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0766 (5)	0.0706 (5)	0.0693 (5)	−0.0249 (4)	0.0075 (4)	−0.0046 (4)
S2	0.0504 (4)	0.0544 (4)	0.0417 (4)	−0.0062 (3)	0.0027 (3)	−0.0028 (3)
O1	0.1156 (17)	0.0536 (12)	0.0607 (13)	−0.0068 (11)	0.0315 (13)	0.0019 (10)
O2	0.1170 (17)	0.0568 (12)	0.0599 (13)	0.0153 (12)	0.0358 (13)	0.0003 (11)
O3	0.0508 (10)	0.0817 (14)	0.0527 (11)	−0.0132 (10)	0.0003 (10)	−0.0086 (11)
O4	0.0678 (11)	0.0693 (11)	0.0459 (10)	−0.0107 (10)	0.0147 (10)	−0.0115 (10)
O5	0.0747 (12)	0.0535 (11)	0.0677 (12)	−0.0128 (10)	0.0109 (11)	−0.0007 (10)
O6	0.0981 (19)	0.0734 (16)	0.143 (3)	−0.0087 (14)	0.0256 (17)	−0.0057 (16)
N1	0.0442 (13)	0.0422 (12)	0.0399 (13)	0.0020 (11)	0.0032 (11)	0.0029 (11)
S1	0.0663 (8)	0.1282 (14)	0.0576 (7)	0.0092 (9)	−0.0056 (6)	0.0178 (8)
C1	0.079 (4)	0.076 (5)	0.052 (3)	−0.006 (3)	0.004 (3)	0.015 (2)
C2	0.060 (3)	0.067 (3)	0.060 (3)	0.022 (3)	0.019 (2)	0.018 (3)
C3	0.056 (4)	0.068 (4)	0.049 (3)	−0.010 (4)	0.003 (3)	0.023 (2)
C4	0.0581 (18)	0.0524 (16)	0.0424 (17)	0.0046 (13)	0.0077 (14)	−0.0041 (13)
S1'	0.065 (4)	0.096 (7)	0.086 (5)	−0.005 (4)	0.023 (3)	0.018 (4)
C1'	0.056 (11)	0.063 (11)	0.054 (10)	−0.006 (8)	−0.002 (8)	0.010 (7)
C2'	0.063 (9)	0.050 (10)	0.036 (8)	−0.025 (7)	−0.002 (7)	0.001 (6)
C3'	0.071 (11)	0.094 (11)	0.065 (11)	0.019 (8)	0.017 (8)	0.028 (8)
C4'	0.0581 (18)	0.0524 (16)	0.0424 (17)	0.0046 (13)	0.0077 (14)	−0.0041 (13)
C5	0.0706 (19)	0.0489 (16)	0.0512 (17)	0.0003 (14)	0.0159 (15)	−0.0015 (13)
C6	0.0604 (16)	0.0541 (15)	0.0456 (15)	−0.0022 (13)	0.0114 (14)	0.0070 (14)
C7	0.0494 (15)	0.0435 (14)	0.0402 (14)	−0.0003 (11)	0.0014 (13)	−0.0018 (13)
C8	0.0573 (15)	0.0470 (16)	0.0443 (15)	0.0071 (13)	0.0043 (14)	0.0038 (14)
C9	0.114 (3)	0.090 (2)	0.063 (2)	0.024 (2)	0.040 (2)	0.0068 (19)
C10	0.0486 (15)	0.0442 (14)	0.0363 (14)	0.0024 (12)	0.0067 (13)	0.0012 (11)
C11	0.0599 (18)	0.0531 (16)	0.071 (2)	0.0039 (14)	−0.0038 (16)	0.0038 (15)
C12	0.066 (2)	0.077 (2)	0.086 (2)	0.0147 (17)	−0.0086 (17)	0.0120 (19)
C13	0.095 (3)	0.069 (2)	0.085 (2)	0.029 (2)	0.008 (2)	0.0193 (18)
C14	0.088 (2)	0.0448 (16)	0.072 (2)	0.0057 (17)	0.0225 (19)	0.0111 (15)
C15	0.0631 (17)	0.0475 (15)	0.0412 (15)	−0.0047 (13)	0.0167 (14)	−0.0008 (13)
C16	0.0644 (17)	0.0670 (18)	0.0516 (16)	0.0198 (15)	0.0014 (14)	−0.0017 (16)
C17	0.0508 (14)	0.0588 (16)	0.0410 (14)	0.0080 (13)	0.0049 (13)	0.0004 (12)
C18	0.074 (2)	0.082 (2)	0.0488 (18)	0.0280 (17)	0.0007 (15)	−0.0035 (15)
C19	0.081 (2)	0.094 (2)	0.067 (2)	0.018 (2)	0.0122 (19)	−0.019 (2)
C20	0.080 (2)	0.110 (3)	0.0417 (16)	0.009 (2)	0.0022 (16)	−0.0083 (18)
C21	0.0567 (17)	0.095 (2)	0.0466 (17)	0.0077 (18)	0.0010 (15)	−0.0069 (17)
C22	0.079 (2)	0.181 (4)	0.072 (2)	0.048 (3)	−0.018 (2)	0.004 (3)
C23	0.085 (2)	0.124 (3)	0.115 (3)	−0.023 (3)	0.015 (3)	−0.036 (3)
C24	0.0628 (19)	0.074 (2)	0.077 (2)	0.0079 (18)	0.0106 (19)	0.0023 (19)
C25	0.093 (3)	0.119 (3)	0.067 (2)	0.017 (2)	0.023 (2)	0.021 (2)
O7	0.187 (3)	0.0668 (16)	0.153 (3)	−0.0252 (18)	−0.005 (3)	0.0062 (18)
C26	0.156 (4)	0.107 (3)	0.095 (3)	0.026 (3)	0.020 (3)	0.021 (3)
C27	0.088 (2)	0.065 (2)	0.084 (3)	−0.0090 (19)	−0.024 (2)	0.005 (2)
C28	0.115 (3)	0.087 (2)	0.090 (3)	−0.009 (2)	−0.008 (2)	−0.007 (2)

Geometric parameters (Å, º) top

Cl1—C15	1.741 (3)	C11—H11	0.9300
S2—O5	1.4418 (18)	C12—C13	1.370 (4)
S2—O3	1.4510 (18)	C12—H12	0.9300
S2—O4	1.4577 (18)	C13—C14	1.369 (5)
S2—C16	1.767 (3)	C13—H13	0.9300
O1—C8	1.188 (3)	C14—C15	1.385 (4)
O2—C8	1.319 (3)	C14—H14	0.9300
O2—C9	1.456 (4)	C16—C17	1.535 (4)
O6—C24	1.210 (4)	C16—H16A	0.9700
N1—C6	1.494 (3)	C16—H16B	0.9700
N1—C7	1.498 (3)	C17—C24	1.519 (4)
N1—H1A	0.88 (3)	C17—C21	1.543 (4)
N1—H1B	0.93 (3)	C17—C18	1.552 (4)
S1—C1	1.706 (5)	C18—C19	1.550 (4)
S1—C4	1.712 (3)	C18—H18A	0.9700
C1—C2	1.333 (6)	C18—H18B	0.9700
C1—H1	0.9300	C19—C20	1.537 (4)
C2—C3	1.472 (7)	C19—H19A	0.9700
C2—H2	0.9300	C19—H19B	0.9700
C3—C4	1.335 (7)	C20—C25	1.501 (5)
C3—H3	0.9300	C20—C21	1.546 (4)
C4—C5	1.504 (4)	C20—H20	0.9800
S1'—C1'	1.709 (10)	C21—C22	1.533 (4)
C1'—C2'	1.338 (9)	C21—C23	1.537 (5)
C1'—H1'	0.9300	C22—H22A	0.9600
C2'—C3'	1.499 (9)	C22—H22B	0.9600
C2'—H2'	0.9300	C22—H22C	0.9600
C3'—H3'	0.9300	C23—H23A	0.9600
C5—C6	1.517 (4)	C23—H23B	0.9600
C5—H5A	0.9700	C23—H23C	0.9600
C5—H5B	0.9700	C24—C25	1.515 (5)
C6—H6A	0.9700	C25—H25A	0.9700
C6—H6B	0.9700	C25—H25B	0.9700
C7—C8	1.514 (3)	O7—C27	1.205 (4)
C7—C10	1.521 (3)	C26—C27	1.474 (5)
C7—H7	0.9800	C26—H26A	0.9600
C9—H9A	0.9600	C26—H26B	0.9600
C9—H9B	0.9600	C26—H26C	0.9600
C9—H9C	0.9600	C27—C28	1.474 (5)
C10—C11	1.385 (3)	C28—H28A	0.9600
C10—C15	1.395 (3)	C28—H28B	0.9600
C11—C12	1.385 (4)	C28—H28C	0.9600

O5—S2—O3	113.33 (12)	C14—C15—C10	121.1 (3)
O5—S2—O4	111.76 (11)	C14—C15—Cl1	118.4 (2)
O3—S2—O4	112.61 (11)	C10—C15—Cl1	120.5 (2)
O5—S2—C16	107.82 (14)	C17—C16—S2	118.91 (18)
O3—S2—C16	106.12 (13)	C17—C16—H16A	107.6
O4—S2—C16	104.52 (12)	S2—C16—H16A	107.6
C8—O2—C9	117.2 (2)	C17—C16—H16B	107.6
C6—N1—C7	114.31 (19)	S2—C16—H16B	107.6
C6—N1—H1A	107.9 (16)	H16A—C16—H16B	107.0
C7—N1—H1A	108.2 (16)	C24—C17—C16	112.7 (2)
C6—N1—H1B	111.0 (18)	C24—C17—C21	100.4 (2)
C7—N1—H1B	107.8 (17)	C16—C17—C21	116.5 (2)
H1A—N1—H1B	107 (2)	C24—C17—C18	102.2 (2)
C1—S1—C4	92.6 (2)	C16—C17—C18	120.1 (2)
C2—C1—S1	111.6 (4)	C21—C17—C18	102.2 (2)
C2—C1—H1	124.2	C19—C18—C17	104.2 (2)
S1—C1—H1	124.2	C19—C18—H18A	110.9
C1—C2—C3	112.2 (4)	C17—C18—H18A	110.9
C1—C2—H2	123.9	C19—C18—H18B	110.9
C3—C2—H2	123.9	C17—C18—H18B	110.9
C4—C3—C2	111.9 (5)	H18A—C18—H18B	108.9
C4—C3—H3	124.1	C20—C19—C18	102.5 (2)
C2—C3—H3	124.1	C20—C19—H19A	111.3
C3—C4—C5	126.0 (4)	C18—C19—H19A	111.3
C3—C4—S1	111.5 (4)	C20—C19—H19B	111.3
C5—C4—S1	122.5 (2)	C18—C19—H19B	111.3
C2'—C1'—S1'	111.5 (9)	H19A—C19—H19B	109.2
C2'—C1'—H1'	124.2	C25—C20—C19	106.6 (3)
S1'—C1'—H1'	124.2	C25—C20—C21	102.8 (3)
C1'—C2'—C3'	110.9 (8)	C19—C20—C21	102.6 (3)
C1'—C2'—H2'	124.5	C25—C20—H20	114.5
C3'—C2'—H2'	124.5	C19—C20—H20	114.5
C2'—C3'—H3'	125.2	C21—C20—H20	114.5
C4—C5—C6	111.7 (2)	C22—C21—C23	108.6 (3)
C4—C5—H5A	109.3	C22—C21—C17	113.0 (3)
C6—C5—H5A	109.3	C23—C21—C17	112.7 (3)
C4—C5—H5B	109.3	C22—C21—C20	113.9 (3)
C6—C5—H5B	109.3	C23—C21—C20	113.9 (3)
H5A—C5—H5B	107.9	C17—C21—C20	94.3 (2)
N1—C6—C5	111.0 (2)	C21—C22—H22A	109.5
N1—C6—H6A	109.4	C21—C22—H22B	109.5
C5—C6—H6A	109.4	H22A—C22—H22B	109.5
N1—C6—H6B	109.4	C21—C22—H22C	109.5
C5—C6—H6B	109.4	H22A—C22—H22C	109.5
H6A—C6—H6B	108.0	H22B—C22—H22C	109.5
N1—C7—C8	107.46 (19)	C21—C23—H23A	109.5
N1—C7—C10	112.3 (2)	C21—C23—H23B	109.5
C8—C7—C10	113.4 (2)	H23A—C23—H23B	109.5
N1—C7—H7	107.8	C21—C23—H23C	109.5
C8—C7—H7	107.8	H23A—C23—H23C	109.5
C10—C7—H7	107.8	H23B—C23—H23C	109.5
O1—C8—O2	124.4 (3)	O6—C24—C25	127.1 (4)
O1—C8—C7	123.9 (2)	O6—C24—C17	126.5 (3)
O2—C8—C7	111.6 (2)	C25—C24—C17	106.4 (3)
O2—C9—H9A	109.5	C20—C25—C24	102.3 (3)
O2—C9—H9B	109.5	C20—C25—H25A	111.3
H9A—C9—H9B	109.5	C24—C25—H25A	111.3
O2—C9—H9C	109.5	C20—C25—H25B	111.3
H9A—C9—H9C	109.5	C24—C25—H25B	111.3
H9B—C9—H9C	109.5	H25A—C25—H25B	109.2
C11—C10—C15	117.9 (2)	C27—C26—H26A	109.5
C11—C10—C7	119.8 (2)	C27—C26—H26B	109.5
C15—C10—C7	122.3 (2)	H26A—C26—H26B	109.5
C10—C11—C12	120.9 (3)	C27—C26—H26C	109.5
C10—C11—H11	119.5	H26A—C26—H26C	109.5
C12—C11—H11	119.5	H26B—C26—H26C	109.5
C13—C12—C11	119.8 (3)	O7—C27—C26	122.7 (4)
C13—C12—H12	120.1	O7—C27—C28	121.0 (4)
C11—C12—H12	120.1	C26—C27—C28	116.2 (3)
C14—C13—C12	120.8 (3)	C27—C28—H28A	109.5
C14—C13—H13	119.6	C27—C28—H28B	109.5
C12—C13—H13	119.6	H28A—C28—H28B	109.5
C13—C14—C15	119.4 (3)	C27—C28—H28C	109.5
C13—C14—H14	120.3	H28A—C28—H28C	109.5
C15—C14—H14	120.3	H28B—C28—H28C	109.5

C4—S1—C1—C2	−3.8 (6)	O3—S2—C16—C17	−57.0 (2)
S1—C1—C2—C3	2.3 (10)	O4—S2—C16—C17	−176.2 (2)
C1—C2—C3—C4	1.0 (13)	S2—C16—C17—C24	116.6 (3)
C2—C3—C4—C5	177.8 (6)	S2—C16—C17—C21	−128.1 (2)
C2—C3—C4—S1	−3.8 (12)	S2—C16—C17—C18	−3.8 (4)
C1—S1—C4—C3	4.4 (8)	C24—C17—C18—C19	71.6 (3)
C1—S1—C4—C5	−177.1 (3)	C16—C17—C18—C19	−162.9 (3)
S1'—C1'—C2'—C3'	−11 (3)	C21—C17—C18—C19	−32.0 (3)
C3—C4—C5—C6	−101.8 (8)	C17—C18—C19—C20	−3.0 (3)
S1—C4—C5—C6	80.0 (3)	C18—C19—C20—C25	−70.6 (3)
C7—N1—C6—C5	−172.8 (2)	C18—C19—C20—C21	37.0 (3)
C4—C5—C6—N1	−176.6 (2)	C24—C17—C21—C22	66.0 (3)
C6—N1—C7—C8	−178.2 (2)	C16—C17—C21—C22	−55.9 (4)
C6—N1—C7—C10	−52.8 (3)	C18—C17—C21—C22	171.1 (3)
C9—O2—C8—O1	3.1 (4)	C24—C17—C21—C23	−170.4 (2)
C9—O2—C8—C7	−179.7 (2)	C16—C17—C21—C23	67.7 (3)
N1—C7—C8—O1	−6.6 (4)	C18—C17—C21—C23	−65.3 (3)
C10—C7—C8—O1	−131.3 (3)	C24—C17—C21—C20	−52.2 (3)
N1—C7—C8—O2	176.3 (2)	C16—C17—C21—C20	−174.2 (2)
C10—C7—C8—O2	51.6 (3)	C18—C17—C21—C20	52.8 (3)
N1—C7—C10—C11	−67.7 (3)	C25—C20—C21—C22	−62.5 (4)
C8—C7—C10—C11	54.3 (3)	C19—C20—C21—C22	−173.0 (3)
N1—C7—C10—C15	113.0 (3)	C25—C20—C21—C23	172.1 (3)
C8—C7—C10—C15	−124.9 (3)	C19—C20—C21—C23	61.6 (4)
C15—C10—C11—C12	−0.2 (4)	C25—C20—C21—C17	55.0 (3)
C7—C10—C11—C12	−179.5 (3)	C19—C20—C21—C17	−55.5 (3)
C10—C11—C12—C13	0.4 (5)	C16—C17—C24—O6	−20.7 (4)
C11—C12—C13—C14	0.0 (5)	C21—C17—C24—O6	−145.4 (3)
C12—C13—C14—C15	−0.5 (5)	C18—C17—C24—O6	109.5 (3)
C13—C14—C15—C10	0.7 (4)	C16—C17—C24—C25	157.9 (3)
C13—C14—C15—Cl1	−178.6 (2)	C21—C17—C24—C25	33.2 (3)
C11—C10—C15—C14	−0.4 (4)	C18—C17—C24—C25	−71.8 (3)
C7—C10—C15—C14	178.9 (2)	C19—C20—C25—C24	71.9 (3)
C11—C10—C15—Cl1	179.0 (2)	C21—C20—C25—C24	−35.6 (3)
C7—C10—C15—Cl1	−1.8 (3)	O6—C24—C25—C20	179.9 (3)
O5—S2—C16—C17	64.8 (2)	C17—C24—C25—C20	1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.93 (3)	1.82 (3)	2.729 (3)	164 (3)
N1—H1A···O5ⁱ	0.88 (3)	2.63 (2)	3.180 (3)	121.1 (19)
N1—H1A···O4ⁱ	0.88 (3)	1.99 (3)	2.856 (3)	169 (2)

Symmetry code: (i) x−1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇ClNO₂S⁺·C₁₀H₁₅O₄S⁻·C₃H₆O
M_r	600.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	12.101 (3), 14.209 (4), 18.325 (5)
V (Å³)	3150.7 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART-CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.912, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	18154, 6435, 4010
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.096, 0.99
No. of reflections	6435
No. of parameters	402
No. of restraints	70
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18
Absolute structure	Flack (1983), 2828 Friedel pairs
Absolute structure parameter	−0.04 (6)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.93 (3)	1.82 (3)	2.729 (3)	164 (3)
N1—H1A···O5ⁱ	0.88 (3)	2.63 (2)	3.180 (3)	121.1 (19)
N1—H1A···O4ⁱ	0.88 (3)	1.99 (3)	2.856 (3)	169 (2)

Symmetry code: (i) x−1/2, −y+3/2, −z+1.

Acknowledgements

The authors thank Mr Hai-Bin Song (Nankai University) for the X-ray crystallographic determination and helpful discussions.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004). J. Chem. Inf. Comput. Sci. 44, 2133–2144. Web of Science CSD CrossRef PubMed CAS Google Scholar
Descamps, M. & Radisson, J. (1992). Eur. Patent EP 0 466569. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kang, W., Theman, T. E., Reed, J. F., Stoltzfus, J. & Weger, N. (2007). J. Surg. Educ. 64, 88–92. CrossRef PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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

(R)-[1-(2-Chloro­phen­yl)-2-meth­­oxy-2-oxoeth­yl][2-(thio­phen-2-yl)eth­yl]ammonium (+)-camphor-10-sulfonate acetone monosolvate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(R)-[1-(2-Chlorophenyl)-2-methoxy-2-oxoethyl][2-(thiophen-2-yl)ethyl]ammonium (+)-camphor-10-sulfonate acetone monosolvate