Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, C15H16NS+·C2H3O2-, has been crystallized as both a pure enantio­mer (1S,5R) and a racemate. The racemate crystallizes in the space group Cc, with mol­ecules of opposite handedness related to each other by the action of the c-glide. The enantio­mer is essentially isostructural with the racemate, except that the glide symmetry is violated by inter­change of CH and CH2 groups within the seven-membered ring. The space-group symmetry is reduced to P1 with two mol­ecules in the asymmetric unit. The enantio­mer structure shows disorder of the thio­phene ring for one of the mol­ecules in the asymmetric unit. The major component of the disorder has the thio­phene ring in the same position as in the racemate, but generates a higher-energy mol­ecular conformation. The minor disorder component has different inter­molecular inter­actions but retains a more stable mol­ecular conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112030569/eg3093sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030569/eg3093Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030569/eg3093IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112030569/eg3093Isup4.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112030569/eg3093sup5.pdf
Supplementary material

CCDC references: 899068; 899069

Comment top

The title compound, (I), shows a pharmacological profile as a triple monoamine re-uptake inhibitor, altering the level of activity of the monoamine neurotransmitters serotonin, noradrenaline and dopamine, for the treatment of neuropathic pain and other disorders of the central nervous system (Peters et al., 2006). The chirality of the molecule depends on the position of the double bond relative to the NH2+ bridge in the bicyclic ring (see scheme). For a given orientation of the seven-membered ring, the NH2+ bridge can lie either above or below the ring. In the solid state (with restricted rotation about the C—C bond between the thiophenyl and bicyclic rings) there is also the possibility for the S atom to lie either adjacent to the double bond (cis) or opposite it (trans).

The racemate, (I) (Fig. 1), and enantiomer, (II) (Fig. 2), are essentially isostructural. The primitive triclinic unit cell used to describe the structure of the enantiomer is transformed to the C-centred monoclinic cell of the racemate by the transformation matrix [0 1 1 / 0 -1 1 / 1 0 0]. Racemate (I) crystallizes in space group Cc, with molecules of opposite handedness related to each other by the action of the c-glide. The thiophenyl ring adopts the cis orientation with respect to the double bond of the bicyclic ring, and there is no indication of any disorder. The molecules form hydrogen-bonded chains along the c axis, with the acetate anions linking between the NH2+ groups (Table 1 and Fig. 3).

Initially, we also solved the structure of enantiomer (II) in space group Cc, with the implication that racemization had occurred at some stage in the synthesis or crystallization process. However, chiral high-performance liquid chromatography (chiral HPLC) clearly showed that the sample was a single enantiomer, causing us to re-examine the diffraction data. Integration of the data for (II) in the reported primitive cell gave Rint = 0.019 for 5001 unique reflections. In the C-centred monoclinic setting used for the racemate, Rint increased to 0.104 for 1972 unique data, and 163 reflections violate the systematic absence conditions for the c-glide at the 3σ(I) level. Thus, application of the primitive setting for (II) is supported by the diffraction data.

The structure of enantiomer (II) in space group P1 contains two molecules in the asymmetric unit. The c-glide present in the structure of (I) is violated in (II) only by the interchange of the CH and CH2 groups in one of the independent molecules. One of the two independent molecules is ordered, while the other displays disorder for the thiophenyl ring. The ordered molecule has the S atom in the cis orientation, while the disordered molecule has a cis:trans ratio of 0.161 (3):0.839 (3). This result was consistent in several crystals examined. The implication is that the orientation of the thiophenyl group is governed principally by the intermolecular interactions, rather than any intramolecular factor. The thiophenyl rings adopt (principally) the same orientation within the structures of (I) and (II), but the interchange of the CH and CH2 groups in one of the two independent molecules of enantiomer (II) results in the trans conformation for the majority component. The principal intermolecular interaction influenced by the disorder involves a neighbouring benzene ring (C1A–C6A) of the thiophenyl group (Fig. 4). The minority cis component makes a C—H···π contact (H7BA···Cgiii = 2.77 Å; Cg is the centroid of the C1A–C6A ring), while the majority trans component makes an S···π contact (S1C···Cgiii = 3.159 (1) Å) [symmetry code: (iii) x - 1, y - 1, z].

The fact that the disorder is observed in (II) suggests that there must be some intramolecular preference for the cis conformation. Calculations for an isolated molecule using density functional theory (DFT) methods support this interpretation (see Supplementary Materials for optimized molecular structures). Geometry optimization of an isolated molecule starting from the trans conformation causes the thiophenyl ring to rotate away from the plane containing the CH group by ca 31°. This alleviates a short H···H contact (H7BA···H10B = 2.29 Å) that exists in the coplanar arrangement observed in the crystal structure. By contrast, optimization of the cis conformation causes essentially no change from the conformation observed in the crystal structure. Thus, the coplanar trans conformation of the major disorder component in (II) is less favourable than the cis conformation in terms of the intramolecular energy, but this is outweighed by more favourable intermolecular interactions for the trans conformation in the crystal structure. In some molecules, the intermolecular preference for the trans conformation is overcome by the intramolecular preference for the cis arrangement.

Isostructural enantiomer/racemate pairs represent a special circumstance with regard to Wallach's rule (Brock et al., 1991). In accordance with expectation, the calculated density of racemate (I) is found to be marginally higher than that of enantiomer (II) (1.304 versus 1.302 Mg m-3), but the difference is barely significant and no firm conclusions can be drawn. Since the crystal structures of the enantiomer and racemate are essentially identical, their simulated powder X-ray diffraction (PXRD) patterns are also essentially identical, and any distinction between the pure enantiomer and the racemate cannot be expected to be made reliably by PXRD analysis. The enantiomer and racemate would also be expected to form solid solutions, which prevents optical resolution by crystallization. A similar case has been reported recently for citalopram oxalate (Lopez de Diego et al., 2011). It is perhaps interesting that the closest comparable compound in the Cambridge Structural Database (Version?; Allen, 2002), also exhibits pseudosymmetry: (1R)-2-(5-pyrimidinyl)-8-azoniabicyclo[3.2.1]oct-2-ene oxalate propan-2-ol solvate (Gundisch et al., 2001) crystallizes in space group P21, but clearly approximates P21/c.

Related literature top

For related literature, see: Accelrys (2011); Allen (2002); Brock et al. (1991); Delley (1990); Gundisch et al. (2001); Lopez de Diego, Bond & Dancer (2011); Malmgren et al. (2011); Peters et al. (2006).

Experimental top

The title compound was synthesized in high enantiomeric purity (ee 98.9%) according to the method of Malmgren et al. (2011).

Refinement top

H atoms bound to C atoms were placed in idealized positions, with C—H = 1.00 (Csp3—H), 0.99 (CH2), 0.98 (CH3) or 0.95 Å (Csp2—H), and refined as riding, with Uiso(H) = 1.2 or 1.5Ueq(C). The H atoms of the NH2+ group were visible in difference Fourier maps in both structures, but placed geometrically (N—H = 0.92 Å) and refined as riding [Uiso(H) = 1.2 Ueq(N)] for the final refinements. In both cases, the absolute structure was established reliably by refinement of the Flack parameter. For the enantiomer, (II), the thiophenyl ring was modelled in cis and trans orientations with respect to the position of the C9BC10B double bond by splitting atoms C7B/C7C and S1B/S1C. The bonds C6B—S1C, C8B—S1C, C1B—S1B and C8B—S1B were restrained to a common refined value with an s.u. value of 0.02 Å, and the bonds C6B—C7B, C7B—C8B, C1B—C7C and C7C—C8B were restrained to a second common refined value with an s.u. value of 0.02 Å. The five atoms of each thiophene ring were restrained to lie in a common plane, with an s.u. value of 0.01 Å. The DFT calculations were carried out using the DMol3 module (Delley, 1990) in Materials Studio (Accelrys, 2011), employing the B3LYP function with the DNP (double numerical plus d-functions plus polarization) basis set and a real-space cutoff of 4.4 Å for numerical integration.

Computing details top

For both compounds, data collection: APEX2 (Bruker Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the racemate, (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The two molecules in the asymmetric unit of the enantiomer, (II), with displacement ellipsoids drawn at the 50% probability level. Two orientations of the thiophene ring are present for one of the two molecules. For clarity, the acetate anions are not shown.
[Figure 3] Fig. 3. The hydrogen-bonded chain along the c axis in racemate (I). [Symmetry code: (i) x, -y + 1, z - 1/2.] In enantiomer (II), these chains lie along the a axis.
[Figure 4] Fig. 4. The intermolecular interactions for the two disorder components in enantiomer (II). For the trans component, a C—H···π contact is highlighted. For the cis component, an S···π contact is highlighted. [Symmetry code: (iii) x - 1, y - 1, z.]
(I) racemic 3-(1-benzothiophen-2-yl)-8-azoniabicyclo[3.2.1]oct-2-ene acetate top
Crystal data top
C15H16NS+·C2H3O2F(000) = 640
Mr = 301.39Dx = 1.304 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 2096 reflections
a = 13.316 (3) Åθ = 2.2–24.1°
b = 14.195 (3) ŵ = 0.22 mm1
c = 9.020 (2) ÅT = 180 K
β = 115.775 (11)°Block, colourless
V = 1535.3 (6) Å30.20 × 0.10 × 0.07 mm
Z = 4
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
2761 independent reflections
Radiation source: fine-focus sealed tube2318 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
thin–slice ω and ϕ scansθmax = 28.3°, θmin = 3.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1617
Tmin = 0.830, Tmax = 0.985k = 1817
6763 measured reflectionsl = 126
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0447P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2761 reflectionsΔρmax = 0.38 e Å3
191 parametersΔρmin = 0.22 e Å3
2 restraintsAbsolute structure: Flack (1983), with 731 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.08 (6)
Crystal data top
C15H16NS+·C2H3O2V = 1535.3 (6) Å3
Mr = 301.39Z = 4
Monoclinic, CcMo Kα radiation
a = 13.316 (3) ŵ = 0.22 mm1
b = 14.195 (3) ÅT = 180 K
c = 9.020 (2) Å0.20 × 0.10 × 0.07 mm
β = 115.775 (11)°
Data collection top
Bruker Nonius X8 APEXII CCD area-detector
diffractometer
2761 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2318 reflections with I > 2σ(I)
Tmin = 0.830, Tmax = 0.985Rint = 0.033
6763 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.38 e Å3
S = 1.03Δρmin = 0.22 e Å3
2761 reflectionsAbsolute structure: Flack (1983), with 731 Friedel pairs
191 parametersAbsolute structure parameter: 0.08 (6)
2 restraints
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
xyzUiso*/Ueq
S10.82597 (4)0.69612 (4)0.69210 (6)0.02854 (16)
N10.58047 (15)0.61525 (13)0.0583 (2)0.0226 (4)
H1A0.56460.56740.11360.027*
H1B0.52690.61640.04910.027*
C10.95027 (18)0.65266 (16)0.8414 (3)0.0221 (5)
C21.0011 (2)0.67765 (16)1.0075 (3)0.0258 (6)
H2A0.96620.72041.05150.031*
C31.1026 (2)0.63897 (16)1.1052 (3)0.0269 (6)
H3A1.13920.65621.21810.032*
C41.1535 (2)0.57451 (16)1.0422 (3)0.0277 (5)
H4A1.22340.54781.11310.033*
C51.1038 (2)0.54946 (17)0.8798 (3)0.0275 (6)
H5A1.13910.50580.83800.033*
C60.99990 (18)0.58867 (15)0.7750 (3)0.0206 (5)
C70.93440 (18)0.57468 (16)0.6004 (3)0.0230 (5)
H7A0.95450.53270.53570.028*
C80.83954 (18)0.62922 (15)0.5387 (3)0.0208 (5)
C90.75738 (18)0.63749 (15)0.3669 (3)0.0213 (5)
C100.7731 (2)0.58023 (17)0.2430 (3)0.0292 (6)
H10A0.76310.51300.26280.035*
H10B0.85060.58840.25730.035*
C110.69385 (19)0.60461 (17)0.0673 (3)0.0261 (5)
H11A0.69510.55540.01120.031*
C120.7142 (2)0.70305 (18)0.0157 (4)0.0374 (6)
H12A0.79310.72170.07950.045*
H12B0.69630.70410.10290.045*
C130.6380 (2)0.76940 (18)0.0511 (3)0.0363 (6)
H13A0.57900.79490.05220.044*
H13B0.68070.82240.12170.044*
C140.5883 (2)0.70743 (15)0.1404 (3)0.0234 (5)
H14A0.51340.73070.12470.028*
C150.6673 (2)0.69675 (16)0.3202 (3)0.0271 (6)
H15A0.65460.73100.40110.033*
O10.43447 (16)0.35790 (13)0.2336 (2)0.0392 (5)
O20.52871 (15)0.48369 (13)0.2234 (2)0.0444 (5)
C160.4560 (2)0.42187 (18)0.1567 (3)0.0282 (5)
C170.3890 (2)0.4266 (2)0.0281 (3)0.0421 (7)
H17A0.32900.37980.06320.063*
H17B0.43780.41340.08140.063*
H17C0.35680.48970.05950.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0257 (3)0.0390 (3)0.0187 (3)0.0054 (3)0.0076 (2)0.0028 (3)
N10.0225 (10)0.0269 (12)0.0143 (11)0.0023 (8)0.0041 (9)0.0016 (9)
C10.0209 (12)0.0235 (12)0.0198 (12)0.0016 (10)0.0069 (11)0.0051 (11)
C20.0321 (15)0.0270 (14)0.0193 (13)0.0041 (11)0.0123 (12)0.0042 (11)
C30.0317 (14)0.0297 (14)0.0156 (13)0.0079 (11)0.0068 (11)0.0013 (11)
C40.0237 (12)0.0308 (13)0.0184 (13)0.0020 (11)0.0004 (11)0.0032 (11)
C50.0270 (13)0.0270 (14)0.0273 (14)0.0041 (11)0.0107 (12)0.0023 (11)
C60.0229 (12)0.0212 (12)0.0171 (12)0.0017 (10)0.0080 (10)0.0005 (10)
C70.0188 (12)0.0275 (12)0.0163 (13)0.0021 (10)0.0017 (10)0.0044 (10)
C80.0238 (12)0.0221 (13)0.0170 (12)0.0030 (10)0.0092 (11)0.0008 (10)
C90.0219 (12)0.0244 (12)0.0169 (13)0.0016 (10)0.0076 (10)0.0030 (10)
C100.0273 (13)0.0369 (14)0.0206 (14)0.0070 (11)0.0078 (12)0.0032 (11)
C110.0241 (13)0.0356 (14)0.0176 (12)0.0075 (10)0.0081 (11)0.0029 (10)
C120.0310 (13)0.0535 (17)0.0302 (14)0.0016 (13)0.0158 (12)0.0042 (13)
C130.0465 (16)0.0311 (14)0.0310 (16)0.0024 (13)0.0167 (14)0.0052 (12)
C140.0241 (12)0.0272 (13)0.0177 (12)0.0065 (10)0.0079 (10)0.0004 (10)
C150.0266 (13)0.0339 (14)0.0167 (13)0.0050 (11)0.0055 (11)0.0028 (11)
O10.0457 (11)0.0416 (10)0.0199 (10)0.0160 (9)0.0046 (9)0.0039 (8)
O20.0494 (12)0.0506 (12)0.0192 (10)0.0246 (10)0.0018 (9)0.0047 (9)
C160.0274 (13)0.0330 (14)0.0198 (13)0.0033 (12)0.0061 (11)0.0003 (11)
C170.0444 (17)0.0483 (16)0.0192 (14)0.0113 (14)0.0002 (13)0.0057 (13)
Geometric parameters (Å, º) top
S1—C11.731 (2)C9—C101.469 (3)
S1—C81.751 (2)C10—C111.514 (3)
N1—C111.484 (3)C10—H10A0.990
N1—C141.484 (3)C10—H10B0.990
N1—H1A0.920C11—C121.534 (3)
N1—H1B0.920C11—H11A1.000
C1—C21.395 (3)C12—C131.517 (4)
C1—C61.402 (3)C12—H12A0.990
C2—C31.367 (4)C12—H12B0.990
C2—H2A0.950C13—C141.524 (3)
C3—C41.398 (3)C13—H13A0.990
C3—H3A0.950C13—H13B0.990
C4—C51.366 (3)C14—C151.509 (3)
C4—H4A0.950C14—H14A1.000
C5—C61.407 (3)C15—H15A0.950
C5—H5A0.950O1—C161.249 (3)
C6—C71.444 (3)O2—C161.250 (3)
C7—C81.376 (3)C16—C171.512 (4)
C7—H7A0.950C17—H17A0.980
C8—C91.462 (3)C17—H17B0.980
C9—C151.373 (3)C17—H17C0.980
C1—S1—C891.68 (11)C11—C10—H10B108.8
C11—N1—C14102.31 (17)H10A—C10—H10B107.7
C11—N1—H1A111.3N1—C11—C10108.04 (18)
C14—N1—H1A111.3N1—C11—C12101.56 (18)
C11—N1—H1B111.3C10—C11—C12113.0 (2)
C14—N1—H1B111.3N1—C11—H11A111.3
H1A—N1—H1B109.2C10—C11—H11A111.3
C2—C1—C6121.7 (2)C12—C11—H11A111.3
C2—C1—S1126.77 (18)C13—C12—C11106.22 (19)
C6—C1—S1111.54 (17)C13—C12—H12A110.5
C3—C2—C1118.2 (2)C11—C12—H12A110.5
C3—C2—H2A120.9C13—C12—H12B110.5
C1—C2—H2A120.9C11—C12—H12B110.5
C2—C3—C4121.3 (2)H12A—C12—H12B108.7
C2—C3—H3A119.4C12—C13—C14103.70 (18)
C4—C3—H3A119.4C12—C13—H13A111.0
C5—C4—C3120.8 (2)C14—C13—H13A111.0
C5—C4—H4A119.6C12—C13—H13B111.0
C3—C4—H4A119.6C14—C13—H13B111.0
C4—C5—C6119.6 (2)H13A—C13—H13B109.0
C4—C5—H5A120.2N1—C14—C15108.21 (18)
C6—C5—H5A120.2N1—C14—C13101.42 (18)
C1—C6—C5118.5 (2)C15—C14—C13111.5 (2)
C1—C6—C7112.4 (2)N1—C14—H14A111.7
C5—C6—C7129.0 (2)C15—C14—H14A111.7
C8—C7—C6112.1 (2)C13—C14—H14A111.7
C8—C7—H7A123.9C9—C15—C14119.9 (2)
C6—C7—H7A123.9C9—C15—H15A120.0
C7—C8—C9127.3 (2)C14—C15—H15A120.0
C7—C8—S1112.18 (17)O1—C16—O2124.1 (2)
C9—C8—S1120.47 (16)O1—C16—C17118.5 (2)
C15—C9—C8121.7 (2)O2—C16—C17117.5 (2)
C15—C9—C10120.0 (2)C16—C17—H17A109.5
C8—C9—C10118.26 (19)C16—C17—H17B109.5
C9—C10—C11113.90 (19)H17A—C17—H17B109.5
C9—C10—H10A108.8C16—C17—H17C109.5
C11—C10—H10A108.8H17A—C17—H17C109.5
C9—C10—H10B108.8H17B—C17—H17C109.5
C8—S1—C1—C2177.6 (2)S1—C8—C9—C150.5 (3)
C8—S1—C1—C60.21 (17)C7—C8—C9—C102.0 (3)
C6—C1—C2—C30.9 (3)S1—C8—C9—C10179.61 (16)
S1—C1—C2—C3176.72 (17)C15—C9—C10—C118.8 (3)
C1—C2—C3—C41.3 (3)C8—C9—C10—C11171.33 (19)
C2—C3—C4—C51.1 (4)C14—N1—C11—C1074.2 (2)
C3—C4—C5—C60.3 (3)C14—N1—C11—C1244.9 (2)
C2—C1—C6—C50.2 (3)C9—C10—C11—N144.6 (3)
S1—C1—C6—C5177.79 (17)C9—C10—C11—C1266.9 (3)
C2—C1—C6—C7178.6 (2)N1—C11—C12—C1323.1 (3)
S1—C1—C6—C70.7 (2)C10—C11—C12—C1392.4 (2)
C4—C5—C6—C10.1 (3)C11—C12—C13—C146.6 (3)
C4—C5—C6—C7178.0 (2)C11—N1—C14—C1567.7 (2)
C1—C6—C7—C81.5 (3)C11—N1—C14—C1349.7 (2)
C5—C6—C7—C8176.8 (2)C12—C13—C14—N133.9 (3)
C6—C7—C8—C9176.19 (19)C12—C13—C14—C1581.1 (2)
C6—C7—C8—S11.6 (2)C8—C9—C15—C14176.35 (19)
C1—S1—C8—C71.07 (17)C10—C9—C15—C143.8 (3)
C1—S1—C8—C9176.92 (18)N1—C14—C15—C934.3 (3)
C7—C8—C9—C15178.1 (2)C13—C14—C15—C976.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.921.742.659 (2)175
N1—H1B···O1i0.921.842.748 (3)168
N1—H1B···O2i0.922.503.125 (2)125
Symmetry code: (i) x, y+1, z1/2.
(II) (1S,5R)-3-(1-benzothiophen-2-yl)-8-azoniabicyclo[3.2.1]oct-2-ene acetate top
Crystal data top
C15H16NS+·C2H3O2Z = 2
Mr = 301.39F(000) = 320
Triclinic, P1Dx = 1.302 Mg m3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0244 (2) ÅCell parameters from 9266 reflections
b = 9.7278 (2) Åθ = 2.7–28.3°
c = 9.7492 (2) ŵ = 0.21 mm1
α = 92.9699 (10)°T = 180 K
β = 107.4568 (10)°Block, colourless
γ = 107.5510 (9)°0.30 × 0.20 × 0.10 mm
V = 768.85 (3) Å3
Data collection top
Bruker Nonius X8APEX-II CCD area-detector
diffractometer
5001 independent reflections
Radiation source: fine-focus sealed tube4845 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
thin–slice ω and ϕ scansθmax = 28.3°, θmin = 3.8°
Absorption correction: multi-scan
SADABS (Sheldrick, 2003)
h = 812
Tmin = 0.686, Tmax = 0.978k = 1212
11591 measured reflectionsl = 1312
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0503P)2 + 0.1048P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
5001 reflectionsΔρmax = 0.28 e Å3
392 parametersΔρmin = 0.30 e Å3
15 restraintsAbsolute structure: Flack (1983), with 1495 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (4)
Crystal data top
C15H16NS+·C2H3O2γ = 107.5510 (9)°
Mr = 301.39V = 768.85 (3) Å3
Triclinic, P1Z = 2
a = 9.0244 (2) ÅMo Kα radiation
b = 9.7278 (2) ŵ = 0.21 mm1
c = 9.7492 (2) ÅT = 180 K
α = 92.9699 (10)°0.30 × 0.20 × 0.10 mm
β = 107.4568 (10)°
Data collection top
Bruker Nonius X8APEX-II CCD area-detector
diffractometer
5001 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 2003)
4845 reflections with I > 2σ(I)
Tmin = 0.686, Tmax = 0.978Rint = 0.019
11591 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.28 e Å3
S = 1.03Δρmin = 0.30 e Å3
5001 reflectionsAbsolute structure: Flack (1983), with 1495 Friedel pairs
392 parametersAbsolute structure parameter: 0.04 (4)
15 restraints
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
xyzUiso*/UeqOcc. (<1)
S1A0.92758 (5)0.78674 (4)0.67832 (5)0.02490 (10)
N1A0.29271 (17)0.62201 (14)0.35050 (14)0.0202 (3)
H1A10.18530.56690.29860.024*
H1A20.34810.65390.28670.024*
C1A1.0775 (2)0.95512 (17)0.75951 (17)0.0199 (3)
C2A1.2436 (2)0.98124 (19)0.83688 (18)0.0230 (4)
H2AA1.28800.90390.84680.028*
C3A1.3410 (2)1.12308 (19)0.89839 (17)0.0244 (4)
H3AA1.45401.14330.95240.029*
C4A1.2772 (2)1.23727 (19)0.88308 (19)0.0260 (4)
H4AA1.34751.33410.92570.031*
C5A1.1127 (2)1.21131 (18)0.80647 (18)0.0250 (4)
H5AA1.06981.28970.79680.030*
C6A1.0092 (2)1.06753 (17)0.74282 (16)0.0195 (3)
C7A0.8359 (2)1.01438 (16)0.66399 (16)0.0190 (3)
H7AA0.77071.07600.64200.023*
C8A0.7738 (2)0.86641 (16)0.62369 (16)0.0186 (3)
C9A0.6018 (2)0.77596 (16)0.54911 (16)0.0178 (3)
C10A0.5530 (2)0.63007 (17)0.52372 (18)0.0211 (3)
H10A0.63320.58300.55170.025*
C11A0.3751 (2)0.53857 (17)0.45227 (18)0.0214 (3)
H11A0.36280.44160.40190.026*
C12A0.2819 (2)0.5227 (2)0.5611 (2)0.0300 (4)
H12A0.34840.50640.65600.036*
H12B0.17590.44110.52370.036*
C13A0.2538 (2)0.6702 (2)0.5748 (2)0.0310 (4)
H13A0.32350.72920.67130.037*
H13B0.13700.65540.56320.037*
C14A0.3014 (2)0.74739 (17)0.45242 (19)0.0225 (3)
H14A0.22100.79630.40410.027*
C15A0.4780 (2)0.85361 (17)0.50280 (19)0.0244 (4)
H15A0.49700.90680.42240.029*
H15B0.49360.92610.58550.029*
S1B0.42432 (6)0.17978 (5)0.28834 (6)0.02165 (17)0.839 (3)
C7B0.3395 (3)0.1674 (2)0.5171 (3)0.0217 (5)0.839 (3)
H7BA0.27560.14590.57980.026*0.839 (3)
S1C0.3073 (4)0.1548 (3)0.5558 (3)0.0212 (10)*0.161 (3)
C7C0.4172 (9)0.1825 (5)0.3422 (16)0.035 (4)*0.161 (3)
H7CA0.41470.17030.24410.042*0.161 (3)
N1B0.20674 (17)0.14930 (14)0.11866 (14)0.0212 (3)
H1B10.15150.21350.14950.025*
H1B20.31390.20100.06280.025*
C1B0.5733 (2)0.26028 (16)0.45439 (17)0.0213 (3)
C2B0.7393 (2)0.33661 (18)0.4762 (2)0.0255 (4)
H2BA0.78060.34440.39690.031*
C3B0.8408 (2)0.39987 (18)0.6156 (2)0.0265 (4)
H3BA0.95330.45360.63230.032*
C4B0.7821 (2)0.38696 (19)0.73292 (19)0.0264 (4)
H4BA0.85520.43090.82820.032*
C5B0.6190 (2)0.31092 (19)0.71210 (18)0.0253 (4)
H5BA0.57950.30270.79240.030*
C6B0.5119 (2)0.24589 (15)0.57087 (17)0.0202 (3)
C8B0.27246 (19)0.12536 (15)0.37092 (16)0.0178 (3)
C9B0.0996 (2)0.05028 (16)0.28095 (16)0.0185 (3)
C10B0.0217 (2)0.0225 (2)0.33677 (18)0.0273 (4)
H10B0.00450.04910.43850.033*
C11B0.1993 (2)0.0497 (2)0.24428 (18)0.0273 (4)
H11B0.26800.10170.30150.033*
C12B0.2687 (3)0.0605 (2)0.1638 (2)0.0374 (5)
H12C0.23140.15500.22830.045*
H12D0.39070.02280.12670.045*
C13B0.1981 (3)0.0766 (2)0.0377 (2)0.0357 (5)
H13C0.28640.06490.05600.043*
H13D0.11310.17370.05380.043*
C14B0.1229 (2)0.04465 (18)0.03746 (17)0.0226 (3)
H14B0.14820.09170.06430.027*
C15B0.0621 (2)0.00580 (19)0.11972 (17)0.0231 (4)
H15C0.10510.07430.10550.028*
H15D0.11860.08970.07960.028*
O1A0.47056 (17)0.73005 (17)0.05354 (14)0.0364 (3)
O2A0.45648 (17)0.70628 (18)0.16624 (14)0.0437 (4)
C16A0.3919 (2)0.68835 (19)0.03088 (18)0.0247 (4)
C17A0.2069 (2)0.6116 (2)0.0333 (2)0.0350 (5)
H17A0.17440.59260.13960.052*
H17B0.14980.67370.00520.052*
H17C0.17720.51890.00370.052*
O1B0.96725 (17)0.44813 (13)0.23143 (17)0.0360 (3)
O2B0.96090 (17)0.66694 (15)0.18906 (18)0.0408 (4)
C16B0.8922 (2)0.53307 (18)0.18487 (19)0.0252 (4)
C17B0.7061 (2)0.4739 (2)0.1185 (3)0.0411 (5)
H17D0.66840.36710.10720.062*
H17E0.67230.50440.02290.062*
H17F0.65720.51210.18230.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0146 (2)0.01952 (18)0.0364 (2)0.00667 (14)0.00257 (16)0.00194 (15)
N1A0.0134 (7)0.0219 (6)0.0218 (6)0.0027 (5)0.0044 (5)0.0012 (5)
C1A0.0153 (8)0.0205 (7)0.0219 (7)0.0033 (6)0.0064 (6)0.0017 (6)
C2A0.0155 (8)0.0268 (8)0.0268 (8)0.0086 (7)0.0050 (6)0.0074 (6)
C3A0.0145 (8)0.0321 (8)0.0227 (7)0.0042 (7)0.0042 (6)0.0054 (6)
C4A0.0187 (8)0.0235 (8)0.0279 (8)0.0009 (6)0.0032 (7)0.0019 (6)
C5A0.0209 (9)0.0205 (8)0.0298 (8)0.0047 (7)0.0054 (7)0.0032 (6)
C6A0.0168 (8)0.0208 (7)0.0195 (7)0.0050 (6)0.0052 (6)0.0038 (5)
C7A0.0154 (8)0.0196 (7)0.0208 (7)0.0075 (6)0.0029 (6)0.0037 (6)
C8A0.0140 (8)0.0216 (7)0.0204 (7)0.0075 (6)0.0044 (6)0.0029 (6)
C9A0.0130 (8)0.0208 (7)0.0191 (7)0.0066 (6)0.0040 (6)0.0025 (5)
C10A0.0141 (8)0.0215 (8)0.0261 (7)0.0070 (6)0.0035 (6)0.0024 (6)
C11A0.0146 (8)0.0179 (7)0.0299 (8)0.0052 (6)0.0052 (6)0.0029 (6)
C12A0.0235 (9)0.0333 (9)0.0323 (9)0.0052 (7)0.0112 (7)0.0115 (7)
C13A0.0251 (10)0.0375 (10)0.0329 (9)0.0098 (8)0.0147 (8)0.0000 (7)
C14A0.0150 (8)0.0199 (7)0.0314 (8)0.0069 (6)0.0052 (6)0.0010 (6)
C15A0.0157 (8)0.0172 (7)0.0356 (9)0.0056 (6)0.0022 (7)0.0017 (6)
S1B0.0145 (3)0.0281 (3)0.0185 (3)0.00221 (18)0.00562 (18)0.00133 (16)
C7B0.0173 (11)0.0280 (11)0.0194 (10)0.0037 (8)0.0094 (9)0.0036 (8)
N1B0.0132 (7)0.0224 (6)0.0248 (7)0.0043 (5)0.0036 (5)0.0029 (5)
C1B0.0216 (9)0.0206 (7)0.0209 (7)0.0102 (6)0.0026 (6)0.0023 (6)
C2B0.0271 (10)0.0244 (8)0.0311 (8)0.0106 (7)0.0156 (7)0.0075 (7)
C3B0.0155 (8)0.0213 (8)0.0409 (9)0.0043 (6)0.0084 (7)0.0071 (7)
C4B0.0164 (8)0.0275 (8)0.0274 (8)0.0043 (6)0.0008 (6)0.0017 (6)
C5B0.0194 (9)0.0298 (8)0.0235 (8)0.0043 (7)0.0065 (7)0.0043 (6)
C6B0.0144 (8)0.0184 (7)0.0260 (8)0.0044 (6)0.0048 (6)0.0034 (6)
C8B0.0144 (8)0.0187 (7)0.0214 (7)0.0048 (6)0.0083 (6)0.0035 (5)
C9B0.0150 (8)0.0187 (7)0.0191 (7)0.0036 (6)0.0040 (6)0.0016 (5)
C10B0.0170 (9)0.0418 (10)0.0193 (7)0.0051 (7)0.0063 (6)0.0006 (7)
C11B0.0149 (8)0.0428 (10)0.0216 (7)0.0056 (7)0.0073 (6)0.0004 (7)
C12B0.0243 (10)0.0386 (10)0.0465 (11)0.0147 (8)0.0063 (8)0.0088 (8)
C13B0.0317 (11)0.0317 (9)0.0419 (11)0.0144 (8)0.0048 (9)0.0112 (8)
C14B0.0165 (8)0.0287 (8)0.0201 (7)0.0049 (6)0.0048 (6)0.0038 (6)
C15B0.0171 (8)0.0300 (8)0.0190 (7)0.0027 (7)0.0069 (6)0.0014 (6)
O1A0.0187 (7)0.0580 (8)0.0237 (6)0.0017 (6)0.0059 (5)0.0057 (6)
O2A0.0200 (7)0.0712 (10)0.0235 (6)0.0047 (7)0.0041 (5)0.0062 (6)
C16A0.0150 (8)0.0297 (8)0.0249 (8)0.0040 (6)0.0041 (6)0.0030 (6)
C17A0.0172 (9)0.0449 (11)0.0316 (9)0.0007 (8)0.0039 (7)0.0017 (8)
O1B0.0198 (7)0.0231 (6)0.0544 (8)0.0055 (5)0.0015 (6)0.0073 (6)
O2B0.0186 (7)0.0238 (6)0.0695 (10)0.0046 (5)0.0016 (7)0.0110 (6)
C16B0.0162 (8)0.0248 (8)0.0284 (8)0.0038 (7)0.0018 (6)0.0021 (6)
C17B0.0175 (10)0.0323 (10)0.0581 (13)0.0017 (8)0.0031 (9)0.0095 (9)
Geometric parameters (Å, º) top
S1A—C1A1.7397 (15)C7C—H7CA0.950
S1A—C8A1.7485 (17)N1B—C14B1.488 (2)
N1A—C11A1.484 (2)N1B—C11B1.494 (2)
N1A—C14A1.500 (2)N1B—H1B10.920
N1A—H1A10.920N1B—H1B20.920
N1A—H1A20.920C1B—C2B1.401 (3)
C1A—C2A1.397 (2)C1B—C6B1.401 (2)
C1A—C6A1.402 (2)C2B—C3B1.375 (3)
C2A—C3A1.379 (2)C2B—H2BA0.950
C2A—H2AA0.950C3B—C4B1.394 (3)
C3A—C4A1.392 (3)C3B—H3BA0.950
C3A—H3AA0.950C4B—C5B1.380 (2)
C4A—C5A1.384 (3)C4B—H4BA0.950
C4A—H4AA0.950C5B—C6B1.404 (2)
C5A—C6A1.410 (2)C5B—H5BA0.950
C5A—H5AA0.950C8B—C9B1.471 (2)
C6A—C7A1.433 (2)C9B—C10B1.327 (2)
C7A—C8A1.365 (2)C9B—C15B1.515 (2)
C7A—H7AA0.950C10B—C11B1.504 (2)
C8A—C9A1.465 (2)C10B—H10B0.950
C9A—C10A1.338 (2)C11B—C12B1.535 (3)
C9A—C15A1.505 (2)C11B—H11B1.000
C10A—C11A1.502 (2)C12B—C13B1.540 (3)
C10A—H10A0.950C12B—H12C0.990
C11A—C12A1.528 (3)C12B—H12D0.990
C11A—H11A1.000C13B—C14B1.529 (3)
C12A—C13A1.536 (3)C13B—H13C0.990
C12A—H12A0.990C13B—H13D0.990
C12A—H12B0.990C14B—C15B1.528 (2)
C13A—C14A1.542 (3)C14B—H14B1.000
C13A—H13A0.990C15B—H15C0.990
C13A—H13B0.990C15B—H15D0.990
C14A—C15A1.528 (2)O1A—C16A1.248 (2)
C14A—H14A1.000O2A—C16A1.251 (2)
C15A—H15A0.990C16A—C17A1.520 (2)
C15A—H15B0.990C17A—H17A0.980
S1B—C1B1.7232 (16)C17A—H17B0.980
S1B—C8B1.7536 (16)C17A—H17C0.980
C7B—C8B1.356 (3)O1B—C16B1.240 (2)
C7B—C6B1.425 (3)O2B—C16B1.255 (2)
C7B—H7BA0.950C16B—C17B1.516 (3)
S1C—C8B1.727 (4)C17B—H17D0.980
S1C—C6B1.747 (4)C17B—H17E0.980
C7C—C8B1.375 (10)C17B—H17F0.980
C7C—C1B1.449 (10)
C1A—S1A—C8A91.90 (8)C6B—C1B—C7C95.9 (6)
C11A—N1A—C14A102.09 (12)C2B—C1B—S1B125.46 (13)
C11A—N1A—H1A1111.4C6B—C1B—S1B113.12 (13)
C14A—N1A—H1A1111.4C3B—C2B—C1B118.04 (16)
C11A—N1A—H1A2111.4C3B—C2B—H2BA121.0
C14A—N1A—H1A2111.4C1B—C2B—H2BA121.0
H1A1—N1A—H1A2109.2C2B—C3B—C4B121.45 (16)
C2A—C1A—C6A122.19 (14)C2B—C3B—H3BA119.3
C2A—C1A—S1A126.93 (13)C4B—C3B—H3BA119.3
C6A—C1A—S1A110.84 (12)C5B—C4B—C3B120.68 (16)
C3A—C2A—C1A117.79 (17)C5B—C4B—H4BA119.7
C3A—C2A—H2AA121.1C3B—C4B—H4BA119.7
C1A—C2A—H2AA121.1C4B—C5B—C6B119.25 (17)
C2A—C3A—C4A121.46 (16)C4B—C5B—H5BA120.4
C2A—C3A—H3AA119.3C6B—C5B—H5BA120.4
C4A—C3A—H3AA119.3C1B—C6B—C5B119.16 (15)
C5A—C4A—C3A120.72 (15)C1B—C6B—C7B109.44 (17)
C5A—C4A—H4AA119.6C5B—C6B—C7B131.34 (18)
C3A—C4A—H4AA119.6C1B—C6B—S1C125.16 (17)
C4A—C5A—C6A119.40 (18)C5B—C6B—S1C115.66 (17)
C4A—C5A—H5AA120.3C7B—C8B—C7C95.8 (6)
C6A—C5A—H5AA120.3C7B—C8B—C9B129.51 (17)
C1A—C6A—C5A118.44 (16)C7C—C8B—C9B134.7 (6)
C1A—C6A—C7A112.34 (13)C7C—C8B—S1C110.4 (6)
C5A—C6A—C7A129.18 (17)C9B—C8B—S1C114.89 (16)
C8A—C7A—C6A113.33 (15)C7B—C8B—S1B110.41 (15)
C8A—C7A—H7AA123.3C9B—C8B—S1B120.03 (11)
C6A—C7A—H7AA123.3S1C—C8B—S1B125.07 (15)
C7A—C8A—C9A127.68 (15)C10B—C9B—C8B122.01 (14)
C7A—C8A—S1A111.57 (12)C10B—C9B—C15B120.16 (14)
C9A—C8A—S1A120.72 (11)C8B—C9B—C15B117.83 (14)
C10A—C9A—C8A122.57 (16)C9B—C10B—C11B122.18 (15)
C10A—C9A—C15A120.18 (15)C9B—C10B—H10B118.9
C8A—C9A—C15A117.25 (13)C11B—C10B—H10B118.9
C9A—C10A—C11A121.94 (16)N1B—C11B—C10B108.52 (15)
C9A—C10A—H10A119.0N1B—C11B—C12B100.41 (14)
C11A—C10A—H10A119.0C10B—C11B—C12B110.77 (16)
N1A—C11A—C10A108.47 (13)N1B—C11B—H11B112.2
N1A—C11A—C12A101.38 (14)C10B—C11B—H11B112.2
C10A—C11A—C12A111.13 (14)C12B—C11B—H11B112.2
N1A—C11A—H11A111.8C11B—C12B—C13B103.48 (16)
C10A—C11A—H11A111.8C11B—C12B—H12C111.1
C12A—C11A—H11A111.8C13B—C12B—H12C111.1
C11A—C12A—C13A102.85 (13)C11B—C12B—H12D111.1
C11A—C12A—H12A111.2C13B—C12B—H12D111.1
C13A—C12A—H12A111.2H12C—C12B—H12D109.0
C11A—C12A—H12B111.2C14B—C13B—C12B105.28 (15)
C13A—C12A—H12B111.2C14B—C13B—H13C110.7
H12A—C12A—H12B109.1C12B—C13B—H13C110.7
C12A—C13A—C14A106.09 (15)C14B—C13B—H13D110.7
C12A—C13A—H13A110.5C12B—C13B—H13D110.7
C14A—C13A—H13A110.5H13C—C13B—H13D108.8
C12A—C13A—H13B110.5N1B—C14B—C15B107.82 (13)
C14A—C13A—H13B110.5N1B—C14B—C13B102.99 (15)
H13A—C13A—H13B108.7C15B—C14B—C13B113.55 (15)
N1A—C14A—C15A107.56 (14)N1B—C14B—H14B110.7
N1A—C14A—C13A101.86 (13)C15B—C14B—H14B110.7
C15A—C14A—C13A113.28 (15)C13B—C14B—H14B110.7
N1A—C14A—H14A111.2C9B—C15B—C14B111.35 (15)
C15A—C14A—H14A111.2C9B—C15B—H15C109.4
C13A—C14A—H14A111.2C14B—C15B—H15C109.4
C9A—C15A—C14A111.74 (13)C9B—C15B—H15D109.4
C9A—C15A—H15A109.3C14B—C15B—H15D109.4
C14A—C15A—H15A109.3H15C—C15B—H15D108.0
C9A—C15A—H15B109.3O1A—C16A—O2A123.78 (16)
C14A—C15A—H15B109.3O1A—C16A—C17A118.57 (15)
H15A—C15A—H15B107.9O2A—C16A—C17A117.64 (16)
C1B—S1B—C8B91.19 (8)C16A—C17A—H17A109.5
C8B—C7B—C6B115.8 (2)C16A—C17A—H17B109.5
C8B—C7B—H7BA122.1H17A—C17A—H17B109.5
C6B—C7B—H7BA122.1C16A—C17A—H17C109.5
C8B—S1C—C6B85.40 (18)H17A—C17A—H17C109.5
C8B—C7C—C1B123.1 (11)H17B—C17A—H17C109.5
C8B—C7C—H7CA118.4O1B—C16B—O2B124.04 (17)
C1B—C7C—H7CA118.4O1B—C16B—C17B118.97 (15)
C14B—N1B—C11B101.97 (13)O2B—C16B—C17B116.99 (17)
C14B—N1B—H1B1111.4C16B—C17B—H17D109.5
C11B—N1B—H1B1111.4C16B—C17B—H17E109.5
C14B—N1B—H1B2111.4H17D—C17B—H17E109.5
C11B—N1B—H1B2111.4C16B—C17B—H17F109.5
H1B1—N1B—H1B2109.2H17D—C17B—H17F109.5
C2B—C1B—C6B121.40 (14)H17E—C17B—H17F109.5
C2B—C1B—C7C142.7 (6)
C8A—S1A—C1A—C2A177.24 (16)C2B—C1B—C6B—C5B0.7 (2)
C8A—S1A—C1A—C6A0.48 (12)C7C—C1B—C6B—C5B177.7 (2)
C6A—C1A—C2A—C3A0.3 (2)S1B—C1B—C6B—C5B177.79 (14)
S1A—C1A—C2A—C3A177.21 (13)C2B—C1B—C6B—C7B178.27 (16)
C1A—C2A—C3A—C4A0.7 (3)C7C—C1B—C6B—C7B0.16 (14)
C2A—C3A—C4A—C5A0.7 (3)S1B—C1B—C6B—C7B0.25 (12)
C3A—C4A—C5A—C6A0.3 (3)C2B—C1B—C6B—S1C179.34 (17)
C2A—C1A—C6A—C5A0.1 (2)C7C—C1B—C6B—S1C0.91 (15)
S1A—C1A—C6A—C5A177.94 (13)C4B—C5B—C6B—C1B0.2 (2)
C2A—C1A—C6A—C7A177.92 (15)C4B—C5B—C6B—C7B177.14 (16)
S1A—C1A—C6A—C7A0.08 (17)C4B—C5B—C6B—S1C178.97 (17)
C4A—C5A—C6A—C1A0.1 (2)C8B—C7B—C6B—C1B0.44 (16)
C4A—C5A—C6A—C7A177.57 (16)C8B—C7B—C6B—C5B176.69 (18)
C1A—C6A—C7A—C8A0.81 (19)C8B—S1C—C6B—C1B1.73 (18)
C5A—C6A—C7A—C8A176.95 (17)C8B—S1C—C6B—C5B176.90 (14)
C6A—C7A—C8A—C9A176.59 (15)C6B—C7B—C8B—C7C0.79 (18)
C6A—C7A—C8A—S1A1.16 (17)C6B—C7B—C8B—C9B176.65 (15)
C1A—S1A—C8A—C7A0.94 (13)C6B—C7B—C8B—S1B0.91 (17)
C1A—S1A—C8A—C9A176.98 (13)C1B—C7C—C8B—C7B1.0 (2)
C7A—C8A—C9A—C10A175.23 (17)C1B—C7C—C8B—C9B176.22 (19)
S1A—C8A—C9A—C10A2.3 (2)C1B—C7C—C8B—S1C2.0 (3)
C7A—C8A—C9A—C15A3.8 (2)C6B—S1C—C8B—C7C1.8 (2)
S1A—C8A—C9A—C15A178.63 (12)C6B—S1C—C8B—C9B176.81 (13)
C8A—C9A—C10A—C11A177.58 (14)C1B—S1B—C8B—C7B0.86 (13)
C15A—C9A—C10A—C11A1.4 (3)C1B—S1B—C8B—C9B176.96 (13)
C14A—N1A—C11A—C10A65.81 (16)C7B—C8B—C9B—C10B5.4 (3)
C14A—N1A—C11A—C12A51.25 (14)C7C—C8B—C9B—C10B171.0 (2)
C9A—C10A—C11A—N1A30.9 (2)S1C—C8B—C9B—C10B7.2 (2)
C9A—C10A—C11A—C12A79.7 (2)S1B—C8B—C9B—C10B171.93 (15)
N1A—C11A—C12A—C13A37.56 (16)C7B—C8B—C9B—C15B175.16 (17)
C10A—C11A—C12A—C13A77.53 (17)C7C—C8B—C9B—C15B8.4 (3)
C11A—C12A—C13A—C14A10.82 (18)S1C—C8B—C9B—C15B173.39 (15)
C11A—N1A—C14A—C15A75.78 (15)S1B—C8B—C9B—C15B7.5 (2)
C11A—N1A—C14A—C13A43.57 (16)C8B—C9B—C10B—C11B177.90 (16)
C12A—C13A—C14A—N1A19.48 (18)C15B—C9B—C10B—C11B1.5 (3)
C12A—C13A—C14A—C15A95.74 (17)C14B—N1B—C11B—C10B65.34 (17)
C10A—C9A—C15A—C14A9.6 (2)C14B—N1B—C11B—C12B50.88 (16)
C8A—C9A—C15A—C14A169.49 (14)C9B—C10B—C11B—N1B30.4 (2)
N1A—C14A—C15A—C9A46.99 (18)C9B—C10B—C11B—C12B79.0 (2)
C13A—C14A—C15A—C9A64.8 (2)N1B—C11B—C12B—C13B37.13 (17)
C8B—C7C—C1B—C2B177.0 (2)C10B—C11B—C12B—C13B77.39 (18)
C8B—C7C—C1B—C6B0.8 (2)C11B—C12B—C13B—C14B10.55 (19)
C8B—C7C—C1B—S1B179.5 (7)C11B—N1B—C14B—C15B75.95 (17)
C8B—S1B—C1B—C2B177.82 (15)C11B—N1B—C14B—C13B44.38 (16)
C8B—S1B—C1B—C6B0.64 (11)C12B—C13B—C14B—N1B20.20 (18)
C6B—C1B—C2B—C3B1.2 (2)C12B—C13B—C14B—C15B96.11 (17)
C7C—C1B—C2B—C3B176.3 (2)C10B—C9B—C15B—C14B9.9 (2)
S1B—C1B—C2B—C3B177.17 (13)C8B—C9B—C15B—C14B169.50 (13)
C1B—C2B—C3B—C4B1.1 (3)N1B—C14B—C15B—C9B47.76 (19)
C2B—C3B—C4B—C5B0.6 (3)C13B—C14B—C15B—C9B65.68 (19)
C3B—C4B—C5B—C6B0.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
X—X···Xi0000
N1A—H1A2···O2A0.921.752.664 (2)177
N1A—H1A1···O1Bii0.921.852.7550 (18)168
N1B—H1B2···O1Aiii0.921.832.7346 (19)169
N1B—H1B1···O2Biii0.921.752.663 (2)173
Symmetry codes: (i) x+3, y+3, z+3; (ii) x1, y, z; (iii) x1, y1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H16NS+·C2H3O2C15H16NS+·C2H3O2
Mr301.39301.39
Crystal system, space groupMonoclinic, CcTriclinic, P1
Temperature (K)180180
a, b, c (Å)13.316 (3), 14.195 (3), 9.020 (2)9.0244 (2), 9.7278 (2), 9.7492 (2)
α, β, γ (°)90, 115.775 (11), 9092.9699 (10), 107.4568 (10), 107.5510 (9)
V3)1535.3 (6)768.85 (3)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.220.21
Crystal size (mm)0.20 × 0.10 × 0.070.30 × 0.20 × 0.10
Data collection
DiffractometerBruker Nonius X8 APEXII CCD area-detector
diffractometer
Bruker Nonius X8APEX-II CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
SADABS (Sheldrick, 2003)
Tmin, Tmax0.830, 0.9850.686, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
6763, 2761, 2318 11591, 5001, 4845
Rint0.0330.019
(sin θ/λ)max1)0.6680.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.084, 1.03 0.028, 0.074, 1.03
No. of reflections27615001
No. of parameters191392
No. of restraints215
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.220.28, 0.30
Absolute structureFlack (1983), with 731 Friedel pairsFlack (1983), with 1495 Friedel pairs
Absolute structure parameter0.08 (6)0.04 (4)

Computer programs: APEX2 (Bruker Nonius, 2004), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.921.742.659 (2)175.3
N1—H1B···O1i0.921.842.748 (3)167.8
N1—H1B···O2i0.922.503.125 (2)125.0
Symmetry code: (i) x, y+1, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
X—X···Xi0000
N1A—H1A2···O2A0.921.752.664 (2)176.9
N1A—H1A1···O1Bii0.921.852.7550 (18)168.2
N1B—H1B2···O1Aiii0.921.832.7346 (19)169.2
N1B—H1B1···O2Biii0.921.752.663 (2)172.9
Symmetry codes: (i) x+3, y+3, z+3; (ii) x1, y, z; (iii) x1, y1, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds