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The closely related compounds cis-(2RS,4SR)-2-(thio­phen-2-yl)-2,3,4,5-tetra­hydro-1H-1-benzazepin-4-ol, C14H15NOS, (I), and cis-(2RS,4SR)-2-(5-methyl­thio­phen-2-yl)-2,3,4,5-tetra­hy­dro-1H-1-benzazepin-4-ol, C15H17NOS, (II), both crystallize with Z' = 2 in the space group P\overline{1}. In (I), the thienyl substituent in one of the two independent mol­ecules is disordered over two sets of atomic sites having occupancies of 0.856 (2) and 0.144 (2). In both compounds, the two independent hy­droxy O atoms are both within 2.8 Å of the hy­droxy O atoms of two neighbouring mol­ecules, and all of the hy­droxy H atoms are disordered, each over two sites. The resulting O-H...O hydrogen bonds generate two similar but distinct C44(8) chains, depending upon which hy­droxy H-atom sites are occupied or vacant, with full correlation of the hy­droxy H-atom occupancies within each chain. Comparisons are made with the supra­molecular assembly in some related compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112003988/yf3011sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112003988/yf3011Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112003988/yf3011IIsup3.hkl
Contains datablock II

CCDC references: 873895; 873896

Comment top

We have recently described a simple and efficient synthetic route to novel fused benzo[b]- and naphtho[1,2-b]tetrahydro-1H-azepines substituted at the C2 position with different aryl and alkenyl fragments (Gómez-Ayala et al., 2006; Palma et al., 2006; Acosta et al., 2010). In addition, the potential application of these types of compounds as promising agents against the parasites Trypanosoma cruzi and Leishmania chagasi has been demonstrated(Palma et al., 2009; Gómez-Ayala et al., 2010). Based on these previous results and as a continuation of a systematic programme to identify new antiparasitic compounds in the tetrahydro-1-benzazepine series, we have now achieved the stereoselective synthesis of the cis-2-(thiophen-2-yl)-2,3,4,5-tetrahydro-1H-benzazepin-4-ols, compounds (I) and (II), by reductive cleavage of the N—O bond in the corresponding 2-exo-1,4-epoxy compounds using an excess of zinc powder in acetic and hydrochloric acids. We report here the molecular and supramolecular structures of (I) and (II) (Figs. 1 and 2), which we compare with the 2-vinyl-substituted analogues (III)-(V) (see scheme), the structures of which were reported recently (Acosta et al., 2009).

Compounds (I) and (II) were prepared by reduction of the corresponding 1,4-epoxy-2-exo-thienyl-2,3,4,5-tetrahydro-1-benzazepine derivatives, which had themselves been synthesized by a straightforward adaptation of the method used for the 2-exo-styryl analogues (Acosta et al., 2008). Both compounds crystallize with Z' = 2 in space group P1, but a search for possible additional crystallographic symmetry revealed none: comparison of the atomic coordinates for corresponding pairs of atoms in the two independent molecules confirmed the absence of any additional symmetry. Moreover, in (I), although not in (II), one of the two independent molecules exhibits orientational disorder of the thienyl substituent; this alone is sufficient to preclude the possibility of any additional crystallographic symmetry in (I).

While the unit-cell repeat vectors a, b and c exhibit somewhat similar sets of values in (I) and (II), the unit-cell angles appear to be significantly different: these angles are all in excess of 100° in (I), while they are all less than 90° in (II), so ruling out any possibility of even approximate isomorphism. However, the cell angle β in (II) is only a little less than 90°, and if the value of this angle is artificially set to be slightly greater than 90° then the resulting reduced cell has all its angles greater than 90°, so showing much greater similarity with the unit cell of (I).

The molecules of (I) and (II) each contain two stereogenic centres and, for each compound, the asymmetric unit was selected so that the two independent molecules were of the same hand, with the R configuration at atoms C12 and C22. On this basis, the configuration at atoms C14 and C24 in the selected asymmetric units is S. Since the centrosymmetric space group P1 accommodates equal numbers of the two enantiomers, both compounds are racemic with relative the configuration 2RS,4SR.

As noted above, the thienyl substituent in molecule 2 of (I) (containing atom N21, see Fig. 1) exhibits orientational disorder, with refined site occupancies for the major and minor components (containing atoms S221 and S321, respectively, Fig. 1) are 0.856 (2) and 0.144 (2), respectively. The torsion angles defining the orientation of the thienyl substituents (Table 1) (a) confirm the approximate 180° rotation relating the major and minor orientations of the disorder components in (I), (b) indicate a significant difference between the two independent molecules in (II), so ruling out any possible additional symmetry, and (c) indicate, for the ordered molecules, a fairly similar but by no means identical conformation in both compounds.

In addition, the hydroxy H atom is disordered over two sites in each of the independent molecules of both compounds (Figs. 1 and 2, Table 2), which has some interesting implications for the hydrogen-bonding scheme, as discussed below.

The supramolecular assembly in both compounds is dominated by O—H···O hydrogen bonds, augmented in each case by a single C—H···π(arene) hydrogen bond (Table 2). There is also a weak C—H···O interaction in (I), but the N—H bonds play no role in the hydrogen bonding. The behaviour of the O—H···O hydrogen bonds is the same for both compounds, so these interactions will be discussed first, in the specific context of (I), followed by a consideration of the other hydrogen bonds and their actions.

The disorder of the hydroxy H atoms means that at any O atom Ox41 (where x = 1 or 2), if the site Hx41 is occupied, then the site Hx42 must be vacant. Within the bimolecular unit defined by the selected asymmetric units of both (I) and (II), atom O141 acts as hydrogen-bond donor via H141 to atom O241, and atom O241 acts in turn as donor via H241 to atom O141. However, the corresponding H141···H241 distances are only ca 1.16 Å in (I) and 1.13 Å in (II), so that in any specific bimolecular unit of this type, if the site H141 is occupied, the two sites H142 and H241 must be vacant, so that the site H242 is also occupied. Similarly, if the site H141 is vacant, so too is the site H242, while the two sites H142 and H241 must both be occupied.

Similar considerations apply to the pairs of hydrogen bonds linking symmetry-related asymmetric units. Atoms O141 and O241 at (x, y, z) act as hydrogen-bond donors via H142 and H242, respectively, to the inversion-related atoms O141 and O241 at (1 - x, 1 - y, 1 - z) and (-x, 1 - y, 1 - z), respectively. The distances between the two inversion-related hydroxy H-atom sites across (1/2, 1/2, 1/2) are 1.28 Å in (I) and 1.16 Å in (II), while the corresponding H···H distances across (0, 1/2, 1/2) are 1.21 Å in (I) and 1.38 Å in (II). Thus, for any specific pair of inversion-related hydroxy O atoms within hydrogen-bonding range, only one of the two H-atom sites can be occupied, while the other must be vacant.

These constraints on the occupancies of the hydroxy H-atom sites give rise to two similar but distinct types of C44(8) chains (Bernstein et al., 1995) running parallel to the [100] direction (Fig. 3). In one such chain, involving the occupied sites H141 and H242 at (x, y, z) and H142 and H241 at (1 - x, 1 - y, 1 - z), together with their equivalents by translation along [100], the O—H···O hydrogen bonds are all directed towards the negative direction of a (Fig. 3a). In the other chain, involving the occupied sites H142 and H241 at (x, y, z), H141 and H242 at (1 - x, 1 - y, 1 - z), and their translational equivalents, the O—H···O hydrogen bonds are all directed towards the positive direction of a (Fig. 3b). Thus, within any given chain, the locations of the hydroxy H atoms within any such chain are fully correlated, but there is no necessary correlation between the sense of the hydrogen-bonds in adjacent chains; the alternative directions of the hydrogen bonds in the chains are likely to be randomly distributed.

Entirely similar comments apply to the O—H···O hydrogen bonds in (II), where the O···O distances in the hydrogen bonds are all slightly longer than the corresponding distances in (I), by ca 2–3% (Table 2). In each compound, each hydroxy O atom has two neighbouring hydroxy O atoms from different molecules, not only within hydrogen-bonding distance but also almost equidistant (Table 2). This almost certainly underlies the twofold positional disorder of the hydroxy H atoms.

A study of the aggregation patterns of mono- and di-alcohols (Taylor & Macrae, 2001), based on analysis of data in the October 2000 version of the Cambridge Structural Database (Allen, 2002), showed that, for the class of all secondary mono-alcohols, chains built from O—H···O hydrogen bonds and rings built from similar interactions were found with approximately equal frequency. However, when steric effects were taken into consideration, as defined by a quantity denoted SSBC (the sum of substituents on the β-C atoms), chain formation was found to be more usually associated with lower values of SSBC, while ring formation was more usually associated with higher values. For (I) and (II) discussed here, the value of SSBC is 2, the lowest value possible for a secondary mono-alcohol, so that, based on the earlier study (Taylor & Macrae, 2001), chain formation is to be expected here in preference to ring formation.

In addition to the O—H···O hydrogen bonds, each of the crystal structures contains a single C—H···π(arene) hydrogen bond, involving the same donor and acceptor groups in both compounds (Table 2). These interactions lie within the chains generated by the O—H···O hydrogen bonds, independent of the directionality of those bonds, and thus they do not influence the dimensionality of the hydrogen-bonded structures. It may be noted here that the metrics of the C—H···π(arene) hydrogen bond in (II) suggest that it is significantly stronger than that in (I).

The only other direction-specific intermolecular interaction is a single C—H···O hydrogen bond in (I) (Table 2), but there is no corresponding interaction in the structure of (II). The effect of this hydrogen bond is to link the chains along [100] into a sheet lying parallel to (001).

It is of interest briefly to compare the structures of the thienyl compounds (I) and (II) reported here with those of the three vinyl-substituted analogues (III)–(V) (Acosta et al., 2009). Compounds (III)–(V), unlike (I) and (II), are all isomorphous, but with sufficient variation in their unit-cell dimensions to influence the range of hydrogen bonds present. All three compounds crystallize in space group P21/n with Z' = 1, as opposed to the Z' = 2 for (I) and (II), and in all of them the hydroxy H atoms are fully ordered. Unlike (I) and (II), O—H···O hydrogen bonds are absent from the structures of (III)–(V), where instead a combination of O—H···N and N—H···O hydrogen bonds generates chains of edge-fused R33(10) rings. When the aryl substituent X = H or F, in (III) and (IV), the chains are linked into sheets by a single C—H···π(arene) hydrogen bond, but this is not the case in (V) where X = Cl.

The absence of any participation in hydrogen bonding by the N—H bonds in (I) and (II) may be a consequence of the greater steric demands of the thienyl substituents, as opposed to the vinyl substituents in (III)–(V).

Related literature top

For related literature, see: Acosta et al. (2008, 2009, 2010); Allen (2002); Bernstein et al. (1995); Gómez-Ayala, Castrillón, Palma, Leal, Escobar & Bahsas (2010); Gómez-Ayala, Stashenko, Palma, Bahsas & Amaro-Luis (2006); Palma et al. (2006, 2009); Taylor & Macrae (2001).

Experimental top

For the synthesis of (I) and (II), zinc powder (15 mmol), glacial acetic acid (7.5 mmol) and concentrated hydrochloric acid (7.5 mmol) were added to a stirred and cooled (ice bath) solution of the corresponding 2-exo-(thiophen-2-yl)- [for (I)] or 2-exo-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-benzazepine [for (II)] (1.5 mmol) in methanol (25 ml). The resulting reaction mixtures were stirred at 273 K for 15 min and then at ambient temperature for a further 1–2 h. The mixtures were filtered and the filtrates were basified to pH 8 with aqueous ammonia solution (25%), and then extracted with ethyl acetate (2 × 50 ml). The combined organic extracts were dried over anhydrous sodium sulfate and then the solvent was removed under reduced pressure. The resulting crude products were purified by silica-gel column chromatography using heptane–ethyl acetate as eluent (from 5:1 to 2:1 v/v). Crystallization from heptane–ethyl acetate (10:1 v/v) gave crystals of (I) and (II) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, yield 84%, m.p. 395 K; MS (70 eV) m/z (%) = 245 (M+, 64), 227 (3), 199 (21), 139 (52), 118 (21), 107 (82), 106 (100). For (II), light-yellow crystals, yield 83%, m.p. 366 K; MS (70 eV) m/z (%) = 259 (M+, 42), 241 (1), 215 (9), 153 (100), 118 (15), 107 (70), 106 (67).

Refinement top

It was apparent from an early stage in the refinement of (I) that in molecule 2, containing atom N21, the thienyl group was disordered over two sets of atomic sites, related to one another by a rotation of approximately 180° around the bond C22—C222 (Fig. 2). In the refinement model used for this disorder, the directly bonded distances and the one-angle non-bonded distances in the minor-occupancy component (containing atom S321) were restrained to be equal to the corresponding distances in the major-occupancy component (containing atom S221), subject to s.u. values of 0.005 Å and 0.01 Å, respectively. In addition, the anisotropic displacement parameter components for partially occupied atomic sites occupying similar regions of space were constrained to be equal. On this basis, the site-occupancy factors for the two components refined to values of 0.856 (2) and 0.144 (2), respectively. All H atoms bonded to C and N atoms, with the exception of those in the minor orientation component of (I), were located in difference maps; these H atoms were then treated as riding atoms. H atoms bonded to C atoms were included in geometrically idealized positions, with C—H = 0.95 (aromatic and thienyl), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. H atoms bonded to N atoms were permitted to ride at the positions located in difference maps, with Uiso(H) = 1.2Ueq(N), giving N—H distances in the range 0.88–0.93 Å. The difference maps showed clearly that each of the hydroxy H atoms was disordered over two sites having approximately equal occupancy in every case. Thereafter, the site occupancies of H atoms bonded to O atoms were all fixed at 0.50. The atomic coordinates were refined subject to a restraint of 0.82 (1) Å, with Uiso(H) = 1.5Ueq(O).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structures of the two independent molecules of (I), showing the atom-labelling schemes for (a) a molecule of type 1 and (b) a molecule of type 2, where the major and minor orientations of the thienyl substituent have occupancies of 0.856 (2) and 0.144 (2), respectively. The disordered hydroxy H atoms were modelled with an occupancy of 0.5, and displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structures of the two independent molecules of (II), showing the atom-labelling schemes for (a) a molecule of type 1 and (b) a molecule of type 2. The disordered hydroxy H atoms were modelled with an occupancy of 0.5, and displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Stereoviews of the two hydrogen-bonded C44(8) chains along [100] in (I), showing (a) the chain resulting from the occupancy of site H141 at (x, y, z) and (b) the chain resulting from the occupancy of site H142 at (x, y, z). For the sake of clarity, only the major orientation of the disordered thienyl substituent is shown, and H atoms bonded to C and N atoms have all been omitted.
(I) cis-(2RS,4SR)-2-(thiophen-2-yl)-2,3,4,5-tetrahydro- 1H-1-benzazepin-4-ol top
Crystal data top
C14H15NOSZ = 4
Mr = 245.34F(000) = 520
Triclinic, P1Dx = 1.313 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.5677 (6) ÅCell parameters from 5703 reflections
b = 9.8798 (4) Åθ = 3.0–27.5°
c = 14.7183 (11) ŵ = 0.24 mm1
α = 104.726 (5)°T = 120 K
β = 104.033 (6)°Block, colourless
γ = 103.273 (4)°0.31 × 0.16 × 0.12 mm
V = 1240.95 (15) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
5703 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode4174 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1212
Tmin = 0.928, Tmax = 0.971l = 1919
31492 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0368P)2 + 0.8514P]
where P = (Fo2 + 2Fc2)/3
5703 reflections(Δ/σ)max = 0.001
332 parametersΔρmax = 0.30 e Å3
14 restraintsΔρmin = 0.36 e Å3
Crystal data top
C14H15NOSγ = 103.273 (4)°
Mr = 245.34V = 1240.95 (15) Å3
Triclinic, P1Z = 4
a = 9.5677 (6) ÅMo Kα radiation
b = 9.8798 (4) ŵ = 0.24 mm1
c = 14.7183 (11) ÅT = 120 K
α = 104.726 (5)°0.31 × 0.16 × 0.12 mm
β = 104.033 (6)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
5703 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4174 reflections with I > 2σ(I)
Tmin = 0.928, Tmax = 0.971Rint = 0.049
31492 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04714 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.30 e Å3
5703 reflectionsΔρmin = 0.36 e Å3
332 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N110.57949 (17)0.35352 (17)0.79018 (12)0.0213 (3)
H110.61840.36790.85750.026*
C120.5071 (2)0.4721 (2)0.79033 (15)0.0220 (4)
H120.40450.43770.79710.026*
C130.4897 (2)0.5138 (2)0.69588 (15)0.0270 (5)
H13A0.44630.59620.70270.032*
H13B0.59180.55020.69060.032*
C140.3919 (2)0.3918 (2)0.60033 (16)0.0315 (5)
H140.29040.35070.60680.038*
C150.4587 (2)0.2674 (2)0.57434 (15)0.0301 (5)
H15A0.41190.21270.50250.036*
H15B0.56850.31070.58700.036*
C15A0.4381 (2)0.1589 (2)0.63009 (14)0.0231 (4)
C160.3664 (2)0.0097 (2)0.57887 (15)0.0289 (5)
H160.32440.02180.50870.035*
C170.3538 (2)0.0950 (2)0.62665 (15)0.0296 (5)
H170.30600.19640.58960.036*
C180.4118 (2)0.0491 (2)0.72882 (15)0.0255 (4)
H180.40480.11940.76250.031*
C190.4802 (2)0.0990 (2)0.78214 (14)0.0219 (4)
H190.51800.12970.85250.026*
C19A0.4947 (2)0.2047 (2)0.73403 (14)0.0200 (4)
S1210.78925 (6)0.68992 (6)0.89056 (4)0.02729 (14)
C1220.6047 (2)0.6018 (2)0.88047 (15)0.0226 (4)
C1230.5713 (2)0.6603 (2)0.96597 (16)0.0281 (5)
H1230.47580.62810.97520.034*
C1240.6994 (3)0.7753 (2)1.03823 (17)0.0343 (5)
H1240.69840.82781.10170.041*
C1250.8227 (2)0.8025 (2)1.00765 (16)0.0279 (5)
H1250.91670.87571.04690.034*
O1410.3719 (2)0.4544 (2)0.52163 (14)0.0573 (6)
H1410.291 (4)0.447 (8)0.484 (4)0.086*0.50
H1420.448 (5)0.508 (6)0.519 (5)0.086*0.50
N210.10253 (17)0.60431 (16)0.19862 (11)0.0185 (3)
H210.12560.65720.15670.022*
C220.0509 (2)0.6820 (2)0.27243 (14)0.0184 (4)
H220.12830.65920.24120.022*
C230.0717 (2)0.6371 (2)0.36554 (14)0.0210 (4)
H23A0.00190.66500.39770.025*
H23B0.17440.69550.41210.025*
C240.0530 (2)0.4746 (2)0.35141 (13)0.0213 (4)
H240.12610.44490.31840.026*
C250.1074 (2)0.3751 (2)0.28838 (14)0.0215 (4)
H25A0.12540.28080.30230.026*
H25B0.18120.42250.30770.026*
C25A0.1346 (2)0.3438 (2)0.17918 (14)0.0178 (4)
C260.1659 (2)0.2007 (2)0.11713 (14)0.0210 (4)
H260.17160.12300.14450.025*
C270.1889 (2)0.1692 (2)0.01630 (15)0.0246 (4)
H270.21110.07080.02510.030*
C280.1791 (2)0.2833 (2)0.02345 (14)0.0237 (4)
H280.19250.26310.09220.028*
C290.1499 (2)0.4262 (2)0.03672 (14)0.0204 (4)
H290.14480.50320.00880.025*
C29A0.12784 (19)0.4579 (2)0.13798 (13)0.0172 (4)
S2210.04453 (8)0.91973 (8)0.35191 (7)0.0301 (2)0.856 (2)
C2220.0727 (2)0.8446 (2)0.29924 (14)0.0200 (4)0.856 (2)
C2230.1810 (9)0.9491 (7)0.2895 (6)0.0255 (8)0.856 (2)
H2230.25560.92800.26060.031*0.856 (2)
C2240.1730 (4)1.0951 (3)0.3268 (4)0.0321 (7)0.856 (2)
H2240.24151.18100.32610.039*0.856 (2)
C2250.0551 (5)1.0954 (3)0.3634 (4)0.0308 (7)0.856 (2)
H2250.03111.18130.39160.037*0.856 (2)
S3210.2005 (13)0.9689 (10)0.2757 (10)0.0255 (8)0.144 (2)
C3220.0727 (2)0.8446 (2)0.29924 (14)0.0200 (4)0.144 (2)
C3230.009 (2)0.9088 (16)0.3490 (19)0.0301 (2)0.144 (2)
H3230.08370.85660.37080.036*0.144 (2)
C3240.028 (3)1.0642 (13)0.366 (3)0.0308 (7)0.144 (2)
H3240.01791.12650.39980.037*0.144 (2)
C3250.138 (3)1.1114 (11)0.327 (2)0.0321 (7)0.144 (2)
H3250.17571.20970.32760.039*0.144 (2)
O2410.0867 (2)0.45443 (18)0.44686 (11)0.0382 (4)
H2410.176 (2)0.471 (7)0.476 (4)0.057*0.50
H2420.053 (6)0.503 (5)0.484 (4)0.057*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0212 (8)0.0224 (8)0.0187 (8)0.0076 (7)0.0018 (7)0.0080 (7)
C120.0183 (9)0.0252 (10)0.0287 (11)0.0093 (8)0.0100 (8)0.0145 (9)
C130.0218 (10)0.0303 (11)0.0326 (12)0.0077 (8)0.0063 (9)0.0191 (10)
C140.0226 (10)0.0416 (13)0.0309 (12)0.0034 (9)0.0020 (9)0.0249 (11)
C150.0261 (11)0.0409 (13)0.0191 (10)0.0020 (9)0.0059 (8)0.0117 (9)
C15A0.0176 (9)0.0304 (11)0.0206 (10)0.0060 (8)0.0063 (8)0.0086 (9)
C160.0268 (11)0.0351 (12)0.0177 (10)0.0034 (9)0.0054 (8)0.0043 (9)
C170.0293 (11)0.0264 (11)0.0246 (11)0.0023 (9)0.0083 (9)0.0005 (9)
C180.0242 (10)0.0260 (11)0.0256 (11)0.0057 (8)0.0079 (8)0.0090 (9)
C190.0201 (9)0.0271 (10)0.0182 (10)0.0080 (8)0.0045 (8)0.0077 (8)
C19A0.0156 (9)0.0230 (10)0.0202 (10)0.0056 (7)0.0050 (7)0.0061 (8)
S1210.0250 (3)0.0276 (3)0.0306 (3)0.0070 (2)0.0114 (2)0.0105 (2)
C1220.0226 (10)0.0215 (10)0.0311 (11)0.0099 (8)0.0125 (8)0.0144 (9)
C1230.0311 (11)0.0198 (10)0.0370 (12)0.0086 (9)0.0158 (10)0.0101 (9)
C1240.0461 (14)0.0268 (12)0.0362 (13)0.0152 (10)0.0220 (11)0.0085 (10)
C1250.0321 (11)0.0184 (10)0.0336 (12)0.0096 (9)0.0098 (9)0.0080 (9)
O1410.0560 (12)0.0581 (12)0.0402 (11)0.0088 (10)0.0142 (9)0.0389 (10)
N210.0191 (8)0.0158 (8)0.0178 (8)0.0051 (6)0.0016 (6)0.0055 (6)
C220.0163 (9)0.0172 (9)0.0197 (9)0.0042 (7)0.0047 (7)0.0044 (8)
C230.0221 (9)0.0205 (10)0.0169 (9)0.0076 (8)0.0027 (8)0.0028 (8)
C240.0288 (10)0.0233 (10)0.0151 (9)0.0134 (8)0.0061 (8)0.0079 (8)
C250.0268 (10)0.0210 (10)0.0213 (10)0.0083 (8)0.0105 (8)0.0112 (8)
C25A0.0155 (9)0.0188 (9)0.0189 (9)0.0042 (7)0.0053 (7)0.0071 (8)
C260.0219 (9)0.0158 (9)0.0233 (10)0.0034 (7)0.0050 (8)0.0077 (8)
C270.0251 (10)0.0178 (10)0.0237 (10)0.0044 (8)0.0028 (8)0.0019 (8)
C280.0250 (10)0.0252 (10)0.0158 (9)0.0064 (8)0.0023 (8)0.0038 (8)
C290.0207 (9)0.0199 (10)0.0191 (10)0.0049 (8)0.0035 (8)0.0077 (8)
C29A0.0146 (8)0.0177 (9)0.0174 (9)0.0044 (7)0.0030 (7)0.0055 (7)
S2210.0315 (5)0.0214 (3)0.0416 (4)0.0143 (3)0.0179 (3)0.0061 (3)
C2220.0223 (9)0.0179 (9)0.0168 (9)0.0061 (8)0.0032 (8)0.0036 (8)
C2230.026 (2)0.0181 (17)0.031 (2)0.0017 (14)0.0158 (11)0.0087 (13)
C2240.036 (2)0.0192 (12)0.0308 (12)0.0001 (10)0.0011 (16)0.0085 (11)
C2250.041 (2)0.0111 (13)0.0333 (13)0.0076 (16)0.0039 (15)0.0036 (16)
S3210.026 (2)0.0181 (17)0.031 (2)0.0017 (14)0.0158 (11)0.0087 (13)
C3220.0223 (9)0.0179 (9)0.0168 (9)0.0061 (8)0.0032 (8)0.0036 (8)
C3230.0315 (5)0.0214 (3)0.0416 (4)0.0143 (3)0.0179 (3)0.0061 (3)
C3240.041 (2)0.0111 (13)0.0333 (13)0.0076 (16)0.0039 (15)0.0036 (16)
C3250.036 (2)0.0192 (12)0.0308 (12)0.0001 (10)0.0011 (16)0.0085 (11)
O2410.0699 (12)0.0316 (9)0.0156 (8)0.0272 (9)0.0053 (8)0.0097 (7)
Geometric parameters (Å, º) top
N11—C19A1.419 (2)C22—C2221.504 (3)
N11—C121.492 (2)C22—C231.527 (3)
N11—H110.9301C22—H221.0000
C12—C1221.503 (3)C23—C241.527 (3)
C12—C131.529 (3)C23—H23A0.9900
C12—H121.0000C23—H23B0.9900
C13—C141.512 (3)C24—O2411.439 (2)
C13—H13A0.9900C24—C251.528 (3)
C13—H13B0.9900C24—H241.0000
C14—O1411.439 (3)C25—C25A1.502 (3)
C14—C151.519 (3)C25—H25A0.9900
C14—H141.0000C25—H25B0.9900
C15—C15A1.513 (3)C25A—C261.393 (3)
C15—H15A0.9900C25A—C29A1.405 (3)
C15—H15B0.9900C26—C271.387 (3)
C15A—C161.390 (3)C26—H260.9500
C15A—C19A1.404 (3)C27—C281.391 (3)
C16—C171.390 (3)C27—H270.9500
C16—H160.9500C28—C291.385 (3)
C17—C181.381 (3)C28—H280.9500
C17—H170.9500C29—C29A1.394 (3)
C18—C191.383 (3)C29—H290.9500
C18—H180.9500S221—C2221.7097 (19)
C19—C19A1.403 (3)S221—C2251.721 (3)
C19—H190.9500C222—C2231.348 (5)
S121—C1251.704 (2)C223—C2241.434 (7)
S121—C1221.7322 (19)C223—H2230.9500
C122—C1231.389 (3)C224—C2251.363 (4)
C123—C1241.428 (3)C224—H2240.9500
C123—H1230.9500C225—H2250.9500
C124—C1251.356 (3)S321—C3251.721 (5)
C124—H1240.9500C323—C3241.435 (8)
C125—H1250.9500C323—H3230.9500
O141—H1410.813 (10)C324—C3251.363 (6)
O141—H1420.813 (10)C324—H3240.9500
N21—C29A1.423 (2)C325—H3250.9500
N21—C221.486 (2)O241—H2410.813 (10)
N21—H210.9237O241—H2420.814 (10)
C19A—N11—C12120.39 (15)N21—C22—C23112.57 (15)
C19A—N11—H11112.6C222—C22—C23110.00 (15)
C12—N11—H11102.3N21—C22—H22108.9
N11—C12—C122106.48 (15)C222—C22—H22108.9
N11—C12—C13112.82 (16)C23—C22—H22108.9
C122—C12—C13111.17 (16)C22—C23—C24116.80 (15)
N11—C12—H12108.8C22—C23—H23A108.1
C122—C12—H12108.8C24—C23—H23A108.1
C13—C12—H12108.8C22—C23—H23B108.1
C14—C13—C12115.80 (17)C24—C23—H23B108.1
C14—C13—H13A108.3H23A—C23—H23B107.3
C12—C13—H13A108.3O241—C24—C23109.16 (15)
C14—C13—H13B108.3O241—C24—C25108.58 (16)
C12—C13—H13B108.3C23—C24—C25112.50 (15)
H13A—C13—H13B107.4O241—C24—H24108.8
O141—C14—C13108.25 (17)C23—C24—H24108.8
O141—C14—C15109.35 (19)C25—C24—H24108.8
C13—C14—C15113.28 (17)C25A—C25—C24112.96 (15)
O141—C14—H14108.6C25A—C25—H25A109.0
C13—C14—H14108.6C24—C25—H25A109.0
C15—C14—H14108.6C25A—C25—H25B109.0
C15A—C15—C14115.43 (17)C24—C25—H25B109.0
C15A—C15—H15A108.4H25A—C25—H25B107.8
C14—C15—H15A108.4C26—C25A—C29A118.94 (17)
C15A—C15—H15B108.4C26—C25A—C25120.24 (16)
C14—C15—H15B108.4C29A—C25A—C25120.82 (16)
H15A—C15—H15B107.5C27—C26—C25A121.41 (18)
C16—C15A—C19A118.22 (18)C27—C26—H26119.3
C16—C15A—C15120.37 (18)C25A—C26—H26119.3
C19A—C15A—C15121.38 (18)C26—C27—C28119.22 (18)
C15A—C16—C17122.34 (19)C26—C27—H27120.4
C15A—C16—H16118.8C28—C27—H27120.4
C17—C16—H16118.8C29—C28—C27120.32 (18)
C18—C17—C16119.0 (2)C29—C28—H28119.8
C18—C17—H17120.5C27—C28—H28119.8
C16—C17—H17120.5C28—C29—C29A120.52 (18)
C17—C18—C19120.1 (2)C28—C29—H29119.7
C17—C18—H18120.0C29A—C29—H29119.7
C19—C18—H18120.0C29—C29A—C25A119.58 (17)
C18—C19—C19A121.05 (18)C29—C29A—N21120.08 (16)
C18—C19—H19119.5C25A—C29A—N21120.32 (16)
C19A—C19—H19119.5C222—S221—C22592.49 (12)
C19—C19A—C15A119.29 (18)C223—C222—C22128.1 (3)
C19—C19A—N11119.45 (17)C223—C222—S221111.0 (3)
C15A—C19A—N11120.95 (17)C22—C222—S221120.85 (13)
C125—S121—C12291.96 (10)C222—C223—C224113.6 (4)
C123—C122—C12128.36 (18)C222—C223—H223123.2
C123—C122—S121111.23 (16)C224—C223—H223123.2
C12—C122—S121120.24 (14)C225—C224—C223111.7 (3)
C122—C123—C124111.09 (19)C225—C224—H224124.2
C122—C123—H123124.5C223—C224—H224124.2
C124—C123—H123124.5C224—C225—S221111.2 (2)
C125—C124—C123113.6 (2)C224—C225—H225124.4
C125—C124—H124123.2S221—C225—H225124.4
C123—C124—H124123.2C324—C323—H323123.5
C124—C125—S121112.10 (17)C325—C324—C323111.8 (6)
C124—C125—H125124.0C325—C324—H324124.1
S121—C125—H125124.0C323—C324—H324124.1
C14—O141—H141125 (5)C324—C325—S321110.8 (5)
C14—O141—H142116 (6)C324—C325—H325124.6
H141—O141—H142118 (7)S321—C325—H325124.6
C29A—N21—C22116.68 (14)C24—O241—H241116 (4)
C29A—N21—H21107.2C24—O241—H242112 (4)
C22—N21—H21110.3H241—O241—H242108 (6)
N21—C22—C222107.55 (15)
C19A—N11—C12—C122160.67 (16)C29A—N21—C22—C2379.95 (19)
C19A—N11—C12—C1377.1 (2)N21—C22—C23—C2460.0 (2)
N11—C12—C13—C1461.2 (2)C222—C22—C23—C24179.89 (16)
C122—C12—C13—C14179.29 (17)C22—C23—C24—O241176.03 (16)
C12—C13—C14—O141172.59 (18)C22—C23—C24—C2563.4 (2)
C12—C13—C14—C1566.0 (2)O241—C24—C25—C25A158.78 (15)
O141—C14—C15—C15A160.27 (17)C23—C24—C25—C25A80.3 (2)
C13—C14—C15—C15A78.9 (2)C24—C25—C25A—C26116.10 (19)
C14—C15—C15A—C16123.2 (2)C24—C25—C25A—C29A63.4 (2)
C14—C15—C15A—C19A58.9 (3)C29A—C25A—C26—C270.6 (3)
C19A—C15A—C16—C172.3 (3)C25—C25A—C26—C27178.92 (17)
C15—C15A—C16—C17175.69 (19)C25A—C26—C27—C280.6 (3)
C15A—C16—C17—C181.3 (3)C26—C27—C28—C291.4 (3)
C16—C17—C18—C190.5 (3)C27—C28—C29—C29A0.9 (3)
C17—C18—C19—C19A1.3 (3)C28—C29—C29A—C25A0.4 (3)
C18—C19—C19A—C15A0.3 (3)C28—C29—C29A—N21178.05 (17)
C18—C19—C19A—N11173.35 (17)C26—C25A—C29A—C291.1 (3)
C16—C15A—C19A—C191.4 (3)C25—C25A—C29A—C29178.43 (16)
C15—C15A—C19A—C19176.52 (18)C26—C25A—C29A—N21177.30 (16)
C16—C15A—C19A—N11174.99 (17)C25—C25A—C29A—N213.2 (3)
C15—C15A—C19A—N113.0 (3)C22—N21—C29A—C29111.87 (19)
C12—N11—C19A—C19121.67 (19)C22—N21—C29A—C25A69.7 (2)
C12—N11—C19A—C15A64.8 (2)N21—C22—C222—C223121.0 (5)
N11—C12—C122—C123110.7 (2)C23—C22—C222—C223116.1 (5)
C13—C12—C122—C123126.0 (2)N21—C22—C222—S22160.73 (19)
N11—C12—C122—S12164.28 (18)C23—C22—C222—S22162.18 (19)
C13—C12—C122—S12159.0 (2)C225—S221—C222—C2231.1 (5)
C125—S121—C122—C1230.52 (16)C225—S221—C222—C22177.5 (2)
C125—S121—C122—C12175.27 (16)C22—C222—C223—C224177.2 (4)
C12—C122—C123—C124174.65 (19)S221—C222—C223—C2241.1 (7)
S121—C122—C123—C1240.7 (2)C222—C223—C224—C2250.6 (8)
C122—C123—C124—C1250.6 (3)C223—C224—C225—S2210.2 (7)
C123—C124—C125—S1210.2 (2)C222—S221—C225—C2240.7 (4)
C122—S121—C125—C1240.18 (17)C323—C324—C325—S3213 (4)
C29A—N21—C22—C222158.73 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O141—H141···O2410.81 (5)1.92 (5)2.684 (3)156 (5)
O141—H142···O141i0.81 (6)1.95 (5)2.695 (3)153 (6)
O241—H241···O1410.81 (4)1.89 (3)2.684 (3)164 (7)
O241—H242···O241ii0.81 (6)1.92 (6)2.691 (3)158 (6)
C225—H225···O241iii0.952.503.361 (4)151
C223—H223···Cgi0.952.933.705 (9)140
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x, y+1, z.
(II) cis-(2RS,4SR)-2-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro- 1H-1-benzazepin-4-ol top
Crystal data top
C15H17NOSZ = 4
Mr = 259.37F(000) = 552
Triclinic, P1Dx = 1.276 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.6764 (5) ÅCell parameters from 6208 reflections
b = 10.6897 (3) Åθ = 2.5–27.5°
c = 14.4433 (5) ŵ = 0.23 mm1
α = 72.018 (3)°T = 120 K
β = 89.108 (3)°Plate, light yellow
γ = 72.494 (3)°0.34 × 0.22 × 0.10 mm
V = 1350.27 (9) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6208 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode4151 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.5°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.927, Tmax = 0.978l = 1818
35561 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0614P)2 + 0.4841P]
where P = (Fo2 + 2Fc2)/3
6208 reflections(Δ/σ)max = 0.001
339 parametersΔρmax = 0.29 e Å3
4 restraintsΔρmin = 0.43 e Å3
Crystal data top
C15H17NOSγ = 72.494 (3)°
Mr = 259.37V = 1350.27 (9) Å3
Triclinic, P1Z = 4
a = 9.6764 (5) ÅMo Kα radiation
b = 10.6897 (3) ŵ = 0.23 mm1
c = 14.4433 (5) ÅT = 120 K
α = 72.018 (3)°0.34 × 0.22 × 0.10 mm
β = 89.108 (3)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6208 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4151 reflections with I > 2σ(I)
Tmin = 0.927, Tmax = 0.978Rint = 0.056
35561 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0494 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.29 e Å3
6208 reflectionsΔρmin = 0.43 e Å3
339 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N110.24021 (19)0.65455 (18)0.78231 (13)0.0273 (4)
H110.23560.64610.84480.033*
C120.3754 (2)0.5492 (2)0.77167 (15)0.0258 (5)
H120.45810.58770.76910.031*
C130.3661 (2)0.5111 (2)0.67924 (15)0.0260 (5)
H13A0.45640.43660.67900.031*
H13B0.28410.47310.68180.031*
C140.3454 (2)0.6288 (2)0.58369 (15)0.0278 (5)
H140.42500.67090.58290.033*
C150.2003 (2)0.7421 (2)0.56950 (15)0.0283 (5)
H15A0.17850.79510.49900.034*
H15B0.12330.69830.59000.034*
C15A0.1945 (2)0.8416 (2)0.62528 (15)0.0258 (5)
C160.1595 (2)0.9830 (2)0.57486 (16)0.0300 (5)
H160.14731.01400.50550.036*
C170.1420 (3)1.0798 (2)0.62367 (16)0.0326 (5)
H170.11491.17580.58820.039*
C180.1645 (2)1.0342 (2)0.72469 (16)0.0294 (5)
H180.15471.09910.75880.035*
C190.2013 (2)0.8942 (2)0.77609 (15)0.0266 (5)
H190.21680.86410.84530.032*
C19A0.2161 (2)0.7964 (2)0.72761 (15)0.0245 (4)
S1210.29583 (7)0.31509 (6)0.88453 (4)0.03310 (16)
C1220.4026 (2)0.4249 (2)0.86183 (15)0.0270 (5)
C1230.5030 (3)0.3838 (3)0.93808 (18)0.0414 (6)
H1230.57230.42990.94030.050*
C1240.4954 (3)0.2655 (3)1.01439 (19)0.0465 (7)
H1240.55860.22561.07270.056*
C1250.3904 (3)0.2152 (2)0.99657 (16)0.0343 (5)
C1260.3549 (3)0.0898 (3)1.06063 (18)0.0456 (6)
H12A0.26200.11951.08810.068*
H12B0.43190.03731.11380.068*
H12C0.34750.03121.02160.068*
O1410.35724 (18)0.57419 (17)0.50309 (11)0.0338 (4)
H1410.278 (3)0.567 (6)0.490 (4)0.051*0.50
H1420.437 (3)0.523 (5)0.498 (4)0.051*0.50
N210.24202 (19)0.40433 (17)0.19255 (12)0.0254 (4)
H210.26970.35410.15350.031*
C220.1690 (2)0.3321 (2)0.27366 (14)0.0235 (4)
H220.06480.35440.25090.028*
C230.1755 (2)0.3775 (2)0.36417 (14)0.0262 (5)
H23A0.13330.32060.41750.031*
H23B0.27890.35680.38550.031*
C240.0974 (2)0.5294 (2)0.35084 (14)0.0258 (5)
H240.00580.55200.32560.031*
C250.1668 (2)0.6268 (2)0.27908 (15)0.0292 (5)
H25A0.13610.71730.29080.035*
H25B0.27380.58830.29250.035*
C25A0.1282 (2)0.6499 (2)0.17348 (15)0.0251 (4)
C260.0589 (2)0.7835 (2)0.11115 (15)0.0311 (5)
H260.03770.85850.13670.037*
C270.0202 (3)0.8105 (2)0.01342 (16)0.0337 (5)
H270.02680.90260.02730.040*
C280.0511 (2)0.7012 (2)0.02419 (16)0.0302 (5)
H280.02270.71790.09070.036*
C290.1232 (2)0.5678 (2)0.03515 (15)0.0260 (5)
H290.14650.49380.00850.031*
C29A0.1621 (2)0.5409 (2)0.13392 (14)0.0236 (4)
S2210.42462 (6)0.10396 (6)0.33827 (4)0.03240 (16)
C2220.2414 (2)0.1788 (2)0.29829 (14)0.0246 (4)
C2230.1818 (2)0.0798 (2)0.29496 (15)0.0276 (5)
H2230.08250.09960.27460.033*
C2240.2827 (2)0.0561 (2)0.32484 (15)0.0296 (5)
H2240.25740.13580.32620.036*
C2250.4181 (2)0.0608 (2)0.35115 (15)0.0289 (5)
C2260.5512 (3)0.1849 (2)0.38635 (19)0.0396 (6)
H22A0.52230.26900.40840.059*
H22B0.60410.17750.44070.059*
H22C0.61420.18920.33290.059*
O2410.09805 (19)0.55203 (17)0.44371 (11)0.0346 (4)
H2410.173 (3)0.562 (6)0.461 (4)0.052*0.50
H2420.068 (5)0.495 (4)0.483 (3)0.052*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0282 (10)0.0288 (10)0.0226 (9)0.0055 (8)0.0045 (7)0.0083 (8)
C120.0239 (11)0.0294 (11)0.0246 (11)0.0066 (9)0.0022 (8)0.0110 (9)
C130.0234 (11)0.0307 (11)0.0254 (11)0.0058 (9)0.0029 (8)0.0133 (9)
C140.0297 (12)0.0340 (12)0.0244 (11)0.0103 (10)0.0050 (9)0.0156 (9)
C150.0256 (11)0.0355 (12)0.0230 (11)0.0074 (9)0.0009 (9)0.0102 (9)
C15A0.0219 (11)0.0305 (12)0.0256 (11)0.0057 (9)0.0034 (8)0.0121 (9)
C160.0321 (12)0.0312 (12)0.0243 (11)0.0078 (10)0.0028 (9)0.0077 (9)
C170.0375 (13)0.0257 (11)0.0316 (13)0.0073 (10)0.0017 (10)0.0074 (10)
C180.0287 (12)0.0303 (12)0.0345 (13)0.0099 (10)0.0066 (9)0.0170 (10)
C190.0242 (11)0.0340 (12)0.0231 (11)0.0088 (9)0.0029 (8)0.0117 (9)
C19A0.0209 (11)0.0256 (11)0.0251 (11)0.0044 (9)0.0034 (8)0.0084 (9)
S1210.0398 (3)0.0313 (3)0.0277 (3)0.0129 (3)0.0012 (2)0.0068 (2)
C1220.0270 (11)0.0275 (11)0.0260 (11)0.0066 (9)0.0036 (9)0.0099 (9)
C1230.0314 (13)0.0528 (16)0.0362 (14)0.0142 (12)0.0051 (10)0.0076 (12)
C1240.0353 (14)0.0547 (17)0.0350 (14)0.0062 (12)0.0088 (11)0.0012 (12)
C1250.0335 (13)0.0317 (12)0.0268 (12)0.0016 (10)0.0037 (10)0.0059 (10)
C1260.0491 (16)0.0350 (14)0.0370 (14)0.0015 (12)0.0084 (12)0.0012 (11)
O1410.0400 (10)0.0377 (10)0.0243 (8)0.0053 (8)0.0046 (8)0.0172 (7)
N210.0287 (10)0.0245 (9)0.0246 (9)0.0091 (8)0.0063 (7)0.0094 (7)
C220.0229 (11)0.0253 (11)0.0220 (10)0.0084 (9)0.0030 (8)0.0065 (8)
C230.0277 (11)0.0306 (12)0.0212 (11)0.0118 (9)0.0020 (8)0.0067 (9)
C240.0316 (12)0.0314 (12)0.0194 (10)0.0139 (10)0.0052 (9)0.0112 (9)
C250.0375 (13)0.0297 (12)0.0273 (12)0.0169 (10)0.0086 (9)0.0128 (9)
C25A0.0283 (11)0.0273 (11)0.0243 (11)0.0138 (9)0.0077 (9)0.0100 (9)
C260.0426 (14)0.0264 (11)0.0278 (12)0.0139 (10)0.0121 (10)0.0107 (9)
C270.0427 (14)0.0255 (12)0.0289 (12)0.0097 (10)0.0102 (10)0.0043 (9)
C280.0347 (13)0.0339 (12)0.0214 (11)0.0123 (10)0.0053 (9)0.0065 (9)
C290.0287 (12)0.0296 (11)0.0235 (11)0.0122 (9)0.0061 (9)0.0112 (9)
C29A0.0236 (11)0.0243 (11)0.0233 (11)0.0090 (9)0.0054 (8)0.0070 (9)
S2210.0269 (3)0.0246 (3)0.0446 (4)0.0083 (2)0.0026 (2)0.0092 (2)
C2220.0250 (11)0.0275 (11)0.0223 (11)0.0093 (9)0.0031 (8)0.0085 (9)
C2230.0286 (12)0.0327 (12)0.0250 (11)0.0134 (10)0.0015 (9)0.0102 (9)
C2240.0377 (13)0.0283 (11)0.0280 (12)0.0163 (10)0.0052 (10)0.0105 (9)
C2250.0346 (13)0.0250 (11)0.0265 (12)0.0096 (9)0.0032 (9)0.0070 (9)
C2260.0392 (14)0.0266 (12)0.0476 (15)0.0057 (10)0.0034 (11)0.0087 (11)
O2410.0539 (11)0.0382 (9)0.0207 (8)0.0218 (9)0.0074 (7)0.0146 (7)
Geometric parameters (Å, º) top
N11—C19A1.425 (3)N21—C29A1.423 (3)
N11—C121.489 (3)N21—C221.487 (2)
N11—H110.8801N21—H210.8798
C12—C1221.504 (3)C22—C2221.503 (3)
C12—C131.522 (3)C22—C231.536 (3)
C12—H121.0000C22—H221.0000
C13—C141.521 (3)C23—C241.523 (3)
C13—H13A0.9900C23—H23A0.9900
C13—H13B0.9900C23—H23B0.9900
C14—O1411.444 (2)C24—O2411.435 (2)
C14—C151.521 (3)C24—C251.531 (3)
C14—H141.0000C24—H241.0000
C15—C15A1.508 (3)C25—C25A1.502 (3)
C15—H15A0.9900C25—H25A0.9900
C15—H15B0.9900C25—H25B0.9900
C15A—C161.397 (3)C25A—C261.396 (3)
C15A—C19A1.403 (3)C25A—C29A1.402 (3)
C16—C171.391 (3)C26—C271.384 (3)
C16—H160.9500C26—H260.9500
C17—C181.386 (3)C27—C281.388 (3)
C17—H170.9500C27—H270.9500
C18—C191.385 (3)C28—C291.386 (3)
C18—H180.9500C28—H280.9500
C19—C19A1.402 (3)C29—C29A1.399 (3)
C19—H190.9500C29—H290.9500
S121—C1251.729 (2)S221—C2251.733 (2)
S121—C1221.741 (2)S221—C2221.735 (2)
C122—C1231.352 (3)C222—C2231.362 (3)
C123—C1241.418 (3)C223—C2241.422 (3)
C123—H1230.9500C223—H2230.9500
C124—C1251.346 (3)C224—C2251.352 (3)
C124—H1240.9500C224—H2240.9500
C125—C1261.508 (3)C225—C2261.501 (3)
C126—H12A0.9800C226—H22A0.9800
C126—H12B0.9800C226—H22B0.9800
C126—H12C0.9800C226—H22C0.9800
O141—H1410.819 (10)O241—H2410.818 (10)
O141—H1420.816 (10)O241—H2420.818 (10)
C19A—N11—C12119.01 (16)C29A—N21—C22117.56 (16)
C19A—N11—H11109.2C29A—N21—H21107.7
C12—N11—H11108.1C22—N21—H21109.3
N11—C12—C122107.27 (16)N21—C22—C222108.36 (16)
N11—C12—C13112.67 (17)N21—C22—C23111.75 (16)
C122—C12—C13111.56 (17)C222—C22—C23110.47 (16)
N11—C12—H12108.4N21—C22—H22108.7
C122—C12—H12108.4C222—C22—H22108.7
C13—C12—H12108.4C23—C22—H22108.7
C14—C13—C12115.58 (17)C24—C23—C22115.84 (17)
C14—C13—H13A108.4C24—C23—H23A108.3
C12—C13—H13A108.4C22—C23—H23A108.3
C14—C13—H13B108.4C24—C23—H23B108.3
C12—C13—H13B108.4C22—C23—H23B108.3
H13A—C13—H13B107.4H23A—C23—H23B107.4
O141—C14—C15108.96 (17)O241—C24—C23109.26 (17)
O141—C14—C13109.28 (17)O241—C24—C25108.97 (16)
C15—C14—C13113.40 (17)C23—C24—C25112.81 (17)
O141—C14—H14108.4O241—C24—H24108.6
C15—C14—H14108.4C23—C24—H24108.6
C13—C14—H14108.4C25—C24—H24108.6
C15A—C15—C14114.41 (17)C25A—C25—C24114.09 (17)
C15A—C15—H15A108.7C25A—C25—H25A108.7
C14—C15—H15A108.7C24—C25—H25A108.7
C15A—C15—H15B108.7C25A—C25—H25B108.7
C14—C15—H15B108.7C24—C25—H25B108.7
H15A—C15—H15B107.6H25A—C25—H25B107.6
C16—C15A—C19A118.84 (19)C26—C25A—C29A118.05 (19)
C16—C15A—C15119.57 (18)C26—C25A—C25119.88 (18)
C19A—C15A—C15121.51 (19)C29A—C25A—C25122.06 (19)
C17—C16—C15A121.7 (2)C27—C26—C25A122.3 (2)
C17—C16—H16119.2C27—C26—H26118.9
C15A—C16—H16119.2C25A—C26—H26118.9
C18—C17—C16119.1 (2)C26—C27—C28119.0 (2)
C18—C17—H17120.4C26—C27—H27120.5
C16—C17—H17120.4C28—C27—H27120.5
C19—C18—C17120.2 (2)C29—C28—C27120.1 (2)
C19—C18—H18119.9C29—C28—H28120.0
C17—C18—H18119.9C27—C28—H28120.0
C18—C19—C19A121.05 (19)C28—C29—C29A120.69 (19)
C18—C19—H19119.5C28—C29—H29119.7
C19A—C19—H19119.5C29A—C29—H29119.7
C19—C19A—C15A119.14 (19)C29—C29A—C25A119.83 (19)
C19—C19A—N11120.01 (18)C29—C29A—N21119.82 (18)
C15A—C19A—N11120.63 (18)C25A—C29A—N21120.29 (18)
C125—S121—C12292.50 (11)C225—S221—C22292.40 (10)
C123—C122—C12127.8 (2)C223—C222—C22128.66 (19)
C123—C122—S121109.60 (17)C223—C222—S221110.10 (16)
C12—C122—S121122.52 (16)C22—C222—S221121.23 (14)
C122—C123—C124113.8 (2)C222—C223—C224113.46 (19)
C122—C123—H123123.1C222—C223—H223123.3
C124—C123—H123123.1C224—C223—H223123.3
C125—C124—C123113.8 (2)C225—C224—C223113.50 (19)
C125—C124—H124123.1C225—C224—H224123.2
C123—C124—H124123.1C223—C224—H224123.2
C124—C125—C126127.6 (2)C224—C225—C226128.4 (2)
C124—C125—S121110.29 (18)C224—C225—S221110.53 (17)
C126—C125—S121122.11 (19)C226—C225—S221121.09 (17)
C125—C126—H12A109.5C225—C226—H22A109.5
C125—C126—H12B109.5C225—C226—H22B109.5
H12A—C126—H12B109.5H22A—C226—H22B109.5
C125—C126—H12C109.5C225—C226—H22C109.5
H12A—C126—H12C109.5H22A—C226—H22C109.5
H12B—C126—H12C109.5H22B—C226—H22C109.5
C14—O141—H141109 (4)C24—O241—H241116 (4)
C14—O141—H142117 (4)C24—O241—H242108 (4)
H141—O141—H142126 (6)H241—O241—H242117 (6)
C19A—N11—C12—C122157.80 (17)C29A—N21—C22—C222157.27 (17)
C19A—N11—C12—C1379.0 (2)C29A—N21—C22—C2380.8 (2)
N11—C12—C13—C1461.9 (2)N21—C22—C23—C2463.0 (2)
C122—C12—C13—C14177.39 (18)C222—C22—C23—C24176.27 (17)
C12—C13—C14—O141172.74 (17)C22—C23—C24—O241173.16 (16)
C12—C13—C14—C1565.5 (2)C22—C23—C24—C2565.5 (2)
O141—C14—C15—C15A159.04 (18)O241—C24—C25—C25A160.01 (18)
C13—C14—C15—C15A79.0 (2)C23—C24—C25—C25A78.5 (2)
C14—C15—C15A—C16122.8 (2)C24—C25—C25A—C26121.0 (2)
C14—C15—C15A—C19A60.7 (3)C24—C25—C25A—C29A60.4 (3)
C19A—C15A—C16—C171.6 (3)C29A—C25A—C26—C271.7 (3)
C15—C15A—C16—C17175.0 (2)C25—C25A—C26—C27179.7 (2)
C15A—C16—C17—C182.1 (3)C25A—C26—C27—C280.0 (3)
C16—C17—C18—C191.2 (3)C26—C27—C28—C291.8 (3)
C17—C18—C19—C19A0.2 (3)C27—C28—C29—C29A1.8 (3)
C18—C19—C19A—C15A0.7 (3)C28—C29—C29A—C25A0.1 (3)
C18—C19—C19A—N11173.98 (18)C28—C29—C29A—N21177.12 (18)
C16—C15A—C19A—C190.2 (3)C26—C25A—C29A—C291.6 (3)
C15—C15A—C19A—C19176.37 (19)C25—C25A—C29A—C29179.74 (18)
C16—C15A—C19A—N11174.83 (18)C26—C25A—C29A—N21175.42 (18)
C15—C15A—C19A—N111.8 (3)C25—C25A—C29A—N213.2 (3)
C12—N11—C19A—C19119.8 (2)C22—N21—C29A—C29114.7 (2)
C12—N11—C19A—C15A65.6 (2)C22—N21—C29A—C25A68.3 (2)
N11—C12—C122—C123104.7 (3)N21—C22—C222—C223119.9 (2)
C13—C12—C122—C123131.4 (2)C23—C22—C222—C223117.4 (2)
N11—C12—C122—S12171.7 (2)N21—C22—C222—S22160.8 (2)
C13—C12—C122—S12152.1 (2)C23—C22—C222—S22161.9 (2)
C125—S121—C122—C1230.37 (18)C225—S221—C222—C2230.53 (16)
C125—S121—C122—C12177.40 (18)C225—S221—C222—C22178.93 (16)
C12—C122—C123—C124176.8 (2)C22—C222—C223—C224179.14 (19)
S121—C122—C123—C1240.0 (3)S221—C222—C223—C2240.3 (2)
C122—C123—C124—C1250.5 (3)C222—C223—C224—C2250.2 (3)
C123—C124—C125—C126178.6 (2)C223—C224—C225—C226180.0 (2)
C123—C124—C125—S1210.8 (3)C223—C224—C225—S2210.6 (2)
C122—S121—C125—C1240.67 (19)C222—S221—C225—C2240.67 (17)
C122—S121—C125—C126178.7 (2)C222—S221—C225—C226179.88 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O141—H141···O2410.82 (4)1.94 (4)2.763 (3)173 (6)
O141—H142···O141i0.82 (4)1.95 (4)2.757 (3)168 (4)
O241—H241···O1410.82 (4)1.95 (3)2.763 (3)177 (7)
O241—H242···O241ii0.82 (4)2.02 (5)2.746 (3)149 (4)
C223—H223···Cgii0.952.743.572 (9)147
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H15NOSC15H17NOS
Mr245.34259.37
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)120120
a, b, c (Å)9.5677 (6), 9.8798 (4), 14.7183 (11)9.6764 (5), 10.6897 (3), 14.4433 (5)
α, β, γ (°)104.726 (5), 104.033 (6), 103.273 (4)72.018 (3), 89.108 (3), 72.494 (3)
V3)1240.95 (15)1350.27 (9)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.240.23
Crystal size (mm)0.31 × 0.16 × 0.120.34 × 0.22 × 0.10
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.928, 0.9710.927, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
31492, 5703, 4174 35561, 6208, 4151
Rint0.0490.056
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.108, 1.06 0.049, 0.131, 1.05
No. of reflections57036208
No. of parameters332339
No. of restraints144
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.360.29, 0.43

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected torsion angles (°) for (I) and (II) top
(I)(II)
N11—C12—C122—S12164.28 (18)71.7 (2)
N21—C22—C222—S22160.73 (19)60.8 (2)
N21—C22—C322—C321-114.9 (2)
Hydrogen-bond parameters (Å, °) for (I) and (II) top
D—H···AD—HH···AD···AD—H···A
(I)
O141—H141···O2410.81 (5)1.92 (5)2.684 (3)156 (5)
O141—H142···O141i0.81 (6)1.95 (5)2.695 (3)153 (6)
O241—H241···O1410.81 (4)1.89 (3)2.684 (3)164 (7)
O241—H242···O241ii0.81 (6)1.92 (6)2.691 (3)158 (6)
C225—H225···O241iii0.952.503.361 (4)151
C223—H223···Cga,i0.952.933.705 (9)140
(II)
O141—H141···O2410.82 (4)1.94 (4)2.763 (3)173 (6)
O141—H142···O141i0.82 (4)1.95 (4)2.757 (3)168 (4)
O241—H241···O1410.82 (4)1.95 (4)2.763 (3)177 (7)
O241—H242···O241ii0.82 (4)2.02 (5)2.746 (3)149 (4)
C223—H223···Cga,ii0.952.743.572 (2)147
Note: (a) Cg represents the centroid of the C15A/C16–C19/C19A ring Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y + 1, -z + 1; (iii) x, y + 1, z.
 

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