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organic compounds
and supramolecular aggregation in four 2,3,4,5-tetrahydro-3,4-diphenylbenzothiazepines
aDepartment of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu 620 024, India, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
In (2RS,4RS)-1-acetyl-2,3,4,5-tetrahydro-2,4-diphenyl-1,5-benzothiazepine, C23H21NOS, (I), and (2RS,4RS)-1-chloroacetyl-2,3,4,5-tetrahydro-2,4-diphenyl-1,5-benzothiazepine,C23H20ClNOS, (II), the seven-membered rings have boat conformations, whereas in (2RS,4RS)-1-benzoyl-2,3,4,5-tetrahydro-2,4-diphenyl-1,5-benzothiazepine, C28H23NOS, (III), this ring has a conformation intermediate between the boat and twist-boat forms. The molecules of (I) are linked into isolated (16) dimers by two C—H⋯O hydrogen bonds [H⋯O = 2.41 and 2.47 Å, C⋯O = 3.268 (3) and 3.336 (3) Å, and C—H⋯O = 150 and 152°]. In (II), the molecules are again linked by two C—H⋯O hydrogen bonds [H⋯O = 2.42 and 2.48 Å, C⋯O = 3.295 (3) and 3.364 (2) Å, and C—H⋯O = 153 and 154°], forming chains of alternating
(18) and
(22) rings. Two C—H⋯O hydrogen bonds [H⋯O = 2.49 and 2.53 Å, C⋯O = 3.347 (2) and 3.295 (2) Å, and C—H⋯O = 150 and 138°] link the molecules of (III) into sheets containing alternating
(22) and
(30) rings. Re-examination of the published structure of (2RS,4RS)-2,3,4,5-tetrahydro-2,4-diphenyl-1,5-benzothiazepine shows that the molecules are linked by three C—H⋯π(arene) hydrogen bonds into a three-dimensional framework.
Comment
We report here the molecular and supramolecular structures of three N-acyl-C-phenylated tetrahydrobenzothiazepines, (I)–(III
), and we compare these with the simpler analogue, (IV
), which is unsubstituted at the N atom and whose structure has recently been reported (Laavanya et al., 2002
). These compounds are of interest as their molecular constitutions all bear some resemblance to that of the calcium antagonist drug diltiazem [or (2S,3S)-3-acetoxy-5-(dimethylaminoethyl)-2-(4-methoxyphenyl)-2,3-dihydro-1,5-benzothiazepine-4(5H)-one,(V)] and its 2R,3R (Kojić-Prodić et al., 1984
).
Each of (I)–(III
) (Figs. 1
–3
) contains two stereogenic C atoms, C2 and C4, and hence the formation of diastereoisomers is possible. However, each of the crystalline samples examined contained a single pair of enantiomers, R,R and S,S, and for each compound the reference molecule was selected as having the R,R configuration. In this respect, the configurations of (I
)–(III
) are identical to that of (IV
) (Laavanya et al., 2002
). It should, however, be noted here that the schematic view of (IV
) in the original report shows the incorrect 2S,4R isomer. The interbond angles at the N atom in each of (I
)–(III
) sum to ∼360.0°, so that no further configurational isomers are possible.
Compound (I) crystallizes with Z′ = 2; the thiazepine rings in the two independent molecules in (I
) and in the molecules of (II
) and (III
) all adopt similar conformations, as shown by the ring torsion angles (Table 5
). Apart from the S1—C10—C11—N5 angle, there are corresponding pairs of torsion angles having similar magnitudes but opposite signs. This fact indicates conformations that, apart from the obvious differences in atom types and bond lengths, approximate in (I
) and (II
) to pseudo-mirror symmetry; this conformation may be best described as the boat conformation (Evans & Boeyens, 1989
). The conformation of the thiazepine ring in (III
) does not exhibit even approximate symmetry and it cannot be described in terms of a single primitive form (Evans & Boeyens, 1989
). Instead, the conformation is intermediate between the boat and twist-boat forms. By contrast, the thiazepine ring in (IV
) exhibits approximate pseudo-twofold rotational symmetry, as the corresponding pairs of torsion angles have similar magnitudes with the same signs, although all four primitive forms contribute to the overall conformation of (IV
).
The only significant difference between the bond lengths in (I)–(III) and those in (IV) occurs for the N5—C11 bond. In (I)–(III), where atom N5 is coplanar with the thiazepine ring, this distance lies in the range 1.427 (3)–1.439 (2) Å, whereas in (IV
), where the configuration involving atom N5 is pyramidal, this distance is 1.395 (3) Å. By contrast, the mean values for bonds of types Caryl—NC2, involving planar N atoms, and Caryl—NHC, involving pyramidal N atoms, are 1.371 and 1.419 Å, respectively (Allen et al., 1987
). The remaining bond lengths in (I)–(III) show no unusual values.
The supramolecular structures of (I)–(III
) all have different dimensionality. In (I
), the two independent molecules are linked by a pair of C—H⋯O hydrogen bonds (Table 1
). Atom C145 in the type 1 molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O25 in the type 2 molecule at (1 − x, 1 − y, 1 − z), while atom C245 at (1 − x, 1 − y, 1 − z) in turn acts as a donor to carbonyl atom O15 at (x, y, z). In this manner, an approximately centrosymmetric
(16) dimer is formed (Fig. 4
). This dimeric aggregate is centred at approximately (0.75, 0.37, 0.75), and this alone precludes the possibility of any additional symmetry. While such an aggregate would normally have been selected as the in this instance the was selected so that each of the independent molecules had the R,R configuration. The
(16) dimer contains one R,R molecule and one S,S molecule. There are four of these dimeric units in each but there are no direction-specific interactions between adjacent dimers.
In (II), the molecules are linked by two C—H⋯O hydrogen bonds (Table 2
) into a chain of rings. Atom C24 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (1 − x, −y, 1 − z), so forming an
(22) ring centred at (
, 0,
), while atom C44 at (x, y, z) acts as a donor to atom O5 at (1 − x, 1 − y, 1 − z), thus forming an
(18) ring centred at (
,
,
). Propagation of these two hydrogen bonds then generates a chain of rings along (
, y,
), with
(18) rings centred at (
, n +
,
) (n = zero or integer) and
(22) rings centred at (
, n,
) (n = zero or integer) (Fig. 5
). Two chains of this type pass through each but there are no direction-specific interactions between adjacent chains.
As in (II), the supramolecular structure of (III
) is again dictated by two intermolecular C—H⋯O hydrogen bonds (Table 3
), but now their effect is to generate a sheet structure, in contrast with the chain of rings in (II
). The stronger of these two hydrogen bonds gives rise to a chain running parallel to the [010] direction. Atom C23 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (
− x,
+ y,
− z), so producing a C(10) chain, generated by the 21 screw axis along (
, y,
) (Fig. 6
). Four of these chains pass through each two, lying in the domain −0.02 < x < 0.52, are generated by screw axes at x =
, while the other two, lying in the domain 0.48 < x < 1.02, are generated by screw axes at x =
. Within each domain, the C(10) chains are linked into sheets by the second of the C—H⋯O hydrogen bonds. Atom C24 in the molecule at (x, y, z), which lies in the C(10) chain along (
, y,
), acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (
− x,
− y, 2 − z), which lies in the C(10) chain along (
, y,
), so forming a centrosymmetric
(22) ring centred at (
,
, 1) (Fig. 7
). The combination of the
(22) rings and the C(10) chains generates a (100) sheet built from
(22) and
(30) rings alternating in a chessboard fashion (Fig. 8
). Two sheets of this type pass through each one in each domain of x as defined above, but there are no direction-specific interactions between adjacent sheets. Despite the presence of at least three independent aryl rings in each of (I
)–(III
), there are neither C—H⋯π(arene) hydrogen bonds nor aromatic π–π stacking interactions present in any of their structures.
In the light of the very different supramolecular structures adopted by (I)–(III
), it seemed of interest to re-examine the supramolecular structure of (IV
) using P21/n, with Z′ = 1, and the atomic coordinates established by Laavanya et al. (2002
), where the atom labelling is identical to that employed in (I
)–(III
). There are, in fact, three C—H⋯π(arene) hydrogen bonds, all with H⋯centroid distances of less than 3.0 Å (Table 4
), which were not noted in the original report but which together link the molecules of (IV
) into a continuous three-dimensional framework.
In the first of these interactions, atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C6–C11 ring in the molecule at ( − x,
+ y,
− z), so producing a [010] chain generated by the 21 screw axis along (
, y,
) (Fig. 9
). In a similar way, atom C21 at (x, y, z) acts as a donor to the C20–C25 ring (original atom numbering) in the molecule at (
− x,
+ y,
− z), so producing a second [010] chain, this time generated by the screw axis along (
, y,
). The combination of these two chains then generates a (001) sheet in the form of a (4,4)-net (Batten & Robson, 1998
), lying in the domain −0.04 < z < 0.54 (Fig. 10
); a second sheet, related to the first by inversion, lies in the domain 0.46 < z < 1.04.
The third C—H⋯π(arene) hydrogen bond links adjacent (001) sheets; atom C34 in the molecule at (x, y, z), which lies in the domain −0.04 < z < 0.54, acts as a hydrogen-bond donor to ring C20–C25 in the molecule at (1 − x, 1 − y, −z), which lies in the domain −0.54 < z < 0.04. The resulting centrosymmetric motif (Fig. 11) thus serves to link sheets in different domains and in this manner to link all of the (001) sheets into a single framework.
It is also timely to re-evaluate the intermolecular N—H⋯S interaction in (IV). This interaction was originally discounted (Laavanya et al., 2002
) as insignificant on the grounds that the shortest intermolecular N⋯S distance (Table 4
) is in excess of the 3.3 Å sum of the van der Waals radii (Bondi, 1964
). However, an analysis (Allen et al., 1997
) of hydrogen bonds having two-coordinate S as the acceptor, using data retrieved from the Cambridge Structural Database (Allen, 2002
), indicated mean H⋯S, N⋯S and N—H⋯S parameters in such bonds where S is bonded to two C atoms of 2.74 (2) Å, 3.58 (3) Å and 145 (3)° respectively. Accordingly, if the N—H⋯S contact in (IV
) is not considered to be a significant intermolecular interaction, it is more soundly rejected on the grounds of the long H⋯S distance and the small N—H⋯S angle than on the grounds of the N⋯S distance.
In summary, we have shown that the very closely related series of compounds (I)–(IV
) exhibit supramolecular aggregation in zero, one, two and three dimensions, respectively, and that while in (I
)–(III
) the aggregation depends solely on C—H⋯O hydrogen bonds, in (IV
) it depends solely on C—H⋯π(arene) hydrogen bonds. The occurrence of such differences resulting from very modest changes in molecular constitution undoubtedly presents a considerable challenge for computational methods that seek to predict, whether from first principles or otherwise, the crystal structures of simple molecular compounds (Lommerse et al., 2000
; Motherwell et al., 2002
).
![]() | Figure 1 The two independent molecules of (I ![]() |
![]() | Figure 2 The molecule of (II ![]() |
![]() | Figure 3 The molecule of (III ![]() |
![]() | Figure 4 Part of the crystal structure of (I ![]() ![]() |
![]() | Figure 5 A stereoview of part of the crystal structure of (II ![]() ![]() ![]() |
![]() | Figure 6 Part of the crystal structure of (III ![]() ![]() ![]() ![]() |
![]() | Figure 7 Part of the crystal structure of (III ![]() ![]() ![]() ![]() |
![]() | Figure 8 A stereoview of part of the crystal structure of (III ![]() ![]() ![]() |
![]() | Figure 9 Part of the crystal structure of (IV ![]() ![]() ![]() ![]() ![]() ![]() ![]() |
![]() | Figure 10 A stereoview of part of the crystal structure of (IV ![]() |
![]() | Figure 11 Part of the crystal structure of (IV ![]() |
Experimental
Compounds (I)–(III
) were prepared by acylation of (IV
) (Laavanya et al., 2002
) with acetic anhydride, chloroacetyl chloride and benzoyl chloride, respectively, in the presence of triethylamine in dry benzene under reflux conditions. Analyses found for (I): C 77.0, H 6.1, N 3.7%; C23H21NOS requires: C 76.8, H 5.9, N 3.9%; found for (II
): C 70.2, H 5.0, N 3.6%; C23H20ClNOS requires: C 70.1, H 5.1, N 3.6%; found for (III
): C 79.5, H 5.6, N 3.3%; C28H23NOS requires: C 79.8, H 5.5, N 3.3%. Crystals of (I
)–(III
) suitable for single-crystal X-ray diffraction were grown from solutions in ethanol; m.p.: (I
) 401–404 K, (II
) 393–397 K, and (III
) 445–449 K.
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Data collection
Refinement
|
|
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Refinement
|
|
Compound (III)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Refinement
|
|
|
|
For (I) and (II
), space groups P21/c and P21/n, respectively, were uniquely assigned from the For (III
), the permitted Cc and C2/c as possible space groups; C2/c was selected and confirmed by successful structure analysis. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.99 (CH2) and 1.00 Å (aliphatic CH). Examination of the refined structure of (I
) for possible additional symmetry using ADDSYM in PLATON (Spek, 2003
) showed that none could be detected.
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell DENZO–SMN (Otwinowski & Minor, 1997
); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003
) and SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270104008753/fa1057sup1.cif
contains datablocks global, I, II, III. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270104008753/fa1057Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S0108270104008753/fa1057IIsup3.hkl
Structure factors: contains datablock III. DOI: 10.1107/S0108270104008753/fa1057IIIsup4.hkl
Compounds (I)–(III) were prepared by acylation of (IV) (Laavanya et al., 2002) with acetic anhydride, chloroacetyl chloride and benzoyl chloride, respectively, in the presence of triethylamine in dry benzene under reflux conditions. Analyses found for (I): C 77.0, H 6.1, N 3.7%; C23H21NOS requires: C 76.8, H 5.9, N 3.9%; found for (II): C 70.2, H 5.0, N 3.6%; C23H20ClNOS requires: C 70.1, H 5.1, N 3.6%; found for (III): C 79.5, H 5.6, N 3.3%; C28H23NOS requires: C 79.8, H 5.5, N 3.3%. Crystals of (I)–(III) suitable for single-crystal X-ray diffraction were grown from solutions in ethanol. M.p. (I) 401–404 K, (II) 393–397 K, (III) 445–449 K.
For (I) and (II), space groups P21/c and P21/n, respectively, were uniquely assigned from the
For (III), the permitted Cc and C2/c as possible space groups; C2/c was selected and confirmed by successful structure analysis. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.99 (CH2) and 1.00 Å (aliphatic CH). Examination of the refined structure of (I) for possible additional symmetry using ADDSYM in PLATON (Spek, 2003) showed that none could be detected.For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell
DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C23H21NOS | F(000) = 1520 |
Mr = 359.48 | Dx = 1.273 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8274 reflections |
a = 20.3579 (4) Å | θ = 3.0–27.1° |
b = 8.3014 (1) Å | µ = 0.18 mm−1 |
c = 22.2513 (4) Å | T = 120 K |
β = 93.865 (1)° | Plate, colourless |
V = 3751.90 (11) Å3 | 0.20 × 0.04 × 0.03 mm |
Z = 8 |
Nonius KappaCCD diffractometer | 8274 independent reflections |
Radiation source: rotating anode | 4659 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.109 |
ϕ scans, and ω scans with κ offsets | θmax = 27.1°, θmin = 3.0° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −25→26 |
Tmin = 0.954, Tmax = 0.994 | k = −10→9 |
51290 measured reflections | l = −26→28 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0541P)2 + 0.0549P] where P = (Fo2 + 2Fc2)/3 |
8274 reflections | (Δ/σ)max = 0.001 |
471 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
C23H21NOS | V = 3751.90 (11) Å3 |
Mr = 359.48 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.3579 (4) Å | µ = 0.18 mm−1 |
b = 8.3014 (1) Å | T = 120 K |
c = 22.2513 (4) Å | 0.20 × 0.04 × 0.03 mm |
β = 93.865 (1)° |
Nonius KappaCCD diffractometer | 8274 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 4659 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.994 | Rint = 0.109 |
51290 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
8274 reflections | Δρmin = −0.40 e Å−3 |
471 parameters |
x | y | z | Uiso*/Ueq | ||
S11 | 0.55232 (3) | −0.07017 (7) | 0.57493 (3) | 0.03099 (16) | |
O15 | 0.67431 (8) | 0.02049 (19) | 0.75018 (7) | 0.0325 (4) | |
N15 | 0.68042 (9) | −0.0501 (2) | 0.65265 (8) | 0.0225 (4) | |
C12 | 0.58165 (11) | 0.1376 (3) | 0.56443 (10) | 0.0254 (5) | |
C13 | 0.65673 (11) | 0.1552 (3) | 0.57227 (10) | 0.0255 (5) | |
C14 | 0.68905 (11) | 0.1205 (2) | 0.63497 (9) | 0.0220 (5) | |
C16 | 0.73112 (12) | −0.2785 (3) | 0.60441 (10) | 0.0270 (5) | |
C17 | 0.72932 (13) | −0.3975 (3) | 0.56066 (11) | 0.0329 (6) | |
C18 | 0.67562 (13) | −0.4102 (3) | 0.51975 (10) | 0.0328 (6) | |
C19 | 0.62276 (13) | −0.3058 (3) | 0.52263 (10) | 0.0313 (6) | |
C110 | 0.62335 (11) | −0.1872 (2) | 0.56696 (10) | 0.0250 (5) | |
C111 | 0.67867 (11) | −0.1736 (2) | 0.60785 (9) | 0.0221 (5) | |
C121 | 0.54498 (11) | 0.2516 (3) | 0.60390 (10) | 0.0262 (5) | |
C122 | 0.53382 (12) | 0.2194 (3) | 0.66392 (11) | 0.0325 (6) | |
C123 | 0.50062 (12) | 0.3283 (3) | 0.69761 (11) | 0.0362 (6) | |
C124 | 0.47750 (13) | 0.4716 (3) | 0.67236 (12) | 0.0411 (7) | |
C125 | 0.48880 (13) | 0.5060 (3) | 0.61306 (12) | 0.0400 (6) | |
C126 | 0.52254 (12) | 0.3968 (3) | 0.57951 (11) | 0.0316 (6) | |
C141 | 0.76039 (11) | 0.1735 (3) | 0.63839 (9) | 0.0231 (5) | |
C142 | 0.80901 (11) | 0.0895 (3) | 0.61025 (10) | 0.0251 (5) | |
C143 | 0.87325 (11) | 0.1438 (3) | 0.61409 (10) | 0.0277 (5) | |
C144 | 0.89028 (12) | 0.2833 (3) | 0.64524 (10) | 0.0315 (6) | |
C145 | 0.84242 (12) | 0.3692 (3) | 0.67280 (11) | 0.0325 (6) | |
C146 | 0.77795 (12) | 0.3143 (3) | 0.66906 (10) | 0.0277 (5) | |
C151 | 0.67074 (11) | −0.0851 (3) | 0.71171 (10) | 0.0249 (5) | |
C152 | 0.65498 (12) | −0.2565 (3) | 0.72614 (10) | 0.0293 (5) | |
S21 | 0.05595 (3) | 0.18797 (7) | 0.07576 (3) | 0.03175 (16) | |
O25 | 0.17490 (8) | 0.28513 (19) | 0.25344 (7) | 0.0326 (4) | |
N25 | 0.18202 (9) | 0.2128 (2) | 0.15618 (8) | 0.0233 (4) | |
C22 | 0.08467 (11) | 0.3966 (3) | 0.06528 (10) | 0.0285 (5) | |
C23 | 0.15942 (11) | 0.4159 (3) | 0.07507 (10) | 0.0258 (5) | |
C24 | 0.19022 (11) | 0.3833 (2) | 0.13820 (9) | 0.0234 (5) | |
C26 | 0.23402 (12) | −0.0194 (3) | 0.11198 (10) | 0.0275 (5) | |
C27 | 0.23264 (13) | −0.1442 (3) | 0.07002 (10) | 0.0316 (6) | |
C28 | 0.18027 (13) | −0.1585 (3) | 0.02737 (10) | 0.0336 (6) | |
C29 | 0.12798 (13) | −0.0516 (3) | 0.02691 (10) | 0.0316 (6) | |
C210 | 0.12758 (12) | 0.0702 (3) | 0.06994 (10) | 0.0265 (5) | |
C211 | 0.18183 (12) | 0.0882 (3) | 0.11200 (9) | 0.0249 (5) | |
C221 | 0.04604 (11) | 0.5107 (3) | 0.10293 (10) | 0.0285 (5) | |
C222 | 0.03703 (12) | 0.4833 (3) | 0.16379 (11) | 0.0330 (6) | |
C223 | 0.00275 (12) | 0.5934 (3) | 0.19640 (12) | 0.0399 (6) | |
C224 | −0.02376 (13) | 0.7306 (3) | 0.16882 (13) | 0.0448 (7) | |
C225 | −0.01514 (13) | 0.7585 (3) | 0.10878 (13) | 0.0443 (7) | |
C226 | 0.01995 (12) | 0.6496 (3) | 0.07629 (12) | 0.0353 (6) | |
C241 | 0.26101 (11) | 0.4412 (2) | 0.14320 (9) | 0.0218 (5) | |
C242 | 0.30873 (12) | 0.3744 (3) | 0.10869 (10) | 0.0306 (6) | |
C243 | 0.37224 (12) | 0.4348 (3) | 0.11246 (11) | 0.0352 (6) | |
C244 | 0.38912 (12) | 0.5630 (3) | 0.14960 (11) | 0.0327 (6) | |
C245 | 0.34213 (12) | 0.6318 (3) | 0.18363 (10) | 0.0307 (5) | |
C246 | 0.27833 (11) | 0.5706 (2) | 0.17998 (10) | 0.0257 (5) | |
C251 | 0.17183 (11) | 0.1786 (3) | 0.21500 (10) | 0.0246 (5) | |
C252 | 0.15496 (13) | 0.0075 (3) | 0.23008 (10) | 0.0307 (6) | |
H12 | 0.5686 | 0.1674 | 0.5218 | 0.030* | |
H192 | 0.5493 | 0.1213 | 0.6818 | 0.039* | |
H123 | 0.4936 | 0.3047 | 0.7385 | 0.043* | |
H124 | 0.4541 | 0.5456 | 0.6955 | 0.049* | |
H125 | 0.4734 | 0.6043 | 0.5954 | 0.048* | |
H126 | 0.5305 | 0.4219 | 0.5390 | 0.038* | |
H13A | 0.6764 | 0.0820 | 0.5433 | 0.031* | |
H13B | 0.6682 | 0.2667 | 0.5611 | 0.031* | |
H14 | 0.6660 | 0.1882 | 0.6642 | 0.026* | |
H142 | 0.7979 | −0.0059 | 0.5883 | 0.030* | |
H143 | 0.9061 | 0.0847 | 0.5951 | 0.033* | |
H144 | 0.9346 | 0.3200 | 0.6477 | 0.038* | |
H145 | 0.8537 | 0.4654 | 0.6942 | 0.039* | |
H146 | 0.7452 | 0.3742 | 0.6878 | 0.033* | |
H15A | 0.6384 | −0.2622 | 0.7664 | 0.044* | |
H15B | 0.6949 | −0.3222 | 0.7251 | 0.044* | |
H15C | 0.6214 | −0.2974 | 0.6964 | 0.044* | |
H16 | 0.7685 | −0.2689 | 0.6321 | 0.032* | |
H17 | 0.7651 | −0.4704 | 0.5589 | 0.040* | |
H18 | 0.6748 | −0.4909 | 0.4894 | 0.039* | |
H19 | 0.5860 | −0.3152 | 0.4942 | 0.038* | |
H22 | 0.0729 | 0.4248 | 0.0222 | 0.034* | |
H222 | 0.0545 | 0.3888 | 0.1829 | 0.040* | |
H223 | −0.0026 | 0.5748 | 0.2379 | 0.048* | |
H224 | −0.0478 | 0.8052 | 0.1912 | 0.054* | |
H225 | −0.0332 | 0.8524 | 0.0897 | 0.053* | |
H226 | 0.0262 | 0.6705 | 0.0351 | 0.042* | |
H23A | 0.1802 | 0.3427 | 0.0468 | 0.031* | |
H23B | 0.1708 | 0.5274 | 0.0639 | 0.031* | |
H24 | 0.1657 | 0.4503 | 0.1666 | 0.028* | |
H242 | 0.2976 | 0.2870 | 0.0824 | 0.037* | |
H243 | 0.4045 | 0.3872 | 0.0892 | 0.042* | |
H244 | 0.4328 | 0.6040 | 0.1518 | 0.039* | |
H245 | 0.3533 | 0.7204 | 0.2094 | 0.037* | |
H246 | 0.2461 | 0.6187 | 0.2032 | 0.031* | |
H25A | 0.1946 | −0.0595 | 0.2297 | 0.046* | |
H25B | 0.1215 | −0.0333 | 0.2002 | 0.046* | |
H25C | 0.1379 | 0.0037 | 0.2702 | 0.046* | |
H26 | 0.2706 | −0.0079 | 0.1405 | 0.033* | |
H27 | 0.2678 | −0.2196 | 0.0707 | 0.038* | |
H28 | 0.1802 | −0.2422 | −0.0018 | 0.040* | |
H29 | 0.0924 | −0.0614 | −0.0028 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S11 | 0.0231 (3) | 0.0268 (3) | 0.0426 (4) | −0.0020 (2) | −0.0014 (3) | 0.0020 (3) |
C12 | 0.0223 (13) | 0.0234 (11) | 0.0300 (12) | 0.0000 (9) | −0.0015 (10) | 0.0066 (10) |
C121 | 0.0158 (12) | 0.0278 (12) | 0.0343 (13) | −0.0013 (10) | −0.0029 (10) | 0.0012 (10) |
C122 | 0.0243 (14) | 0.0346 (13) | 0.0376 (14) | −0.0003 (10) | −0.0043 (11) | 0.0049 (11) |
C123 | 0.0250 (14) | 0.0475 (15) | 0.0360 (13) | 0.0012 (12) | 0.0013 (11) | −0.0034 (12) |
C124 | 0.0328 (15) | 0.0380 (15) | 0.0527 (17) | 0.0034 (12) | 0.0038 (13) | −0.0135 (13) |
C125 | 0.0374 (16) | 0.0276 (13) | 0.0543 (17) | 0.0035 (11) | −0.0022 (13) | 0.0006 (12) |
C126 | 0.0269 (14) | 0.0293 (13) | 0.0382 (13) | −0.0009 (11) | −0.0022 (11) | 0.0034 (11) |
C13 | 0.0231 (13) | 0.0260 (12) | 0.0273 (12) | 0.0005 (10) | −0.0001 (10) | 0.0066 (10) |
C14 | 0.0218 (12) | 0.0185 (10) | 0.0256 (11) | 0.0007 (9) | 0.0021 (9) | 0.0018 (9) |
C141 | 0.0223 (12) | 0.0236 (11) | 0.0230 (11) | 0.0020 (10) | −0.0010 (9) | 0.0044 (9) |
C142 | 0.0255 (13) | 0.0252 (11) | 0.0243 (11) | 0.0011 (10) | 0.0000 (10) | 0.0006 (9) |
C143 | 0.0220 (13) | 0.0334 (13) | 0.0278 (12) | 0.0049 (10) | 0.0020 (10) | 0.0036 (10) |
C144 | 0.0220 (13) | 0.0366 (13) | 0.0353 (13) | −0.0053 (11) | −0.0020 (11) | 0.0050 (11) |
C145 | 0.0308 (14) | 0.0288 (13) | 0.0371 (13) | −0.0037 (11) | −0.0029 (11) | −0.0037 (11) |
C146 | 0.0264 (13) | 0.0246 (11) | 0.0319 (12) | 0.0020 (10) | 0.0010 (10) | 0.0019 (10) |
N15 | 0.0260 (11) | 0.0202 (9) | 0.0212 (9) | 0.0009 (8) | 0.0006 (8) | 0.0014 (8) |
C151 | 0.0184 (12) | 0.0296 (12) | 0.0263 (12) | 0.0027 (10) | −0.0011 (10) | 0.0017 (10) |
O15 | 0.0413 (11) | 0.0301 (9) | 0.0262 (8) | 0.0008 (8) | 0.0024 (8) | −0.0046 (7) |
C152 | 0.0314 (14) | 0.0303 (12) | 0.0267 (12) | 0.0011 (11) | 0.0050 (10) | 0.0054 (10) |
C16 | 0.0321 (14) | 0.0232 (11) | 0.0259 (12) | 0.0009 (10) | 0.0022 (10) | 0.0025 (10) |
C17 | 0.0385 (15) | 0.0261 (12) | 0.0356 (13) | 0.0040 (11) | 0.0131 (12) | 0.0050 (11) |
C18 | 0.0491 (17) | 0.0257 (12) | 0.0248 (12) | −0.0025 (11) | 0.0117 (12) | −0.0038 (10) |
C19 | 0.0406 (15) | 0.0303 (13) | 0.0225 (12) | −0.0090 (11) | −0.0009 (11) | 0.0022 (10) |
C110 | 0.0275 (13) | 0.0221 (11) | 0.0256 (11) | −0.0028 (10) | 0.0022 (10) | 0.0018 (10) |
C111 | 0.0260 (13) | 0.0196 (11) | 0.0211 (11) | 0.0003 (9) | 0.0042 (9) | −0.0002 (9) |
S21 | 0.0263 (4) | 0.0311 (3) | 0.0371 (3) | −0.0078 (3) | −0.0034 (3) | 0.0034 (3) |
C22 | 0.0251 (13) | 0.0311 (13) | 0.0282 (12) | −0.0068 (10) | −0.0059 (10) | 0.0057 (10) |
C221 | 0.0187 (12) | 0.0302 (12) | 0.0356 (13) | −0.0056 (10) | −0.0067 (10) | 0.0053 (11) |
C222 | 0.0222 (13) | 0.0386 (14) | 0.0376 (14) | −0.0001 (11) | −0.0037 (11) | 0.0047 (11) |
C223 | 0.0266 (15) | 0.0479 (16) | 0.0448 (15) | −0.0004 (12) | −0.0002 (12) | −0.0025 (13) |
C224 | 0.0344 (16) | 0.0391 (15) | 0.0606 (19) | 0.0019 (12) | 0.0011 (14) | −0.0092 (14) |
C225 | 0.0345 (16) | 0.0327 (14) | 0.0642 (19) | 0.0006 (12) | −0.0072 (14) | 0.0072 (14) |
C226 | 0.0314 (15) | 0.0313 (13) | 0.0419 (14) | −0.0083 (11) | −0.0057 (12) | 0.0077 (12) |
C23 | 0.0235 (13) | 0.0259 (12) | 0.0276 (12) | −0.0042 (10) | −0.0005 (10) | 0.0037 (10) |
C24 | 0.0251 (13) | 0.0198 (11) | 0.0253 (11) | −0.0014 (9) | 0.0008 (10) | −0.0019 (9) |
C241 | 0.0207 (12) | 0.0205 (11) | 0.0237 (11) | 0.0007 (9) | −0.0021 (9) | 0.0018 (9) |
C242 | 0.0295 (14) | 0.0301 (12) | 0.0323 (13) | −0.0035 (11) | 0.0019 (11) | −0.0108 (11) |
C243 | 0.0256 (14) | 0.0396 (14) | 0.0410 (14) | −0.0016 (11) | 0.0062 (11) | −0.0100 (12) |
C244 | 0.0264 (14) | 0.0337 (13) | 0.0378 (13) | −0.0044 (11) | 0.0009 (11) | −0.0031 (11) |
C245 | 0.0295 (14) | 0.0271 (12) | 0.0343 (13) | −0.0039 (10) | −0.0065 (11) | −0.0060 (10) |
C246 | 0.0256 (13) | 0.0232 (11) | 0.0280 (12) | 0.0029 (10) | −0.0002 (10) | −0.0001 (10) |
N25 | 0.0254 (11) | 0.0232 (9) | 0.0213 (9) | −0.0030 (8) | 0.0004 (8) | 0.0011 (8) |
C251 | 0.0205 (12) | 0.0300 (12) | 0.0231 (11) | 0.0023 (10) | 0.0003 (9) | 0.0014 (10) |
O25 | 0.0383 (10) | 0.0354 (9) | 0.0240 (8) | 0.0002 (8) | 0.0018 (7) | −0.0033 (7) |
C252 | 0.0332 (14) | 0.0332 (13) | 0.0260 (12) | −0.0018 (11) | 0.0039 (11) | 0.0051 (10) |
C26 | 0.0316 (14) | 0.0257 (12) | 0.0256 (12) | −0.0033 (10) | 0.0042 (10) | 0.0038 (10) |
C27 | 0.0437 (16) | 0.0228 (12) | 0.0291 (12) | −0.0005 (11) | 0.0082 (11) | 0.0028 (10) |
C28 | 0.0525 (17) | 0.0228 (12) | 0.0261 (12) | −0.0102 (12) | 0.0077 (12) | −0.0017 (10) |
C29 | 0.0409 (16) | 0.0296 (13) | 0.0242 (12) | −0.0146 (11) | 0.0003 (11) | 0.0026 (10) |
C210 | 0.0294 (14) | 0.0252 (12) | 0.0248 (11) | −0.0087 (10) | 0.0010 (10) | 0.0040 (10) |
C211 | 0.0303 (13) | 0.0228 (11) | 0.0218 (11) | −0.0043 (10) | 0.0033 (10) | 0.0025 (9) |
S11—C110 | 1.761 (2) | S21—C210 | 1.768 (2) |
S11—C12 | 1.845 (2) | S21—C22 | 1.848 (2) |
C12—C121 | 1.521 (3) | C22—C221 | 1.518 (3) |
C12—C13 | 1.534 (3) | C22—C23 | 1.531 (3) |
C12—H12 | 1.00 | C22—H22 | 1.00 |
C121—C126 | 1.386 (3) | C221—C226 | 1.386 (3) |
C121—C122 | 1.396 (3) | C221—C222 | 1.398 (3) |
C122—C123 | 1.380 (3) | C222—C223 | 1.384 (3) |
C122—H192 | 0.95 | C222—H222 | 0.95 |
C123—C124 | 1.385 (4) | C223—C224 | 1.386 (4) |
C123—H123 | 0.95 | C223—H223 | 0.95 |
C124—C125 | 1.384 (4) | C224—C225 | 1.379 (4) |
C124—H124 | 0.95 | C224—H224 | 0.95 |
C125—C126 | 1.386 (3) | C225—C226 | 1.385 (4) |
C125—H125 | 0.95 | C225—H225 | 0.95 |
C126—H126 | 0.95 | C226—H226 | 0.95 |
C13—C14 | 1.529 (3) | C23—C24 | 1.523 (3) |
C13—H13A | 0.99 | C23—H23A | 0.99 |
C13—H13B | 0.99 | C23—H23B | 0.99 |
C14—N15 | 1.483 (3) | C24—N25 | 1.483 (3) |
C14—C141 | 1.515 (3) | C24—C241 | 1.516 (3) |
C14—H14 | 1.00 | C24—H24 | 1.00 |
C141—C146 | 1.388 (3) | C241—C246 | 1.382 (3) |
C141—C142 | 1.393 (3) | C241—C242 | 1.393 (3) |
C142—C143 | 1.380 (3) | C242—C243 | 1.384 (3) |
C142—H142 | 0.95 | C242—H242 | 0.95 |
C143—C144 | 1.382 (3) | C243—C244 | 1.377 (3) |
C143—H143 | 0.95 | C243—H243 | 0.95 |
C144—C145 | 1.384 (3) | C244—C245 | 1.383 (3) |
C144—H144 | 0.95 | C244—H244 | 0.95 |
C145—C146 | 1.386 (3) | C245—C246 | 1.392 (3) |
C145—H145 | 0.95 | C245—H245 | 0.95 |
C146—H146 | 0.95 | C246—H246 | 0.95 |
N15—C151 | 1.373 (3) | N25—C251 | 1.368 (3) |
N15—C111 | 1.429 (3) | N25—C211 | 1.427 (3) |
C151—O15 | 1.224 (3) | C251—O25 | 1.229 (3) |
C151—C152 | 1.498 (3) | C251—C252 | 1.505 (3) |
C152—H15A | 0.98 | C252—H25A | 0.98 |
C152—H15B | 0.98 | C252—H25B | 0.98 |
C152—H15C | 0.98 | C252—H25C | 0.98 |
C16—C111 | 1.384 (3) | C26—C211 | 1.388 (3) |
C16—C17 | 1.386 (3) | C26—C27 | 1.394 (3) |
C16—H16 | 0.95 | C26—H26 | 0.95 |
C17—C18 | 1.379 (4) | C27—C28 | 1.384 (3) |
C17—H17 | 0.95 | C27—H27 | 0.95 |
C18—C19 | 1.386 (3) | C28—C29 | 1.385 (4) |
C18—H18 | 0.95 | C28—H28 | 0.95 |
C19—C110 | 1.393 (3) | C29—C210 | 1.393 (3) |
C19—H19 | 0.95 | C29—H29 | 0.95 |
C110—C111 | 1.404 (3) | C210—C211 | 1.407 (3) |
C110—S11—C12 | 103.17 (10) | C210—S21—C22 | 103.86 (10) |
C121—C12—C13 | 113.52 (18) | C221—C22—C23 | 113.77 (18) |
C121—C12—S11 | 109.46 (15) | C221—C22—S21 | 109.57 (15) |
C13—C12—S11 | 113.79 (15) | C23—C22—S21 | 113.57 (16) |
C121—C12—H12 | 106.5 | C221—C22—H22 | 106.5 |
C13—C12—H12 | 106.5 | C23—C22—H22 | 106.5 |
S11—C12—H12 | 106.5 | S21—C22—H22 | 106.5 |
C126—C121—C122 | 118.1 (2) | C226—C221—C222 | 118.5 (2) |
C126—C121—C12 | 118.5 (2) | C226—C221—C22 | 118.7 (2) |
C122—C121—C12 | 123.4 (2) | C222—C221—C22 | 122.7 (2) |
C123—C122—C121 | 120.8 (2) | C223—C222—C221 | 120.3 (2) |
C123—C122—H192 | 119.6 | C223—C222—H222 | 119.9 |
C121—C122—H192 | 119.6 | C221—C222—H222 | 119.9 |
C122—C123—C124 | 120.5 (2) | C222—C223—C224 | 120.4 (3) |
C122—C123—H123 | 119.7 | C222—C223—H223 | 119.8 |
C124—C123—H123 | 119.7 | C224—C223—H223 | 119.8 |
C125—C124—C123 | 119.4 (2) | C225—C224—C223 | 119.7 (3) |
C125—C124—H124 | 120.3 | C225—C224—H224 | 120.1 |
C123—C124—H124 | 120.3 | C223—C224—H224 | 120.1 |
C124—C125—C126 | 119.9 (2) | C224—C225—C226 | 120.0 (2) |
C124—C125—H125 | 120.0 | C224—C225—H225 | 120.0 |
C126—C125—H125 | 120.0 | C226—C225—H225 | 120.0 |
C125—C126—C121 | 121.3 (2) | C225—C226—C221 | 121.1 (2) |
C125—C126—H126 | 119.3 | C225—C226—H226 | 119.5 |
C121—C126—H126 | 119.3 | C221—C226—H226 | 119.5 |
C14—C13—C12 | 116.75 (18) | C24—C23—C22 | 117.13 (18) |
C14—C13—H13A | 108.1 | C24—C23—H23A | 108.0 |
C12—C13—H13A | 108.1 | C22—C23—H23A | 108.0 |
C14—C13—H13B | 108.1 | C24—C23—H23B | 108.0 |
C12—C13—H13B | 108.1 | C22—C23—H23B | 108.0 |
H13A—C13—H13B | 107.3 | H23A—C23—H23B | 107.3 |
N15—C14—C141 | 113.22 (17) | N25—C24—C241 | 113.98 (18) |
N15—C14—C13 | 111.74 (17) | N25—C24—C23 | 111.82 (17) |
C141—C14—C13 | 110.08 (17) | C241—C24—C23 | 109.96 (18) |
N15—C14—H14 | 107.2 | N25—C24—H24 | 106.9 |
C141—C14—H14 | 107.2 | C241—C24—H24 | 106.9 |
C13—C14—H14 | 107.2 | C23—C24—H24 | 106.9 |
C146—C141—C142 | 118.4 (2) | C246—C241—C242 | 118.4 (2) |
C146—C141—C14 | 118.9 (2) | C246—C241—C24 | 119.56 (19) |
C142—C141—C14 | 122.66 (19) | C242—C241—C24 | 121.88 (19) |
C143—C142—C141 | 120.5 (2) | C243—C242—C241 | 120.4 (2) |
C143—C142—H142 | 119.8 | C243—C242—H242 | 119.8 |
C141—C142—H142 | 119.8 | C241—C242—H242 | 119.8 |
C142—C143—C144 | 120.6 (2) | C244—C243—C242 | 120.7 (2) |
C142—C143—H143 | 119.7 | C244—C243—H243 | 119.7 |
C144—C143—H143 | 119.7 | C242—C243—H243 | 119.7 |
C143—C144—C145 | 119.6 (2) | C243—C244—C245 | 119.6 (2) |
C143—C144—H144 | 120.2 | C243—C244—H244 | 120.2 |
C145—C144—H144 | 120.2 | C245—C244—H244 | 120.2 |
C144—C145—C146 | 119.8 (2) | C244—C245—C246 | 119.6 (2) |
C144—C145—H145 | 120.1 | C244—C245—H245 | 120.2 |
C146—C145—H145 | 120.1 | C246—C245—H245 | 120.2 |
C145—C146—C141 | 121.2 (2) | C241—C246—C245 | 121.2 (2) |
C145—C146—H146 | 119.4 | C241—C246—H246 | 119.4 |
C141—C146—H146 | 119.4 | C245—C246—H246 | 119.4 |
C151—N15—C111 | 121.14 (17) | C251—N25—C211 | 121.01 (18) |
C151—N15—C14 | 118.90 (17) | C251—N25—C24 | 118.86 (18) |
C111—N15—C14 | 119.87 (16) | C211—N25—C24 | 120.07 (16) |
O15—C151—N15 | 120.8 (2) | O25—C251—N25 | 120.9 (2) |
O15—C151—C152 | 122.3 (2) | O25—C251—C252 | 121.72 (19) |
N15—C151—C152 | 116.93 (19) | N25—C251—C252 | 117.41 (19) |
C151—C152—H15A | 109.5 | C251—C252—H25A | 109.5 |
C151—C152—H15B | 109.5 | C251—C252—H25B | 109.5 |
H15A—C152—H15B | 109.5 | H25A—C252—H25B | 109.5 |
C151—C152—H15C | 109.5 | C251—C252—H25C | 109.5 |
H15A—C152—H15C | 109.5 | H25A—C252—H25C | 109.5 |
H15B—C152—H15C | 109.5 | H25B—C252—H25C | 109.5 |
C111—C16—C17 | 120.2 (2) | C211—C26—C27 | 119.8 (2) |
C111—C16—H16 | 119.9 | C211—C26—H26 | 120.1 |
C17—C16—H16 | 119.9 | C27—C26—H26 | 120.1 |
C18—C17—C16 | 120.0 (2) | C28—C27—C26 | 120.2 (2) |
C18—C17—H17 | 120.0 | C28—C27—H27 | 119.9 |
C16—C17—H17 | 120.0 | C26—C27—H27 | 119.9 |
C17—C18—C19 | 120.3 (2) | C27—C28—C29 | 120.4 (2) |
C17—C18—H18 | 119.8 | C27—C28—H28 | 119.8 |
C19—C18—H18 | 119.8 | C29—C28—H28 | 119.8 |
C18—C19—C110 | 120.3 (2) | C28—C29—C210 | 120.0 (2) |
C18—C19—H19 | 119.8 | C28—C29—H29 | 120.0 |
C110—C19—H19 | 119.8 | C210—C29—H29 | 120.0 |
C19—C110—C111 | 118.9 (2) | C29—C210—C211 | 119.6 (2) |
C19—C110—S11 | 119.55 (18) | C29—C210—S21 | 119.66 (18) |
C111—C110—S11 | 121.26 (16) | C211—C210—S21 | 120.49 (17) |
C16—C111—C110 | 120.13 (19) | C26—C211—C210 | 119.9 (2) |
C16—C111—N15 | 120.5 (2) | C26—C211—N25 | 120.0 (2) |
C110—C111—N15 | 119.40 (19) | C210—C211—N25 | 120.0 (2) |
C110—S11—C12—C121 | −146.32 (15) | C210—S21—C22—C221 | −146.81 (15) |
C110—S11—C12—C13 | −18.1 (2) | C210—S21—C22—C23 | −18.37 (19) |
C13—C12—C121—C126 | 95.0 (2) | C23—C22—C221—C226 | 99.2 (2) |
S11—C12—C121—C126 | −136.62 (19) | S21—C22—C221—C226 | −132.44 (19) |
C13—C12—C121—C122 | −83.6 (3) | C23—C22—C221—C222 | −79.2 (3) |
S11—C12—C121—C122 | 44.7 (3) | S21—C22—C221—C222 | 49.1 (3) |
C126—C121—C122—C123 | 0.8 (4) | C226—C221—C222—C223 | −0.1 (3) |
C12—C121—C122—C123 | 179.5 (2) | C22—C221—C222—C223 | 178.4 (2) |
C121—C122—C123—C124 | 0.3 (4) | C221—C222—C223—C224 | 0.9 (4) |
C122—C123—C124—C125 | −0.9 (4) | C222—C223—C224—C225 | −0.9 (4) |
C123—C124—C125—C126 | 0.5 (4) | C223—C224—C225—C226 | 0.0 (4) |
C124—C125—C126—C121 | 0.6 (4) | C224—C225—C226—C221 | 0.9 (4) |
C122—C121—C126—C125 | −1.3 (4) | C222—C221—C226—C225 | −0.9 (4) |
C12—C121—C126—C125 | 180.0 (2) | C22—C221—C226—C225 | −179.4 (2) |
C121—C12—C13—C14 | 61.4 (3) | C221—C22—C23—C24 | 61.8 (3) |
S11—C12—C13—C14 | −64.6 (2) | S21—C22—C23—C24 | −64.5 (2) |
C12—C13—C14—N15 | 64.1 (2) | C22—C23—C24—N25 | 64.2 (2) |
C12—C13—C14—C141 | −169.21 (18) | C22—C23—C24—C241 | −168.13 (18) |
N15—C14—C141—C146 | −129.7 (2) | N25—C24—C241—C246 | −121.1 (2) |
C13—C14—C141—C146 | 104.4 (2) | C23—C24—C241—C246 | 112.4 (2) |
N15—C14—C141—C142 | 52.5 (3) | N25—C24—C241—C242 | 63.2 (3) |
C13—C14—C141—C142 | −73.4 (3) | C23—C24—C241—C242 | −63.3 (3) |
C146—C141—C142—C143 | 1.4 (3) | C246—C241—C242—C243 | 1.4 (3) |
C14—C141—C142—C143 | 179.2 (2) | C24—C241—C242—C243 | 177.2 (2) |
C141—C142—C143—C144 | −0.8 (3) | C241—C242—C243—C244 | −1.0 (4) |
C142—C143—C144—C145 | 0.0 (3) | C242—C243—C244—C245 | 0.2 (4) |
C143—C144—C145—C146 | 0.2 (4) | C243—C244—C245—C246 | 0.0 (4) |
C144—C145—C146—C141 | 0.4 (4) | C242—C241—C246—C245 | −1.2 (3) |
C142—C141—C146—C145 | −1.2 (3) | C24—C241—C246—C245 | −177.1 (2) |
C14—C141—C146—C145 | −179.1 (2) | C244—C245—C246—C241 | 0.5 (3) |
C141—C14—N15—C151 | 91.6 (2) | C241—C24—N25—C251 | 90.3 (2) |
C13—C14—N15—C151 | −143.5 (2) | C23—C24—N25—C251 | −144.2 (2) |
C141—C14—N15—C111 | −91.9 (2) | C241—C24—N25—C211 | −92.6 (2) |
C13—C14—N15—C111 | 33.1 (3) | C23—C24—N25—C211 | 32.9 (3) |
C111—N15—C151—O15 | 177.7 (2) | C211—N25—C251—O25 | 176.8 (2) |
C14—N15—C151—O15 | −5.7 (3) | C24—N25—C251—O25 | −6.1 (3) |
C111—N15—C151—C152 | −3.0 (3) | C211—N25—C251—C252 | −4.9 (3) |
C14—N15—C151—C152 | 173.53 (19) | C24—N25—C251—C252 | 172.23 (19) |
C111—C16—C17—C18 | 1.0 (3) | C211—C26—C27—C28 | 1.8 (3) |
C16—C17—C18—C19 | −1.0 (3) | C26—C27—C28—C29 | −1.6 (3) |
C17—C18—C19—C110 | −0.1 (3) | C27—C28—C29—C210 | −0.7 (3) |
C18—C19—C110—C111 | 1.0 (3) | C28—C29—C210—C211 | 2.8 (3) |
C18—C19—C110—S11 | −173.21 (17) | C28—C29—C210—S21 | −171.13 (17) |
C12—S11—C110—C19 | −121.78 (18) | C22—S21—C210—C29 | −122.94 (18) |
C12—S11—C110—C111 | 64.11 (19) | C22—S21—C210—C211 | 63.2 (2) |
C17—C16—C111—C110 | −0.1 (3) | C27—C26—C211—C210 | 0.4 (3) |
C17—C16—C111—N15 | −179.64 (19) | C27—C26—C211—N25 | 177.87 (19) |
C19—C110—C111—C16 | −1.0 (3) | C29—C210—C211—C26 | −2.7 (3) |
S11—C110—C111—C16 | 173.18 (16) | S21—C210—C211—C26 | 171.23 (16) |
C19—C110—C111—N15 | 178.62 (18) | C29—C210—C211—N25 | 179.85 (19) |
S11—C110—C111—N15 | −7.2 (3) | S21—C210—C211—N25 | −6.3 (3) |
C151—N15—C111—C16 | −75.7 (3) | C251—N25—C211—C26 | −72.4 (3) |
C14—N15—C111—C16 | 107.7 (2) | C24—N25—C211—C26 | 110.6 (2) |
C151—N15—C111—C110 | 104.7 (2) | C251—N25—C211—C210 | 105.1 (2) |
C14—N15—C111—C110 | −71.8 (3) | C24—N25—C211—C210 | −72.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C145—H145···O25i | 0.95 | 2.47 | 3.336 (3) | 152 |
C245—H245···O15i | 0.95 | 2.41 | 3.268 (3) | 150 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C23H20ClNOS | F(000) = 824 |
Mr = 393.92 | Dx = 1.358 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4418 reflections |
a = 12.6348 (4) Å | θ = 3.2–27.5° |
b = 11.9337 (5) Å | µ = 0.32 mm−1 |
c = 12.7904 (5) Å | T = 120 K |
β = 92.549 (2)° | Plate, colourless |
V = 1926.63 (13) Å3 | 0.28 × 0.24 × 0.04 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 4418 independent reflections |
Radiation source: rotating anode | 2950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −16→16 |
Tmin = 0.926, Tmax = 0.987 | k = −15→15 |
26344 measured reflections | l = −16→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3 |
4418 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C23H20ClNOS | V = 1926.63 (13) Å3 |
Mr = 393.92 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.6348 (4) Å | µ = 0.32 mm−1 |
b = 11.9337 (5) Å | T = 120 K |
c = 12.7904 (5) Å | 0.28 × 0.24 × 0.04 mm |
β = 92.549 (2)° |
Nonius KappaCCD diffractometer | 4418 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 2950 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.987 | Rint = 0.081 |
26344 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
4418 reflections | Δρmin = −0.37 e Å−3 |
244 parameters |
x | y | z | Uiso*/Ueq | ||
Cl5 | 0.91507 (4) | 0.23886 (5) | 0.38523 (4) | 0.03279 (15) | |
S1 | 0.62010 (4) | 0.10640 (4) | 0.09520 (4) | 0.02562 (14) | |
O5 | 0.68726 (10) | 0.23583 (11) | 0.41271 (10) | 0.0254 (3) | |
N5 | 0.62888 (12) | 0.29611 (13) | 0.25199 (12) | 0.0210 (3) | |
C2 | 0.48382 (14) | 0.11544 (15) | 0.14149 (15) | 0.0211 (4) | |
C3 | 0.45311 (15) | 0.23221 (15) | 0.18065 (15) | 0.0223 (4) | |
C4 | 0.51655 (14) | 0.27594 (15) | 0.27657 (15) | 0.0213 (4) | |
C6 | 0.68342 (15) | 0.43814 (16) | 0.12682 (15) | 0.0239 (4) | |
C7 | 0.71108 (15) | 0.46821 (17) | 0.02638 (15) | 0.0266 (4) | |
C8 | 0.70979 (16) | 0.38876 (16) | −0.05196 (15) | 0.0262 (4) | |
C9 | 0.67862 (15) | 0.27932 (16) | −0.03213 (15) | 0.0245 (4) | |
C10 | 0.65120 (15) | 0.24793 (15) | 0.06785 (15) | 0.0219 (4) | |
C11 | 0.65492 (15) | 0.32806 (15) | 0.14771 (14) | 0.0207 (4) | |
C21 | 0.46712 (14) | 0.02588 (15) | 0.22280 (15) | 0.0216 (4) | |
C22 | 0.53824 (15) | 0.00511 (15) | 0.30613 (15) | 0.0235 (4) | |
C23 | 0.51420 (16) | −0.07096 (16) | 0.38456 (16) | 0.0264 (4) | |
C24 | 0.41872 (17) | −0.12711 (17) | 0.37951 (17) | 0.0315 (5) | |
C25 | 0.34730 (17) | −0.10777 (17) | 0.29671 (18) | 0.0324 (5) | |
C26 | 0.37133 (15) | −0.03237 (16) | 0.21828 (16) | 0.0264 (4) | |
C41 | 0.46579 (14) | 0.37879 (15) | 0.32295 (15) | 0.0218 (4) | |
C42 | 0.42153 (15) | 0.36996 (17) | 0.42056 (15) | 0.0251 (4) | |
C43 | 0.37349 (15) | 0.46205 (18) | 0.46527 (16) | 0.0288 (5) | |
C44 | 0.36970 (15) | 0.56379 (18) | 0.41354 (16) | 0.0291 (5) | |
C45 | 0.41336 (16) | 0.57349 (17) | 0.31652 (17) | 0.0299 (5) | |
C46 | 0.45954 (16) | 0.48096 (16) | 0.27098 (16) | 0.0274 (5) | |
C51 | 0.70636 (15) | 0.26827 (15) | 0.32498 (15) | 0.0218 (4) | |
C52 | 0.81861 (15) | 0.27880 (19) | 0.28850 (16) | 0.0294 (5) | |
H2 | 0.4348 | 0.0978 | 0.0802 | 0.025* | |
H22 | 0.6043 | 0.0432 | 0.3100 | 0.028* | |
H23 | 0.5636 | −0.0840 | 0.4414 | 0.032* | |
H24 | 0.4022 | −0.1789 | 0.4328 | 0.038* | |
H25 | 0.2814 | −0.1461 | 0.2933 | 0.039* | |
H26 | 0.3220 | −0.0205 | 0.1611 | 0.032* | |
H3A | 0.4607 | 0.2863 | 0.1228 | 0.027* | |
H3B | 0.3773 | 0.2306 | 0.1972 | 0.027* | |
H4 | 0.5163 | 0.2157 | 0.3309 | 0.026* | |
H42 | 0.4242 | 0.3005 | 0.4568 | 0.030* | |
H43 | 0.3432 | 0.4550 | 0.5316 | 0.035* | |
H44 | 0.3373 | 0.6268 | 0.4444 | 0.035* | |
H45 | 0.4117 | 0.6435 | 0.2811 | 0.036* | |
H46 | 0.4872 | 0.4876 | 0.2034 | 0.033* | |
H52A | 0.8314 | 0.3575 | 0.2680 | 0.035* | |
H52B | 0.8261 | 0.2313 | 0.2258 | 0.035* | |
H6 | 0.6840 | 0.4927 | 0.1809 | 0.029* | |
H7 | 0.7308 | 0.5433 | 0.0119 | 0.032* | |
H8 | 0.7303 | 0.4089 | −0.1200 | 0.031* | |
H9 | 0.6761 | 0.2257 | −0.0871 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0297 (3) | 0.0194 (2) | 0.0285 (3) | 0.0014 (2) | 0.0100 (2) | 0.0002 (2) |
C2 | 0.0211 (9) | 0.0201 (9) | 0.0222 (10) | −0.0001 (8) | 0.0011 (7) | −0.0001 (8) |
C21 | 0.0223 (10) | 0.0157 (9) | 0.0272 (11) | 0.0008 (8) | 0.0047 (8) | −0.0049 (8) |
C22 | 0.0246 (10) | 0.0196 (9) | 0.0266 (11) | −0.0006 (8) | 0.0038 (8) | −0.0025 (8) |
C23 | 0.0363 (11) | 0.0198 (9) | 0.0233 (11) | 0.0030 (9) | 0.0046 (9) | 0.0005 (8) |
C24 | 0.0424 (13) | 0.0212 (10) | 0.0323 (12) | −0.0009 (9) | 0.0176 (10) | −0.0006 (9) |
C25 | 0.0312 (11) | 0.0226 (10) | 0.0445 (14) | −0.0079 (9) | 0.0145 (10) | −0.0070 (9) |
C26 | 0.0236 (10) | 0.0229 (10) | 0.0329 (12) | −0.0009 (9) | 0.0017 (8) | −0.0064 (9) |
C3 | 0.0219 (9) | 0.0211 (10) | 0.0240 (10) | 0.0027 (8) | 0.0014 (8) | −0.0008 (8) |
C4 | 0.0234 (9) | 0.0201 (9) | 0.0206 (10) | 0.0005 (8) | 0.0030 (8) | 0.0008 (8) |
C41 | 0.0211 (9) | 0.0226 (10) | 0.0216 (10) | 0.0002 (8) | −0.0003 (8) | −0.0028 (8) |
C42 | 0.0210 (9) | 0.0286 (11) | 0.0256 (11) | −0.0023 (8) | 0.0014 (8) | −0.0006 (9) |
C43 | 0.0229 (10) | 0.0368 (12) | 0.0270 (11) | −0.0006 (9) | 0.0044 (8) | −0.0085 (9) |
C44 | 0.0233 (10) | 0.0285 (11) | 0.0353 (12) | 0.0031 (9) | −0.0022 (9) | −0.0126 (9) |
C45 | 0.0346 (11) | 0.0203 (10) | 0.0344 (12) | 0.0026 (9) | −0.0015 (9) | −0.0039 (9) |
C46 | 0.0311 (11) | 0.0247 (10) | 0.0267 (11) | 0.0029 (9) | 0.0045 (9) | −0.0016 (8) |
N5 | 0.0227 (8) | 0.0228 (8) | 0.0176 (8) | −0.0002 (7) | 0.0033 (6) | 0.0027 (6) |
C51 | 0.0277 (10) | 0.0183 (9) | 0.0196 (10) | 0.0000 (8) | 0.0015 (8) | −0.0021 (8) |
O5 | 0.0304 (8) | 0.0288 (7) | 0.0170 (7) | −0.0003 (6) | 0.0027 (6) | 0.0022 (6) |
C52 | 0.0241 (10) | 0.0399 (12) | 0.0240 (11) | 0.0002 (9) | −0.0011 (8) | 0.0062 (9) |
Cl5 | 0.0266 (3) | 0.0420 (3) | 0.0293 (3) | 0.0002 (2) | −0.0039 (2) | 0.0037 (2) |
C6 | 0.0270 (10) | 0.0224 (10) | 0.0222 (10) | −0.0021 (8) | 0.0001 (8) | −0.0008 (8) |
C7 | 0.0299 (10) | 0.0246 (10) | 0.0254 (11) | −0.0031 (9) | 0.0010 (8) | 0.0057 (9) |
C8 | 0.0284 (10) | 0.0307 (11) | 0.0197 (10) | −0.0014 (9) | 0.0025 (8) | 0.0079 (9) |
C9 | 0.0284 (11) | 0.0265 (10) | 0.0186 (10) | 0.0008 (9) | 0.0030 (8) | −0.0019 (8) |
C10 | 0.0224 (9) | 0.0224 (10) | 0.0212 (10) | 0.0018 (8) | 0.0022 (8) | 0.0015 (8) |
C11 | 0.0215 (9) | 0.0235 (10) | 0.0172 (10) | 0.0019 (8) | 0.0014 (7) | 0.0031 (8) |
S1—C10 | 1.7725 (19) | C42—H42 | 0.95 |
S1—C2 | 1.8487 (18) | C43—C44 | 1.383 (3) |
C2—C21 | 1.513 (3) | C43—H43 | 0.95 |
C2—C3 | 1.536 (2) | C44—C45 | 1.385 (3) |
C2—H2 | 1.00 | C44—H44 | 0.95 |
C21—C22 | 1.386 (3) | C45—C46 | 1.389 (3) |
C21—C26 | 1.395 (3) | C45—H45 | 0.95 |
C22—C23 | 1.396 (3) | C46—H46 | 0.95 |
C22—H22 | 0.95 | N5—C51 | 1.363 (2) |
C23—C24 | 1.379 (3) | N5—C11 | 1.439 (2) |
C23—H23 | 0.95 | C51—O5 | 1.221 (2) |
C24—C25 | 1.380 (3) | C51—C52 | 1.518 (3) |
C24—H24 | 0.95 | C52—Cl5 | 1.763 (2) |
C25—C26 | 1.391 (3) | C52—H52A | 0.99 |
C25—H25 | 0.95 | C52—H52B | 0.99 |
C26—H26 | 0.95 | C6—C11 | 1.391 (3) |
C3—C4 | 1.527 (3) | C6—C7 | 1.393 (3) |
C3—H3A | 0.99 | C6—H6 | 0.95 |
C3—H3B | 0.99 | C7—C8 | 1.379 (3) |
C4—N5 | 1.487 (2) | C7—H7 | 0.95 |
C4—C41 | 1.518 (3) | C8—C9 | 1.391 (3) |
C4—H4 | 1.00 | C8—H8 | 0.95 |
C41—C46 | 1.389 (3) | C9—C10 | 1.391 (3) |
C41—C42 | 1.394 (3) | C9—H9 | 0.95 |
C42—C43 | 1.391 (3) | C10—C11 | 1.399 (3) |
C10—S1—C2 | 103.03 (8) | C44—C43—C42 | 120.24 (18) |
C21—C2—C3 | 111.82 (15) | C44—C43—H43 | 119.9 |
C21—C2—S1 | 109.84 (12) | C42—C43—H43 | 119.9 |
C3—C2—S1 | 114.18 (13) | C43—C44—C45 | 119.70 (18) |
C21—C2—H2 | 106.9 | C43—C44—H44 | 120.1 |
C3—C2—H2 | 106.9 | C45—C44—H44 | 120.1 |
S1—C2—H2 | 106.9 | C44—C45—C46 | 120.06 (19) |
C22—C21—C26 | 118.33 (18) | C44—C45—H45 | 120.0 |
C22—C21—C2 | 123.36 (16) | C46—C45—H45 | 120.0 |
C26—C21—C2 | 118.10 (17) | C45—C46—C41 | 120.86 (18) |
C21—C22—C23 | 120.97 (18) | C45—C46—H46 | 119.6 |
C21—C22—H22 | 119.5 | C41—C46—H46 | 119.6 |
C23—C22—H22 | 119.5 | C51—N5—C11 | 120.82 (15) |
C24—C23—C22 | 120.0 (2) | C51—N5—C4 | 118.61 (14) |
C24—C23—H23 | 120.0 | C11—N5—C4 | 119.90 (15) |
C22—C23—H23 | 120.0 | O5—C51—N5 | 122.77 (17) |
C23—C24—C25 | 119.71 (19) | O5—C51—C52 | 122.29 (17) |
C23—C24—H24 | 120.1 | N5—C51—C52 | 114.93 (16) |
C25—C24—H24 | 120.1 | C51—C52—Cl5 | 112.83 (14) |
C24—C25—C26 | 120.35 (19) | C51—C52—H52A | 109.0 |
C24—C25—H25 | 119.8 | Cl5—C52—H52A | 109.0 |
C26—C25—H25 | 119.8 | C51—C52—H52B | 109.0 |
C25—C26—C21 | 120.6 (2) | Cl5—C52—H52B | 109.0 |
C25—C26—H26 | 119.7 | H52A—C52—H52B | 107.8 |
C21—C26—H26 | 119.7 | C11—C6—C7 | 119.87 (18) |
C4—C3—C2 | 116.15 (16) | C11—C6—H6 | 120.1 |
C4—C3—H3A | 108.2 | C7—C6—H6 | 120.1 |
C2—C3—H3A | 108.2 | C8—C7—C6 | 119.84 (18) |
C4—C3—H3B | 108.2 | C8—C7—H7 | 120.1 |
C2—C3—H3B | 108.2 | C6—C7—H7 | 120.1 |
H3A—C3—H3B | 107.4 | C7—C8—C9 | 120.49 (18) |
N5—C4—C41 | 112.07 (15) | C7—C8—H8 | 119.8 |
N5—C4—C3 | 110.93 (14) | C9—C8—H8 | 119.8 |
C41—C4—C3 | 112.00 (15) | C8—C9—C10 | 120.31 (18) |
N5—C4—H4 | 107.2 | C8—C9—H9 | 119.8 |
C41—C4—H4 | 107.2 | C10—C9—H9 | 119.8 |
C3—C4—H4 | 107.2 | C9—C10—C11 | 119.05 (17) |
C46—C41—C42 | 118.57 (17) | C9—C10—S1 | 120.30 (15) |
C46—C41—C4 | 122.60 (16) | C11—C10—S1 | 120.53 (14) |
C42—C41—C4 | 118.82 (17) | C6—C11—C10 | 120.39 (17) |
C43—C42—C41 | 120.54 (19) | C6—C11—N5 | 120.00 (17) |
C43—C42—H42 | 119.7 | C10—C11—N5 | 119.61 (16) |
C41—C42—H42 | 119.7 | ||
C10—S1—C2—C21 | −147.32 (13) | C4—C41—C46—C45 | −179.36 (18) |
C10—S1—C2—C3 | −20.80 (16) | C41—C4—N5—C51 | 93.70 (19) |
C3—C2—C21—C22 | −80.5 (2) | C3—C4—N5—C51 | −140.30 (17) |
S1—C2—C21—C22 | 47.4 (2) | C41—C4—N5—C11 | −95.62 (19) |
C3—C2—C21—C26 | 94.2 (2) | C3—C4—N5—C11 | 30.4 (2) |
S1—C2—C21—C26 | −138.00 (15) | C11—N5—C51—O5 | −176.57 (17) |
C26—C21—C22—C23 | −0.9 (3) | C4—N5—C51—O5 | −6.0 (3) |
C2—C21—C22—C23 | 173.68 (17) | C11—N5—C51—C52 | 2.5 (3) |
C21—C22—C23—C24 | 0.3 (3) | C4—N5—C51—C52 | 173.09 (16) |
C22—C23—C24—C25 | 0.0 (3) | O5—C51—C52—Cl5 | 0.3 (3) |
C23—C24—C25—C26 | 0.3 (3) | N5—C51—C52—Cl5 | −178.73 (14) |
C24—C25—C26—C21 | −0.9 (3) | C11—C6—C7—C8 | 0.2 (3) |
C22—C21—C26—C25 | 1.2 (3) | C6—C7—C8—C9 | 1.5 (3) |
C2—C21—C26—C25 | −173.69 (17) | C7—C8—C9—C10 | −1.8 (3) |
C21—C2—C3—C4 | 62.1 (2) | C8—C9—C10—C11 | 0.3 (3) |
S1—C2—C3—C4 | −63.4 (2) | C8—C9—C10—S1 | −175.75 (15) |
C2—C3—C4—N5 | 66.3 (2) | C2—S1—C10—C9 | −121.43 (16) |
C2—C3—C4—C41 | −167.65 (15) | C2—S1—C10—C11 | 62.6 (2) |
N5—C4—C41—C46 | 58.2 (2) | C7—C6—C11—C10 | −1.7 (3) |
C3—C4—C41—C46 | −67.2 (2) | C7—C6—C11—N5 | 178.44 (17) |
N5—C4—C41—C42 | −123.23 (18) | C9—C10—C11—C6 | 1.4 (3) |
C3—C4—C41—C42 | 111.4 (2) | S1—C10—C11—C6 | 177.46 (14) |
C46—C41—C42—C43 | −0.8 (3) | C9—C10—C11—N5 | −178.70 (17) |
C4—C41—C42—C43 | −179.44 (17) | S1—C10—C11—N5 | −2.6 (2) |
C41—C42—C43—C44 | −0.4 (3) | C51—N5—C11—C6 | −83.9 (2) |
C42—C43—C44—C45 | 0.4 (3) | C4—N5—C11—C6 | 105.6 (2) |
C43—C44—C45—C46 | 0.8 (3) | C51—N5—C11—C10 | 96.2 (2) |
C44—C45—C46—C41 | −2.1 (3) | C4—N5—C11—C10 | −74.3 (2) |
C42—C41—C46—C45 | 2.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O5i | 0.95 | 2.42 | 3.295 (3) | 153 |
C44—H44···O5ii | 0.95 | 2.48 | 3.364 (2) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
C28H23NOS | F(000) = 1776 |
Mr = 421.53 | Dx = 1.309 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4894 reflections |
a = 30.1891 (8) Å | θ = 3.0–27.5° |
b = 14.8005 (3) Å | µ = 0.17 mm−1 |
c = 9.7965 (3) Å | T = 120 K |
β = 102.2570 (16)° | Block, colourless |
V = 4277.43 (19) Å3 | 0.36 × 0.26 × 0.16 mm |
Z = 8 |
Nonius KappaCCD diffractometer | 4894 independent reflections |
Radiation source: rotating anode | 3535 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −39→35 |
Tmin = 0.937, Tmax = 0.973 | k = −19→18 |
21732 measured reflections | l = −11→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0545P)2 + 1.1026P] where P = (Fo2 + 2Fc2)/3 |
4894 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C28H23NOS | V = 4277.43 (19) Å3 |
Mr = 421.53 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.1891 (8) Å | µ = 0.17 mm−1 |
b = 14.8005 (3) Å | T = 120 K |
c = 9.7965 (3) Å | 0.36 × 0.26 × 0.16 mm |
β = 102.2570 (16)° |
Nonius KappaCCD diffractometer | 4894 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 3535 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.973 | Rint = 0.060 |
21732 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
4894 reflections | Δρmin = −0.38 e Å−3 |
280 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.094107 (14) | 0.42954 (3) | 0.77386 (4) | 0.02642 (13) | |
O5 | 0.17444 (4) | 0.15956 (8) | 0.69736 (13) | 0.0315 (3) | |
N5 | 0.12068 (4) | 0.26493 (8) | 0.62342 (14) | 0.0208 (3) | |
C2 | 0.14420 (5) | 0.46165 (11) | 0.70379 (17) | 0.0232 (4) | |
C3 | 0.14544 (6) | 0.41805 (10) | 0.56286 (17) | 0.0228 (3) | |
C4 | 0.15486 (5) | 0.31680 (10) | 0.56536 (16) | 0.0213 (3) | |
C6 | 0.04472 (6) | 0.24342 (11) | 0.47728 (17) | 0.0252 (4) | |
C7 | 0.00021 (6) | 0.27212 (12) | 0.43145 (18) | 0.0289 (4) | |
C8 | −0.01450 (6) | 0.35052 (12) | 0.48598 (18) | 0.0297 (4) | |
C9 | 0.01483 (6) | 0.39916 (11) | 0.58627 (18) | 0.0256 (4) | |
C10 | 0.05930 (5) | 0.37055 (11) | 0.63496 (17) | 0.0222 (3) | |
C11 | 0.07424 (5) | 0.29148 (10) | 0.57957 (16) | 0.0212 (3) | |
C21 | 0.18738 (5) | 0.44868 (10) | 0.81379 (16) | 0.0211 (3) | |
C22 | 0.22147 (6) | 0.51296 (11) | 0.82174 (18) | 0.0258 (4) | |
C23 | 0.26166 (6) | 0.50527 (12) | 0.92018 (19) | 0.0300 (4) | |
C24 | 0.26810 (6) | 0.43394 (12) | 1.01364 (19) | 0.0290 (4) | |
C25 | 0.23471 (6) | 0.36931 (11) | 1.00595 (17) | 0.0274 (4) | |
C26 | 0.19454 (6) | 0.37592 (11) | 0.90624 (17) | 0.0234 (4) | |
C41 | 0.15783 (5) | 0.27965 (10) | 0.42232 (16) | 0.0205 (3) | |
C42 | 0.12596 (6) | 0.30039 (11) | 0.30132 (17) | 0.0237 (4) | |
C43 | 0.12925 (6) | 0.26244 (12) | 0.17391 (18) | 0.0270 (4) | |
C44 | 0.16410 (6) | 0.20381 (11) | 0.16507 (18) | 0.0285 (4) | |
C45 | 0.19614 (6) | 0.18313 (12) | 0.28431 (18) | 0.0291 (4) | |
C46 | 0.19296 (6) | 0.22055 (11) | 0.41200 (18) | 0.0251 (4) | |
C51 | 0.10328 (6) | 0.12645 (10) | 0.74628 (17) | 0.0239 (4) | |
C52 | 0.07184 (6) | 0.15941 (11) | 0.81872 (18) | 0.0290 (4) | |
C53 | 0.04732 (7) | 0.10049 (13) | 0.8830 (2) | 0.0378 (5) | |
C54 | 0.05359 (7) | 0.00808 (13) | 0.8753 (2) | 0.0428 (5) | |
C55 | 0.08459 (7) | −0.02543 (12) | 0.8026 (2) | 0.0427 (5) | |
C56 | 0.10975 (6) | 0.03312 (11) | 0.7399 (2) | 0.0332 (4) | |
C57 | 0.13505 (6) | 0.18430 (11) | 0.68621 (17) | 0.0243 (4) | |
H2 | 0.1415 | 0.5282 | 0.6860 | 0.028* | |
H22 | 0.2171 | 0.5627 | 0.7589 | 0.031* | |
H23 | 0.2849 | 0.5491 | 0.9236 | 0.036* | |
H24 | 0.2954 | 0.4295 | 1.0827 | 0.035* | |
H25 | 0.2392 | 0.3199 | 1.0693 | 0.033* | |
H26 | 0.1719 | 0.3307 | 0.9011 | 0.028* | |
H3A | 0.1159 | 0.4292 | 0.4985 | 0.027* | |
H3B | 0.1690 | 0.4489 | 0.5235 | 0.027* | |
H4 | 0.1850 | 0.3068 | 0.6292 | 0.026* | |
H42 | 0.1018 | 0.3407 | 0.3058 | 0.028* | |
H43 | 0.1073 | 0.2770 | 0.0921 | 0.032* | |
H44 | 0.1661 | 0.1779 | 0.0778 | 0.034* | |
H45 | 0.2204 | 0.1433 | 0.2789 | 0.035* | |
H46 | 0.2150 | 0.2057 | 0.4934 | 0.030* | |
H52 | 0.0672 | 0.2227 | 0.8240 | 0.035* | |
H53 | 0.0260 | 0.1235 | 0.9329 | 0.045* | |
H54 | 0.0366 | −0.0322 | 0.9198 | 0.051* | |
H55 | 0.0886 | −0.0888 | 0.7958 | 0.051* | |
H56 | 0.1316 | 0.0099 | 0.6922 | 0.040* | |
H6 | 0.0550 | 0.1906 | 0.4384 | 0.030* | |
H7 | −0.0201 | 0.2382 | 0.3630 | 0.035* | |
H8 | −0.0448 | 0.3706 | 0.4541 | 0.036* | |
H9 | 0.0046 | 0.4529 | 0.6226 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0271 (2) | 0.0301 (2) | 0.0232 (2) | −0.00194 (18) | 0.00794 (17) | −0.00742 (18) |
C2 | 0.0304 (9) | 0.0193 (8) | 0.0210 (8) | −0.0017 (7) | 0.0079 (7) | −0.0007 (7) |
C21 | 0.0266 (8) | 0.0202 (8) | 0.0184 (8) | −0.0001 (6) | 0.0092 (6) | −0.0043 (6) |
C22 | 0.0338 (9) | 0.0232 (8) | 0.0244 (9) | −0.0018 (7) | 0.0155 (7) | −0.0006 (7) |
C23 | 0.0274 (9) | 0.0324 (9) | 0.0329 (10) | −0.0069 (7) | 0.0124 (8) | −0.0079 (8) |
C24 | 0.0249 (9) | 0.0380 (10) | 0.0245 (9) | 0.0021 (8) | 0.0060 (7) | −0.0084 (8) |
C25 | 0.0365 (10) | 0.0260 (8) | 0.0209 (9) | 0.0034 (7) | 0.0090 (7) | −0.0009 (7) |
C26 | 0.0292 (9) | 0.0200 (8) | 0.0220 (9) | −0.0040 (7) | 0.0073 (7) | −0.0034 (7) |
C3 | 0.0277 (8) | 0.0223 (8) | 0.0190 (8) | −0.0016 (7) | 0.0063 (7) | 0.0003 (7) |
C4 | 0.0245 (8) | 0.0221 (8) | 0.0178 (8) | −0.0003 (6) | 0.0057 (6) | 0.0003 (6) |
C41 | 0.0239 (8) | 0.0192 (7) | 0.0199 (8) | −0.0034 (6) | 0.0080 (6) | −0.0005 (6) |
C42 | 0.0254 (8) | 0.0245 (8) | 0.0228 (9) | 0.0024 (7) | 0.0083 (7) | −0.0009 (7) |
C43 | 0.0294 (9) | 0.0326 (9) | 0.0192 (9) | 0.0020 (7) | 0.0053 (7) | 0.0003 (7) |
C44 | 0.0352 (10) | 0.0305 (9) | 0.0223 (9) | 0.0009 (8) | 0.0121 (7) | −0.0039 (7) |
C45 | 0.0305 (9) | 0.0306 (9) | 0.0286 (9) | 0.0062 (7) | 0.0120 (7) | −0.0023 (8) |
C46 | 0.0254 (8) | 0.0255 (8) | 0.0250 (9) | 0.0013 (7) | 0.0064 (7) | 0.0019 (7) |
N5 | 0.0260 (7) | 0.0185 (6) | 0.0192 (7) | 0.0020 (5) | 0.0074 (6) | 0.0032 (5) |
C57 | 0.0322 (9) | 0.0218 (8) | 0.0199 (8) | 0.0037 (7) | 0.0080 (7) | −0.0002 (7) |
O5 | 0.0314 (7) | 0.0292 (6) | 0.0357 (7) | 0.0084 (5) | 0.0110 (5) | 0.0087 (5) |
C51 | 0.0329 (9) | 0.0210 (8) | 0.0179 (8) | 0.0030 (7) | 0.0057 (7) | 0.0028 (7) |
C52 | 0.0419 (10) | 0.0220 (8) | 0.0257 (9) | 0.0052 (7) | 0.0128 (8) | 0.0036 (7) |
C53 | 0.0498 (12) | 0.0326 (10) | 0.0382 (11) | 0.0089 (9) | 0.0253 (9) | 0.0064 (8) |
C54 | 0.0541 (12) | 0.0297 (10) | 0.0526 (13) | 0.0012 (9) | 0.0289 (10) | 0.0127 (9) |
C55 | 0.0593 (13) | 0.0206 (9) | 0.0556 (14) | 0.0039 (9) | 0.0292 (11) | 0.0067 (9) |
C56 | 0.0426 (11) | 0.0248 (9) | 0.0376 (11) | 0.0068 (8) | 0.0206 (9) | 0.0021 (8) |
C6 | 0.0319 (9) | 0.0222 (8) | 0.0228 (9) | −0.0043 (7) | 0.0089 (7) | −0.0019 (7) |
C7 | 0.0283 (9) | 0.0357 (10) | 0.0217 (9) | −0.0090 (7) | 0.0031 (7) | −0.0001 (8) |
C8 | 0.0247 (9) | 0.0351 (10) | 0.0286 (9) | 0.0000 (7) | 0.0042 (7) | 0.0054 (8) |
C9 | 0.0282 (9) | 0.0235 (8) | 0.0259 (9) | 0.0022 (7) | 0.0072 (7) | 0.0040 (7) |
C10 | 0.0262 (8) | 0.0217 (8) | 0.0191 (8) | −0.0012 (6) | 0.0060 (6) | 0.0019 (7) |
C11 | 0.0257 (8) | 0.0203 (8) | 0.0185 (8) | −0.0001 (6) | 0.0064 (6) | 0.0036 (6) |
S1—C10 | 1.7637 (16) | C44—H44 | 0.95 |
S1—C2 | 1.8507 (16) | C45—C46 | 1.390 (2) |
C2—C21 | 1.517 (2) | C45—H45 | 0.95 |
C2—C3 | 1.532 (2) | C46—H46 | 0.95 |
C2—H2 | 1.00 | N5—C57 | 1.370 (2) |
C21—C22 | 1.391 (2) | N5—C11 | 1.431 (2) |
C21—C26 | 1.394 (2) | C57—O5 | 1.227 (2) |
C22—C23 | 1.385 (3) | C57—C51 | 1.496 (2) |
C22—H22 | 0.95 | C51—C52 | 1.389 (2) |
C23—C24 | 1.384 (3) | C51—C56 | 1.398 (2) |
C23—H23 | 0.95 | C52—C53 | 1.380 (3) |
C24—C25 | 1.380 (2) | C52—H52 | 0.95 |
C24—H24 | 0.95 | C53—C54 | 1.385 (3) |
C25—C26 | 1.390 (2) | C53—H53 | 0.95 |
C25—H25 | 0.95 | C54—C55 | 1.383 (3) |
C26—H26 | 0.95 | C54—H54 | 0.95 |
C3—C4 | 1.525 (2) | C55—C56 | 1.379 (3) |
C3—H3A | 0.99 | C55—H55 | 0.95 |
C3—H3B | 0.99 | C56—H56 | 0.95 |
C4—N5 | 1.492 (2) | C6—C11 | 1.388 (2) |
C4—C41 | 1.526 (2) | C6—C7 | 1.390 (2) |
C4—H4 | 1.00 | C6—H6 | 0.95 |
C41—C42 | 1.393 (2) | C7—C8 | 1.389 (3) |
C41—C46 | 1.395 (2) | C7—H7 | 0.95 |
C42—C43 | 1.391 (2) | C8—C9 | 1.378 (2) |
C42—H42 | 0.95 | C8—H8 | 0.95 |
C43—C44 | 1.381 (2) | C9—C10 | 1.392 (2) |
C43—H43 | 0.95 | C9—H9 | 0.95 |
C44—C45 | 1.384 (2) | C10—C11 | 1.404 (2) |
C10—S1—C2 | 103.94 (7) | C44—C45—C46 | 120.14 (16) |
C21—C2—C3 | 113.92 (13) | C44—C45—H45 | 119.9 |
C21—C2—S1 | 110.53 (11) | C46—C45—H45 | 119.9 |
C3—C2—S1 | 113.85 (11) | C45—C46—C41 | 120.93 (16) |
C21—C2—H2 | 105.9 | C45—C46—H46 | 119.5 |
C3—C2—H2 | 105.9 | C41—C46—H46 | 119.5 |
S1—C2—H2 | 105.9 | C57—N5—C11 | 124.79 (13) |
C22—C21—C26 | 118.75 (15) | C57—N5—C4 | 116.13 (13) |
C22—C21—C2 | 117.84 (14) | C11—N5—C4 | 117.18 (12) |
C26—C21—C2 | 123.41 (14) | O5—C57—N5 | 120.57 (15) |
C23—C22—C21 | 120.73 (16) | O5—C57—C51 | 118.97 (14) |
C23—C22—H22 | 119.6 | N5—C57—C51 | 120.43 (14) |
C21—C22—H22 | 119.6 | C52—C51—C56 | 119.12 (15) |
C24—C23—C22 | 120.18 (16) | C52—C51—C57 | 124.39 (14) |
C24—C23—H23 | 119.9 | C56—C51—C57 | 116.14 (15) |
C22—C23—H23 | 119.9 | C53—C52—C51 | 120.17 (15) |
C25—C24—C23 | 119.61 (16) | C53—C52—H52 | 119.9 |
C25—C24—H24 | 120.2 | C51—C52—H52 | 119.9 |
C23—C24—H24 | 120.2 | C52—C53—C54 | 120.42 (17) |
C24—C25—C26 | 120.52 (16) | C52—C53—H53 | 119.8 |
C24—C25—H25 | 119.7 | C54—C53—H53 | 119.8 |
C26—C25—H25 | 119.7 | C55—C54—C53 | 119.84 (17) |
C25—C26—C21 | 120.18 (15) | C55—C54—H54 | 120.1 |
C25—C26—H26 | 119.9 | C53—C54—H54 | 120.1 |
C21—C26—H26 | 119.9 | C56—C55—C54 | 120.05 (17) |
C4—C3—C2 | 116.10 (13) | C56—C55—H55 | 120.0 |
C4—C3—H3A | 108.3 | C54—C55—H55 | 120.0 |
C2—C3—H3A | 108.3 | C55—C56—C51 | 120.37 (16) |
C4—C3—H3B | 108.3 | C55—C56—H56 | 119.8 |
C2—C3—H3B | 108.3 | C51—C56—H56 | 119.8 |
H3A—C3—H3B | 107.4 | C11—C6—C7 | 120.36 (15) |
N5—C4—C3 | 111.71 (13) | C11—C6—H6 | 119.8 |
N5—C4—C41 | 110.18 (12) | C7—C6—H6 | 119.8 |
C3—C4—C41 | 112.75 (13) | C8—C7—C6 | 119.82 (16) |
N5—C4—H4 | 107.3 | C8—C7—H7 | 120.1 |
C3—C4—H4 | 107.3 | C6—C7—H7 | 120.1 |
C41—C4—H4 | 107.3 | C9—C8—C7 | 120.07 (16) |
C42—C41—C46 | 118.36 (15) | C9—C8—H8 | 120.0 |
C42—C41—C4 | 122.51 (14) | C7—C8—H8 | 120.0 |
C46—C41—C4 | 119.11 (15) | C8—C9—C10 | 120.83 (16) |
C43—C42—C41 | 120.42 (15) | C8—C9—H9 | 119.6 |
C43—C42—H42 | 119.8 | C10—C9—H9 | 119.6 |
C41—C42—H42 | 119.8 | C9—C10—C11 | 119.13 (15) |
C44—C43—C42 | 120.70 (16) | C9—C10—S1 | 119.14 (13) |
C44—C43—H43 | 119.7 | C11—C10—S1 | 121.54 (12) |
C42—C43—H43 | 119.7 | C6—C11—C10 | 119.77 (15) |
C43—C44—C45 | 119.45 (16) | C6—C11—N5 | 120.93 (14) |
C43—C44—H44 | 120.3 | C10—C11—N5 | 119.17 (14) |
C45—C44—H44 | 120.3 | ||
C10—S1—C2—C21 | −138.65 (11) | C11—N5—C57—O5 | 166.53 (15) |
C10—S1—C2—C3 | −9.0 (2) | C4—N5—C57—O5 | 2.7 (2) |
C3—C2—C21—C22 | 89.28 (17) | C11—N5—C57—C51 | −15.4 (2) |
S1—C2—C21—C22 | −141.05 (12) | C4—N5—C57—C51 | −179.24 (13) |
C3—C2—C21—C26 | −90.52 (18) | O5—C57—C51—C52 | 138.48 (18) |
S1—C2—C21—C26 | 39.15 (19) | N5—C57—C51—C52 | −39.6 (2) |
C26—C21—C22—C23 | −0.4 (2) | O5—C57—C51—C56 | −34.6 (2) |
C2—C21—C22—C23 | 179.76 (14) | N5—C57—C51—C56 | 147.28 (16) |
C21—C22—C23—C24 | −1.0 (3) | C56—C51—C52—C53 | −0.2 (3) |
C22—C23—C24—C25 | 1.6 (3) | C57—C51—C52—C53 | −173.12 (17) |
C23—C24—C25—C26 | −0.7 (2) | C51—C52—C53—C54 | −0.4 (3) |
C24—C25—C26—C21 | −0.7 (2) | C52—C53—C54—C55 | −0.1 (3) |
C22—C21—C26—C25 | 1.3 (2) | C53—C54—C55—C56 | 1.1 (3) |
C2—C21—C26—C25 | −178.91 (15) | C54—C55—C56—C51 | −1.7 (3) |
C21—C2—C3—C4 | 57.31 (18) | C52—C51—C56—C55 | 1.2 (3) |
S1—C2—C3—C4 | −70.67 (16) | C57—C51—C56—C55 | 174.73 (18) |
C2—C3—C4—N5 | 58.11 (18) | C11—C6—C7—C8 | 1.5 (3) |
C2—C3—C4—C41 | −177.16 (13) | C6—C7—C8—C9 | −0.7 (3) |
N5—C4—C41—C42 | 78.61 (18) | C7—C8—C9—C10 | −0.4 (3) |
C3—C4—C41—C42 | −47.0 (2) | C8—C9—C10—C11 | 0.6 (2) |
N5—C4—C41—C46 | −99.49 (16) | C8—C9—C10—S1 | −174.59 (13) |
C3—C4—C41—C46 | 134.95 (15) | C2—S1—C10—C9 | −124.66 (14) |
C46—C41—C42—C43 | 0.3 (2) | C2—S1—C10—C11 | 60.3 (2) |
C4—C41—C42—C43 | −177.82 (14) | C7—C6—C11—C10 | −1.3 (2) |
C41—C42—C43—C44 | −0.1 (2) | C7—C6—C11—N5 | −177.27 (15) |
C42—C43—C44—C45 | −0.3 (3) | C9—C10—C11—C6 | 0.2 (2) |
C43—C44—C45—C46 | 0.6 (3) | S1—C10—C11—C6 | 175.31 (12) |
C44—C45—C46—C41 | −0.4 (3) | C9—C10—C11—N5 | 176.30 (14) |
C42—C41—C46—C45 | −0.1 (2) | S1—C10—C11—N5 | −8.6 (2) |
C4—C41—C46—C45 | 178.12 (15) | C57—N5—C11—C6 | −62.8 (2) |
C3—C4—N5—C57 | −152.61 (14) | C4—N5—C11—C6 | 100.87 (17) |
C41—C4—N5—C57 | 81.25 (17) | C57—N5—C11—C10 | 121.19 (17) |
C3—C4—N5—C11 | 42.3 (2) | C4—N5—C11—C10 | −75.1 (2) |
C41—C4—N5—C11 | −83.85 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O5i | 0.95 | 2.49 | 3.347 (2) | 150 |
C24—H24···O5ii | 0.95 | 2.53 | 3.295 (2) | 138 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C23H21NOS | C23H20ClNOS | C28H23NOS |
Mr | 359.48 | 393.92 | 421.53 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, C2/c |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 20.3579 (4), 8.3014 (1), 22.2513 (4) | 12.6348 (4), 11.9337 (5), 12.7904 (5) | 30.1891 (8), 14.8005 (3), 9.7965 (3) |
β (°) | 93.865 (1) | 92.549 (2) | 102.2570 (16) |
V (Å3) | 3751.90 (11) | 1926.63 (13) | 4277.43 (19) |
Z | 8 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.18 | 0.32 | 0.17 |
Crystal size (mm) | 0.20 × 0.04 × 0.03 | 0.28 × 0.24 × 0.04 | 0.36 × 0.26 × 0.16 |
Data collection | |||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.954, 0.994 | 0.926, 0.987 | 0.937, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 51290, 8274, 4659 | 26344, 4418, 2950 | 21732, 4894, 3535 |
Rint | 0.109 | 0.081 | 0.060 |
(sin θ/λ)max (Å−1) | 0.641 | 0.650 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.125, 1.00 | 0.043, 0.098, 1.00 | 0.043, 0.109, 1.03 |
No. of reflections | 8274 | 4418 | 4894 |
No. of parameters | 471 | 244 | 280 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.40 | 0.22, −0.37 | 0.21, −0.38 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C145—H145···O25i | 0.95 | 2.47 | 3.336 (3) | 152 |
C245—H245···O15i | 0.95 | 2.41 | 3.268 (3) | 150 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O5i | 0.95 | 2.42 | 3.295 (3) | 153 |
C44—H44···O5ii | 0.95 | 2.48 | 3.364 (2) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O5i | 0.95 | 2.49 | 3.347 (2) | 150 |
C24—H24···O5ii | 0.95 | 2.53 | 3.295 (2) | 138 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2. |
D-H···A | D-H | H···A | D···A | D-H···A |
C6-H6···Cg1i | 0.98 | 2.82 | 3.521 (3) | 129 |
C21-H21···Cg2ii | 0.94 | 2.99 | 3.746 (3) | 139 |
C34-H34···Cg2iii | 0.91 | 2.98 | 3.669 (4) | 133 |
N5-H5···S1iv | 0.82 (2) | 3.05 (2) | 3.490 (3) | 116 (2) |
Original atom numbering (Laavanya et al., 2002). Cg1 and Cg2 are centroids of the rings C6-C11 and C20-C25 respectively. Symmetry codes: i (0.5 − x, 0.5 + y, 0.5 − z), ii (1.5 − x, 0.5 + y, 0.5 − z), iii (1 − x, 1 − y, −z), iv (x, 1 + y, z) |
Parameter | (I) | (I) | (II) | (III) | (IV) | |
Mol 1 | Mol 2 | |||||
x = | 1 | 2 | nil | nil | nil | |
Sx1—Cx10—Cx11—Xx5 | -7.2 (3) | -6.3 (2) | -2.6 (2) | -8.6 (2) | 0.7 (3) | |
Cx11—Cx10—Sx1—Cx2 | 64.1 (2) | 63.2 (2) | 62.6 (2) | 60.3 (2) | 32.2 (2) | |
Cx10—Cx11—Xx5—Cx4 | -71.8 (3) | -72.0 (3) | -74.3 (2) | -75.1 (2) | 38.4 (3) | |
Sx1—Cx2—Cx3–Cx4 | -64.6 (2) | -64.5 (2) | -63.4 (2) | -70.7 (2) | 45.9 (3) | |
Xx5—Cx4—Cx3—Cx2 | 64.1 (2) | 64.2 (2) | 66.3 (2) | 58.1 (2) | 45.3 (3) | |
Cx10—Sx1—Cx2—Cx3 | -18.1 (2) | -18.4 (2) | -20.8 (2) | -9.0 (2) | -83.4 (2) | |
Cx11—Xx5—Cx4—Cx3 | 33.1 (3) | 32.9 (3) | 30.4 (2) | 42.3 (2) | -96.3 (3) |
Footnotes
‡Postal address: Department of Electrical Engineering and Physics, University of Dundee, Dundee DD1 4HN, Scotland.
Acknowledgements
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work.
References
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We report here the molecular and supramolecular structures of three N-acyl-C-phenylated tetrahydrobenzothiazepines, (I)–(III), and we compare these with the simpler analogue, (IV), which is unsubstituted at N, whose structure has recently been reported (Laavanya et al., 2002). These compounds are of interest as their molecular constitutions all have some resemblance to that of the calcium antagonist drug diltiazem [(2S,3S)-3-acetoxy-5-(dimethylaminoethyl)-2-(4-methoxyphenyl)- 2,3-dihydro-1,5-benzothiazepine-4(5H)-one, (V)] and its (2R,3R) enantiomer (Kojić-Prodić et al., 1984).
Each of the compounds (I)–(III) (Figs. 1–3) contains two stereogenic C atoms, C2 and C4, and hence the formation of diastereoisomers is possible. However, each of the crystalline samples examined contained a single pair of enantiomers, (R,R) and (S,S), and for each compound the reference molecule was selected as having the (R,R) configuration. In this respect, the configurations of (I)–(III) are identical to that of (IV) (Laavanya et al., 2002). It should, however, be noted here that the schematic view of (IV) in the original report shows the incorrect (2S,4R) isomer. The interbond angles at the N atom in each of (I)-(III) sum to ca 360.0°, so that no further configurational isomers are possible.
Compound (I) crystallizes with Z' = 2; the thiazepine rings in the two independent molecules in (I) and in the molecules of (II) and (III) all adopt similar conformations, as shown by the ring torsion angles (Table 1). Apart from the S1—C10—C11—N5 angle, there are corresponding pairs of torsion angles having similar magnitudes but opposite signs. This fact indicates conformations that, apart from the obvious differences in atom types and bond lengths, approximate in (I) and (II) to pseudo-mirror symmetry; this conformation may be best described as the boat conformation (Evans & Boeyens, 1989). The conformation of the thiazepine ring in (III) does not exhibit even approximate symmetry and it cannot be described in terms of a single primitive form (Evans & Boeyens, 1989). Instead, the conformation is intermediate between the boat and the twist-boat forms. By contrast, the thiazepine ring in (IV) exhibits approximate pseudo-twofold rotational symmetry, as the corresponding pairs of torsion angles have similar magnitudes with the same signs, although all four primitive forms contribute to the overall conformation of (IV).
The only significant difference between the bond lengths in (I)–(III) and those in (IV) occurs for the N5—C11 bond. In (I)–(III), where atom N5 is planar, this distances lies in the range 1.427 (3)–1.439 (2) Å, whereas in (IV), where N5 is pyramidal, this distance is 1.395 (3) Å. By contrast, the mean values for bonds of types C(aryl)—NC2, involving planar N atoms, and C(aryl)—NHC, involving pyramidal N atoms, are 1.371 and 1.419 Å, respectively (Allen et al., 1987). The remaining bond lengths in (I)–(III) show no unusual values.
The supramolecular structures of (I)–(III) all have different dimensionality. In (I), the two independent molecules are linked by a pair of C—H····O hydrogen bonds (Table 2). Atom C145 in the type 1 molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O25 in the type 2 molecule at (1 − x, 1 − y, 1 − z), while atom C245 at (1 − x, 1 − y, 1 − z) in turn acts as a donor to carbonyl atom O15 at (x, y, z). In this manner, an approximately centrosymmetric R22(16) dimer is formed (Fig. 4). This dimeric aggregate is centred at approximately (3/4, 0.370, 3/4), and this fact alone precludes the possibility of any additional symmetry. While such an aggregate would normally have been selected as the asymmetric unit, in this instance the asymmetric unit was selected so that each of the independent molecules had the (R,R) configuration. The R22(16) dimer contains one (R,R) molecule and one (S,S) molecule. There are four of these dimeric units in each unit cell, but there are no direction-specific interactions between adjacent dimers.
In (II), the molecules are linked by two C—H···O hydrogen bonds (Table 3) into a chain of rings. Atom C24 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (1 − x, −y, 1 − z), so forming an R22(22) ring centred at (1/2, 0, 1/2), while atom C44 at (x, y, z) acts as a donor to atom O5 at (1 − x, 1 − y, 1 − z), thus forming an R22(18) ring centred at (1/2, 1/2, 1/2). Propagation of these two hydrogen bonds then generates a chain of rings along (1/2, y, 1/2), with R22(18) rings centred at (1/2, n + 1/2, 1/2) (n = zero or integer) and R22(22) rings centred at (1/2, n, 1/2) (n = zero or integer) (Fig. 5). Two chains of this type pass through each unit cell, but there are no direction-specific interactions between adjacent chains.
As in (II), the supramolecular structure of (III) is again directed by two intermolecular C—H···O hydrogen bonds (Table 4), but now their effect is to generate a sheet structure, in contrast to the chain of rings in (II). The stronger of these two hydrogen bonds gives rise to a chain running parallel to the [010] direction. Atom C23 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (0.5 − x, 0.5 + y, 1.5 − z), so producing a C(10) chain, generated by the 21 screw axis along (1/4, y, 3/4) (Fig. 6). Four of these chains pass through each unit cell; two, lying in the domain −0.02 < x < 0.52, are generated by screw axes at x = 1/4, while the other two, lying in the domain 0.48 < x < 1.02, are generated by screw axes at x = 0.75. Within each domain, the C(10) chains are linked into sheets by the second of the C—H···O hydrogen bonds. Atom C24 in the molecule at (x, y, z), which lies in the C(10) chain along (1/4, y, 3/4), acts as a hydrogen-bond donor to carbonyl atom O5 in the molecule at (0.5 − x, 0.5 − y, 2 − z), which lies in the C(10) chain along (1/4, y, 1.25), so forming a centrosymmetric R22(22) ring centred at (1/4, 1/4, 1) (Fig. 7). The combination of the R22(22) rings and the C(10) chains generates a (100) sheet built from R22(22) and R46(30) rings alternating in a chess-board fashion (Fig. 8). Two sheets of this type pass through each unit cell, one in each domain of x as defined above, but there are no direction-specific interactions between adjacent sheets. Despite the presence of at least three independent aryl rings in each of (I)–(III), there are neither C—H···π(arene) hydrogen bonds, nor aromatic π–π stacking interactions present in any of their structures.
In the light of the very different supramolecular structures adopted by (I)–(III), it seemed of interest to re-examine the supramolecular structure of (IV) using space group P21/n, with Z' = 1, and the atomic coordinates established by the recent study (Laavanya et al., 2002), where the atom-labelling is identical to that employed in (I)–(III). There are, in fact, three C—H···π(arene) hydrogen bonds, all with H···centroid distances of less than 3.0 Å (Table 5), which were not noted in the original report but which together link the molecules of (IV) into a continuous three-dimensional framework.
In the first of these interactions, atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C6—C11 ring in the molecule at (0.5 − x, 0.5 + y, 0.5 − z), so producing a [010] chain generated by the 21 screw axis along (1/4, y, 1/4) (Fig. 9). In a similar way, atom C21 at (x, y, z) acts as a donor to the C20—C25 ring (original atom numbering) in the molecule at (1.5 − x, 0.5 + y, 0.5 − z), so producing a second [010] chain, this time generated by the screw axis along (3/4, y, 1/4). The combination of these two chains then generates a (001) sheet in the form of a (4,4) net (Batten & Robson, 1998), lying in the domain −0.04 < z < 0.54 (Fig. 10); a second sheet, related to the first by inversion, lies in the domain 0.46 < z < 1.04.
The third C—H···π(arene) hydrogen bond links adjacent (001) sheets; atom C34 in the molecule at (x, y, z), which lies in the domain −0.04 < z < 0.54, acts as a hydrogen bond donor to ring C20—C25 in the molecule at (1 − x, 1 − y, −z), which lies in the domain −0.54 < z < 0.04. The resulting centrosymmetric motif (Fig. 11) thus serves to link sheets in different domains and in this manner to link all of the (001) sheets into a single framework.
It is also timely to re-evaluate the intermolecular N—H···S interaction in (IV). This interaction was originally discounted (Laavanya et al., 2002) as insignificant on the grounds that the shortest intermolecular N···S distance (Table 5) is somewhat in excess of the 3.3 Å sum of the van der Waals radii (Bondi, 1964). However, an analysis (Allen et al., 1997) of hydrogen bonds having two-coordinate S as the acceptor, using data retrieved from the Cambridge Structural Database (Allen, 2002), indicated mean H···S, N···S and N—H···S parameters in such bonds where S is bonded to two C atoms of 2.74 (2) Å, 3.58 (3) Å and 145 (3)° respectively. Accordingly, if the N—H···S contact in (IV) is not considered to be a significant intermolecular interaction, it is more soundly rejected on the grounds of the long H···S distance and the small N—H···S angle rather than on the grounds of the N···S distance.
In summary, we have shown that the very closely-related series of compounds (I)–(IV) exhibit supramolecular aggregation in zero, one, two and three dimensions, respectively, and that while in (I)–(III) the aggregation depends solely on C—H···O hydrogen bonds, in (IV) it depends solely on C—H···π(arene) hydrogen bonds. The occurrence of such differences resulting from very modest changes in molecular constitution undoubtedly presents a considerable challenge for computational methods that seek to predict, whether from first principles or otherwise, the crystal structures of simple molecular compounds (Lommerse et al., 2000; Motherwell et al., 2002).