(R)-2,3,4,5-Tetra­hydro-2,2,4-tri­methyl-1,5-benzo­thia­zepine and rac-5-benzoyl-2,3,4,5-tetra­hydro-2,2,4-tri­methyl-1,5-benzo­thia­zepine: chains built from N—H⋯S and C—H⋯π(arene) hydrogen bonds

Muthukumar, M.; Thanikasalam, K.; Mohamed, E.M.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270104006857

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 5| May 2004| Pages o346-o349

doi:10.1107/S0108270104006857

(R)-2,3,4,5-Tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine and rac-5-benzoyl-2,3,4,5-tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine: chains built from N—H⋯S and C—H⋯π(arene) hydrogen bonds

Manivannan Muthukumar,^a Kanagasabapathy Thanikasalam,^a E. Mothi Mohamed,^a John N. Low ^b ‡ and Christopher Glidewell ^c ^*

^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

(Received 12 March 2004; accepted 23 March 2004; online 21 April 2004)

Molecules of (R)-2,3,4,5-tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine, C₁₂H₁₇NS, are linked into spiral C(5) chains by a single N—H⋯S hydrogen bond, while molecules of rac-5-benzoyl-2,3,4,5-tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine, C₁₉H₂₁NOS, are linked into zigzag chains by a C—H⋯π(arene) hydrogen bond.

Comment

We report here the molecular and supramolecular structures of two trimethylbenzothiazepines, (I) and (II), and we compare them with the N-nitroso analogue, (III), whose structure has been reported recently (Laavanya et al., 2002 ). These compounds are of interest because their molecular constitutions 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-benzothiazepin-4(5H)-one, (IV)] and its 2R,3R enantiomer (Kojić-Prodić et al., 1984 ).

Compounds (I) and (II) (Figs. 1 and 2) both contain a stereogenic centre at atom C4, so giving rise to the possibility of R and S enantiomers. In (I), which crystallizes in the chiral space group P2₁, the crystal examined contained the R enantiomer only. By contrast, (II) crystallizes as a racemic mixture in space group Pna2₁; the reference molecule in (II) was selected as having the R configuration. Compound (III) also crystallizes as a racemate, in space group C2/c (Laavanya et al., 2002), with the reference molecule again selected as the R enantiomer.

In the thiazepine rings of each of (I)–(III), the C11—C10—S1—C2 and C10—C11—N5—C4 torsion angles (Table 1) have similar magnitudes with opposite signs, as do the S1—C2—C3—C4 and N5—C4—C3—C2 angles, indicative of approximate pseudo-mirror symmetry for these portions of the ring, making due allowance for the differing atom types and bond distances. However, the magnitudes of the final pair of torsion angles, C10—S1—C2—C3 and C1—N5—C4—C3, differ markedly, although they still have opposite signs. Accordingly, it is not possible to describe any of these ring conformations in terms of a single primitive form (Evans & Boeyens, 1989 ). In (I), the thiazepine conformation is a mixture of boat, chair and twist-chair forms; in (II), the boat form is dominant, with a small contribution from the twist-chair form; and in (III), the conformation is best described as intermediate between boat and twist-boat. The bond lengths and angles in (I) and (II) show no unusual features.

The only direction-specific interaction between the molecules of (I) (Fig. 1) is an N—H⋯S hydrogen bond (Table 1). Although the N⋯S distance is greater than the sum (3.3 Å) of the conventional van der Waals radii (Bondi, 1964 ), an analysis (Allen et al., 1997 ) of hydrogen bonds having two-coordinate sulfur 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, the N—H⋯S interaction in (I) appears to be typical of such hydrogen bonds. The status of N—H⋯S hydrogen bonds remains uncertain. While Desiraju & Steiner (1999 ) regard sulfur as a conventional hydrogen-bond acceptor, Allen et al. (1997) concluded that two-coordinate sulfur is a poor hydrogen-bond acceptor and that only in dialkyl sulfides lacking any other potential acceptors are X—H⋯S hydrogen bonds (X = N or O) likely to be significant contributors to molecular aggregation. Against that view, we note that in triphenylmethanesulfenamide, Ph₃SNH₂, the molecules are linked into centrosymmetric R₂²(6) dimers by paired N—H⋯S hydrogen bonds (Glidewell & Ferguson, 1994 ). The action of the N—H⋯S hydrogen bond in (I), where atom N5 in the molecule at (x, y, z) acts as a donor to atom S1 in the molecule at (1 − x, − $[1 \over 2]$ + y, z), is to link the molecules into a spiral C(5) (Bernstein et al., 1995 ) chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[1 \over 2]$ , y, 0) (Fig. 3).

In (II), the molecules are linked by a single C—H⋯π(arene) hydrogen bond (Table 2). Atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C51–C56 acyl ring in the molecule at (− $[1 \over 2]$ + x, $[3 \over 2]$ − y, z), so forming a zigzag [100] chain generated by the a-glide plane at y = $[3 \over 4]$ (Fig. 4). Two chains of this type pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

In contrast to the N—H⋯S and C—H⋯π(arene) hydrogen bonds in (I) and (II), respectively, the structure of (III) (Laavanya et al., 2002) contains no hydrogen bonds or direction-specific interactions of any kind between the molecules.

Figure 1
The R enantiomer of (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The R enantiomer of (II

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
Part of the crystal structure of (I

), showing the formation of a C(5) chain along [010]. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 − x, − $[1 \over 2]$ + y, z), (x, −1 + y, z), (1 − x, $[1 \over 2]$ + y, z) and (x, 1 + y, z), respectively.

Figure 4
A stereoview of part of the crystal structure of (II

), showing the formation of a C—H⋯π(arene) chain along [100]. For clarity, H atoms that are not involved in the motif shown have been omitted.

Experimental

Compound (I) was synthesized by reducing 2,3-dihydro-2,2,4-trimethyl-1,5-benzodiazepine with sodium borohydride in methanol at 273 K (Hsing et al., 1966 ). Compound (II) was prepared by benzoylation of (I) with benzoyl chloride and triethylamine in dry benzene under reflux conditions. Analysis for (II) found: C 73.3, H 6.9, N 4.3%; C₁₉H₂₁NOS requires: C 73.3, H 6.8, N 4.5%. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown from solutions in light petroleum [m.p. 358–361 K for (I) and 383–386 K for (II)].

Compound (I)

Crystal data

C₁₂H₁₇NS
M_r = 207.34
Monoclinic, P2₁
a = 7.2644 (4) Å
b = 7.8657 (3) Å
c = 10.1522 (5) Å
β = 103.190 (2)°
V = 564.79 (5) Å³
Z = 2
D_x = 1.219 Mg m⁻³
Mo Kα radiation
Cell parameters from 2550 reflections
θ = 3.1–27.4°
μ = 0.25 mm⁻¹
T = 120 (2) K
Plate, colourless
0.38 × 0.18 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995 , 1997 ) T_min = 0.922, T_max = 0.980
8535 measured reflections
2550 independent reflections
2422 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 27.4°
h = −9 → 9
k = −10 → 10
l = −13 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.070
S = 1.06
2550 reflections
130 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0361P)² + 0.0718P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1163 Friedel pairs
Flack parameter = −0.03 (6)

Table 2
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯S1ⁱ	0.95	2.75	3.5556 (13)	144
Symmetry code: (i) $[1-x,y-{\script{1\over 2}},-z]$ .

Compound (II)

Crystal data

C₁₉H₂₁NOS
M_r = 311.43
Orthorhombic, Pna2₁
a = 16.1757 (2) Å
b = 12.5444 (3) Å
c = 8.2147 (2) Å
V = 1666.88 (6) Å³
Z = 4
D_x = 1.241 Mg m⁻³
Mo Kα radiation
Cell parameters from 3762 reflections
θ = 3.0–27.5°
μ = 0.20 mm⁻¹
T = 120 (2) K
Block, colourless
0.30 × 0.08 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) T_min = 0.866, T_max = 0.983
19 245 measured reflections
3762 independent reflections
3605 reflections with I > 2σ(I)
R_int = 0.064
θ_max = 27.5°
h = −20 → 19
k = −16 → 16
l = −10 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.130
S = 1.26
3762 reflections
203 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0742P)² + 0.2569P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.84 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.145 (9)
Absolute structure: Flack (1983), 1719 Friedel pairs
Flack parameter = 0.01 (9)

Table 3
Hydrogen-bonding geometry (Å, °) for (II)

Cg1 is the centroid of the C51–C56 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cg1ⁱ	0.95	2.88	3.674 (2)	142
Symmetry code: (i) $[x-{\script{1\over 2}},{\script{3\over 2}}-y,z]$ .

Table 1
Selected torsion angles (°) for compounds (I)–(III)

	(I)	(II)	(III)
S1—C10—C11—N5	−6.53 (19)	7.4 (3)	5.7 (5)
C11—C10—S1—C2	62.97 (13)	−69.29 (18)	−60.4 (4)
C10—C11—N5—C4	−69.68 (18)	74.6 (2)	75.1 (4)
S1—C2—C3—C4	63.33 (14)	60.3 (2)	65.2 (5)
N5—C4—C3—C2	−67.82 (17)	−62.3 (2)	−60.2 (5)
C10—S1—C2—C3	−70.33 (13)	24.40 (17)	15.7 (3)
C11—N5—C4—C3	90.42 (16)	−36.1 (2)	−39.6 (5)

For (I), the systematic absences permitted P2₁ and P2₁/m as possible space groups; P2₁ was selected and confirmed by the subsequent structure analysis. For (II), the systematic absences permitted Pna2₁ and Pnam (= Pnma) as possible space groups; Pna2₁ was selected and confirmed by the subsequent structure analysis. All H atoms bonded to C atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (aliphatic CH). The H atom bonded to the N atom in (I) was located from a difference map and then allowed to ride at the N—H distance (0.95 Å) deduced from the map. The absolute configuration in (I) and the correct orientation of the structure with respect to the polar axis (Jones, 1986 ) in (II) were both established from the values [−0.03 (6) and 0.01 (9), respectively] of the Flack (1983) parameter.

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: 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

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270104006857/sk1712sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104006857/sk1712Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104006857/sk1712IIsup3.hkl

Comment top

We report here the molecular and supramolecular structures of two trimethyl benzothiazepines, (I) and (II), and we compare them with the N-nitroso analogue, (III), whose structure has recently been reported (Laavanya et al., 2002). These compounds are of interest as their molecular constitutions 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 (IV)] and its (2R,3R) enantiomer (Kojić-Prodić et al., 1984).

Compounds (I) and (II) (Figs. 1 and 2) both contain a stereogenic centre at atom C4, so giving rise to the possibility of R and S enantiomers. In (I), which crystallizes in the chiral space group P2₁, the crystal examined contained the R enantiomer only. By contrast, (II) crystallizes as a racemic mixture in space group Pna2₁; the reference molecule in (II) was selected as having the R configuration. Compound (III) also crystallizes as a racemate, in space group C2/c (Laavanya et al., 2002), with the reference molecule again selected as the R enantiomer.

In the thiazepine rings of each of (I)-(III), the C11—C10—S1—C2 and C10—C11—N5—C4 pair of torsion angles, and the S1—C2—C3—C4 and N5—C4—C3—C2 angles, have similar magnitudes with opposite signs, indicative of approximate pseudo-mirror symmetry for these portions of the ring, making due allowance for the differing atom types and bond distances. However, the magnitudes of the final pair of torsion angles, C10—S1—C2—C3 and C1—N5—C4—C3 differ markedly, although they still have opposite signs. Accordingly, it is not possible to describe any of these ring conformations in terms of a single primitive form (Evans & Boeyens, 1989). In (I), the thiazepine conformation is a mixture of boat, chair and twist-chair forms; in (II), the boat form is dominant, with a small contribution from the twist-chair form; and in (III), the conformation is best described as intermediate between boat and twist-boat. The bond lengths and angles in (I) and (II) show no unusual features.

The only direction-specific interaction between the molecules of (I) (Fig. 1) is the N—H···S hydrogen bond (Table 2). Although the N···S distance is greater than the sum (3.3 Å) of the conventional van der Waals radii (Bondi, 1964), 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, the N—H···S interaction in (I) appears to be typical of such hydrogen bonds. The status of N—H···S hydrogen bonds remains uncertain. While Desiraju & Steiner (1999) regard S as a conventional hydrogen-bond acceptor, Allen et al. (1997) concluded that two-coordinate S is a poor hydrogen-bond acceptor and that only in dialkyl sulfides lacking any other potential acceptors are X—H···S hydrogen bonds (X = N or O) likely to be significant contributors to molecular aggregation. Against that view, we note that in triphenylmethanesulfenamide, Ph₃SNH₂, the molecules are linked into centrosymmetric R²₂(6) dimers by paired N—H···S hydrogen bonds (Glidewell & Ferguson, 1994). The action of the N—H···S hydrogen bond in (I), where atom N5 in the molecule at (x, y, z) acts as a donor to atom S1 in the molecule at (1 − x, −0.5 + y, z), is to link the molecules into a spiral C(5) (Bernstein et al., 1995) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 0) (Fig. 3).

In (II), the molecules are linked by a single C—H···π(arene) hydrogen bond (Table 3). Atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C51—C56 acyl ring in the molecule at (−0.5 + x, 1.5 − y, z), so forming a zigzag [100] chain generated by the a-glide plane at y = 0.75 (Fig. 4). Two chains of this type pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

In contrast to the N—H···S and C—H···π(arene) hydrogen bonds in (I) and (II), respectively, the structure of (III) (Laavanya et al., 2002) contains no hydrogen bonds or direction-specific interactions of any kind between the molecules.

Experimental top

Compound (I) was synthesized by reducing 2,3-dihydro-2,2',4-trimethyl-1,5-benzodiazepine with sodium borohydride in methanol at 273 K (Hsing et al., 1966). Compound (II) was prepared by benzoylation of (I) with benzoyl chloride and triethylamine in dry benzene under reflux conditions. Analysis for (II) found: C 73.3, H 6.9, N 4.3%; C₁₉H₂₁NOS requires: C 73.3, H 6.8, N 4.5%. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown from solutions in light petroleum. M.p. (I) 358–361 K, (II) 383–386 K. Cg1 is the centroid of ring C51–C56.

Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: 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).

Figures top

	Fig. 1. The R enantiomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The R enantiomer of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C(5) chain along [010]. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign () or an ampersand (&) are at the symmetry positions (1 − x, −0.5 + y, z), (x, −1 + y, z), (1 − x, 0.5 + y, z) and (x, 1 + y, z), respectively.
	Fig. 4. A stereoview of part of the crystal structure of (II), showing the formation of a C—H···π(arene) chain along [100]. For clarity, H atoms that are not involved in the motif shown have been omitted.

(I) (R)-2,3,4,5-Tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine top

Crystal data top

C₁₂H₁₇NS	F(000) = 224
M_r = 207.34	D_x = 1.219 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2550 reflections
a = 7.2644 (4) Å	θ = 3.1–27.4°
b = 7.8657 (3) Å	µ = 0.25 mm⁻¹
c = 10.1522 (5) Å	T = 120 K
β = 103.190 (2)°	Plate, colourless
V = 564.79 (5) Å³	0.38 × 0.18 × 0.08 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	2550 independent reflections
Radiation source: rotating anode	2422 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ scans, and ω scans with κ offsets	θ_max = 27.4°, θ_min = 3.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −9→9
T_min = 0.922, T_max = 0.980	k = −10→10
8535 measured reflections	l = −13→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0361P)² + 0.0718P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2550 reflections	Δρ_max = 0.15 e Å⁻³
130 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1163 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (6)

Crystal data top

C₁₂H₁₇NS	V = 564.79 (5) Å³
M_r = 207.34	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.2644 (4) Å	µ = 0.25 mm⁻¹
b = 7.8657 (3) Å	T = 120 K
c = 10.1522 (5) Å	0.38 × 0.18 × 0.08 mm
β = 103.190 (2)°

Data collection top

Nonius KappaCCD diffractometer	2550 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	2422 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.980	R_int = 0.039
8535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.15 e Å⁻³
S = 1.06	Δρ_min = −0.20 e Å⁻³
2550 reflections	Absolute structure: Flack (1983), 1163 Friedel pairs
130 parameters	Absolute structure parameter: −0.03 (6)
1 restraint

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

	x	y	z	U_iso*/U_eq
S1	0.65175 (4)	0.59519 (4)	0.23697 (3)	0.01927 (10)
N5	0.46296 (17)	0.27383 (17)	0.09340 (12)	0.0199 (3)
C2	0.41383 (19)	0.6000 (2)	0.27237 (13)	0.0200 (3)
C3	0.2687 (2)	0.5047 (2)	0.16415 (15)	0.0220 (3)
C4	0.2946 (2)	0.3147 (2)	0.14725 (15)	0.0211 (3)
C6	0.71740 (19)	0.0847 (2)	0.20656 (14)	0.0217 (3)
C7	0.8880 (2)	0.05871 (19)	0.29864 (16)	0.0246 (4)
C8	0.9793 (2)	0.1924 (2)	0.37585 (16)	0.0237 (3)
C9	0.8985 (2)	0.3531 (2)	0.35941 (15)	0.0209 (3)
C10	0.7285 (2)	0.38228 (18)	0.26592 (15)	0.0180 (3)
C11	0.6348 (2)	0.24709 (19)	0.18887 (14)	0.0180 (3)
C21	0.3609 (2)	0.7895 (2)	0.26204 (16)	0.0285 (4)
C22	0.4233 (2)	0.5345 (2)	0.41487 (16)	0.0268 (3)
C41	0.1203 (2)	0.2441 (2)	0.04820 (16)	0.0264 (4)
H3A	0.1427	0.5223	0.1839	0.026*
H3B	0.2660	0.5596	0.0760	0.026*
H4	0.3073	0.2577	0.2369	0.025*
H5	0.4397	0.1812	0.0322	0.024*
H6	0.6557	−0.0083	0.1549	0.026*
H7	0.9428	−0.0515	0.3089	0.030*
H8	1.0958	0.1741	0.4393	0.028*
H9	0.9600	0.4448	0.4128	0.025*
H21A	0.2366	0.8048	0.2828	0.043*
H21B	0.3565	0.8299	0.1701	0.043*
H21C	0.4557	0.8545	0.3267	0.043*
H22A	0.2982	0.5438	0.4353	0.040*
H22B	0.5144	0.6024	0.4799	0.040*
H22C	0.4633	0.4153	0.4211	0.040*
H41A	0.1100	0.2960	−0.0409	0.040*
H41B	0.0068	0.2705	0.0811	0.040*
H41C	0.1326	0.1206	0.0410	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01718 (17)	0.01833 (16)	0.02206 (17)	−0.00159 (16)	0.00397 (12)	0.00181 (16)
N5	0.0164 (6)	0.0241 (7)	0.0182 (6)	−0.0013 (5)	0.0015 (5)	−0.0052 (5)
C2	0.0178 (6)	0.0225 (7)	0.0206 (6)	−0.0007 (8)	0.0058 (5)	−0.0010 (7)
C3	0.0163 (7)	0.0290 (9)	0.0203 (8)	0.0009 (6)	0.0034 (6)	0.0004 (6)
C4	0.0154 (7)	0.0270 (8)	0.0210 (7)	−0.0036 (6)	0.0040 (6)	−0.0008 (6)
C6	0.0215 (7)	0.0210 (7)	0.0238 (7)	−0.0020 (7)	0.0077 (5)	−0.0010 (7)
C7	0.0245 (8)	0.0242 (10)	0.0273 (8)	0.0054 (6)	0.0104 (6)	0.0038 (6)
C8	0.0168 (7)	0.0319 (9)	0.0220 (8)	0.0035 (7)	0.0038 (6)	0.0065 (6)
C9	0.0172 (7)	0.0269 (8)	0.0182 (7)	−0.0023 (6)	0.0031 (6)	−0.0014 (6)
C10	0.0161 (7)	0.0200 (8)	0.0192 (7)	−0.0005 (6)	0.0066 (6)	0.0011 (6)
C11	0.0167 (7)	0.0224 (8)	0.0155 (7)	0.0001 (6)	0.0048 (5)	−0.0006 (6)
C21	0.0267 (9)	0.0256 (9)	0.0337 (9)	0.0066 (7)	0.0078 (7)	−0.0018 (7)
C22	0.0266 (8)	0.0336 (8)	0.0211 (8)	−0.0016 (7)	0.0076 (6)	−0.0009 (6)
C41	0.0192 (8)	0.0354 (10)	0.0236 (8)	−0.0067 (7)	0.0023 (6)	−0.0041 (7)

Geometric parameters (Å, º) top

S1—C10	1.7682 (15)	C4—H4	1.00
S1—C2	1.8443 (13)	C41—H41A	0.98
C2—C22	1.522 (2)	C41—H41B	0.98
C2—C3	1.534 (2)	C41—H41C	0.98
C2—C21	1.537 (3)	N5—C11	1.4107 (18)
C21—H21A	0.98	N5—H5	0.9475
C21—H21B	0.98	C6—C7	1.387 (2)
C21—H21C	0.98	C6—C11	1.406 (2)
C22—H22A	0.98	C6—H6	0.95
C22—H22B	0.98	C7—C8	1.386 (2)
C22—H22C	0.98	C7—H7	0.95
C3—C4	1.521 (2)	C8—C9	1.388 (2)
C3—H3A	0.99	C8—H8	0.95
C3—H3B	0.99	C9—C10	1.394 (2)
C4—N5	1.4842 (19)	C9—H9	0.95
C4—C41	1.530 (2)	C10—C11	1.401 (2)

C10—S1—C2	105.12 (8)	C3—C4—H4	109.0
C22—C2—C3	112.96 (14)	C41—C4—H4	109.0
C22—C2—C21	110.43 (13)	C4—C41—H41A	109.5
C3—C2—C21	107.72 (12)	C4—C41—H41B	109.5
C22—C2—S1	109.71 (10)	H41A—C41—H41B	109.5
C3—C2—S1	111.85 (10)	C4—C41—H41C	109.5
C21—C2—S1	103.76 (11)	H41A—C41—H41C	109.5
C2—C21—H21A	109.5	H41B—C41—H41C	109.5
C2—C21—H21B	109.5	C11—N5—C4	116.98 (11)
H21A—C21—H21B	109.5	C11—N5—H5	109.5
C2—C21—H21C	109.5	C4—N5—H5	111.7
H21A—C21—H21C	109.5	C7—C6—C11	120.64 (15)
H21B—C21—H21C	109.5	C7—C6—H6	119.7
C2—C22—H22A	109.5	C11—C6—H6	119.7
C2—C22—H22B	109.5	C8—C7—C6	120.54 (14)
H22A—C22—H22B	109.5	C8—C7—H7	119.7
C2—C22—H22C	109.5	C6—C7—H7	119.7
H22A—C22—H22C	109.5	C7—C8—C9	119.22 (14)
H22B—C22—H22C	109.5	C7—C8—H8	120.4
C4—C3—C2	118.57 (14)	C9—C8—H8	120.4
C4—C3—H3A	107.7	C8—C9—C10	121.10 (14)
C2—C3—H3A	107.7	C8—C9—H9	119.4
C4—C3—H3B	107.7	C10—C9—H9	119.4
C2—C3—H3B	107.7	C9—C10—C11	119.80 (14)
H3A—C3—H3B	107.1	C9—C10—S1	117.76 (11)
N5—C4—C3	112.83 (13)	C11—C10—S1	122.12 (11)
N5—C4—C41	107.88 (12)	C10—C11—C6	118.68 (13)
C3—C4—C41	108.99 (13)	C10—C11—N5	120.75 (13)
N5—C4—H4	109.0	C6—C11—N5	120.55 (13)

C10—S1—C2—C22	55.83 (14)	C8—C9—C10—C11	1.3 (2)
C10—S1—C2—C3	−70.33 (13)	C8—C9—C10—S1	−172.23 (12)
C10—S1—C2—C21	173.84 (10)	C2—S1—C10—C9	−123.64 (12)
C22—C2—C3—C4	−61.03 (18)	C2—S1—C10—C11	62.97 (13)
C21—C2—C3—C4	176.73 (13)	C9—C10—C11—C6	−1.1 (2)
S1—C2—C3—C4	63.33 (16)	S1—C10—C11—C6	172.19 (11)
C2—C3—C4—N5	−67.82 (17)	C9—C10—C11—N5	−179.79 (13)
C2—C3—C4—C41	172.36 (12)	S1—C10—C11—N5	−6.53 (19)
C3—C4—N5—C11	90.42 (16)	C7—C6—C11—C10	0.1 (2)
C41—C4—N5—C11	−149.12 (13)	C7—C6—C11—N5	178.84 (13)
C11—C6—C7—C8	0.6 (2)	C4—N5—C11—C10	−69.68 (18)
C6—C7—C8—C9	−0.4 (2)	C4—N5—C11—C6	111.62 (15)
C7—C8—C9—C10	−0.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···S1ⁱ	0.95	2.75	3.5556 (13)	144

Symmetry code: (i) −x+1, y−1/2, −z.

(II) rac-5-benzoyl-2,3,4,5-tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine top

Crystal data top

C₁₉H₂₁NOS	F(000) = 664
M_r = 311.43	D_x = 1.241 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3762 reflections
a = 16.1757 (2) Å	θ = 3.0–27.5°
b = 12.5444 (3) Å	µ = 0.20 mm⁻¹
c = 8.2147 (2) Å	T = 120 K
V = 1666.88 (6) Å³	Block, colourless
Z = 4	0.30 × 0.08 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	3762 independent reflections
Radiation source: rotating anode	3605 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −20→19
T_min = 0.866, T_max = 0.983	k = −16→16
19245 measured reflections	l = −10→10

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0742P)² + 0.2569P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.130	(Δ/σ)_max = 0.001
S = 1.26	Δρ_max = 0.63 e Å⁻³
3762 reflections	Δρ_min = −0.84 e Å⁻³
203 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.145 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1719 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (9)

Crystal data top

C₁₉H₂₁NOS	V = 1666.88 (6) Å³
M_r = 311.43	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 16.1757 (2) Å	µ = 0.20 mm⁻¹
b = 12.5444 (3) Å	T = 120 K
c = 8.2147 (2) Å	0.30 × 0.08 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	3762 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	3605 reflections with I > 2σ(I)
T_min = 0.866, T_max = 0.983	R_int = 0.064
19245 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.130	Δρ_max = 0.63 e Å⁻³
S = 1.26	Δρ_min = −0.84 e Å⁻³
3762 reflections	Absolute structure: Flack (1983), 1719 Friedel pairs
203 parameters	Absolute structure parameter: 0.01 (9)
1 restraint

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

	x	y	z	U_iso*/U_eq
S1	0.35861 (3)	1.00783 (4)	0.65275 (8)	0.02546 (17)
O5	0.46969 (10)	0.75387 (13)	1.0173 (2)	0.0321 (4)
N5	0.36028 (10)	0.84474 (14)	0.9163 (2)	0.0194 (4)
C2	0.36814 (13)	1.09036 (17)	0.8392 (3)	0.0224 (4)
C3	0.33323 (12)	1.03476 (16)	0.9894 (3)	0.0216 (4)
C4	0.37080 (13)	0.92861 (16)	1.0427 (2)	0.0202 (4)
C6	0.22101 (13)	0.77625 (18)	0.8617 (3)	0.0251 (4)
C7	0.14577 (13)	0.7840 (2)	0.7786 (3)	0.0310 (5)
C8	0.13534 (13)	0.86172 (19)	0.6599 (4)	0.0326 (5)
C9	0.19989 (14)	0.93082 (18)	0.6213 (3)	0.0295 (5)
C10	0.27479 (13)	0.92396 (16)	0.7038 (3)	0.0232 (4)
C11	0.28502 (12)	0.84576 (16)	0.8245 (3)	0.0208 (4)
C21	0.31840 (18)	1.19232 (19)	0.8090 (3)	0.0367 (5)
C22	0.45944 (15)	1.1166 (2)	0.8593 (3)	0.0367 (6)
C41	0.33211 (15)	0.89267 (19)	1.2033 (3)	0.0285 (5)
C51	0.40869 (12)	0.68026 (16)	0.7812 (3)	0.0219 (4)
C52	0.39837 (12)	0.70733 (18)	0.6177 (3)	0.0252 (4)
C53	0.39977 (13)	0.6278 (2)	0.4995 (3)	0.0311 (5)
C54	0.41053 (14)	0.5217 (2)	0.5445 (3)	0.0330 (6)
C55	0.42120 (15)	0.49529 (18)	0.7042 (4)	0.0323 (6)
C56	0.42168 (13)	0.57368 (17)	0.8238 (3)	0.0270 (5)
C57	0.41511 (12)	0.76167 (17)	0.9146 (3)	0.0222 (4)
H21A	0.3182	1.2359	0.9079	0.055*
H21B	0.2615	1.1736	0.7799	0.055*
H21C	0.3437	1.2326	0.7197	0.055*
H22A	0.4911	1.0504	0.8700	0.055*
H22B	0.4672	1.1602	0.9571	0.055*
H22C	0.4788	1.1561	0.7638	0.055*
H3A	0.2735	1.0229	0.9704	0.026*
H3B	0.3380	1.0849	1.0821	0.026*
H4	0.4313	0.9395	1.0609	0.024*
H41A	0.3551	0.8234	1.2346	0.043*
H41B	0.2721	0.8863	1.1900	0.043*
H41C	0.3443	0.9452	1.2882	0.043*
H52	0.3904	0.7797	0.5871	0.030*
H53	0.3934	0.6460	0.3879	0.037*
H54	0.4104	0.4676	0.4637	0.040*
H55	0.4284	0.4227	0.7339	0.039*
H56	0.4308	0.5548	0.9344	0.032*
H6	0.2283	0.7235	0.9435	0.030*
H7	0.1019	0.7363	0.8033	0.037*
H8	0.0839	0.8678	0.6047	0.039*
H9	0.1927	0.9828	0.5384	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0344 (3)	0.0239 (3)	0.0181 (3)	−0.00135 (18)	0.0035 (2)	−0.0022 (2)
C2	0.0268 (10)	0.0204 (9)	0.0198 (10)	−0.0012 (7)	−0.0027 (7)	−0.0023 (8)
C21	0.0580 (15)	0.0251 (11)	0.0271 (11)	0.0094 (10)	−0.0062 (11)	−0.0014 (9)
C22	0.0277 (12)	0.0530 (16)	0.0294 (12)	−0.0157 (10)	−0.0022 (9)	0.0086 (11)
C3	0.0221 (9)	0.0242 (10)	0.0185 (9)	−0.0011 (8)	0.0001 (8)	−0.0036 (8)
C4	0.0215 (9)	0.0218 (10)	0.0173 (9)	−0.0021 (7)	−0.0010 (7)	−0.0040 (8)
C41	0.0334 (12)	0.0332 (12)	0.0189 (9)	−0.0050 (9)	0.0022 (8)	0.0007 (9)
N5	0.0204 (9)	0.0202 (9)	0.0175 (8)	−0.0005 (6)	−0.0019 (6)	−0.0019 (7)
C57	0.0216 (9)	0.0253 (10)	0.0198 (9)	0.0004 (7)	0.0014 (8)	−0.0002 (8)
O5	0.0296 (8)	0.0369 (9)	0.0297 (9)	0.0088 (6)	−0.0107 (7)	−0.0051 (7)
C51	0.0150 (9)	0.0235 (10)	0.0274 (11)	0.0011 (7)	0.0002 (7)	−0.0018 (8)
C52	0.0228 (10)	0.0276 (10)	0.0251 (11)	0.0041 (8)	−0.0012 (8)	−0.0024 (8)
C53	0.0260 (10)	0.0410 (13)	0.0263 (11)	0.0049 (9)	−0.0034 (9)	−0.0077 (10)
C54	0.0233 (10)	0.0325 (12)	0.0432 (15)	−0.0025 (9)	0.0016 (9)	−0.0182 (11)
C55	0.0246 (11)	0.0205 (10)	0.0518 (17)	−0.0021 (7)	0.0048 (10)	−0.0030 (10)
C56	0.0209 (10)	0.0276 (11)	0.0323 (11)	0.0011 (8)	0.0042 (8)	0.0041 (9)
C6	0.0230 (10)	0.0265 (10)	0.0259 (10)	−0.0012 (8)	0.0040 (8)	−0.0067 (8)
C7	0.0216 (11)	0.0340 (12)	0.0374 (13)	−0.0022 (8)	0.0020 (8)	−0.0150 (10)
C8	0.0216 (10)	0.0403 (12)	0.0359 (12)	0.0078 (8)	−0.0084 (9)	−0.0180 (12)
C9	0.0323 (11)	0.0309 (11)	0.0253 (11)	0.0094 (8)	−0.0090 (8)	−0.0076 (9)
C10	0.0256 (10)	0.0228 (10)	0.0211 (9)	0.0034 (7)	−0.0026 (8)	−0.0065 (8)
C11	0.0187 (9)	0.0221 (9)	0.0215 (9)	0.0019 (7)	−0.0007 (7)	−0.0050 (8)

Geometric parameters (Å, º) top

S1—C10	1.767 (2)	C57—C51	1.501 (3)
S1—C2	1.855 (2)	C51—C52	1.396 (3)
C2—C22	1.522 (3)	C51—C56	1.398 (3)
C2—C3	1.526 (3)	C52—C53	1.392 (3)
C2—C21	1.531 (3)	C52—H52	0.95
C21—H21A	0.98	C53—C54	1.392 (4)
C21—H21B	0.98	C53—H53	0.95
C21—H21C	0.98	C54—C55	1.364 (4)
C22—H22A	0.98	C54—H54	0.95
C22—H22B	0.98	C55—C56	1.390 (4)
C22—H22C	0.98	C55—H55	0.95
C3—C4	1.528 (3)	C56—H56	0.95
C3—H3A	0.99	C6—C11	1.388 (3)
C3—H3B	0.99	C6—C7	1.399 (3)
C4—N5	1.488 (3)	C6—H6	0.95
C4—C41	1.528 (3)	C7—C8	1.390 (4)
C4—H4	1.00	C7—H7	0.95
C41—H41A	0.98	C8—C9	1.393 (4)
C41—H41B	0.98	C8—H8	0.95
C41—H41C	0.98	C9—C10	1.391 (3)
N5—C57	1.369 (3)	C9—H9	0.95
N5—C11	1.432 (2)	C10—C11	1.404 (3)
C57—O5	1.225 (3)

C10—S1—C2	101.53 (10)	O5—C57—N5	121.39 (19)
C22—C2—C3	111.73 (17)	O5—C57—C51	119.87 (18)
C22—C2—C21	110.3 (2)	N5—C57—C51	118.72 (18)
C3—C2—C21	108.58 (18)	C52—C51—C56	119.5 (2)
C22—C2—S1	106.91 (16)	C52—C51—C57	123.04 (19)
C3—C2—S1	112.46 (14)	C56—C51—C57	117.2 (2)
C21—C2—S1	106.76 (15)	C53—C52—C51	119.7 (2)
C2—C21—H21A	109.5	C53—C52—H52	120.2
C2—C21—H21B	109.5	C51—C52—H52	120.2
H21A—C21—H21B	109.5	C52—C53—C54	120.1 (2)
C2—C21—H21C	109.5	C52—C53—H53	119.9
H21A—C21—H21C	109.5	C54—C53—H53	119.9
H21B—C21—H21C	109.5	C55—C54—C53	120.3 (2)
C2—C22—H22A	109.5	C55—C54—H54	119.9
C2—C22—H22B	109.5	C53—C54—H54	119.9
H22A—C22—H22B	109.5	C54—C55—C56	120.6 (2)
C2—C22—H22C	109.5	C54—C55—H55	119.7
H22A—C22—H22C	109.5	C56—C55—H55	119.7
H22B—C22—H22C	109.5	C55—C56—C51	119.9 (2)
C2—C3—C4	118.88 (17)	C55—C56—H56	120.1
C2—C3—H3A	107.6	C51—C56—H56	120.1
C4—C3—H3A	107.6	C11—C6—C7	119.9 (2)
C2—C3—H3B	107.6	C11—C6—H6	120.1
C4—C3—H3B	107.6	C7—C6—H6	120.1
H3A—C3—H3B	107.0	C8—C7—C6	119.8 (2)
N5—C4—C41	110.31 (17)	C8—C7—H7	120.1
N5—C4—C3	111.75 (16)	C6—C7—H7	120.1
C41—C4—C3	109.98 (18)	C7—C8—C9	120.3 (2)
N5—C4—H4	108.2	C7—C8—H8	119.8
C41—C4—H4	108.2	C9—C8—H8	119.8
C3—C4—H4	108.2	C10—C9—C8	120.2 (2)
C4—C41—H41A	109.5	C10—C9—H9	119.9
C4—C41—H41B	109.5	C8—C9—H9	119.9
H41A—C41—H41B	109.5	C9—C10—C11	119.3 (2)
C4—C41—H41C	109.5	C9—C10—S1	121.06 (18)
H41A—C41—H41C	109.5	C11—C10—S1	119.55 (15)
H41B—C41—H41C	109.5	C6—C11—C10	120.43 (18)
C57—N5—C11	123.53 (17)	C6—C11—N5	120.84 (19)
C57—N5—C4	118.12 (17)	C10—C11—N5	118.56 (18)
C11—N5—C4	117.28 (16)

C10—S1—C2—C22	147.38 (16)	C52—C53—C54—C55	−1.2 (4)
C10—S1—C2—C3	24.40 (17)	C53—C54—C55—C56	−0.2 (4)
C10—S1—C2—C21	−94.59 (17)	C54—C55—C56—C51	1.9 (3)
C22—C2—C3—C4	−60.0 (3)	C52—C51—C56—C55	−2.3 (3)
C21—C2—C3—C4	178.19 (18)	C57—C51—C56—C55	−176.37 (19)
S1—C2—C3—C4	60.3 (2)	C11—C6—C7—C8	−0.4 (3)
C2—C3—C4—N5	−62.3 (2)	C6—C7—C8—C9	1.0 (3)
C2—C3—C4—C41	174.84 (17)	C7—C8—C9—C10	−1.3 (3)
C41—C4—N5—C57	−82.1 (2)	C8—C9—C10—C11	0.9 (3)
C3—C4—N5—C57	155.24 (18)	C8—C9—C10—S1	177.97 (17)
C41—C4—N5—C11	86.5 (2)	C2—S1—C10—C9	113.68 (18)
C3—C4—N5—C11	−36.1 (2)	C2—S1—C10—C11	−69.29 (18)
C11—N5—C57—O5	−165.3 (2)	C7—C6—C11—C10	0.0 (3)
C4—N5—C57—O5	2.6 (3)	C7—C6—C11—N5	175.18 (19)
C11—N5—C57—C51	16.1 (3)	C9—C10—C11—C6	−0.3 (3)
C4—N5—C57—C51	−176.06 (17)	S1—C10—C11—C6	−177.36 (16)
O5—C57—C51—C52	−133.1 (2)	C9—C10—C11—N5	−175.56 (18)
N5—C57—C51—C52	45.5 (3)	S1—C10—C11—N5	7.4 (3)
O5—C57—C51—C56	40.7 (3)	C57—N5—C11—C6	67.3 (3)
N5—C57—C51—C56	−140.68 (19)	C4—N5—C11—C6	−100.6 (2)
C56—C51—C52—C53	1.1 (3)	C57—N5—C11—C10	−117.4 (2)
C57—C51—C52—C53	174.71 (19)	C4—N5—C11—C10	74.6 (2)
C51—C52—C53—C54	0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg1ⁱ	0.95	2.88	3.674 (2)	142

Symmetry code: (i) x−1/2, −y+3/2, z.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₂H₁₇NS	C₁₉H₂₁NOS
M_r	207.34	311.43
Crystal system, space group	Monoclinic, P2₁	Orthorhombic, Pna2₁
Temperature (K)	120	120
a, b, c (Å)	7.2644 (4), 7.8657 (3), 10.1522 (5)	16.1757 (2), 12.5444 (3), 8.2147 (2)
α, β, γ (°)	90, 103.190 (2), 90	90, 90, 90
V (Å³)	564.79 (5)	1666.88 (6)
Z	2	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.25	0.20
Crystal size (mm)	0.38 × 0.18 × 0.08	0.30 × 0.08 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995, 1997)	Multi-scan (SORTAV; Blessing, 1995, 1997)
T_min, T_max	0.922, 0.980	0.866, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8535, 2550, 2422	19245, 3762, 3605
R_int	0.039	0.064
(sin θ/λ)_max (Å⁻¹)	0.648	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.070, 1.06	0.045, 0.130, 1.26
No. of reflections	2550	3762
No. of parameters	130	203
No. of restraints	1	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.20	0.63, −0.84
Absolute structure	Flack (1983), 1163 Friedel pairs	Flack (1983), 1719 Friedel pairs
Absolute structure parameter	−0.03 (6)	0.01 (9)

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).

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···S1ⁱ	0.95	2.75	3.5556 (13)	144

Symmetry code: (i) −x+1, y−1/2, −z.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg1ⁱ	0.95	2.88	3.674 (2)	142

Symmetry code: (i) x−1/2, −y+3/2, z.

Selected torsional (°) for compounds (I) - (III) top

Parameter	(I)	(II)	(III)
S1-C10-C11-N5	-6.53 (19)	7.4 (3)	5.7 (5)
C11-C10-S1-C2	62.97 (13)	-69.29 (18)	-60.4 (4)
C10-C11-N5-C4	-69.68 (18)	74.6 (2)	75.1 (4)
S1-C2-C3-C4	63.33 (14)	60.3 (2)	65.2 (5)
N5-C4-C3-C2	-67.82 (17)	-62.3 (2)	-60.2 (5)
C10-S1-C2-C3	-70.33 (13)	24.40 (17)	15.7 (3)
C11-N5-C4-C3	90.42 (16)	-36.1 (2)	-39.6 (5)

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

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Allen, F. H., Bird, C. M., Rowland, R. S. & Raithby, P. R. (1997). Acta Cryst. B53, 696–701. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–37. CrossRef CAS Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1997). J. Appl. Cryst. 30, 421–426. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, p. 226. Oxford University Press. Google Scholar
Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Glidewell, C. & Ferguson, G. (1994). Acta Cryst. C50, 1362–1366. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hsing, C.-I., Chin, S. & Li, C.-P. (1966). Hua Hsueh Hsueh Pao, 32, 247–251; Chem. Abstr. (1967), 66, 28751g. Google Scholar
Jones, P. G. (1986). Acta Cryst. A42, 57. CrossRef Web of Science IUCr Journals Google Scholar
Kojić-Prodić, B., Ruz˘ić-Toros˘, Z., S˘unjić, V., Decorte, E. & Moimas, F. (1984). Helv. Chim. Acta, 67, 916–925. CSD CrossRef Web of Science Google Scholar
Laavanya, P., Panchanatheswaran, K., Muthukumar, M., Jeyaraman, R. & Kraus Bauer, J. A. (2002). Z. Kristallogr. New Cryst. Struct. 217, 605–606. CAS Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 60| Part 5| May 2004| Pages o346-o349

doi:10.1107/S0108270104006857

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

(R)-2,3,4,5-Tetra­hydro-2,2,4-tri­methyl-1,5-benzo­thia­zepine and rac-5-benzoyl-2,3,4,5-tetra­hydro-2,2,4-tri­methyl-1,5-benzo­thia­zepine: chains built from N—H⋯S and C—H⋯π(arene) hydrogen bonds

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

(R)-2,3,4,5-Tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine and rac-5-benzoyl-2,3,4,5-tetrahydro-2,2,4-trimethyl-1,5-benzothiazepine: chains built from N—H⋯S and C—H⋯π(arene) hydrogen bonds