2-[(E)-(4-Chloro­phenyl)­methyl­ene­amino]-N-(X-methyl­phenyl)-4,5,6,7-tetra­hydro-1-benzo­thio­phene-3-carbox­amide, where X = 2 and 3

The title compounds, both C₂₃H₂₁ClN₂OS, are isomeric, with (I) and (II) being the N-3-methyl­phenyl and N-2-methyl­phenyl derivatives, respectively. The dihedral angle between the 4-chloro­phenyl group and the thio­phene ring in (II) [38.1 (1)°] is larger than that in (I) [7.1 (1)°], indicating steric repulsion between the chloro­phenyl and o-toluidine groups in (II). In both compounds, an intramolecular N-H...N hydrogen bond forms a pseudo-six-membered ring, thus locking the molecular conformation. In the crystal structures, mol­ecules are connected via N-H...O hydrogen bonds, forming chains along the b axis in (I) and along the c axis in (II). Intermolecular C-H...O/S and [pi]-[pi] interactions are also observed in (II), but not in (I).

S1. Comment

The design and synthesis of compounds which possess important pharmacological properties, such as antibacterial, anticancer, antiinflamatory and antitoxic properties, is an area of research with widespread potential applications in medicine (Pellis & West, 1968; Cohen et al., 1977; Csaszar & Morvay, 1983; Lakshmi et al., 1985), and in this regard we have selected thiophene derivatives (El-Maghraby et al., 1984; Dzhurayev et al., 1992; Gewald et al., 1966) which have been found to exhibit these activities. In this context, S-containing Schiff bases are most effective. We have already reported the crystal structures of biologically active thiophene-3-carboxamide derivatives (Vasu Nirmala Choudhury et al., 2003; Vasu Nirmala Chopra et al., 2003). In this paper, structure analyses are presented for the title two compounds, (I) and (II), which show antibacterial and antifungal activities (Mohan & Saravanan, 2002, 2003). The compounds are isomers of each other, differing only in the position of attachment of the methyl at the meta and ortho positions. \sch

Compounds (I) (Fig. 1) and (II) (Fig. 2) contain three different structural moieties and these will be discussed separately. The thiophene ring is essentially planar. The six-membered cyclohexene ring adopts a half-chair conformation, with atoms C6 and C7 deviating from the C5/C3/C4/C8 plane by −0.246 (7) and 0.218 (7) Å, respectively, in (I), and by −0.249 (5) and 0.320 (1) Å, respectively, in (II). The puckering parameters (Cremer & Pople, 1975) generated by PLATON (Spek, 1990) for the cyclohexene ring are q₂ = 0.138 (4) Å, ϕ₂ = −151.(2)° and τ = 25 (1)° in (I), and the corresponding values are 0.126 (3) Å, −131 (2)° and 26 (1)°, respectively, in (II).

The bond angles in the methyl-phenyl ring, C20—C21—C22 in (I) [118.6 (1)°] and C17—C22—C21 in (II) [117.6 (2)°], deviate significantly from the ideal value of 120°. This deviation is due to the electron-donating inductive effect of the methyl group (Vasu Nirmala Choudhury et al., 2003; Vasu Nirmala Chopra et al., 2003). Please check both references were intended here - original CIF did not give a unique citation. The angle between the mean planes of the m-toluidine and thiophene rings is 18.4 (1)° in (I), whereas that between the o-toluidine and thiophene rings is 12.9 (1)° in (II). The C16—N2—C17—C18 torsion angle is 11.4 (5)° in (I) and 27.4 (4)° in (II), indicating that the presence of a methyl group in the ortho position in (II) causes rotation about the N2—C17 bond to minimize steric repulsion with the amino H atom. An intramolecular N—H···N hydrogen bond (Tables 2 and 4) in each structure locks the molecule into a rigid pseudo-six-membered ring conformation and removes the conformational flexibility.

The amino H atom is also involved in an intermolecular N—H···O hydrogen bond, and molecular chains are formed. In (I), the chains are along the b axis related by a b-glide plane (1/2 − x, 1/2 + y, z) orthogonal to the a axis. In (II), the chains are along the b axis related by a c-glide plane (x, 1/2 − y, z + 1/2) orthogonal to the b axis. There is no intermolecular C—H···O/S nor π–π interaction in (I). On the other hand, in (II), the chlorophenyl rings are oriented in a manner that facilitates intermolecular π–π interactions, the centre-to-centre distance between the chlorophenyl rings being 3.863 Å. In (II), there are also intermolecular C—H···O/S interactions (Fig. 4 and Table 4).

S2. Experimental

The title compounds were synthesized using the Gewald reaction (Gewald et al., 1966). For compound (I), m-cyanotoluidine was refluxed with cyclohexanone in the presence of sulfur, dimethylamine and ethanol at 313–323 K for 1 h. The resulting product was then treated with 4-chlorobenzaldehyde in an equimolar ratio in the presence of ethanol, which yielded (I). This was then recrystallized from a solution of dichloromethane and ethylacetate (1:2) by slow evaporation. Yellow crystals of (I) were obtained after four weeks and used for single-crystal data collection. For compound (II), a similar procedure was followed using o-cyanotoluidine, and later 4-chlorobenzaldehyde was added. The compound was purified and crystallized using the same procedure as (I).

S3. Refinement

For both compounds, amino atom H2N and atom H9 (bonded to C9) were located from difference Fourier maps and refined isotropically. Other H atoms were constrained to ride on their parent atom, with C—H = 0.93–0.97 Å and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl). The methyl groups were allowed to rotate freely about the C—C bond. In both compounds, the C6—C7 bond length is shorter than the expected value. These C atoms of the cyclohexene moiety have a large vibrational degree of freedom and this is reflected in the large atomic displacement parameters, resulting in the short C—C bond length.

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and most H atoms have been omitted for clarity. The broken lines show the N—H···N intramolecular hydrogen bond.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and most H atoms have been omitted for clarity. The broken lines show the N—H···N intramolecular hydrogen bond.
	Fig. 3. A packing diagram for (I). The dotted lines show the formation of N—H···O hydrogen-bonded chains.
	Fig. 4. A packing diagram for (II). The dotted lines show N—H···O hydrogen bonds, and C—H···O, C—H···S and π–π interactions.

(I) 2-[(1E)-(4-Chlorophenyl)methyleneamino]-N-(3-methylphenyl)-4,5,6,7- tetrahydro-1-benzothiophene-3-carboxamide

Crystal data

C23H21ClN2OS	F(000) = 1712
Mr = 408.93	Dx = 1.326 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 650 reflections
a = 13.785 (11) Å	θ = 1.6–26.4°
b = 8.554 (7) Å	µ = 0.31 mm^−1
c = 34.74 (3) Å	T = 293 K
V = 4096 (6) Å^3	Blocks, yellow
Z = 8	0.30 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4113 independent reflections
Radiation source: fine-focus sealed tube	2436 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
ϕ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
Tmin = 0.908, Tmax = 0.956	k = −10→10
29534 measured reflections	l = −42→42

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 2.7373P] where P = (Fo^2 + 2Fc^2)/3
4113 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.92208 (6)	0.70576 (10)	0.33068 (2)	0.0602 (3)
Cl1	0.29069 (7)	0.76530 (18)	0.27328 (3)	0.1112 (5)
N1	0.73401 (17)	0.6108 (3)	0.34342 (6)	0.0457 (6)
N2	0.72118 (18)	0.4374 (3)	0.41452 (7)	0.0458 (6)
O1	0.84827 (15)	0.2705 (2)	0.41780 (6)	0.0574 (6)
C1	0.8307 (2)	0.6006 (3)	0.35358 (8)	0.0434 (7)
C2	0.86855 (19)	0.5004 (3)	0.38087 (7)	0.0394 (6)
C3	0.9725 (2)	0.5082 (3)	0.38288 (8)	0.0459 (7)
C4	1.0096 (2)	0.6141 (4)	0.35767 (9)	0.0545 (8)
C5	1.0371 (2)	0.4144 (4)	0.40892 (9)	0.0585 (9)
C6	1.1396 (3)	0.4738 (7)	0.40844 (15)	0.1224 (19)
C7	1.1754 (3)	0.5376 (7)	0.37429 (14)	0.1170 (18)
C8	1.1155 (2)	0.6520 (5)	0.35284 (12)	0.0817 (12)
C9	0.7036 (2)	0.7164 (4)	0.32054 (8)	0.0470 (7)
C10	0.6025 (2)	0.7268 (3)	0.30893 (8)	0.0461 (7)
C11	0.5326 (2)	0.6282 (4)	0.32424 (9)	0.0573 (8)
C12	0.4377 (3)	0.6386 (4)	0.31303 (10)	0.0672 (10)
C13	0.4111 (2)	0.7507 (5)	0.28681 (9)	0.0651 (9)
C14	0.4779 (3)	0.8502 (4)	0.27108 (9)	0.0663 (10)
C15	0.5740 (2)	0.8385 (4)	0.28237 (8)	0.0564 (8)
C16	0.8125 (2)	0.3922 (3)	0.40592 (8)	0.0395 (6)
C17	0.6523 (2)	0.3637 (3)	0.43844 (8)	0.0411 (7)
C18	0.6736 (2)	0.2406 (3)	0.46303 (8)	0.0522 (8)
C19	0.6005 (3)	0.1797 (4)	0.48564 (9)	0.0672 (10)
C20	0.5078 (3)	0.2399 (4)	0.48442 (9)	0.0668 (10)
C21	0.4860 (2)	0.3629 (4)	0.46018 (9)	0.0544 (8)
C22	0.5585 (2)	0.4233 (3)	0.43739 (8)	0.0486 (7)
C23	0.3849 (2)	0.4315 (5)	0.45889 (11)	0.0762 (11)
HN2	0.702 (2)	0.524 (4)	0.4055 (9)	0.061 (10)*
H5A	1.0363	0.3059	0.4008	0.070*
H5B	1.0121	0.4192	0.4350	0.070*
H6A	1.1453	0.5528	0.4283	0.147*
H6B	1.1817	0.3879	0.4157	0.147*
H7A	1.1895	0.4515	0.3570	0.140*
H7B	1.2368	0.5877	0.3802	0.140*
H8A	1.1325	0.6491	0.3257	0.098*
H8B	1.1282	0.7566	0.3624	0.098*
H9	0.748 (2)	0.797 (3)	0.3115 (7)	0.052 (8)*
H11	0.5505	0.5539	0.3424	0.069*
H12	0.3917	0.5704	0.3231	0.081*
H14	0.4591	0.9246	0.2531	0.080*
H15	0.6198	0.9063	0.2720	0.068*
H18	0.7361	0.1999	0.4642	0.063*
H19	0.6141	0.0966	0.5020	0.081*
H20	0.4597	0.1974	0.5000	0.080*
H22	0.5444	0.5058	0.4209	0.058*
H23A	0.3791	0.5118	0.4781	0.114*
H23B	0.3382	0.3507	0.4639	0.114*
H23C	0.3732	0.4754	0.4339	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0566 (5)	0.0630 (5)	0.0609 (5)	−0.0031 (4)	0.0093 (4)	0.0196 (4)
Cl1	0.0551 (6)	0.1986 (14)	0.0798 (7)	0.0124 (7)	−0.0116 (5)	0.0233 (8)
O1	0.0471 (12)	0.0467 (12)	0.0784 (15)	0.0063 (10)	0.0026 (11)	0.0196 (11)
N1	0.0483 (15)	0.0471 (14)	0.0416 (13)	0.0045 (12)	−0.0009 (11)	0.0049 (12)
N2	0.0437 (16)	0.0430 (15)	0.0509 (15)	0.0037 (12)	0.0048 (12)	0.0135 (12)
C1	0.0431 (18)	0.0435 (16)	0.0436 (16)	0.0017 (14)	0.0026 (13)	0.0024 (13)
C2	0.0404 (17)	0.0383 (15)	0.0395 (16)	0.0015 (13)	0.0020 (12)	−0.0011 (13)
C3	0.0422 (18)	0.0512 (17)	0.0441 (17)	0.0026 (14)	0.0002 (14)	−0.0018 (14)
C4	0.0468 (19)	0.060 (2)	0.0564 (19)	−0.0050 (16)	0.0057 (15)	0.0036 (16)
C5	0.0418 (18)	0.075 (2)	0.059 (2)	0.0019 (17)	−0.0052 (15)	0.0051 (17)
C6	0.042 (2)	0.191 (5)	0.135 (4)	−0.009 (3)	−0.012 (3)	0.070 (4)
C7	0.043 (2)	0.178 (5)	0.130 (4)	−0.006 (3)	0.001 (3)	0.050 (4)
C8	0.049 (2)	0.103 (3)	0.093 (3)	−0.016 (2)	0.012 (2)	0.015 (2)
C9	0.056 (2)	0.0471 (17)	0.0376 (16)	0.0053 (16)	0.0026 (14)	0.0044 (14)
C10	0.0517 (19)	0.0513 (17)	0.0354 (15)	0.0089 (15)	−0.0011 (13)	0.0004 (14)
C11	0.060 (2)	0.058 (2)	0.0536 (19)	0.0044 (17)	−0.0049 (17)	0.0083 (16)
C12	0.062 (2)	0.080 (2)	0.060 (2)	−0.009 (2)	0.0011 (17)	0.0036 (19)
C13	0.053 (2)	0.098 (3)	0.0439 (18)	0.012 (2)	−0.0037 (16)	0.0001 (19)
C14	0.066 (2)	0.087 (3)	0.0459 (18)	0.016 (2)	−0.0062 (17)	0.0170 (18)
C15	0.056 (2)	0.068 (2)	0.0453 (17)	0.0063 (17)	0.0022 (15)	0.0103 (16)
C16	0.0401 (17)	0.0377 (15)	0.0407 (15)	−0.0022 (14)	−0.0032 (13)	0.0009 (13)
C17	0.0450 (18)	0.0399 (15)	0.0383 (15)	−0.0037 (13)	0.0007 (13)	0.0006 (12)
C18	0.058 (2)	0.0531 (18)	0.0451 (17)	0.0001 (16)	0.0048 (15)	0.0093 (15)
C19	0.081 (3)	0.061 (2)	0.059 (2)	−0.0041 (19)	0.0108 (19)	0.0188 (17)
C20	0.067 (2)	0.076 (2)	0.057 (2)	−0.023 (2)	0.0147 (18)	0.0080 (18)
C21	0.047 (2)	0.066 (2)	0.0504 (18)	−0.0161 (16)	0.0037 (15)	−0.0052 (17)
C22	0.050 (2)	0.0479 (17)	0.0480 (17)	−0.0068 (15)	−0.0013 (14)	0.0051 (14)
C23	0.043 (2)	0.104 (3)	0.082 (3)	−0.012 (2)	0.0069 (18)	−0.008 (2)

Geometric parameters (Å, º)

S1—C4	1.717 (3)	C21—C20	1.381 (4)
S1—C1	1.740 (3)	C21—C23	1.512 (4)
Cl1—C13	1.729 (4)	C5—C6	1.501 (5)
O1—C16	1.224 (3)	C5—H5A	0.9700
N2—C16	1.350 (4)	C5—H5B	0.9700
N2—C17	1.411 (4)	C4—C8	1.506 (4)
N2—HN2	0.85 (3)	C15—C14	1.385 (4)
N1—C9	1.274 (3)	C15—H15	0.9300
N1—C1	1.382 (4)	C13—C14	1.367 (5)
C2—C1	1.380 (4)	C13—C12	1.373 (5)
C2—C3	1.436 (4)	C14—H14	0.9300
C2—C16	1.487 (4)	C20—C19	1.378 (5)
C3—C4	1.359 (4)	C20—H20	0.9300
C3—C5	1.501 (4)	C12—H12	0.9300
C18—C19	1.380 (4)	C19—H19	0.9300
C18—C17	1.388 (4)	C23—H23A	0.9600
C18—H18	0.9300	C23—H23B	0.9600
C17—C22	1.390 (4)	C23—H23C	0.9600
C22—C21	1.376 (4)	C6—C7	1.396 (6)
C22—H22	0.9300	C6—H6A	0.9700
C10—C15	1.385 (4)	C6—H6B	0.9700
C10—C11	1.387 (4)	C7—C8	1.482 (5)
C10—C9	1.454 (4)	C7—H7A	0.9700
C9—H9	0.98 (3)	C7—H7B	0.9700
C11—C12	1.368 (4)	C8—H8A	0.9700
C11—H11	0.9300	C8—H8B	0.9700
C4—S1—C1	91.28 (15)	C3—C4—S1	113.1 (2)
C16—N2—C17	129.1 (3)	C8—C4—S1	121.4 (2)
C16—N2—HN2	117 (2)	C14—C15—C10	120.7 (3)
C17—N2—HN2	114 (2)	C14—C15—H15	119.7
C9—N1—C1	121.4 (3)	C10—C15—H15	119.7
C1—C2—C3	112.4 (3)	C14—C13—C12	121.3 (3)
C1—C2—C16	126.3 (3)	C14—C13—Cl1	119.5 (3)
C3—C2—C16	121.3 (2)	C12—C13—Cl1	119.2 (3)
C4—C3—C2	112.0 (3)	C13—C14—C15	119.1 (3)
C4—C3—C5	121.4 (3)	C13—C14—H14	120.5
C2—C3—C5	126.5 (3)	C15—C14—H14	120.5
C2—C1—N1	125.4 (3)	C19—C20—C21	120.4 (3)
C2—C1—S1	111.2 (2)	C19—C20—H20	119.8
N1—C1—S1	123.3 (2)	C21—C20—H20	119.8
O1—C16—N2	123.0 (3)	C11—C12—C13	119.3 (3)
O1—C16—C2	121.1 (3)	C11—C12—H12	120.3
N2—C16—C2	115.9 (2)	C13—C12—H12	120.3
C19—C18—C17	118.8 (3)	C20—C19—C18	121.3 (3)
C19—C18—H18	120.6	C20—C19—H19	119.4
C17—C18—H18	120.6	C18—C19—H19	119.4
C18—C17—C22	119.5 (3)	C21—C23—H23A	109.5
C18—C17—N2	124.0 (3)	C21—C23—H23B	109.5
C22—C17—N2	116.6 (2)	H23A—C23—H23B	109.5
C21—C22—C17	121.5 (3)	C21—C23—H23C	109.5
C21—C22—H22	119.2	H23A—C23—H23C	109.5
C17—C22—H22	119.2	H23B—C23—H23C	109.5
C15—C10—C11	118.5 (3)	C7—C6—C5	118.3 (4)
C15—C10—C9	120.0 (3)	C7—C6—H6A	107.7
C11—C10—C9	121.5 (3)	C5—C6—H6A	107.7
N1—C9—C10	122.1 (3)	C7—C6—H6B	107.7
N1—C9—H9	119.4 (17)	C5—C6—H6B	107.7
C10—C9—H9	118.4 (17)	H6A—C6—H6B	107.1
C12—C11—C10	121.1 (3)	C6—C7—C8	119.2 (4)
C12—C11—H11	119.5	C6—C7—H7A	107.5
C10—C11—H11	119.5	C8—C7—H7A	107.5
C22—C21—C20	118.6 (3)	C6—C7—H7B	107.5
C22—C21—C23	120.5 (3)	C8—C7—H7B	107.5
C20—C21—C23	121.0 (3)	H7A—C7—H7B	107.0
C3—C5—C6	111.7 (3)	C7—C8—C4	110.0 (3)
C3—C5—H5A	109.3	C7—C8—H8A	109.7
C6—C5—H5A	109.3	C4—C8—H8A	109.7
C3—C5—H5B	109.3	C7—C8—H8B	109.7
C6—C5—H5B	109.3	C4—C8—H8B	109.7
H5A—C5—H5B	107.9	H8A—C8—H8B	108.2
C3—C4—C8	125.5 (3)
C1—C2—C3—C4	0.7 (4)	C9—C10—C11—C12	−179.8 (3)
C16—C2—C3—C4	180.0 (2)	C17—C22—C21—C20	−0.3 (5)
C1—C2—C3—C5	−179.3 (3)	C17—C22—C21—C23	179.1 (3)
C16—C2—C3—C5	0.0 (4)	C4—C3—C5—C6	10.6 (5)
C3—C2—C1—N1	175.4 (3)	C2—C3—C5—C6	−169.4 (3)
C16—C2—C1—N1	−3.8 (4)	C2—C3—C4—C8	179.2 (3)
C3—C2—C1—S1	−0.6 (3)	C5—C3—C4—C8	−0.8 (5)
C16—C2—C1—S1	−179.8 (2)	C2—C3—C4—S1	−0.5 (3)
C9—N1—C1—C2	173.3 (3)	C5—C3—C4—S1	179.5 (2)
C9—N1—C1—S1	−11.1 (4)	C1—S1—C4—C3	0.2 (3)
C4—S1—C1—C2	0.3 (2)	C1—S1—C4—C8	−179.6 (3)
C4—S1—C1—N1	−175.8 (3)	C11—C10—C15—C14	−0.7 (5)
C17—N2—C16—O1	2.4 (5)	C9—C10—C15—C14	−179.8 (3)
C17—N2—C16—C2	−177.4 (3)	C12—C13—C14—C15	−1.0 (5)
C1—C2—C16—O1	151.5 (3)	Cl1—C13—C14—C15	179.4 (3)
C3—C2—C16—O1	−27.7 (4)	C10—C15—C14—C13	0.6 (5)
C1—C2—C16—N2	−28.7 (4)	C22—C21—C20—C19	0.2 (5)
C3—C2—C16—N2	152.1 (3)	C23—C21—C20—C19	−179.2 (3)
C19—C18—C17—C22	0.5 (4)	C10—C11—C12—C13	−1.4 (5)
C19—C18—C17—N2	178.8 (3)	C14—C13—C12—C11	1.4 (5)
C16—N2—C17—C18	11.4 (5)	Cl1—C13—C12—C11	−179.0 (3)
C16—N2—C17—C22	−170.2 (3)	C21—C20—C19—C18	0.3 (5)
C18—C17—C22—C21	0.0 (4)	C17—C18—C19—C20	−0.6 (5)
N2—C17—C22—C21	−178.5 (3)	C3—C5—C6—C7	−32.9 (6)
C1—N1—C9—C10	178.7 (3)	C5—C6—C7—C8	46.7 (8)
C15—C10—C9—N1	−176.5 (3)	C6—C7—C8—C4	−32.8 (6)
C11—C10—C9—N1	4.4 (4)	C3—C4—C8—C7	10.3 (5)
C15—C10—C11—C12	1.1 (5)	S1—C4—C8—C7	−170.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···N1	0.85 (3)	2.32 (3)	2.887 (4)	125 (3)
N2—HN2···O1^i	0.85 (3)	2.26 (3)	3.009 (4)	147 (3)

Symmetry code: (i) −x+3/2, y+1/2, z.

(II) 2-[(1E)-(4-Chlorophenyl)methyleneamino]-N-(2-methylphenyl)-4,5,6,7- tetrahydro-1-benzothiophene-3-carboxamide

Crystal data

C23H21ClN2OS	F(000) = 856
Mr = 408.94	Dx = 1.354 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 725 reflections
a = 17.511 (4) Å	θ = 1.7–25.4°
b = 12.519 (3) Å	µ = 0.31 mm^−1
c = 9.232 (2) Å	T = 293 K
β = 97.406 (4)°	Blocks, yellow
V = 2006.9 (8) Å^3	0.30 × 0.15 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3994 independent reflections
Radiation source: fine-focus sealed tube	3307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ϕ and ω scans	θmax = 26.4°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
Tmin = 0.921, Tmax = 0.970	k = −15→15
15187 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.1224P)^2 + 0.6875P] where P = (Fo^2 + 2Fc^2)/3
3994 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.66585 (3)	0.40800 (4)	0.65249 (6)	0.04534 (19)
Cl1	0.50494 (4)	−0.25980 (5)	0.61720 (8)	0.0663 (2)
O1	0.83579 (9)	0.34669 (12)	0.28231 (16)	0.0505 (4)
N1	0.69212 (9)	0.20662 (13)	0.55121 (17)	0.0382 (4)
N2	0.84504 (11)	0.20856 (14)	0.4411 (2)	0.0478 (5)
C1	0.71378 (11)	0.31339 (15)	0.55888 (19)	0.0357 (4)
C2	0.76870 (10)	0.36134 (15)	0.48729 (19)	0.0347 (4)
C3	0.77158 (11)	0.47495 (15)	0.5072 (2)	0.0393 (4)
C4	0.71986 (12)	0.51050 (16)	0.5939 (2)	0.0434 (5)
C5	0.82347 (14)	0.55131 (18)	0.4399 (3)	0.0554 (6)
C6	0.8163 (2)	0.6639 (2)	0.4930 (5)	0.1014 (13)
C7	0.7479 (3)	0.6968 (2)	0.5419 (6)	0.1273 (19)
C8	0.70773 (16)	0.62482 (19)	0.6342 (3)	0.0611 (6)
C9	0.65647 (11)	0.16723 (17)	0.6516 (2)	0.0386 (4)
C10	0.62410 (11)	0.05980 (16)	0.6434 (2)	0.0381 (4)
C11	0.61818 (13)	−0.00057 (18)	0.5163 (2)	0.0466 (5)
C12	0.58287 (13)	−0.09903 (18)	0.5077 (2)	0.0507 (5)
C13	0.55294 (11)	−0.13765 (17)	0.6287 (2)	0.0456 (5)
C14	0.55863 (13)	−0.08096 (18)	0.7570 (2)	0.0490 (5)
C15	0.59416 (12)	0.01777 (18)	0.7637 (2)	0.0447 (5)
C16	0.81961 (10)	0.30465 (15)	0.3939 (2)	0.0363 (4)
C17	0.89367 (12)	0.13949 (17)	0.3719 (2)	0.0464 (5)
C18	0.94546 (16)	0.1793 (2)	0.2831 (4)	0.0735 (8)
C19	0.99307 (19)	0.1103 (3)	0.2199 (4)	0.0876 (11)
C20	0.99065 (17)	0.0025 (2)	0.2465 (4)	0.0769 (9)
C21	0.94035 (15)	−0.0360 (2)	0.3348 (3)	0.0599 (6)
C22	0.89009 (12)	0.03026 (17)	0.3988 (2)	0.0452 (5)
C23	0.83408 (16)	−0.01454 (19)	0.4917 (3)	0.0626 (7)
H2N	0.8317 (16)	0.190 (2)	0.513 (3)	0.059 (8)*
H5A	0.8764	0.5280	0.4633	0.066*
H5B	0.8107	0.5498	0.3345	0.066*
H6A	0.8575	0.6754	0.5722	0.122*
H6B	0.8258	0.7113	0.4142	0.122*
H7A	0.7119	0.7142	0.4563	0.153*
H7B	0.7588	0.7627	0.5959	0.153*
H8A	0.6531	0.6409	0.6209	0.073*
H8B	0.7273	0.6361	0.7362	0.073*
H9	0.6531 (13)	0.206 (2)	0.736 (3)	0.049 (6)*
H11	0.6385	0.0260	0.4353	0.056*
H12	0.5792	−0.1388	0.4220	0.061*
H14	0.5389	−0.1086	0.8380	0.059*
H15	0.5981	0.0568	0.8500	0.054*
H18	0.9480	0.2524	0.2664	0.088*
H19	1.0269	0.1369	0.1589	0.105*
H20	1.0231	−0.0439	0.2046	0.092*
H21	0.9395	−0.1091	0.3531	0.072*
H23A	0.8432	−0.0897	0.5053	0.094*
H23B	0.7826	−0.0033	0.4446	0.094*
H23C	0.8405	0.0206	0.5849	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0531 (3)	0.0430 (3)	0.0442 (3)	0.0040 (2)	0.0224 (2)	−0.0010 (2)
Cl1	0.0584 (4)	0.0466 (4)	0.0957 (5)	−0.0143 (3)	0.0170 (3)	0.0031 (3)
O1	0.0611 (9)	0.0468 (9)	0.0482 (8)	0.0099 (7)	0.0244 (7)	0.0077 (7)
N1	0.0383 (8)	0.0369 (9)	0.0408 (8)	−0.0030 (7)	0.0104 (7)	0.0011 (7)
N2	0.0524 (10)	0.0363 (9)	0.0605 (12)	0.0079 (8)	0.0299 (9)	0.0078 (8)
C1	0.0388 (10)	0.0357 (10)	0.0338 (9)	0.0019 (8)	0.0089 (7)	0.0006 (7)
C2	0.0362 (9)	0.0328 (9)	0.0359 (9)	0.0014 (7)	0.0076 (7)	0.0016 (7)
C3	0.0405 (10)	0.0338 (10)	0.0445 (10)	0.0012 (8)	0.0084 (8)	0.0001 (8)
C4	0.0493 (11)	0.0360 (10)	0.0458 (11)	0.0033 (9)	0.0104 (9)	−0.0011 (8)
C5	0.0590 (14)	0.0355 (11)	0.0766 (15)	−0.0048 (10)	0.0276 (12)	0.0008 (11)
C6	0.118 (3)	0.0380 (14)	0.164 (4)	−0.0109 (16)	0.080 (3)	−0.0101 (18)
C7	0.153 (4)	0.0352 (15)	0.219 (5)	0.0004 (18)	0.118 (4)	−0.007 (2)
C8	0.0742 (16)	0.0409 (12)	0.0720 (15)	0.0100 (11)	0.0242 (13)	−0.0080 (11)
C9	0.0399 (10)	0.0416 (11)	0.0353 (9)	−0.0004 (8)	0.0081 (8)	0.0017 (8)
C10	0.0340 (9)	0.0419 (10)	0.0390 (10)	−0.0010 (8)	0.0068 (7)	0.0052 (8)
C11	0.0496 (12)	0.0523 (12)	0.0409 (10)	−0.0086 (9)	0.0173 (9)	0.0020 (9)
C12	0.0546 (12)	0.0509 (13)	0.0487 (12)	−0.0074 (10)	0.0145 (10)	−0.0074 (9)
C13	0.0371 (10)	0.0404 (11)	0.0598 (12)	−0.0025 (8)	0.0082 (9)	0.0083 (9)
C14	0.0528 (12)	0.0497 (13)	0.0472 (12)	−0.0020 (10)	0.0169 (10)	0.0139 (9)
C15	0.0504 (12)	0.0474 (12)	0.0377 (10)	−0.0018 (9)	0.0108 (9)	0.0043 (8)
C16	0.0324 (9)	0.0341 (10)	0.0438 (10)	−0.0024 (7)	0.0101 (8)	−0.0001 (8)
C17	0.0436 (11)	0.0397 (11)	0.0591 (12)	0.0074 (9)	0.0188 (9)	0.0005 (9)
C18	0.0686 (17)	0.0502 (14)	0.113 (2)	0.0150 (12)	0.0532 (16)	0.0159 (14)
C19	0.0774 (19)	0.078 (2)	0.121 (3)	0.0244 (16)	0.065 (2)	0.0163 (19)
C20	0.0733 (18)	0.0677 (18)	0.097 (2)	0.0269 (14)	0.0390 (16)	−0.0042 (15)
C21	0.0662 (15)	0.0420 (12)	0.0730 (16)	0.0121 (11)	0.0140 (12)	−0.0104 (11)
C22	0.0472 (11)	0.0385 (11)	0.0502 (11)	0.0036 (9)	0.0074 (9)	−0.0043 (9)
C23	0.0786 (18)	0.0352 (11)	0.0788 (17)	−0.0037 (11)	0.0279 (14)	−0.0001 (11)

Geometric parameters (Å, º)

S1—C4	1.722 (2)	C10—C11	1.388 (3)
S1—C1	1.7438 (19)	C10—C9	1.458 (3)
Cl1—C13	1.741 (2)	C14—H14	0.9300
O1—C16	1.222 (2)	C9—H9	0.92 (2)
N2—C16	1.336 (3)	C11—H11	0.9300
N2—C17	1.421 (3)	C5—C6	1.503 (4)
N2—H2N	0.77 (3)	C5—H5A	0.9700
N1—C9	1.281 (2)	C5—H5B	0.9700
N1—C1	1.389 (3)	C8—C7	1.479 (4)
C3—C4	1.359 (3)	C8—H8A	0.9700
C3—C2	1.434 (3)	C8—H8B	0.9700
C3—C5	1.507 (3)	C21—C20	1.363 (4)
C4—C8	1.501 (3)	C21—H21	0.9300
C22—C17	1.393 (3)	C23—H23A	0.9600
C22—C21	1.395 (3)	C23—H23B	0.9600
C22—C23	1.493 (3)	C23—H23C	0.9600
C16—C2	1.496 (2)	C18—C19	1.382 (4)
C2—C1	1.373 (3)	C18—H18	0.9300
C15—C14	1.382 (3)	C20—C19	1.373 (4)
C15—C10	1.391 (3)	C20—H20	0.9300
C15—H15	0.9300	C6—C7	1.395 (5)
C12—C11	1.377 (3)	C6—H6A	0.9700
C12—C13	1.381 (3)	C6—H6B	0.9700
C12—H12	0.9300	C19—H19	0.9300
C13—C14	1.373 (3)	C7—H7A	0.9700
C17—C18	1.391 (3)	C7—H7B	0.9700
C4—S1—C1	91.81 (10)	C12—C11—H11	119.3
C16—N2—C17	126.53 (19)	C10—C11—H11	119.3
C16—N2—H2N	115 (2)	C6—C5—C3	112.4 (2)
C17—N2—H2N	118 (2)	C6—C5—H5A	109.1
C9—N1—C1	119.27 (17)	C3—C5—H5A	109.1
C4—C3—C2	112.66 (17)	C6—C5—H5B	109.1
C4—C3—C5	121.21 (18)	C3—C5—H5B	109.1
C2—C3—C5	126.12 (17)	H5A—C5—H5B	107.9
C3—C4—C8	125.8 (2)	C7—C8—C4	110.2 (2)
C3—C4—S1	112.08 (15)	C7—C8—H8A	109.6
C8—C4—S1	122.13 (17)	C4—C8—H8A	109.6
C17—C22—C21	117.6 (2)	C7—C8—H8B	109.6
C17—C22—C23	121.29 (19)	C4—C8—H8B	109.6
C21—C22—C23	121.1 (2)	H8A—C8—H8B	108.1
O1—C16—N2	123.95 (18)	C20—C21—C22	122.3 (2)
O1—C16—C2	120.09 (17)	C20—C21—H21	118.8
N2—C16—C2	115.96 (17)	C22—C21—H21	118.8
C1—C2—C3	112.77 (16)	C22—C23—H23A	109.5
C1—C2—C16	125.17 (17)	C22—C23—H23B	109.5
C3—C2—C16	122.03 (16)	H23A—C23—H23B	109.5
C14—C15—C10	121.1 (2)	C22—C23—H23C	109.5
C14—C15—H15	119.4	H23A—C23—H23C	109.5
C10—C15—H15	119.4	H23B—C23—H23C	109.5
C2—C1—N1	126.85 (17)	C19—C18—C17	120.0 (3)
C2—C1—S1	110.68 (14)	C19—C18—H18	120.0
N1—C1—S1	122.23 (14)	C17—C18—H18	120.0
C11—C12—C13	118.8 (2)	C21—C20—C19	119.5 (2)
C11—C12—H12	120.6	C21—C20—H20	120.3
C13—C12—H12	120.6	C19—C20—H20	120.3
C14—C13—C12	121.6 (2)	C7—C6—C5	119.6 (3)
C14—C13—Cl1	119.17 (16)	C7—C6—H6A	107.4
C12—C13—Cl1	119.24 (18)	C5—C6—H6A	107.4
C18—C17—C22	120.3 (2)	C7—C6—H6B	107.4
C18—C17—N2	121.4 (2)	C5—C6—H6B	107.4
C22—C17—N2	118.28 (19)	H6A—C6—H6B	107.0
C11—C10—C15	118.30 (19)	C20—C19—C18	120.3 (3)
C11—C10—C9	122.18 (17)	C20—C19—H19	119.8
C15—C10—C9	119.43 (18)	C18—C19—H19	119.8
C13—C14—C15	118.87 (19)	C6—C7—C8	119.9 (3)
C13—C14—H14	120.6	C6—C7—H7A	107.4
C15—C14—H14	120.6	C8—C7—H7A	107.4
N1—C9—C10	122.67 (19)	C6—C7—H7B	107.4
N1—C9—H9	119.7 (15)	C8—C7—H7B	107.4
C10—C9—H9	117.5 (15)	H7A—C7—H7B	106.9
C12—C11—C10	121.31 (19)
C2—C3—C4—C8	−179.1 (2)	C23—C22—C17—N2	3.0 (3)
C5—C3—C4—C8	−0.4 (4)	C16—N2—C17—C18	27.4 (4)
C2—C3—C4—S1	−0.5 (2)	C16—N2—C17—C22	−154.6 (2)
C5—C3—C4—S1	178.25 (17)	C14—C15—C10—C11	−0.7 (3)
C1—S1—C4—C3	0.20 (17)	C14—C15—C10—C9	175.86 (19)
C1—S1—C4—C8	178.9 (2)	C12—C13—C14—C15	1.0 (3)
C17—N2—C16—O1	−0.4 (4)	Cl1—C13—C14—C15	−177.53 (17)
C17—N2—C16—C2	179.88 (19)	C10—C15—C14—C13	−0.2 (3)
C4—C3—C2—C1	0.7 (2)	C1—N1—C9—C10	172.85 (17)
C5—C3—C2—C1	−178.0 (2)	C11—C10—C9—N1	−11.1 (3)
C4—C3—C2—C16	178.99 (18)	C15—C10—C9—N1	172.51 (19)
C5—C3—C2—C16	0.3 (3)	C13—C12—C11—C10	0.0 (3)
O1—C16—C2—C1	142.1 (2)	C15—C10—C11—C12	0.8 (3)
N2—C16—C2—C1	−38.2 (3)	C9—C10—C11—C12	−175.7 (2)
O1—C16—C2—C3	−36.0 (3)	C4—C3—C5—C6	6.0 (4)
N2—C16—C2—C3	143.71 (19)	C2—C3—C5—C6	−175.4 (3)
C3—C2—C1—N1	174.00 (18)	C3—C4—C8—C7	12.1 (4)
C16—C2—C1—N1	−4.3 (3)	S1—C4—C8—C7	−166.4 (3)
C3—C2—C1—S1	−0.5 (2)	C17—C22—C21—C20	−1.2 (4)
C16—C2—C1—S1	−178.76 (14)	C23—C22—C21—C20	178.2 (3)
C9—N1—C1—C2	161.01 (19)	C22—C17—C18—C19	0.7 (5)
C9—N1—C1—S1	−25.1 (2)	N2—C17—C18—C19	178.7 (3)
C4—S1—C1—C2	0.18 (15)	C22—C21—C20—C19	0.7 (5)
C4—S1—C1—N1	−174.62 (16)	C3—C5—C6—C7	−26.1 (5)
C11—C12—C13—C14	−0.9 (3)	C21—C20—C19—C18	0.6 (6)
C11—C12—C13—Cl1	177.61 (17)	C17—C18—C19—C20	−1.3 (6)
C21—C22—C17—C18	0.5 (4)	C5—C6—C7—C8	41.6 (7)
C23—C22—C17—C18	−179.0 (2)	C4—C8—C7—C6	−32.2 (6)
C21—C22—C17—N2	−177.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1	0.77 (3)	2.52 (3)	2.985 (3)	121 (2)
N2—H2N···O1^i	0.77 (3)	2.52 (3)	3.250 (3)	159 (3)
C11—H11···S1^ii	0.93	2.84	3.747 (2)	166
C23—H23C···O1^i	0.96	2.48	3.406 (3)	163

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.