Planarity of benzoyl­hydrazine-dithio­carbazoate tuberculostatics. I. N'-Methyl-substituted 3,4-dichloro­benzoyl monoesters

Methyl 2-(3,4-dichloro­benzoyl)-1-methyl­hydrazine­carbo­di­thio­­ate, C₁₀H₁₀Cl₂N₂OS₂, (F1), butyl 2-(3,4-dichloro­ben­zoyl)-1-methyl­hydrazine­carbodithio­ate, C₁₃H₁₆Cl₂N₂OS₂, (F2), and 3,4-dichloro-N-(2-sulfanylidene-1,3-thia­zinan-3-yl)benz­amide, C₁₁H₁₀Cl₂N₂OS₂, (F3), were studied by X-ray diffraction to test our hypothesis that planarity of aryl­­oylhydrazinedithio­carbazic acid esters is a prerequisite for tuberculostatic activity. All compounds examined in this study are inactive and nonplanar due to twists along two specific bonds in the central frame of the mol­ecules. The significant twist at the N-N bond, with an C-N-N-C(S) torsion angle of about 85°, results from repulsion caused by a methyl substituent at the N' atom of the hydrazide group. The other twist is that within the benzoyl group at the C(O)-Ph bond, i.e. the N-C(=O)-C(phenyl)-C torsion angle: the values found in the studied structures (25-30°) are in agreement with those observed in other compounds containing a similar fragment. As some nonplanar benzoyl derivatives are active, it seems that planarity of the hydrazine­dithio­ate fragment is more important for tuberculostatic activity than planarity of the aryloyl group.

S1. Comment

Our earlier studies of compounds containing a pyrazine ring with an N atom in the ortho position suggested that the N—H···N(ortho) intramolecular contact [see (A), (B) and (C) in Scheme 1] is at least partially responsible for the planarity of the studied heteroaryloylhydrazinedithiocarbazic acid derivatives and their tuberculostastic activity (Olczak et al., 2007, 2011; Szczesio et al., 2011). Recently, we have shown that phenyl analogues of pyrazine derivatives [(D) in Scheme 1] may also reveal activity, even though they are unable to maintain planarity of the benzoyl fragment (Szczesio et al., 2011). The only condition was that the remaining part of the molecule [(D1 but not D2)], apart from the terminal thioester groups, be planar.

Now, to verify further the hypothesis of planarity being the prerequisite for tuberculostatic activity, we have forced the molecules to twist at the N—N bond as well, by substitution of one N atom with a methyl group [(F) in Scheme 1]. As expected, all type (F) compounds studied were inactive. We present here the crystal structures of three of them, (F1), (F2) and (F3) (Scheme 2).

The C1—N2—N3—C4 torsion angle is between -83 and -90° in the title compounds (Table 1). In similar structures not substituted at the N atoms [(E) in Scheme 1], the values of the C1—N2—N3—C4 torsion angle are distributed over a significantly wider range. We found four examples with the angle within 85–110°, two within 145–160° and six over 170° (Fig. 4a). This observation suggests that the antiperiplanar conformation along the N—N bond dominates and this is probably on active form [Meaning not clear]. At the same time, a moderate twist of 23–30° along the C4—C41(phenyl) bond (the N3—C4—C41—C42 torsion angle) is observed, in agreement with common values between 0 and 40° (average 20°) (Table 1 and Fig. 4b). In this respect it is of interest that some benzoyl derivatives of unsubstituted hydrazinedithioates (E) show significant tuberculostatic activity (Foks, 2011), suggesting that planarity of the hydrazinedithioate group is more important than that of the aryloyl one.

The molecular packing in (F1), (F2) and (F3) is determined mainly by intermolecular N3—H···O4 hydrogen bonds, which form infinite C(4) (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) chains parallel to the [100] direction for (F1) and (F2), and to the [001] direction for (F3). The numerical values of the hydrogen bonds are listed in Tables 2–4.

Related literature

For related literature, see: Bernstein et al. (1995); Bruker (2009); Etter (1990); Etter, MacDonald & Bernstein (1990); Foks (2011); Olczak et al. (2007, 2011); Sheldrick (2004, 2008b); Szczesio et al. (2011).

S2. Experimental

To N'-methylcarbohydrazide suspended in methanol, triethylamine and CS₂ were added and stirred at room temperature to dissolve. Next, the respective iodide was added and the mixtures were stirred for 1 h. After adding ice and acetic acid, the mixtures were cooled in an ice-bath and the oily precipitates were crystallized, filtered off, washed with water, dried and recrystallized from methanol [for (F1)] or a methanol–water mixture [Solvent ratio? for (F2)]. In the case of (F3), to an ethanol suspension of 3,4-dichlorobenzohydrazide, water, triethylamine and CS₂ were added and stirred at room temperature to dissolve. 1,3-Dibromopropane was then added and the mixture was stirred for 45 min. The precipitate was processed as described above and recrystallized from acetonitrile. [Please provide all quantities, or at least molar ratios, for all stages]

For (F3), the crystal used was found to exhibit nonmerohedral twinning, which was handled by a combination of CELL_NOW (Sheldrick, 2004) and TWINABS (Sheldrick, 2008b), with successive refinement of the unit-cell parameters by SAINT (Bruker, 2009). The refined twin scale factor was 0.416 (1) and the two components were related by 180° rotation around the c* axis.

S3. Refinement

H atoms were located in difference Fourier maps, and subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic C—H groups, 0.97 Å for secondary CH₂ groups and 0.96 Å for methyl groups, and N—H = 0.86 Å, with U_iso(H) = 1.2U_eq(C,N). The only exception was atom H3 in (F2), which was refined without any constraints.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (F1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (F2), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The molecular structure of (F3), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The planarity of (a) hydrazinedithioate and (b) benzoyl fragments in crystal structures deposited in the Cambridge Structural Database (CSD, Version 5.33; Allen, 2002).
	Fig. 5. The intermolecular hydrogen bonds in (F1) (dotted lines) determining the packing of molecules in the crystal structure. [Symmetry code: (i) x - 1, y, z.]
	Fig. 6. The intermolecular hydrogen bonds in (F2) (dotted lines) determining the packing of molecules in the crystal structure. [Symmetry code: (i) x - 1, y, z.]
	Fig. 7. The intermolecular hydrogen bonds in (F3) (dotted lines) determining the packing of molecules in the crystal structure. [Symmetry code: (i) x, -y + 3/2, z + 1/2.]

(F1) Methyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate

Crystal data

C10H10Cl2N2OS2	F(000) = 632
Mr = 309.22	Dx = 1.556 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7396 reflections
a = 4.5696 (3) Å	θ = 2.4–30.5°
b = 24.7384 (17) Å	µ = 0.79 mm^−1
c = 11.7638 (8) Å	T = 292 K
β = 96.940 (1)°	Needle, colourless
V = 1320.09 (15) Å^3	0.6 × 0.06 × 0.06 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1947 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −5→5
Tmin = 0.852, Tmax = 1	k = −29→29
14761 measured reflections	l = −13→13
2337 independent reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0399P)^2 + 0.4951P] where P = (Fo^2 + 2Fc^2)/3
2337 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.26 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
C1	0.9525 (5)	0.68563 (9)	0.77226 (19)	0.0417 (5)
C2	0.7006 (7)	0.69895 (11)	0.5760 (2)	0.0668 (8)
H2A	0.8355	0.6878	0.5239	0.100*
H2B	0.7237	0.7370	0.5910	0.100*
H2C	0.5022	0.6918	0.5426	0.100*
C4	0.7933 (4)	0.57437 (9)	0.65656 (17)	0.0363 (5)
C11	1.2264 (7)	0.67130 (13)	0.9941 (2)	0.0738 (8)
H11A	1.1410	0.7048	1.0151	0.111*
H11B	1.4107	0.6784	0.9656	0.111*
H11C	1.2592	0.6483	1.0601	0.111*
C41	0.6652 (4)	0.52118 (8)	0.68073 (17)	0.0350 (5)
C42	0.7192 (5)	0.47715 (9)	0.61316 (19)	0.0423 (5)
H42	0.8335	0.4815	0.5535	0.051*
C43	0.6057 (5)	0.42733 (9)	0.6335 (2)	0.0465 (5)
H43	0.6418	0.3982	0.5872	0.056*
C44	0.4382 (5)	0.42015 (9)	0.72222 (19)	0.0428 (5)
C45	0.3909 (5)	0.46361 (9)	0.79256 (18)	0.0400 (5)
C46	0.5022 (4)	0.51392 (9)	0.77104 (18)	0.0380 (5)
H46	0.4674	0.5430	0.8175	0.046*
Cl4	0.28831 (16)	0.35746 (2)	0.74307 (6)	0.0628 (2)
Cl5	0.19399 (15)	0.45590 (3)	0.90798 (6)	0.0623 (2)
N2	0.7621 (4)	0.66912 (7)	0.68263 (16)	0.0438 (4)
N3	0.6401 (4)	0.61809 (7)	0.68698 (17)	0.0434 (4)
H3	0.4684	0.6140	0.7088	0.052*
O4	1.0253 (3)	0.57952 (6)	0.61597 (14)	0.0464 (4)
S1	0.98179 (16)	0.63880 (3)	0.88581 (5)	0.0550 (2)
S2	1.13835 (16)	0.74260 (3)	0.77344 (7)	0.0649 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0384 (12)	0.0365 (11)	0.0524 (13)	0.0059 (9)	0.0142 (10)	−0.0012 (10)
C2	0.0759 (19)	0.0600 (17)	0.0615 (17)	0.0011 (14)	−0.0033 (14)	0.0181 (13)
C4	0.0286 (11)	0.0435 (12)	0.0362 (11)	−0.0004 (9)	0.0016 (9)	0.0005 (9)
C11	0.076 (2)	0.088 (2)	0.0540 (16)	0.0019 (17)	−0.0036 (14)	−0.0139 (15)
C41	0.0266 (10)	0.0412 (12)	0.0363 (11)	0.0011 (8)	−0.0005 (8)	0.0018 (9)
C42	0.0367 (12)	0.0508 (13)	0.0406 (12)	0.0022 (10)	0.0088 (10)	−0.0013 (10)
C43	0.0473 (13)	0.0417 (13)	0.0498 (13)	0.0021 (10)	0.0034 (11)	−0.0065 (10)
C44	0.0398 (12)	0.0392 (12)	0.0466 (13)	−0.0024 (9)	−0.0061 (10)	0.0063 (10)
C45	0.0334 (11)	0.0488 (12)	0.0370 (11)	−0.0018 (9)	0.0010 (9)	0.0081 (9)
C46	0.0337 (11)	0.0424 (12)	0.0372 (11)	0.0027 (9)	0.0018 (9)	−0.0006 (9)
Cl4	0.0719 (4)	0.0433 (3)	0.0705 (4)	−0.0125 (3)	−0.0016 (3)	0.0097 (3)
Cl5	0.0676 (4)	0.0712 (4)	0.0520 (4)	−0.0093 (3)	0.0228 (3)	0.0115 (3)
N2	0.0423 (11)	0.0370 (10)	0.0517 (11)	−0.0003 (8)	0.0049 (9)	0.0047 (8)
N3	0.0298 (9)	0.0407 (10)	0.0612 (12)	−0.0023 (8)	0.0116 (8)	0.0007 (8)
O4	0.0327 (8)	0.0515 (9)	0.0571 (10)	−0.0023 (7)	0.0138 (7)	0.0005 (7)
S1	0.0667 (4)	0.0510 (4)	0.0468 (4)	−0.0054 (3)	0.0043 (3)	0.0041 (3)
S2	0.0691 (5)	0.0424 (4)	0.0837 (5)	−0.0152 (3)	0.0118 (4)	−0.0016 (3)

Geometric parameters (Å, º)

C1—N2	1.347 (3)	C41—C46	1.381 (3)
C1—S2	1.645 (2)	C41—C42	1.388 (3)
C1—S1	1.761 (2)	C42—C43	1.369 (3)
C2—N2	1.453 (3)	C42—H42	0.9300
C2—H2A	0.9600	C43—C44	1.378 (3)
C2—H2B	0.9600	C43—H43	0.9300
C2—H2C	0.9600	C44—C45	1.389 (3)
C4—O4	1.221 (2)	C44—Cl4	1.725 (2)
C4—N3	1.360 (3)	C45—C46	1.379 (3)
C4—C41	1.482 (3)	C45—Cl5	1.728 (2)
C11—S1	1.782 (3)	C46—H46	0.9300
C11—H11A	0.9600	N2—N3	1.384 (2)
C11—H11B	0.9600	N3—H3	0.8600
C11—H11C	0.9600
N2—C1—S2	123.40 (17)	C43—C42—H42	119.7
N2—C1—S1	112.16 (16)	C41—C42—H42	119.7
S2—C1—S1	124.43 (14)	C42—C43—C44	120.3 (2)
N2—C2—H2A	109.5	C42—C43—H43	119.8
N2—C2—H2B	109.5	C44—C43—H43	119.8
H2A—C2—H2B	109.5	C43—C44—C45	119.5 (2)
N2—C2—H2C	109.5	C43—C44—Cl4	119.34 (18)
H2A—C2—H2C	109.5	C45—C44—Cl4	121.20 (18)
H2B—C2—H2C	109.5	C46—C45—C44	120.1 (2)
O4—C4—N3	121.27 (19)	C46—C45—Cl5	118.84 (17)
O4—C4—C41	123.34 (19)	C44—C45—Cl5	121.06 (17)
N3—C4—C41	115.33 (18)	C45—C46—C41	120.2 (2)
S1—C11—H11A	109.5	C45—C46—H46	119.9
S1—C11—H11B	109.5	C41—C46—H46	119.9
H11A—C11—H11B	109.5	C1—N2—N3	118.21 (18)
S1—C11—H11C	109.5	C1—N2—C2	124.1 (2)
H11A—C11—H11C	109.5	N3—N2—C2	117.30 (19)
H11B—C11—H11C	109.5	C4—N3—N2	119.57 (17)
C46—C41—C42	119.2 (2)	C4—N3—H3	120.2
C46—C41—C4	121.70 (19)	N2—N3—H3	120.2
C42—C41—C4	119.03 (19)	C1—S1—C11	103.25 (14)
C43—C42—C41	120.6 (2)
O4—C4—C41—C46	147.6 (2)	Cl5—C45—C46—C41	178.80 (16)
N3—C4—C41—C46	−29.9 (3)	C42—C41—C46—C45	−1.0 (3)
O4—C4—C41—C42	−30.1 (3)	C4—C41—C46—C45	−178.72 (19)
N3—C4—C41—C42	152.4 (2)	S2—C1—N2—N3	173.80 (15)
C46—C41—C42—C43	1.8 (3)	S1—C1—N2—N3	−5.3 (2)
C4—C41—C42—C43	179.62 (19)	S2—C1—N2—C2	0.9 (3)
C41—C42—C43—C44	−0.6 (3)	S1—C1—N2—C2	−178.19 (19)
C42—C43—C44—C45	−1.4 (3)	O4—C4—N3—N2	−6.4 (3)
C42—C43—C44—Cl4	177.96 (17)	C41—C4—N3—N2	171.10 (17)
C43—C44—C45—C46	2.3 (3)	C1—N2—N3—C4	−83.2 (3)
Cl4—C44—C45—C46	−177.12 (16)	C2—N2—N3—C4	90.2 (3)
C43—C44—C45—Cl5	−177.58 (17)	N2—C1—S1—C11	−177.00 (18)
Cl4—C44—C45—Cl5	3.0 (3)	S2—C1—S1—C11	3.89 (19)
C44—C45—C46—C41	−1.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.86	2.34	2.989 (2)	132

Symmetry code: (i) x−1, y, z.

(F2) Butyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate

Crystal data

C13H16Cl2N2OS2	F(000) = 728
Mr = 351.30	Dx = 1.451 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9381 reflections
a = 4.5467 (1) Å	θ = 2.2–35.1°
b = 13.7623 (4) Å	µ = 0.66 mm^−1
c = 25.7328 (7) Å	T = 100 K
β = 93.117 (1)°	Prism, colourless
V = 1607.80 (7) Å^3	0.4 × 0.2 × 0.2 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	6412 independent reflections
Radiation source: fine-focus sealed tube	5098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 33.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.659, Tmax = 0.747	k = −21→21
32865 measured reflections	l = −40→40

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.3873P] where P = (Fo^2 + 2Fc^2)/3
6412 reflections	(Δ/σ)max = 0.002
187 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.25 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
C1	0.5980 (2)	0.33828 (8)	0.25795 (4)	0.0176 (2)
C2	0.3197 (3)	0.25068 (9)	0.32407 (5)	0.0241 (2)
H2A	0.2996	0.1993	0.2989	0.036*
H2B	0.1317	0.2638	0.3378	0.036*
H2C	0.4569	0.2314	0.3518	0.036*
C4	0.5938 (2)	0.45312 (8)	0.36332 (4)	0.01535 (18)
C11	0.9228 (3)	0.43499 (11)	0.18530 (5)	0.0260 (3)
H11A	1.0828	0.4814	0.1842	0.031*
H11B	1.0084	0.3704	0.1873	0.031*
C12	0.7289 (3)	0.44336 (9)	0.13524 (5)	0.0223 (2)
H12A	0.8362	0.4183	0.1066	0.027*
H12B	0.5552	0.4033	0.1383	0.027*
C13	0.6327 (3)	0.54707 (9)	0.12279 (5)	0.0250 (2)
H13A	0.5274	0.5725	0.1516	0.030*
H13B	0.8063	0.5870	0.1193	0.030*
C14	0.4364 (3)	0.55489 (11)	0.07324 (5)	0.0313 (3)
H14A	0.5402	0.5308	0.0444	0.047*
H14B	0.3840	0.6217	0.0672	0.047*
H14C	0.2611	0.5172	0.0768	0.047*
C41	0.5219 (2)	0.54325 (8)	0.39186 (4)	0.01590 (18)
C42	0.6610 (2)	0.55652 (8)	0.44100 (4)	0.01747 (19)
H42	0.7901	0.5096	0.4548	0.021*
C43	0.6069 (3)	0.63963 (8)	0.46931 (4)	0.0184 (2)
C44	0.4163 (3)	0.71054 (8)	0.44832 (5)	0.0208 (2)
C45	0.2802 (3)	0.69772 (9)	0.39920 (5)	0.0241 (2)
H45	0.1538	0.7453	0.3853	0.029*
C46	0.3318 (3)	0.61422 (9)	0.37080 (5)	0.0203 (2)
H46	0.2402	0.6057	0.3379	0.024*
Cl3	0.78138 (7)	0.65278 (2)	0.530349 (11)	0.02526 (7)
Cl4	0.34931 (8)	0.81517 (2)	0.482620 (13)	0.03074 (8)
N2	0.4277 (2)	0.33803 (7)	0.29928 (4)	0.01746 (17)
N3	0.3865 (2)	0.42482 (7)	0.32589 (4)	0.01681 (17)
H3	0.213 (4)	0.4388 (13)	0.3291 (7)	0.038 (5)*
O4	0.82683 (17)	0.40938 (6)	0.37106 (3)	0.01932 (16)
S2	0.68028 (7)	0.23787 (2)	0.226379 (13)	0.02539 (7)
S1	0.72360 (6)	0.45670 (2)	0.243154 (11)	0.01984 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0137 (4)	0.0209 (5)	0.0179 (5)	0.0016 (4)	−0.0029 (3)	−0.0040 (4)
C2	0.0244 (5)	0.0189 (5)	0.0288 (6)	−0.0001 (4)	0.0010 (4)	0.0024 (4)
C4	0.0143 (4)	0.0181 (5)	0.0139 (4)	−0.0005 (4)	0.0027 (3)	−0.0005 (4)
C11	0.0188 (5)	0.0370 (7)	0.0227 (6)	−0.0012 (5)	0.0049 (4)	−0.0020 (5)
C12	0.0255 (5)	0.0237 (6)	0.0181 (5)	−0.0035 (4)	0.0057 (4)	−0.0043 (4)
C13	0.0330 (6)	0.0211 (6)	0.0214 (5)	−0.0061 (5)	0.0048 (5)	−0.0030 (4)
C14	0.0407 (7)	0.0298 (7)	0.0235 (6)	−0.0066 (6)	0.0019 (5)	0.0050 (5)
C41	0.0161 (4)	0.0166 (5)	0.0152 (4)	−0.0001 (4)	0.0029 (3)	−0.0003 (4)
C42	0.0182 (5)	0.0173 (5)	0.0169 (5)	0.0015 (4)	0.0012 (4)	−0.0009 (4)
C43	0.0219 (5)	0.0189 (5)	0.0147 (5)	−0.0021 (4)	0.0034 (4)	−0.0008 (4)
C44	0.0278 (6)	0.0146 (5)	0.0204 (5)	0.0002 (4)	0.0065 (4)	−0.0006 (4)
C45	0.0303 (6)	0.0167 (5)	0.0254 (6)	0.0053 (4)	0.0014 (5)	0.0024 (4)
C46	0.0236 (5)	0.0185 (5)	0.0188 (5)	0.0024 (4)	−0.0004 (4)	0.0012 (4)
Cl3	0.03500 (16)	0.02383 (14)	0.01667 (12)	−0.00193 (11)	−0.00111 (10)	−0.00418 (10)
Cl4	0.04676 (19)	0.01676 (13)	0.02938 (16)	0.00452 (12)	0.00828 (13)	−0.00475 (11)
N2	0.0165 (4)	0.0157 (4)	0.0201 (4)	0.0000 (3)	0.0003 (3)	−0.0038 (3)
N3	0.0122 (4)	0.0180 (4)	0.0201 (4)	0.0023 (3)	0.0000 (3)	−0.0043 (3)
O4	0.0151 (3)	0.0242 (4)	0.0185 (4)	0.0045 (3)	−0.0009 (3)	−0.0028 (3)
S2	0.02626 (14)	0.02478 (15)	0.02489 (15)	0.00528 (11)	−0.00095 (11)	−0.01001 (12)
S1	0.01900 (12)	0.02366 (14)	0.01677 (12)	−0.00289 (10)	0.00023 (9)	−0.00236 (10)

Geometric parameters (Å, º)

C1—N2	1.3493 (15)	C13—H13A	0.9700
C1—S2	1.6560 (11)	C13—H13B	0.9700
C1—S1	1.7749 (12)	C14—H14A	0.9600
C2—N2	1.4584 (16)	C14—H14B	0.9600
C2—H2A	0.9600	C14—H14C	0.9600
C2—H2B	0.9600	C41—C46	1.3940 (16)
C2—H2C	0.9600	C41—C42	1.3948 (15)
C4—O4	1.2255 (13)	C42—C43	1.3853 (15)
C4—N3	1.3670 (14)	C42—H42	0.9300
C4—C41	1.4869 (15)	C43—C44	1.3944 (17)
C11—C12	1.5250 (18)	C43—Cl3	1.7302 (11)
C11—S1	1.8090 (12)	C44—C45	1.3879 (18)
C11—H11A	0.9700	C44—Cl4	1.7247 (12)
C11—H11B	0.9700	C45—C46	1.3888 (17)
C12—C13	1.5218 (18)	C45—H45	0.9300
C12—H12A	0.9700	C46—H46	0.9300
C12—H12B	0.9700	N2—N3	1.3946 (13)
C13—C14	1.5200 (18)	N3—H3	0.821 (18)
N2—C1—S2	122.62 (9)	C13—C14—H14B	109.5
N2—C1—S1	112.12 (8)	H14A—C14—H14B	109.5
S2—C1—S1	125.25 (7)	C13—C14—H14C	109.5
N2—C2—H2A	109.5	H14A—C14—H14C	109.5
N2—C2—H2B	109.5	H14B—C14—H14C	109.5
H2A—C2—H2B	109.5	C46—C41—C42	120.11 (10)
N2—C2—H2C	109.5	C46—C41—C4	122.74 (10)
H2A—C2—H2C	109.5	C42—C41—C4	117.12 (10)
H2B—C2—H2C	109.5	C43—C42—C41	120.01 (10)
O4—C4—N3	122.09 (10)	C43—C42—H42	120.0
O4—C4—C41	122.75 (10)	C41—C42—H42	120.0
N3—C4—C41	115.08 (9)	C42—C43—C44	119.90 (10)
C12—C11—S1	112.99 (8)	C42—C43—Cl3	118.56 (9)
C12—C11—H11A	109.0	C44—C43—Cl3	121.54 (9)
S1—C11—H11A	109.0	C45—C44—C43	120.05 (11)
C12—C11—H11B	109.0	C45—C44—Cl4	119.32 (9)
S1—C11—H11B	109.0	C43—C44—Cl4	120.62 (9)
H11A—C11—H11B	107.8	C44—C45—C46	120.31 (11)
C13—C12—C11	113.27 (10)	C44—C45—H45	119.8
C13—C12—H12A	108.9	C46—C45—H45	119.8
C11—C12—H12A	108.9	C45—C46—C41	119.61 (11)
C13—C12—H12B	108.9	C45—C46—H46	120.2
C11—C12—H12B	108.9	C41—C46—H46	120.2
H12A—C12—H12B	107.7	C1—N2—N3	118.88 (9)
C14—C13—C12	113.08 (11)	C1—N2—C2	124.63 (10)
C14—C13—H13A	109.0	N3—N2—C2	115.71 (9)
C12—C13—H13A	109.0	C4—N3—N2	118.96 (9)
C14—C13—H13B	109.0	C4—N3—H3	119.5 (13)
C12—C13—H13B	109.0	N2—N3—H3	113.9 (13)
H13A—C13—H13B	107.8	C1—S1—C11	101.90 (6)
C13—C14—H14A	109.5
S1—C11—C12—C13	70.16 (13)	Cl4—C44—C45—C46	179.74 (10)
C11—C12—C13—C14	−179.28 (10)	C44—C45—C46—C41	−0.12 (18)
O4—C4—C41—C46	152.41 (11)	C42—C41—C46—C45	−0.52 (17)
N3—C4—C41—C46	−24.62 (15)	C4—C41—C46—C45	−178.47 (11)
O4—C4—C41—C42	−25.60 (16)	S2—C1—N2—N3	175.47 (8)
N3—C4—C41—C42	157.38 (10)	S1—C1—N2—N3	−3.49 (12)
C46—C41—C42—C43	1.01 (17)	S2—C1—N2—C2	6.06 (15)
C4—C41—C42—C43	179.07 (10)	S1—C1—N2—C2	−172.90 (9)
C41—C42—C43—C44	−0.86 (17)	O4—C4—N3—N2	6.65 (16)
C41—C42—C43—Cl3	179.43 (8)	C41—C4—N3—N2	−176.31 (9)
C42—C43—C44—C45	0.23 (18)	C1—N2—N3—C4	−83.82 (13)
Cl3—C43—C44—C45	179.93 (9)	C2—N2—N3—C4	86.52 (12)
C42—C43—C44—Cl4	−179.24 (9)	N2—C1—S1—C11	−176.88 (8)
Cl3—C43—C44—Cl4	0.46 (14)	S2—C1—S1—C11	4.19 (9)
C43—C44—C45—C46	0.26 (19)	C12—C11—S1—C1	89.50 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.821 (18)	2.149 (19)	2.8624 (12)	145.3 (17)

Symmetry code: (i) x−1, y, z.

(F3) 3,4-dichloro-N-(2-sulfanylidene-1,3-thiazinan-3-yl)benzamide

Crystal data

C11H10Cl2N2OS2	F(000) = 656
Mr = 321.23	Dx = 1.545 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 12303 reflections
a = 13.3534 (10) Å	θ = 3.4–69.3°
b = 11.6813 (8) Å	µ = 6.97 mm^−1
c = 8.9908 (7) Å	T = 290 K
β = 99.995 (3)°	Needle, colourless
V = 1381.15 (18) Å^3	0.6 × 0.02 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3801 independent reflections
Radiation source: fine-focus sealed tube	3652 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 69.7°, θmin = 3.4°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008b)	h = −16→15
Tmin = 0.447, Tmax = 0.753	k = 0→14
3801 measured reflections	l = 0→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0535P)^2 + 0.3664P] where P = (Fo^2 + 2Fc^2)/3
3801 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.36 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
C1	0.44936 (11)	0.10160 (12)	0.27872 (17)	0.0325 (3)
C4	0.27875 (13)	0.23257 (13)	0.4140 (2)	0.0314 (3)
C11	0.64722 (13)	0.10597 (15)	0.4559 (2)	0.0509 (4)
H11A	0.6396	0.0782	0.5550	0.061*
H11B	0.7171	0.0932	0.4437	0.061*
C12	0.62462 (15)	0.23183 (16)	0.4458 (3)	0.0488 (5)
H12A	0.6362	0.2604	0.3489	0.059*
H12B	0.6708	0.2716	0.5241	0.059*
C13	0.51648 (16)	0.25741 (13)	0.4632 (3)	0.0441 (5)
H13A	0.5063	0.2321	0.5622	0.053*
H13B	0.5060	0.3396	0.4579	0.053*
C41	0.18032 (11)	0.29693 (13)	0.37860 (17)	0.0348 (3)
C42	0.09696 (16)	0.24998 (13)	0.4273 (3)	0.0438 (5)
H42	0.1031	0.1807	0.4789	0.053*
C43	0.00396 (13)	0.30597 (18)	0.3993 (2)	0.0531 (5)
C44	−0.00520 (13)	0.40949 (18)	0.3244 (2)	0.0550 (5)
C45	0.07894 (16)	0.45765 (17)	0.2777 (3)	0.0580 (5)
H45	0.0730	0.5276	0.2275	0.070*
C46	0.17166 (13)	0.40200 (15)	0.3055 (2)	0.0464 (4)
H46	0.2283	0.4350	0.2753	0.056*
Cl3	−0.09901 (5)	0.24448 (6)	0.46258 (15)	0.0938 (3)
Cl4	−0.12079 (4)	0.47972 (6)	0.28823 (9)	0.0856 (2)
N2	0.44045 (9)	0.20211 (11)	0.34791 (14)	0.0334 (3)
N3	0.34589 (12)	0.25613 (10)	0.3215 (2)	0.0346 (3)
H3	0.3306	0.3035	0.2479	0.042*
O4	0.29657 (8)	0.16518 (9)	0.51921 (12)	0.0380 (2)
S1	0.56318 (3)	0.02626 (3)	0.31259 (6)	0.04931 (14)
S2	0.35775 (3)	0.04147 (3)	0.15478 (5)	0.04419 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0291 (7)	0.0333 (7)	0.0366 (7)	0.0011 (5)	0.0098 (6)	0.0059 (6)
C4	0.0269 (8)	0.0339 (7)	0.0331 (8)	0.0023 (6)	0.0044 (7)	−0.0033 (6)
C11	0.0305 (8)	0.0501 (10)	0.0687 (12)	0.0041 (7)	−0.0010 (8)	0.0027 (9)
C12	0.0335 (10)	0.0505 (9)	0.0615 (13)	−0.0016 (7)	0.0058 (9)	0.0005 (9)
C13	0.0338 (10)	0.0467 (10)	0.0505 (12)	0.0016 (6)	0.0038 (10)	−0.0101 (7)
C41	0.0280 (7)	0.0403 (8)	0.0357 (7)	0.0054 (6)	0.0041 (6)	−0.0027 (6)
C42	0.0330 (10)	0.0474 (11)	0.0513 (12)	0.0037 (6)	0.0084 (10)	0.0031 (6)
C43	0.0285 (8)	0.0663 (12)	0.0654 (12)	0.0026 (8)	0.0106 (8)	−0.0050 (10)
C44	0.0351 (9)	0.0661 (11)	0.0621 (11)	0.0195 (8)	0.0036 (8)	−0.0032 (9)
C45	0.0510 (11)	0.0531 (11)	0.0697 (13)	0.0190 (9)	0.0101 (10)	0.0120 (9)
C46	0.0396 (9)	0.0462 (9)	0.0558 (10)	0.0104 (7)	0.0148 (7)	0.0083 (8)
Cl3	0.0369 (3)	0.1055 (6)	0.1458 (9)	−0.0012 (2)	0.0350 (5)	0.0146 (4)
Cl4	0.0453 (3)	0.1012 (5)	0.1079 (5)	0.0392 (3)	0.0065 (3)	0.0062 (4)
N2	0.0250 (6)	0.0375 (7)	0.0382 (7)	0.0060 (5)	0.0066 (5)	−0.0012 (5)
N3	0.0297 (8)	0.0386 (7)	0.0364 (8)	0.0108 (4)	0.0081 (7)	0.0058 (4)
O4	0.0367 (5)	0.0413 (6)	0.0362 (6)	0.0068 (4)	0.0068 (4)	0.0048 (5)
S1	0.0348 (2)	0.0404 (2)	0.0711 (3)	0.01133 (16)	0.0045 (2)	−0.00761 (19)
S2	0.0397 (2)	0.0396 (2)	0.0507 (2)	−0.00385 (15)	0.00070 (17)	−0.00315 (16)

Geometric parameters (Å, º)

C1—N2	1.3437 (19)	C13—H13B	0.9700
C1—S2	1.6608 (15)	C41—C42	1.378 (3)
C1—S1	1.7369 (14)	C41—C46	1.387 (2)
C4—O4	1.222 (2)	C42—C43	1.387 (3)
C4—N3	1.353 (2)	C42—H42	0.9300
C4—C41	1.500 (2)	C43—C44	1.379 (3)
C11—C12	1.500 (3)	C43—Cl3	1.7326 (19)
C11—S1	1.8121 (19)	C44—C45	1.385 (3)
C11—H11A	0.9700	C44—Cl4	1.7283 (17)
C11—H11B	0.9700	C45—C46	1.382 (3)
C12—C13	1.509 (3)	C45—H45	0.9300
C12—H12A	0.9700	C46—H46	0.9300
C12—H12B	0.9700	N2—N3	1.3946 (18)
C13—N2	1.469 (2)	N3—H3	0.8600
C13—H13A	0.9700
N2—C1—S2	124.48 (11)	C42—C41—C4	117.35 (15)
N2—C1—S1	120.44 (11)	C46—C41—C4	122.82 (14)
S2—C1—S1	115.06 (9)	C41—C42—C43	120.11 (17)
O4—C4—N3	123.10 (15)	C41—C42—H42	119.9
O4—C4—C41	122.23 (15)	C43—C42—H42	119.9
N3—C4—C41	114.67 (14)	C44—C43—C42	120.18 (17)
C12—C11—S1	111.56 (14)	C44—C43—Cl3	121.04 (14)
C12—C11—H11A	109.3	C42—C43—Cl3	118.78 (16)
S1—C11—H11A	109.3	C43—C44—C45	119.75 (16)
C12—C11—H11B	109.3	C43—C44—Cl4	120.59 (15)
S1—C11—H11B	109.3	C45—C44—Cl4	119.66 (16)
H11A—C11—H11B	108.0	C46—C45—C44	120.15 (18)
C11—C12—C13	111.95 (15)	C46—C45—H45	119.9
C11—C12—H12A	109.2	C44—C45—H45	119.9
C13—C12—H12A	109.2	C45—C46—C41	120.01 (17)
C11—C12—H12B	109.2	C45—C46—H46	120.0
C13—C12—H12B	109.2	C41—C46—H46	120.0
H12A—C12—H12B	107.9	C1—N2—N3	117.84 (13)
N2—C13—C12	113.37 (17)	C1—N2—C13	127.24 (13)
N2—C13—H13A	108.9	N3—N2—C13	114.56 (13)
C12—C13—H13A	108.9	C4—N3—N2	118.72 (14)
N2—C13—H13B	108.9	C4—N3—H3	120.6
C12—C13—H13B	108.9	N2—N3—H3	120.6
H13A—C13—H13B	107.7	C1—S1—C11	106.23 (8)
C42—C41—C46	119.78 (15)
S1—C11—C12—C13	58.7 (2)	C44—C45—C46—C41	0.9 (3)
C11—C12—C13—N2	−59.7 (3)	C42—C41—C46—C45	−1.9 (3)
O4—C4—C41—C42	−23.8 (2)	C4—C41—C46—C45	−179.24 (18)
N3—C4—C41—C42	156.85 (16)	S2—C1—N2—N3	4.38 (19)
O4—C4—C41—C46	153.55 (17)	S1—C1—N2—N3	−177.16 (11)
N3—C4—C41—C46	−25.8 (2)	S2—C1—N2—C13	177.03 (14)
C46—C41—C42—C43	1.9 (3)	S1—C1—N2—C13	−4.5 (2)
C4—C41—C42—C43	179.37 (18)	C12—C13—N2—C1	31.3 (3)
C41—C42—C43—C44	−0.8 (3)	C12—C13—N2—N3	−155.80 (16)
C41—C42—C43—Cl3	−179.85 (16)	O4—C4—N3—N2	−0.7 (2)
C42—C43—C44—C45	−0.2 (3)	C41—C4—N3—N2	178.64 (13)
Cl3—C43—C44—C45	178.75 (18)	C1—N2—N3—C4	90.28 (19)
C42—C43—C44—Cl4	179.72 (17)	C13—N2—N3—C4	−83.29 (18)
Cl3—C43—C44—Cl4	−1.3 (3)	N2—C1—S1—C11	3.77 (15)
C43—C44—C45—C46	0.2 (3)	S2—C1—S1—C11	−177.62 (9)
Cl4—C44—C45—C46	−179.74 (17)	C12—C11—S1—C1	−30.38 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.86	2.06	2.837 (2)	150

Symmetry code: (i) x, −y+1/2, z−1/2.