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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.
Supporting information
CCDC references: 906566; 906567; 906568
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.
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 Uiso(H) = 1.2Ueq(C,N).
The only exception was atom H3 in (F2), which was refined without any
constraints.
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).
(F1) Methyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate
top
Crystal data top
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) Å3 | 0.6 × 0.06 × 0.06 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.4951P] where P = (Fo2 + 2Fc2)/3 |
2337 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C10H10Cl2N2OS2 | V = 1320.09 (15) Å3 |
Mr = 309.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.5696 (3) Å | µ = 0.79 mm−1 |
b = 24.7384 (17) Å | T = 292 K |
c = 11.7638 (8) Å | 0.6 × 0.06 × 0.06 mm |
β = 96.940 (1)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 2337 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1947 reflections with I > 2σ(I) |
Tmin = 0.852, Tmax = 1 | Rint = 0.048 |
14761 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.25 e Å−3 |
2337 reflections | Δρmin = −0.26 e Å−3 |
156 parameters | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.86 | 2.34 | 2.989 (2) | 132 |
Symmetry code: (i) x−1, y, z. |
(F2) Butyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate
top
Crystal data top
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) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.3873P] where P = (Fo2 + 2Fc2)/3 |
6412 reflections | (Δ/σ)max = 0.002 |
187 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C13H16Cl2N2OS2 | V = 1607.80 (7) Å3 |
Mr = 351.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.5467 (1) Å | µ = 0.66 mm−1 |
b = 13.7623 (4) Å | T = 100 K |
c = 25.7328 (7) Å | 0.4 × 0.2 × 0.2 mm |
β = 93.117 (1)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 6412 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5098 reflections with I > 2σ(I) |
Tmin = 0.659, Tmax = 0.747 | Rint = 0.038 |
32865 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.50 e Å−3 |
6412 reflections | Δρmin = −0.25 e Å−3 |
187 parameters | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 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
top
Crystal data top
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) Å3 | 0.6 × 0.02 × 0.02 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0535P)2 + 0.3664P] where P = (Fo2 + 2Fc2)/3 |
3801 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C11H10Cl2N2OS2 | V = 1381.15 (18) Å3 |
Mr = 321.23 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.3534 (10) Å | µ = 6.97 mm−1 |
b = 11.6813 (8) Å | T = 290 K |
c = 8.9908 (7) Å | 0.6 × 0.02 × 0.02 mm |
β = 99.995 (3)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3801 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008b) | 3652 reflections with I > 2σ(I) |
Tmin = 0.447, Tmax = 0.753 | Rint = 0.041 |
3801 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
3801 reflections | Δρmin = −0.36 e Å−3 |
164 parameters | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.86 | 2.06 | 2.837 (2) | 150 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
| (F1) | (F2) | (F3) |
Crystal data |
Chemical formula | C10H10Cl2N2OS2 | C13H16Cl2N2OS2 | C11H10Cl2N2OS2 |
Mr | 309.22 | 351.30 | 321.23 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 292 | 100 | 290 |
a, b, c (Å) | 4.5696 (3), 24.7384 (17), 11.7638 (8) | 4.5467 (1), 13.7623 (4), 25.7328 (7) | 13.3534 (10), 11.6813 (8), 8.9908 (7) |
β (°) | 96.940 (1) | 93.117 (1) | 99.995 (3) |
V (Å3) | 1320.09 (15) | 1607.80 (7) | 1381.15 (18) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.79 | 0.66 | 6.97 |
Crystal size (mm) | 0.6 × 0.06 × 0.06 | 0.4 × 0.2 × 0.2 | 0.6 × 0.02 × 0.02 |
|
Data collection |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (TWINABS; Sheldrick, 2008b) |
Tmin, Tmax | 0.852, 1 | 0.659, 0.747 | 0.447, 0.753 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14761, 2337, 1947 | 32865, 6412, 5098 | 3801, 3801, 3652 |
Rint | 0.048 | 0.038 | 0.041 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.089, 1.06 | 0.034, 0.083, 1.04 | 0.034, 0.095, 1.05 |
No. of reflections | 2337 | 6412 | 3801 |
No. of parameters | 156 | 187 | 164 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.26 | 0.50, −0.25 | 0.32, −0.36 |
Hydrogen-bond geometry (Å, º) for (F1) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.86 | 2.34 | 2.989 (2) | 132.2 |
Symmetry code: (i) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (F2) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.821 (18) | 2.149 (19) | 2.8624 (12) | 145.3 (17) |
Symmetry code: (i) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (F3) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.86 | 2.06 | 2.837 (2) | 149.8 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Selected torsion angles (°) topStructure | S1—C1—N2—N3 | C1—N2—N3—C4 | N2—N3—C4—C41 | O4—C4—C41—C42 |
(F1) | -5.3 (2) | -83.2 (3) | 171.10 (17) | -30.1 (3) |
(F2) | -3.49 (12) | -83.82 (13) | -176.31 (9) | -25.60 (16) |
(F3) | -177.16 (11) | 90.28 (19) | 178.64 (13) | -23.8 (2) |
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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.