Planarity of benzoylhydrazinedithiocarbazoate tuberculostatics. I. N′-Methyl-substituted 3,4-dichlorobenzoyl monoesters

Article abstract of DOI:10.1107/S0108270112036001

Methyl 2-(3,4-dichloro-benzoyl)-1-methylhydrazinecarbodithio-ate, C ₁₀H₁₀Cl₂N₂OS₂, (F1), butyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithio-ate, C ₁₃H₁₆Cl₂N₂OS₂, (F2), and 3,4-dichloro-N-(2-sulfanylidene-1,3-thia-zinan-3-yl)benz-amide, C ₁₁H₁₀Cl₂N₂OS₂, (F3), were studied by X-ray diffraction to test our hypothesis that planarity of aryl - oylhydrazinedithio-carbazic 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 hydrazine-dithio-ate fragment is more important for tuberculostatic activity than planarity of the aryloyl group.

Full text of DOI:10.1107/S0108270112036001

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
(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.
ISSN 0108-2701
Planarity of benzoylhydrazine–
dithiocarbazoate tuberculostatics. I.
N0-Methyl-substituted 3,4-dichloro-
benzoyl monoesters
Małgorzata Szczesio,a Andrzej Olczak,a Katarzyna
b
b
a
´
Gobis, Henryk Foks and Marek L. Głowka *
aInstitute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University
of Technology, Poland, and bDepartment of Organic Chemistry, Medical University
´
of Gdansk, Poland
Correspondence e-mail: marek.glowka@p.lodz.pl
Received 12 June 2012
Accepted 15 August 2012
Online 1 September 2012
Methyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodi-
thioate, C10H10Cl2N2OS2, (F1), butyl 2-(3,4-dichloroben-
zoyl)-1-methylhydrazinecarbodithioate, C13H16Cl2N2OS2, (F2),
and 3,4-dichloro-N-(2-sulfanylidene-1,3-thiazinan-3-yl)benz-
amide, C11H10Cl2N2OS2, (F3), were studied by X-ray diffrac-
tion to test our hypothesis that planarity of aryloylhydra-
zinedithiocarbazic acid esters is a prerequisite for tuberculo-
static 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 85ꢀ, results from repulsion caused by a methyl
substituent at the N0 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 (25–30ꢀ) 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.
Now, to test 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, viz. (F1),
(F2) and (F3) (Scheme 2).
Comment
Our earlier studies of compounds containing a pyrazine ring
with an N atom in the ortho position suggested that the N—
Hꢁ ꢁ ꢁN(ortho) intramolecular contact [see (A), (B), (C1) and
(C2) 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
The absolute value of the C1—N2—N3—C4 torsion angle is
between 83.2 (3) and 90.28 (19)ꢀ 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 in the range 85–110ꢀ, two
Acta Cryst. (2012). C68, o373–o376
doi:10.1107/S0108270112036001
# 2012 International Union of Crystallography o373

organic compounds
Figure 1
The molecular structure of (F1), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 2
The molecular structure of (F2), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 4
Distributions of the torsion angles (a) C1—N2—N3—C4 and (b) N3—
C4—C41—C42 in crystal structures deposited in the Cambridge
Structural Database (CSD, Version 5.33; Allen, 2002).
The molecular packing in (F1), (F2) and (F3) is determined
mainly by intermolecular N3—Hꢁ ꢁ ꢁ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.
Figure 3
The molecular structure of (F3), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
in the range 145–160ꢀ and six over 170ꢀ (Fig. 4a). This
observation suggests that the antiperiplanar conformation
along the N—N bond dominates and this is probably an active
form. At the same time, a moderate twist of 23–30ꢀ along the
C4—C41(phenyl) bond (the N3—C4—C41—C42 torsion
angle) is observed, in agreement with common values between
0 and 40ꢀ (average 20ꢀ) (Table 1 and Fig. 4b). In this respect, it
is of interest that some benzoyl derivatives of unsubstituted
hydrazinedithioates [(E) in Scheme 1] show significant
tuberculostatic activity (Foks, 2011), suggesting that planarity
of the hydrazinedithioate group is more important than that of
the aryloyl one.
Experimental
To 3,4-dichloro-N0-methylbenzohydrazide suspended in methanol,
triethylamine and CS2 were added and stirred at room temperature
until fully dissolved. 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 from a methanol–water mixture (1:1 v/v)
[for (F2)]. In the case of (F3), water, triethylamine and CS2 were
added to an ethanol suspension of 3,4-dichlorobenzohydrazide and
the resulting mixture stirred at room temperature until fully
dissolved. 1,3-Dibromopropane was then added and the mixture
ꢂ
o374 Szczesio et al. C10H10Cl2N2OS2 and two analogues
Acta Cryst. (2012). C68, o373–o376

organic compounds
Table 1
Selected torsion angles (ꢀ).
S1—C1—
N2—N3
C1—N2—
N3—C4
N2—N3—
C4—C41
O4—C4—
C41—C42
(F1)
(F2)
(F3)
ꢃ5.3 (2)
ꢃ3.49 (12)
ꢃ177.16 (11)
ꢃ83.2 (3)
ꢃ83.82 (13)
90.28 (19)
171.10 (17)
ꢃ176.31 (9)
178.64 (13)
ꢃ30.1 (3)
ꢃ25.60 (16)
ꢃ23.8 (2)
Table 2
Hydrogen-bond geometry (A, ) for (F1).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
N3—H3ꢁ ꢁ ꢁO4i
Symmetry code: (i) x ꢃ 1; y; z.
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
Figure 5
0.86
2.34
2.989 (2)
132
The intermolecular hydrogen bonds in (F1) (dotted lines) determining
the packing of molecules in the crystal structure. [Symmetry code: (i)
x ꢃ 1, y, z.]
Compound (F1)
Crystal data
3
˚
C10H10Cl2N2OS2
Mr = 309.22
V = 1320.09 (15) A
Z = 4
Monoclinic, P21=c
Mo Kꢁ radiation
ꢂ = 0.79 mmꢃ1
T = 292 K
0.6 ꢄ 0.06 ꢄ 0.06 mm
˚
a = 4.5696 (3) A
˚
b = 24.7384 (17) A
˚
c = 11.7638 (8) A
ꢀ = 96.940 (1)ꢀ
Figure 6
Data collection
The intermolecular hydrogen bonds in (F2) (dotted lines) determining
the packing of molecules in the crystal structure. [Symmetry code: (i)
x ꢃ 1, y, z.]
Bruker SMART APEXII CCD
area-detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.852, Tmax = 1.000
14761 measured reflections
2337 independent reflections
1947 reflections with I > 2ꢃ(I)
Rint = 0.048
Refinement
R[F2 > 2ꢃ(F2)] = 0.034
wR(F2) = 0.089
S = 1.06
156 parameters
H-atom parameteꢃrs3 constrained
˚
Áꢄmax = 0.25 e A
ꢃ3
˚
2337 reflections
Áꢄmin = ꢃ0.26 e A
Compound (F2)
Crystal data
3
˚
V = 1607.80 (7) A
Z = 4
C13H16Cl2N2OS2
Mr = 351.30
Monoclinic, P21=n
Mo Kꢁ radiation
ꢂ = 0.66 mmꢃ1
T = 100 K
0.4 ꢄ 0.2 ꢄ 0.2 mm
˚
a = 4.5467 (1) A
b = 13.7623 (4) A
˚
˚
c = 25.7328 (7) A
ꢀ = 93.117 (1)ꢀ
Figure 7
The intermolecular hydrogen bonds in (F3) (dotted lines) determining
Data collection
the packing of molecules in the crystal structure. [Symmetry code: (i) x,
3
1
Bruker SMART APEXII CCD
area-detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.659, Tmax = 0.747
32865 measured reflections
6412 independent reflections
5098 reflections with I > 2ꢃ(I)
Rint = 0.038
ꢃy + , z + .]
2
2
stirred for 45 min. The precipitate was processed as described above
and recrystallized from acetonitrile.
For (F3), the crystal used exhibited 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 180ꢀ rotation around the c* axis.
Refinement
R[F2 > 2ꢃ(F2)] = 0.034
wR(F2) = 0.083
S = 1.04
6412 reflections
187 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢄmax = 0.50 e A
ꢃ3
˚
Áꢄmin = ꢃ0.25 e A
ꢂ
Acta Cryst. (2012). C68, o373–o376
Szczesio et al.
C10H10Cl2N2OS2 and two analogues o375

organic compounds
˚
for aromatic C—H groups, 0.97 A for secondary CH2 groups and
Table 3
Hydrogen-bond geometry (A, ) for (F2).
ꢀ
˚
˚
˚
0.96 A for methyl groups, and N—H = 0.86 A, with Uiso(H) =
1.2Ueq(C,N) or 1.5Ueq(C) for methyl groups. 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; 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 publica-
tion: PLATON.
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N3—H3ꢁ ꢁ ꢁO4i
0.821 (18)
2.149 (19)
2.8624 (12)
145.3 (17)
Symmetry code: (i) x ꢃ 1; y; z.
Table 4
Hydrogen-bond geometry (A, ) for (F3).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N3—H3ꢁ ꢁ ꢁO4i
Symmetry code: (i) x; ꢃy þ ; z ꢃ .
0.86
2.06
2.837 (2)
150
This study was supported by the Ministry of Science and
Higher Education under project No. N204 111735.
1
2
1
2
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OV3016). Services for accessing these data are
described at the back of the journal.
Compound (F3)
Crystal data
3
˚
C11H10Cl2N2OS2
Mr = 321.23
V = 1381.15 (18) A
Z = 4
References
Monoclinic, P21=c
Cu Kꢁ radiation
ꢂ = 6.97 mmꢃ1
T = 290 K
0.6 ꢄ 0.02 ꢄ 0.02 mm
˚
a = 13.3534 (10) A
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bruker (2002). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2009). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–
262.
Foks, H. (2011). Personal communication.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,
P. A. (2008). J. Appl. Cryst. 41, 466–470.
˚
b = 11.6813 (8) A
˚
c = 8.9908 (7) A
ꢀ = 99.995 (3)ꢀ
Data collection
Bruker SMART APEXII CCD
area-detector diffractometer
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2008b)
Tmin = 0.447, Tmax = 0.753
3801 measured reflections
3801 independent reflections
3652 reflections with I > 2ꢃ(I)
Rint = 0.041
´
Olczak, A., Glowka, M. L., Golka, J., Szczesio, M., Bojarska, J., Kozlowska, K.,
Foks, H. & Orlewska, C. (2007). J. Mol. Struct. 830, 171–175.
Refinement
Olczak, A., Szczesio, M., Gołka, J., Orlewska, C., Gobis, K., Foks, H. &
´
R[F2 > 2ꢃ(F2)] = 0.034
wR(F2) = 0.095
S = 1.05
164 parameters
H-atom parameteꢃrs3 constrained
Głowka, M. L. (2011). Acta Cryst. C67, o37–o42.
Sheldrick, G. M. (2003). SADABS. University of Go¨ttingen, Germany.
¨
Sheldrick, G. M. (2004). CELL_NOW. University of Gottingen, Germany.
˚
Áꢄmax = 0.32 e A
ꢃ3
˚
3801 reflections
Áꢄmin = ꢃ0.36 e A
Sheldrick, G. M. (2008a). Acta Cryst. A64, 112–122.
Sheldrick, G. M. (2008b). TWINABS. University of Gottingen, Germany.
¨
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Szczesio, M., Olczak, A., Gołka, J., Gobis, K., Foks, H. & Głowka, M. L. (2011).
Acta Cryst. C67, o235–o240.
H atoms could be located in difference Fourier maps, but were
˚
placed geometrically and refined as riding atoms, with C—H = 0.95 A
´
ꢂ
o376 Szczesio et al. C10H10Cl2N2OS2 and two analogues
Acta Cryst. (2012). C68, o373–o376

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o373–o376 [doi:10.1107/S0108270112036001]
Planarity of benzoylhydrazine–dithiocarbazoate tuberculostatics. I. N′-Methyl-
substituted 3,4-dichlorobenzoyl monoesters
Małgorzata Szczesio, Andrzej Olczak, Katarzyna Gobis, Henryk Foks and Marek L. Główka
(F1) Methyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate
Crystal data
C10H10Cl2N2OS2
Mr = 309.22
F(000) = 632
Dx = 1.556 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7396 reflections
θ = 2.4–30.5°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 4.5696 (3) Å
b = 24.7384 (17) Å
c = 11.7638 (8) Å
β = 96.940 (1)°
V = 1320.09 (15) Å3
Z = 4
µ = 0.79 mm−1
T = 292 K
Needle, colourless
0.6 × 0.06 × 0.06 mm
Data collection
Bruker SMART APEXII CCD area-detector
diffractometer
Graphite monochromator
ω scans
2337 independent reflections
1947 reflections with I > 2σ(I)
Rint = 0.048
θ
max = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = −5→5
k = −29→29
l = −13→13
T
min = 0.852, Tmax = 1
14761 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.089
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.06
2337 reflections
156 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0399P)2 + 0.4951P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.25 e Å−3
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.
Acta Cryst. (2012). C68, o373–o376
sup-1

supplementary materials
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)
x
y
z
Uiso*/Ueq
C1
0.9525 (5)
0.7006 (7)
0.8355
0.68563 (9)
0.69895 (11)
0.6878
0.77226 (19)
0.5760 (2)
0.5239
0.0417 (5)
0.0668 (8)
0.100*
C2
H2A
H2B
H2C
C4
0.7237
0.7370
0.5910
0.100*
0.5022
0.6918
0.5426
0.100*
0.7933 (4)
1.2264 (7)
1.1410
0.57437 (9)
0.67130 (13)
0.7048
0.65656 (17)
0.9941 (2)
1.0151
0.0363 (5)
0.0738 (8)
0.111*
C11
H11A
H11B
H11C
C41
C42
H42
C43
H43
C44
C45
C46
H46
Cl4
1.4107
0.6784
0.9656
0.111*
1.2592
0.6483
1.0601
0.111*
0.6652 (4)
0.7192 (5)
0.8335
0.52118 (8)
0.47715 (9)
0.4815
0.68073 (17)
0.61316 (19)
0.5535
0.0350 (5)
0.0423 (5)
0.051*
0.6057 (5)
0.6418
0.42733 (9)
0.3982
0.6335 (2)
0.5872
0.0465 (5)
0.056*
0.4382 (5)
0.3909 (5)
0.5022 (4)
0.4674
0.42015 (9)
0.46361 (9)
0.51392 (9)
0.5430
0.72222 (19)
0.79256 (18)
0.77104 (18)
0.8175
0.0428 (5)
0.0400 (5)
0.0380 (5)
0.046*
0.28831 (16)
0.19399 (15)
0.7621 (4)
0.6401 (4)
0.4684
0.35746 (2)
0.45590 (3)
0.66912 (7)
0.61809 (7)
0.6140
0.74307 (6)
0.90798 (6)
0.68263 (16)
0.68698 (17)
0.7088
0.0628 (2)
0.0623 (2)
0.0438 (4)
0.0434 (4)
0.052*
Cl5
N2
N3
H3
O4
1.0253 (3)
0.98179 (16)
1.13835 (16)
0.57952 (6)
0.63880 (3)
0.74260 (3)
0.61597 (14)
0.88581 (5)
0.77344 (7)
0.0464 (4)
0.0550 (2)
0.0649 (2)
S1
S2
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
0.0384 (12)
0.0759 (19)
0.0286 (11)
0.076 (2)
0.0365 (11)
0.0600 (17)
0.0435 (12)
0.088 (2)
0.0524 (13)
0.0059 (9)
0.0011 (14)
−0.0004 (9)
0.0019 (17)
0.0011 (8)
0.0142 (10)
−0.0033 (14)
0.0016 (9)
−0.0012 (10)
0.0181 (13)
0.0005 (9)
C2
0.0615 (17)
0.0362 (11)
0.0540 (16)
0.0363 (11)
0.0406 (12)
0.0498 (13)
0.0466 (13)
0.0370 (11)
0.0372 (11)
0.0705 (4)
C4
C11
C41
C42
C43
C44
C45
C46
Cl4
−0.0036 (14)
−0.0005 (8)
0.0088 (10)
0.0034 (11)
−0.0061 (10)
0.0010 (9)
−0.0139 (15)
0.0018 (9)
0.0266 (10)
0.0367 (12)
0.0473 (13)
0.0398 (12)
0.0334 (11)
0.0337 (11)
0.0719 (4)
0.0412 (12)
0.0508 (13)
0.0417 (13)
0.0392 (12)
0.0488 (12)
0.0424 (12)
0.0433 (3)
0.0022 (10)
0.0021 (10)
−0.0024 (9)
−0.0018 (9)
0.0027 (9)
−0.0125 (3)
−0.0013 (10)
−0.0065 (10)
0.0063 (10)
0.0081 (9)
0.0018 (9)
−0.0006 (9)
0.0097 (3)
−0.0016 (3)
Acta Cryst. (2012). C68, o373–o376
sup-2

supplementary materials
Cl5
N2
N3
O4
S1
0.0676 (4)
0.0423 (11)
0.0298 (9)
0.0327 (8)
0.0667 (4)
0.0691 (5)
0.0712 (4)
0.0370 (10)
0.0407 (10)
0.0515 (9)
0.0510 (4)
0.0424 (4)
0.0520 (4)
0.0517 (11)
0.0612 (12)
0.0571 (10)
0.0468 (4)
0.0837 (5)
−0.0093 (3)
−0.0003 (8)
−0.0023 (8)
−0.0023 (7)
−0.0054 (3)
−0.0152 (3)
0.0228 (3)
0.0049 (9)
0.0116 (8)
0.0138 (7)
0.0043 (3)
0.0118 (4)
0.0115 (3)
0.0047 (8)
0.0007 (8)
0.0005 (7)
0.0041 (3)
−0.0016 (3)
S2
Geometric parameters (Å, º)
C1—N2
1.347 (3)
C41—C46
1.381 (3)
C1—S2
1.645 (2)
1.761 (2)
1.453 (3)
0.9600
C41—C42
C42—C43
C42—H42
C43—C44
C43—H43
C44—C45
C44—Cl4
C45—C46
C45—Cl5
C46—H46
N2—N3
1.388 (3)
1.369 (3)
0.9300
C1—S1
C2—N2
C2—H2A
C2—H2B
C2—H2C
C4—O4
1.378 (3)
0.9300
0.9600
0.9600
1.389 (3)
1.725 (2)
1.379 (3)
1.728 (2)
0.9300
1.221 (2)
1.360 (3)
1.482 (3)
1.782 (3)
0.9600
C4—N3
C4—C41
C11—S1
C11—H11A
C11—H11B
C11—H11C
1.384 (2)
0.8600
0.9600
N3—H3
0.9600
N2—C1—S2
123.40 (17)
112.16 (16)
124.43 (14)
109.5
C43—C42—H42
C41—C42—H42
C42—C43—C44
C42—C43—H43
C44—C43—H43
C43—C44—C45
C43—C44—Cl4
C45—C44—Cl4
C46—C45—C44
C46—C45—Cl5
C44—C45—Cl5
C45—C46—C41
C45—C46—H46
C41—C46—H46
C1—N2—N3
119.7
N2—C1—S1
119.7
S2—C1—S1
120.3 (2)
119.8
N2—C2—H2A
N2—C2—H2B
H2A—C2—H2B
N2—C2—H2C
H2A—C2—H2C
H2B—C2—H2C
O4—C4—N3
109.5
119.8
109.5
119.5 (2)
119.34 (18)
121.20 (18)
120.1 (2)
118.84 (17)
121.06 (17)
120.2 (2)
119.9
109.5
109.5
109.5
121.27 (19)
123.34 (19)
115.33 (18)
109.5
O4—C4—C41
N3—C4—C41
S1—C11—H11A
S1—C11—H11B
H11A—C11—H11B
S1—C11—H11C
H11A—C11—H11C
H11B—C11—H11C
C46—C41—C42
C46—C41—C4
C42—C41—C4
C43—C42—C41
109.5
119.9
109.5
118.21 (18)
124.1 (2)
117.30 (19)
119.57 (17)
120.2
109.5
C1—N2—C2
109.5
N3—N2—C2
109.5
C4—N3—N2
119.2 (2)
121.70 (19)
119.03 (19)
120.6 (2)
C4—N3—H3
N2—N3—H3
120.2
C1—S1—C11
103.25 (14)
O4—C4—C41—C46
N3—C4—C41—C46
O4—C4—C41—C42
147.6 (2)
−29.9 (3)
−30.1 (3)
Cl5—C45—C46—C41
C42—C41—C46—C45
C4—C41—C46—C45
178.80 (16)
−1.0 (3)
−178.72 (19)
Acta Cryst. (2012). C68, o373–o376
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supplementary materials
N3—C4—C41—C42
C46—C41—C42—C43
C4—C41—C42—C43
C41—C42—C43—C44
C42—C43—C44—C45
C42—C43—C44—Cl4
C43—C44—C45—C46
Cl4—C44—C45—C46
C43—C44—C45—Cl5
Cl4—C44—C45—Cl5
C44—C45—C46—C41
152.4 (2)
1.8 (3)
S2—C1—N2—N3
S1—C1—N2—N3
S2—C1—N2—C2
S1—C1—N2—C2
O4—C4—N3—N2
173.80 (15)
−5.3 (2)
179.62 (19)
−0.6 (3)
0.9 (3)
−178.19 (19)
−6.4 (3)
−1.4 (3)
177.96 (17)
2.3 (3)
C41—C4—N3—N2
C1—N2—N3—C4
C2—N2—N3—C4
N2—C1—S1—C11
S2—C1—S1—C11
171.10 (17)
−83.2 (3)
90.2 (3)
−177.12 (16)
−177.58 (17)
3.0 (3)
−177.00 (18)
3.89 (19)
−1.1 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
N3—H3···O4i
D—H
0.86
H···A
D···A
D—H···A
132
2.34
2.989 (2)
Symmetry code: (i) x−1, y, z.
(F2) Butyl 2-(3,4-dichlorobenzoyl)-1-methylhydrazinecarbodithioate
Crystal data
C13H16Cl2N2OS2
Mr = 351.30
F(000) = 728
Dx = 1.451 Mg m−3
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 4.5467 (1) Å
b = 13.7623 (4) Å
c = 25.7328 (7) Å
β = 93.117 (1)°
V = 1607.80 (7) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9381 reflections
θ = 2.2–35.1°
µ = 0.66 mm−1
T = 100 K
Prism, colourless
0.4 × 0.2 × 0.2 mm
Data collection
Bruker SMART APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
32865 measured reflections
6412 independent reflections
5098 reflections with I > 2σ(I)
Rint = 0.038
θ
max = 33.7°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = −7→7
k = −21→21
l = −40→40
T
min = 0.659, Tmax = 0.747
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.083
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.04
6412 reflections
187 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.038P)2 + 0.3873P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max = 0.002
Δρmax = 0.50 e Å−3
Δρmin = −0.25 e Å−3
Acta Cryst. (2012). C68, o373–o376
sup-4

supplementary materials
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 (Å2)
x
y
z
Uiso*/Ueq
C1
0.5980 (2)
0.3197 (3)
0.2996
0.33828 (8)
0.25068 (9)
0.1993
0.25795 (4)
0.32407 (5)
0.2989
0.0176 (2)
0.0241 (2)
0.036*
C2
H2A
H2B
H2C
C4
0.1317
0.2638
0.3378
0.036*
0.4569
0.2314
0.3518
0.036*
0.5938 (2)
0.9228 (3)
1.0828
0.45312 (8)
0.43499 (11)
0.4814
0.36332 (4)
0.18530 (5)
0.1842
0.01535 (18)
0.0260 (3)
0.031*
C11
H11A
H11B
C12
H12A
H12B
C13
H13A
H13B
C14
H14A
H14B
H14C
C41
C42
H42
C43
C44
C45
H45
C46
H46
Cl3
1.0084
0.3704
0.1873
0.031*
0.7289 (3)
0.8362
0.44336 (9)
0.4183
0.13524 (5)
0.1066
0.0223 (2)
0.027*
0.5552
0.4033
0.1383
0.027*
0.6327 (3)
0.5274
0.54707 (9)
0.5725
0.12279 (5)
0.1516
0.0250 (2)
0.030*
0.8063
0.5870
0.1193
0.030*
0.4364 (3)
0.5402
0.55489 (11)
0.5308
0.07324 (5)
0.0444
0.0313 (3)
0.047*
0.3840
0.6217
0.0672
0.047*
0.2611
0.5172
0.0768
0.047*
0.5219 (2)
0.6610 (2)
0.7901
0.54325 (8)
0.55652 (8)
0.5096
0.39186 (4)
0.44100 (4)
0.4548
0.01590 (18)
0.01747 (19)
0.021*
0.6069 (3)
0.4163 (3)
0.2802 (3)
0.1538
0.63963 (8)
0.71054 (8)
0.69772 (9)
0.7453
0.46931 (4)
0.44832 (5)
0.39920 (5)
0.3853
0.0184 (2)
0.0208 (2)
0.0241 (2)
0.029*
0.3318 (3)
0.2402
0.61422 (9)
0.6057
0.37080 (5)
0.3379
0.0203 (2)
0.024*
0.78138 (7)
0.34931 (8)
0.4277 (2)
0.3865 (2)
0.213 (4)
0.82683 (17)
0.68028 (7)
0.72360 (6)
0.65278 (2)
0.81517 (2)
0.33803 (7)
0.42482 (7)
0.4388 (13)
0.40938 (6)
0.23787 (2)
0.45670 (2)
0.530349 (11)
0.482620 (13)
0.29928 (4)
0.32589 (4)
0.3291 (7)
0.37106 (3)
0.226379 (13)
0.243154 (11)
0.02526 (7)
0.03074 (8)
0.01746 (17)
0.01681 (17)
0.038 (5)*
0.01932 (16)
0.02539 (7)
0.01984 (6)
Cl4
N2
N3
H3
O4
S2
S1
Acta Cryst. (2012). C68, o373–o376
sup-5

supplementary materials
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
0.0137 (4)
0.0244 (5)
0.0143 (4)
0.0188 (5)
0.0255 (5)
0.0330 (6)
0.0407 (7)
0.0161 (4)
0.0182 (5)
0.0219 (5)
0.0278 (6)
0.0303 (6)
0.0236 (5)
0.03500 (16)
0.04676 (19)
0.0165 (4)
0.0122 (4)
0.0151 (3)
0.02626 (14)
0.01900 (12)
0.0209 (5)
0.0189 (5)
0.0181 (5)
0.0370 (7)
0.0237 (6)
0.0211 (6)
0.0298 (7)
0.0166 (5)
0.0173 (5)
0.0189 (5)
0.0146 (5)
0.0167 (5)
0.0185 (5)
0.02383 (14)
0.01676 (13)
0.0157 (4)
0.0180 (4)
0.0242 (4)
0.02478 (15)
0.02366 (14)
0.0179 (5)
0.0288 (6)
0.0139 (4)
0.0227 (6)
0.0181 (5)
0.0214 (5)
0.0235 (6)
0.0152 (4)
0.0169 (5)
0.0147 (5)
0.0204 (5)
0.0254 (6)
0.0188 (5)
0.01667 (12)
0.02938 (16)
0.0201 (4)
0.0201 (4)
0.0185 (4)
0.02489 (15)
0.01677 (12)
0.0016 (4)
−0.0029 (3)
0.0010 (4)
0.0027 (3)
0.0049 (4)
0.0057 (4)
0.0048 (5)
0.0019 (5)
0.0029 (3)
0.0012 (4)
0.0034 (4)
0.0065 (4)
0.0014 (5)
−0.0004 (4)
−0.00111 (10)
0.00828 (13)
0.0003 (3)
0.0000 (3)
−0.0009 (3)
−0.00095 (11)
0.00023 (9)
−0.0040 (4)
0.0024 (4)
C2
−0.0001 (4)
−0.0005 (4)
−0.0012 (5)
−0.0035 (4)
−0.0061 (5)
−0.0066 (6)
−0.0001 (4)
0.0015 (4)
C4
−0.0005 (4)
−0.0020 (5)
−0.0043 (4)
−0.0030 (4)
0.0050 (5)
C11
C12
C13
C14
C41
C42
C43
C44
C45
C46
Cl3
Cl4
N2
−0.0003 (4)
−0.0009 (4)
−0.0008 (4)
−0.0006 (4)
0.0024 (4)
−0.0021 (4)
0.0002 (4)
0.0053 (4)
0.0024 (4)
0.0012 (4)
−0.00193 (11)
0.00452 (12)
0.0000 (3)
−0.00418 (10)
−0.00475 (11)
−0.0038 (3)
−0.0043 (3)
−0.0028 (3)
−0.01001 (12)
−0.00236 (10)
N3
0.0023 (3)
O4
0.0045 (3)
S2
0.00528 (11)
−0.00289 (10)
S1
Geometric parameters (Å, º)
C1—N2
1.3493 (15)
C13—H13A
C13—H13B
C14—H14A
C14—H14B
C14—H14C
C41—C46
C41—C42
C42—C43
C42—H42
C43—C44
C43—Cl3
C44—C45
C44—Cl4
C45—C46
C45—H45
C46—H46
N2—N3
0.9700
C1—S2
1.6560 (11)
1.7749 (12)
1.4584 (16)
0.9600
0.9700
C1—S1
0.9600
C2—N2
0.9600
C2—H2A
C2—H2B
C2—H2C
C4—O4
0.9600
0.9600
1.3940 (16)
1.3948 (15)
1.3853 (15)
0.9300
0.9600
1.2255 (13)
1.3670 (14)
1.4869 (15)
1.5250 (18)
1.8090 (12)
0.9700
C4—N3
C4—C41
C11—C12
C11—S1
C11—H11A
C11—H11B
C12—C13
C12—H12A
C12—H12B
C13—C14
1.3944 (17)
1.7302 (11)
1.3879 (18)
1.7247 (12)
1.3888 (17)
0.9300
0.9700
1.5218 (18)
0.9700
0.9300
0.9700
1.3946 (13)
0.821 (18)
1.5200 (18)
N3—H3
N2—C1—S2
N2—C1—S1
S2—C1—S1
N2—C2—H2A
N2—C2—H2B
122.62 (9)
112.12 (8)
125.25 (7)
109.5
C13—C14—H14B
H14A—C14—H14B
C13—C14—H14C
H14A—C14—H14C
H14B—C14—H14C
109.5
109.5
109.5
109.5
109.5
109.5
Acta Cryst. (2012). C68, o373–o376
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supplementary materials
H2A—C2—H2B
N2—C2—H2C
109.5
C46—C41—C42
C46—C41—C4
C42—C41—C4
C43—C42—C41
C43—C42—H42
C41—C42—H42
C42—C43—C44
C42—C43—Cl3
C44—C43—Cl3
C45—C44—C43
C45—C44—Cl4
C43—C44—Cl4
C44—C45—C46
C44—C45—H45
C46—C45—H45
C45—C46—C41
C45—C46—H46
C41—C46—H46
C1—N2—N3
120.11 (10)
122.74 (10)
117.12 (10)
120.01 (10)
120.0
109.5
H2A—C2—H2C
H2B—C2—H2C
O4—C4—N3
109.5
109.5
122.09 (10)
122.75 (10)
115.08 (9)
112.99 (8)
109.0
O4—C4—C41
120.0
N3—C4—C41
119.90 (10)
118.56 (9)
121.54 (9)
120.05 (11)
119.32 (9)
120.62 (9)
120.31 (11)
119.8
C12—C11—S1
C12—C11—H11A
S1—C11—H11A
C12—C11—H11B
S1—C11—H11B
H11A—C11—H11B
C13—C12—C11
C13—C12—H12A
C11—C12—H12A
C13—C12—H12B
C11—C12—H12B
H12A—C12—H12B
C14—C13—C12
C14—C13—H13A
C12—C13—H13A
C14—C13—H13B
C12—C13—H13B
H13A—C13—H13B
C13—C14—H14A
109.0
109.0
109.0
107.8
113.27 (10)
108.9
119.8
108.9
119.61 (11)
120.2
108.9
108.9
120.2
107.7
118.88 (9)
124.63 (10)
115.71 (9)
118.96 (9)
119.5 (13)
113.9 (13)
101.90 (6)
113.08 (11)
109.0
C1—N2—C2
N3—N2—C2
109.0
C4—N3—N2
109.0
C4—N3—H3
109.0
N2—N3—H3
107.8
C1—S1—C11
109.5
S1—C11—C12—C13
C11—C12—C13—C14
O4—C4—C41—C46
N3—C4—C41—C46
O4—C4—C41—C42
N3—C4—C41—C42
C46—C41—C42—C43
C4—C41—C42—C43
C41—C42—C43—C44
C41—C42—C43—Cl3
C42—C43—C44—C45
Cl3—C43—C44—C45
C42—C43—C44—Cl4
Cl3—C43—C44—Cl4
C43—C44—C45—C46
70.16 (13)
−179.28 (10)
152.41 (11)
−24.62 (15)
−25.60 (16)
157.38 (10)
1.01 (17)
Cl4—C44—C45—C46
C44—C45—C46—C41
C42—C41—C46—C45
C4—C41—C46—C45
S2—C1—N2—N3
S1—C1—N2—N3
S2—C1—N2—C2
S1—C1—N2—C2
O4—C4—N3—N2
C41—C4—N3—N2
C1—N2—N3—C4
C2—N2—N3—C4
N2—C1—S1—C11
S2—C1—S1—C11
C12—C11—S1—C1
179.74 (10)
−0.12 (18)
−0.52 (17)
−178.47 (11)
175.47 (8)
−3.49 (12)
6.06 (15)
179.07 (10)
−0.86 (17)
179.43 (8)
0.23 (18)
−172.90 (9)
6.65 (16)
−176.31 (9)
−83.82 (13)
86.52 (12)
−176.88 (8)
4.19 (9)
179.93 (9)
−179.24 (9)
0.46 (14)
0.26 (19)
89.50 (10)
Hydrogen-bond geometry (Å, º)
D—H···A
N3—H3···O4i
D—H
0.821 (18)
H···A
D···A
D—H···A
145.3 (17)
2.149 (19)
2.8624 (12)
Symmetry code: (i) x−1, y, z.
Acta Cryst. (2012). C68, o373–o376
sup-7

supplementary materials
(F3) 3,4-dichloro-N-(2-sulfanylidene-1,3-thiazinan-3-yl)benzamide
Crystal data
C11H10Cl2N2OS2
Mr = 321.23
F(000) = 656
Dx = 1.545 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 13.3534 (10) Å
b = 11.6813 (8) Å
c = 8.9908 (7) Å
β = 99.995 (3)°
V = 1381.15 (18) Å3
Z = 4
Cu Kα radiation, λ = 1.54178 Å
Cell parameters from 12303 reflections
θ = 3.4–69.3°
µ = 6.97 mm−1
T = 290 K
Needle, colourless
0.6 × 0.02 × 0.02 mm
Data collection
Bruker SMART APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
3801 measured reflections
3801 independent reflections
3652 reflections with I > 2σ(I)
Rint = 0.041
ω scans
θmax = 69.7°, θmin = 3.4°
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2008b)
h = −16→15
k = 0→14
l = 0→10
T
min = 0.447, Tmax = 0.753
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.095
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.05
3801 reflections
164 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0535P)2 + 0.3664P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.32 e Å−3
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 (Å2)
x
y
z
Uiso*/Ueq
C1
0.44936 (11)
0.27875 (13)
0.64722 (13)
0.6396
0.10160 (12)
0.23257 (13)
0.10597 (15)
0.0782
0.27872 (17)
0.4140 (2)
0.4559 (2)
0.5550
0.0325 (3)
0.0314 (3)
0.0509 (4)
0.061*
C4
C11
H11A
H11B
0.7171
0.0932
0.4437
0.061*
Acta Cryst. (2012). C68, o373–o376
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supplementary materials
C12
H12A
H12B
C13
H13A
H13B
C41
C42
H42
C43
C44
C45
H45
C46
H46
Cl3
0.62462 (15)
0.6362
0.23183 (16)
0.2604
0.4458 (3)
0.3489
0.0488 (5)
0.059*
0.6708
0.2716
0.5241
0.059*
0.51648 (16)
0.5063
0.25741 (13)
0.2321
0.4632 (3)
0.5622
0.0441 (5)
0.053*
0.5060
0.3396
0.4579
0.053*
0.18032 (11)
0.09696 (16)
0.1031
0.29693 (13)
0.24998 (13)
0.1807
0.37860 (17)
0.4273 (3)
0.4789
0.0348 (3)
0.0438 (5)
0.053*
0.00396 (13)
−0.00520 (13)
0.07894 (16)
0.0730
0.30597 (18)
0.40949 (18)
0.45765 (17)
0.5276
0.3993 (2)
0.3244 (2)
0.2777 (3)
0.2275
0.0531 (5)
0.0550 (5)
0.0580 (5)
0.070*
0.17166 (13)
0.2283
0.40200 (15)
0.4350
0.3055 (2)
0.2753
0.0464 (4)
0.056*
−0.09901 (5)
−0.12079 (4)
0.44045 (9)
0.34589 (12)
0.3306
0.24448 (6)
0.47972 (6)
0.20211 (11)
0.25613 (10)
0.3035
0.46258 (15)
0.28823 (9)
0.34791 (14)
0.3215 (2)
0.2479
0.0938 (3)
0.0856 (2)
0.0334 (3)
0.0346 (3)
0.042*
Cl4
N2
N3
H3
O4
0.29657 (8)
0.56318 (3)
0.35775 (3)
0.16518 (9)
0.02626 (3)
0.04147 (3)
0.51921 (12)
0.31259 (6)
0.15478 (5)
0.0380 (2)
0.04931 (14)
0.04419 (13)
S1
S2
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
0.0291 (7)
0.0269 (8)
0.0305 (8)
0.0335 (10)
0.0338 (10)
0.0280 (7)
0.0330 (10)
0.0285 (8)
0.0351 (9)
0.0510 (11)
0.0396 (9)
0.0369 (3)
0.0453 (3)
0.0250 (6)
0.0297 (8)
0.0367 (5)
0.0348 (2)
0.0397 (2)
0.0333 (7)
0.0339 (7)
0.0501 (10)
0.0505 (9)
0.0467 (10)
0.0403 (8)
0.0474 (11)
0.0663 (12)
0.0661 (11)
0.0531 (11)
0.0462 (9)
0.1055 (6)
0.1012 (5)
0.0375 (7)
0.0386 (7)
0.0413 (6)
0.0404 (2)
0.0396 (2)
0.0366 (7)
0.0331 (8)
0.0687 (12)
0.0615 (13)
0.0505 (12)
0.0357 (7)
0.0513 (12)
0.0654 (12)
0.0621 (11)
0.0697 (13)
0.0558 (10)
0.1458 (9)
0.1079 (5)
0.0382 (7)
0.0364 (8)
0.0362 (6)
0.0711 (3)
0.0507 (2)
0.0011 (5)
0.0023 (6)
0.0041 (7)
−0.0016 (7)
0.0016 (6)
0.0054 (6)
0.0037 (6)
0.0026 (8)
0.0195 (8)
0.0190 (9)
0.0104 (7)
−0.0012 (2)
0.0392 (3)
0.0060 (5)
0.0108 (4)
0.0068 (4)
0.01133 (16)
−0.00385 (15)
0.0098 (6)
0.0044 (7)
−0.0010 (8)
0.0058 (9)
0.0038 (10)
0.0041 (6)
0.0084 (10)
0.0106 (8)
0.0036 (8)
0.0101 (10)
0.0148 (7)
0.0350 (5)
0.0065 (3)
0.0066 (5)
0.0081 (7)
0.0068 (4)
0.0045 (2)
0.00070 (17)
0.0059 (6)
−0.0033 (6)
0.0027 (9)
0.0005 (9)
−0.0101 (7)
−0.0027 (6)
0.0031 (6)
−0.0050 (10)
−0.0032 (9)
0.0120 (9)
0.0083 (8)
0.0146 (4)
0.0062 (4)
−0.0012 (5)
0.0058 (4)
0.0048 (5)
−0.00761 (19)
−0.00315 (16)
C4
C11
C12
C13
C41
C42
C43
C44
C45
C46
Cl3
Cl4
N2
N3
O4
S1
S2
Geometric parameters (Å, º)
C1—N2
C1—S2
1.3437 (19)
1.6608 (15)
C13—H13B
C41—C42
0.9700
1.378 (3)
Acta Cryst. (2012). C68, o373–o376
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supplementary materials
C1—S1
1.7369 (14)
1.222 (2)
1.353 (2)
1.500 (2)
1.500 (3)
1.8121 (19)
0.9700
C41—C46
C42—C43
C42—H42
C43—C44
C43—Cl3
C44—C45
C44—Cl4
C45—C46
C45—H45
C46—H46
N2—N3
1.387 (2)
1.387 (3)
0.9300
C4—O4
C4—N3
C4—C41
1.379 (3)
1.7326 (19)
1.385 (3)
1.7283 (17)
1.382 (3)
0.9300
C11—C12
C11—S1
C11—H11A
C11—H11B
C12—C13
C12—H12A
C12—H12B
C13—N2
C13—H13A
0.9700
1.509 (3)
0.9700
0.9300
0.9700
1.3946 (18)
0.8600
1.469 (2)
0.9700
N3—H3
N2—C1—S2
124.48 (11)
120.44 (11)
115.06 (9)
123.10 (15)
122.23 (15)
114.67 (14)
111.56 (14)
109.3
C42—C41—C4
C46—C41—C4
C41—C42—C43
C41—C42—H42
C43—C42—H42
C44—C43—C42
C44—C43—Cl3
C42—C43—Cl3
C43—C44—C45
C43—C44—Cl4
C45—C44—Cl4
C46—C45—C44
C46—C45—H45
C44—C45—H45
C45—C46—C41
C45—C46—H46
C41—C46—H46
C1—N2—N3
117.35 (15)
122.82 (14)
120.11 (17)
119.9
N2—C1—S1
S2—C1—S1
O4—C4—N3
O4—C4—C41
119.9
N3—C4—C41
120.18 (17)
121.04 (14)
118.78 (16)
119.75 (16)
120.59 (15)
119.66 (16)
120.15 (18)
119.9
C12—C11—S1
C12—C11—H11A
S1—C11—H11A
C12—C11—H11B
S1—C11—H11B
H11A—C11—H11B
C11—C12—C13
C11—C12—H12A
C13—C12—H12A
C11—C12—H12B
C13—C12—H12B
H12A—C12—H12B
N2—C13—C12
N2—C13—H13A
C12—C13—H13A
N2—C13—H13B
C12—C13—H13B
H13A—C13—H13B
C42—C41—C46
109.3
109.3
109.3
108.0
111.95 (15)
109.2
119.9
109.2
120.01 (17)
120.0
109.2
109.2
120.0
107.9
117.84 (13)
127.24 (13)
114.56 (13)
118.72 (14)
120.6
113.37 (17)
108.9
C1—N2—C13
N3—N2—C13
C4—N3—N2
108.9
108.9
C4—N3—H3
108.9
N2—N3—H3
120.6
107.7
C1—S1—C11
106.23 (8)
119.78 (15)
S1—C11—C12—C13
C11—C12—C13—N2
O4—C4—C41—C42
N3—C4—C41—C42
O4—C4—C41—C46
N3—C4—C41—C46
C46—C41—C42—C43
C4—C41—C42—C43
C41—C42—C43—C44
58.7 (2)
C44—C45—C46—C41
C42—C41—C46—C45
C4—C41—C46—C45
S2—C1—N2—N3
0.9 (3)
−59.7 (3)
−23.8 (2)
156.85 (16)
153.55 (17)
−25.8 (2)
1.9 (3)
−1.9 (3)
−179.24 (18)
4.38 (19)
−177.16 (11)
177.03 (14)
−4.5 (2)
S1—C1—N2—N3
S2—C1—N2—C13
S1—C1—N2—C13
C12—C13—N2—C1
C12—C13—N2—N3
179.37 (18)
−0.8 (3)
31.3 (3)
−155.80 (16)
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supplementary materials
C41—C42—C43—Cl3
C42—C43—C44—C45
Cl3—C43—C44—C45
C42—C43—C44—Cl4
Cl3—C43—C44—Cl4
C43—C44—C45—C46
Cl4—C44—C45—C46
−179.85 (16)
−0.2 (3)
O4—C4—N3—N2
−0.7 (2)
C41—C4—N3—N2
C1—N2—N3—C4
C13—N2—N3—C4
N2—C1—S1—C11
S2—C1—S1—C11
C12—C11—S1—C1
178.64 (13)
90.28 (19)
−83.29 (18)
3.77 (15)
178.75 (18)
179.72 (17)
−1.3 (3)
0.2 (3)
−177.62 (9)
−30.38 (17)
−179.74 (17)
Hydrogen-bond geometry (Å, º)
D—H···A
N3—H3···O4i
D—H
H···A
D···A
D—H···A
150
0.86
2.06
2.837 (2)
Symmetry code: (i) x, −y+1/2, z−1/2.
Selected torsion angles (°)
Structure
(F1)
S1—C1—N2—N3
C1—N2—N3—C4
-83.2 (3)
N2—N3—C4—C41 O4—C4—C41—C42
-5.3 (2)
171.10 (17)
-176.31 (9)
178.64 (13)
-30.1 (3)
-25.60 (16)
-23.8 (2)
(F2)
-3.49 (12)
-177.16 (11)
-83.82 (13)
(F3)
90.28 (19)
Acta Cryst. (2012). C68, o373–o376
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