(E)-2-[1-(1-Benzothio­phen-3-yl)ethyl­idene]hydrazinecarbothio­amide methanol hemisolvate

Kayed, S.F.; Farina, Y.; Kassim, M.; Simpson, J.

doi:10.1107/S160053680801297X

(E)-2-[1-(1-Benzothiophen-3-yl)ethylidene]hydrazinecarbothioamide methanol hemisolvate

S. F. Kayed, Y. Farina, M. Kassim and J. Simpson

The asymmetric unit of the title compound, C₁₁H₁₁N₃S₂·0.5CH₄O, contains four thiosemicarbazone molecules and two methanol solvent molecules. Each hydrazinecarbothioamide molecule adopts an E configuration with respect to the C=N double bond and is stabilized by an intramolecular N—H

N hydrogen bond, resulting in an S(5) ring motif. In the crystal structure, an extensive network of N—H

O, N—H

N, O—H

S and N—H

S hydrogen bonds and weak C—H

O, C—H

N and C—H

S contacts together with an S

S [3.5958 (14) Å] and a C—H

π interaction form a three-dimensional network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680801297X/hb2725sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680801297X/hb2725Isup2.hkl Contains datablock I

CCDC reference: 690925

checkCIF report

Key indicators

Single-crystal X-ray study
T = 92 K
Mean (C-C) = 0.005 Å
R factor = 0.067
wR factor = 0.203
Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
DIFMN02_ALERT_2_B  The minimum difference density is < -0.1*ZMAX*1.00
            _refine_diff_density_min given =     -2.305
            Test value =     -1.600
DIFMX01_ALERT_2_B  The maximum difference density is > 0.1*ZMAX*1.00
            _refine_diff_density_max given =      1.713
            Test value =      1.600
PLAT097_ALERT_2_B Maximum (Positive) Residual Density ............       1.71 e/A   
PLAT098_ALERT_2_B Minimum (Negative) Residual Density ............      -2.31 e/A   
PLAT420_ALERT_2_B D-H Without Acceptor       O2S    -   H2S    ...          ?

Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.420
            Value of mu given      =     0.415
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.777     0.947
            Tmin(prime) and Tmax expected:      0.877     0.947
            RR(prime) =      0.886
            Please check that your absorption correction is appropriate.
CHEMW01_ALERT_1_C  The ratio of given/expected molecular weight as calculated
            from the _chemical_formula_sum lies outside
            the range 0.99 <> 1.01
            Calculated formula weight =   273.3687
            Formula weight given      =   265.3800
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT413_ALERT_2_C Short Inter XH3 .. XHn     H3B    ..  H2S3    ..       2.12 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N2D    -   H2ND   ...          ?
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT061_ALERT_4_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3N6   ..  N3B     ..       2.72 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2S    ..  S2D     ..       2.97 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A    ..  S2A     ..       2.97 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10A   ..  S2B     ..       2.91 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2S1   ..  N2D     ..       2.74 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10F   ..  C~G~    ..       2.91 Ang.
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........       C~G~
                    H10F   C~G~
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........       C~G~
                    C10B   C~G~
PLAT718_ALERT_1_C D-H..A  Unknown or Inconsistent Label ..........       C~G~
                    C10B   H10F   C~G~
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........         18
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.839(10) ......       4.00 su-Ra
              N3A  -H3N1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.843(10) ......       3.00 su-Ra
              N3A  -H3N2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.838(10) ......       3.00 su-Ra
              N3B  -H3N3    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.839(10) ......       3.00 su-Ra
              N3B  -H3N4    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.842(10) ......       4.00 su-Ra
              N2C  -H2NC    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.842(10) ......       4.00 su-Ra
              N3C  -H3N5    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              N3C  -H3N6    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.842(10) ......       4.00 su-Ra
              N2D  -H2ND    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.841(10) ......       4.00 su-Ra
              N3D  -H3N7    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              N3D  -H3N8    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.843(10) ......       3.00 su-Ra
              N3A  -H3#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.838(10) ......       3.00 su-Ra
              N3B  -H5#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.842(10) ......       4.00 su-Ra
              N3C  -H8#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.841(10) ......       4.00 su-Ra
              N3D  -H11#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(4), Rep   0.839(10) ......       4.00 su-Ra
              N3A  -H2#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.839(10) ......       3.00 su-Ra
              N3B  -H6#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              N3C  -H9#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              N3C  -H9#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.842(10) ......       4.00 su-Ra
              N2C  -H7#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              N3D  -H12#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.841(10) ......       4.00 su-Ra
              N3D  -H11#    1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.51(3), Rep   2.500(14) ......       2.14 su-Ra
              H2#  -S2B     1.555   1.655
PLAT736_ALERT_1_C H...A   Calc     2.59(3), Rep   2.585(13) ......       2.31 su-Ra
              H4#  -S2A     1.555   4.475
PLAT736_ALERT_1_C H...A   Calc     2.74(4), Rep   2.738(15) ......       2.67 su-Ra
              H12# -S2A     1.555   2.646

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C11.5 H13 N3 O1 S2
            Atom count from _chemical_formula_moiety:C11.5 H13 N3 O0.5 S2
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C11.5 H13 N3 O1 S2
            Atom count from the _atom_site data:  C11.5 H13 N3 O0.5 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z   16
           From the CIF: _chemical_formula_sum  C11.5 H13 N3 O S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        184.00    184.00    0.00
           H        208.00    208.00    0.00
           N         48.00     48.00    0.00
           O         16.00      8.00    8.00
           S         32.00     32.00    0.00
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

   0 ALERT level A = In general: serious problem
   5 ALERT level B = Potentially serious problem
  47 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

  38 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Structures similar to the title compound, (I), have been reported including the thiosemicarbazone derived from 2-acetylthiophene (Lima et al., 2002); and a pryazoline derivative (Işık et al., 2006).

The asymmetric unit of (I) contains four molecules, labeled A—D (Figs 1—4) and two methanol solvate molecules, with the complete assemblage shown in Fig. 5. Each molecule adopts an E configuration with respect to the C=N bond and bond distances and angles are normal (Allen et al., 1987). Intramolecular N3—H···N1 hydrogen bonds (Table 1) form between each of the the NH₂ groups and the imine N atoms generating S(5) ring motifs (Bernstein et al., 1995). These contribute to the planarity of the molecules.

In the crystal of (I), N2—H2···S2 hydrogen bonds generate centrosymmetric R²₂(8) rings in molecules A—C. For molecule D, C2S—H2S1···S2D hydrogen bonding to a methanol solvate within the asymmetric unit obviates such an interaction. Other N—H···O, N—H···N, O—H···S and N—H···S hydrogen bonds together with weak C—H···O, C—H···N and C—H···S contacts, an S···S interaction (d(S1D···S1Bⁱ) = 3.5958 (14) Å; i = x, 3/2 - y, -1/2 + z) and a C10B—H10F···Cgⁱⁱ interaction (ii = -x, 1 - y, -z; Cg is the centroid of the C1B···C6B ring) form a complex three dimensional network (Fig 6).

Related literature top

For related structures, see: de Lima et al. (2002); Işık et al. (2006). For reference structural data, see: Allen et al. (1987). For graph-set analysis of hydrogen bonding, see: Bernstein et al., (1995). Cg is the centroid of C1B–C6B.

Experimental top

A 1:1 mixture of 2-acetylbenzothiophene and thiosemicarbazide was heated under reflux in ethanol for 2 h. The solid product which separated upon cooling was filtered and recrystallized from a 1:1 mixture of acetonitrile and methanol to afford colourless, blocks of (I) in 68% yield (m.p. 483–485 K).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006) and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The structure of molecule A in (I) showing 50% probability displacement ellipsoids for the non-H atoms. The intramolecular N—H···N hydrogen bond is drawn as a dashed line.
	Fig. 2. The structure of molecule B in (I) showing 50% probability displacement ellipsoids for the non-H atoms. The intramolecular N—H···N hydrogen bond is drawn as a dashed line.
	Fig. 3. The structure of molecule C in (I) showing 50% probability displacement ellipsoids for the non-H atoms. The intramolecular N—H···N hydrogen bond is drawn as a dashed line.
	Fig. 4. The structure of molecule D in (I) showing 50% probability displacement ellipsoids for the non-H atoms. The intramolecular N—H···N hydrogen bond is drawn as a dashed line.
	Fig. 5. The asymmetric unit of (I) with intermolecular hydrogen bonds drawn as dashed lines.
	Fig. 6. Crystal packing of (I) viewed down the a axis with hydrogen bonds drawn as dashed lines.

(E)-2-[1-(1-Benzothiophen-3-yl)ethylidene]hydrazinecarbothioamide methanol hemisolvate top

Crystal data top

C₁₁H₁₁N₃S₂·0.5(CH₄O)	F(000) = 2224
M_r = 265.38	D_x = 1.428 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8980 reflections
a = 18.9438 (12) Å	θ = 2.3–25.6°
b = 17.7076 (11) Å	µ = 0.42 mm⁻¹
c = 15.4145 (10) Å	T = 92 K
β = 107.238 (3)°	Block, colourless
V = 4938.5 (5) Å³	0.31 × 0.20 × 0.13 mm
Z = 16

Data collection top

Bruker APEXII CCD area-detector diffractometer	10871 independent reflections
Radiation source: fine-focus sealed tube	8171 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
ω scans	θ_max = 27.1°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −24→24
T_min = 0.777, T_max = 0.947	k = −22→22
65034 measured reflections	l = −19→18

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.203	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.1068P)² + 8.4506P] where P = (F_o² + 2F_c²)/3
10871 reflections	(Δ/σ)_max = 0.001
655 parameters	Δρ_max = 1.71 e Å⁻³
12 restraints	Δρ_min = −2.31 e Å⁻³

Crystal data top

C₁₁H₁₁N₃S₂·0.5(CH₄O)	V = 4938.5 (5) Å³
M_r = 265.38	Z = 16
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.9438 (12) Å	µ = 0.42 mm⁻¹
b = 17.7076 (11) Å	T = 92 K
c = 15.4145 (10) Å	0.31 × 0.20 × 0.13 mm
β = 107.238 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	10871 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	8171 reflections with I > 2σ(I)
T_min = 0.777, T_max = 0.947	R_int = 0.086
65034 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	12 restraints
wR(F²) = 0.203	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.71 e Å⁻³
10871 reflections	Δρ_min = −2.31 e Å⁻³
655 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	U_iso*/U_eq
C1A	0.40620 (18)	0.50684 (18)	0.8528 (2)	0.0201 (7)
C2A	0.36631 (19)	0.44650 (19)	0.8029 (2)	0.0241 (7)
H2A	0.3746	0.4300	0.7480	0.029*
C3A	0.3144 (2)	0.41176 (19)	0.8364 (2)	0.0254 (7)
H3A	0.2872	0.3700	0.8046	0.030*
C4A	0.3010 (2)	0.4368 (2)	0.9163 (3)	0.0263 (8)
H4A	0.2643	0.4125	0.9370	0.032*
C5A	0.3402 (2)	0.4960 (2)	0.9651 (3)	0.0252 (7)
H5A	0.3309	0.5124	1.0193	0.030*
C6A	0.39438 (18)	0.53217 (18)	0.9341 (2)	0.0212 (7)
S1A	0.47650 (5)	0.55720 (5)	0.82797 (6)	0.0235 (2)
C7A	0.44278 (18)	0.59319 (19)	0.9744 (2)	0.0224 (7)
H7A	0.4422	0.6176	1.0291	0.027*
C8A	0.48976 (18)	0.61239 (18)	0.9258 (2)	0.0200 (7)
C9A	0.54827 (18)	0.66957 (18)	0.9473 (2)	0.0207 (7)
C10A	0.56188 (18)	0.71682 (19)	1.0314 (2)	0.0223 (7)
H10A	0.6108	0.7051	1.0729	0.033*
H10B	0.5241	0.7058	1.0614	0.033*
H10C	0.5596	0.7704	1.0150	0.033*
N1A	0.58542 (15)	0.67430 (16)	0.8893 (2)	0.0213 (6)
N2A	0.64370 (16)	0.72396 (16)	0.9091 (2)	0.0211 (6)
H2NA	0.659 (2)	0.743 (2)	0.9613 (13)	0.025*
C11A	0.67880 (18)	0.73726 (18)	0.8465 (2)	0.0194 (7)
S2A	0.75517 (5)	0.79377 (5)	0.87472 (6)	0.02159 (19)
N3A	0.65198 (17)	0.70631 (19)	0.7655 (2)	0.0261 (6)
H3N1	0.676 (2)	0.714 (2)	0.729 (2)	0.031*
H3N2	0.6187 (17)	0.6733 (18)	0.758 (3)	0.031*
C1B	0.1144 (2)	0.9732 (2)	0.6666 (2)	0.0259 (7)
C2B	0.1682 (2)	1.0138 (2)	0.7312 (3)	0.0377 (10)
H2B	0.1676	1.0165	0.7926	0.045*
C3B	0.2225 (2)	1.0503 (2)	0.7030 (3)	0.0347 (9)
H3B	0.2594	1.0787	0.7458	0.042*
C4B	0.2239 (2)	1.0461 (2)	0.6135 (3)	0.0295 (8)
H4B	0.2614	1.0720	0.5959	0.035*
C5B	0.1714 (2)	1.0047 (2)	0.5495 (3)	0.0267 (8)
H5B	0.1730	1.0015	0.4886	0.032*
C6B	0.11558 (18)	0.96745 (18)	0.5761 (2)	0.0213 (7)
S1B	0.04048 (5)	0.92419 (5)	0.68465 (6)	0.0294 (2)
C7B	0.05600 (19)	0.92149 (19)	0.5224 (2)	0.0227 (7)
H7B	0.0484	0.9107	0.4600	0.027*
C8B	0.01121 (18)	0.89489 (18)	0.5715 (2)	0.0203 (7)
C9B	−0.05345 (18)	0.84574 (18)	0.5407 (2)	0.0217 (7)
C10B	−0.0764 (2)	0.8167 (2)	0.4454 (2)	0.0269 (8)
H10D	−0.0763	0.7614	0.4461	0.040*
H10E	−0.0417	0.8349	0.4138	0.040*
H10F	−0.1262	0.8349	0.4137	0.040*
N1B	−0.08527 (15)	0.83003 (16)	0.6022 (2)	0.0212 (6)
N2B	−0.14681 (16)	0.78420 (16)	0.5770 (2)	0.0216 (6)
H2NB	−0.166 (2)	0.768 (2)	0.5243 (13)	0.026*
C11B	−0.17783 (18)	0.76294 (19)	0.6424 (2)	0.0202 (7)
S2B	−0.25346 (5)	0.70679 (5)	0.61499 (6)	0.0227 (2)
N3B	−0.14553 (16)	0.78669 (17)	0.7263 (2)	0.0233 (6)
H3N3	−0.1059 (13)	0.811 (2)	0.735 (3)	0.028*
H3N4	−0.165 (2)	0.770 (2)	0.765 (2)	0.028*
C1C	0.3583 (2)	0.7371 (2)	0.6860 (2)	0.0258 (7)
C2C	0.4354 (2)	0.7437 (2)	0.7138 (3)	0.0297 (8)
H2C	0.4661	0.7002	0.7229	0.036*
C3C	0.4653 (2)	0.8154 (2)	0.7275 (3)	0.0323 (9)
H3C	0.5175	0.8214	0.7466	0.039*
C4C	0.4199 (2)	0.8795 (2)	0.7138 (3)	0.0351 (9)
H4C	0.4419	0.9281	0.7243	0.042*
C5C	0.3439 (2)	0.8733 (2)	0.6853 (3)	0.0351 (9)
H5C	0.3138	0.9172	0.6760	0.042*
C6C	0.3117 (2)	0.8011 (2)	0.6700 (2)	0.0266 (8)
S1C	0.30752 (5)	0.65375 (5)	0.66624 (7)	0.0281 (2)
C7C	0.2349 (2)	0.7803 (2)	0.6387 (3)	0.0287 (8)
H7C	0.1955	0.8158	0.6234	0.034*
C8C	0.2248 (2)	0.70426 (19)	0.6336 (2)	0.0244 (7)
C9C	0.1548 (2)	0.6635 (2)	0.6066 (2)	0.0258 (7)
C10C	0.0836 (2)	0.7064 (2)	0.5745 (3)	0.0319 (9)
H10G	0.0759	0.7230	0.5117	0.048*
H10H	0.0857	0.7506	0.6135	0.048*
H10I	0.0426	0.6737	0.5773	0.048*
N1C	0.16139 (17)	0.59049 (17)	0.6156 (2)	0.0297 (7)
N2C	0.09860 (18)	0.54666 (18)	0.5948 (2)	0.0346 (8)
H2NC	0.0583 (14)	0.559 (3)	0.556 (3)	0.042*
C11C	0.1060 (2)	0.4744 (2)	0.6250 (3)	0.0298 (8)
S2C	0.03402 (6)	0.41383 (6)	0.60223 (8)	0.0448 (3)
N3C	0.17357 (19)	0.45564 (18)	0.6749 (2)	0.0322 (8)
H3N5	0.2098 (18)	0.485 (2)	0.688 (3)	0.050 (15)*
H3N6	0.184 (3)	0.4118 (12)	0.696 (3)	0.051 (15)*
C1D	0.1294 (2)	0.7575 (2)	0.3394 (3)	0.0292 (8)
C2D	0.0537 (2)	0.7729 (3)	0.3080 (3)	0.0398 (10)
H2D	0.0181	0.7340	0.3021	0.048*
C3D	0.0326 (3)	0.8473 (3)	0.2858 (3)	0.0445 (11)
H3D	−0.0184	0.8593	0.2636	0.053*
C4D	0.0844 (3)	0.9040 (3)	0.2953 (3)	0.0412 (10)
H4D	0.0682	0.9543	0.2798	0.049*
C5D	0.1592 (2)	0.8893 (2)	0.3268 (3)	0.0347 (9)
H5D	0.1940	0.9291	0.3334	0.042*
C6D	0.1832 (2)	0.8146 (2)	0.3492 (2)	0.0277 (8)
S1D	0.16977 (5)	0.66977 (5)	0.37222 (7)	0.0311 (2)
C7D	0.2567 (2)	0.7850 (2)	0.3818 (2)	0.0272 (8)
H7D	0.3000	0.8149	0.3917	0.033*
C8D	0.2576 (2)	0.7092 (2)	0.3971 (2)	0.0252 (7)
C9D	0.32188 (19)	0.6605 (2)	0.4331 (2)	0.0245 (7)
C10D	0.3983 (2)	0.6910 (2)	0.4466 (3)	0.0341 (9)
H10J	0.4262	0.6885	0.5112	0.051*
H10K	0.3951	0.7436	0.4261	0.051*
H10L	0.4234	0.6608	0.4113	0.051*
N1D	0.30772 (17)	0.59253 (17)	0.4530 (2)	0.0291 (7)
N2D	0.36755 (19)	0.54664 (19)	0.4909 (3)	0.0376 (8)
H2ND	0.4088 (15)	0.560 (3)	0.486 (4)	0.060 (17)*
C11D	0.3565 (2)	0.4790 (2)	0.5254 (3)	0.0313 (8)
S2D	0.43168 (7)	0.42374 (7)	0.57328 (9)	0.0476 (3)
N3D	0.28874 (19)	0.45965 (18)	0.5210 (2)	0.0317 (7)
H3N7	0.2536 (17)	0.489 (2)	0.496 (3)	0.038*
H3N8	0.284 (3)	0.4170 (13)	0.542 (3)	0.038 (13)*
O1S	0.1306 (3)	0.4894 (3)	0.4258 (4)	0.0888 (14)
H1S	0.0944	0.5187	0.4186	0.133*
C1S	0.1058 (5)	0.4166 (4)	0.4115 (5)	0.087 (2)
H1S1	0.1150	0.3907	0.4700	0.130*
H1S2	0.1321	0.3903	0.3743	0.130*
H1S3	0.0527	0.4166	0.3799	0.130*
O2S	0.5431 (3)	0.5968 (3)	0.6341 (4)	0.0867 (12)
H2S	0.5637	0.6279	0.6084	0.130*
C2S	0.5875 (4)	0.5453 (4)	0.6686 (5)	0.0867 (12)
H2S1	0.5690	0.4972	0.6390	0.130*
H2S2	0.5925	0.5417	0.7336	0.130*
H2S3	0.6357	0.5565	0.6604	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0172 (16)	0.0190 (15)	0.0232 (16)	0.0036 (12)	0.0044 (13)	0.0020 (13)
C2A	0.0233 (18)	0.0233 (17)	0.0233 (17)	0.0026 (13)	0.0034 (14)	0.0008 (14)
C3A	0.0215 (17)	0.0193 (16)	0.0299 (18)	0.0008 (13)	−0.0009 (14)	0.0008 (14)
C4A	0.0233 (18)	0.0225 (17)	0.0321 (19)	−0.0027 (14)	0.0066 (15)	0.0042 (14)
C5A	0.0221 (17)	0.0248 (17)	0.0305 (18)	−0.0023 (13)	0.0106 (14)	−0.0021 (14)
C6A	0.0184 (16)	0.0195 (15)	0.0250 (17)	0.0019 (13)	0.0051 (13)	0.0008 (13)
S1A	0.0239 (4)	0.0254 (4)	0.0230 (4)	−0.0015 (3)	0.0099 (3)	−0.0025 (3)
C7A	0.0177 (16)	0.0219 (16)	0.0264 (17)	−0.0003 (13)	0.0048 (13)	−0.0024 (14)
C8A	0.0181 (16)	0.0184 (15)	0.0220 (16)	0.0021 (12)	0.0036 (13)	0.0009 (13)
C9A	0.0183 (16)	0.0207 (15)	0.0246 (17)	0.0035 (13)	0.0087 (13)	0.0047 (13)
C10A	0.0161 (16)	0.0240 (16)	0.0264 (17)	−0.0022 (13)	0.0058 (13)	−0.0026 (14)
N1A	0.0154 (13)	0.0234 (14)	0.0245 (14)	−0.0005 (11)	0.0052 (11)	0.0016 (11)
N2A	0.0171 (14)	0.0252 (14)	0.0227 (14)	−0.0016 (11)	0.0084 (11)	0.0004 (12)
C11A	0.0165 (15)	0.0199 (15)	0.0217 (16)	0.0059 (12)	0.0055 (12)	0.0045 (13)
S2A	0.0189 (4)	0.0245 (4)	0.0226 (4)	−0.0021 (3)	0.0080 (3)	0.0015 (3)
N3A	0.0196 (15)	0.0372 (17)	0.0234 (15)	−0.0058 (13)	0.0094 (12)	−0.0016 (13)
C1B	0.0258 (18)	0.0249 (17)	0.0278 (18)	−0.0029 (14)	0.0094 (14)	−0.0011 (14)
C2B	0.041 (2)	0.042 (2)	0.030 (2)	−0.0145 (19)	0.0110 (18)	−0.0093 (18)
C3B	0.030 (2)	0.033 (2)	0.040 (2)	−0.0115 (16)	0.0085 (17)	−0.0105 (17)
C4B	0.0217 (18)	0.0255 (18)	0.044 (2)	−0.0058 (14)	0.0135 (16)	−0.0048 (16)
C5B	0.0233 (18)	0.0245 (17)	0.035 (2)	−0.0019 (14)	0.0126 (15)	−0.0027 (15)
C6B	0.0189 (16)	0.0187 (15)	0.0256 (17)	0.0002 (12)	0.0055 (13)	−0.0002 (13)
S1B	0.0309 (5)	0.0340 (5)	0.0245 (4)	−0.0113 (4)	0.0102 (4)	−0.0034 (4)
C7B	0.0190 (16)	0.0217 (16)	0.0270 (17)	−0.0013 (13)	0.0061 (13)	−0.0008 (14)
C8B	0.0190 (16)	0.0177 (15)	0.0236 (16)	−0.0005 (12)	0.0051 (13)	0.0003 (13)
C9B	0.0186 (16)	0.0203 (16)	0.0256 (17)	0.0032 (13)	0.0056 (13)	0.0015 (13)
C10B	0.0220 (18)	0.0335 (19)	0.0258 (18)	−0.0078 (15)	0.0080 (14)	−0.0050 (15)
N1B	0.0161 (14)	0.0225 (14)	0.0252 (14)	−0.0016 (11)	0.0068 (11)	0.0015 (11)
N2B	0.0172 (14)	0.0250 (14)	0.0227 (14)	−0.0032 (11)	0.0061 (11)	−0.0004 (12)
C11B	0.0160 (15)	0.0221 (16)	0.0228 (16)	0.0048 (12)	0.0062 (12)	0.0022 (13)
S2B	0.0205 (4)	0.0264 (4)	0.0220 (4)	−0.0052 (3)	0.0075 (3)	−0.0001 (3)
N3B	0.0171 (14)	0.0313 (16)	0.0217 (14)	−0.0048 (12)	0.0060 (11)	−0.0023 (12)
C1C	0.0257 (18)	0.0245 (17)	0.0251 (17)	−0.0020 (14)	0.0045 (14)	0.0001 (14)
C2C	0.0250 (19)	0.0319 (19)	0.0292 (19)	−0.0023 (15)	0.0036 (15)	−0.0008 (16)
C3C	0.0253 (19)	0.039 (2)	0.031 (2)	−0.0068 (16)	0.0054 (16)	0.0047 (17)
C4C	0.038 (2)	0.0288 (19)	0.036 (2)	−0.0118 (17)	0.0081 (17)	0.0033 (17)
C5C	0.038 (2)	0.0220 (18)	0.042 (2)	−0.0034 (16)	0.0062 (18)	0.0031 (16)
C6C	0.0262 (19)	0.0250 (17)	0.0275 (18)	−0.0027 (14)	0.0061 (14)	0.0033 (14)
S1C	0.0214 (4)	0.0215 (4)	0.0368 (5)	0.0010 (3)	0.0014 (4)	−0.0024 (4)
C7C	0.0283 (19)	0.0264 (18)	0.0300 (19)	−0.0002 (15)	0.0065 (15)	0.0014 (15)
C8C	0.0240 (18)	0.0226 (17)	0.0244 (17)	0.0028 (14)	0.0035 (14)	0.0041 (14)
C9C	0.0237 (18)	0.0235 (17)	0.0267 (18)	0.0004 (14)	0.0019 (14)	0.0020 (14)
C10C	0.0204 (18)	0.0278 (19)	0.041 (2)	0.0020 (14)	−0.0009 (16)	0.0064 (16)
N1C	0.0202 (15)	0.0247 (15)	0.0375 (18)	−0.0022 (12)	−0.0019 (13)	0.0025 (13)
N2C	0.0241 (17)	0.0233 (15)	0.045 (2)	−0.0010 (13)	−0.0070 (14)	0.0090 (14)
C11C	0.030 (2)	0.0226 (17)	0.0310 (19)	0.0027 (15)	0.0001 (15)	0.0013 (15)
S2C	0.0349 (6)	0.0298 (5)	0.0523 (7)	−0.0090 (4)	−0.0136 (5)	0.0164 (5)
N3C	0.0283 (17)	0.0222 (16)	0.0359 (18)	0.0032 (13)	−0.0060 (14)	0.0041 (14)
C1D	0.028 (2)	0.0323 (19)	0.0278 (18)	0.0034 (15)	0.0088 (15)	0.0008 (15)
C2D	0.027 (2)	0.054 (3)	0.040 (2)	0.0070 (19)	0.0124 (17)	0.008 (2)
C3D	0.036 (2)	0.057 (3)	0.042 (2)	0.021 (2)	0.0135 (19)	0.009 (2)
C4D	0.050 (3)	0.037 (2)	0.043 (2)	0.016 (2)	0.023 (2)	0.0097 (19)
C5D	0.043 (2)	0.0285 (19)	0.036 (2)	0.0057 (17)	0.0164 (18)	0.0034 (17)
C6D	0.030 (2)	0.0279 (18)	0.0256 (18)	0.0026 (15)	0.0094 (15)	0.0015 (15)
S1D	0.0210 (5)	0.0279 (5)	0.0415 (5)	−0.0019 (4)	0.0045 (4)	0.0037 (4)
C7D	0.0275 (19)	0.0286 (18)	0.0246 (18)	0.0000 (14)	0.0064 (14)	0.0024 (14)
C8D	0.0223 (17)	0.0237 (17)	0.0275 (18)	−0.0039 (14)	0.0041 (14)	−0.0005 (14)
C9D	0.0198 (17)	0.0278 (18)	0.0239 (17)	−0.0037 (14)	0.0033 (13)	0.0030 (14)
C10D	0.0218 (19)	0.0304 (19)	0.046 (2)	−0.0019 (15)	0.0044 (17)	0.0099 (18)
N1D	0.0234 (16)	0.0246 (15)	0.0361 (17)	0.0020 (12)	0.0038 (13)	0.0047 (13)
N2D	0.0237 (17)	0.0310 (17)	0.057 (2)	0.0019 (14)	0.0092 (16)	0.0149 (16)
C11D	0.032 (2)	0.0236 (18)	0.036 (2)	0.0032 (15)	0.0071 (16)	0.0038 (16)
S2D	0.0374 (6)	0.0426 (6)	0.0628 (8)	0.0165 (5)	0.0150 (5)	0.0240 (6)
N3D	0.0286 (18)	0.0218 (15)	0.045 (2)	0.0031 (13)	0.0112 (15)	0.0087 (14)
O1S	0.089 (4)	0.094 (4)	0.089 (3)	0.009 (3)	0.035 (3)	−0.003 (3)
C1S	0.111 (6)	0.074 (5)	0.080 (5)	−0.010 (4)	0.034 (4)	−0.018 (4)
O2S	0.099 (3)	0.064 (2)	0.097 (3)	0.013 (2)	0.030 (2)	−0.002 (2)
C2S	0.099 (3)	0.064 (2)	0.097 (3)	0.013 (2)	0.030 (2)	−0.002 (2)

Geometric parameters (Å, º) top

C1A—C2A	1.400 (5)	C3C—H3C	0.9500
C1A—C6A	1.410 (5)	C4C—C5C	1.379 (6)
C1A—S1A	1.737 (3)	C4C—H4C	0.9500
C2A—C3A	1.384 (5)	C5C—C6C	1.406 (5)
C2A—H2A	0.9500	C5C—H5C	0.9500
C3A—C4A	1.400 (5)	C6C—C7C	1.439 (5)
C3A—H3A	0.9500	S1C—C8C	1.744 (4)
C4A—C5A	1.373 (5)	C7C—C8C	1.359 (5)
C4A—H4A	0.9500	C7C—H7C	0.9500
C5A—C6A	1.407 (5)	C8C—C9C	1.458 (5)
C5A—H5A	0.9500	C9C—N1C	1.303 (5)
C6A—C7A	1.434 (5)	C9C—C10C	1.499 (5)
S1A—C8A	1.751 (3)	C10C—H10G	0.9800
C7A—C8A	1.366 (5)	C10C—H10H	0.9800
C7A—H7A	0.9500	C10C—H10I	0.9800
C8A—C9A	1.465 (5)	N1C—N2C	1.376 (4)
C9A—N1A	1.294 (4)	N2C—C11C	1.355 (5)
C9A—C10A	1.501 (5)	N2C—H2NC	0.842 (10)
C10A—H10A	0.9800	C11C—N3C	1.326 (5)
C10A—H10B	0.9800	C11C—S2C	1.687 (4)
C10A—H10C	0.9800	N3C—H3N5	0.842 (10)
N1A—N2A	1.373 (4)	N3C—H3N6	0.840 (10)
N2A—C11A	1.346 (4)	C1D—C2D	1.396 (5)
N2A—H2NA	0.841 (10)	C1D—C6D	1.412 (5)
C11A—N3A	1.319 (4)	C1D—S1D	1.740 (4)
C11A—S2A	1.706 (3)	C2D—C3D	1.390 (6)
N3A—H3N1	0.839 (10)	C2D—H2D	0.9500
N3A—H3N2	0.843 (10)	C3D—C4D	1.382 (7)
C1B—C2B	1.395 (5)	C3D—H3D	0.9500
C1B—C6B	1.405 (5)	C4D—C5D	1.379 (6)
C1B—S1B	1.739 (4)	C4D—H4D	0.9500
C2B—C3B	1.390 (6)	C5D—C6D	1.408 (5)
C2B—H2B	0.9500	C5D—H5D	0.9500
C3B—C4B	1.390 (6)	C6D—C7D	1.432 (5)
C3B—H3B	0.9500	S1D—C8D	1.739 (4)
C4B—C5B	1.386 (5)	S1D—S1Bⁱ	3.5958 (14)
C4B—H4B	0.9500	C7D—C8D	1.362 (5)
C5B—C6B	1.407 (5)	C7D—H7D	0.9500
C5B—H5B	0.9500	C8D—C9D	1.461 (5)
C6B—C7B	1.438 (5)	C9D—N1D	1.290 (5)
S1B—C8B	1.746 (3)	C9D—C10D	1.500 (5)
C7B—C8B	1.376 (5)	C10D—H10J	0.9800
C7B—H7B	0.9500	C10D—H10K	0.9800
C8B—C9B	1.462 (5)	C10D—H10L	0.9800
C9B—N1B	1.296 (5)	N1D—N2D	1.376 (4)
C9B—C10B	1.495 (5)	N2D—C11D	1.352 (5)
C10B—H10D	0.9800	N2D—H2ND	0.842 (10)
C10B—H10E	0.9800	C11D—N3D	1.311 (5)
C10B—H10F	0.9800	C11D—S2D	1.705 (4)
N1B—N2B	1.379 (4)	N3D—H3N7	0.841 (10)
N2B—C11B	1.362 (4)	N3D—H3N8	0.840 (10)
N2B—H2NB	0.839 (10)	O1S—C1S	1.367 (8)
C11B—N3B	1.325 (4)	O1S—H1S	0.8400
C11B—S2B	1.692 (3)	C1S—H1S1	0.9800
N3B—H3N3	0.838 (10)	C1S—H1S2	0.9800
N3B—H3N4	0.839 (10)	C1S—H1S3	0.9800
C1C—C2C	1.399 (5)	O2S—C2S	1.248 (8)
C1C—C6C	1.413 (5)	O2S—H2S	0.8400
C1C—S1C	1.738 (4)	C2S—H2S1	0.9800
C2C—C3C	1.381 (5)	C2S—H2S2	0.9800
C2C—H2C	0.9500	C2S—H2S3	0.9800
C3C—C4C	1.401 (6)

C2A—C1A—C6A	121.9 (3)	C4C—C3C—H3C	119.5
C2A—C1A—S1A	126.5 (3)	C5C—C4C—C3C	121.3 (4)
C6A—C1A—S1A	111.5 (2)	C5C—C4C—H4C	119.3
C3A—C2A—C1A	117.5 (3)	C3C—C4C—H4C	119.3
C3A—C2A—H2A	121.3	C4C—C5C—C6C	119.0 (4)
C1A—C2A—H2A	121.3	C4C—C5C—H5C	120.5
C2A—C3A—C4A	121.4 (3)	C6C—C5C—H5C	120.5
C2A—C3A—H3A	119.3	C5C—C6C—C1C	118.9 (3)
C4A—C3A—H3A	119.3	C5C—C6C—C7C	129.4 (4)
C5A—C4A—C3A	120.9 (3)	C1C—C6C—C7C	111.7 (3)
C5A—C4A—H4A	119.5	C1C—S1C—C8C	91.05 (17)
C3A—C4A—H4A	119.5	C8C—C7C—C6C	112.6 (3)
C4A—C5A—C6A	119.5 (3)	C8C—C7C—H7C	123.7
C4A—C5A—H5A	120.3	C6C—C7C—H7C	123.7
C6A—C5A—H5A	120.3	C7C—C8C—C9C	127.4 (3)
C5A—C6A—C1A	118.7 (3)	C7C—C8C—S1C	113.1 (3)
C5A—C6A—C7A	129.2 (3)	C9C—C8C—S1C	119.5 (3)
C1A—C6A—C7A	112.1 (3)	N1C—C9C—C8C	114.2 (3)
C1A—S1A—C8A	91.19 (16)	N1C—C9C—C10C	125.9 (3)
C8A—C7A—C6A	112.7 (3)	C8C—C9C—C10C	119.8 (3)
C8A—C7A—H7A	123.6	C9C—C10C—H10G	109.5
C6A—C7A—H7A	123.6	C9C—C10C—H10H	109.5
C7A—C8A—C9A	128.3 (3)	H10G—C10C—H10H	109.5
C7A—C8A—S1A	112.5 (3)	C9C—C10C—H10I	109.5
C9A—C8A—S1A	119.1 (3)	H10G—C10C—H10I	109.5
N1A—C9A—C8A	114.7 (3)	H10H—C10C—H10I	109.5
N1A—C9A—C10A	124.9 (3)	C9C—N1C—N2C	119.1 (3)
C8A—C9A—C10A	120.4 (3)	C11C—N2C—N1C	117.3 (3)
C9A—C10A—H10A	109.5	C11C—N2C—H2NC	117 (3)
C9A—C10A—H10B	109.5	N1C—N2C—H2NC	124 (3)
H10A—C10A—H10B	109.5	N3C—C11C—N2C	114.8 (3)
C9A—C10A—H10C	109.5	N3C—C11C—S2C	122.9 (3)
H10A—C10A—H10C	109.5	N2C—C11C—S2C	122.3 (3)
H10B—C10A—H10C	109.5	C11C—N3C—H3N5	124 (4)
C9A—N1A—N2A	117.0 (3)	C11C—N3C—H3N6	122 (4)
C11A—N2A—N1A	119.2 (3)	H3N5—N3C—H3N6	114 (5)
C11A—N2A—H2NA	120 (3)	C2D—C1D—C6D	122.1 (4)
N1A—N2A—H2NA	120 (3)	C2D—C1D—S1D	126.4 (3)
N3A—C11A—N2A	118.2 (3)	C6D—C1D—S1D	111.5 (3)
N3A—C11A—S2A	123.0 (3)	C3D—C2D—C1D	117.4 (4)
N2A—C11A—S2A	118.8 (3)	C3D—C2D—H2D	121.3
C11A—N3A—H3N1	116 (3)	C1D—C2D—H2D	121.3
C11A—N3A—H3N2	119 (3)	C4D—C3D—C2D	121.3 (4)
H3N1—N3A—H3N2	124 (4)	C4D—C3D—H3D	119.3
C2B—C1B—C6B	121.5 (3)	C2D—C3D—H3D	119.3
C2B—C1B—S1B	126.5 (3)	C5D—C4D—C3D	121.5 (4)
C6B—C1B—S1B	111.9 (3)	C5D—C4D—H4D	119.2
C3B—C2B—C1B	117.9 (4)	C3D—C4D—H4D	119.2
C3B—C2B—H2B	121.0	C4D—C5D—C6D	119.2 (4)
C1B—C2B—H2B	121.0	C4D—C5D—H5D	120.4
C2B—C3B—C4B	121.3 (4)	C6D—C5D—H5D	120.4
C2B—C3B—H3B	119.4	C5D—C6D—C1D	118.4 (4)
C4B—C3B—H3B	119.4	C5D—C6D—C7D	129.8 (4)
C5B—C4B—C3B	120.9 (4)	C1D—C6D—C7D	111.8 (3)
C5B—C4B—H4B	119.5	C8D—S1D—C1D	90.87 (18)
C3B—C4B—H4B	119.5	C8D—S1D—S1Bⁱ	137.93 (13)
C4B—C5B—C6B	118.9 (4)	C1D—S1D—S1Bⁱ	92.50 (13)
C4B—C5B—H5B	120.5	C8D—C7D—C6D	112.5 (3)
C6B—C5B—H5B	120.5	C8D—C7D—H7D	123.8
C1B—C6B—C5B	119.3 (3)	C6D—C7D—H7D	123.8
C1B—C6B—C7B	111.8 (3)	C7D—C8D—C9D	127.8 (3)
C5B—C6B—C7B	128.9 (3)	C7D—C8D—S1D	113.3 (3)
C1B—S1B—C8B	91.17 (17)	C9D—C8D—S1D	118.8 (3)
C8B—C7B—C6B	112.6 (3)	N1D—C9D—C8D	115.6 (3)
C8B—C7B—H7B	123.7	N1D—C9D—C10D	124.3 (3)
C6B—C7B—H7B	123.7	C8D—C9D—C10D	120.1 (3)
C7B—C8B—C9B	128.3 (3)	C9D—C10D—H10J	109.5
C7B—C8B—S1B	112.5 (3)	C9D—C10D—H10K	109.5
C9B—C8B—S1B	119.2 (3)	H10J—C10D—H10K	109.5
N1B—C9B—C8B	114.7 (3)	C9D—C10D—H10L	109.5
N1B—C9B—C10B	125.7 (3)	H10J—C10D—H10L	109.5
C8B—C9B—C10B	119.7 (3)	H10K—C10D—H10L	109.5
C9B—C10B—H10D	109.5	C9D—N1D—N2D	116.7 (3)
C9B—C10B—H10E	109.5	C11D—N2D—N1D	119.1 (3)
H10D—C10B—H10E	109.5	C11D—N2D—H2ND	123 (4)
C9B—C10B—H10F	109.5	N1D—N2D—H2ND	117 (4)
H10D—C10B—H10F	109.5	N3D—C11D—N2D	118.3 (3)
H10E—C10B—H10F	109.5	N3D—C11D—S2D	123.5 (3)
C9B—N1B—N2B	117.2 (3)	N2D—C11D—S2D	118.2 (3)
C11B—N2B—N1B	117.9 (3)	C11D—N3D—H3N7	120 (3)
C11B—N2B—H2NB	118 (3)	C11D—N3D—H3N8	116 (3)
N1B—N2B—H2NB	125 (3)	H3N7—N3D—H3N8	124 (5)
N3B—C11B—N2B	117.4 (3)	C1S—O1S—H1S	109.5
N3B—C11B—S2B	122.8 (3)	O1S—C1S—H1S1	109.5
N2B—C11B—S2B	119.8 (3)	O1S—C1S—H1S2	109.5
C11B—N3B—H3N3	116 (3)	H1S1—C1S—H1S2	109.5
C11B—N3B—H3N4	115 (3)	O1S—C1S—H1S3	109.5
H3N3—N3B—H3N4	129 (4)	H1S1—C1S—H1S3	109.5
C2C—C1C—C6C	121.8 (3)	H1S2—C1S—H1S3	109.5
C2C—C1C—S1C	126.7 (3)	C2S—O2S—H2S	109.5
C6C—C1C—S1C	111.5 (3)	O2S—C2S—H2S1	109.5
C3C—C2C—C1C	117.9 (4)	O2S—C2S—H2S2	109.5
C3C—C2C—H2C	121.1	H2S1—C2S—H2S2	109.5
C1C—C2C—H2C	121.1	O2S—C2S—H2S3	109.5
C2C—C3C—C4C	121.0 (4)	H2S1—C2S—H2S3	109.5
C2C—C3C—H3C	119.5	H2S2—C2S—H2S3	109.5

Symmetry code: (i) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3N2···N1A	0.84 (1)	2.29 (4)	2.641 (4)	105 (3)
N3B—H3N3···N1B	0.84 (1)	2.21 (4)	2.617 (4)	110 (3)
N3C—H3N5···N1C	0.84 (1)	2.22 (5)	2.543 (4)	102 (4)
N3D—H3N7···N1D	0.84 (1)	2.29 (5)	2.643 (4)	105 (4)
N3A—H3N1···S2Bⁱⁱ	0.84 (1)	2.50 (1)	3.325 (3)	168 (4)
N3B—H3N4···S2Aⁱⁱⁱ	0.84 (1)	2.62 (2)	3.367 (3)	149 (4)
N2B—H2NB···S2A^iv	0.84 (1)	2.59 (1)	3.412 (3)	169 (4)
N3C—H3N6···S2A^v	0.84 (1)	2.76 (4)	3.352 (3)	129 (4)
N3C—H3N6···N3B^vi	0.84 (1)	2.72 (3)	3.468 (5)	149 (5)
N2C—H2NC···S2C^vii	0.84 (1)	2.60 (2)	3.392 (3)	158 (4)
N3D—H3N8···S2A^v	0.84 (1)	2.74 (2)	3.563 (3)	168 (4)
N3D—H3N7···O1S	0.84 (1)	2.26 (3)	2.967 (6)	142 (4)
O1S—H1S···S2C^vii	0.84	2.64	3.471 (5)	169
O2S—H2S···S2D^viii	0.84	2.97	3.389 (6)	113
C3A—H3A···S2A^v	0.95	2.97	3.762 (4)	142
C10A—H10A···S2B^ix	0.98	2.91	3.613 (3)	129
C2B—H2B···O1S^x	0.95	2.36	3.282 (7)	163
C2S—H2S1···N2D^viii	0.98	2.74	3.266 (9)	115
C10B—H10F···C_g^xi	0.98	2.91	3.594 (4)	129

Symmetry codes: (ii) x+1, y, z; (iii) x−1, y, z; (iv) x−1, −y+3/2, z−1/2; (v) −x+1, y−1/2, −z+3/2; (vi) −x, y−1/2, −z+3/2; (vii) −x, −y+1, −z+1; (viii) −x+1, −y+1, −z+1; (ix) x+1, −y+3/2, z+1/2; (x) x, −y+3/2, z+1/2; (xi) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁N₃S₂·0.5(CH₄O)
M_r	265.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	92
a, b, c (Å)	18.9438 (12), 17.7076 (11), 15.4145 (10)
β (°)	107.238 (3)
V (Å³)	4938.5 (5)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.31 × 0.20 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.777, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	65034, 10871, 8171
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.203, 1.03
No. of reflections	10871
No. of parameters	655
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.71, −2.31

Computer programs: , APEX2 (Bruker, 2006) and SAINT (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).