Crystal structure of (2E)-N-methyl-2-(2-oxo-1,2-di­hydroacenaphthylen-1-ylidene)hydrazinecarbo­thioamide

Vimala, G.; Govindaraj, J.; Haribabu, J.; Karvembu, R.; SubbiahPandi, A.

doi:10.1107/S1600536814023216

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 415-417

doi:10.1107/S1600536814023216

Open

access

Crystal structure of (2E)-N-methyl-2-(2-oxo-1,2-dihydroacenaphthylen-1-ylidene)hydrazinecarbothioamide

G. Vimala,^a J. Govindaraj,^b J. Haribabu,^c R. Karvembu ^c and A. SubbiahPandi ^a,^c ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^bDepartment of Physics, Pachaiyappa's College for Men, Kancheepuram 631 501, India, and ^cDepartment of Chemistry, National Institute of Technology, Trichy 620 015, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 9 October 2014; accepted 21 October 2014; online 24 October 2014)

In the title compound, C₁₄H₁₁N₃OS, the acenaphthylene ring system and hydrazinecarbothioamide unit (=N—NH—C=S—NH–) are essentially coplanar [with maximum deviations from their mean planes of −0.009 (2) and 0.033 (2) Å, respectively], and make a dihedral angle of 1.59 (9)°. The molecular conformation is stabilized by two weak intramolecular hydrogen bonds (N—H⋯O and N—H⋯N), which generate S(6) and S(5) ring motifs. In the crystal, molecules are linked by N—H⋯S hydrogen bonds, forming chains along [010]. The chains are linked via pairs of C—H⋯O hydrogen bonds, enclosing R²₂(10) ring motifs, and C—H⋯π interactions, forming a three-dimensional framework. The absolute structure of the title compound was determined by resonant scattering.

Keywords: crystal structure; acenaphthylene; hydrazinecarbothioamide; thiosemicarbazones; hydrogen bonding; C—H⋯π interactions.

CCDC reference: 1030348

1. Chemical context

The design and synthesis of thiosemicarbazones are of considerable interest because of their versatile chemistry and various biological activities, such as antitumor, antibacterial, antiviral, antiamoebic and antimalarial (Kelly et al., 1996 ). They comprise an intriguing class of chelating molecules, which possess a wide range of beneficial medicinal properties (Prabhakaran et al. 2008 ). Thiosemicarbazones are a versatile class of ligands that have been studied for their biological activity (Chellan et al., 2010 ), their interesting binding motifs (Lobana et al., 2009 ) and their use as ligands in catalysis (Xie et al., 2010 ). In view of their biological importance, the crystal structure of the title compound has been determined and the results are presented herein.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The atoms of both the acenaphthylene ring system and the =N—NH—C=S—NH– segment are essentially coplanar, the maximum deviations from their mean planes being −0.009 (2) and 0.033 (2) Å for atoms C12 and C14, respectively. The dihedral angle between the benzene and cyclopentane rings of the acenapthalene unit is 1.59 (9)°. The molecular structure is stabilized by N—H⋯O and N—H⋯N hydrogen bonds, forming S(6) and S(5) ring motifs, respectively (Table 1 and Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of ring C1/C6–C10.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.03	2.7178 (19)	136
N3—H3⋯N1	0.86	2.26	2.6437 (19)	107
N3—H3⋯S1ⁱ	0.86	2.64	3.4407 (15)	156
C4—H4⋯O1ⁱⁱ	0.93	2.47	3.246 (2)	141
C2—H2A⋯Cgⁱⁱⁱ	0.93	2.76	3.502 (2)	137
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z]$ .

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines (see Table 1

for details).

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯S hydrogen bonds (Table 1 and Fig. 2), forming chains along [010]. The chains are linked via pairs of C—H⋯O hydrogen bonds, enclosing R₂²(10) ring motifs, and C—H⋯π interactions, forming a three-dimensional framework (Table 1 and Fig. 2).

Figure 2
The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1

for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014 ) for the substructure 2-(imino)acenaphthylen-1(2H)-one gave 13 hits, including that of the ethyl analogue of the title compound, acenaphthylene-1,2-dione 4-ethylthiosemicarbazone (GURHAD; Pascu et al., 2010 ). The two molecules differ in the dihedral angle between the mean planes of the acenaphthylene ring system and hydrazinecarbothioamide unit (=N—NH—C=S—NH–) which is 1.59 (9)° in the title compound but 9.14 (6)° in the ethyl analogue (GURHAD; Pascu et al., 2010). In the crystals of both compounds, molecules are linked via N—H⋯S hydrogen bonds, forming chains along [010].

5. Synthesis and crystallization

An ethanolic solution of N-methylhydrazinecarbothioamide (0.01 mol) was added to an ethanolic solution (50 ml) containing acenaphthylene-1,2-dione (0.01 mol). The mixture was refluxed for 2 h during which time a yellow precipitate separated out. The reaction mixture was then cooled to room temperature and the precipitate was filtered off. It was then washed with ethanol and dried under vacuum. The yield of the isolated product was 89%. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in ethanol at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were fixed geometrically and allowed to ride on their parent atoms: N—H = 0.86 and C—H = 0.93–0.97 Å and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms. The absolute structure of the title compound was determined by resonant scattering, with a Flack parameter of 0.02 (8).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃OS
M_r	269.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.1110 (6), 10.0547 (11), 21.497 (2)
V (Å³)	1320.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.932, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	23135, 3941, 2929
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 0.99
No. of reflections	3941
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21
Absolute structure	Flack (1983 ); Friedel pairs
Absolute structure parameter	−0.02 (8)
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1030348

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814023216/su2796sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814023216/su2796Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814023216/su2796Isup3.cml

checkCIF report

Chemical context top

The design and synthesis of thiosemicarbazones are of considerable interest because of their versatile chemistry and various biological activities, such as antitumor, antibacterial, antiviral, antiamoebic and antimalarial (Kelly et al., 1996). They comprise an intriguing class of chelating molecules, which possess a wide range of beneficial medicinal properties (Prabhakaran et al. 2008). Thiosemicarbazones are a versatile class of ligands that have been studied for their biological activity (Chellan et al., 2010), their interesting binding motifs (Lobana et al., 2009) and their use as ligands in catalysis (Xie et al., 2010). In view of their biological importance, the crystal structure of the title compound has been determined and the results are presented herein.

Structural commentary top

The molecular structure of the title compound is illustrated in Fig. 1. The atoms of both the acenaphthylene ring system and the =N—NH—C=S—NH– segment are essentially coplanar, the maximum deviations from their mean planes being -0.009 (2) and 0.033 (2) Å for C12 and C14, respectively. The dihedral angle between the benzene and cyclopentane rings of the acenapthalene unit is 1.59 (9)°. The molecular structure is stabilized by N—H···O and N—H···N hydrogen bonds, forming S(6) and S(5) ring motifs, respectively (Table 1 and Fig. 1).

Supramolecular features top

In the crystal, molecules are linked by N—H···S hydrogen bonds (Table 1 and Fig. 2), forming chains along [010]. The chains are linked via pairs of C—H···O hydrogen bonds, enclosing R²₂(10) ring motifs, and C—H···π interactions, forming a three-dimensional framework (Table 1 and Fig. 2).

Database survey top

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014) for the substructure 2-(imino)acenaphthylen-1(2H)-one gave 13 hits, including that of the ethyl analogue of the title compound, acenaphthylene-1,2-dione 4-ethylthiosemicarbazone (GURHAD; Pascu et al., 2010). The two molecules differ in the dihedral angle between the mean planes of the acenaphthylene ring system and hydrazinecarbothioamide unit (=N—NH—C=S—NH–) which is 1.59 (9)° in the title compound but 9.14 (6)° in the ethyl analogue (GURHAD; Pascu et al., 2010). In the crystals of both compounds, molecules are linked via N—H···S hydrogen bonds, forming chains along [010].

Synthesis and crystallization top

An ethanolic solution of N-methylhydrazinecarbothioamide (0.01 mol) was added to an ethanolic solution (50 ml) containing acenaphthylene-1,2-dione (0.01 mol). The mixture was refluxed for 2 h during which time an yellow precipitate separated out. The reaction mixture was then cooled to room temperature and the precipitate was filtered off. It was then washed with ethanol and dried under vacuum. The yield of the isolated product was 89%. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in ethanol at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were fixed geometrically and allowed to ride on their parent atoms: N—H = 0.86 and C—H = 0.93–0.97 Å and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms. The absolute structure of the title compound was determined by resonant scattering, with a Flack parameter of 0.02 (8).

Related literature top

For related literature, see: Groom & Allen (2014); Chellan et al. (2010); Kelly et al. (1996); Lobana et al. (2009); Pascu et al. (2010); Prabhakaran et al. (2008); Xie et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

(2E)-N-Methyl-2-(2-oxo-1,2-dihydroacenaphthylen-1-ylidene)hydrazinecarbothioamide top

Crystal data top

C₁₄H₁₁N₃OS	Z = 4
M_r = 269.33	F(000) = 560
Orthorhombic, P2₁2₁2₁	D_x = 1.354 Mg m⁻³
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 6.1110 (6) Å	µ = 0.24 mm⁻¹
b = 10.0547 (11) Å	T = 293 K
c = 21.497 (2) Å	Block, yellow
V = 1320.8 (2) Å³	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3941 independent reflections
Radiation source: fine-focus sealed tube	2929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scans	θ_max = 30.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.932, T_max = 0.954	k = −13→14
23135 measured reflections	l = −29→29

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0532P)² + 0.2048P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
3941 reflections	Δρ_max = 0.19 e Å⁻³
173 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983); Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (8)

Crystal data top

C₁₄H₁₁N₃OS	V = 1320.8 (2) Å³
M_r = 269.33	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1110 (6) Å	µ = 0.24 mm⁻¹
b = 10.0547 (11) Å	T = 293 K
c = 21.497 (2) Å	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3941 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2929 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.954	R_int = 0.030
23135 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.100	Δρ_max = 0.19 e Å⁻³
S = 0.99	Δρ_min = −0.21 e Å⁻³
3941 reflections	Absolute structure: Flack (1983); Friedel pairs
173 parameters	Absolute structure parameter: −0.02 (8)
0 restraints

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
S1	0.25692 (8)	0.16757 (4)	0.21243 (2)	0.04960 (13)
N1	0.7542 (2)	−0.05741 (12)	0.17414 (6)	0.0365 (3)
C6	1.2232 (3)	−0.09719 (15)	0.07905 (7)	0.0371 (3)
O1	0.8428 (2)	0.16301 (14)	0.08374 (6)	0.0550 (4)
N2	0.6084 (2)	0.04380 (14)	0.17558 (7)	0.0416 (3)
H2	0.6259	0.1109	0.1513	0.050*
C7	1.0847 (3)	−0.14650 (15)	0.12619 (7)	0.0342 (3)
C13	0.4342 (3)	0.04074 (16)	0.21510 (8)	0.0380 (3)
N3	0.4208 (2)	−0.06205 (15)	0.25248 (7)	0.0445 (3)
H3	0.5225	−0.1210	0.2506	0.053*
C12	0.9103 (3)	−0.04864 (16)	0.13442 (7)	0.0350 (3)
C5	1.1533 (3)	0.02565 (17)	0.05510 (8)	0.0425 (4)
C11	0.9539 (3)	0.06370 (17)	0.08912 (8)	0.0403 (4)
C8	1.1346 (3)	−0.26514 (17)	0.15336 (8)	0.0416 (4)
H8	1.0445	−0.3015	0.1838	0.050*
C9	1.3268 (3)	−0.3313 (2)	0.13404 (9)	0.0492 (4)
H9	1.3632	−0.4114	0.1530	0.059*
C14	0.2450 (4)	−0.0824 (2)	0.29673 (10)	0.0634 (5)
H14A	0.2421	−0.0099	0.3258	0.095*
H14B	0.2686	−0.1642	0.3187	0.095*
H14C	0.1080	−0.0866	0.2750	0.095*
C1	1.4122 (3)	−0.16161 (19)	0.05877 (8)	0.0435 (4)
C2	1.5292 (4)	−0.0968 (2)	0.01114 (10)	0.0604 (6)
H2A	1.6559	−0.1356	−0.0045	0.072*
C4	1.2699 (4)	0.0860 (2)	0.00894 (9)	0.0578 (5)
H4	1.2252	0.1668	−0.0078	0.069*
C3	1.4596 (4)	0.0221 (2)	−0.01250 (11)	0.0671 (6)
H3A	1.5408	0.0621	−0.0439	0.080*
C10	1.4618 (3)	−0.2829 (2)	0.08867 (9)	0.0505 (5)
H10	1.5867	−0.3300	0.0775	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0421 (2)	0.0413 (2)	0.0654 (3)	0.0080 (2)	0.0033 (2)	−0.01024 (19)
N1	0.0345 (6)	0.0331 (6)	0.0420 (7)	0.0008 (6)	0.0020 (7)	−0.0007 (5)
C6	0.0373 (9)	0.0370 (8)	0.0369 (8)	−0.0031 (7)	−0.0004 (7)	−0.0047 (6)
O1	0.0621 (8)	0.0423 (7)	0.0605 (8)	0.0123 (7)	0.0046 (7)	0.0140 (6)
N2	0.0397 (7)	0.0361 (7)	0.0488 (8)	0.0054 (6)	0.0055 (7)	0.0043 (6)
C7	0.0353 (8)	0.0338 (8)	0.0336 (7)	0.0004 (6)	−0.0001 (6)	−0.0013 (6)
C13	0.0337 (8)	0.0365 (8)	0.0438 (8)	−0.0028 (6)	0.0001 (7)	−0.0089 (7)
N3	0.0401 (8)	0.0406 (7)	0.0528 (8)	0.0015 (6)	0.0077 (7)	−0.0009 (7)
C12	0.0356 (8)	0.0326 (7)	0.0368 (7)	0.0007 (6)	−0.0014 (7)	0.0021 (6)
C5	0.0498 (10)	0.0395 (9)	0.0381 (8)	−0.0029 (8)	0.0047 (8)	−0.0009 (7)
C11	0.0436 (9)	0.0357 (8)	0.0415 (8)	−0.0005 (7)	−0.0003 (7)	0.0040 (7)
C8	0.0454 (10)	0.0386 (9)	0.0407 (9)	0.0029 (8)	0.0000 (8)	0.0019 (7)
C9	0.0523 (10)	0.0432 (9)	0.0521 (10)	0.0129 (9)	−0.0088 (8)	−0.0013 (8)
C14	0.0583 (12)	0.0610 (12)	0.0707 (13)	−0.0037 (11)	0.0226 (12)	0.0021 (9)
C1	0.0388 (9)	0.0476 (9)	0.0441 (9)	−0.0044 (8)	0.0042 (7)	−0.0129 (8)
C2	0.0513 (12)	0.0702 (14)	0.0596 (12)	−0.0090 (10)	0.0196 (10)	−0.0180 (10)
C4	0.0742 (14)	0.0496 (10)	0.0495 (10)	−0.0103 (11)	0.0164 (11)	0.0068 (8)
C3	0.0747 (16)	0.0684 (15)	0.0581 (12)	−0.0179 (12)	0.0285 (12)	−0.0009 (10)
C10	0.0397 (10)	0.0547 (11)	0.0572 (11)	0.0100 (8)	−0.0044 (8)	−0.0157 (9)

Geometric parameters (Å, º) top

S1—C13	1.6744 (17)	C5—C11	1.472 (3)
N1—C12	1.283 (2)	C8—C9	1.412 (2)
N1—N2	1.3528 (19)	C8—H8	0.9300
C6—C1	1.394 (2)	C9—C10	1.367 (3)
C6—C5	1.405 (2)	C9—H9	0.9300
C6—C7	1.410 (2)	C14—H14A	0.9600
O1—C11	1.213 (2)	C14—H14B	0.9600
N2—C13	1.362 (2)	C14—H14C	0.9600
N2—H2	0.8600	C1—C2	1.409 (3)
C7—C8	1.363 (2)	C1—C10	1.411 (3)
C7—C12	1.461 (2)	C2—C3	1.367 (3)
C13—N3	1.312 (2)	C2—H2A	0.9300
N3—C14	1.449 (2)	C4—C3	1.403 (3)
N3—H3	0.8600	C4—H4	0.9300
C12—C11	1.515 (2)	C3—H3A	0.9300
C5—C4	1.364 (3)	C10—H10	0.9300

C12—N1—N2	116.93 (13)	C7—C8—H8	120.9
C1—C6—C5	123.08 (16)	C9—C8—H8	120.9
C1—C6—C7	123.95 (16)	C10—C9—C8	122.95 (18)
C5—C6—C7	112.96 (15)	C10—C9—H9	118.5
N1—N2—C13	120.78 (14)	C8—C9—H9	118.5
N1—N2—H2	119.6	N3—C14—H14A	109.5
C13—N2—H2	119.6	N3—C14—H14B	109.5
C8—C7—C6	118.78 (16)	H14A—C14—H14B	109.5
C8—C7—C12	134.48 (16)	N3—C14—H14C	109.5
C6—C7—C12	106.73 (13)	H14A—C14—H14C	109.5
N3—C13—N2	116.67 (15)	H14B—C14—H14C	109.5
N3—C13—S1	125.49 (13)	C6—C1—C2	115.65 (19)
N2—C13—S1	117.84 (13)	C6—C1—C10	115.92 (16)
C13—N3—C14	124.05 (16)	C2—C1—C10	128.43 (18)
C13—N3—H3	118.0	C3—C2—C1	121.1 (2)
C14—N3—H3	118.0	C3—C2—H2A	119.4
N1—C12—C7	125.20 (14)	C1—C2—H2A	119.4
N1—C12—C11	127.56 (15)	C5—C4—C3	117.9 (2)
C7—C12—C11	107.22 (14)	C5—C4—H4	121.1
C4—C5—C6	119.92 (18)	C3—C4—H4	121.1
C4—C5—C11	132.73 (18)	C2—C3—C4	122.4 (2)
C6—C5—C11	107.34 (15)	C2—C3—H3A	118.8
O1—C11—C5	129.05 (16)	C4—C3—H3A	118.8
O1—C11—C12	125.21 (16)	C9—C10—C1	120.19 (17)
C5—C11—C12	105.74 (14)	C9—C10—H10	119.9
C7—C8—C9	118.19 (17)	C1—C10—H10	119.9

C12—N1—N2—C13	178.14 (14)	C6—C5—C11—C12	−0.95 (18)
C1—C6—C7—C8	−1.1 (2)	N1—C12—C11—O1	−0.7 (3)
C5—C6—C7—C8	−179.95 (15)	C7—C12—C11—O1	−179.08 (17)
C1—C6—C7—C12	178.56 (15)	N1—C12—C11—C5	179.18 (16)
C5—C6—C7—C12	−0.34 (19)	C7—C12—C11—C5	0.76 (18)
N1—N2—C13—N3	2.3 (2)	C6—C7—C8—C9	1.7 (2)
N1—N2—C13—S1	−178.08 (12)	C12—C7—C8—C9	−177.74 (17)
N2—C13—N3—C14	−179.01 (17)	C7—C8—C9—C10	−1.3 (3)
S1—C13—N3—C14	1.4 (3)	C5—C6—C1—C2	−1.3 (2)
N2—N1—C12—C7	179.26 (15)	C7—C6—C1—C2	179.96 (16)
N2—N1—C12—C11	1.1 (2)	C5—C6—C1—C10	178.58 (16)
C8—C7—C12—N1	0.8 (3)	C7—C6—C1—C10	−0.2 (2)
C6—C7—C12—N1	−178.75 (15)	C6—C1—C2—C3	0.6 (3)
C8—C7—C12—C11	179.24 (18)	C10—C1—C2—C3	−179.2 (2)
C6—C7—C12—C11	−0.29 (17)	C6—C5—C4—C3	−0.7 (3)
C1—C6—C5—C4	1.4 (3)	C11—C5—C4—C3	178.57 (19)
C7—C6—C5—C4	−179.72 (17)	C1—C2—C3—C4	0.0 (4)
C1—C6—C5—C11	−178.08 (15)	C5—C4—C3—C2	0.1 (3)
C7—C6—C5—C11	0.83 (19)	C8—C9—C10—C1	0.0 (3)
C4—C5—C11—O1	−0.5 (4)	C6—C1—C10—C9	0.7 (2)
C6—C5—C11—O1	178.88 (19)	C2—C1—C10—C9	−179.5 (2)
C4—C5—C11—C12	179.7 (2)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of ring C1/C6–C10.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.03	2.7178 (19)	136
N3—H3···N1	0.86	2.26	2.6437 (19)	107
N3—H3···S1ⁱ	0.86	2.64	3.4407 (15)	156
C4—H4···O1ⁱⁱ	0.93	2.47	3.246 (2)	141
C2—H2A···Cgⁱⁱⁱ	0.93	2.76	3.502 (2)	137

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of ring C1/C6–C10.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.03	2.7178 (19)	136
N3—H3···N1	0.86	2.26	2.6437 (19)	107
N3—H3···S1ⁱ	0.86	2.64	3.4407 (15)	156
C4—H4···O1ⁱⁱ	0.93	2.47	3.246 (2)	141
C2—H2A···Cgⁱⁱⁱ	0.93	2.76	3.502 (2)	137

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃OS
M_r	269.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.1110 (6), 10.0547 (11), 21.497 (2)
V (Å³)	1320.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.932, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	23135, 3941, 2929
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 0.99
No. of reflections	3941
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21
Absolute structure	Flack (1983); Friedel pairs
Absolute structure parameter	−0.02 (8)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India for the data collection.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chellan, P., Shunmoogam-Gounden, N., Hendricks, D. T., Gut, J., Rosenthal, P. J., Lategan, C., Smith, P. J., Chibale, K. & Smith, G. S. (2010). Eur. J. Inorg. Chem. pp, 3520–3528. Web of Science CSD CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1996). J. Chem. Soc. Dalton Trans. pp. 53–59. CSD CrossRef Web of Science Google Scholar
Lobana, T. S., Sharma, R., Bawa, G. & Khanna, S. (2009). Coord. Chem. Rev. 253, 977–1055. Web of Science CrossRef CAS Google Scholar
Pascu, S. I., Waghorn, P. A., Kennedy, B. W. C., Arrowsmith, R. L., Bayly, S. R., Dilworth, J. R., Christlieb, M., Tyrrell, R. M., Zhong, J., Kowalczyk, R. M., Collison, D., Aley, P. K., Churchill, G. C. & Aigbirhio, F. I. (2010). Chem. Asian J. 5, 506–519. Web of Science CrossRef CAS PubMed Google Scholar
Prabhakaran, R., Huang, R., Renukadevi, S. V., Karvembu, R., Zeller, M. & Natarajan, K. (2008). Inorg. Chim. Acta, 361, 2547–2552. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, G., Chellan, P., Mao, J., Chibale, K. & Smith, G. S. (2010). Adv. Synth. Catal. 352, 1641–1647. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 415-417

doi:10.1107/S1600536814023216

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (2E)-N-methyl-2-(2-oxo-1,2-di­hydroace­naphthylen-1-yl­idene)hydrazinecarbo­thio­amide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of (2E)-N-methyl-2-(2-oxo-1,2-dihydroacenaphthylen-1-ylidene)hydrazinecarbothioamide

3. Supramolecular features