S-Quinolin-2-ylmethyl­dithio­carbazate

In the title compound, C₁₁H₁₁N₂S₂, there is an intra­molecular N—H...N [2.778 (2) Å] hydrogen bond linking the quinoline N atom and the imino N atom. The planar quinoline ring system forms an angle of 67.7 (1)° with the dithio­carbazate group. Bond angles for both S—C—S [115.66 (8)°] and N—C—S [119.05 (11)°] are comparable with cis–trans S-methyl­dithio­carbazate but differ from those found in trans–cis S-methyl­dithio­carbazate and trans–cis S-benzyl­dithio­carbazate. This is due to the N—H...N hydrogen bond that exists only in the cis–trans conformation found for the title compound.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.079
• Data-to-parameter ratio = 18.7

checkCIF/PLATON results

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S1. Comment

There has been considerable work done on the synthesis and characterization of new compounds derived from S-methyl and S-benzyldithiocarbazate due to the fact that these compounds have donor atoms that chelate with metal ions to form metal complexes with various coordination modes or they can react with carbonyl compounds to yield Schiff bases which may also be multidentate ligands. Most importantly, they and/or their metal complexes are often biologically active. [Crouse et al., 2004; Neelam et al., 2000 & Tarafder et al., 2002]. Our attempt to synthesize a novel dithiocarbazate ligand was very successful, and eventually led us to the title compound. [Fig. 1.]

The C—N bond [1.3142 (17) Å] has some double-bond character. [1.296 (2) Å for S-2-picolyldithiocarbazate; Crouse et al., 2003] and [1.320 (3) Å for S-benzyldithiocarbazate; Shanmuga Sundara Raj et al., 2000]. The N10—N11 [1.4056 (17) Å] is slightly shorter than in cis-trans S-methyldithiocarbazate [1.415 (3) Å; Lanfredi et al., 1977] and S-2-picolyldithiocarbazate [1.437 (2) Å; Crouse et al., 2003] but comparable with trans-cis Sbenzyldithiocarbazate. [1.406 (3) Å; Shanmuga Sundara Raj et al., 2000]

The C=S bond length [1.6804 (14) Å] agrees well with both literature values of 1.679 (4) Å (Lanfredi et al., 1977) and 1.678 (3) Å (Shanmuga Sundara Raj et al., 2000) proposed as an intermediate between a single [1.82 Å] and a double bond [1.56 Å] character [Sutton, 1965]. This was attributed to delocalization of negative charge over the C–N–N–C–S chain, which was generated upon deprotonation of the ligands during coordination.

The conformations of the structures were assigned based on significant differences in the bond angles and not the bond lengths. Bond angles of S—C—S and N—C—S differ significantly for both cis-trans and trans-cis conformations. [Mattes & Weber, 1980]

The bond angles, S8—C9—S12 [115.66 (8)°] and N10—C9—S8 [119.05 (11)°] are agreeable with cis-trans S-methyldithiocarbazate [116.2 (1)° and 119.3 (1)°; Lanfredi et al., 1977] but was significantly different from trans-cis S-methyldithiocarbazate [125.5 (3)° and 113.6 (3)°; Mattes & Weber, 1980] and trans-cis S-benzyldithiocarbazate [125.5 (2)° and 113.5 (2)°; Shanmuga Sundara Raj et al., 2000]

The significance of the bond angles is related to the existence of intramolecular hydrogen bonds in both cis-trans and trans-cis conformers. N—H···N hydrogen bonds only exists in cis-trans conformer while the trans-cis conformer have N—H···S hydrogen bonds. [Lanfredi et al., 1977, Mattes & Weber, 1980 & Shanmuga Sundara Raj et al., 2000]. The type of hydrogen bonding and the bond angles help differentiate between the types of conformation. Therefore, the title compound is confirmed as cis-trans S-quinolin-2ylmethyldithiocarbazate.

The crystal structure consists of layers of aromatic residues lying parallel to the bc plane at a=0.5. [Fig. 2.] The dithiocarbazate moieties protrude above and below this plane. Pairs of quinoline rings lie parallel and overlapping with each other (mean separation of 3.4 Å). This exhibits the characteristic of a π-π interaction between the rings. [Fig. 3.]

There is an intramolecular hydrogen bond N10—H1···N6 [2.778 (2)°] is slightly shorter than in cis-trans S-methyldithiocarbazate. [2.968 (4)°; Lanfredi et al., 1977], which stabillizes the conformation of the molecule. [Fig. 1.]

The N11—H3···S8 contacts could be considered as a weak intermolecular hydrogen bond because the distance of H3···S8 is 2.832 (1)°, is smaller than the total radii of H(1.20) and S(1.80), which is 3.0° [Fig. 2].

Related literature

For chemical properties, see: Wang et al. (2002); Zhou et al. (2007). For biological activity, see: Crouse et al. (2004); Ali et al. (2004); Tarafder et al. (2002); Neelam et al. (2000). For similar structures, see: Das & Livingstone (1976); Crouse et al. (2004); Sutton (1965); Shanmuga Sundara Raj et al. (2000).

For related literature, see: Crouse et al. (2003); Lanfredi et al. (1977); Mattes & Weber (1980).

S2. Experimental

Potassium hydroxide (0.2 mol) was dissolved in 90% ethanol (70 ml) and mixed with hydrazine hydrate (0.2 mol). The mixture was placed in an ice salt bath to cool to 273 K. Carbon disulfide (0.2 mol) was added dropwise below 265 K with constant stirring over a period of 1 h. Upon addition of carbon disulfide, two layers were formed. 40% ethanol (60 ml) was added to the brown oil (lower layer) and the mixture was kept in an ice bath. 2-chloromethylquinoline hydrochloride (0.2 mol) dissolved in 80% ethanol (80 ml) was added dropwise with vigorous stirring. The product, cream coloured SQ2MDTC, (I) formed was filtered, recrystallized from ethanol and dried in vacuo over silica gel. (yield 75%, m.p 414.2–415.7 K). Cystals of SQ2MDTC suitable for X-ray analysis were grown in ethanol through slow evaporation.

S3. Refinement

The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints. The other atoms were refined with anisotropic atomic displacement parameters.

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures

	Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. The molecule is stabilized by intramolecular N—H—N hydrogen bond. Dotted line denotes the N—H—N hydrogen bond.
	Fig. 2. The packing of the molecule viewed along the b axis showing the aromatic layer lying parallel to the bc plane at a=0.5.
	Fig. 3. The stacking π-π interaction of pairs of the quinoline rings.

S-quinolin-2-ylmethyldithiocarbazate

Crystal data

C11H11N3S2	Dx = 1.437 Mg m^−3
Mr = 249.36	Melting point: 415.7 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.0514 (2) Å	Cell parameters from 2735 reflections
b = 10.0620 (2) Å	θ = 5–28°
c = 11.2780 (2) Å	µ = 0.44 mm^−1
β = 113.2607 (11)°	T = 150 K
V = 1152.17 (4) Å^3	Plate, yellow
Z = 4	0.36 × 0.26 × 0.20 mm
F(000) = 520

Data collection

Nonius KappaCCD area-detector diffractometer	2717 reflections with I > −3σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.9°, θmin = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.78, Tmax = 0.92	k = −11→13
11993 measured reflections	l = −14→14
2717 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.079	Method = modified Sheldrick w = 1/[σ^2(F^2) + ( 0.02P)^2 + 0.66P], where P = [max(Fo^2,0) + 2Fc^2]/3
S = 0.97	(Δ/σ)max = 0.001
2717 reflections	Δρmax = 0.37 e Å^−3
145 parameters	Δρmin = −0.41 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.48620 (13)	0.67545 (14)	0.41804 (12)	0.0223
C2	0.60247 (14)	0.60714 (15)	0.42925 (14)	0.0260
C3	0.58815 (16)	0.48964 (16)	0.35641 (15)	0.0328
C4	0.46609 (16)	0.44675 (15)	0.27809 (14)	0.0311
C5	0.35528 (14)	0.52185 (14)	0.26985 (13)	0.0252
N6	0.36434 (11)	0.63152 (12)	0.33708 (11)	0.0233
C7	0.21899 (16)	0.48171 (16)	0.17912 (14)	0.0326
S8	0.16795 (4)	0.56396 (4)	0.02240 (3)	0.0284
C9	0.11613 (13)	0.72301 (15)	0.04637 (13)	0.0235
N10	0.14555 (12)	0.76515 (13)	0.16482 (11)	0.0250
N11	0.11690 (13)	0.89477 (13)	0.19239 (12)	0.0307
S12	0.03297 (4)	0.81044 (4)	−0.08834 (3)	0.0302
C13	0.72616 (16)	0.65867 (18)	0.51324 (16)	0.0369
C14	0.73288 (17)	0.77111 (19)	0.58239 (16)	0.0413
C15	0.61735 (18)	0.83803 (17)	0.57193 (15)	0.0372
C16	0.49628 (16)	0.79170 (15)	0.49167 (14)	0.0291
H31	0.6658	0.4422	0.3632	0.0419*
H41	0.4521	0.3684	0.2293	0.0390*
H71	0.1548	0.5028	0.2159	0.0368*
H72	0.2190	0.3877	0.1611	0.0368*
H131	0.8015	0.6126	0.5194	0.0431*
H141	0.8138	0.8033	0.6377	0.0442*
H151	0.6249	0.9149	0.6204	0.0422*
H161	0.4192	0.8344	0.4858	0.0353*
H1	0.1992	0.7206	0.2298	0.0303*
H2	0.0887	0.9460	0.1277	0.0390*
H3	0.0912	0.8983	0.2537	0.0395*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0250 (7)	0.0228 (7)	0.0189 (6)	0.0008 (5)	0.0085 (5)	0.0039 (5)
C2	0.0258 (7)	0.0294 (7)	0.0237 (7)	0.0042 (6)	0.0105 (6)	0.0084 (6)
C3	0.0370 (8)	0.0352 (8)	0.0309 (8)	0.0145 (7)	0.0183 (7)	0.0072 (7)
C4	0.0459 (9)	0.0252 (7)	0.0233 (7)	0.0072 (6)	0.0148 (7)	0.0006 (6)
C5	0.0327 (8)	0.0231 (7)	0.0182 (6)	−0.0009 (6)	0.0083 (6)	0.0040 (5)
N6	0.0239 (6)	0.0243 (6)	0.0203 (5)	0.0014 (5)	0.0072 (5)	0.0026 (5)
C7	0.0394 (9)	0.0266 (7)	0.0257 (7)	−0.0068 (6)	0.0063 (6)	0.0029 (6)
S8	0.0326 (2)	0.02827 (19)	0.01951 (18)	−0.00116 (15)	0.00525 (15)	−0.00155 (14)
C9	0.0186 (6)	0.0308 (7)	0.0206 (6)	−0.0027 (5)	0.0074 (5)	−0.0001 (6)
N10	0.0236 (6)	0.0315 (6)	0.0182 (5)	0.0040 (5)	0.0063 (5)	0.0022 (5)
N11	0.0331 (7)	0.0355 (7)	0.0216 (6)	0.0093 (6)	0.0089 (5)	0.0004 (5)
S12	0.0314 (2)	0.0362 (2)	0.01872 (18)	0.00486 (15)	0.00525 (15)	0.00255 (15)
C13	0.0243 (7)	0.0456 (9)	0.0362 (8)	0.0023 (7)	0.0071 (6)	0.0147 (8)
C14	0.0340 (9)	0.0454 (10)	0.0301 (8)	−0.0136 (7)	−0.0028 (7)	0.0114 (7)
C15	0.0518 (10)	0.0280 (8)	0.0250 (7)	−0.0102 (7)	0.0079 (7)	0.0002 (6)
C16	0.0369 (8)	0.0249 (7)	0.0248 (7)	0.0016 (6)	0.0114 (6)	0.0005 (6)

Geometric parameters (Å, º)

C1—C2	1.4181 (19)	S8—C9	1.7563 (15)
C1—N6	1.3680 (18)	C9—N10	1.3142 (17)
C1—C16	1.413 (2)	C9—S12	1.6804 (14)
C2—C3	1.413 (2)	N10—N11	1.4056 (17)
C2—C13	1.418 (2)	N10—H1	0.864
C3—C4	1.358 (2)	N11—H2	0.846
C3—H31	0.958	N11—H3	0.845
C4—C5	1.410 (2)	C13—C14	1.359 (3)
C4—H41	0.938	C13—H131	0.931
C5—N6	1.3201 (18)	C14—C15	1.407 (3)
C5—C7	1.504 (2)	C14—H141	0.924
C7—S8	1.8275 (15)	C15—C16	1.368 (2)
C7—H71	0.976	C15—H151	0.932
C7—H72	0.967	C16—H161	0.933
C2—C1—N6	121.42 (13)	C7—S8—C9	104.99 (7)
C2—C1—C16	119.36 (13)	S8—C9—N10	119.05 (11)
N6—C1—C16	119.21 (13)	S8—C9—S12	115.66 (8)
C1—C2—C3	117.67 (14)	N10—C9—S12	125.28 (11)
C1—C2—C13	118.86 (14)	C9—N10—N11	122.50 (12)
C3—C2—C13	123.47 (14)	C9—N10—H1	120.4
C2—C3—C4	119.90 (14)	N11—N10—H1	115.7
C2—C3—H31	118.6	N10—N11—H2	114.4
C4—C3—H31	121.5	N10—N11—H3	113.4
C3—C4—C5	119.09 (14)	H2—N11—H3	123.4
C3—C4—H41	122.6	C2—C13—C14	120.48 (16)
C5—C4—H41	118.3	C2—C13—H131	117.7
C4—C5—N6	122.89 (14)	C14—C13—H131	121.8
C4—C5—C7	120.75 (14)	C13—C14—C15	120.54 (15)
N6—C5—C7	116.34 (13)	C13—C14—H141	119.9
C1—N6—C5	119.01 (12)	C15—C14—H141	119.6
C5—C7—S8	112.34 (10)	C14—C15—C16	120.71 (16)
C5—C7—H71	110.7	C14—C15—H151	118.7
S8—C7—H71	108.3	C16—C15—H151	120.6
C5—C7—H72	108.8	C1—C16—C15	120.04 (15)
S8—C7—H72	105.4	C1—C16—H161	118.8
H71—C7—H72	111.2	C15—C16—H161	121.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H1···N6	0.86	1.96	2.778 (2)	157