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The mol­ecules in the crystal structure of the title compound, C19H17N3S2, are linked by an inter­molecular N—H...N [2.839 (5) Å] hydrogen bond via the α-N and the pyridyl N atoms. The thione S atom is in a trans position with respect to the methyl­pyridine fragment across the C—N bond but adopts a cis position with respect to the naphthalene ring across the C—S bond. There is a π–π stacking inter­action between the naphthalene rings, with a centroid–centroid distance of 3.397 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025652/lw2018sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025652/lw2018Isup2.hkl
Contains datablock I

CCDC reference: 654899

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.073
  • wR factor = 0.211
  • Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.760 0.990 Tmin(prime) and Tmax expected: 0.884 0.988 RR(prime) = 0.858 Please check that your absorption correction is appropriate. RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.133 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.13 PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.86 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT414_ALERT_2_C Short Intra D-H..H-X H1 .. H153 .. 1.98 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Dithiocarbazate and its substituted compounds are of interest for researchers because these compound have various chemical properties [Wang et al., 2002 and Zhou et al., 2007] and they are biologically active [Crouse et al., 2004 and Tarafder et al., 2002].

The C5—N6 bond [1.351 (5) Å] has a partial double bond character. It is comparable with Schiff bases derived from S-napthalen-2-yl- and -quinolin-2-yl-methyldithiocarbazate. [1.352 (4) Å; How et al., 2007a and 1.352 (2) Å; How et al., 2007b].

The C5—S16 bond [1.660 (4) Å] displays a double bond character. It is comparable with previous literature [1.659 (4) Å; How et al., 2007a and 1.6593 (17) Å; How et al., 2007b]

The bond angle N7—N6—C5 [117.0 (3)°] and S16—C5—S4 [126.3 (2)°] are comparable with schiff base derived from S-quinolin-2-yldithiocarbazate. and S-napthalen-2-ylmethyldithiocarbazate [117.61 (13)° and 125.7 (2)°; How et al., 2007b] and [116.9 (3)° and 125.7 (2)°; How et al., 2007a] respectively.

There are two planar fragment in the molecule of the crystal structure. The C1/C2/C3/C17/C18/C19/C20/C21/C22/C23/C24 fragment inclines with the S4/C5/N6/N7/C8/C9/C10/C11/N12/C13/C14/C15/C16 fragment in an angle of 79.2 (1)°.

The single molecule formed L-shaped but packed as W-shaped as the naphthalene fragments formed stacked as rows parallel to each other [Fig 2.]

The naphthalene ring defined by the atoms C1/C2/C3/C17/C18/C19/C20 at (x,y,z) and (1 - x,-y, 1 - z) are stacked parallel to each other with a separation of 3.589 (2) Å between the centres-of-gravity, an interplanar spacing of 3.407 Å and an offset of 1.130 Å giving a ππ stacking interaction, [Fig. 5].

The whole pyridine fragment C8/C9/C10/N11/C12/C13/C14 behaves as a rigid body (R-factor= 6.73) and undergoes substantial libration with mean square displacement of 121.73°^2^.

The intermolecular N—H—N hydrogen bond [2.839 (5) Å] via the pyridyl nitrogen atom and the \a-nitrogen atom linking the molecules [Fig. 3] is comparable with Schiff base derived from pyridine-3-carboxaldehyde [2.825 (2) Å; How et al., 2007a].

Related literature top

The title compound was prepared from S-napthalen-2-ylmethyldithiocarbazate. Interatomic parameters of the crystal structure are comparable with previous literature. (How et al., 2007a,b). For other relevant literature, see: Crouse et al. (2004); Shanmuga Sundara Raj et al. (2000); Tarafder et al. (2002); Wang et al. (2002); Zhou et al. (2007).

Experimental top

S-Napthalen-2-ylmethyldithiocarbazate (SNMDTC) was used as a starting ligand for the synthesis of Schiff base. S-napthalen-2-ylmethyldithiocarbazate (SNMDTC) was prepared as previously reported for S-substituted dithiocarbazates [Shanmuga Sundara Raj et al., 2000] except the addition of benzyl chloride being replaced with 1-(chloromethyl) naphthalene (29.9 ml, 0.2 mol).

SNMDTC (0.02 mol) was dissolved in hot acetonitrile (30 ml) with dropwise addition of equimolar amount of 4-acetylpyridine. The mixture was left heated with stirring to reduce half the volume. The mixture was allowed to stand for 1 day. Precipitates formed were filtered and recrystallized from ethanol. The recrystallized product was then dried over silica gel. (yield: 62.7%, m.p.= 460.15 K) Yellow needle like crystals were formed upon slow evaporation in a ethanol solution.

Refinement top

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 Uĩso~(H) (in the range 1.2–1.5 times U~eq~ of the parent atom), after which the positions were refined with riding constraints.

Structure description top

Dithiocarbazate and its substituted compounds are of interest for researchers because these compound have various chemical properties [Wang et al., 2002 and Zhou et al., 2007] and they are biologically active [Crouse et al., 2004 and Tarafder et al., 2002].

The C5—N6 bond [1.351 (5) Å] has a partial double bond character. It is comparable with Schiff bases derived from S-napthalen-2-yl- and -quinolin-2-yl-methyldithiocarbazate. [1.352 (4) Å; How et al., 2007a and 1.352 (2) Å; How et al., 2007b].

The C5—S16 bond [1.660 (4) Å] displays a double bond character. It is comparable with previous literature [1.659 (4) Å; How et al., 2007a and 1.6593 (17) Å; How et al., 2007b]

The bond angle N7—N6—C5 [117.0 (3)°] and S16—C5—S4 [126.3 (2)°] are comparable with schiff base derived from S-quinolin-2-yldithiocarbazate. and S-napthalen-2-ylmethyldithiocarbazate [117.61 (13)° and 125.7 (2)°; How et al., 2007b] and [116.9 (3)° and 125.7 (2)°; How et al., 2007a] respectively.

There are two planar fragment in the molecule of the crystal structure. The C1/C2/C3/C17/C18/C19/C20/C21/C22/C23/C24 fragment inclines with the S4/C5/N6/N7/C8/C9/C10/C11/N12/C13/C14/C15/C16 fragment in an angle of 79.2 (1)°.

The single molecule formed L-shaped but packed as W-shaped as the naphthalene fragments formed stacked as rows parallel to each other [Fig 2.]

The naphthalene ring defined by the atoms C1/C2/C3/C17/C18/C19/C20 at (x,y,z) and (1 - x,-y, 1 - z) are stacked parallel to each other with a separation of 3.589 (2) Å between the centres-of-gravity, an interplanar spacing of 3.407 Å and an offset of 1.130 Å giving a ππ stacking interaction, [Fig. 5].

The whole pyridine fragment C8/C9/C10/N11/C12/C13/C14 behaves as a rigid body (R-factor= 6.73) and undergoes substantial libration with mean square displacement of 121.73°^2^.

The intermolecular N—H—N hydrogen bond [2.839 (5) Å] via the pyridyl nitrogen atom and the \a-nitrogen atom linking the molecules [Fig. 3] is comparable with Schiff base derived from pyridine-3-carboxaldehyde [2.825 (2) Å; How et al., 2007a].

The title compound was prepared from S-napthalen-2-ylmethyldithiocarbazate. Interatomic parameters of the crystal structure are comparable with previous literature. (How et al., 2007a,b). For other relevant literature, see: Crouse et al. (2004); Shanmuga Sundara Raj et al. (2000); Tarafder et al. (2002); Wang et al. (2002); Zhou et al. (2007).

Computing details top

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 top
[Figure 1] Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
[Figure 2] Fig. 2. The packing of the molecule viewed along the a axis.
[Figure 3] Fig. 3. The molecules are stabilized by intermolecular N—H—N hydrogen bond. Dotted line denotes the N—H—N hydrogen bond.
[Figure 4] Fig. 4. The \ip-π interaction of pairs of the naphthalene rings at (x,y,z) and (x,y + 1,z)
2-Naphthylmethyl N-[1-(4-pyridyl)ethylidene]hydrazinecarbodithioate top
Crystal data top
C19H17N3S2Dx = 1.328 Mg m3
Mr = 351.50Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 3836 reflections
a = 16.0781 (7) Åθ = 5–27°
b = 9.8406 (4) ŵ = 0.31 mm1
c = 22.2201 (8) ÅT = 150 K
V = 3515.6 (2) Å3Plate, yellow
Z = 80.40 × 0.06 × 0.04 mm
F(000) = 1472
Data collection top
Nonius KappaCCD
diffractometer
2209 reflections with I > 2.0σ(I)
Graphite monochromatorRint = 0.133
ω scansθmax = 27.1°, θmin = 5.1°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 2020
Tmin = 0.76, Tmax = 0.99k = 1212
14358 measured reflectionsl = 2828
3811 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.211 Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.12P)2 + 0.6P] ,
where P = (max(Fo2,0) + 2Fc2)/3
S = 0.92(Δ/σ)max = 0.000424
3811 reflectionsΔρmax = 0.79 e Å3
217 parametersΔρmin = 0.82 e Å3
0 restraints
Crystal data top
C19H17N3S2V = 3515.6 (2) Å3
Mr = 351.50Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 16.0781 (7) ŵ = 0.31 mm1
b = 9.8406 (4) ÅT = 150 K
c = 22.2201 (8) Å0.40 × 0.06 × 0.04 mm
Data collection top
Nonius KappaCCD
diffractometer
3811 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
2209 reflections with I > 2.0σ(I)
Tmin = 0.76, Tmax = 0.99Rint = 0.133
14358 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0730 restraints
wR(F2) = 0.211H-atom parameters constrained
S = 0.92Δρmax = 0.79 e Å3
3811 reflectionsΔρmin = 0.82 e Å3
217 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5625 (3)0.0827 (4)0.56610 (15)0.0356
C20.4905 (3)0.1605 (4)0.55211 (15)0.0362
C30.4983 (3)0.3005 (4)0.52538 (15)0.0392
S40.53368 (6)0.42180 (11)0.58251 (4)0.0331
C50.4391 (2)0.4928 (4)0.60772 (16)0.0298
N60.4480 (2)0.5648 (4)0.65904 (13)0.0342
N70.52675 (18)0.5734 (3)0.68279 (12)0.0319
C80.5395 (2)0.6455 (4)0.73024 (15)0.0340
C90.6280 (2)0.6436 (4)0.74997 (16)0.0336
C100.6864 (3)0.5634 (5)0.7215 (2)0.0533
C110.7675 (3)0.5652 (6)0.7404 (2)0.0615
N120.7939 (2)0.6385 (4)0.78781 (14)0.0486
C130.7375 (3)0.7141 (5)0.81497 (17)0.0492
C140.6561 (3)0.7204 (5)0.79824 (17)0.0440
C150.4774 (3)0.7254 (6)0.76459 (19)0.0588
S160.34742 (6)0.48061 (12)0.57372 (4)0.0409
C170.4128 (3)0.1115 (4)0.56429 (16)0.0394
C180.4028 (3)0.0166 (5)0.59089 (19)0.0463
C190.4696 (3)0.0934 (5)0.60457 (18)0.0474
C200.5509 (3)0.0485 (4)0.59193 (16)0.0411
C210.6216 (3)0.1300 (5)0.60357 (18)0.0502
C220.6993 (3)0.0859 (6)0.5917 (2)0.0558
C230.7113 (3)0.0428 (5)0.56598 (18)0.0484
C240.6448 (3)0.1243 (5)0.55388 (17)0.0402
H310.44380.33030.51090.0467*
H320.53920.30190.49310.0474*
H1010.66990.50710.68980.0702*
H1110.80710.51340.71940.0772*
H1310.75500.76700.84770.0624*
H1410.61900.77590.81860.0572*
H1510.49680.81670.77080.0862*
H1520.46900.68350.80310.0863*
H1530.42530.72780.74410.0864*
H1710.36620.16260.55380.0465*
H1810.34960.04930.59950.0578*
H1910.46270.17950.62110.0558*
H2110.61350.21650.61980.0598*
H2210.74460.14110.60110.0669*
H2310.76490.07350.55670.0587*
H2410.65340.20970.53800.0485*
H10.40460.60110.67670.0425*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.051 (2)0.036 (2)0.0197 (16)0.000 (2)0.0003 (15)0.0063 (15)
C20.055 (3)0.035 (2)0.0184 (14)0.007 (2)0.0034 (17)0.0016 (15)
C30.051 (2)0.047 (3)0.0197 (15)0.002 (2)0.0037 (16)0.0026 (16)
S40.0363 (5)0.0370 (6)0.0259 (4)0.0008 (4)0.0010 (4)0.0016 (4)
C50.032 (2)0.031 (2)0.0266 (16)0.0041 (16)0.0003 (14)0.0044 (15)
N60.0356 (17)0.045 (2)0.0215 (13)0.0033 (15)0.0006 (12)0.0001 (13)
N70.0349 (17)0.0388 (19)0.0220 (13)0.0007 (15)0.0002 (12)0.0015 (13)
C80.032 (2)0.045 (2)0.0248 (16)0.0051 (18)0.0025 (15)0.0012 (16)
C90.038 (2)0.039 (2)0.0234 (16)0.0002 (18)0.0030 (15)0.0019 (16)
C100.041 (2)0.072 (3)0.047 (2)0.015 (2)0.0072 (19)0.020 (2)
C110.043 (3)0.095 (4)0.046 (2)0.020 (3)0.002 (2)0.019 (3)
N120.042 (2)0.078 (3)0.0261 (15)0.0045 (19)0.0056 (14)0.0014 (17)
C130.047 (3)0.067 (3)0.0331 (18)0.004 (2)0.0052 (19)0.014 (2)
C140.039 (2)0.062 (3)0.0308 (18)0.006 (2)0.0000 (16)0.0132 (19)
C150.047 (3)0.085 (4)0.044 (2)0.020 (3)0.004 (2)0.033 (3)
S160.0342 (6)0.0581 (7)0.0305 (5)0.0036 (5)0.0045 (4)0.0014 (5)
C170.045 (2)0.040 (2)0.0337 (19)0.002 (2)0.0008 (17)0.0024 (17)
C180.048 (3)0.046 (3)0.044 (2)0.010 (2)0.008 (2)0.003 (2)
C190.071 (3)0.041 (3)0.0301 (18)0.004 (2)0.008 (2)0.0004 (18)
C200.059 (3)0.043 (3)0.0210 (16)0.004 (2)0.0002 (17)0.0028 (16)
C210.072 (3)0.047 (3)0.0322 (19)0.007 (2)0.001 (2)0.0055 (19)
C220.064 (3)0.056 (3)0.047 (2)0.018 (3)0.008 (2)0.010 (2)
C230.039 (2)0.066 (3)0.041 (2)0.004 (2)0.0003 (18)0.015 (2)
C240.049 (2)0.038 (2)0.0331 (19)0.006 (2)0.0030 (18)0.0029 (17)
Geometric parameters (Å, º) top
C1—C21.423 (6)N12—C131.319 (5)
C1—C201.425 (6)C13—C141.361 (6)
C1—C241.412 (6)C13—H1310.937
C2—C31.505 (6)C14—H1410.927
C2—C171.366 (6)C15—H1510.962
C3—S41.833 (4)C15—H1520.960
C3—H310.979C15—H1530.953
C3—H320.973C17—C181.401 (6)
S4—C51.765 (4)C17—H1710.932
C5—N61.351 (5)C18—C191.347 (7)
C5—S161.660 (4)C18—H1810.934
N6—N71.374 (4)C19—C201.408 (6)
N6—H10.876C19—H1910.930
N7—C81.287 (5)C20—C211.416 (6)
C8—C91.488 (5)C21—C221.348 (7)
C8—C151.483 (5)C21—H2110.933
C9—C101.381 (6)C22—C231.403 (7)
C9—C141.388 (5)C22—H2210.933
C10—C111.369 (7)C23—C241.363 (6)
C10—H1010.934C23—H2310.936
C11—N121.346 (6)C24—H2410.922
C11—H1110.941
C2—C1—C20118.0 (4)C14—C13—H131118.4
C2—C1—C24124.4 (4)C9—C14—C13120.0 (4)
C20—C1—C24117.6 (4)C9—C14—H141119.3
C1—C2—C3120.7 (4)C13—C14—H141120.8
C1—C2—C17120.7 (4)C8—C15—H151110.5
C3—C2—C17118.6 (4)C8—C15—H152109.0
C2—C3—S4110.4 (2)H151—C15—H152108.5
C2—C3—H31109.2C8—C15—H153111.1
S4—C3—H31108.1H151—C15—H153109.3
C2—C3—H32111.1H152—C15—H153108.3
S4—C3—H32107.1C2—C17—C18120.4 (4)
H31—C3—H32110.9C2—C17—H171119.7
C3—S4—C5102.14 (19)C18—C17—H171119.9
S4—C5—N6112.6 (3)C17—C18—C19120.6 (4)
S4—C5—S16126.3 (2)C17—C18—H181120.1
N6—C5—S16121.1 (3)C19—C18—H181119.4
C5—N6—N7117.0 (3)C18—C19—C20121.2 (4)
C5—N6—H1120.5C18—C19—H191120.3
N7—N6—H1122.4C20—C19—H191118.4
N6—N7—C8119.7 (3)C1—C20—C19119.1 (4)
N7—C8—C9112.7 (3)C1—C20—C21118.8 (4)
N7—C8—C15127.3 (3)C19—C20—C21122.1 (4)
C9—C8—C15120.0 (3)C20—C21—C22121.7 (5)
C8—C9—C10121.5 (4)C20—C21—H211118.4
C8—C9—C14122.1 (4)C22—C21—H211119.9
C10—C9—C14116.4 (4)C21—C22—C23119.9 (5)
C9—C10—C11120.0 (4)C21—C22—H221119.5
C9—C10—H101119.4C23—C22—H221120.6
C11—C10—H101120.6C22—C23—C24120.2 (4)
C10—C11—N12123.2 (4)C22—C23—H231120.6
C10—C11—H111119.1C24—C23—H231119.2
N12—C11—H111117.7C1—C24—C23121.8 (4)
C11—N12—C13116.4 (4)C1—C24—H241118.5
N12—C13—C14124.1 (4)C23—C24—H241119.7
N12—C13—H131117.4
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H1···N12i0.881.982.839 (5)166
Symmetry code: (i) x1/2, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC19H17N3S2
Mr351.50
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)16.0781 (7), 9.8406 (4), 22.2201 (8)
V3)3515.6 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.40 × 0.06 × 0.04
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.76, 0.99
No. of measured, independent and
observed [I > 2.0σ(I)] reflections
14358, 3811, 2209
Rint0.133
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.073, 0.211, 0.92
No. of reflections3811
No. of parameters217
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.79, 0.82

Computer programs: COLLECT (Nonius, 2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H1···N12i0.881.982.839 (5)166
Symmetry code: (i) x1/2, y, z+3/2.
 

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