Octyl (2E)-2-[2-(di­phenyl­phosphan­yl)benzyl­idene]hydrazinecarbodi­thio­ate

Izuddin Asri; Malai Haniti S A Hamid; Aminul Huq Mirza; Mohammad Akbar Ali; Mohammad Rezaul Karim

doi:10.1107/S1600536814008459

. 2014 May 3;70(Pt 6):o633–o634. doi: 10.1107/S1600536814008459

Octyl (2E)-2-[2-(diphenylphosphanyl)benzylidene]hydrazinecarbodithioate

Izuddin Asri ^a, Malai Haniti S A Hamid ^a, Aminul Huq Mirza ^a, Mohammad Akbar Ali ^a, Mohammad Rezaul Karim ^b,^*

PMCID: PMC4051045 PMID: 24940222

Abstract

The title compound, C₂₈H₃₃N₂S₂P, adopts the thione tautomeric form, as supported by the C—S distance [1.6744 (18) Å]. The Schiff base exhibits an E conformation about the C=N bond but a Z conformation about the C—N bond. The terminal chain is disordered over two sets of sites with an occupancy ratio of 0.732 (3):0.268 (3). In the crystal, pairs of N—N—H hydrogen bonds between the thione groups link neighbouring molecules into centrosymmetric dimers.

Related literature

For Schiff bases derived from S-alkyl/aryl esters of dithiocarbazic acid, see: Akbar Ali et al. (2012 ▶, 2013 ▶); Hamid et al. (2009 ▶); Akbar Ali et al. (2005 ▶). For their chemotherapeutic properties, see: Tarafder et al. (2002 ▶); Akbar Ali & Livingstone (1974 ▶); Akbar Ali et al. (2002 ▶); Hossain et al. (1996 ▶). For related structures, see: Su et al. (1999 ▶); Song et al. (2009 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-70-0o633-scheme1.jpg

Experimental

Crystal data

C₂₈H₃₃N₂PS₂
M _r = 492.65
Triclinic,
a = 11.2068 (12) Å
b = 11.4956 (12) Å
c = 11.7728 (13) Å
α = 86.623 (1)°
β = 70.538 (1)°
γ = 65.013 (1)°
V = 1290.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.60 × 0.60 × 0.38 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.846, T _max = 0.899
15526 measured reflections
5343 independent reflections
4954 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.111
S = 1.04
5343 reflections
356 parameters
209 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.30 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814008459/bq2394sup1.cif

e-70-0o633-sup1.cif^{(37.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008459/bq2394Isup2.hkl

e-70-0o633-Isup2.hkl^{(292.9KB, hkl)}

Click here for additional data file.^{(9.4KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008459/bq2394Isup3.cml

CCDC reference: 997277

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S2ⁱ	0.90 (2)	2.45 (2)	3.3337 (17)	168 (2)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

IA, MHSAH, MAA and AHM thank University Brunei Darussalam for support. MRK acknowledges support from the Department of Chemistry at Tennessee State University.

supplementary crystallographic information

1. Comment

In recent years, considerable attention has been focused on Schiff bases derived from S-alkyl/aryl esters of dithiocarbazic acid (M. Akbar Ali et al. 2013, M. Akbar Ali et al. 2012) as they belong to a promising class of potentially bioactive chelating agents containing mixed hard and soft donor atoms. These organic chelators could also lead to the formation of coordination compounds with useful chemotherapeutic properties (Tarafder et al., 2002; Akbar Ali et al., 2002; Akbar Ali et al., 1974; Hossain et al., 1996). In view of less crystallographic data available on Schiff bases containing mixed hard and soft donor atoms such as nitrogen, sulfur and phosphorus, the new Schiff base, C₂₈H₃₃N₂S₂P (I) was synthesized by the reaction of S-octyl dithiocarbazate with 2-(diphenylphosphino)benzaldehyde in ethanol. The crystal is triclinic, space group P-1. The asymmetric unit contains one molecule of the compound C₂₈H₃₃N₂S₂P. The terminal chain C11 to C16 is disordered into two positions with occupancy ratio = 73:27. Restraints in bond lengths and thermal parameters were applied to the disordered parts. H atom of N2 was located from different map and refined with restraints in bond length and thermal parameters. Final R values are R1 = 0.0429 and wR2 = 0.1084 for 2-theta up to 55°. Like most Schiff bases derived from S-alkyl/aryl esters of dithiocarbazic acid, the Schiff base, I also remains in its thione tautomeric form as supported by the C8-S2 distance [1.6744 (18) Å], which is typical of double bonds and are by far the shortest C-S distances observed so far among the Schiff bases derived from S-alkyl/aryl dithiocarbazates (Hamid et al. 2009, Akbar Ali et al. 2005). The Schiff base also remains in an E configuration about the C7-N1 bond but a Z configuration about the C8-N2 bond. The C7-N1 bond distance compares well with that of the C=N double bonds in other related compounds (Su et al. 1999, Song et al. 2009). The C8-N2 bond distance [1.337 (2) Å] indicates that the N2 nitrogen atom is sp² hybridized and the bond is closer to a double than a single bond (Allen et al. 1987). The N1–N2 bond in the Schiff base is shorter than a single N-N bond. A comparison of the N1—N2 distance [1.378 (2) Å] with that in S-benzyl dithiocarbazate [1.406 (3) Å] (Shanmuga Sundara Raj et al. 2000) indicates that there is a significant π-charge delocalization along the C-N-N-C chain. There is intermolecular hydrogen bonding between the hydrazine nitrogen atom N(2) of one molecule and the thione sulfur atom S2 of another molecule ( Fig. 2) resulting in H-bonded centrosymmetric dimers. The H-bonding stabilizes the E and Z conformations about the C7-N1 and C8-N2 bonds, respectively.

2. Experimental

A hot solution of S-n-octyldithiocarbazate (0.16 g, 0.7 mmol) in absolute ethanol (10 ml) was mixed with a solution of 2-di(phenylphosphino) benzaldehyde (0.21 g, 0.71 mmol) in the same solvent (5 ml). The resulting mixture was heated on a steam bath for 15 minutes and then left to cool. The yellow crystals that had formed were filtered off, recrystallized from an ethanol/chloroform mixture and dried in vacuo. Yield = 0.14 g (90%); m.p. = 114–116 °C; IR (cm^-1): 3106 (N—H), 3068, 3048 (=CH, Ar), 1560 (C=N), 1024 (C—S), 1097 (C=S); UV-Vis: λ_max/nm, (log ε (dm³ cm^-1 mol^-1): 374(5.369); ¹H NMR (p.p.m., CDCl₃): 10.23 (1H, s, –NH), 8.64 (1H, d, CH=N), 8.13 (1H, d, Ar), 7.66 – 7.22 (12H, m, Ar), 6.91 (1H, m, Ar), 3.25 (2H, t, CH₂), 1.77 – 1.22 (12H, m, aliphatic protons), 0.88 (3H, t, CH₃); ¹³ C NMR [p.p.m., CDCl₃]: 199.6 (C=S), 143.7 – 126.7 (C=N, Ar—C), 34.7 (–CH2—C=S), 31.8, 29.2, 29.2, 29.1, 28.5, 22.7 (6xCH₂), 14.1 (–CH₃); Anal.calcd. for C₂₈H₃₃N₂S₂P: C 68.26, H 6.75, N 5.69; Found (%) C 69.35, H 6.15 N 5.68; MS/EI, m/z (I,%) for C₂₈H₃₃N₂S₂P (481.59 g/mol): 304.1 [M±C=SSOctyl] (17), 288.1 [M±NHC=SSOctyl] (100), 183.0 [PPh2] (22), 146.1 [SOctyl] (5).

The IR spectrum was recorded as KBr disc on a Perkin-Elmer 1600 F T IR spectrometer. The 1H NMR spectrum was run in CDCl3 on a Bruker Advance, 400 MHz spectrometer in the Department of Chemistry, Tennessee State University, USA. Elemental analysis for C, H and N was done by the Elemental Analysis Laboratory, Department of Chemistry, National University of Singapore. The EI mass spectrum was recorded on an Agilent Mass Spectrometer 5975 C MSD (with direct probe). The X-ray data were collected at the X-ray Diffraction Laboratory, Department of Chemistry, National University of Singapore using a Bruker-AXS Smart Apex CCD single-crystal diffractometer.