Benzyl (E)-3-(4-meth­oxy­benzyl­idene)dithio­carbazate

The title compound, C₁₆H₁₆N₂OS₂, was obtained from a condensation reaction of benzyl dithio­carbazate and 4-meth­oxy­benzaldehyde. In the mol­ecule, the meth­oxy­phenyl ring and dithio­carbazate fragment are located on opposite sides of the C=N double bond, showing an E configuration. The dithio­carbazate fragment is approximately planar (r.m.s. deviation = 0.0052 Å); its mean plane is oriented at dihedral angles of 8.19 (15) and 85.70 (13)°, respectively, to the meth­oxy­phenyl and phenyl rings. Inter­molecular N—H...S hydrogen bonds and weak C—H...π inter­actions are observed in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.055
• wR factor = 0.129
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...        4.3 Ratio
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C14

Alert level C
PLAT234_ALERT_4_C Large Hirshfeld Difference C12    --  C13     ..       0.17 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C14    --  C15     ..       0.19 Ang.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.2
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0067 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.599          6

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Hydrazone and its derivatives have shown the potential application in the biological field (Okabe et al., 1993; Hu et al., 2001). As part of the ongoing investigation on anti-cancer compounds, the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

In the molecules, the methoxylphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C═N double bond, showing the E-configuration. The dithiocarbazate fragment is approximately planar [r.m.s deviation 0.0052 Å]; the mean plane of dithiocarbazate is oriented with respect to the methoxylphenyl and phenyl rings at 8.19 (15) and 85.70 (13)°, similar to those found in related structures (Shan et al. 2008a,b). Intermolecular N—H···S hydrogen bonding and weak C—H···π interaction are observed in the crystal structure (Table 1).

Related literature

For applications of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993); Hu et al. (2001). For related structures, see: Shan et al. (2008a,b). For the synthesis, see: Hu et al. (2001).

S2. Experimental

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.40 g, 2 mmol) and 4-methoxybenzaldehyde (0.27 g, 2 mmol) were dissolved in ethanol (20 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The mixture solution was refluxed for 6 h. After cooling to room temperature, microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain colourless single crystals of the title compound.

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and refined in riding mode with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C,N) for the others.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of the title compound with 30% probability displacement (arbitrary spheres for H atoms).

Benzyl (E)-3-(4-methoxybenzylidene)dithiocarbazate

Crystal data

C16H16N2OS2	F(000) = 664
Mr = 316.43	Dx = 1.264 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2982 reflections
a = 10.267 (5) Å	θ = 3.4–25.2°
b = 5.150 (2) Å	µ = 0.32 mm^−1
c = 31.686 (11) Å	T = 294 K
β = 97.141 (5)°	Block, colorless
V = 1662.4 (12) Å^3	0.32 × 0.25 × 0.23 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	2982 independent reflections
Radiation source: fine-focus sealed tube	1869 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 10.0 pixels mm^-1	θmax = 25.2°, θmin = 3.5°
ω scans	h = −12→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −5→6
Tmin = 0.84, Tmax = 0.92	l = −31→37
6025 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0512P)^2] where P = (Fo^2 + 2Fc^2)/3
2982 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.65124 (8)	0.64526 (18)	0.54959 (2)	0.0628 (3)
S2	0.57408 (9)	0.40404 (17)	0.63003 (2)	0.0631 (3)
O1	−0.0078 (2)	−0.7274 (5)	0.62062 (8)	0.0810 (7)
N1	0.4039 (2)	0.1129 (5)	0.57509 (7)	0.0545 (7)
N2	0.4768 (2)	0.2797 (5)	0.55381 (7)	0.0552 (7)
H2	0.4665	0.2815	0.5265	0.066*
C1	0.2443 (3)	−0.2240 (6)	0.56941 (8)	0.0491 (7)
C2	0.1678 (3)	−0.3916 (6)	0.54309 (9)	0.0582 (9)
H2A	0.1740	−0.3887	0.5141	0.070*
C3	0.0825 (3)	−0.5632 (6)	0.55848 (10)	0.0608 (8)
H3	0.0315	−0.6738	0.5400	0.073*
C4	0.0734 (3)	−0.5699 (6)	0.60140 (10)	0.0572 (8)
C5	0.1509 (3)	−0.4053 (7)	0.62824 (10)	0.0663 (9)
H5	0.1456	−0.4105	0.6573	0.080*
C6	0.2355 (3)	−0.2346 (6)	0.61278 (9)	0.0596 (9)
H6	0.2871	−0.1255	0.6313	0.072*
C7	0.3302 (3)	−0.0417 (6)	0.55184 (9)	0.0553 (8)
H7	0.3314	−0.0376	0.5226	0.066*
C8	0.5635 (3)	0.4391 (6)	0.57512 (8)	0.0498 (8)
C9	0.6968 (4)	0.6468 (7)	0.64781 (9)	0.0725 (10)
H9A	0.7778	0.6104	0.6361	0.087*
H9B	0.6662	0.8177	0.6383	0.087*
C10	0.7200 (5)	0.6388 (8)	0.69529 (11)	0.0815 (12)
C11	0.8198 (6)	0.4920 (11)	0.71552 (14)	0.1309 (19)
H11	0.8712	0.3939	0.6993	0.157*
C12	0.8464 (8)	0.4854 (16)	0.7592 (2)	0.189 (4)
H12	0.9153	0.3870	0.7727	0.226*
C13	0.7687 (13)	0.6270 (17)	0.7815 (2)	0.199 (5)
H13	0.7830	0.6173	0.8110	0.239*
C14	0.6712 (12)	0.7826 (15)	0.7635 (2)	0.212 (5)
H14	0.6231	0.8854	0.7801	0.255*
C15	0.6444 (7)	0.7838 (11)	0.71840 (14)	0.138 (2)
H15	0.5758	0.8830	0.7049	0.166*
C16	−0.0915 (4)	−0.8990 (7)	0.59433 (13)	0.0942 (13)
H16A	−0.1487	−0.7997	0.5741	0.141*
H16B	−0.1431	−0.9991	0.6117	0.141*
H16C	−0.0392	−1.0135	0.5795	0.141*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0604 (6)	0.0731 (6)	0.0556 (5)	−0.0213 (5)	0.0101 (4)	0.0138 (4)
S2	0.0699 (6)	0.0685 (6)	0.0511 (4)	−0.0216 (5)	0.0086 (4)	0.0112 (4)
O1	0.0753 (19)	0.0729 (16)	0.0980 (16)	−0.0258 (14)	0.0229 (14)	0.0156 (14)
N1	0.0472 (16)	0.0563 (16)	0.0604 (14)	−0.0115 (14)	0.0078 (12)	0.0121 (13)
N2	0.0510 (17)	0.0639 (17)	0.0514 (13)	−0.0149 (14)	0.0087 (12)	0.0088 (13)
C1	0.0451 (19)	0.0492 (18)	0.0530 (17)	−0.0071 (15)	0.0060 (14)	0.0066 (14)
C2	0.056 (2)	0.067 (2)	0.0508 (16)	−0.0112 (18)	0.0042 (14)	0.0004 (16)
C3	0.053 (2)	0.058 (2)	0.069 (2)	−0.0126 (17)	−0.0002 (15)	−0.0007 (17)
C4	0.050 (2)	0.0486 (19)	0.074 (2)	−0.0096 (16)	0.0093 (16)	0.0115 (17)
C5	0.074 (2)	0.073 (2)	0.0528 (17)	−0.016 (2)	0.0123 (16)	0.0100 (17)
C6	0.063 (2)	0.060 (2)	0.0542 (18)	−0.0183 (18)	0.0026 (15)	−0.0033 (16)
C7	0.0455 (19)	0.064 (2)	0.0565 (17)	−0.0062 (17)	0.0073 (14)	0.0112 (16)
C8	0.0430 (18)	0.0526 (19)	0.0544 (16)	−0.0034 (15)	0.0088 (14)	0.0089 (15)
C9	0.088 (3)	0.071 (2)	0.0579 (18)	−0.030 (2)	0.0062 (17)	0.0061 (17)
C10	0.120 (4)	0.066 (2)	0.057 (2)	−0.034 (2)	0.006 (2)	0.004 (2)
C11	0.157 (5)	0.132 (4)	0.094 (3)	−0.011 (4)	−0.023 (3)	0.025 (3)
C12	0.271 (10)	0.173 (7)	0.099 (4)	−0.046 (7)	−0.069 (5)	0.040 (5)
C13	0.408 (15)	0.124 (7)	0.064 (4)	−0.114 (8)	0.031 (6)	−0.006 (4)
C14	0.433 (16)	0.110 (6)	0.105 (5)	−0.051 (7)	0.080 (7)	−0.021 (4)
C15	0.228 (7)	0.119 (4)	0.073 (3)	−0.013 (4)	0.040 (4)	−0.005 (3)
C16	0.072 (3)	0.067 (3)	0.145 (3)	−0.028 (2)	0.019 (2)	0.016 (3)

Geometric parameters (Å, º)

S1—C8	1.665 (3)	C6—H6	0.9300
S2—C8	1.739 (3)	C7—H7	0.9300
S2—C9	1.814 (3)	C9—C10	1.494 (4)
O1—C4	1.360 (4)	C9—H9A	0.9700
O1—C16	1.427 (4)	C9—H9B	0.9700
N1—C7	1.269 (4)	C10—C15	1.356 (6)
N1—N2	1.371 (3)	C10—C11	1.367 (6)
N2—C8	1.331 (3)	C11—C12	1.376 (7)
N2—H2	0.8600	C11—H11	0.9300
C1—C2	1.376 (4)	C12—C13	1.345 (11)
C1—C6	1.390 (4)	C12—H12	0.9300
C1—C7	1.446 (4)	C13—C14	1.352 (13)
C2—C3	1.376 (4)	C13—H13	0.9300
C2—H2A	0.9300	C14—C15	1.423 (8)
C3—C4	1.375 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.381 (4)	C16—H16A	0.9600
C5—C6	1.368 (4)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600
C8—S2—C9	101.16 (14)	C10—C9—S2	108.1 (2)
C4—O1—C16	117.8 (3)	C10—C9—H9A	110.1
C7—N1—N2	115.5 (2)	S2—C9—H9A	110.1
C8—N2—N1	120.6 (2)	C10—C9—H9B	110.1
C8—N2—H2	119.7	S2—C9—H9B	110.1
N1—N2—H2	119.7	H9A—C9—H9B	108.4
C2—C1—C6	118.2 (3)	C15—C10—C11	119.8 (4)
C2—C1—C7	120.2 (3)	C15—C10—C9	119.9 (4)
C6—C1—C7	121.6 (3)	C11—C10—C9	120.2 (4)
C3—C2—C1	121.9 (3)	C10—C11—C12	121.9 (6)
C3—C2—H2A	119.0	C10—C11—H11	119.1
C1—C2—H2A	119.0	C12—C11—H11	119.1
C4—C3—C2	119.4 (3)	C13—C12—C11	117.3 (8)
C4—C3—H3	120.3	C13—C12—H12	121.3
C2—C3—H3	120.3	C11—C12—H12	121.3
O1—C4—C3	125.3 (3)	C12—C13—C14	123.8 (7)
O1—C4—C5	115.4 (3)	C12—C13—H13	118.1
C3—C4—C5	119.2 (3)	C14—C13—H13	118.1
C6—C5—C4	121.1 (3)	C13—C14—C15	117.8 (8)
C6—C5—H5	119.4	C13—C14—H14	121.1
C4—C5—H5	119.4	C15—C14—H14	121.1
C5—C6—C1	120.1 (3)	C10—C15—C14	119.2 (7)
C5—C6—H6	119.9	C10—C15—H15	120.4
C1—C6—H6	119.9	C14—C15—H15	120.4
N1—C7—C1	122.2 (3)	O1—C16—H16A	109.5
N1—C7—H7	118.9	O1—C16—H16B	109.5
C1—C7—H7	118.9	H16A—C16—H16B	109.5
N2—C8—S1	121.0 (2)	O1—C16—H16C	109.5
N2—C8—S2	113.5 (2)	H16A—C16—H16C	109.5
S1—C8—S2	125.59 (18)	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	0.86	2.59	3.397 (4)	158
C16—H16C···Cg^ii	0.96	2.83	3.671 (5)	147

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