Benzyl N'-(2-methoxy­benzo­yl)hydrazine­carbo­dithio­ate

The title dithio ester, C₁₆H₁₆N₂O₂S₂, was synthesized by the reaction of potassium N'-(2-methoxy­benzo­yl)hydra­zine­carbodithio­ate and benzyl chloride in chloro­form. The dihedral angle between the 2-methoxy­phenyl ring and the benzyl ring is 85.06 (2) Å. In the crystal structure, intra- and inter­molecular hydrogen bonding stabilizes the mol­ecule and the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.083
• wR factor = 0.273
• Data-to-parameter ratio = 27.3

checkCIF/PLATON results

No syntax errors found



Alert level A
ABSTM02_ALERT_3_A  The ratio of expected to reported Tmax/Tmin(RR') is < 0.50
            Tmin and Tmax reported:      0.332     1.000
            Tmin(prime) and Tmax expected:      0.827     0.931
            RR(prime) =      0.373
            Please check that your absorption correction is appropriate.

Author Response: The absorption correction was of the multi-scan type (Blessing, R. H. (1995). Acta Cryst. A5I, 33-38) which looks at agreement of eqivalent reflections. This is a standard type of absorption correction. There is no control over the values for Tmin and Tmax. A numerical correction was not possible as the crystal was an irregular chunk cut from a larger crystal.

PLAT061_ALERT_3_A Tmax/Tmin Range Test RR' too Large .............       0.37

Author Response: The absorption correction was of the multi-scan type (Blessing, R. H. (1995). Acta Cryst. A5I, 33-38) which looks at agreement of eqivalent reflections. This is a standard type of absorption correction. There is no control over the values for Tmin and Tmax. A numerical correction was not possible as the crystal was an irregular chunk cut from a larger crystal.

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.273
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.93
PLAT084_ALERT_2_C High R2 Value ..................................       0.27
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C2      ..       5.75 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.11
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C11    -C16           1.36 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.931
            Tmax scaled      0.931 Tmin scaled      0.309

Author Response: The absorption correction was of the multi-scan type (Blessing, R. H. (1995). Acta Cryst. A5I, 33-38) which looks at agreement of eqivalent reflections. This is a standard type of absorption correction. There is no control over the values for Tmin and Tmax. A numerical correction was not possible as the crystal was an irregular chunk cut from a larger crystal.

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   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
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Dithioligands are very promising compounds from the view point of coordination chemistry because of their ability towards complexation and involvement in a wide range of biological (Trarafder et al., 2001, Bhardawaj & Musker, 1987) and non-biological processes (Singh & Gupta, 2002). As not much data is available on the synthesis and structural characterization of N'-acylhydrazine carbodithio acid esters, the syntheses and elucidation of crystal structure of compound (I) has been undertaken. The molecular structure of (I) together with the atom labeling scheme, is shown in Fig 1. In the title compound, the o-methoxyphenyl ring unit and benzyl ring are in two different planes. The dihedral angle between o-methoxyphenyl ring and benzyl ring is 85.06 (2) Å. Hydrazinic atoms H1D and H2A are trans to each other, as are the C(9)—S(1) and C(8)—O(2) groups [torsional angles, N2—N1—C8—C7 and C10—S2—C9-(N2) = -173.3 (2)° and 170.75 (19)°, respectively]. The C—S and C=S bonds present in the molecule are 1.656 Å and 1.740 Å (3) which agree well with equivalent bonds, being intermediate between 1.82 Å for a C—S single bond and 1.56 Å for a C=S double bond (Wu et al., 2000). The C—N bond distance is 1.375 (2) Å, which is also intermediate between C—N (1.450 Å) and C=N (1.250 Å). The intermediate bond distances in compound (I) illustrate the extensive electron delocalization which provides stability to the molecule. The three dimensional structure of (I) demonstrates that atoms O, N and S are available as donor sites for coordination to metals either as a tridentate neutral or mononegative ligand. The H3A hydrogen of two different o-methoxyphenyl rings form weak Van der Waals interaction with each other (H3A···H3A = 2.398 Å).

Related literature

For related literature, see: Trarafder et al. (2001); Bhardawaj et al. (1987); Singh & Gupta (2002); Wu et al. (2000); Singh et al. (2007).

S2. Experimental

The potassium[N'-(2-methoxy-benzoyl)-hydrazinecarbodithioate] was synthesized according to earlier reported literature method (Singh et al., 2007). Compound (I) was synthesized by the reaction of benzyl chloride (1.7 ml, 14.26 mmol) suspension of to a freshly prepared potassium[N'-(2-methoxy-benzoyl)-hydrazinecarbodithioate] (4 g, 14.26 mmol) in choloroform (15 ml) and stirring the reaction mixture continuously for 2 h at room temperature. The resulting solution was filtered and kept in a freezer for crystallization. White plate-shaped single crystals of (I) (m.p. 453 K) suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution over a period of 1 d. (yield 2.08 g, 52%). Analysis found (%) for C₁₆H₁₆N₂O₂S₂ (332.43): C, 57.83; H, 4.90; N, 8.39; S, 19.30. Calculated (%): C, 57.81; H, 4.85; N, 8.43; S, 19.29.

S3. Refinement

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.96 Å and U_iso (H) = 1.5 U_eq (C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with an N—H distance of 0.86 Å and C—H distances in the range of 0.93–0.97 Å and U_iso(H) = 1.2 U_eq (C, N).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. The molecular structure of (I), showing the atom numbering scheme with displacement ellipsoid drawn at the 20% probability level. The dashed line indicates intramolecular hydrogen bonding NH···O.
	Fig. 2. The crystal packing of (I), showing hydrogen bonding interactions by dashed lines.

Benzyl N'-(2-methoxybenzoyl)hydrazinecarbodithioate

Crystal data

C16H16N2O2S2	F(000) = 348
Mr = 332.43	Dx = 1.371 Mg m^−3
Triclinic, P1	Melting point: 453 K
a = 7.493 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.230 (3) Å	Cell parameters from 8677 reflections
c = 11.212 (4) Å	θ = 4.7–32.4°
α = 74.56 (3)°	µ = 0.34 mm^−1
β = 81.49 (3)°	T = 295 K
γ = 77.61 (2)°	Irregular chunk, pale yellow
V = 805.3 (4) Å^3	0.55 × 0.37 × 0.21 mm
Z = 2

Data collection

Oxford Diffraction Gemini diffractometer	5465 independent reflections
Radiation source: fine-focus sealed tube	2864 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 10.5081 pixels mm^-1	θmax = 32.6°, θmin = 4.8°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −15→15
Tmin = 0.332, Tmax = 1.000	l = −16→16
23923 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.083	w = 1/[σ^2(Fo^2) + (0.1384P)^2 + 0.286P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.273	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.83 e Å^−3
5465 reflections	Δρmin = −0.57 e Å^−3
200 parameters

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	−0.09425 (9)	0.45170 (6)	0.72229 (6)	0.06447 (19)
S2	0.23392 (9)	0.22193 (7)	0.71650 (6)	0.0718 (2)
O1	−0.5450 (2)	0.39719 (18)	0.90884 (18)	0.0693 (5)
O2	−0.2038 (2)	0.03963 (18)	1.06503 (17)	0.0718 (5)
N1	−0.2336 (2)	0.2310 (2)	0.91251 (19)	0.0581 (5)
H1D	−0.3015	0.3076	0.8796	0.070*
N2	−0.0554 (2)	0.19913 (19)	0.86344 (18)	0.0556 (5)
H2A	0.0097	0.1193	0.8911	0.067*
C1	−0.6582 (4)	0.5247 (3)	0.8573 (3)	0.0772 (8)
H1A	−0.5846	0.5834	0.7986	0.116*
H1B	−0.7151	0.5688	0.9225	0.116*
H1C	−0.7513	0.5078	0.8158	0.116*
C2	−0.6188 (3)	0.3006 (2)	0.9996 (2)	0.0545 (5)
C3	−0.8027 (3)	0.3183 (3)	1.0435 (3)	0.0688 (7)
H3A	−0.8816	0.3992	1.0103	0.083*
C4	−0.8691 (4)	0.2182 (3)	1.1348 (3)	0.0752 (8)
H4A	−0.9929	0.2322	1.1635	0.090*
C5	−0.7563 (4)	0.0969 (3)	1.1854 (3)	0.0718 (8)
H5A	−0.8031	0.0292	1.2477	0.086*
C6	−0.5734 (3)	0.0775 (3)	1.1422 (2)	0.0627 (6)
H6A	−0.4965	−0.0045	1.1753	0.075*
C7	−0.5017 (3)	0.1778 (2)	1.0502 (2)	0.0480 (5)
C8	−0.3025 (3)	0.1435 (2)	1.0113 (2)	0.0493 (5)
C9	0.0156 (3)	0.2919 (2)	0.77336 (19)	0.0490 (5)
C10	0.2901 (4)	0.3524 (3)	0.5800 (2)	0.0709 (7)
H10A	0.1953	0.3775	0.5235	0.085*
H10B	0.3039	0.4345	0.6029	0.085*
C11	0.4685 (3)	0.2867 (3)	0.5222 (2)	0.0592 (6)
C12	0.4727 (5)	0.2113 (3)	0.4372 (3)	0.0822 (9)
H12A	0.3641	0.2046	0.4103	0.099*
C13	0.6400 (7)	0.1448 (4)	0.3915 (3)	0.1008 (12)
H13A	0.6442	0.0917	0.3352	0.121*
C14	0.7985 (5)	0.1580 (4)	0.4300 (3)	0.1010 (13)
H14A	0.9110	0.1138	0.3995	0.121*
C15	0.7933 (5)	0.2343 (5)	0.5116 (4)	0.1004 (12)
H15A	0.9018	0.2432	0.5370	0.120*
C16	0.6313 (4)	0.2976 (4)	0.5564 (3)	0.0786 (8)
H16A	0.6298	0.3505	0.6124	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0643 (3)	0.0451 (3)	0.0641 (4)	−0.0005 (3)	−0.0045 (3)	0.0123 (3)
S2	0.0597 (3)	0.0582 (3)	0.0619 (4)	0.0051 (3)	0.0137 (3)	0.0232 (3)
O1	0.0521 (8)	0.0509 (9)	0.0782 (11)	0.0065 (7)	−0.0011 (8)	0.0145 (8)
O2	0.0511 (8)	0.0573 (9)	0.0712 (11)	0.0083 (7)	0.0069 (8)	0.0244 (8)
N1	0.0426 (9)	0.0505 (10)	0.0587 (11)	0.0034 (7)	0.0018 (8)	0.0118 (8)
N2	0.0448 (9)	0.0464 (9)	0.0555 (10)	0.0008 (7)	0.0041 (8)	0.0096 (8)
C1	0.0713 (15)	0.0486 (13)	0.0913 (19)	0.0108 (11)	−0.0183 (14)	0.0063 (12)
C2	0.0480 (10)	0.0509 (11)	0.0552 (12)	0.0041 (9)	−0.0058 (9)	−0.0068 (9)
C3	0.0462 (11)	0.0684 (15)	0.0762 (16)	0.0077 (11)	−0.0014 (11)	−0.0077 (13)
C4	0.0481 (12)	0.0830 (18)	0.0763 (17)	−0.0001 (12)	0.0091 (12)	−0.0061 (14)
C5	0.0541 (12)	0.0755 (16)	0.0683 (16)	−0.0107 (12)	0.0121 (11)	0.0016 (13)
C6	0.0549 (12)	0.0566 (13)	0.0601 (14)	−0.0041 (10)	0.0017 (10)	0.0050 (10)
C7	0.0426 (9)	0.0457 (10)	0.0469 (10)	0.0000 (8)	−0.0032 (8)	−0.0034 (8)
C8	0.0420 (9)	0.0445 (10)	0.0486 (11)	−0.0009 (8)	0.0008 (8)	0.0021 (8)
C9	0.0505 (10)	0.0459 (10)	0.0404 (10)	−0.0027 (8)	−0.0067 (8)	0.0035 (8)
C10	0.0742 (15)	0.0591 (14)	0.0562 (14)	−0.0076 (12)	0.0083 (12)	0.0141 (11)
C11	0.0666 (13)	0.0557 (12)	0.0432 (11)	−0.0200 (10)	0.0063 (10)	0.0092 (9)
C12	0.104 (2)	0.0827 (19)	0.0594 (16)	−0.0291 (17)	−0.0100 (15)	−0.0062 (14)
C13	0.146 (3)	0.077 (2)	0.0666 (18)	−0.009 (2)	0.012 (2)	−0.0177 (16)
C14	0.088 (2)	0.101 (3)	0.075 (2)	0.0041 (19)	0.0265 (17)	0.0102 (18)
C15	0.0666 (17)	0.122 (3)	0.097 (3)	−0.0169 (19)	0.0049 (17)	−0.006 (2)
C16	0.0774 (17)	0.0896 (19)	0.0693 (17)	−0.0286 (15)	0.0037 (14)	−0.0154 (15)

Geometric parameters (Å, º)

S1—C9	1.656 (2)	C5—C6	1.375 (4)
S2—C9	1.740 (2)	C5—H5A	0.9300
S2—C10	1.807 (3)	C6—C7	1.383 (3)
O1—C2	1.361 (3)	C6—H6A	0.9300
O1—C1	1.422 (3)	C7—C8	1.485 (3)
O2—C8	1.222 (3)	C10—C11	1.500 (4)
N1—C8	1.340 (3)	C10—H10A	0.9700
N1—N2	1.372 (3)	C10—H10B	0.9700
N1—H1D	0.8600	C11—C16	1.367 (4)
N2—C9	1.323 (3)	C11—C12	1.370 (4)
N2—H2A	0.8600	C12—C13	1.388 (5)
C1—H1A	0.9600	C12—H12A	0.9300
C1—H1B	0.9600	C13—C14	1.367 (6)
C1—H1C	0.9600	C13—H13A	0.9300
C2—C3	1.383 (3)	C14—C15	1.343 (6)
C2—C7	1.401 (3)	C14—H14A	0.9300
C3—C4	1.361 (4)	C15—C16	1.342 (5)
C3—H3A	0.9300	C15—H15A	0.9300
C4—C5	1.376 (4)	C16—H16A	0.9300
C4—H4A	0.9300
C9—S2—C10	104.13 (12)	C2—C7—C8	125.06 (19)
C2—O1—C1	119.7 (2)	O2—C8—N1	120.48 (19)
C8—N1—N2	120.43 (17)	O2—C8—C7	122.33 (19)
C8—N1—H1D	119.8	N1—C8—C7	117.18 (17)
N2—N1—H1D	119.8	N2—C9—S1	123.36 (17)
C9—N2—N1	119.61 (17)	N2—C9—S2	110.94 (15)
C9—N2—H2A	120.2	S1—C9—S2	125.69 (13)
N1—N2—H2A	120.2	C11—C10—S2	104.53 (17)
O1—C1—H1A	109.5	C11—C10—H10A	111.0
O1—C1—H1B	109.5	S2—C10—H10A	110.9
H1A—C1—H1B	109.5	C11—C10—H10B	110.9
O1—C1—H1C	109.5	S2—C10—H10B	110.7
H1A—C1—H1C	109.5	H10A—C10—H10B	108.8
H1B—C1—H1C	109.5	C16—C11—C12	118.4 (3)
O1—C2—C3	123.0 (2)	C16—C11—C10	120.3 (3)
O1—C2—C7	117.93 (19)	C12—C11—C10	121.3 (3)
C3—C2—C7	119.0 (2)	C11—C12—C13	119.6 (3)
C4—C3—C2	120.6 (2)	C11—C12—H12A	120.2
C4—C3—H3A	119.7	C13—C12—H12A	120.2
C2—C3—H3A	119.7	C14—C13—C12	119.4 (4)
C3—C4—C5	121.2 (2)	C14—C13—H13A	120.3
C3—C4—H4A	119.4	C12—C13—H13A	120.3
C5—C4—H4A	119.4	C15—C14—C13	120.5 (3)
C6—C5—C4	118.8 (3)	C15—C14—H14A	119.7
C6—C5—H5A	120.6	C13—C14—H14A	119.7
C4—C5—H5A	120.6	C16—C15—C14	119.9 (4)
C5—C6—C7	121.2 (2)	C16—C15—H15A	120.0
C5—C6—H6A	119.4	C14—C15—H15A	120.0
C7—C6—H6A	119.4	C15—C16—C11	122.0 (3)
C6—C7—C2	119.1 (2)	C15—C16—H16A	119.0
C6—C7—C8	115.81 (19)	C11—C16—H16A	119.0
C8—N1—N2—C9	−173.7 (2)	C6—C7—C8—N1	172.1 (2)
C1—O1—C2—C3	1.6 (4)	C2—C7—C8—N1	−6.6 (4)
C1—O1—C2—C7	−178.4 (3)	N1—N2—C9—S1	4.9 (3)
O1—C2—C3—C4	−179.8 (3)	N1—N2—C9—S2	−174.10 (18)
C7—C2—C3—C4	0.2 (4)	C10—S2—C9—N2	170.75 (19)
C2—C3—C4—C5	−0.4 (5)	C10—S2—C9—S1	−8.2 (2)
C3—C4—C5—C6	0.0 (5)	C9—S2—C10—C11	−173.74 (19)
C4—C5—C6—C7	0.5 (5)	S2—C10—C11—C16	−89.0 (3)
C5—C6—C7—C2	−0.7 (4)	S2—C10—C11—C12	89.1 (3)
C5—C6—C7—C8	−179.6 (3)	C16—C11—C12—C13	2.1 (4)
O1—C2—C7—C6	−179.6 (2)	C10—C11—C12—C13	−176.0 (3)
C3—C2—C7—C6	0.3 (4)	C11—C12—C13—C14	−1.4 (5)
O1—C2—C7—C8	−0.9 (4)	C12—C13—C14—C15	0.1 (5)
C3—C2—C7—C8	179.1 (2)	C13—C14—C15—C16	0.4 (6)
N2—N1—C8—O2	5.8 (4)	C14—C15—C16—C11	0.4 (6)
N2—N1—C8—C7	−173.3 (2)	C12—C11—C16—C15	−1.6 (5)
C6—C7—C8—O2	−7.0 (4)	C10—C11—C16—C15	176.5 (3)
C2—C7—C8—O2	174.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1	0.86	1.88	2.574 (3)	136
N2—H2A···O2^i	0.86	1.94	2.786 (3)	167

Symmetry code: (i) −x, −y, −z+2.