Benzyl 3-(10-oxo-9,10-dihydrophenanthren-9-ylidene)dithiocarbazate

Liu, Q.-R.; Chu, S.-M.; Zhao, G.-Q.; Chen, L.-H.; Han, Y.-J.

doi:10.1107/S160053680904272X

Benzyl 3-(10-oxo-9,10-dihydrophenanthren-9-ylidene)dithiocarbazate

Q.-R. Liu, S.-M. Chu, G.-Q. Zhao, L.-H. Chen and Y.-J. Han

In the title compound, C₂₂H₁₆N₂OS₂, the phenanthrene ring is nearly perpendicular to the phenyl ring, making a dihedral angle of 87.2 (2)°. Intramolecular N—H

O interactions are present. In the crystal structure, the molecules are linked through intermolecular C—H

O interactions. The crystal structure is also stabilized by C—H

π interactions and weak π–π contacts [centroid-centroid distance = 3.36 (6) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680904272X/hg2573sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680904272X/hg2573Isup2.hkl Contains datablock I

CCDC reference: 754411

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.036
wR factor = 0.098
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.596          9

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1     -C14           1.45 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Schiff bases are versatile compounds which possess excellent biologically properties (Bhandari et al.,2008). Recently, some Schiff bases derived from the reaction of S-benzyldithiocarbazate with aldehydes or ketones have been reported (Zhou et al., 2002; Ali et al., 2003a,b; How et al., 2007; Tarafder et al., 2008). We synthesized the title compound ((Fig. 1)) and report herein its crystal structure.

In the title compound, the bond lengths and angles are comparable to the values in the similar Schiff bases (Zhou et al., 2002). The phenanthrene ring (C1···C14) and dithiocarbazate (N1/N2/S1/S2/C15) fragments lie essentially in the same plane, with a mean deviation from the least-squares plane of 0.0385 Å. The phenanthrene ring (C1···C14) is nearly perpendicular to the phenyl ring (C17···C22) with a dihedral angle of 87.2°.

In the crystal structure, there are intramolecular N—H···O type hydrogen bonds (Table 1). The crystal structure is consolidated by intermolecular C—H···O [3.239 Å] (Fig. 2). It is also stabilized by C—H···Π interactions such as C5—H5···Π (3.642 Å) and C9—H9···Π (3.643 Å) involving phenanthrene ring and phenyl ring of the adjacent molecules respectively. In addition, π-π interactions between the adjacent phenanthrene rings (centroid-centroid distance = 3.36 (6) Å) may also stabilize the crystal packing.

Related literature top

For the biological properties of Schiff bases, see: Bhandari et al. (2008). Recently, some Schiff bases derived from the reaction of S-benzyldithiocarbazate with aldehydes or ketones have been reported, see: Ali et al. (2003a,b); How et al. (2007); Tarafder et al. (2008); Zhou et al. (2002). For the synthesis of S-benzyldithiocarbazate, see: Chew et al. (2004). For the synthesis of the title compound, see: Ali et al. (2004).

Experimental top

S-benzyldithiocarbazate was synthesized as described in the literature (Chew et al., 2004). The title compound was synthesized as described in the literature (Ali et al., 2004). To 9,10-phenanthrenequinone in 60 ml of absolute ethyl alcohol was added a solution of S-benzyldithiocarbazate (1.00 mmol) in 20 ml of absolute ethyl alcohol dropwise. The red-brown solution was refluxed for 5.0 h at 353 K. The resultant solution was filtered and left in air for a few days, yielding brown block-like crystals.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A view of the crystal packing along the b axis. Intermolecular Hydrogen bonds are shown as dashed lines.

Benzyl 3-(10-oxo-9,10-dihydrophenanthren-9-ylidene)dithiocarbazate top

Crystal data top

C₂₂H₁₆N₂OS₂	F(000) = 808
M_r = 388.49	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3545 reflections
a = 14.4945 (19) Å	θ = 2.2–27.1°
b = 5.6978 (7) Å	µ = 0.30 mm⁻¹
c = 22.816 (3) Å	T = 296 K
β = 93.610 (2)°	Block, brown
V = 1880.6 (4) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3316 independent reflections
Radiation source: fine-focus sealed tube	2638 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→12
T_min = 0.916, T_max = 0.943	k = −6→6
9220 measured reflections	l = −27→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0436P)² + 0.4502P] where P = (F_o² + 2F_c²)/3
3316 reflections	(Δ/σ)_max < 0.001
244 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₂H₁₆N₂OS₂	V = 1880.6 (4) Å³
M_r = 388.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.4945 (19) Å	µ = 0.30 mm⁻¹
b = 5.6978 (7) Å	T = 296 K
c = 22.816 (3) Å	0.30 × 0.30 × 0.20 mm
β = 93.610 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3316 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2638 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.943	R_int = 0.022
9220 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	Δρ_max = 0.16 e Å⁻³
3316 reflections	Δρ_min = −0.22 e Å⁻³
244 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.12004 (12)	0.9543 (3)	0.10487 (7)	0.0410 (4)
C2	0.07744 (12)	0.7660 (3)	0.13826 (7)	0.0404 (4)
C3	0.13280 (14)	0.6058 (3)	0.17087 (8)	0.0505 (5)
H3	0.1968	0.6203	0.1718	0.061*
C4	0.09428 (15)	0.4277 (3)	0.20145 (8)	0.0570 (5)
H4	0.1320	0.3226	0.2230	0.068*
C5	−0.00057 (15)	0.4045 (3)	0.20025 (8)	0.0551 (5)
H5	−0.0269	0.2837	0.2209	0.066*
C6	−0.05593 (14)	0.5600 (3)	0.16850 (7)	0.0496 (5)
H6	−0.1198	0.5422	0.1679	0.060*
C7	−0.01904 (12)	0.7447 (3)	0.13706 (7)	0.0413 (4)
C8	−0.07862 (12)	0.9126 (3)	0.10288 (7)	0.0428 (4)
C9	−0.17451 (14)	0.8986 (4)	0.10096 (9)	0.0601 (5)
H9	−0.2023	0.7801	0.1217	0.072*
C10	−0.22943 (14)	1.0568 (4)	0.06899 (10)	0.0663 (6)
H10	−0.2934	1.0431	0.0684	0.080*
C11	−0.19058 (14)	1.2346 (4)	0.03787 (9)	0.0594 (5)
H11	−0.2279	1.3411	0.0165	0.071*
C12	−0.09620 (13)	1.2524 (3)	0.03891 (8)	0.0496 (5)
H12	−0.0693	1.3716	0.0179	0.059*
C13	−0.04017 (12)	1.0942 (3)	0.07096 (7)	0.0407 (4)
C14	0.06035 (12)	1.1237 (3)	0.07105 (7)	0.0427 (4)
C15	0.34732 (13)	1.1176 (4)	0.07602 (8)	0.0513 (5)
C16	0.51902 (14)	0.9484 (5)	0.11012 (11)	0.0836 (8)
H16A	0.5363	0.9037	0.0713	0.100*
H16B	0.5310	1.1148	0.1154	0.100*
C17	0.57478 (13)	0.8104 (4)	0.15607 (10)	0.0635 (6)
C18	0.61629 (15)	0.6028 (5)	0.14199 (11)	0.0716 (6)
H18	0.6081	0.5433	0.1041	0.086*
C19	0.67014 (17)	0.4821 (5)	0.18405 (14)	0.0816 (7)
H19	0.6984	0.3422	0.1743	0.098*
C20	0.68202 (17)	0.5671 (6)	0.23965 (13)	0.0863 (8)
H20	0.7184	0.4851	0.2677	0.104*
C21	0.64071 (19)	0.7725 (6)	0.25452 (12)	0.0867 (8)
H21	0.6489	0.8302	0.2926	0.104*
C22	0.58678 (16)	0.8938 (5)	0.21272 (12)	0.0777 (7)
H22	0.5583	1.0329	0.2229	0.093*
N1	0.20996 (10)	0.9575 (3)	0.10711 (6)	0.0466 (4)
N2	0.25374 (10)	1.1215 (3)	0.07714 (7)	0.0524 (4)
H2	0.2225	1.2296	0.0586	0.063*
O1	0.09460 (9)	1.2850 (2)	0.04354 (6)	0.0577 (4)
S1	0.39768 (3)	0.88888 (10)	0.11712 (2)	0.06204 (18)
S2	0.39996 (4)	1.31825 (12)	0.03859 (3)	0.0741 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0420 (10)	0.0423 (10)	0.0385 (9)	−0.0001 (8)	0.0004 (7)	−0.0020 (7)
C2	0.0478 (10)	0.0376 (10)	0.0356 (8)	0.0010 (8)	0.0018 (7)	−0.0025 (7)
C3	0.0527 (11)	0.0492 (11)	0.0495 (10)	0.0071 (9)	0.0025 (8)	0.0036 (9)
C4	0.0754 (15)	0.0458 (12)	0.0496 (11)	0.0112 (10)	0.0018 (10)	0.0057 (9)
C5	0.0771 (15)	0.0438 (11)	0.0445 (10)	−0.0062 (10)	0.0052 (10)	0.0042 (8)
C6	0.0570 (11)	0.0479 (11)	0.0439 (10)	−0.0082 (9)	0.0034 (8)	−0.0003 (8)
C7	0.0492 (11)	0.0387 (10)	0.0360 (8)	−0.0024 (8)	0.0016 (7)	−0.0041 (7)
C8	0.0434 (10)	0.0463 (11)	0.0386 (9)	−0.0028 (8)	0.0016 (7)	−0.0045 (8)
C9	0.0489 (12)	0.0670 (14)	0.0646 (12)	−0.0066 (10)	0.0040 (10)	0.0138 (11)
C10	0.0422 (11)	0.0809 (16)	0.0754 (14)	0.0002 (11)	0.0008 (10)	0.0102 (12)
C11	0.0511 (12)	0.0635 (13)	0.0625 (12)	0.0100 (10)	−0.0056 (9)	0.0059 (10)
C12	0.0516 (11)	0.0474 (11)	0.0491 (10)	0.0019 (9)	−0.0015 (8)	0.0040 (9)
C13	0.0439 (10)	0.0404 (10)	0.0374 (9)	−0.0004 (8)	−0.0002 (7)	−0.0031 (7)
C14	0.0489 (10)	0.0405 (10)	0.0384 (9)	−0.0010 (8)	0.0000 (7)	0.0014 (8)
C15	0.0449 (11)	0.0611 (12)	0.0479 (10)	−0.0051 (9)	0.0027 (8)	0.0007 (9)
C16	0.0429 (12)	0.112 (2)	0.0963 (17)	0.0000 (13)	0.0097 (12)	0.0408 (16)
C17	0.0373 (11)	0.0768 (16)	0.0769 (15)	−0.0056 (11)	0.0074 (10)	0.0214 (12)
C18	0.0517 (13)	0.0797 (17)	0.0837 (16)	−0.0092 (12)	0.0081 (11)	0.0086 (13)
C19	0.0622 (15)	0.0702 (16)	0.114 (2)	0.0016 (13)	0.0165 (15)	0.0235 (16)
C20	0.0586 (15)	0.099 (2)	0.100 (2)	−0.0074 (15)	−0.0065 (14)	0.0410 (18)
C21	0.0824 (18)	0.098 (2)	0.0784 (17)	−0.0195 (17)	−0.0051 (14)	0.0110 (16)
C22	0.0680 (16)	0.0705 (16)	0.0959 (19)	−0.0032 (13)	0.0151 (14)	0.0108 (14)
N1	0.0442 (9)	0.0510 (9)	0.0446 (8)	−0.0017 (7)	0.0026 (7)	0.0025 (7)
N2	0.0441 (9)	0.0563 (10)	0.0567 (9)	−0.0018 (8)	0.0021 (7)	0.0118 (8)
O1	0.0509 (8)	0.0552 (8)	0.0664 (8)	−0.0035 (7)	0.0000 (6)	0.0211 (7)
S1	0.0432 (3)	0.0684 (4)	0.0752 (4)	0.0020 (3)	0.0088 (2)	0.0171 (3)
S2	0.0586 (4)	0.0827 (4)	0.0809 (4)	−0.0146 (3)	0.0027 (3)	0.0257 (3)

Geometric parameters (Å, º) top

C1—N1	1.301 (2)	C12—H12	0.9300
C1—C2	1.474 (2)	C13—C14	1.467 (2)
C1—C14	1.480 (2)	C14—O1	1.235 (2)
C2—C3	1.398 (2)	C15—N2	1.358 (2)
C2—C7	1.402 (2)	C15—S2	1.6432 (19)
C3—C4	1.370 (3)	C15—S1	1.739 (2)
C3—H3	0.9300	C16—C17	1.505 (3)
C4—C5	1.380 (3)	C16—S1	1.808 (2)
C4—H4	0.9300	C16—H16A	0.9700
C5—C6	1.371 (3)	C16—H16B	0.9700
C5—H5	0.9300	C17—C18	1.374 (3)
C6—C7	1.399 (2)	C17—C22	1.378 (3)
C6—H6	0.9300	C18—C19	1.382 (3)
C7—C8	1.478 (2)	C18—H18	0.9300
C8—C9	1.390 (3)	C19—C20	1.359 (4)
C8—C13	1.401 (2)	C19—H19	0.9300
C9—C10	1.380 (3)	C20—C21	1.367 (4)
C9—H9	0.9300	C20—H20	0.9300
C10—C11	1.378 (3)	C21—C22	1.380 (3)
C10—H10	0.9300	C21—H21	0.9300
C11—C12	1.371 (3)	C22—H22	0.9300
C11—H11	0.9300	N1—N2	1.341 (2)
C12—C13	1.390 (2)	N2—H2	0.8600

N1—C1—C2	116.18 (15)	C12—C13—C14	118.28 (16)
N1—C1—C14	124.21 (16)	C8—C13—C14	120.78 (15)
C2—C1—C14	119.60 (15)	O1—C14—C13	121.05 (16)
C3—C2—C7	119.49 (16)	O1—C14—C1	120.66 (16)
C3—C2—C1	120.34 (16)	C13—C14—C1	118.29 (15)
C7—C2—C1	120.17 (15)	N2—C15—S2	119.68 (15)
C4—C3—C2	121.05 (18)	N2—C15—S1	112.82 (14)
C4—C3—H3	119.5	S2—C15—S1	127.49 (12)
C2—C3—H3	119.5	C17—C16—S1	108.87 (15)
C3—C4—C5	119.87 (18)	C17—C16—H16A	109.9
C3—C4—H4	120.1	S1—C16—H16A	109.9
C5—C4—H4	120.1	C17—C16—H16B	109.9
C6—C5—C4	119.87 (18)	S1—C16—H16B	109.9
C6—C5—H5	120.1	H16A—C16—H16B	108.3
C4—C5—H5	120.1	C18—C17—C22	119.0 (2)
C5—C6—C7	121.82 (18)	C18—C17—C16	120.7 (2)
C5—C6—H6	119.1	C22—C17—C16	120.3 (2)
C7—C6—H6	119.1	C17—C18—C19	120.2 (2)
C6—C7—C2	117.90 (16)	C17—C18—H18	119.9
C6—C7—C8	121.88 (16)	C19—C18—H18	119.9
C2—C7—C8	120.22 (15)	C20—C19—C18	120.3 (3)
C9—C8—C13	117.11 (17)	C20—C19—H19	119.9
C9—C8—C7	121.96 (17)	C18—C19—H19	119.9
C13—C8—C7	120.92 (15)	C19—C20—C21	120.3 (3)
C10—C9—C8	121.44 (19)	C19—C20—H20	119.8
C10—C9—H9	119.3	C21—C20—H20	119.8
C8—C9—H9	119.3	C20—C21—C22	119.7 (3)
C11—C10—C9	120.78 (19)	C20—C21—H21	120.2
C11—C10—H10	119.6	C22—C21—H21	120.2
C9—C10—H10	119.6	C17—C22—C21	120.5 (3)
C12—C11—C10	119.03 (19)	C17—C22—H22	119.7
C12—C11—H11	120.5	C21—C22—H22	119.7
C10—C11—H11	120.5	C1—N1—N2	119.66 (15)
C11—C12—C13	120.71 (18)	N1—N2—C15	120.22 (16)
C11—C12—H12	119.6	N1—N2—H2	119.9
C13—C12—H12	119.6	C15—N2—H2	119.9
C12—C13—C8	120.93 (16)	C15—S1—C16	100.92 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.89	2.560 (2)	134
C12—H12···O1ⁱ	0.93	2.42	3.239 (2)	147
C5—H5···Cg1ⁱⁱ	0.93	2.76	3.559 (2)	144

Symmetry codes: (i) −x, −y+3, −z; (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₆N₂OS₂
M_r	388.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.4945 (19), 5.6978 (7), 22.816 (3)
β (°)	93.610 (2)
V (Å³)	1880.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.916, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	9220, 3316, 2638
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.06
No. of reflections	3316
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.22

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.89	2.560 (2)	134
C12—H12···O1ⁱ	0.93	2.42	3.239 (2)	147
C5—H5···Cg1ⁱⁱ	0.93	2.76	3.559 (2)	144

Symmetry codes: (i) −x, −y+3, −z; (ii) −x, y−1/2, −z+1/2.

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