Methyl β-N-(3-nitro­phenyl­methyl­ene)­di­thio­carb­aza­te

Crystals of the title compound, C₉H₉N₃O₂S₂, were obtained from a condensation reaction of S-methyl di­thio­carb­aza­te and 3-nitro­benz­aldehyde. The planar di­thio­carb­aza­te moiety subtends an angle of 10.54 (8)° with respect to the plane of the nitro­phenyl ring. Electron delocalization occurs between the imino and di­thio­carboxyl groups. The partially overlapped arrangement of parallel benzene rings of neighboring mol­ecules, with a face-to-face distance of 3.343 (8) Å, suggests the existence of π–π stacking.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.032
• wR factor = 0.079
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   N1      ..       6.92 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; 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, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Methyl β-N-(3-nitrophenylmethylene)dithiocarbazate

Crystal data

C9H9N3O2S2	F(000) = 528
Mr = 255.31	Dx = 1.489 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 4542 reflections
a = 8.7176 (4) Å	θ = 2.4–27.0°
b = 7.5589 (3) Å	µ = 0.46 mm^−1
c = 17.5879 (7) Å	T = 295 K
β = 100.666 (2)°	Needle, yellow
V = 1138.94 (8) Å^3	0.50 × 0.13 × 0.10 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2611 independent reflections
Radiation source: fine-focus sealed tube	1703 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 10.00 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
Tmin = 0.770, Tmax = 0.952	l = −22→22
4646 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0448P)^2] where P = (Fo^2 + 2Fc^2)/3
2611 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.19 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	0.09695 (6)	0.48574 (7)	0.39342 (3)	0.04758 (15)
S2	0.10856 (6)	0.62236 (8)	0.23266 (3)	0.05584 (17)
N1	0.53123 (18)	0.1284 (2)	0.66293 (8)	0.0434 (4)
N2	0.39713 (16)	0.37137 (19)	0.39098 (7)	0.0377 (3)
N3	0.33002 (17)	0.44926 (19)	0.32250 (7)	0.0421 (4)
H3	0.3809	0.4545	0.2851	0.050*
O1	0.42125 (18)	0.2272 (2)	0.66359 (8)	0.0672 (4)
O2	0.57772 (17)	0.0236 (2)	0.71532 (7)	0.0628 (4)
C1	0.60959 (18)	0.2208 (2)	0.46639 (8)	0.0341 (4)
C2	0.54034 (18)	0.2238 (2)	0.53179 (8)	0.0338 (4)
H2	0.4491	0.2874	0.5319	0.041*
C3	0.60982 (19)	0.1308 (2)	0.59610 (8)	0.0344 (4)
C4	0.7453 (2)	0.0358 (3)	0.59985 (9)	0.0447 (4)
H4	0.7896	−0.0251	0.6445	0.054*
C5	0.8132 (2)	0.0342 (3)	0.53498 (11)	0.0519 (5)
H5	0.9047	−0.0294	0.5355	0.062*
C6	0.7467 (2)	0.1262 (3)	0.46917 (10)	0.0455 (5)
H6	0.7947	0.1246	0.4261	0.055*
C7	0.5337 (2)	0.3088 (2)	0.39532 (9)	0.0382 (4)
H7	0.5850	0.3189	0.3536	0.046*
C8	0.1858 (2)	0.5173 (2)	0.31329 (9)	0.0383 (4)
C9	−0.0876 (2)	0.5930 (3)	0.36350 (13)	0.0679 (6)
H9A	−0.0709	0.7141	0.3507	0.102*
H9B	−0.1457	0.5886	0.4048	0.102*
H9C	−0.1451	0.5336	0.3189	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0403 (3)	0.0614 (3)	0.0416 (2)	0.0008 (2)	0.00913 (18)	0.0023 (2)
S2	0.0557 (3)	0.0646 (4)	0.0430 (3)	0.0052 (3)	−0.0019 (2)	0.0136 (2)
N1	0.0454 (9)	0.0538 (10)	0.0328 (7)	−0.0100 (8)	0.0116 (6)	−0.0052 (7)
N2	0.0392 (8)	0.0423 (8)	0.0308 (7)	0.0022 (7)	0.0041 (6)	0.0029 (6)
N3	0.0433 (9)	0.0535 (9)	0.0302 (7)	0.0051 (7)	0.0087 (6)	0.0062 (6)
O1	0.0656 (10)	0.0867 (11)	0.0583 (8)	0.0213 (9)	0.0350 (7)	0.0038 (8)
O2	0.0733 (10)	0.0794 (11)	0.0391 (7)	0.0048 (8)	0.0194 (6)	0.0152 (7)
C1	0.0311 (9)	0.0389 (10)	0.0323 (8)	−0.0022 (7)	0.0061 (7)	−0.0018 (7)
C2	0.0283 (8)	0.0388 (10)	0.0347 (8)	−0.0006 (7)	0.0067 (6)	−0.0050 (7)
C3	0.0339 (9)	0.0413 (10)	0.0289 (8)	−0.0058 (8)	0.0081 (6)	−0.0038 (7)
C4	0.0350 (10)	0.0588 (12)	0.0389 (9)	0.0012 (9)	0.0032 (7)	0.0098 (8)
C5	0.0310 (10)	0.0730 (14)	0.0536 (10)	0.0146 (10)	0.0127 (8)	0.0107 (10)
C6	0.0358 (10)	0.0641 (13)	0.0401 (9)	0.0041 (9)	0.0161 (7)	0.0021 (9)
C7	0.0391 (10)	0.0430 (10)	0.0337 (8)	−0.0017 (8)	0.0102 (7)	−0.0001 (8)
C8	0.0404 (10)	0.0370 (10)	0.0357 (8)	−0.0033 (8)	0.0022 (7)	−0.0028 (8)
C9	0.0408 (12)	0.0903 (17)	0.0733 (14)	0.0088 (11)	0.0122 (10)	0.0031 (13)

Geometric parameters (Å, º)

S1—C8	1.7457 (17)	C2—C3	1.373 (2)
S1—C9	1.791 (2)	C2—H2	0.9300
S2—C8	1.6559 (17)	C3—C4	1.373 (2)
N1—O1	1.2171 (19)	C4—C5	1.379 (2)
N1—O2	1.2258 (18)	C4—H4	0.9300
N1—C3	1.4661 (19)	C5—C6	1.382 (2)
N2—C7	1.270 (2)	C5—H5	0.9300
N2—N3	1.3707 (18)	C6—H6	0.9300
N3—C8	1.340 (2)	C7—H7	0.9300
N3—H3	0.8600	C9—H9A	0.9600
C1—C6	1.386 (2)	C9—H9B	0.9600
C1—C2	1.395 (2)	C9—H9C	0.9600
C1—C7	1.462 (2)
C8—S1—C9	102.10 (9)	C5—C4—H4	121.3
O1—N1—O2	122.74 (15)	C4—C5—C6	120.72 (17)
O1—N1—C3	119.06 (15)	C4—C5—H5	119.6
O2—N1—C3	118.18 (15)	C6—C5—H5	119.6
C7—N2—N3	117.10 (13)	C5—C6—C1	120.94 (15)
C8—N3—N2	120.62 (13)	C5—C6—H6	119.5
C8—N3—H3	119.7	C1—C6—H6	119.5
N2—N3—H3	119.7	N2—C7—C1	119.44 (14)
C6—C1—C2	118.78 (15)	N2—C7—H7	120.3
C6—C1—C7	121.04 (14)	C1—C7—H7	120.3
C2—C1—C7	120.11 (15)	N3—C8—S2	120.76 (13)
C3—C2—C1	118.60 (15)	N3—C8—S1	113.36 (12)
C3—C2—H2	120.7	S1—C8—S2	125.87 (11)
C1—C2—H2	120.7	S1—C9—H9A	109.5
C2—C3—C4	123.47 (15)	S1—C9—H9B	109.5
C2—C3—N1	117.79 (15)	H9A—C9—H9B	109.5
C4—C3—N1	118.70 (15)	S1—C9—H9C	109.5
C3—C4—C5	117.49 (16)	H9A—C9—H9C	109.5
C3—C4—H4	121.3	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2^i	0.86	2.29	3.125 (2)	163

Symmetry code: (i) x, −y+1/2, z−1/2.