1-[4-(Dimethyl­amino)benzyl­idene]-4-(4-nitro­phen­yl)thio­semicarbazide

In the title compound, C₁₆H₁₇N₅O₂S, the configuration is trans about the formal C=N bond. The mol­ecular conformation is stabilized by an intra­molecular N—H...N hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.141
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.99 Deg.
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H1A    ..  H8A     ..       1.75 Ang.
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H2B    ..  H4B     ..       1.78 Ang.

Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         400 Deg.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C10     ..       5.09 su

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

1-(4-(Dimethylamino)benzylidene)-4-(4-nitrophenyl)thiosemicarbazide

Crystal data

C16H17N5O2S	V = 812.9 (3) Å^3
Mr = 343.41	Z = 2
Triclinic, P1	F(000) = 360
Hall symbol: -P 1	Dx = 1.403 Mg m^−3
a = 7.213 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.487 (2) Å	θ = 2.7–28.2°
c = 15.452 (4) Å	µ = 0.22 mm^−1
α = 80.920 (4)°	T = 123 K
β = 80.634 (4)°	Block, red
γ = 89.247 (4)°	0.39 × 0.26 × 0.19 mm

Data collection

Bruker SMART APEX 2000 CCD diffractometer	2820 independent reflections
Radiation source: fine-focus sealed tube	2567 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.920, Tmax = 0.966	k = −8→8
5827 measured reflections	l = −18→18

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0834P)^2 + 0.7024P] where P = (Fo^2 + 2Fc^2)/3
2820 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

Special details

Experimental. IR (KBr, νcm^-1) 3314 (Ar—OH), 3172, 2947, 2910, 1831 (CO), 1690, 1514, 1320, 1216, 825; ¹H NMR (DMSO): δ 10.26 (s, 1H), 9.18 (s, 1H), 9.14 (s, 1H), 8.67 (s, 1H), 8.07–8.04 (m, 1H), 7.70 (d, J = 8.7 Hz, 1H), 7.66 (d, J = 8.7 Hz, 1H), 7.38–7.33 (m, 2H), 7.05 (d, J = 8.7 Hz, 1H), 7.01–6.98 (m, 1H), 6.76 (dd, J = 8.7, 2.1 Hz, 1H), 6.16 (s, 1H), 4.01 (s, 3H); ¹³C NMR (DMSO): δ 170.5, 156.3, 153.9, 137.5, 136.9, 136.2, 132.4, 130.4, 130.3, 129.8, 129.6, 127.6, 125.2, 124.5, 123.5, 119.3, 115.6, 115.1, 113.2, 107.9, 106.3, 53.8; FAB-MS, m*/z* (%): 360 ([M]⁺, 16). Analysis calculated for C₂₂H₁₆O₅: C 73.33, H 4.48%; found: C 72.63, H 4.54.

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 > 2σ(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	0.77905 (7)	0.56132 (8)	0.60339 (4)	0.0234 (2)
N1	0.4862 (3)	0.7608 (3)	−0.03125 (14)	0.0353 (5)
N2	0.7079 (3)	0.6433 (2)	0.35652 (12)	0.0204 (4)
N3	0.7891 (2)	0.5989 (2)	0.43109 (12)	0.0210 (4)
H3A	0.8991	0.5459	0.4281	0.025*
N4	0.5387 (2)	0.7306 (2)	0.50123 (12)	0.0201 (4)
H4A	0.5127	0.7509	0.4469	0.024*
N5	−0.0172 (3)	1.0188 (3)	0.73415 (14)	0.0281 (5)
O1	−0.1576 (3)	1.0740 (3)	0.70487 (13)	0.0415 (5)
O2	0.0059 (3)	1.0219 (3)	0.81083 (12)	0.0378 (5)
C1	0.2959 (4)	0.8237 (4)	−0.02975 (17)	0.0355 (6)
H1A	0.2393	0.8336	0.0314	0.053*
H1B	0.2225	0.7376	−0.0525	0.053*
H1C	0.2966	0.9424	−0.0671	0.053*
C2	0.5938 (4)	0.7377 (4)	−0.11652 (17)	0.0401 (7)
H2B	0.7195	0.6944	−0.1084	0.060*
H2C	0.6045	0.8538	−0.1565	0.060*
H2D	0.5300	0.6492	−0.1423	0.060*
C3	0.5608 (3)	0.7204 (3)	0.04448 (15)	0.0251 (5)
C4	0.7426 (3)	0.6498 (3)	0.04504 (16)	0.0273 (5)
H4B	0.8171	0.6306	−0.0093	0.033*
C5	0.8138 (3)	0.6084 (3)	0.12271 (16)	0.0278 (5)
H5A	0.9364	0.5596	0.1210	0.033*
C6	0.7116 (3)	0.6356 (3)	0.20397 (15)	0.0228 (5)
C7	0.5314 (3)	0.7071 (3)	0.20373 (15)	0.0237 (5)
H7A	0.4585	0.7275	0.2582	0.028*
C8	0.4581 (3)	0.7481 (3)	0.12713 (15)	0.0243 (5)
H8A	0.3352	0.7963	0.1294	0.029*
C9	0.7918 (3)	0.5959 (3)	0.28440 (15)	0.0233 (5)
H9A	0.9078	0.5342	0.2838	0.028*
C10	0.6983 (3)	0.6372 (3)	0.50896 (15)	0.0192 (5)
C11	0.4078 (3)	0.8006 (3)	0.56342 (14)	0.0197 (5)
C12	0.4456 (3)	0.8416 (3)	0.64352 (15)	0.0238 (5)
H12A	0.5665	0.8206	0.6596	0.029*
C13	0.3054 (3)	0.9129 (3)	0.69930 (15)	0.0252 (5)
H13A	0.3288	0.9405	0.7545	0.030*
C14	0.1318 (3)	0.9440 (3)	0.67481 (15)	0.0222 (5)
C15	0.0938 (3)	0.9098 (3)	0.59467 (16)	0.0236 (5)
H15A	−0.0260	0.9357	0.5780	0.028*
C16	0.2329 (3)	0.8375 (3)	0.53922 (15)	0.0216 (5)
H16A	0.2089	0.8124	0.4837	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0182 (3)	0.0299 (3)	0.0216 (3)	0.0057 (2)	−0.0042 (2)	−0.0022 (2)
N1	0.0336 (12)	0.0515 (14)	0.0196 (11)	0.0033 (10)	−0.0035 (9)	−0.0031 (9)
N2	0.0188 (9)	0.0208 (9)	0.0218 (10)	−0.0003 (7)	−0.0039 (8)	−0.0031 (7)
N3	0.0162 (9)	0.0227 (10)	0.0242 (10)	0.0040 (7)	−0.0039 (8)	−0.0033 (8)
N4	0.0189 (9)	0.0231 (10)	0.0193 (9)	0.0043 (7)	−0.0048 (7)	−0.0046 (7)
N5	0.0262 (11)	0.0239 (10)	0.0319 (12)	0.0013 (8)	0.0039 (9)	−0.0062 (8)
O1	0.0287 (10)	0.0537 (12)	0.0416 (11)	0.0196 (9)	−0.0015 (8)	−0.0116 (9)
O2	0.0366 (10)	0.0493 (12)	0.0273 (10)	0.0017 (8)	0.0041 (8)	−0.0155 (8)
C1	0.0358 (14)	0.0415 (15)	0.0291 (13)	−0.0014 (12)	−0.0097 (11)	−0.0005 (11)
C2	0.0460 (16)	0.0522 (17)	0.0212 (13)	0.0016 (13)	−0.0041 (11)	−0.0048 (11)
C3	0.0276 (12)	0.0231 (12)	0.0235 (12)	−0.0036 (9)	−0.0030 (10)	−0.0014 (9)
C4	0.0289 (13)	0.0299 (12)	0.0224 (12)	0.0007 (10)	0.0012 (10)	−0.0078 (10)
C5	0.0233 (12)	0.0317 (13)	0.0286 (13)	0.0051 (10)	−0.0004 (10)	−0.0094 (10)
C6	0.0227 (11)	0.0213 (11)	0.0244 (12)	0.0007 (9)	−0.0024 (9)	−0.0054 (9)
C7	0.0226 (12)	0.0251 (12)	0.0228 (12)	0.0011 (9)	0.0009 (9)	−0.0068 (9)
C8	0.0227 (12)	0.0232 (11)	0.0267 (12)	0.0006 (9)	−0.0028 (9)	−0.0039 (9)
C9	0.0208 (11)	0.0227 (11)	0.0259 (12)	0.0033 (9)	−0.0013 (9)	−0.0056 (9)
C10	0.0158 (10)	0.0168 (10)	0.0244 (11)	−0.0020 (8)	−0.0015 (9)	−0.0037 (8)
C11	0.0202 (11)	0.0157 (10)	0.0221 (11)	0.0012 (8)	−0.0013 (9)	−0.0015 (8)
C12	0.0214 (11)	0.0255 (12)	0.0257 (12)	0.0037 (9)	−0.0065 (9)	−0.0055 (9)
C13	0.0290 (12)	0.0257 (12)	0.0215 (12)	0.0021 (10)	−0.0032 (9)	−0.0063 (9)
C14	0.0220 (11)	0.0172 (11)	0.0251 (12)	0.0020 (9)	0.0021 (9)	−0.0026 (9)
C15	0.0205 (11)	0.0204 (11)	0.0296 (12)	0.0023 (9)	−0.0053 (9)	−0.0020 (9)
C16	0.0208 (11)	0.0223 (11)	0.0227 (11)	0.0022 (9)	−0.0050 (9)	−0.0048 (9)

Geometric parameters (Å, º)

S1—C10	1.672 (2)	C3—C8	1.412 (3)
N1—C3	1.356 (3)	C4—C5	1.371 (3)
N1—C1	1.443 (3)	C4—H4B	0.9500
N1—C2	1.450 (3)	C5—C6	1.392 (3)
N2—C9	1.278 (3)	C5—H5A	0.9500
N2—N3	1.369 (3)	C6—C7	1.399 (3)
N3—C10	1.344 (3)	C6—C9	1.443 (3)
N3—H3A	0.8800	C7—C8	1.364 (3)
N4—C10	1.351 (3)	C7—H7A	0.9500
N4—C11	1.393 (3)	C8—H8A	0.9500
N4—H4A	0.8800	C9—H9A	0.9500
N5—O1	1.217 (3)	C11—C16	1.386 (3)
N5—O2	1.227 (3)	C11—C12	1.390 (3)
N5—C14	1.461 (3)	C12—C13	1.378 (3)
C1—H1A	0.9800	C12—H12A	0.9500
C1—H1B	0.9800	C13—C14	1.373 (3)
C1—H1C	0.9800	C13—H13A	0.9500
C2—H2B	0.9800	C14—C15	1.373 (3)
C2—H2C	0.9800	C15—C16	1.374 (3)
C2—H2D	0.9800	C15—H15A	0.9500
C3—C4	1.408 (3)	C16—H16A	0.9500
C3—N1—C1	121.3 (2)	C5—C6—C7	117.4 (2)
C3—N1—C2	121.0 (2)	C5—C6—C9	120.8 (2)
C1—N1—C2	117.6 (2)	C7—C6—C9	121.8 (2)
C9—N2—N3	117.8 (2)	C8—C7—C6	121.5 (2)
C10—N3—N2	119.0 (2)	C8—C7—H7A	119.2
C10—N3—H3A	120.5	C6—C7—H7A	119.2
N2—N3—H3A	120.5	C7—C8—C3	121.5 (2)
C10—N4—C11	131.9 (2)	C7—C8—H8A	119.3
C10—N4—H4A	114.1	C3—C8—H8A	119.3
C11—N4—H4A	114.1	N2—C9—C6	120.4 (2)
O1—N5—O2	123.6 (2)	N2—C9—H9A	119.8
O1—N5—C14	118.2 (2)	C6—C9—H9A	119.8
O2—N5—C14	118.2 (2)	N3—C10—N4	113.2 (3)
N1—C1—H1A	109.5	N3—C10—S1	120.3 (2)
N1—C1—H1B	109.5	N4—C10—S1	126.4 (2)
H1A—C1—H1B	109.5	C16—C11—C12	119.9 (2)
N1—C1—H1C	109.5	C16—C11—N4	115.66 (19)
H1A—C1—H1C	109.5	C12—C11—N4	124.3 (2)
H1B—C1—H1C	109.5	C13—C12—C11	119.2 (2)
N1—C2—H2B	109.5	C13—C12—H12A	120.4
N1—C2—H2C	109.5	C11—C12—H12A	120.4
H2B—C2—H2C	109.5	C14—C13—C12	119.8 (2)
N1—C2—H2D	109.5	C14—C13—H13A	120.1
H2B—C2—H2D	109.5	C12—C13—H13A	120.1
H2C—C2—H2D	109.5	C13—C14—C15	121.8 (2)
N1—C3—C4	122.2 (2)	C13—C14—N5	119.8 (2)
N1—C3—C8	121.0 (2)	C15—C14—N5	118.4 (2)
C4—C3—C8	116.8 (2)	C14—C15—C16	118.5 (2)
C5—C4—C3	121.0 (2)	C14—C15—H15A	120.8
C5—C4—H4B	119.5	C16—C15—H15A	120.8
C3—C4—H4B	119.5	C15—C16—C11	120.8 (2)
C4—C5—C6	121.9 (2)	C15—C16—H16A	119.6
C4—C5—H5A	119.1	C11—C16—H16A	119.6
C6—C5—H5A	119.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1^i	0.88	2.44	3.315 (2)	170
N4—H4A···N2	0.88	2.07	2.543 (3)	113

Symmetry code: (i) −x+2, −y+1, −z+1.