1-[4-(Dimethyl­amino)benzyl­idene]-4-methyl­thio­semicarbazide

In the title compound, C₁₁H₁₆N₄S, an intra­molecular N—H...N hydrogen bond generates an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H...S bonds occur, generating an R₂²(8) loop.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.055
• wR factor = 0.178
• Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H1A    ..  H8A     ..       1.79 Ang.

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C10     ..       5.10 su
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H2B    ..  H4B     ..       1.81 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT152_ALERT_1_C The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C11 H16 N4 S
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          4

Alert level G
PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large.       0.12
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C2
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C11

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

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


checkCIF publication errors

Alert level G
PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

   0 ALERT level A = Data missing that is essential or data in wrong format
   1 ALERT level G = General alerts. Data that may be required is missing

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Related literature

For a related structure, see: Girgis (2006).

S1. Experimental

A mixture of 4-(dimethylamino)benzaldehyde (0.10 mol), and 4-methylthiosemicarbazide (0.10 mol) was stirred in refluxing ethanol (10 ml) for 4 h to afford the title compound (0.083 mol, yield 83%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

S2. Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93-0.97 Å; N—H = 0.86Å and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Structure description

For a related structure, see: Girgis (2006).

Computing details

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT (Bruker 1997); 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

Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids.

1-(4-(Dimethylamino)benzylidene)-4-methylthiosemicarbazide

Crystal data

C11H16N4S	F(000) = 504
Mr = 236.34	Dx = 1.259 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2391 reflections
a = 10.517 (2) Å	θ = 3.2–27.5°
b = 12.873 (3) Å	µ = 0.24 mm^−1
c = 10.552 (2) Å	T = 293 K
β = 119.19 (3)°	Block, colorless
V = 1247.3 (4) Å^3	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2391 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 3.2°
phi and ω scans	h = −13→11
11842 measured reflections	k = −15→16
2847 independent reflections	l = −13→13

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) = 0.178	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1186P)^2 + 0.111P] where P = (Fo^2 + 2Fc^2)/3
2847 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.60342 (4)	0.15360 (4)	0.05021 (6)	0.0595 (2)
N2	0.17952 (14)	0.12707 (11)	−0.13146 (16)	0.0468 (3)
N3	0.32723 (14)	0.10421 (10)	−0.05970 (16)	0.0491 (4)
H3A	0.3569	0.0426	−0.0272	0.059*
C6	−0.06129 (17)	0.06639 (12)	−0.20701 (17)	0.0435 (4)
N4	0.36809 (16)	0.27166 (11)	−0.09695 (18)	0.0537 (4)
H4A	0.2749	0.2772	−0.1463	0.064*
C3	−0.36590 (17)	0.09210 (14)	−0.32393 (17)	0.0481 (4)
C7	−0.13111 (19)	0.15789 (12)	−0.2769 (2)	0.0495 (4)
H7A	−0.0763	0.2116	−0.2848	0.059*
C10	0.42361 (17)	0.17963 (13)	−0.04141 (17)	0.0433 (4)
C9	0.09536 (17)	0.05248 (12)	−0.13907 (18)	0.0448 (4)
H9A	0.1355	−0.0119	−0.1002	0.054*
C5	−0.14729 (19)	−0.01233 (13)	−0.1990 (2)	0.0501 (4)
H5A	−0.1036	−0.0746	−0.1543	0.060*
C8	−0.27852 (19)	0.17078 (14)	−0.3344 (2)	0.0537 (4)
H8A	−0.3215	0.2327	−0.3812	0.064*
C4	−0.29596 (19)	−0.00089 (14)	−0.2553 (2)	0.0529 (4)
H4B	−0.3502	−0.0552	−0.2478	0.063*
N1	−0.51338 (16)	0.10490 (14)	−0.38125 (18)	0.0634 (4)
C2	−0.5998 (2)	0.0282 (2)	−0.3574 (3)	0.0758 (6)
H2B	−0.5423	−0.0329	−0.3152	0.114*
H2C	−0.6834	0.0107	−0.4484	0.114*
H2D	−0.6313	0.0560	−0.2929	0.114*
C11	0.4544 (2)	0.36333 (16)	−0.0797 (3)	0.0730 (6)
H12A	0.3912	0.4207	−0.1293	0.109*
H12B	0.5174	0.3507	−0.1201	0.109*
H12C	0.5120	0.3795	0.0216	0.109*
C1	−0.5822 (2)	0.2016 (2)	−0.4442 (3)	0.0929 (8)
H1A	−0.5142	0.2460	−0.4541	0.139*
H1B	−0.6138	0.2345	−0.3828	0.139*
H1C	−0.6647	0.1893	−0.5381	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0340 (3)	0.0526 (3)	0.0744 (4)	−0.00233 (15)	0.0127 (2)	−0.00072 (19)
N2	0.0336 (7)	0.0484 (7)	0.0547 (8)	0.0008 (5)	0.0187 (6)	0.0001 (6)
N3	0.0335 (6)	0.0439 (7)	0.0637 (8)	0.0010 (5)	0.0188 (6)	0.0032 (6)
C6	0.0375 (8)	0.0465 (8)	0.0464 (8)	−0.0018 (6)	0.0205 (6)	−0.0026 (6)
N4	0.0395 (7)	0.0477 (8)	0.0626 (9)	−0.0017 (5)	0.0160 (6)	0.0071 (6)
C3	0.0382 (8)	0.0593 (10)	0.0458 (8)	−0.0015 (6)	0.0197 (6)	−0.0050 (7)
C7	0.0438 (9)	0.0455 (9)	0.0594 (10)	−0.0032 (6)	0.0253 (8)	0.0021 (7)
C10	0.0382 (7)	0.0455 (8)	0.0436 (8)	−0.0027 (6)	0.0180 (6)	−0.0032 (6)
C9	0.0391 (8)	0.0437 (8)	0.0504 (8)	−0.0006 (6)	0.0210 (6)	−0.0012 (6)
C5	0.0446 (9)	0.0455 (8)	0.0572 (10)	−0.0021 (6)	0.0226 (8)	0.0055 (7)
C8	0.0447 (9)	0.0481 (9)	0.0653 (11)	0.0052 (7)	0.0245 (8)	0.0049 (7)
C4	0.0433 (9)	0.0567 (9)	0.0582 (10)	−0.0095 (7)	0.0245 (8)	0.0025 (7)
N1	0.0370 (8)	0.0805 (11)	0.0677 (10)	−0.0010 (7)	0.0218 (7)	0.0000 (8)
C2	0.0468 (10)	0.1131 (18)	0.0689 (12)	−0.0167 (11)	0.0293 (9)	−0.0044 (12)
C11	0.0597 (12)	0.0529 (10)	0.0951 (16)	−0.0073 (9)	0.0289 (11)	0.0121 (10)
C1	0.0477 (11)	0.0861 (17)	0.128 (2)	0.0166 (11)	0.0301 (13)	−0.0016 (16)

Geometric parameters (Å, º)

S1—C10	1.6852 (17)	C9—H9A	0.9300
N2—C9	1.282 (2)	C5—C4	1.383 (3)
N2—N3	1.3877 (19)	C5—H5A	0.9300
N3—C10	1.348 (2)	C8—H8A	0.9300
N3—H3A	0.8600	C4—H4B	0.9300
C6—C5	1.388 (2)	N1—C1	1.431 (3)
C6—C7	1.394 (2)	N1—C2	1.444 (3)
C6—C9	1.452 (2)	C2—H2B	0.9600
N4—C10	1.325 (2)	C2—H2C	0.9600
N4—C11	1.445 (2)	C2—H2D	0.9600
N4—H4A	0.8600	C11—H12A	0.9600
C3—N1	1.372 (2)	C11—H12B	0.9600
C3—C4	1.407 (2)	C11—H12C	0.9600
C3—C8	1.408 (2)	C1—H1A	0.9600
C7—C8	1.372 (2)	C1—H1B	0.9600
C7—H7A	0.9300	C1—H1C	0.9600
C9—N2—N3	115.50 (14)	C7—C8—H8A	119.4
C10—N3—N2	119.27 (14)	C3—C8—H8A	119.4
C10—N3—H3A	120.4	C5—C4—C3	120.64 (15)
N2—N3—H3A	120.4	C5—C4—H4B	119.7
C5—C6—C7	117.29 (14)	C3—C4—H4B	119.7
C5—C6—C9	119.74 (14)	C3—N1—C1	121.07 (17)
C7—C6—C9	122.92 (14)	C3—N1—C2	120.89 (18)
C10—N4—C11	124.08 (16)	C1—N1—C2	117.18 (18)
C10—N4—H4A	118.0	N1—C2—H2B	109.5
C11—N4—H4A	118.0	N1—C2—H2C	109.5
N1—C3—C4	121.59 (16)	H2B—C2—H2C	109.5
N1—C3—C8	121.31 (16)	N1—C2—H2D	109.5
C4—C3—C8	117.07 (14)	H2B—C2—H2D	109.5
C8—C7—C6	121.76 (15)	H2C—C2—H2D	109.5
C8—C7—H7A	119.1	N4—C11—H12A	109.5
C6—C7—H7A	119.1	N4—C11—H12B	109.5
N4—C10—N3	116.27 (14)	H12A—C11—H12B	109.5
N4—C10—S1	124.11 (13)	N4—C11—H12C	109.5
N3—C10—S1	119.61 (13)	H12A—C11—H12C	109.5
N2—C9—C6	121.42 (15)	H12B—C11—H12C	109.5
N2—C9—H9A	119.3	N1—C1—H1A	109.5
C6—C9—H9A	119.3	N1—C1—H1B	109.5
C4—C5—C6	121.98 (15)	H1A—C1—H1B	109.5
C4—C5—H5A	119.0	N1—C1—H1C	109.5
C6—C5—H5A	119.0	H1A—C1—H1C	109.5
C7—C8—C3	121.23 (16)	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2	0.86	2.22	2.613 (2)	108
N3—H3A···S1^i	0.86	2.59	3.3890 (16)	155

Symmetry code: (i) −x+1, −y, −z.