4-Methyl-N-phenyl­piperazine-1-carbothio­amide

The title compound, C₁₂H₁₆N₃S, was prepared by the reaction of phenyl isothio­cyanate with N-methyl­piperazine. The crystal structure is stabilized by inter­molecular N—H...S hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.113
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.225
            Value of mu given      =     0.228
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.51 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1     ..  H2A     ..       1.98 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 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
   0 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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S1. Comment

Thiourea derivatives have been used extensively as organical intermediate in the field of high polymer chemistry (Ballabeni et al., 1999). As part of our search for new compounds we synthesized the title compound (I), and describe its structure here.

Bond lengths and angles in (I) are normal. The C1—S1 distance of 1.688 (2) Å is longer than the distance of 1.700 Å reported by Ramnathan et al. (1996). The C1—N2 distance [1.339 (2) Å] is longer than the reported distance [1.339 Å] (Guzmán et al., 1991). The crystal structure of (I) is stabilized by intermolecular N—H···S hydrogen bonding interactions.

Related literature

For related literature, see: Ballabeni et al. (1999); Guzmán et al. (1991); Ramnathan et al. (1996).

S2. Experimental

A mixture of the phenyl isothiocyanate (0.1 mol), and N-methypiperazine (0.1 mol) was stirred in refluxing ethanol (30 ml) for 5 h to afford the title compound (0.085 mol, yield 85%). Single crystals suitable of (I) for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

The H atom bonded to the N atom was found from a difference Fourier map and refined freely. The other H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H = 0.93 - 0.97 Å, and U_iso(H) = 1.2–1.5U_eq(C).

Computing details

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

Figures

Fig. 1. The molecular structure of the title compound (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.

4-Methyl-N-phenylpiperazine-1-carbothioamide

Crystal data

C12H17N3S	F(000) = 1008
Mr = 235.35	Dx = 1.189 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2706 reflections
a = 12.615 (3) Å	θ = 2.5–22.9°
b = 9.564 (3) Å	µ = 0.23 mm^−1
c = 21.792 (6) Å	T = 294 K
V = 2629.4 (12) Å^3	Block, colourless
Z = 8	0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2683 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
φ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −15→15
Tmin = 0.944, Tmax = 0.956	k = −11→11
14113 measured reflections	l = −12→27

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.208P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.002
2683 reflections	Δρmax = 0.19 e Å^−3
150 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0063 (8)

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	0.36106 (5)	0.99131 (5)	0.40936 (3)	0.0514 (2)
N1	0.28317 (14)	0.76356 (17)	0.35338 (9)	0.0524 (5)
H1	0.2645 (18)	0.680 (3)	0.3598 (11)	0.079*
N3	0.61274 (14)	0.5946 (2)	0.44451 (8)	0.0578 (5)
C1	0.35271 (15)	0.81840 (19)	0.39467 (9)	0.0398 (5)
N2	0.41289 (14)	0.72436 (17)	0.42397 (8)	0.0513 (5)
C2	0.43330 (17)	0.5809 (2)	0.40281 (12)	0.0640 (7)
H2A	0.3932	0.5626	0.3657	0.077*
H2B	0.4110	0.5147	0.4339	0.077*
C3	0.55023 (19)	0.5640 (3)	0.39033 (11)	0.0649 (7)
H3A	0.5642	0.4689	0.3772	0.078*
H3B	0.5710	0.6264	0.3574	0.078*
C5	0.59229 (19)	0.7363 (2)	0.46428 (11)	0.0610 (7)
H5A	0.6144	0.8008	0.4324	0.073*
H5B	0.6336	0.7561	0.5008	0.073*
C6	0.47721 (17)	0.7581 (2)	0.47785 (10)	0.0563 (6)
H6A	0.4562	0.6991	0.5120	0.068*
H6B	0.4653	0.8547	0.4895	0.068*
C7	0.7257 (2)	0.5730 (4)	0.43281 (13)	0.1001 (10)
H7A	0.7372	0.4786	0.4194	0.150*
H7B	0.7650	0.5895	0.4698	0.150*
H7C	0.7490	0.6367	0.4016	0.150*
C8	0.22016 (16)	0.8339 (2)	0.30953 (10)	0.0432 (5)
C9	0.25884 (19)	0.9421 (2)	0.27394 (10)	0.0520 (6)
H9	0.3279	0.9738	0.2793	0.062*
C10	0.1938 (2)	1.0030 (3)	0.23032 (11)	0.0689 (7)
H10	0.2191	1.0776	0.2072	0.083*
C11	0.0929 (3)	0.9551 (3)	0.22057 (12)	0.0768 (8)
H11	0.0503	0.9964	0.1909	0.092*
C12	0.0551 (2)	0.8459 (3)	0.25482 (12)	0.0694 (7)
H12	−0.0128	0.8117	0.2479	0.083*
C13	0.11814 (17)	0.7868 (2)	0.29968 (11)	0.0549 (6)
H13	0.0915	0.7143	0.3236	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0658 (4)	0.0334 (3)	0.0552 (4)	0.0038 (2)	−0.0001 (3)	−0.0056 (3)
N1	0.0498 (11)	0.0314 (9)	0.0759 (14)	−0.0014 (8)	−0.0252 (10)	0.0078 (10)
N3	0.0471 (12)	0.0745 (14)	0.0518 (12)	0.0137 (9)	−0.0161 (9)	−0.0033 (10)
C1	0.0358 (11)	0.0343 (10)	0.0492 (13)	0.0015 (9)	−0.0011 (10)	0.0026 (9)
N2	0.0522 (11)	0.0359 (9)	0.0659 (13)	0.0059 (8)	−0.0233 (10)	−0.0039 (9)
C2	0.0610 (16)	0.0316 (12)	0.099 (2)	0.0065 (10)	−0.0346 (14)	−0.0050 (12)
C3	0.0723 (17)	0.0549 (14)	0.0675 (17)	0.0161 (13)	−0.0263 (14)	−0.0118 (13)
C5	0.0598 (16)	0.0717 (16)	0.0514 (15)	−0.0095 (12)	−0.0195 (12)	−0.0046 (13)
C6	0.0581 (16)	0.0569 (14)	0.0539 (14)	0.0070 (11)	−0.0159 (12)	−0.0036 (11)
C7	0.0569 (19)	0.165 (3)	0.078 (2)	0.0280 (19)	−0.0138 (15)	−0.020 (2)
C8	0.0415 (13)	0.0350 (11)	0.0531 (13)	0.0123 (9)	−0.0082 (10)	−0.0058 (10)
C9	0.0538 (14)	0.0532 (13)	0.0491 (14)	0.0089 (11)	0.0043 (12)	−0.0009 (12)
C10	0.089 (2)	0.0688 (16)	0.0495 (15)	0.0142 (15)	0.0017 (14)	0.0138 (13)
C11	0.086 (2)	0.0806 (19)	0.0639 (18)	0.0311 (17)	−0.0278 (16)	0.0033 (15)
C12	0.0587 (16)	0.0634 (16)	0.0861 (19)	0.0130 (13)	−0.0292 (15)	−0.0067 (16)
C13	0.0508 (15)	0.0406 (12)	0.0733 (17)	0.0069 (10)	−0.0160 (12)	−0.0010 (11)

Geometric parameters (Å, º)

S1—C1	1.6878 (19)	C5—H5B	0.9700
N1—C1	1.362 (2)	C6—H6A	0.9700
N1—C8	1.414 (3)	C6—H6B	0.9700
N1—H1	0.84 (3)	C7—H7A	0.9600
N3—C5	1.446 (3)	C7—H7B	0.9600
N3—C3	1.450 (3)	C7—H7C	0.9600
N3—C7	1.462 (3)	C8—C13	1.380 (3)
C1—N2	1.339 (2)	C8—C9	1.382 (3)
N2—C6	1.463 (3)	C9—C10	1.384 (3)
N2—C2	1.470 (3)	C9—H9	0.9300
C2—C3	1.509 (3)	C10—C11	1.369 (4)
C2—H2A	0.9700	C10—H10	0.9300
C2—H2B	0.9700	C11—C12	1.369 (4)
C3—H3A	0.9700	C11—H11	0.9300
C3—H3B	0.9700	C12—C13	1.381 (3)
C5—C6	1.496 (3)	C12—H12	0.9300
C5—H5A	0.9700	C13—H13	0.9300
C1—N1—C8	128.72 (17)	N2—C6—C5	110.41 (19)
C1—N1—H1	115.7 (17)	N2—C6—H6A	109.6
C8—N1—H1	113.9 (17)	C5—C6—H6A	109.6
C5—N3—C3	109.57 (18)	N2—C6—H6B	109.6
C5—N3—C7	111.0 (2)	C5—C6—H6B	109.6
C3—N3—C7	111.1 (2)	H6A—C6—H6B	108.1
N2—C1—N1	114.94 (17)	N3—C7—H7A	109.5
N2—C1—S1	122.16 (15)	N3—C7—H7B	109.5
N1—C1—S1	122.89 (14)	H7A—C7—H7B	109.5
C1—N2—C6	123.29 (17)	N3—C7—H7C	109.5
C1—N2—C2	125.20 (18)	H7A—C7—H7C	109.5
C6—N2—C2	111.13 (16)	H7B—C7—H7C	109.5
N2—C2—C3	109.16 (18)	C13—C8—C9	119.1 (2)
N2—C2—H2A	109.8	C13—C8—N1	118.29 (19)
C3—C2—H2A	109.8	C9—C8—N1	122.50 (19)
N2—C2—H2B	109.8	C8—C9—C10	119.4 (2)
C3—C2—H2B	109.8	C8—C9—H9	120.3
H2A—C2—H2B	108.3	C10—C9—H9	120.3
N3—C3—C2	111.3 (2)	C11—C10—C9	121.1 (3)
N3—C3—H3A	109.4	C11—C10—H10	119.4
C2—C3—H3A	109.4	C9—C10—H10	119.4
N3—C3—H3B	109.4	C12—C11—C10	119.6 (2)
C2—C3—H3B	109.4	C12—C11—H11	120.2
H3A—C3—H3B	108.0	C10—C11—H11	120.2
N3—C5—C6	111.28 (19)	C11—C12—C13	119.8 (2)
N3—C5—H5A	109.4	C11—C12—H12	120.1
C6—C5—H5A	109.4	C13—C12—H12	120.1
N3—C5—H5B	109.4	C8—C13—C12	120.9 (2)
C6—C5—H5B	109.4	C8—C13—H13	119.6
H5A—C5—H5B	108.0	C12—C13—H13	119.6
C8—N1—C1—N2	−170.3 (2)	C1—N2—C6—C5	−117.2 (2)
C8—N1—C1—S1	11.1 (3)	C2—N2—C6—C5	56.1 (2)
N1—C1—N2—C6	−167.85 (19)	N3—C5—C6—N2	−57.2 (2)
S1—C1—N2—C6	10.8 (3)	C1—N1—C8—C13	−140.8 (2)
N1—C1—N2—C2	19.8 (3)	C1—N1—C8—C9	43.0 (3)
S1—C1—N2—C2	−161.54 (17)	C13—C8—C9—C10	1.5 (3)
C1—N2—C2—C3	117.1 (2)	N1—C8—C9—C10	177.64 (19)
C6—N2—C2—C3	−56.1 (3)	C8—C9—C10—C11	−1.9 (3)
C5—N3—C3—C2	−59.1 (3)	C9—C10—C11—C12	0.5 (4)
C7—N3—C3—C2	177.9 (2)	C10—C11—C12—C13	1.3 (4)
N2—C2—C3—N3	57.9 (3)	C9—C8—C13—C12	0.3 (3)
C3—N3—C5—C6	58.4 (3)	N1—C8—C13—C12	−176.03 (19)
C7—N3—C5—C6	−178.6 (2)	C11—C12—C13—C8	−1.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.84 (3)	2.64 (3)	3.403 (2)	152 (2)

Symmetry code: (i) −x+1/2, y−1/2, z.