Crystal structure of 4-meth-oxy-N-(piperidine-1-carbono-thio-yl)benzamide.

In the title compound, C14H18N2O2S, the piperidine ring has a chair conformation. Its mean plane is twisted with respect to the 4-meth-oxy-benzoyl ring, with a dihedral angle of 63.0 (3)°. The central N-C(=S)-N(H)-C(=O) bridge is twisted with an N-C-N-C torsion angle of 74.8 (6)°. In the crystal, mol-ecules are linked by N-H⋯O and C-H⋯O hydrogen bonds, forming chains along the c-axis direction. Adjacent chains are linked by C-H⋯π inter-actions, forming layers parallel to the ac plane. The layers are linked by offset π-π inter-actions [inter-centroid distance = 3.927 (3) Å], forming a supra-molecular three-dimensional structure.

Chemical context

Benzoyl­thio­urea compounds exhibit anti-inflammatory (Brachmachari & Das, 2012 ▸), anti-cancer, anti-diabetic and anti-virus activity (Kovačková et al., 2011 ▸), and have applications as ionic sensors (Suhud et al. 2015b ▸) and pharmaceutical drugs (Watson et al., 2000 ▸). Benzoyl­thio­urea mol­ecules containing thio­amide (NH—C=S) and carbonyl (C=O) electron-rich donating groups facilitate the formation of coordination bonds with metal ions such as Co3+ (Tan et al., 2014 ▸), Ru2+ (Małecki & Nycz, 2013 ▸), Ag+ (Isab et al., 2010 ▸) and Ni2+ (Arslan et al., 2006 ▸). Bivalent and trivalent metal ions prefer to coordinate via the S and O atoms from the thiono and carbonyl units, respectively, but monovalent metal ions tend to coordinate via the S atom.

Herein, we report on the crystal structure of 4-meth­oxy-N-(piperidine-1-carbono­thio­yl)benzamide (MPiCB) and its chemical structural data in comparison with the previously reported compound 4-meth­oxy-N-[(pyrrolidin-1-yl)carbono­thio­yl]benzamide (MPCB; Suhud et al., 2015a ▸,b ▸).

Structural commentary

The mol­ecular structure of the title compound, MPiCB, is illustrated in Fig. 1 ▸. The geometrical parameters are similar to those observed for 4-meth­oxy-N-[(pyrrolidin-1-yl)carbo­thio­yl]benzamide (MPCB; Suhud et al. 2015a ▸). The 4-meth­oxy­benzoyl and piperidine fragments adopt a trans–cis conformation with respect to the thiono S atom across the C8—N1 bond, with the piperidine ring having a chair conformation. The mean plane of the piperidine ring is twisted with respect to the 4-meth­oxy benzoyl ring with a dihedral angle of 63.0 (3)°. The central N—C(=S)—N(H)—C(=O) bridge is twisted with an N2—C8—N1—C7 torsion angle of 74.8 (6)°. The meth­oxy group lies in the plane of the benzene ring, with the C14—O2—C4—C3 torsion angle being 180.0 (4)°.

Figure 1

A view of the mol­ecular structure of the title compound (MPiCB), with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal of MPiCB, neighbouring mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming chains along the c-axis direction (Table 1 ▸ and Fig. 2 ▸). Adjacent chains are linked by C—H⋯π inter­actions, involving a piperidine H atom and the π electrons of the benzene ring, forming layers parallel to the ac plane (Table 1 ▸ and Fig. 3 ▸). The layers are linked by offset π–π stacking inter­actions involving the benzene rings, forming a supra­molecular three-dimensional structure as illustrated in Fig. 3 ▸ [Cg⋯Cg i = 3.927 (3) Å; Cg is the centroid of the C1–C6 ring; inter­planar distance = 3.517 (2) Å; slippage = 1.747 Å; symmetry code: (i) −x, −y + 2, −z + 2].

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.84 (4)	2.12 (4)	2.897 (4)	154 (4)
C6—H6⋯O1i	0.93	2.40	3.294 (5)	160
C10—H10A⋯Cg ii	0.97	2.89	3.851 (8)	170

Symmetry codes: (i) ; (ii) .

Figure 2

A view along the a axis of the crystal packing of the title compound (MPiCB). Hydrogen bonds (see Table 1 ▸) are shown as dashed lines.

Figure 3

A view normal to the ac plane of the crystal packing of the title compound (MPiCB), showing the offset π–π stacking inter­actions that add further stabilization to the crystal structure, and the hydrogen bonds (dashed lines).

Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ▸) for the 4-meth­oxy-N-(carbono­thio­yl)benzamide skeleton gave 37 hits. Two compounds are of particular inter­est, namely 4-meth­oxy-N-(pyrrolidin-1-ylcarbono­thio­yl)benzamide (DUDYOS; Suhud et al., 2015a ▸) mentioned previously (MPCB), and N-(2,6-di­meth­yl­piperidine-1-carbono­thio­yl)-3,4,5-tri­meth­oxy­benz­amide (HESLEX; Dillen et al., 2006 ▸). The 4-meth­oxy­benzoyl ring and the mean plane of the piperidine ring in MPiCB form a smaller angle [63.13 (3)°] compared with the angle of 72.60 (14)° for similar mean planes found in DUDYOS (Suhud et al. 2015a ▸). The bond lengths for C8=S1 [1.651 (4) Å] and C7=O1 [1.226 (4) Å] in MPiCB are comparable to those observed for DUDYOS [C=S = 1.662 (2) Å and C=O = 1.220 (2) Å]. Other bond lengths and angles in the MPiCB mol­ecule are comparable with those reported for DUDYOS and N-(pyrrolidin-1-ylcarbo­thio­yl)benzamide (SAGYOQ; Al-abbasi et al., 2012 ▸). Compound HESLEX also involves a piperidine ring with a chair conformation linked by the C(=S)—N(H)—C(=O) bridge to a 3,4,5-tri­meth­oxy­benzene ring. It crystallizes with two independent mol­ecules in the asymmetric unit with slightly different conformations. For example, the mean plane of the piperidine rings are inclined to the benzene rings by 58.97 (11) and 64.11 (11)°, compared to 63.13 (3)° in the title compound. The central N—C(=S)—N(H)—C(=O) bridge is twisted in each compound, with an N2—C8—N1—C7 torsion angle of 74.8 (6)° in MPiCB, 63.0 (3)° in DUDYOS, 65.5 (3) and 79.9 (3)° in HESLEX, and finally −59.7 (2)° in SAGYOQ.

Synthesis and crystallization

Benzoyl chloride (0.01 mol) was added slowly to ammonium thio­cyanate (0.01 mol) in acetone and the mixture was stirred for 30 min at room temperature. A white precipitate of ammonium chloride was filtered off and the filtrate was cooled in an ice bath (278–283 K) for about 15 min. A cold solution (278–283 K) of piperidine (0.01 mol) in acetone was added to the benzoyl iso­thio­cyanate and the mixture was left for 3 h at room temperature. A yellowish precipitate was formed, filtered and washed with cold water to give pale-yellow crystals (yield 87%, m.p. 401-402 K).

The infrared spectrum of MPiCB shows the characteristic signals for ν(NH) 3300, ν(O—CH3) 2900, ν(C=O) 1609, ν(C—Cbenzene) 1460, ν(C—Ostretching) 1327 and v(C=S) 1252 cm−1. The 1H NMR spectrum exhibits the H(N) group at 8.35 Hz, while the 13C NMR signal of the C=S and C=O groups appear at 174.66 and 163.19 Hz, respectively.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The NH H atom was located in a difference-Fourier map and freely refined. The C-bound H atoms were included in calculated positions and refined in a riding-model approximation: C—H = 0.93–0.97 Å with U iso(H) = 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	C14H18N2O2S
M r	278.36
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	8.2228 (9), 18.1289 (19), 9.945 (1)
β (°)	106.612 (3)
V (Å3)	1420.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.23
Crystal size (mm)	0.50 × 0.35 × 0.16
Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2007 ▸)
T min, T max	0.895, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	38784, 2500, 1955
R int	0.049
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.081, 0.251, 1.03
No. of reflections	2500
No. of parameters	178
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.99, −0.52

Computer programs: SMART and SAINT (Bruker, 2007 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL97 (Sheldrick, 2015 ▸), OLEX2 (Dolomanov et al., 2009 ▸), PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017013317/su4162sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013317/su4162Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017013317/su4162Isup3.cml

CCDC reference: 1575129

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H18N2O2S	F(000) = 592
Mr = 278.36	Dx = 1.301 Mg m−3
Monoclinic, P21/c	Melting point = 402–401 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.2228 (9) Å	Cell parameters from 9933 reflections
b = 18.1289 (19) Å	θ = 3.1–25.0°
c = 9.945 (1) Å	µ = 0.23 mm−1
β = 106.612 (3)°	T = 296 K
V = 1420.6 (3) Å3	Block, pale-yellow
Z = 4	0.50 × 0.35 × 0.16 mm

Bruker SMART APEX CCD area-detector diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	1955 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scan	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
Tmin = 0.895, Tmax = 0.965	k = −21→21
38784 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.081	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.251	w = 1/[σ2(Fo2) + (0.1213P)2 + 2.9951P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2500 reflections	Δρmax = 0.99 e Å−3
178 parameters	Δρmin = −0.52 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (4)

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
S1	0.10498 (18)	0.58727 (6)	1.00073 (14)	0.0680 (5)
O1	0.0919 (5)	0.77247 (17)	0.7982 (3)	0.0700 (10)
O2	−0.3058 (4)	1.02962 (17)	0.9922 (3)	0.0636 (9)
N1	0.1299 (4)	0.73279 (18)	1.0176 (3)	0.0460 (8)
N2	0.3615 (6)	0.6709 (2)	0.9800 (6)	0.0807 (15)
C1	−0.0338 (5)	0.8445 (2)	0.9412 (4)	0.0416 (9)
C2	−0.1170 (5)	0.8893 (3)	0.8297 (4)	0.0529 (11)
H2	−0.1117	0.8781	0.7397	0.064*
C3	−0.2068 (6)	0.9496 (3)	0.8504 (4)	0.0587 (11)
H3	−0.2622	0.9788	0.7742	0.070*
C4	−0.2165 (5)	0.9679 (2)	0.9832 (4)	0.0487 (10)
C5	−0.1338 (5)	0.9242 (2)	1.0951 (4)	0.0496 (10)
H5	−0.1389	0.9357	1.1850	0.059*
C6	−0.0434 (5)	0.8633 (2)	1.0739 (4)	0.0482 (10)
H6	0.0123	0.8342	1.1502	0.058*
C7	0.0655 (5)	0.7812 (2)	0.9123 (4)	0.0460 (10)
C8	0.2076 (6)	0.6650 (2)	0.9959 (4)	0.0502 (10)
C9	0.4655 (9)	0.7393 (3)	0.9999 (9)	0.102 (2)
H9A	0.3928	0.7814	0.9997	0.122*
H9B	0.5499	0.7374	1.0907	0.122*
C10	0.5469 (9)	0.7491 (4)	0.8969 (9)	0.105 (2)
H10A	0.6200	0.7920	0.9201	0.126*
H10B	0.4624	0.7588	0.8082	0.126*
C11	0.6528 (7)	0.6829 (4)	0.8795 (8)	0.0910 (18)
H11A	0.6892	0.6889	0.7956	0.109*
H11B	0.7533	0.6796	0.9593	0.109*
C12	0.5502 (10)	0.6128 (4)	0.8685 (10)	0.119 (3)
H12A	0.4694	0.6110	0.7759	0.143*
H12B	0.6262	0.5711	0.8762	0.143*
C13	0.4638 (11)	0.6046 (3)	0.9654 (10)	0.119 (3)
H13A	0.5442	0.5940	1.0557	0.143*
H13B	0.3885	0.5625	0.9396	0.143*
C14	−0.3187 (7)	1.0502 (3)	1.1266 (6)	0.0678 (13)
H14A	−0.3689	1.0106	1.1649	0.102*
H14B	−0.3884	1.0934	1.1179	0.102*
H14C	−0.2076	1.0605	1.1877	0.102*
H1	0.085 (5)	0.732 (2)	1.084 (4)	0.043 (11)*

	U11	U22	U33	U12	U13	U23
S1	0.0856 (10)	0.0478 (7)	0.0731 (9)	−0.0160 (6)	0.0266 (7)	0.0031 (5)
O1	0.124 (3)	0.0583 (19)	0.0390 (16)	−0.0046 (18)	0.0422 (17)	−0.0021 (13)
O2	0.0632 (19)	0.0547 (18)	0.070 (2)	0.0078 (15)	0.0152 (15)	0.0078 (15)
N1	0.064 (2)	0.0447 (19)	0.0374 (17)	−0.0028 (15)	0.0268 (16)	−0.0016 (14)
N2	0.094 (3)	0.042 (2)	0.133 (4)	−0.009 (2)	0.075 (3)	−0.019 (2)
C1	0.049 (2)	0.042 (2)	0.0356 (19)	−0.0123 (16)	0.0146 (16)	0.0004 (15)
C2	0.062 (2)	0.063 (3)	0.032 (2)	−0.008 (2)	0.0096 (17)	0.0012 (18)
C3	0.060 (3)	0.065 (3)	0.044 (2)	0.001 (2)	0.0033 (19)	0.012 (2)
C4	0.043 (2)	0.046 (2)	0.055 (2)	−0.0077 (17)	0.0115 (17)	0.0005 (18)
C5	0.062 (2)	0.050 (2)	0.040 (2)	−0.0004 (19)	0.0181 (18)	−0.0006 (17)
C6	0.064 (2)	0.048 (2)	0.033 (2)	0.0011 (19)	0.0133 (17)	0.0059 (16)
C7	0.064 (2)	0.047 (2)	0.0309 (19)	−0.0177 (18)	0.0199 (17)	−0.0060 (16)
C8	0.070 (3)	0.044 (2)	0.042 (2)	−0.0095 (19)	0.0253 (19)	−0.0063 (16)
C9	0.103 (5)	0.054 (3)	0.175 (7)	−0.021 (3)	0.084 (5)	−0.028 (4)
C10	0.084 (4)	0.079 (4)	0.174 (7)	−0.015 (3)	0.075 (5)	−0.011 (4)
C11	0.064 (3)	0.095 (4)	0.124 (5)	0.012 (3)	0.041 (3)	−0.005 (4)
C12	0.094 (5)	0.088 (5)	0.189 (8)	0.018 (4)	0.064 (5)	−0.036 (5)
C13	0.142 (6)	0.055 (3)	0.195 (9)	0.010 (4)	0.105 (6)	−0.010 (4)
C14	0.069 (3)	0.053 (3)	0.087 (4)	0.004 (2)	0.031 (3)	−0.006 (2)

S1—C8	1.651 (4)	C5—H5	0.9300
O1—C7	1.226 (4)	C6—H6	0.9300
O2—C4	1.356 (5)	C9—C10	1.385 (9)
O2—C14	1.421 (6)	C9—H9A	0.9700
N1—C7	1.352 (5)	C9—H9B	0.9700
N1—C8	1.430 (5)	C10—C11	1.521 (8)
N1—H1	0.84 (4)	C10—H10A	0.9700
N2—C8	1.323 (6)	C10—H10B	0.9700
N2—C9	1.487 (6)	C11—C12	1.511 (9)
N2—C13	1.497 (7)	C11—H11A	0.9700
C1—C2	1.386 (6)	C11—H11B	0.9700
C1—C6	1.387 (5)	C12—C13	1.358 (10)
C1—C7	1.484 (6)	C12—H12A	0.9700
C2—C3	1.367 (6)	C12—H12B	0.9700
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.386 (6)	C13—H13B	0.9700
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.377 (6)	C14—H14B	0.9600
C5—C6	1.381 (6)	C14—H14C	0.9600
C4—O2—C14	117.8 (3)	C10—C9—H9B	109.0
C7—N1—C8	122.2 (3)	N2—C9—H9B	109.0
C7—N1—H1	117 (3)	H9A—C9—H9B	107.8
C8—N1—H1	115 (3)	C9—C10—C11	113.3 (6)
C8—N2—C9	125.8 (4)	C9—C10—H10A	108.9
C8—N2—C13	122.0 (4)	C11—C10—H10A	108.9
C9—N2—C13	111.3 (5)	C9—C10—H10B	108.9
C2—C1—C6	117.9 (4)	C11—C10—H10B	108.9
C2—C1—C7	118.1 (3)	H10A—C10—H10B	107.7
C6—C1—C7	123.9 (3)	C12—C11—C10	110.2 (5)
C3—C2—C1	120.8 (4)	C12—C11—H11A	109.6
C3—C2—H2	119.6	C10—C11—H11A	109.6
C1—C2—H2	119.6	C12—C11—H11B	109.6
C2—C3—C4	121.0 (4)	C10—C11—H11B	109.6
C2—C3—H3	119.5	H11A—C11—H11B	108.1
C4—C3—H3	119.5	C13—C12—C11	115.8 (6)
O2—C4—C5	124.9 (4)	C13—C12—H12A	108.3
O2—C4—C3	116.1 (4)	C11—C12—H12A	108.3
C5—C4—C3	119.0 (4)	C13—C12—H12B	108.3
C4—C5—C6	119.9 (4)	C11—C12—H12B	108.3
C4—C5—H5	120.0	H12A—C12—H12B	107.4
C6—C5—H5	120.0	C12—C13—N2	113.8 (6)
C5—C6—C1	121.4 (4)	C12—C13—H13A	108.8
C5—C6—H6	119.3	N2—C13—H13A	108.8
C1—C6—H6	119.3	C12—C13—H13B	108.8
O1—C7—N1	120.0 (4)	N2—C13—H13B	108.8
O1—C7—C1	122.1 (4)	H13A—C13—H13B	107.7
N1—C7—C1	117.9 (3)	O2—C14—H14A	109.5
N2—C8—N1	115.7 (3)	O2—C14—H14B	109.5
N2—C8—S1	125.9 (3)	H14A—C14—H14B	109.5
N1—C8—S1	118.4 (3)	O2—C14—H14C	109.5
C10—C9—N2	112.9 (6)	H14A—C14—H14C	109.5
C10—C9—H9A	109.0	H14B—C14—H14C	109.5
N2—C9—H9A	109.0
C6—C1—C2—C3	−0.5 (6)	C2—C1—C7—N1	−172.4 (4)
C7—C1—C2—C3	−178.3 (4)	C6—C1—C7—N1	10.0 (6)
C1—C2—C3—C4	0.3 (7)	C9—N2—C8—N1	7.8 (8)
C14—O2—C4—C5	−1.5 (6)	C13—N2—C8—N1	176.1 (6)
C14—O2—C4—C3	180.0 (4)	C9—N2—C8—S1	−168.8 (5)
C2—C3—C4—O2	178.7 (4)	C13—N2—C8—S1	−0.6 (9)
C2—C3—C4—C5	0.0 (6)	C7—N1—C8—N2	74.8 (6)
O2—C4—C5—C6	−178.6 (4)	C7—N1—C8—S1	−108.2 (4)
C3—C4—C5—C6	−0.1 (6)	C8—N2—C9—C10	−137.5 (7)
C4—C5—C6—C1	−0.2 (6)	C13—N2—C9—C10	53.2 (9)
C2—C1—C6—C5	0.5 (6)	N2—C9—C10—C11	−53.7 (9)
C7—C1—C6—C5	178.1 (4)	C9—C10—C11—C12	48.7 (9)
C8—N1—C7—O1	−9.5 (6)	C10—C11—C12—C13	−47.0 (10)
C8—N1—C7—C1	171.5 (3)	C11—C12—C13—N2	49.2 (11)
C2—C1—C7—O1	8.6 (6)	C8—N2—C13—C12	139.6 (7)
C6—C1—C7—O1	−169.0 (4)	C9—N2—C13—C12	−50.6 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.84 (4)	2.12 (4)	2.897 (4)	154 (4)
C6—H6···O1i	0.93	2.40	3.294 (5)	160
C10—H10A···Cgii	0.97	2.89	3.851 (8)	170