A new monoclinic polymorph of N-(3-methyl­phen­yl)eth­oxy­carbo­thio­amide: crystal structure and Hirshfeld surface analysis

Jotani, M.M.; Yeo, C.I.; Tiekink, E.R.T.

doi:10.1107/S2056989017016280

research communications

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ISSN: 2056-9890

Volume 73| Part 12| December 2017| Pages 1889-1897

https://doi.org/10.1107/S2056989017016280

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A new monoclinic polymorph of N-(3-methylphenyl)ethoxycarbothioamide: crystal structure and Hirshfeld surface analysis

Mukesh M. Jotani,^a ‡ Chien Ing Yeo ^b and Edward R. T. Tiekink ^b ^*

^aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and ^bResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 November 2017; accepted 12 November 2017; online 17 November 2017)

The title compound, C₁₀H₁₃NOS, is a second monoclinic polymorph (space group P2₁/c, Z′ = 2) of the previously reported C2/c (Z = 1) polymorph [Tadbuppa & Tiekink (2005 ). Z. Kristallogr. New Cryst. Struct. 220, 395–396]. Two independent molecules comprise the asymmetric unit of the new polymorph and each of these exists as a thioamide–thione tautomer. In each molecule, the central CNOS chromophore is strictly planar [r.m.s. deviations = 0.0003 and 0.0015 Å] and forms dihedral angles of 6.17 (5) and 20.78 (5)° with the N-bound 3-tolyl rings, thereby representing the major difference between the molecules. The thione-S and thioamide-N—H atoms are syn in each molecule and this facilitates the formation of an eight-membered thioamide {⋯SCNH}₂ synthon between them; the dimeric aggregates are consolidated by pairwise 3-tolyl-C—H⋯S interactions. In the extended structure, supramolecular layers parallel to (102) are formed via a combination of 3-tolyl-C—H⋯π(3-tolyl) and weak π–π interactions [inter-centroid distance between 3-tolyl rings = 3.8535 (12) Å]. An analysis of the Hirshfeld surfaces calculated for both polymorphs reveals the near equivalence of one of the independent molecules of the P2₁/c form to that in the C2/c form.

Keywords: crystal structure; carbothioamide; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1585129

1. Chemical context

Molecules of the general formula ROC(=S)N(H)R′ [R = alkyl, aryl], O-thiocarbamates, are readily prepared from the reaction of an alcohol, ROH, with an isothiocyanide derivative, R′N=C=S. Since the first report of the structure of EtOC(=S)N(H)Ph (Taylor & Tiekink, 1994 ), these molecules have attracted the interest of the crystal engineering community. This interest arises primarily because of the propensity of these molecules to form thioamide-N—H⋯S(thione) hydrogen bonds (Ho et al., 2005 ; Kuan et al., 2007 ; Slater et al., 2016 ) and the ability of these molecules to form co-crystals with pyridyl-like molecules (Ellis et al., 2009 ). The neutral molecules can complex bis(phosphane)copper(I) chloride to reveal fascinating intramolecular phenyl-C—H⋯π(quasi-chelate ring) interactions where the π-system is the hydrogen-bond mediated (CuCl⋯HNCS) ring (Yeo et al., 2014 ); intermolecular versions of C—H⋯π(quasi-chelate ring) interactions are also known (Zukerman-Schpector et al., 2016 ). The anions form very stable compounds with phosphanegold(I) moieties to yield luminescent materials in the solid state (Ho et al., 2006 ) as well as potential anti-bacterial (Yeo et al., 2013 ) and anti-cancer (Ooi et al., 2017 ) agents. It was in the latter context that the title polymorph (I) was discovered. Thus, (I) was synthesized afresh for complexation to phosphanegold(I) and during characterization exhibited distinctive crystallographic properties from a previously described material, i.e. a C2/c form (Tadbuppa & Tiekink, 2005), hereafter (Ic). In the present report, the crystal and molecule structures of a new monoclinic polymorph of (I), i.e. (Ip), are described along with a Hirshfeld surface analysis of both polymorphs, conducted in order to discover distinctive packing patterns.

2. Structural commentary

The crystallographic asymmetric unit of (Ip), Fig. 1, comprises two independent molecules which are chemically indistinguishable, Table 1. The thione-S and thioamide-N—H atoms are syn in each molecule and each exists as a thioamide–thione tautomer. The central OC(=S)N chromophores are strictly planar with the r.m.s. deviation of the four fitted atoms being 0.0003 Å [0.0015 Å for the S11-molecule]. The bond lengths follow the expected trends with the C1—O1, N1 bonds being significantly shorter than the C9—O1 and C2—N1 bonds, respectively. The angles about the quaternary atom vary systematically, with those involving the thione-S1 atom being greater than the O1—C1—N1 bond angle. Of the bond angles involving the thione-S1 atom, the angle involving the O1 atom is greater by 2–3° than that formed by the sterically less encumbered N1 atom. The major difference between the key geometric parameters listed in Table 1 is found in the angles subtended at the N1 atom with the angle for the S1-molecule being nearly 3° wider than that for the S1-molecule. There is also a conformational difference between the two molecules, readily quantified in terms of the dihedral angles formed between the central chromophore and 3-tolyl rings of 6.17 (5) and 20.78 (5)° for the S1- and S11-molecules, respectively. As seen from the overlay diagram, Fig. 2, the ethyl groups have an open conformation and overlap closely with the C1—O1—C9—C10 and C11—O11—C19—C20 torsion angles being −178.76 (17) and 177.42 (18)°, respectively.

Table 1
Selected geometric parameters (Å, °) in (Ip) and (Ic)

Parameter	(Ip), S1-molecule	(Ip), S11-molecule^a	(Ic)
C1—S1	1.6768 (19)	1.6752 (19)	1.6720 (18)
C1—O1	1.321 (2)	1.319 (2)	1.325 (2)
C1—N1	1.338 (2)	1.339 (2)	1.337 (2)
C9—O1	1.457 (2)	1.454 (2)	1.451 (2)
C2—N1	1.421 (2)	1.423 (2)	1.426 (2)
S1—C1—O1	124.23 (14)	125.00 (15)	124.53 (12)
S1—C1—N1	122.06 (14)	121.61 (15)	122.11 (13)
O1—C1—N1	113.71 (16)	113.39 (16)	113.37 (15)
C1—O1—C9	118.72 (15)	119.01 (15)	119.29 (15)
C1—N1—C2	132.48 (16)	129.60 (16)	130.17 (15)
Note: (a) add 10 to atom labels to tally with the numbering in Fig. 1b.

Figure 1
The molecular structures of the two independent molecules comprising the asymmetric unit of (Ip) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Figure 2
Overlay diagram of the two independent molecules of (Ip) (S1-molecule, red image; S11-molecule, green) and that of the original C2/c polymorph (blue image), (Ic). The molecules have been superimposed so that the central S, O and N atoms are coincident.

Geometric parameters for the original polymorph of (I), i.e. (Ic), are also included in Table 1. A comparison of these show the values in (Ip) and (Ic) to be equal within experimental error and those of (Ic) often lying between the two independent values found for (Ip). As evidenced from Fig. 2, there is a greater twist in the molecule as indicated by the dihedral angle of 30.44 (6)° formed between the central chromophore and the 3-tolyl ring. The orientation of the O-bound ethyl group is as for both molecules of (Ip) with the C1—O1—C9—C10 torsion angle being −176.96 (17)°.

3. Supramolecular features

The most notable feature of the molecular packing of (I) is the presence of an eight-membered thioamide synthon, {⋯SCNH}₂, formed via thioamide-N—H⋯S(thione) hydrogen bonds, between the two independent molecules comprising the asymmetric unit, Fig. 3 and Table 2. As shown in Fig. 3, the N—H⋯S hydrogen bonds are supported by 3-tolyl-C—H⋯S interactions, Table 2, with that involving the S1 atom being slightly beyond the standard distance criteria in PLATON (Spek, 2009 ). Globally, like molecules stack along the b-axis direction. The S1-molecules are connected via weak π–π interactions between the 3-tolyl rings with the inter-centroid distance being 3.8535 (12) Å for the symmetry operation 1 − x, 2 − y, 1 − z. The connections between the S11-molecules are of the type 3-tolyl-C—H⋯π(3-tolyl), Table 2. The columns pack into alternating layers of S1- and S11-molecules parallel to [001], Fig. 4a, and connections between them are made through the thioamide-N—H⋯S(thione) hydrogen bonds mentioned above, resulting in supramolecular layers parallel to (102), Fig. 4b. The layers, Fig. 4c, stack with no directional interactions between them.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the (C12–C17) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S11	0.87 (1)	2.62 (1)	3.4859 (16)	174 (2)
N11—H11N⋯S1	0.87 (1)	2.54 (1)	3.3985 (15)	171 (2)
C3—H3⋯S11	0.95	2.86	3.708 (2)	150
C13—H13⋯S1	0.95	2.94	3.7090 (19)	139
C17—H17⋯Cg1ⁱ	0.95	2.82	3.471 (2)	127
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
A view of the supramolecular dimer in (Ip) sustained by thioamide-N—H⋯S(thione) hydrogen bonds and supported by 3-tolyl-C—H⋯S(thione) interactions, shown as orange and green dashed lines, respectively.

Figure 4
Molecular packing in (Ip): (a) a view of the unit-cell contents shown in projection down the c axis, (b) a view of the unit-cell contents shown in projection down the b axis and (c) a view of the supramolecular layer. Molecular packing in (Ic): (d) a view of the unit-cell contents shown in projection down the c axis, (e) a view of the unit-cell contents shown in projection down the b axis and (f) a view of the supramolecular layer. The thioamide-N—H⋯S(thione), C—H⋯π and π–π interactions are shown as orange, purple and blue dashed lines, respectively.

The molecular packing in (Ic) has not been discussed in any detail (Tadbuppa & Tiekink, 2005) and hence, is now described. The eight-membered thioamide synthon, {⋯SCNH}₂, seen in the packing of (Ip) is also found in the packing of (Ic), Table 3, with an important difference, that being the synthon has crystallographic twofold symmetry; the putative 3-tolyl-C—H⋯S interaction is long at 2.92 Å. Globally, molecules pack into columns parallel to the b axis and are sustained by 3-tolyl-C—H⋯π(3-tolyl) interactions, Fig. 4d and Table 3. Connections between columns are made by the aforementioned thioamide-N—H⋯S(thione) hydrogen bonds. The result is supramolecular layers that stack along the c axis, Fig. 4e. A view of the layer is shown in Fig. 4f.

Table 3
Hydrogen-bond geometry (Å, °) for (Ic)

Cg1 is the centroid of the (C2–C7) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯S1ⁱ	0.87	2.58	3.4142 (16)	160
C7—H7⋯Cg1ⁱⁱ	0.94	2.91	3.4973 (17)	122
Symmetry code: (i) −x, y, $[{1\over 2}]$ − z; (ii) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.

From the images of Fig. 4, it is obvious that despite some similarities, the molecular packing in polymorphs (Ip) and (Ic) are distinct. This point is highlighted in the analysis of the Hirshfeld surfaces of (Ip) and (Ic) discussed in the next section.

4. Analysis of the Hirshfeld surfaces of (Ip) and (Ic)

The Hirshfeld surfaces for the individual molecules in (Ip), overall (Ip) and for (Ic) were calculated in accord with a recent report on a pair of polymorphs (Kuan et al., 2017 ). The calculations clearly reveal the similarities and differences in the intermolecular interactions instrumental in the crystals of the polymorphs.

The appearance of bright-red spots near the thioamide-H and thione-S atoms, diminutive red spots near the 3-tolyl-H, ethoxy-H atoms and thione-S atoms on the Hirshfeld surfaces mapped over d_norm shown in Fig. 5 for both independent molecules of (Ip) as well as for polymorph (Ic) are indicative of comparable thioamide-N—H⋯S(thione) and 3-tolyl-C—H⋯S(thione) interactions, and short interatomic H⋯H contacts in their respective crystals, Table 4; values in Table 4 were obtained from an analysis employing the CrystalExplorer package (Wolff et al. 2012 ). As there are two independent molecules in monoclinic polymorph (Ip), it exhibits a pair of the above-mentioned intermolecular interactions shown with labels 1 to 4 in Fig. 5a–c, whereas in form (Ic) they are labelled as 1 and 2 in Fig. 5d and e. In addition to the above, the faint-red spots viewed near 3-tolyl-C14 in Fig. 5b and ethoxy-H20B in Fig. 5c indicate the significance of short interatomic C⋯H/H⋯C contacts, Table 4, in the packing of (Ip). The donors and acceptors of intermolecular interactions are also represented with blue and red regions, respectively, on the Hirshfeld surfaces mapped over electrostatic potential in Fig. 6. The new monoclinic polymorph (Ip) has distinct and a greater number of short interatomic contacts than for (Ic) owing, in part, to the presence of two distinct molecules per asymmetric unit, Table 4. The short interatomic H⋯H contacts together with intermolecular N—H⋯S and C—H⋯S interactions formed with the atoms of reference molecules within Hirshfeld surfaces mapped over electrostatic potential for (Ip) and (Ic) are highlighted in Fig. 7.

Table 4
Summary of short interatomic contacts (Å) in (Ip) and (Ic)^a

Contact	Distance	Symmetry operation
(Ip)
H3⋯H14	2.35	x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z
H5⋯H9B	2.28	x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
H15⋯H19A	2.31	x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z
H19B⋯H19B	2.08	2 − x, 2 − y, 1 − z
C10⋯H20C	2.87	−1 + x, y, z
C14⋯H20B	2.77	2 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
N1⋯H18B	2.73	2 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
(Ic)
H7⋯H9b	2.37	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
H9a⋯H9a	2.11	−x, −y, −z
H10b⋯H10b	2.32	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z
Note: (a) the atom numbering for the molecule in (Ic) follows that for the S1-molecule in (Ip).

Figure 5
Views of the Hirshfeld surfaces mapped over d_norm for the (a) S1-containing molecule of (Ip) in the range −0.147 to +1.345 au, (b) and (c) S11-containing molecule in (Ip) in the range −0.149 to +1.274 au and (d) and (e) molecule of polymorph (Ic) in the range −0.109 to 1.397 au.

Figure 6
Views of Hirshfeld surfaces mapped over the electrostatic potential for (a) the asymmetric unit of (Ip) in the ±0.046 au range and (b) molecule of (Ic) in ±0.069 au range. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 7
Views of the Hirshfeld surfaces about a reference molecule mapped over the electrostatic potential highlighting the short interatomic H⋯H contacts (red dashed lines) and intermolecular N—H⋯S and C—H⋯ S interactions (black dashed lines) in (a) (Ip) and (b) (Ic).

The overall two-dimensional fingerprint plots for the S1 and S11-containing molecules of (Ip), the whole asymmetric unit of (Ip) and for the polymorph (Ic) are illustrated in Fig. 8a–d, respectively. In addition, the fingerprint plots delineated into H⋯H, S⋯H/H⋯S, C⋯H/H⋯C, C⋯C and N⋯H/H⋯N contacts (McKinnon et al., 2007 ) are included in Fig. 8; the relative contributions from different interatomic contacts to the Hirshfeld surfaces are summarized in Table 5. The nearly similar distribution of points in the fingerprint plots for S11-containing molecule of (Ip) and that of (Ic) indicate similarity in their molecular environments although some of the equivalent interatomic distances differ, Tables 2–4 .

Table 5
Percentage contributions of interatomic contacts to the Hirshfeld surfaces for the individual molecules in (Ip), overall (Ip) and (Ic)

Contact	Percentage contribution
	(Ip), S1-molecule	(Ip), S11-molecule	overall (Ip)	(Ic)
H⋯H	57.4	55.5	61.7	57.0
S⋯H/H⋯S	17.6	17.4	10.0	17.3
C⋯H/H⋯C	14.0	18.8	17.8	17.3
C⋯C	3.9	1.5	3.0	1.9
N⋯H/H⋯N	2.6	2.9	3.0	2.6
C⋯O/O⋯C	2.5	2.5	2.7	2.4
O⋯H/H⋯O	1.0	1.2	1.2	1.1
C⋯N/N⋯C	0.9	0.3	0.6	0.4

Figure 8
The full two-dimensional fingerprint plot and those delineated into H⋯H, S⋯H/H⋯S, C⋯H/H⋯C, C⋯C and N⋯H/H⋯N (left to right) contacts for (a) S1-molecule of (Ip), (b) S11-molecule of (Ip), (c) overall (Ip) and (d) (Ic).

The fingerprint plots delineated into H⋯H contacts, Fig. 8b and d, have needle-like tips pointing at d_e + d_i ∼ 2.1 Å indicating short interatomic H⋯H contacts, Table 4, for the S11-containing molecule of (Ip) and for (Ic), both involving ethoxy-H atoms. The other short interatomic contacts in both forms are characterized from the points located within the pair of short peaks in (Ip) and a single short peak in (Ic), respectively, at d_e + d_i < 2.4 Å, i.e. at the sum of their van der Waals radii.

The involvement of ethoxy-H atoms in short interatomic C⋯H/H⋯C contacts decreases the percentage contribution from H⋯H contacts to the Hirshfeld surface of the S11-containing molecule whereas the contribution from equivalent contacts to the surface of the S1-containing molecule of (Ip) and that of (Ic) are almost same, Table 5. The increase in percentage contribution from these contacts to the Hirshfeld surface of overall asymmetric unit of (Ip) is due to the intermolecular N—H⋯S and C—H⋯S interactions between the respective atoms of S1- and S11-containing molecules thereby decreasing the contribution from S⋯H/H⋯S contacts to the overall surface, Table 5. This fact is confirmed from the nearly same percentage contribution from S⋯H/H⋯S contacts to the Hirshfeld surfaces of the individual S1- and S11-containing molecules of (Ip) and of the molecule of the (Ic) form, Table 5, and also from pair of forceps-like tips at d_e + d_i ∼ 2.6 Å with the nearly same distribution of points in their respective fingerprint plots in Fig. 8.

The similar distribution of points in the fingerprint plot delineated into C⋯H/H⋯C contacts for the S11-containing molecule of (Ip), Fig. 8b, and of (Ic), Fig. 8d, indicate their involvement in the intermolecular C—H⋯π contacts showing pairs of tips at d_e + d_i ∼ 2.8 and 2.9 Å, respectively. This is confirmed by the slight increase in the percentage contribution from these contacts to the Hirshfeld surface of the S11-containing molecule of (Ip) cf. the S1-containing molecule, Table 5. In other words, the contribution from C⋯H/H⋯C contacts to the surface of the S1-containing molecule of (Ip), Table 5, is decreased due to the absence of C—H⋯π contacts involving this molecule whereas the greater percentage contribution from C⋯C contacts to the Hirshfeld surface of this molecule results from the presence of π–π stacking interactions between the symmetry-related 3-tolyl rings. This is also evident from the arrow-like distribution of points around d_e = d_i = 1.8 Å in the C⋯C delineated fingerprint plot shown in Fig. 8a.

The contribution of 3.0% from N⋯H/H⋯N contacts to the Hirshfeld surface of whole asymmetric unit of polymorph (Ip) indicate the presence of short interatomic N⋯H/H⋯N contacts between the thioamide-N1 and tolyl-H18B atoms, Table 4, although all of the delineated fingerprint plots have a similar distributions of points, Fig. 8, at least to a first approximation. The other interatomic contacts summarized in Table 4 make only small contributions to the Hirshfeld surfaces and have negligible contributions on the respective molecular packings.

5. Database survey

According to a search of the Cambridge Structural Database (Version 5.38, May update; Groom et al., 2016 ), there are 22 monofunctional carbothioamide molecules related to the title compound, with (Ip) and (Ic) being the only pair of polymorphs characterized thus far. Referring to Table 6, the overwhelming majority of the 24 crystallographically characterized thioamides feature an eight-membered thioamide, {⋯SCNH}₂, synthon. Thus, in 13 of the characterized structures, the synthon is formed about a centre of inversion, motif A. In five structures, two independent molecules (Z′ = 2) comprise the asymmetric unit, as in (Ip), and these associated via the {⋯SCNH}₂ synthon but with no crystallographically imposed symmetry, motif A′. There is a single example of a structure with Z′ = 3 (Taylor & Tiekink, 1994). Here, one of the independent molecules self-associates about a centre of inversion, as in motif A, whereas the two remaining independent molecules are connected by the {⋯SCNH}₂ synthon, as found in motif A′. This is motif A′′. Two structures feature the {⋯SCNH}₂ synthon located about a twofold axis of symmetry, as in (Ic), i.e. motif A′′′. The remaining three structures do not feature thioamide-N—H⋯S(thione) hydrogen bonding. In the structure of MeOC(=S)N(H)(4-C(=O)Me-phenyl) (VI) (Ho et al., 2005), motif B, thioamide-N—H⋯O(carboxy) hydrogen bonding is observed, leading to a linear supramolecular chain as shown in Fig. 9a. This structure is noteworthy as being the only example where the conformation of the thioamide moiety is anti rather than the normally observed syn. The final variation, motif C, is found in two structures, Table 6. The structure of (4-pyridyl)CH₂OC(=S)N(H)phenyl (XIX) (Xiao et al., 2006 ) serves as an exemplar. Thus, in the crystal of (XIX), thioamide-N—H⋯N(pyridyl) hydrogen bonds lead to a zigzag chain as shown in Fig. 9b. In summary, an inspection of the data in Table 6 indicates the predominance of thioamide-N—H⋯S(thione) hydrogen bonding in these carbothioamides, at least in the absence of competing synthons, as seen in motifs B and C

Table 6
Hydrogen-bonding patterns in ROC(=S)N(H)R′

Number	R	R′	Z′	Hydrogen bonds	Motif	Refcode	Ref.
(II)	Me	phenyl	1	N—H⋯S	A	OJIHAQ	Ho et al. (2003 )
(III)	Me	4-NO₂-phenyl	1	N—H⋯S	A	CAZFUF	Ho et al. (2005)
(IV)	Me	4-C(=O)OMe-phenyl	1	N—H⋯S	A	CAZGAM	Ho et al. (2005)
(V)	Me	4-Cl-phenyl	2	N—H⋯S	A′	CAZCEQ	Ho et al. (2005)
(VI)	Me	4-C(=O)Me-phenyl	1	N—H⋯O	B	CAZGIU	Ho et al. (2005)
(VII)	Me	2-tolyl	1	N—H⋯S	A	TAZSIX	Kuan et al. (2005 )
(VIII)	Me	4-tolyl	2	N—H⋯S	A′	TIBYUZ	Ho et al. (2007 )
(IX)	Et	phenyl	3	N—H⋯S	A′′	PINPIL	Taylor & Tiekink (1994)
(Ip)	Et	3-tolyl	2	N—H⋯S	A′	–	This work
(Ip)	Et	3-tolyl	1	N—H⋯S	A′′′	TAZTUK	Tadbuppa & Tiekink (2005)
(X)	Et	4-tolyl	1	N—H⋯S	A	TIBYOT	Tadbuppa & Tiekink (2007a )
(XI)	Et	3-OMe-phenyl	1	N—H⋯S	A	UDUPAL	Hanif et al. (2007 )
(XII)	Et	4-NO₂-phenyl	1	N—H⋯S	A	NENLAU	Benson et al. (2006 )
(XIII)	Et	4-Cl-phenyl	1	N—H⋯S	A	DEYQEE	Tadbuppa & Tiekink (2007b )
(XIV)	n-Pr	phenyl	2	N—H⋯S	A′	PAWKAB	Sudkaow et al. (2012 )
(XV)	i-Pr	Ph	1	N—H⋯S	A	ADOGUW	Kuan et al. (2007)
(XVI)	i-Pr	4-tolyl	1	N—H⋯S	A	ADOGOQ	Kuan et al. (2007)
(XVII)	i-Pr	4-Cl-phenyl	1	N—H⋯S	A	ADOHAD	Kuan et al. (2007)
(XVIII)	i-Pr	4-NO₂-phenyl	1	N—H⋯S	A	MISDEY	Ellis et al. (2008 )
(XIX)	4-pyridylmethyl	phenyl	2	N—H⋯N	C	IFACOI	Xiao et al. (2006)
(XX)	i-Bu	phenyl	1	N—H⋯S	A′′′	KEQJAS	Jian et al. (2006 )
(XXI)	2,4-Me₂-phenyl	phenyl	1	N—H⋯S	A	POVVOL	Abraham et al. (1995 )
(XXII)	2,4-(OMe)₂-phenyl	R^1a	1	N—H⋯N	C	OSIZOG	Zhou et al. (2010 )
(XXIII)	Cy	phenyl	2	N—H⋯S	A′	VEFKUO	Sahoo et al. (2012 )
Note: (a) see Scheme 2 for the chemical diagram of (XXII).

Figure 9
Supramolecular aggregation in related carbothioamide structures: (a) linear supramolecular chain in the crystal of MeOC(=S)N(H)(4-C(=O)Me-phenyl) (VI) mediated by thioamide-N—H⋯O(carboxy) hydrogen bonding shown as orange dashed lines and (b) zigzag chain in the crystal of (4-pyridyl)CH₂OC(=S)N(H)phenyl mediated by thioamide-N—H⋯N(pyridyl) hydrogen bonding shown as blue dashed lines.

6. Synthesis and crystallization

All chemicals and solvents were used as purchased without purification. To prepare (Ip), 3-tolyl isothiocyanate (Merck; 2.5 mmol, 0.34 ml) was added to NaOH (Merck; 2.5 mmol, 0.10 g) in EtOH (Merck; 3 ml) and the mixture was stirred at room temperature for 2 h, followed by the addition of excess 5 M HCl solution. The resulting mixture was stirred for another 1.5 h. The final product was extracted with chloroform (Merck; 10 ml) and left for evaporation at room temperature, yielding brown crystals after 1 week. M.p. (Krüss KSP1N melting point meter): 339–340 K. IR (Perkin Elmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer; cm⁻¹): 3211 (s) (N—H), 1451 (s) (C—N), 1209 (s) (C=S), 1064 (s) (C—O).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The nitrogen-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with U_iso(H) set to 1.2U_eq(N). Owing to poor agreement, one reflection, i.e. ( $[\overline{15}]$ 1 4), was omitted from the final cycles of refinement.

Table 7
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃NOS
M_r	195.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.3999 (5), 7.0388 (3), 19.9725 (7)
β (°)	91.727 (3)
V (Å³)	2023.45 (13)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.20 × 0.20 × 0.05

Data collection
Diffractometer	Agilent SuperNova, Dual, Mo at zero, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.662, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15588, 4577, 3514
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 1.03
No. of reflections	4577
No. of parameters	245
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.24
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), QMol (Gans & Shalloway, 2001 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1585129

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017016280/hb7715sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016280/hb7715Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

N-(3-Methylphenyl)ethoxycarbothioamide top

Crystal data top

C₁₀H₁₃NOS	F(000) = 832
M_r = 195.27	D_x = 1.282 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3999 (5) Å	Cell parameters from 6144 reflections
b = 7.0388 (3) Å	θ = 2.4–27.5°
c = 19.9725 (7) Å	µ = 0.28 mm⁻¹
β = 91.727 (3)°	T = 100 K
V = 2023.45 (13) Å³	Slab, colourless
Z = 8	0.20 × 0.20 × 0.05 mm

Data collection top

Agilent SuperNova, Dual, Mo at zero, Atlas diffractometer	4577 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3514 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.5°
ω scan	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −9→9
T_min = 0.662, T_max = 1.000	l = −18→25
15588 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0629P)² + 0.8006P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.125	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.72 e Å⁻³
4577 reflections	Δρ_min = −0.24 e Å⁻³
245 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.63595 (3)	0.62560 (8)	0.29847 (2)	0.02560 (15)
O1	0.48087 (9)	0.6728 (2)	0.36508 (7)	0.0205 (3)
N1	0.61175 (11)	0.6959 (2)	0.42674 (8)	0.0176 (3)
H1N	0.6720 (7)	0.683 (3)	0.4295 (11)	0.021*
C1	0.57256 (13)	0.6663 (3)	0.36605 (10)	0.0183 (4)
C2	0.57411 (12)	0.7410 (3)	0.48972 (9)	0.0157 (4)
C3	0.63901 (13)	0.7851 (3)	0.54059 (10)	0.0198 (4)
H3	0.7035	0.7828	0.5318	0.024*
C4	0.60988 (14)	0.8320 (3)	0.60359 (10)	0.0224 (4)
H4	0.6545	0.8604	0.6382	0.027*
C5	0.51590 (14)	0.8380 (3)	0.61691 (10)	0.0214 (4)
H5	0.4963	0.8719	0.6603	0.026*
C6	0.45044 (13)	0.7944 (3)	0.56662 (10)	0.0189 (4)
C7	0.47948 (13)	0.7455 (3)	0.50316 (10)	0.0185 (4)
H7	0.4349	0.7151	0.4688	0.022*
C8	0.34802 (13)	0.8043 (3)	0.58036 (11)	0.0258 (5)
H8A	0.3157	0.6989	0.5576	0.039*
H8B	0.3227	0.9252	0.5637	0.039*
H8C	0.3391	0.7952	0.6287	0.039*
C9	0.43042 (14)	0.6465 (3)	0.30146 (10)	0.0250 (5)
H9A	0.4433	0.5193	0.2827	0.030*
H9B	0.4489	0.7440	0.2687	0.030*
C10	0.33069 (15)	0.6655 (4)	0.31611 (12)	0.0334 (5)
H10A	0.2934	0.6493	0.2747	0.050*
H10B	0.3192	0.7917	0.3349	0.050*
H10C	0.3135	0.5680	0.3485	0.050*
S11	0.85195 (3)	0.66025 (9)	0.45041 (2)	0.02577 (15)
O11	0.99877 (9)	0.7448 (2)	0.37829 (6)	0.0192 (3)
N11	0.86976 (10)	0.6753 (2)	0.31952 (8)	0.0175 (3)
H11N	0.8103 (7)	0.652 (3)	0.3174 (11)	0.021*
C11	0.91055 (13)	0.6951 (3)	0.38026 (10)	0.0185 (4)
C12	0.90609 (12)	0.7096 (3)	0.25516 (9)	0.0156 (4)
C13	0.84323 (12)	0.7751 (3)	0.20604 (9)	0.0179 (4)
H13	0.7802	0.7967	0.2165	0.021*
C14	0.87304 (13)	0.8082 (3)	0.14206 (9)	0.0193 (4)
H14	0.8303	0.8523	0.1084	0.023*
C15	0.96520 (13)	0.7774 (3)	0.12656 (9)	0.0192 (4)
H15	0.9854	0.8019	0.0825	0.023*
C16	1.02797 (13)	0.7108 (3)	0.17527 (10)	0.0177 (4)
C17	0.99808 (13)	0.6749 (3)	0.23923 (9)	0.0176 (4)
H17	1.0404	0.6265	0.2724	0.021*
C18	1.12821 (13)	0.6769 (3)	0.15808 (10)	0.0245 (5)
H18A	1.1566	0.5877	0.1904	0.037*
H18B	1.1622	0.7975	0.1599	0.037*
H18C	1.1308	0.6234	0.1129	0.037*
C19	1.05091 (14)	0.7744 (3)	0.44091 (10)	0.0256 (5)
H19A	1.0493	0.6584	0.4689	0.031*
H19B	1.0238	0.8806	0.4663	0.031*
C20	1.14753 (15)	0.8193 (4)	0.42346 (12)	0.0349 (5)
H20A	1.1840	0.8490	0.4643	0.052*
H20B	1.1477	0.9291	0.3933	0.052*
H20C	1.1750	0.7096	0.4012	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0230 (3)	0.0401 (3)	0.0140 (3)	−0.0017 (2)	0.00422 (18)	−0.0020 (2)
O1	0.0190 (7)	0.0284 (8)	0.0141 (7)	0.0011 (6)	−0.0009 (5)	−0.0020 (6)
N1	0.0155 (7)	0.0236 (9)	0.0139 (8)	0.0005 (7)	0.0022 (6)	−0.0005 (7)
C1	0.0200 (9)	0.0174 (10)	0.0176 (10)	−0.0011 (8)	0.0017 (7)	0.0017 (8)
C2	0.0211 (9)	0.0129 (9)	0.0132 (9)	0.0008 (7)	0.0039 (7)	0.0011 (7)
C3	0.0182 (9)	0.0233 (11)	0.0178 (10)	0.0014 (8)	0.0019 (7)	0.0004 (8)
C4	0.0251 (10)	0.0262 (11)	0.0157 (10)	−0.0002 (9)	−0.0014 (8)	−0.0010 (8)
C5	0.0279 (10)	0.0234 (11)	0.0133 (9)	0.0026 (8)	0.0052 (7)	−0.0009 (8)
C6	0.0205 (9)	0.0181 (10)	0.0184 (10)	−0.0003 (8)	0.0052 (7)	0.0035 (8)
C7	0.0199 (9)	0.0203 (10)	0.0154 (10)	−0.0016 (8)	0.0014 (7)	0.0020 (8)
C8	0.0226 (10)	0.0331 (12)	0.0221 (11)	0.0014 (9)	0.0077 (8)	0.0024 (9)
C9	0.0254 (10)	0.0337 (12)	0.0155 (10)	−0.0020 (9)	−0.0057 (8)	−0.0002 (9)
C10	0.0267 (11)	0.0404 (14)	0.0329 (13)	−0.0041 (10)	−0.0037 (9)	−0.0003 (11)
S11	0.0225 (3)	0.0423 (3)	0.0127 (3)	0.0072 (2)	0.00474 (18)	0.0035 (2)
O11	0.0203 (7)	0.0236 (8)	0.0137 (7)	0.0012 (6)	−0.0003 (5)	−0.0007 (6)
N11	0.0147 (7)	0.0238 (9)	0.0141 (8)	0.0025 (7)	0.0027 (6)	0.0016 (7)
C11	0.0200 (9)	0.0200 (10)	0.0155 (9)	0.0075 (8)	0.0027 (7)	0.0009 (8)
C12	0.0196 (9)	0.0152 (9)	0.0121 (9)	−0.0005 (7)	0.0031 (7)	0.0003 (7)
C13	0.0154 (9)	0.0225 (10)	0.0158 (10)	−0.0017 (8)	0.0006 (7)	−0.0010 (8)
C14	0.0219 (9)	0.0217 (10)	0.0141 (9)	−0.0031 (8)	−0.0032 (7)	0.0010 (8)
C15	0.0242 (10)	0.0225 (10)	0.0110 (9)	−0.0033 (8)	0.0030 (7)	0.0001 (8)
C16	0.0198 (9)	0.0161 (9)	0.0175 (10)	−0.0014 (8)	0.0042 (7)	−0.0007 (8)
C17	0.0201 (9)	0.0165 (9)	0.0162 (10)	0.0029 (8)	0.0010 (7)	0.0010 (8)
C18	0.0236 (10)	0.0286 (12)	0.0217 (11)	0.0038 (9)	0.0090 (8)	0.0029 (9)
C19	0.0265 (10)	0.0323 (12)	0.0176 (10)	0.0042 (9)	−0.0044 (8)	−0.0055 (9)
C20	0.0302 (12)	0.0359 (14)	0.0382 (14)	−0.0012 (10)	−0.0047 (10)	−0.0008 (11)

Geometric parameters (Å, º) top

S1—C1	1.6768 (19)	S11—C11	1.6752 (19)
O1—C1	1.321 (2)	O11—C11	1.319 (2)
O1—C9	1.457 (2)	O11—C19	1.454 (2)
N1—C1	1.338 (2)	N11—C11	1.339 (2)
N1—C2	1.421 (2)	N11—C12	1.423 (2)
N1—H1N	0.872 (9)	N11—H11N	0.872 (9)
C2—C3	1.394 (3)	C12—C13	1.393 (3)
C2—C7	1.397 (2)	C12—C17	1.393 (2)
C3—C4	1.378 (3)	C13—C14	1.380 (3)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.388 (3)	C14—C15	1.389 (3)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.391 (3)	C15—C16	1.389 (3)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.390 (3)	C16—C17	1.383 (3)
C6—C8	1.510 (3)	C16—C18	1.513 (2)
C7—H7	0.9500	C17—H17	0.9500
C8—H8A	0.9800	C18—H18A	0.9800
C8—H8B	0.9800	C18—H18B	0.9800
C8—H8C	0.9800	C18—H18C	0.9800
C9—C10	1.480 (3)	C19—C20	1.479 (3)
C9—H9A	0.9900	C19—H19A	0.9900
C9—H9B	0.9900	C19—H19B	0.9900
C10—H10A	0.9800	C20—H20A	0.9800
C10—H10B	0.9800	C20—H20B	0.9800
C10—H10C	0.9800	C20—H20C	0.9800

C1—O1—C9	118.72 (15)	C11—O11—C19	119.01 (15)
C1—N1—C2	132.48 (16)	C11—N11—C12	129.60 (16)
C1—N1—H1N	115.6 (15)	C11—N11—H11N	117.9 (15)
C2—N1—H1N	111.9 (15)	C12—N11—H11N	112.0 (15)
O1—C1—N1	113.71 (16)	O11—C11—N11	113.39 (16)
O1—C1—S1	124.23 (14)	O11—C11—S11	125.00 (15)
N1—C1—S1	122.06 (14)	N11—C11—S11	121.61 (15)
C3—C2—C7	119.42 (17)	C13—C12—C17	119.95 (17)
C3—C2—N1	115.45 (16)	C13—C12—N11	116.33 (16)
C7—C2—N1	125.13 (17)	C17—C12—N11	123.68 (17)
C4—C3—C2	120.17 (17)	C14—C13—C12	119.62 (17)
C4—C3—H3	119.9	C14—C13—H13	120.2
C2—C3—H3	119.9	C12—C13—H13	120.2
C3—C4—C5	120.51 (18)	C13—C14—C15	120.40 (17)
C3—C4—H4	119.7	C13—C14—H14	119.8
C5—C4—H4	119.7	C15—C14—H14	119.8
C4—C5—C6	119.90 (18)	C14—C15—C16	120.16 (17)
C4—C5—H5	120.0	C14—C15—H15	119.9
C6—C5—H5	120.0	C16—C15—H15	119.9
C7—C6—C5	119.81 (17)	C17—C16—C15	119.61 (17)
C7—C6—C8	119.97 (18)	C17—C16—C18	120.42 (18)
C5—C6—C8	120.21 (17)	C15—C16—C18	119.96 (17)
C6—C7—C2	120.18 (18)	C16—C17—C12	120.22 (18)
C6—C7—H7	119.9	C16—C17—H17	119.9
C2—C7—H7	119.9	C12—C17—H17	119.9
C6—C8—H8A	109.5	C16—C18—H18A	109.5
C6—C8—H8B	109.5	C16—C18—H18B	109.5
H8A—C8—H8B	109.5	H18A—C18—H18B	109.5
C6—C8—H8C	109.5	C16—C18—H18C	109.5
H8A—C8—H8C	109.5	H18A—C18—H18C	109.5
H8B—C8—H8C	109.5	H18B—C18—H18C	109.5
O1—C9—C10	106.11 (17)	O11—C19—C20	107.04 (17)
O1—C9—H9A	110.5	O11—C19—H19A	110.3
C10—C9—H9A	110.5	C20—C19—H19A	110.3
O1—C9—H9B	110.5	O11—C19—H19B	110.3
C10—C9—H9B	110.5	C20—C19—H19B	110.3
H9A—C9—H9B	108.7	H19A—C19—H19B	108.6
C9—C10—H10A	109.5	C19—C20—H20A	109.5
C9—C10—H10B	109.5	C19—C20—H20B	109.5
H10A—C10—H10B	109.5	H20A—C20—H20B	109.5
C9—C10—H10C	109.5	C19—C20—H20C	109.5
H10A—C10—H10C	109.5	H20A—C20—H20C	109.5
H10B—C10—H10C	109.5	H20B—C20—H20C	109.5

C9—O1—C1—N1	178.80 (17)	C19—O11—C11—N11	178.92 (17)
C9—O1—C1—S1	−1.1 (3)	C19—O11—C11—S11	−0.6 (3)
C2—N1—C1—O1	−3.2 (3)	C12—N11—C11—O11	−3.8 (3)
C2—N1—C1—S1	176.68 (16)	C12—N11—C11—S11	175.77 (16)
C1—N1—C2—C3	−172.1 (2)	C11—N11—C12—C13	−147.0 (2)
C1—N1—C2—C7	7.3 (3)	C11—N11—C12—C17	35.4 (3)
C7—C2—C3—C4	0.2 (3)	C17—C12—C13—C14	−1.1 (3)
N1—C2—C3—C4	179.66 (18)	N11—C12—C13—C14	−178.82 (17)
C2—C3—C4—C5	−0.7 (3)	C12—C13—C14—C15	−0.3 (3)
C3—C4—C5—C6	0.7 (3)	C13—C14—C15—C16	0.7 (3)
C4—C5—C6—C7	−0.2 (3)	C14—C15—C16—C17	0.1 (3)
C4—C5—C6—C8	−178.83 (19)	C14—C15—C16—C18	179.80 (18)
C5—C6—C7—C2	−0.3 (3)	C15—C16—C17—C12	−1.5 (3)
C8—C6—C7—C2	178.33 (18)	C18—C16—C17—C12	178.84 (18)
C3—C2—C7—C6	0.3 (3)	C13—C12—C17—C16	2.0 (3)
N1—C2—C7—C6	−179.08 (18)	N11—C12—C17—C16	179.53 (17)
C1—O1—C9—C10	−178.76 (17)	C11—O11—C19—C20	177.42 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C12–C17) ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S11	0.87 (1)	2.62 (1)	3.4859 (16)	174 (2)
N11—H11N···S1	0.87 (1)	2.54 (1)	3.3985 (15)	171 (2)
C3—H3···S11	0.95	2.86	3.708 (2)	150
C13—H13···S1	0.95	2.94	3.7090 (19)	139
C17—H17···Cg1ⁱ	0.95	2.82	3.471 (2)	127

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Selected geometric parameters (Å, °) in (Ip) and (Ic) top

Parameter	(Ip), S1-molecule	(Ip), S11-molecule^a	(Ic)
C1—S1	1.6768 (19)	1.6752 (19)	1.6720 (18)
C1—O1	1.321 (2)	1.319 (2)	1.325 (2)
C1—N1	1.338 (2)	1.339 (2)	1.337 (2)
C9—O1	1.457 (2)	1.454 (2)	1.451 (2)
C2—N1	1.421 (2)	1.423 (2)	1.426 (2)
S1—C1—O1	124.23 (14)	125.00 (15)	124.53 (12)
S1—C1—N1	122.06 (14)	121.61 (15)	122.11 (13)
O1—C1—N1	113.71 (16)	113.39 (16)	113.37 (15)
C1—O1—C9	118.72 (15)	119.01 (15)	119.29 (15)
C1—N1—C2	132.48 (16)	129.60 (16)	130.17 (15)

Note: (a) add 10 to atom labels to tally with the numbering in Fig. 1b.

Hydrogen-bond geometry (Å, °) for (Ic) top

Cg1 is the centroid of the (C2–C7) ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···S1ⁱ	0.87	2.58	3.4142 (16)	160
C7—H7···Cg1ⁱⁱ	0.94	2.91	3.4973 (17)	122

Symmetry code: (i) -x, y, 1/2 - z; (ii) 1/2 - x, -1/2 + y, 1/2 - z.

Summary of short interatomic contacts (Å) in (Ip) and (Ic)^a top

Contact	Distance	Symmetry operation
(Ip)
H3···H14	2.35	x, 3/2 - y, -1/2 + z
H5···H9B	2.28	x, 3/2 - y, 1/2 + z
H15···H19A	2.31	x, 3/2 - y, -1/2 + z
H19B···H19B	2.08	2 - x, 2 - y, 1 - z
C10···H20C	2.87	-1 + x, y, z
C14···H20B	2.77	2 - x, -1/2 + yy, 1/2 - z
N1···H18B	2.73	2 - x, -1/2 + yy, 1/2 - z
(Ic)
H7···H9b	2.37	1/2 + x, 1/2 - y, 1/2 + z
H9a···H9a	2.11	-x, -y, -z
H10b···H10b	2.32	1/2 - x, 1/2 - y, -z

Note: (a) the atom numbering for the molecule in (Ic) follows that for the S1-molecule in (Ip).

Percentage contributions of interatomic contacts to the Hirshfeld surfaces for the individual molecules in (Ip), overall (Ip) and (Ic) top

Contact			Percentage contribution
	(Ip), S1-molecule	(Ip), S11-molecule	overall (Ip)	(Ic)
H···H	57.4	55.5	61.7	57.0
S···H/H···S	17.6	17.4	10.0	17.3
C···H/H···C	14.0	18.8	17.8	17.3
C···C	3.9	1.5	3.0	1.9
N···H/H···N	2.6	2.9	3.0	2.6
C···O/O···C	2.5	2.5	2.7	2.4
O···H/H···O	1.0	1.2	1.2	1.1
C···N/N···C	0.9	0.3	0.6	0.4

Hydrogen-bonding patterns in ROC(═S)N(H)R' top

Number	R	R'	Z'	Hydrogen bonds	Motif	Refcode	Ref.
(II)	Me	phenyl	1	N—H···S	A	OJIHAQ	Ho et al. (2003)
(III)	Me	4-NO₂-phenyl	1	N—H···S	A	CAZFUF	Ho et al. (2005)
(IV)	Me	4-C(═O)OMe-phenyl	1	N—H···S	A	CAZGAM	Ho et al. (2005)
(V)	Me	4-Cl-phenyl	2	N—H···S	A'	CAZCEQ	Ho et al. (2005)
(VI)	Me	4-C(═O)Me-phenyl	1	N—H···O	B	CAZGIU	Ho et al. (2005)
(VII)	Me	2-tolyl	1	N—H···S	A	TAZSIX	Kuan et al. (2005)
(VIII)	Me	4-tolyl	2	N—H···S	A'	TIBYUZ	Ho et al. (2007)
(IX)	Et	phenyl	3	N—H···S	A''	PINPIL	Taylor & Tiekink (1994)
(Ip)	Et	3-tolyl	2	N—H···S	A'	–	This work
(Ip)	Et	3-tolyl	1	N—H···S	A'''	TAZTUK	Tadbuppa & Tiekink (2005)
(X)	Et	4-tolyl	1	N—H···S	A	TIBYOT	Tadbuppa & Tiekink (2007a)
(XI)	Et	3-OMe-phenyl	1	N—H···S	A	UDUPAL	Hanif et al. (2007)
(XII)	Et	4-NO₂-phenyl	1	N—H···S	A	NENLAU	Benson et al. (2006)
(XIII)	Et	4-Cl-phenyl	1	N—H···S	A	DEYQEE	Tadbuppa & Tiekink (2007b)
(XIV)	n-Pr	phenyl	2	N—H···S	A'	PAWKAB	Sudkaow et al. (2012)
(XV)	i-Pr	Ph	1	N—H···S	A	ADOGUW	Kuan et al. (2007)
(XVI)	i-Pr	4-tolyl	1	N—H···S	A	ADOGOQ	Kuan et al. (2007)
(XVII)	i-Pr	4-Cl-phenyl	1	N—H···S	A	ADOHAD	Kuan et al. (2007)
(XVIII)	i-Pr	4-NO₂-phenyl	1	N—H···S	A	MISDEY	Ellis et al. (2008)
(XIX)	4-pyridylmethyl	phenyl	2	N—H···N	C	IFACOI	Xiao et al. (2006)
(XX)	i-Bu	phenyl	1	N—H···S	A'''	KEQJAS	Jian et al. (2006)
(XXI)	2,4-Me₂-phenyl	phenyl	1	N—H···S	A	POVVOL	Abraham et al. (1995)
(XXII)	2,4-(OMe)₂-phenyl	R¹ ^a	1	N—H···N	C	OSIZOG	Zhou et al. (2010)
(XXIII)	Cy	phenyl	2	N—H···S	A'	VEFKUO	Sahoo et al. (2012)

Note: (a) see Scheme 2 for the chemical diagram of (XXII).

Footnotes

‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.

Acknowledgements

The authors thank the staff of the University of Malaya's X-ray diffraction laboratory for the data collection. Sunway University is thanked for support of biological and crystal engineering studies of carbothioamides and their coinage metal complexes.

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