research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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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[Tadbuppa, P. P. & Tiekink, E. R. T. (2005). Z. Kristallogr. New Cryst. Struct. 220, 395-396.]). 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 ππ 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.

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[Taylor, R. L. & Tiekink, E. R. T. (1994). Z. Kristallogr. 209, 64-67.]), 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[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.]; Kuan et al., 2007[Kuan, F. S., Mohr, F., Tadbuppa, P. P. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 574-581.]; Slater et al., 2016[Slater, N. H., Buckley, B. R., Elsegood, M. R. J., Teat, S. J. & Kimber, M. C. (2016). Cryst. Growth Des. 16, 3846-3852.]) and the ability of these mol­ecules to form co-crystals with pyridyl-like mol­ecules (Ellis et al., 2009[Ellis, C. A., Miller, M. A., Spencer, J., Zukerman-Schpector, J. & Tiekink, E. R. T. (2009). CrystEngComm, 11, 1352-1361.]). 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[Yeo, C. I., Halim, S. N. A., Ng, S. W., Tan, S. L., Zukerman-Schpector, J., Ferreira, M. A. B. & Tiekink, E. R. T. (2014). Chem. Commun. 50, 5984-5986.]); inter­molecular versions of C—H⋯π(quasi-chelate ring) inter­actions are also known (Zukerman-Schpector et al., 2016[Zukerman-Schpector, J., Yeo, C. I. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 55-64.]). The anions form very stable compounds with phosphanegold(I) moieties to yield luminescent materials in the solid state (Ho et al., 2006[Ho, S. Y., Cheng, E. C.-C., Tiekink, E. R. T. & Yam, V. W.-W. (2006). Inorg. Chem. 45, 8165-8174.]) as well as potential anti-bacterial (Yeo et al., 2013[Yeo, C. I., Sim, J.-H., Khoo, C.-H., Goh, Z.-J., Ang, K.-P., Cheah, Y.-K., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Gold Bull. 46, 145-152.]) and anti-cancer (Ooi et al., 2017[Ooi, K. K., Yeo, C. I., Mahandaran, T., Ang, K. P., Akim, A. M., Cheah, Y.-K., Seng, H.-L. & Tiekink, E. R. T. (2017). J. Inorg. Biochem. 166, 173-181.]) agents. It was in the latter context that the title polymorph (I)[link] was discovered. Thus, (I)[link] 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[Tadbuppa, P. P. & Tiekink, E. R. T. (2005). Z. Kristallogr. New Cryst. Struct. 220, 395-396.]), hereafter (Ic). In the present report, the crystal and mol­ecule structures of a new monoclinic polymorph of (I)[link], i.e. (Ip), are described along with a Hirshfeld surface analysis of both polymorphs, conducted in order to discover distinctive packing patterns.

[Scheme 1]

2. Structural commentary

The crystallographic asymmetric unit of (Ip), Fig. 1[link], comprises two independent mol­ecules which are chemically indistinguishable, Table 1[link]. 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[link] 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[link], 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-mol­eculea (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. 1[link]b.
[Figure 1]
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]
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)[link], i.e. (Ic), are also included in Table 1[link]. 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[link], 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)[link] 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[link] and Table 2[link]. As shown in Fig. 3[link], the N—H⋯S hydrogen bonds are supported by 3-tolyl-C—H⋯S inter­actions, Table 2[link], with that involving the S1 atom being slightly beyond the standard distance criteria in PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). Globally, like mol­ecules stack along the b-axis direction. The S1-mol­ecules are connected via weak ππ 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[link]. The columns pack into alternating layers of S1- and S11-mol­ecules parallel to [001], Fig. 4[link]a, 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. 4[link]b. The layers, Fig. 4[link]c, 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 DA 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]
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]
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 ππ 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[Tadbuppa, P. P. & Tiekink, E. R. T. (2005). Z. Kristallogr. New Cryst. Struct. 220, 395-396.]) 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[link], 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. 4[link]d and Table 3[link]. 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. 4[link]e. A view of the layer is shown in Fig. 4[link]f.

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[link], 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[Kuan, F. S., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 1465-1471.]). 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 dnorm shown in Fig. 5[link] 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[link]; values in Table 4[link] were obtained from an analysis employing the CrystalExplorer package (Wolff et al. 2012[Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). University of Western Australia.]). 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. 5[link]ac, whereas in form (Ic) they are labelled as 1 and 2 in Fig. 5[link]d and e. In addition to the above, the faint-red spots viewed near 3-tolyl-C14 in Fig. 5[link]b and eth­oxy-H20B in Fig. 5[link]c indicate the significance of short inter­atomic C⋯H/H⋯C contacts, Table 4[link], 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[link]. 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[link]. 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[link].

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]
Figure 5
Views of the Hirshfeld surfaces mapped over dnorm 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]
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]
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. 8[link]ad, 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[McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814-3816.]) are included in Fig. 8[link]; the relative contributions from different inter­atomic contacts to the Hirshfeld surfaces are summarized in Table 5[link]. 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[link]–4[link][link].

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]
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. 8[link]b and d, have needle-like tips pointing at de + di ∼ 2.1 Å indicating short inter­atomic H⋯H contacts, Table 4[link], 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 de + di < 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[link]. 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[link]. 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[link], and also from pair of forceps-like tips at de + di ∼ 2.6 Å with the nearly same distribution of points in their respective fingerprint plots in Fig. 8[link].

The similar distribution of points in the fingerprint plot delineated into C⋯H/H⋯C contacts for the S11-containing mol­ecule of (Ip), Fig. 8[link]b, and of (Ic), Fig. 8[link]d, indicate their involvement in the inter­molecular C—H⋯π contacts showing pairs of tips at de + di ∼ 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[link]. In other words, the contribution from C⋯H/H⋯C contacts to the surface of the S1-containing mol­ecule of (Ip), Table 5[link], 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 ππ stacking inter­actions between the symmetry-related 3-tolyl rings. This is also evident from the arrow-like distribution of points around de = di = 1.8 Å in the C⋯C delineated fingerprint plot shown in Fig. 8[link]a.

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[link], although all of the delineated fingerprint plots have a similar distributions of points, Fig. 8[link], at least to a first approximation. The other inter­atomic contacts summarized in Table 4[link] 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[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]), 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[link], 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[Taylor, R. L. & Tiekink, E. R. T. (1994). Z. Kristallogr. 209, 64-67.]). 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[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.]), motif B, thioamide-N—H⋯O(carb­oxy) hydrogen bonding is observed, leading to a linear supra­molecular chain as shown in Fig. 9[link]a. 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[link]. The structure of (4-pyrid­yl)CH2OC(=S)N(H)phenyl (XIX) (Xiao et al., 2006[Xiao, H.-L., Wang, K.-F. & Jian, F.-F. (2006). Acta Cryst. E62, o2852-o2853.]) 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. 9[link]b. In summary, an inspection of the data in Table 6[link] 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

[Scheme 2]
.

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[Ho, S. Y., Lai, C. S. & Tiekink, E. R. T. (2003). Acta Cryst. E59, o1155-o1156.])
(III) Me 4-NO2-phen­yl 1 N—H⋯S A CAZFUF Ho et al. (2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.])
(IV) Me 4-C(=O)OMe-phen­yl 1 N—H⋯S A CAZGAM Ho et al. (2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.])
(V) Me 4-Cl-phen­yl 2 N—H⋯S A′ CAZCEQ Ho et al. (2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.])
(VI) Me 4-C(=O)Me-phen­yl 1 N—H⋯O B CAZGIU Ho et al. (2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.])
(VII) Me 2-tol­yl 1 N—H⋯S A TAZSIX Kuan et al. (2005[Kuan, F. S., Tadbuppa, P. P. & Tiekink, E. R. T. (2005). Z. Kristallogr. New Cryst. Struct. 220, 393-394.])
(VIII) Me 4-tol­yl 2 N—H⋯S A′ TIBYUZ Ho et al. (2007[Ho, S. Y., Kuan, F. S. & Tiekink, E. R. T. (2007). Acta Cryst. E63, o1723-o1724.])
(IX) Et phen­yl 3 N—H⋯S A′′ PINPIL Taylor & Tiekink (1994[Taylor, R. L. & Tiekink, E. R. T. (1994). Z. Kristallogr. 209, 64-67.])
(Ip) Et 3-tol­yl 2 N—H⋯S A′ This work
(Ip) Et 3-tol­yl 1 N—H⋯S A′′′ TAZTUK Tadbuppa & Tiekink (2005[Tadbuppa, P. P. & Tiekink, E. R. T. (2005). Z. Kristallogr. New Cryst. Struct. 220, 395-396.])
(X) Et 4-tol­yl 1 N—H⋯S A TIBYOT Tadbuppa & Tiekink (2007a[Tadbuppa, P. P. & Tiekink, E. R. T. (2007a). Acta Cryst. E63, o1779-o1780.])
(XI) Et 3-OMe-phen­yl 1 N—H⋯S A UDUPAL Hanif et al. (2007[Hanif, M., Qadeer, G., Shi, L. & Rama, N. H. (2007). Acta Cryst. E63, o3062.])
(XII) Et 4-NO2-phen­yl 1 N—H⋯S A NENLAU Benson et al. (2006[Benson, R. E., Broker, G. A., Daniels, L. M., Tiekink, E. R. T., Wardell, J. L. & Young, D. J. (2006). Acta Cryst. E62, o4106-o4108.])
(XIII) Et 4-Cl-phen­yl 1 N—H⋯S A DEYQEE Tadbuppa & Tiekink (2007b[Tadbuppa, P. P. & Tiekink, E. R. T. (2007b). Acta Cryst. E63, o1885-o1886.])
(XIV) n-Pr phen­yl 2 N—H⋯S A′ PAWKAB Sudkaow et al. (2012[Sudkaow, P., Yeo, C. I., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o1774.])
(XV) i-Pr Ph 1 N—H⋯S A ADOGUW Kuan et al. (2007[Kuan, F. S., Mohr, F., Tadbuppa, P. P. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 574-581.])
(XVI) i-Pr 4-tol­yl 1 N—H⋯S A ADOGOQ Kuan et al. (2007[Kuan, F. S., Mohr, F., Tadbuppa, P. P. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 574-581.])
(XVII) i-Pr 4-Cl-phen­yl 1 N—H⋯S A ADOHAD Kuan et al. (2007[Kuan, F. S., Mohr, F., Tadbuppa, P. P. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 574-581.])
(XVIII) i-Pr 4-NO2-phen­yl 1 N—H⋯S A MISDEY Ellis et al. (2008[Ellis, C. A., Tiekink, E. R. T. & Zukerman-Schpector, J. (2008). Acta Cryst. E64, o345.])
(XIX) 4-pyridyl­meth­yl phen­yl 2 N—H⋯N C IFACOI Xiao et al. (2006[Xiao, H.-L., Wang, K.-F. & Jian, F.-F. (2006). Acta Cryst. E62, o2852-o2853.])
(XX) i-Bu phen­yl 1 N—H⋯S A′′′ KEQJAS Jian et al. (2006[Jian, F.-F., Yu, H.-Q., Qiao, Y.-B. & Liang, T.-L. (2006). Acta Cryst. E62, o3416-o3417.])
(XXI) 2,4-Me2-phen­yl phen­yl 1 N—H⋯S A POVVOL Abraham et al. (1995[Abraham, S. P., Samuelson, A. G. & Nethaji, M. (1995). Proc. Indian Acad. Sci. Chem. Sci. 107, 255-271.])
(XXII) 2,4-(OMe)2-phen­yl R1a 1 N—H⋯N C OSIZOG Zhou et al. (2010[Zhou, L., Tan, C. K., Jiang, X., Chen, F. & Yeung, Y.-Y. (2010). J. Am. Chem. Soc. 132, 15474-15476.])
(XXIII) Cy phen­yl 2 N—H⋯S A′ VEFKUO Sahoo et al. (2012[Sahoo, S. K., Chakraborty, S. & Patel, B. K. (2012). J. Sulfur Chem. 33, 143-153.])
Note: (a) see Scheme 2 for the chemical diagram of (XXII)[link].
[Figure 9]
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[link]. 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 Uiso(H) set to 1.2–1.5Ueq(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 Uiso(H) set to 1.2Ueq(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
Mr 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)
V3) 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[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.662, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 15588, 4577, 3514
Rint 0.040
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.72, −0.24
Computer programs: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), QMol (Gans & Shalloway, 2001[Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, 557-609.]), DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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
C10H13NOSF(000) = 832
Mr = 195.27Dx = 1.282 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.3999 (5) ÅCell parameters from 6144 reflections
b = 7.0388 (3) Åθ = 2.4–27.5°
c = 19.9725 (7) ŵ = 0.28 mm1
β = 91.727 (3)°T = 100 K
V = 2023.45 (13) Å3Slab, colourless
Z = 80.20 × 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 Source3514 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.040
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 2.5°
ω scanh = 1818
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 99
Tmin = 0.662, Tmax = 1.000l = 1825
15588 measured reflections
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0629P)2 + 0.8006P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.125(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.72 e Å3
4577 reflectionsΔρmin = 0.24 e Å3
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
xyzUiso*/Ueq
S10.63595 (3)0.62560 (8)0.29847 (2)0.02560 (15)
O10.48087 (9)0.6728 (2)0.36508 (7)0.0205 (3)
N10.61175 (11)0.6959 (2)0.42674 (8)0.0176 (3)
H1N0.6720 (7)0.683 (3)0.4295 (11)0.021*
C10.57256 (13)0.6663 (3)0.36605 (10)0.0183 (4)
C20.57411 (12)0.7410 (3)0.48972 (9)0.0157 (4)
C30.63901 (13)0.7851 (3)0.54059 (10)0.0198 (4)
H30.70350.78280.53180.024*
C40.60988 (14)0.8320 (3)0.60359 (10)0.0224 (4)
H40.65450.86040.63820.027*
C50.51590 (14)0.8380 (3)0.61691 (10)0.0214 (4)
H50.49630.87190.66030.026*
C60.45044 (13)0.7944 (3)0.56662 (10)0.0189 (4)
C70.47948 (13)0.7455 (3)0.50316 (10)0.0185 (4)
H70.43490.71510.46880.022*
C80.34802 (13)0.8043 (3)0.58036 (11)0.0258 (5)
H8A0.31570.69890.55760.039*
H8B0.32270.92520.56370.039*
H8C0.33910.79520.62870.039*
C90.43042 (14)0.6465 (3)0.30146 (10)0.0250 (5)
H9A0.44330.51930.28270.030*
H9B0.44890.74400.26870.030*
C100.33069 (15)0.6655 (4)0.31611 (12)0.0334 (5)
H10A0.29340.64930.27470.050*
H10B0.31920.79170.33490.050*
H10C0.31350.56800.34850.050*
S110.85195 (3)0.66025 (9)0.45041 (2)0.02577 (15)
O110.99877 (9)0.7448 (2)0.37829 (6)0.0192 (3)
N110.86976 (10)0.6753 (2)0.31952 (8)0.0175 (3)
H11N0.8103 (7)0.652 (3)0.3174 (11)0.021*
C110.91055 (13)0.6951 (3)0.38026 (10)0.0185 (4)
C120.90609 (12)0.7096 (3)0.25516 (9)0.0156 (4)
C130.84323 (12)0.7751 (3)0.20604 (9)0.0179 (4)
H130.78020.79670.21650.021*
C140.87304 (13)0.8082 (3)0.14206 (9)0.0193 (4)
H140.83030.85230.10840.023*
C150.96520 (13)0.7774 (3)0.12656 (9)0.0192 (4)
H150.98540.80190.08250.023*
C161.02797 (13)0.7108 (3)0.17527 (10)0.0177 (4)
C170.99808 (13)0.6749 (3)0.23923 (9)0.0176 (4)
H171.04040.62650.27240.021*
C181.12821 (13)0.6769 (3)0.15808 (10)0.0245 (5)
H18A1.15660.58770.19040.037*
H18B1.16220.79750.15990.037*
H18C1.13080.62340.11290.037*
C191.05091 (14)0.7744 (3)0.44091 (10)0.0256 (5)
H19A1.04930.65840.46890.031*
H19B1.02380.88060.46630.031*
C201.14753 (15)0.8193 (4)0.42346 (12)0.0349 (5)
H20A1.18400.84900.46430.052*
H20B1.14770.92910.39330.052*
H20C1.17500.70960.40120.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0230 (3)0.0401 (3)0.0140 (3)0.0017 (2)0.00422 (18)0.0020 (2)
O10.0190 (7)0.0284 (8)0.0141 (7)0.0011 (6)0.0009 (5)0.0020 (6)
N10.0155 (7)0.0236 (9)0.0139 (8)0.0005 (7)0.0022 (6)0.0005 (7)
C10.0200 (9)0.0174 (10)0.0176 (10)0.0011 (8)0.0017 (7)0.0017 (8)
C20.0211 (9)0.0129 (9)0.0132 (9)0.0008 (7)0.0039 (7)0.0011 (7)
C30.0182 (9)0.0233 (11)0.0178 (10)0.0014 (8)0.0019 (7)0.0004 (8)
C40.0251 (10)0.0262 (11)0.0157 (10)0.0002 (9)0.0014 (8)0.0010 (8)
C50.0279 (10)0.0234 (11)0.0133 (9)0.0026 (8)0.0052 (7)0.0009 (8)
C60.0205 (9)0.0181 (10)0.0184 (10)0.0003 (8)0.0052 (7)0.0035 (8)
C70.0199 (9)0.0203 (10)0.0154 (10)0.0016 (8)0.0014 (7)0.0020 (8)
C80.0226 (10)0.0331 (12)0.0221 (11)0.0014 (9)0.0077 (8)0.0024 (9)
C90.0254 (10)0.0337 (12)0.0155 (10)0.0020 (9)0.0057 (8)0.0002 (9)
C100.0267 (11)0.0404 (14)0.0329 (13)0.0041 (10)0.0037 (9)0.0003 (11)
S110.0225 (3)0.0423 (3)0.0127 (3)0.0072 (2)0.00474 (18)0.0035 (2)
O110.0203 (7)0.0236 (8)0.0137 (7)0.0012 (6)0.0003 (5)0.0007 (6)
N110.0147 (7)0.0238 (9)0.0141 (8)0.0025 (7)0.0027 (6)0.0016 (7)
C110.0200 (9)0.0200 (10)0.0155 (9)0.0075 (8)0.0027 (7)0.0009 (8)
C120.0196 (9)0.0152 (9)0.0121 (9)0.0005 (7)0.0031 (7)0.0003 (7)
C130.0154 (9)0.0225 (10)0.0158 (10)0.0017 (8)0.0006 (7)0.0010 (8)
C140.0219 (9)0.0217 (10)0.0141 (9)0.0031 (8)0.0032 (7)0.0010 (8)
C150.0242 (10)0.0225 (10)0.0110 (9)0.0033 (8)0.0030 (7)0.0001 (8)
C160.0198 (9)0.0161 (9)0.0175 (10)0.0014 (8)0.0042 (7)0.0007 (8)
C170.0201 (9)0.0165 (9)0.0162 (10)0.0029 (8)0.0010 (7)0.0010 (8)
C180.0236 (10)0.0286 (12)0.0217 (11)0.0038 (9)0.0090 (8)0.0029 (9)
C190.0265 (10)0.0323 (12)0.0176 (10)0.0042 (9)0.0044 (8)0.0055 (9)
C200.0302 (12)0.0359 (14)0.0382 (14)0.0012 (10)0.0047 (10)0.0008 (11)
Geometric parameters (Å, º) top
S1—C11.6768 (19)S11—C111.6752 (19)
O1—C11.321 (2)O11—C111.319 (2)
O1—C91.457 (2)O11—C191.454 (2)
N1—C11.338 (2)N11—C111.339 (2)
N1—C21.421 (2)N11—C121.423 (2)
N1—H1N0.872 (9)N11—H11N0.872 (9)
C2—C31.394 (3)C12—C131.393 (3)
C2—C71.397 (2)C12—C171.393 (2)
C3—C41.378 (3)C13—C141.380 (3)
C3—H30.9500C13—H130.9500
C4—C51.388 (3)C14—C151.389 (3)
C4—H40.9500C14—H140.9500
C5—C61.391 (3)C15—C161.389 (3)
C5—H50.9500C15—H150.9500
C6—C71.390 (3)C16—C171.383 (3)
C6—C81.510 (3)C16—C181.513 (2)
C7—H70.9500C17—H170.9500
C8—H8A0.9800C18—H18A0.9800
C8—H8B0.9800C18—H18B0.9800
C8—H8C0.9800C18—H18C0.9800
C9—C101.480 (3)C19—C201.479 (3)
C9—H9A0.9900C19—H19A0.9900
C9—H9B0.9900C19—H19B0.9900
C10—H10A0.9800C20—H20A0.9800
C10—H10B0.9800C20—H20B0.9800
C10—H10C0.9800C20—H20C0.9800
C1—O1—C9118.72 (15)C11—O11—C19119.01 (15)
C1—N1—C2132.48 (16)C11—N11—C12129.60 (16)
C1—N1—H1N115.6 (15)C11—N11—H11N117.9 (15)
C2—N1—H1N111.9 (15)C12—N11—H11N112.0 (15)
O1—C1—N1113.71 (16)O11—C11—N11113.39 (16)
O1—C1—S1124.23 (14)O11—C11—S11125.00 (15)
N1—C1—S1122.06 (14)N11—C11—S11121.61 (15)
C3—C2—C7119.42 (17)C13—C12—C17119.95 (17)
C3—C2—N1115.45 (16)C13—C12—N11116.33 (16)
C7—C2—N1125.13 (17)C17—C12—N11123.68 (17)
C4—C3—C2120.17 (17)C14—C13—C12119.62 (17)
C4—C3—H3119.9C14—C13—H13120.2
C2—C3—H3119.9C12—C13—H13120.2
C3—C4—C5120.51 (18)C13—C14—C15120.40 (17)
C3—C4—H4119.7C13—C14—H14119.8
C5—C4—H4119.7C15—C14—H14119.8
C4—C5—C6119.90 (18)C14—C15—C16120.16 (17)
C4—C5—H5120.0C14—C15—H15119.9
C6—C5—H5120.0C16—C15—H15119.9
C7—C6—C5119.81 (17)C17—C16—C15119.61 (17)
C7—C6—C8119.97 (18)C17—C16—C18120.42 (18)
C5—C6—C8120.21 (17)C15—C16—C18119.96 (17)
C6—C7—C2120.18 (18)C16—C17—C12120.22 (18)
C6—C7—H7119.9C16—C17—H17119.9
C2—C7—H7119.9C12—C17—H17119.9
C6—C8—H8A109.5C16—C18—H18A109.5
C6—C8—H8B109.5C16—C18—H18B109.5
H8A—C8—H8B109.5H18A—C18—H18B109.5
C6—C8—H8C109.5C16—C18—H18C109.5
H8A—C8—H8C109.5H18A—C18—H18C109.5
H8B—C8—H8C109.5H18B—C18—H18C109.5
O1—C9—C10106.11 (17)O11—C19—C20107.04 (17)
O1—C9—H9A110.5O11—C19—H19A110.3
C10—C9—H9A110.5C20—C19—H19A110.3
O1—C9—H9B110.5O11—C19—H19B110.3
C10—C9—H9B110.5C20—C19—H19B110.3
H9A—C9—H9B108.7H19A—C19—H19B108.6
C9—C10—H10A109.5C19—C20—H20A109.5
C9—C10—H10B109.5C19—C20—H20B109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
C9—C10—H10C109.5C19—C20—H20C109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5
C9—O1—C1—N1178.80 (17)C19—O11—C11—N11178.92 (17)
C9—O1—C1—S11.1 (3)C19—O11—C11—S110.6 (3)
C2—N1—C1—O13.2 (3)C12—N11—C11—O113.8 (3)
C2—N1—C1—S1176.68 (16)C12—N11—C11—S11175.77 (16)
C1—N1—C2—C3172.1 (2)C11—N11—C12—C13147.0 (2)
C1—N1—C2—C77.3 (3)C11—N11—C12—C1735.4 (3)
C7—C2—C3—C40.2 (3)C17—C12—C13—C141.1 (3)
N1—C2—C3—C4179.66 (18)N11—C12—C13—C14178.82 (17)
C2—C3—C4—C50.7 (3)C12—C13—C14—C150.3 (3)
C3—C4—C5—C60.7 (3)C13—C14—C15—C160.7 (3)
C4—C5—C6—C70.2 (3)C14—C15—C16—C170.1 (3)
C4—C5—C6—C8178.83 (19)C14—C15—C16—C18179.80 (18)
C5—C6—C7—C20.3 (3)C15—C16—C17—C121.5 (3)
C8—C6—C7—C2178.33 (18)C18—C16—C17—C12178.84 (18)
C3—C2—C7—C60.3 (3)C13—C12—C17—C162.0 (3)
N1—C2—C7—C6179.08 (18)N11—C12—C17—C16179.53 (17)
C1—O1—C9—C10178.76 (17)C11—O11—C19—C20177.42 (18)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the (C12–C17) ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···S110.87 (1)2.62 (1)3.4859 (16)174 (2)
N11—H11N···S10.87 (1)2.54 (1)3.3985 (15)171 (2)
C3—H3···S110.952.863.708 (2)150
C13—H13···S10.952.943.7090 (19)139
C17—H17···Cg1i0.952.823.471 (2)127
Symmetry code: (i) x+2, y1/2, z+1/2.
Selected geometric parameters (Å, °) in (Ip) and (Ic) top
Parameter(Ip), S1-molecule(Ip), S11-moleculea(Ic)
C1—S11.6768 (19)1.6752 (19)1.6720 (18)
C1—O11.321 (2)1.319 (2)1.325 (2)
C1—N11.338 (2)1.339 (2)1.337 (2)
C9—O11.457 (2)1.454 (2)1.451 (2)
C2—N11.421 (2)1.423 (2)1.426 (2)
S1—C1—O1124.23 (14)125.00 (15)124.53 (12)
S1—C1—N1122.06 (14)121.61 (15)122.11 (13)
O1—C1—N1113.71 (16)113.39 (16)113.37 (15)
C1—O1—C9118.72 (15)119.01 (15)119.29 (15)
C1—N1—C2132.48 (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···AD—HH···AD···AD—H···A
N1—H1n···S1i0.872.583.4142 (16)160
C7—H7···Cg1ii0.942.913.4973 (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
ContactDistanceSymmetry operation
(Ip)
H3···H142.35x, 3/2 - y, -1/2 + z
H5···H9B2.28x, 3/2 - y, 1/2 + z
H15···H19A2.31x, 3/2 - y, -1/2 + z
H19B···H19B2.082 - x, 2 - y, 1 - z
C10···H20C2.87-1 + x, y, z
C14···H20B2.772 - x, -1/2 + yy, 1/2 - z
N1···H18B2.732 - x, -1/2 + yy, 1/2 - z
(Ic)
H7···H9b2.371/2 + x, 1/2 - y, 1/2 + z
H9a···H9a2.11-x, -y, -z
H10b···H10b2.321/2 - 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
ContactPercentage contribution
(Ip), S1-molecule(Ip), S11-moleculeoverall (Ip)(Ic)
H···H57.455.561.757.0
S···H/H···S17.617.410.017.3
C···H/H···C14.018.817.817.3
C···C3.91.53.01.9
N···H/H···N2.62.93.02.6
C···O/O···C2.52.52.72.4
O···H/H···O1.01.21.21.1
C···N/N···C0.90.30.60.4
Hydrogen-bonding patterns in ROC(S)N(H)R' top
NumberRR'Z'Hydrogen bondsMotifRefcodeRef.
(II)Mephenyl1N—H···SAOJIHAQHo et al. (2003)
(III)Me4-NO2-phenyl1N—H···SACAZFUFHo et al. (2005)
(IV)Me4-C(O)OMe-phenyl1N—H···SACAZGAMHo et al. (2005)
(V)Me4-Cl-phenyl2N—H···SA'CAZCEQHo et al. (2005)
(VI)Me4-C(O)Me-phenyl1N—H···OBCAZGIUHo et al. (2005)
(VII)Me2-tolyl1N—H···SATAZSIXKuan et al. (2005)
(VIII)Me4-tolyl2N—H···SA'TIBYUZHo et al. (2007)
(IX)Etphenyl3N—H···SA''PINPILTaylor & Tiekink (1994)
(Ip)Et3-tolyl2N—H···SA'This work
(Ip)Et3-tolyl1N—H···SA'''TAZTUKTadbuppa & Tiekink (2005)
(X)Et4-tolyl1N—H···SATIBYOTTadbuppa & Tiekink (2007a)
(XI)Et3-OMe-phenyl1N—H···SAUDUPALHanif et al. (2007)
(XII)Et4-NO2-phenyl1N—H···SANENLAUBenson et al. (2006)
(XIII)Et4-Cl-phenyl1N—H···SADEYQEETadbuppa & Tiekink (2007b)
(XIV)n-Prphenyl2N—H···SA'PAWKABSudkaow et al. (2012)
(XV)i-PrPh1N—H···SAADOGUWKuan et al. (2007)
(XVI)i-Pr4-tolyl1N—H···SAADOGOQKuan et al. (2007)
(XVII)i-Pr4-Cl-phenyl1N—H···SAADOHADKuan et al. (2007)
(XVIII)i-Pr4-NO2-phenyl1N—H···SAMISDEYEllis et al. (2008)
(XIX)4-pyridylmethylphenyl2N—H···NCIFACOIXiao et al. (2006)
(XX)i-Buphenyl1N—H···SA'''KEQJASJian et al. (2006)
(XXI)2,4-Me2-phenylphenyl1N—H···SAPOVVOLAbraham et al. (1995)
(XXII)2,4-(OMe)2-phenylR1 a1N—H···NCOSIZOGZhou et al. (2010)
(XXIII)Cyphenyl2N—H···SA'VEFKUOSahoo 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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