research communications
A new monoclinic polymorph of N-(3-methylphenyl)ethoxycarbothioamide: and Hirshfeld surface analysis
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
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 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.
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 , 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.
of (Ip), Fig. 1Geometric 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 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 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.
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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.
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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 dnorm 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 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.
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The overall two-dimensional fingerprint plots for the S1 and S11-containing molecules of (Ip), the whole a–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.
of (Ip) and for the polymorph (Ic) are illustrated in Fig. 8
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The fingerprint plots delineated into H⋯H contacts, Fig. 8b and d, have needle-like tips pointing at de + di ∼ 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 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. The increase in percentage contribution from these contacts to the Hirshfeld surface of overall 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 de + di ∼ 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 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. 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 de = di = 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 B 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.
of polymorph (Ip) indicate the presence of short interatomic N⋯H/H⋯N contacts between the thioamide-N1 and tolyl-H185. 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 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
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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 . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the 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. ( 1 4), was omitted from the final cycles of refinement.
details are summarized in Table 7
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Supporting information
CCDC reference: 1585129
https://doi.org/10.1107/S2056989017016280/hb7715sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016280/hb7715Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2011); cell
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).C10H13NOS | F(000) = 832 |
Mr = 195.27 | Dx = 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 |
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 | Rint = 0.040 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.5° |
ω scan | h = −18→18 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −9→9 |
Tmin = 0.662, Tmax = 1.000 | l = −18→25 |
15588 measured reflections |
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(Fo2) + (0.0629P)2 + 0.8006P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.72 e Å−3 |
4577 reflections | Δρmin = −0.24 e Å−3 |
245 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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. |
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. 1b. |
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. |
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). |
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 |
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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