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Two new polymorph forms, (Ia) and (Ib), of the title compound, C14H17N3S, and its solvate with aceto­nitrile, C14H17N3S·0.25C2H3N, (Ic), have been investigated. Crystals of the two polymorphs were grown from different solvents, viz. ethanol and N,N-di­methyl­form­amide, respectively. The polymorphs have different orientations of the thio­amide group relative to the CN substituent, with s-cis and s-trans geometry of the C=C-C=S diene fragment, respectively. Compound (Ic) contains two independent mol­ecules, A and B, with s-cis geometry, and the solvate mol­ecule lies on a twofold axis. The core of each mol­ecule is slightly non-planar; the dihedral angles between the conjugated C=C-CN linkage and the phenyl ring, and between this linkage and the thio­amide group are 13.4 (2) and 12.0 (2)° in (Ia), 14.0 (2) and 18.2 (2)° in (Ib), 2.3 (3) and 12.7 (4)° in molecule A of (Ic), and 23.2 (3) and 8.1 (4)° in molecule B of (Ic). As a result of strong conjugation between donor and acceptor parts, the substituted phenyl rings have noticeable quinoid character. In (Ib), there exists a very strong intramolecular steric interaction (H...H = 1.95 Å) between the bridging and thio­amide parts of the mol­ecule, which makes such a form less stable. In the crystal structure of (Ia), intermolecular N-H...N and N-H...S hydrogen bonds link mol­ecules into infinite tapes along the [1\overline 10] direction. In (Ib), such intermolecular hydrogen bonds link mol­ecules into infinite (101) planes. In (Ic), intermolecular N-H...N hydrogen bonds link mol­ecules A and B into dimers, which are connected via N-H...S hydrogen bonds and form infinite chains along the c direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010402150X/sq1169sup1.cif
Contains datablocks Ia, Ib, Ic, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Ibsup3.hkl
Contains datablock Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Icsup4.hkl
Contains datablock Ic

CCDC references: 257005; 257006; 257007

Comment top

The present investigation is a continuation of a project that includes the syntheses and structural studies of polar conjugated organic compounds that crystallize in non-centrosymmetric space groups (Antipin et al., 1998; V. N. Nesterov et al., 1998, 2000; V. V. Nesterov et al., 2004a,2004b). These compounds may find application in nonlinear optical materials (Zyss et al., 1994; Kuzyk & Dirk, 1998) and in the syntheses of heterocyclic compounds (Brunskill et al., 1984; Nesterov et al., 2002). Moreover, related compounds have found application as potential antitumor drugs (Hutchinson et al., 2001; Thacher et al., 2001; Wermuth, 2004). During thorough and systematic work, we have found many compounds that crystallize in different space groups and reveal polymorphism (Timofeeva et al., 2000, 2003a, 2003b; Wang et al., 2001). Thus, cocrystallization of such compounds with chiral molecules can build acentric crystalline structures or polymorphs (Timofeeva et al., 2000), and polymorphism is a very important phenomenon in the pharmaceutical industry (Davey et al., 1997; Bernstein, 2002).

In this paper, we present interesting results that were obtained working with compound (I). X-ray structural investigations have been carried out for two polymorphs, viz. orange triclinic (Ia) and red monoclinic (Ib) (Figs. 1 and 2), and for a complex, (Ic) (Fig. 3), of (I) with acetonitrile. In an attempt to find other crystalline forms, crystals of (I) have been grown from several solvents, including ethanol, propane-2-ol, acetonitrile, toluene, chloroform and their mixtures. In almost all cases, we obtained crystals of the (Ia) modification, and only from acetonitrile did we obtain complex (Ic). Starting with (I), we have synthesized several thiazole derivative compounds, using dimethylformamide (DMF) as a solvent. In one case, from the reaction mixture were separated crystals with different shapes, viz. red prisms (several crystals) and orange plates. The first crystals were another monoclinic modification, (Ib), of the starting material, while the second crystals were the thiazole product. According to the Cambridge Structural Database (CSD; Allen, 2003), the structure of another monoclinic modification, (Id), of (I) has been investigated (Brunskill et al., 1984). All our attempts to obtain complexes of (I) with L-proline and L-tartaric acid, using different solvents and different crystallization conditions, gave only good crystals of polymorph (Ia).

As seen in Figs. 1 and 2, the main distinction between (Ia) and (Ib) is the different orientation of the thioamide group relative to the CN substituent (two rotamers). ?In accordance with the results of Brunskill et al. (1984), in these cases we obtained two forms with s-cis and s-trans geometry of the C=C—C=S fragment. Although conformer (Id) has a structure similar to that of (Ib), the values of the C7—C8—C10—S1 torsion angles are different [159.4 (1)° in (Ib) and −158.5° in (Id)]. In both independent molecules, A and B, of (Ic), the orientation of this substituent is similar to that in (Ia) (Fig. 3), but compounds (Ic) and (Ia) also have different dihedral angles (see below). The rotatation of the thioamide group about the C8—C10 single bond is a possible reason for the existence of the three modifications.

Most of the geometric parameters in the investigated molecules (Ia)–(Ic) are very similar. The molecular skeleton of each molecule is slightly non-planar; the dihedral angles between the conjugated linkage (C=C—CN) and the phenyl ring, and between this linkage and the thioamide group, are 13.4 (2) and 12.0 (2)° in (Ia), 14.0 (2) and 18.2 (2) in (Ib), and 2.3 (3)/23.2 (3) and 12.7 (4)/8.1 (4)° in (Ic) for the two independent molecules A and B, respectively. Such slight non-planarity is not sufficient to preclude conjugation between aryl and CN groups via a C=C-bridged fragment. Really, because of the strong conjugation between donor and acceptor parts in these molecules, the substituted phenyl rings have a noticeably quinoid character (Tables 1, 3 and 5). Moreover, the dihedral angles between the trigonal diethylamine substituent [in all structures the sum of bond angles around the N atom is 359.5 (2)°] and the phenyl ring are small [5.6 (2)° in (Ia), 10.7 (2)° in (Ib), and 10.6 (4) and 10.4 (4)° in molecules A and B of (Ic)]. In all compounds, the N3—C4 bond length [range 1.351 (4)–1.369 (4) Å] is comparable to the average conjugated C—N single bond (1.370 Å) and is distinctly shorter than the average non-conjugated C—N single bond (1.430 Å) found in the CSD. Furthermore, the C1—C7 and C7=C8 bond lengths also have noticeable differences in comparison with standard distances (Allen et al., 1987).

As seen in Tables 1, 3 and 5, all of the molecules possess a strong conjugation in the thioamide fragment. The C=S bond lengths are distinctly elongated, while the C—N bonds have a partly double-bond character. In our previous work (Nesterov et al., 1986), we have analyzed such conjugation in the thioamide fragments. As mentioned above, the deviations of the thioamide groups in (Ia)–(Ic) from the bridged plane are not significant, but the C8—C10 bond lengths are equal or slightly elongated compared with the conjugated C—C bond (1.470 Å; Allen et al., 1987).

The planarity of the molecules leads to the existence of shortened H···C/H intramolecular contacts [H6A···C9 = 2.38 Å and H2A···C9 = 2.28 Å in (Ia); H6A···C9 = 2.52 Å and H7A···H2A = 1.95 Å in (Ib); and H6AA···C9A = 2.44 Å and H2AA···C9A = 2.25 Å, and H6BA···C9B 2.48 Å and H2BA···C9B 2.33 Å, in molecules A and B of (Ic), respectively]. In (Ib) there exists a very strong steric H···H interaction between the bridging and thioamide parts of the molecule. The same short steric contact is also found in the monoclinic form (Id) at 2.04 Å. Probably, the presence of such short contacts indicates that polymorphs (Ib) and (Id) are energetically less stable than (Ia). This is perhaps the reason that we were unable to obtain polymorphs (Ib) and (Id) again in our work. Such intramolecular interactions are the reason for the elongation of the C8—C10 bond lengths.

The crystal packings of (Ia) and (Ib) are different. In (Ia), intermolecular N—H···N and N—H···S hydrogen bonds link molecules in two centrosymmetric dimmers to build infinite tapes along the [1–10] direction (Fig. 4 and Table 2). However, in (Ib), such hydrogen bonds link molecules into infinite planes (101) (Fig. 5 and Table 4). In the case of (Ic), intermolecular N—H···N hydrogen bonds link molecules A and B into dimers, which are connected via N—H···S hydrogen bonds and form infinite chains along the c direction (Fig. 6 and Table 6). In molecule B, one atom of the NH2 group (H2BB) does not participate in hydrogen bonding. The intermolecular distance between atoms H2BB and S1A of molecules A and B (3.05 Å) is greater than the sum of van der Waals radii of the atoms (Rowland & Taylor, 1996).

According to the foregoing results, previously studied compounds (Nesterov et al., 2003) having 4-diethylamine substituents that occupy different positions relative to the phenyl ring (two CH3 groups above a plane or disordered) might also yield polymorphic forms.

Experimental top

The title compound, (I), was synthesized by the reaction of 4-diethylaminobenzaldehyde with 2-cyanothioacetamide in the presence of a catalytic amount of morpholine in ethanol at room temperature. The precipitate was separated from the solution, and the structure and purity were investigated by NMR (m.p. 421–425 K, yield 83%). Probably, the reason for the large melting interval is the mixture of isomers present. After recrystallization from ethanol, only crystals of (Ia) (m.p. 424–425 K) were found. Crystals of (Ic) were obtained by slow isothermal evaporation from an acetonitrilic solution of (I). Compound (I) was used to synthesize a 2,4-disubstituted thiazole derivative, using DMF as a solvent. From one such reaction mixture were extracted two types of crystals with different shapes. X-ray analysis revealed that one of these forms was (Ia)? and another was a monoclinic modification, (Ib). All attempts to re-obtain polymorph (Ib), complex (Ic) and the literature polymorph (Id), using exactly the same conditions and variations of them, gave us only (Ia). Polymorph (Ia) is probably the most stable energetically. 1H NMR (CDCl3, 300 MHz): δ 8.65 (s, 1H, C7H), 7.96 (d, 2H, J = 9.2 Hz, C2, C6), 7.57 (br s, 1H, NH), 7.36 (br s, 1H, NH), 6.69 (d, 2H, J = 9.2 Hz, C3, C5), 3.47 (q, 4H, J = 7.1 Hz, 2CH2), 1.24 (t, 6H, J = 7.2 Hz, 2CH3). 13C NMR (CDCl3, 75 MHz): δ 193.6 (C=S), 158.1 (C7), 152.0 (C4), 134.9 (C2, C6), 119.3 (C1), 118.3 (C9), 111.3 (C3, C5), 98.7 (C8), 44.8 (2CH2), 12.5 (2CH3).

Refinement top

For all molecules of (Ia)–(Ic), H atoms were placed in calculated positions and included in the refinement using a riding model, with C—H or N—H distances of 0.93 Å for aromatic H atoms, 0.97 Å for CH2 atoms and 0.86 Å for NH2 atoms [Uiso(H) = 1.2Ueq(C,N)], and with C—H distances of 0.96 Å for CH3 groups [Uiso(H) = 1.5Ueq(C)]. The H atoms in the disordered acetonitrile molecule (which lies on a twofold axis) were found from a difference Fourier map and included using AFIX 33, with an occupancy of 0.5 and with C—H = 0.96 Å and Uiso(H) values of 1.5Ueq(C).

Computing details top

For all compounds, data collection: CAD-4 Software (Enraf–Nonuis, 1989); cell refinement: CAD-4 Software; data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of polymorph (Ia), showing the atom numbering used. The non-H atoms in Figs. 1–3 are shown with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of polymorph (Ib), showing the atom numbering used.
[Figure 3] Fig. 3. A view of complex (Ic), showing the atom numbering used. The dashed line represents the intermolecular N—H···S hydrogen bond.
[Figure 4] Fig. 4. A projection of the crystal packing of (Ia) along the b axis. Dashed lines represent intermolecular N—H···N and N—H···S hydrogen bonds.
[Figure 5] Fig. 5. A projection of the crystal packing of (Ib) along the a axis. Dashed lines represent intermolecular N—H···N and N—H···S hydrogen bonds.
[Figure 6] Fig. 6. A projection of the crystal packing of (Ic) along the b axis. Dashed lines represent intermolecular N—H···N and N—H···S hydrogen bonds.
(Ia) 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide top
Crystal data top
C14H17N3SZ = 2
Mr = 259.38F(000) = 276
Triclinic, P1Dx = 1.220 Mg m3
a = 8.753 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.890 (3) ÅCell parameters from 24 reflections
c = 10.830 (4) Åθ = 11–12°
α = 85.44 (3)°µ = 0.22 mm1
β = 69.76 (2)°T = 298 K
γ = 63.65 (3)°Plate, orange
V = 705.8 (5) Å30.50 × 0.40 × 0.20 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.016
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 2.0°
Graphite monochromatorh = 010
θ/2θ scansk = 910
2639 measured reflectionsl = 1212
2465 independent reflections3 standard reflections every 97 reflections
1811 reflections with I > 2σ(I) intensity decay: 3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.06P)2]
where P = (Fo2 + 2Fc2)/3
2465 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C14H17N3Sγ = 63.65 (3)°
Mr = 259.38V = 705.8 (5) Å3
Triclinic, P1Z = 2
a = 8.753 (3) ÅMo Kα radiation
b = 8.890 (3) ŵ = 0.22 mm1
c = 10.830 (4) ÅT = 298 K
α = 85.44 (3)°0.50 × 0.40 × 0.20 mm
β = 69.76 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.016
2639 measured reflections3 standard reflections every 97 reflections
2465 independent reflections intensity decay: 3%
1811 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.00Δρmax = 0.15 e Å3
2465 reflectionsΔρmin = 0.18 e Å3
165 parameters
Special details top

Experimental. 1H NMR (CDCl3, 300 MHz) δ 8.65 (s, 1H, C7H), 7.96 (d, 2H, J = 9.2 Hz, C2, C6), 7.57 (br s, 1H, NH), 7.36 (br s, 1H, NH), 6.69 (d, 2H, J = 9.2 Hz, C3, C5), 3.47 (q, 4H, J = 7.1 Hz, 2CH2), 1.24 (t, 6H, J = 7.2 Hz, 2CH3) p.p.m.. 13C NMR (CDCl3, 75 MHz) δ 193.6 (C=S), 158.1 (C7), 152.0 (C4), 134.9 (C2, C6), 119.3 (C1), 118.3 (C9), 111.3 (C3, C5), 98.7 (C8), 44.8 (2CH2), 12.5 (2CH3) p.p.m..

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S11.34596 (6)0.02000 (6)0.23115 (5)0.06403 (19)
N10.9459 (3)0.6025 (2)0.13473 (16)0.0829 (6)
N21.2768 (2)0.2136 (2)0.04250 (15)0.0717 (5)
H2A1.21330.30430.01360.086*
H2B1.37220.13490.01190.086*
N30.32237 (18)0.78661 (18)0.76587 (13)0.0560 (4)
C10.8086 (2)0.4485 (2)0.47908 (16)0.0489 (4)
C20.7254 (2)0.3960 (2)0.59772 (16)0.0564 (5)
H2C0.78000.28320.61330.068*
C30.5674 (2)0.5034 (2)0.69165 (17)0.0569 (5)
H3A0.51670.46180.76830.068*
C40.4797 (2)0.6764 (2)0.67435 (16)0.0495 (4)
C50.5639 (2)0.7303 (2)0.55641 (17)0.0597 (5)
H5A0.51170.84350.54150.072*
C60.7201 (2)0.6210 (2)0.46323 (17)0.0594 (5)
H6A0.77020.66210.38600.071*
C70.9722 (2)0.3269 (2)0.38408 (16)0.0488 (4)
H7A1.02570.22320.41580.059*
C81.0623 (2)0.33738 (19)0.25591 (16)0.0479 (4)
C90.9949 (2)0.4865 (2)0.19119 (17)0.0571 (5)
C101.2277 (2)0.1950 (2)0.17130 (17)0.0520 (4)
C110.2325 (2)0.7332 (2)0.88957 (17)0.0617 (5)
H11A0.25180.61910.87400.074*
H11B0.10270.80580.91820.074*
C120.3009 (3)0.7389 (3)0.9972 (2)0.0857 (7)
H12A0.24100.69921.07510.129*
H12B0.27600.85281.01660.129*
H12C0.42970.66840.96910.129*
C130.2428 (2)0.9689 (2)0.75219 (18)0.0582 (5)
H13A0.34041.00090.71090.070*
H13B0.17391.02860.83950.070*
C140.1208 (3)1.0228 (3)0.6723 (2)0.0759 (6)
H14A0.07121.14280.66880.114*
H14D0.02370.99170.71250.114*
H14C0.18930.96840.58430.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0421 (3)0.0609 (3)0.0601 (3)0.0007 (2)0.0123 (2)0.0145 (2)
N10.0969 (14)0.0565 (10)0.0507 (9)0.0111 (9)0.0042 (9)0.0041 (8)
N20.0513 (9)0.0687 (10)0.0508 (9)0.0015 (7)0.0020 (7)0.0105 (7)
N30.0417 (7)0.0525 (8)0.0479 (8)0.0096 (6)0.0014 (6)0.0083 (6)
C10.0400 (8)0.0450 (9)0.0461 (9)0.0103 (7)0.0066 (7)0.0076 (7)
C20.0529 (10)0.0447 (9)0.0489 (10)0.0072 (8)0.0107 (8)0.0015 (7)
C30.0528 (10)0.0532 (10)0.0417 (9)0.0132 (8)0.0036 (7)0.0017 (7)
C40.0407 (8)0.0487 (9)0.0434 (9)0.0116 (7)0.0053 (7)0.0079 (7)
C50.0544 (10)0.0389 (9)0.0559 (10)0.0102 (8)0.0019 (8)0.0021 (7)
C60.0551 (10)0.0444 (9)0.0499 (10)0.0152 (8)0.0068 (8)0.0039 (7)
C70.0394 (8)0.0432 (9)0.0499 (9)0.0085 (7)0.0109 (7)0.0063 (7)
C80.0366 (8)0.0432 (9)0.0503 (9)0.0108 (7)0.0059 (7)0.0106 (7)
C90.0557 (10)0.0503 (11)0.0425 (9)0.0142 (9)0.0004 (8)0.0117 (8)
C100.0365 (8)0.0554 (10)0.0528 (10)0.0151 (7)0.0059 (7)0.0126 (8)
C110.0430 (9)0.0698 (12)0.0511 (10)0.0187 (9)0.0028 (8)0.0109 (8)
C120.0824 (15)0.1120 (18)0.0547 (12)0.0428 (14)0.0137 (11)0.0009 (12)
C130.0421 (9)0.0508 (10)0.0594 (11)0.0098 (8)0.0024 (8)0.0165 (8)
C140.0633 (12)0.0589 (12)0.0972 (16)0.0174 (10)0.0305 (12)0.0014 (10)
Geometric parameters (Å, º) top
S1—C101.669 (2)C6—H6A0.9300
N1—C91.145 (2)C7—C81.358 (2)
N2—C101.330 (2)C7—H7A0.9300
N2—H2A0.8600C8—C91.428 (3)
N2—H2B0.8600C8—C101.476 (2)
N3—C41.361 (2)C11—C121.497 (3)
N3—C111.463 (2)C11—H11A0.9700
N3—C131.471 (2)C11—H11B0.9700
C1—C21.399 (3)C12—H12A0.9600
C1—C61.406 (3)C12—H12B0.9600
C1—C71.435 (2)C12—H12C0.9600
C2—C31.367 (3)C13—C141.496 (3)
C2—H2C0.9300C13—H13A0.9700
C3—C41.412 (3)C13—H13B0.9700
C3—H3A0.9300C14—H14A0.9600
C4—C51.403 (3)C14—H14D0.9600
C5—C61.361 (3)C14—H14C0.9600
C5—H5A0.9300
C10—N2—H2A120.0C9—C8—C10115.16 (15)
C10—N2—H2B120.0N1—C9—C8177.31 (18)
H2A—N2—H2B120.0N2—C10—C8115.65 (16)
C4—N3—C11121.94 (16)N2—C10—S1121.47 (13)
C4—N3—C13121.80 (15)C8—C10—S1122.88 (14)
C11—N3—C13115.99 (14)N3—C11—C12112.69 (16)
C2—C1—C6115.45 (15)N3—C11—H11A109.1
C2—C1—C7119.34 (16)C12—C11—H11A109.1
C6—C1—C7125.21 (16)N3—C11—H11B109.1
C3—C2—C1122.77 (17)C12—C11—H11B109.1
C3—C2—H2C118.6H11A—C11—H11B107.8
C1—C2—H2C118.6C11—C12—H12A109.5
C2—C3—C4121.18 (17)C11—C12—H12B109.5
C2—C3—H3A119.4H12A—C12—H12B109.5
C4—C3—H3A119.4C11—C12—H12C109.5
N3—C4—C5121.03 (16)H12A—C12—H12C109.5
N3—C4—C3122.66 (16)H12B—C12—H12C109.5
C5—C4—C3116.32 (15)N3—C13—C14113.52 (16)
C6—C5—C4121.66 (17)N3—C13—H13A108.9
C6—C5—H5A119.2C14—C13—H13A108.9
C4—C5—H5A119.2N3—C13—H13B108.9
C5—C6—C1122.61 (17)C14—C13—H13B108.9
C5—C6—H6A118.7H13A—C13—H13B107.7
C1—C6—H6A118.7C13—C14—H14A109.5
C8—C7—C1131.08 (16)C13—C14—H14D109.5
C8—C7—H7A114.5H14A—C14—H14D109.5
C1—C7—H7A114.5C13—C14—H14C109.5
C7—C8—C9121.42 (14)H14A—C14—H14C109.5
C7—C8—C10123.31 (16)H14D—C14—H14C109.5
C6—C1—C2—C31.0 (3)C7—C1—C6—C5179.34 (17)
C7—C1—C2—C3178.50 (16)C2—C1—C7—C8167.98 (17)
C1—C2—C3—C40.9 (3)C6—C1—C7—C811.4 (3)
C11—N3—C4—C5179.88 (16)C1—C7—C8—C91.9 (3)
C13—N3—C4—C56.1 (3)C1—C7—C8—C10177.86 (16)
C11—N3—C4—C30.1 (3)C7—C8—C10—N2166.16 (17)
C13—N3—C4—C3173.85 (16)C9—C8—C10—N210.0 (2)
C2—C3—C4—N3179.99 (17)C7—C8—C10—S113.1 (2)
C2—C3—C4—C50.0 (3)C9—C8—C10—S1170.72 (13)
N3—C4—C5—C6179.14 (17)C4—N3—C11—C1287.8 (2)
C3—C4—C5—C60.9 (3)C13—N3—C11—C1286.3 (2)
C4—C5—C6—C10.8 (3)C4—N3—C13—C1486.9 (2)
C2—C1—C6—C50.1 (3)C11—N3—C13—C1499.00 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.353.069 (2)141
N2—H2B···S1ii0.862.663.481 (2)160
Symmetry codes: (i) x+2, y+1, z; (ii) x+3, y, z.
(Ib) 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide top
Crystal data top
C14H17N3SF(000) = 552
Mr = 259.38Dx = 1.189 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.1670 (18) ÅCell parameters from 24 reflections
b = 13.023 (3) Åθ = 11–12°
c = 12.172 (2) ŵ = 0.21 mm1
β = 93.97 (3)°T = 295 K
V = 1449.6 (5) Å3Prism, red
Z = 40.50 × 0.35 × 0.25 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.3°
Graphite monochromatorh = 011
θ/2θ scansk = 016
3307 measured reflectionsl = 1515
3114 independent reflections3 standard reflections every 97 reflections
2316 reflections with I > 2σ(I) intensity decay: 3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.06P)2 + 0.25P]
where P = (Fo2 + 2Fc2)/3
3114 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C14H17N3SV = 1449.6 (5) Å3
Mr = 259.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.1670 (18) ŵ = 0.21 mm1
b = 13.023 (3) ÅT = 295 K
c = 12.172 (2) Å0.50 × 0.35 × 0.25 mm
β = 93.97 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.027
3307 measured reflections3 standard reflections every 97 reflections
3114 independent reflections intensity decay: 3%
2316 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.03Δρmax = 0.21 e Å3
3114 reflectionsΔρmin = 0.15 e Å3
165 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.08338 (5)0.35087 (3)0.92865 (3)0.05656 (16)
N10.3091 (2)0.24156 (11)0.72955 (14)0.0679 (4)
N20.09034 (18)0.54174 (10)0.85958 (12)0.0574 (4)
H2A0.11060.58820.81280.069*
H2B0.04950.55850.91850.069*
N30.38319 (17)0.47951 (11)0.22219 (12)0.0568 (4)
C10.24136 (19)0.47803 (12)0.54408 (14)0.0505 (4)
C20.1954 (2)0.55290 (14)0.46559 (15)0.0671 (5)
H2C0.13270.60460.48610.080*
C30.2390 (2)0.55270 (15)0.36095 (16)0.0687 (5)
H3A0.20240.60220.31130.082*
C40.33829 (19)0.47901 (12)0.32654 (14)0.0514 (4)
C50.38953 (19)0.40580 (12)0.40595 (13)0.0523 (4)
H5A0.45740.35700.38690.063*
C60.34196 (19)0.40492 (12)0.50953 (14)0.0508 (4)
H6A0.37690.35470.55890.061*
C70.18521 (18)0.48488 (12)0.65037 (14)0.0490 (4)
H7A0.13420.54530.66150.059*
C80.19161 (17)0.42019 (11)0.73893 (13)0.0438 (3)
C90.25688 (18)0.32041 (11)0.73484 (13)0.0490 (4)
C100.12203 (17)0.44415 (11)0.84082 (12)0.0440 (3)
C110.3110 (2)0.54304 (15)0.13463 (15)0.0634 (5)
H11A0.21010.55420.15080.076*
H11B0.31060.50610.06540.076*
C120.3839 (3)0.64552 (18)0.1218 (2)0.0909 (7)
H12A0.33210.68360.06380.136*
H12B0.48310.63510.10380.136*
H12C0.38280.68320.18950.136*
C130.4912 (2)0.40610 (13)0.18761 (15)0.0568 (4)
H13A0.56240.39300.24870.068*
H13B0.54250.43570.12820.068*
C140.4224 (3)0.30572 (15)0.14940 (18)0.0750 (6)
H14D0.49600.26160.12270.112*
H14A0.34840.31870.09130.112*
H14B0.37900.27310.20990.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0813 (3)0.0369 (2)0.0531 (2)0.00360 (19)0.0160 (2)0.00204 (16)
N10.0897 (11)0.0407 (7)0.0758 (10)0.0093 (7)0.0235 (8)0.0005 (7)
N20.0842 (10)0.0332 (6)0.0579 (8)0.0029 (6)0.0275 (7)0.0029 (6)
N30.0666 (9)0.0524 (8)0.0528 (8)0.0088 (7)0.0133 (7)0.0043 (6)
C10.0582 (9)0.0391 (8)0.0552 (9)0.0051 (7)0.0117 (7)0.0026 (6)
C20.0844 (13)0.0523 (10)0.0674 (11)0.0285 (9)0.0260 (10)0.0134 (8)
C30.0871 (14)0.0573 (10)0.0643 (11)0.0273 (10)0.0227 (10)0.0202 (9)
C40.0578 (10)0.0449 (8)0.0523 (9)0.0052 (7)0.0106 (7)0.0034 (7)
C50.0601 (10)0.0418 (8)0.0560 (9)0.0114 (7)0.0111 (8)0.0008 (7)
C60.0608 (9)0.0409 (8)0.0511 (8)0.0097 (7)0.0068 (7)0.0043 (6)
C70.0551 (9)0.0368 (7)0.0560 (9)0.0043 (6)0.0114 (7)0.0020 (6)
C80.0495 (8)0.0326 (7)0.0497 (8)0.0021 (6)0.0064 (6)0.0048 (6)
C90.0581 (9)0.0374 (7)0.0522 (9)0.0015 (7)0.0090 (7)0.0029 (6)
C100.0493 (8)0.0350 (7)0.0480 (8)0.0050 (6)0.0056 (6)0.0039 (6)
C110.0676 (11)0.0690 (12)0.0534 (10)0.0006 (9)0.0037 (8)0.0052 (8)
C120.1061 (18)0.0754 (15)0.0913 (16)0.0014 (13)0.0082 (14)0.0262 (12)
C130.0612 (10)0.0569 (10)0.0536 (9)0.0009 (8)0.0124 (8)0.0054 (8)
C140.0894 (14)0.0589 (11)0.0749 (13)0.0013 (10)0.0065 (11)0.0130 (10)
Geometric parameters (Å, º) top
S1—C101.6723 (15)C6—H6A0.9300
N1—C91.137 (2)C7—C81.366 (2)
N2—C101.3270 (19)C7—H7A0.9300
N2—H2A0.8600C8—C91.433 (2)
N2—H2B0.8600C8—C101.467 (2)
N3—C41.362 (2)C11—C121.505 (3)
N3—C131.459 (2)C11—H11A0.9700
N3—C111.470 (2)C11—H11B0.9700
C1—C21.409 (2)C12—H12A0.9600
C1—C61.410 (2)C12—H12B0.9600
C1—C71.428 (2)C12—H12C0.9600
C2—C31.361 (3)C13—C141.511 (3)
C2—H2C0.9300C13—H13A0.9700
C3—C41.406 (2)C13—H13B0.9700
C3—H3A0.9300C14—H14D0.9600
C4—C51.415 (2)C14—H14A0.9600
C5—C61.362 (2)C14—H14B0.9600
C5—H5A0.9300
C10—N2—H2A120.0C9—C8—C10115.42 (13)
C10—N2—H2B120.0N1—C9—C8178.70 (18)
H2A—N2—H2B120.0N2—C10—C8117.54 (13)
C4—N3—C13121.38 (14)N2—C10—S1121.81 (12)
C4—N3—C11121.92 (15)C8—C10—S1120.65 (11)
C13—N3—C11116.11 (14)N3—C11—C12113.17 (18)
C2—C1—C6115.86 (15)N3—C11—H11A108.9
C2—C1—C7117.48 (15)C12—C11—H11A108.9
C6—C1—C7126.64 (15)N3—C11—H11B108.9
C3—C2—C1122.68 (16)C12—C11—H11B108.9
C3—C2—H2C118.7H11A—C11—H11B107.8
C1—C2—H2C118.7C11—C12—H12A109.5
C2—C3—C4121.20 (16)C11—C12—H12B109.5
C2—C3—H3A119.4H12A—C12—H12B109.5
C4—C3—H3A119.4C11—C12—H12C109.5
N3—C4—C3121.21 (15)H12A—C12—H12C109.5
N3—C4—C5122.20 (15)H12B—C12—H12C109.5
C3—C4—C5116.59 (15)N3—C13—C14112.25 (16)
C6—C5—C4121.71 (15)N3—C13—H13A109.2
C6—C5—H5A119.1C14—C13—H13A109.2
C4—C5—H5A119.1N3—C13—H13B109.2
C5—C6—C1121.89 (15)C14—C13—H13B109.2
C5—C6—H6A119.1H13A—C13—H13B107.9
C1—C6—H6A119.1C13—C14—H14D109.5
C8—C7—C1132.68 (14)C13—C14—H14A109.5
C8—C7—H7A113.7H14D—C14—H14A109.5
C1—C7—H7A113.7C13—C14—H14B109.5
C7—C8—C9121.81 (14)H14D—C14—H14B109.5
C7—C8—C10122.58 (13)H14A—C14—H14B109.5
C6—C1—C2—C33.1 (3)C7—C1—C6—C5179.46 (17)
C7—C1—C2—C3178.4 (2)C2—C1—C7—C8170.58 (19)
C1—C2—C3—C42.6 (4)C6—C1—C7—C811.1 (3)
C13—N3—C4—C3177.21 (18)C1—C7—C8—C94.3 (3)
C11—N3—C4—C311.9 (3)C1—C7—C8—C10179.09 (17)
C13—N3—C4—C52.1 (3)C7—C8—C10—N220.1 (2)
C11—N3—C4—C5168.79 (17)C9—C8—C10—N2164.83 (16)
C2—C3—C4—N3179.2 (2)C7—C8—C10—S1159.37 (13)
C2—C3—C4—C50.1 (3)C9—C8—C10—S115.7 (2)
N3—C4—C5—C6178.85 (17)C4—N3—C11—C1294.3 (2)
C3—C4—C5—C61.8 (3)C13—N3—C11—C1294.4 (2)
C4—C5—C6—C11.3 (3)C4—N3—C13—C1485.6 (2)
C2—C1—C6—C51.1 (3)C11—N3—C13—C1485.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.202.989 (2)152
N2—H2B···S1ii0.862.583.421 (2)167
Symmetry codes: (i) x+1/2, y+1/2, z+3/2; (ii) x, y+1, z+2.
(Ic) 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide acetonitrile 0.25-solvate top
Crystal data top
C14H17N3S·0.25C2H3NF(000) = 2296
Mr = 269.64Dx = 1.225 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 39.370 (8) ÅCell parameters from 24 reflections
b = 8.8800 (18) Åθ = 10–11°
c = 17.056 (3) ŵ = 0.21 mm1
β = 101.19 (3)°T = 298 K
V = 5850 (2) Å3Plate, orange
Z = 160.50 × 0.40 × 0.20 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.050
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 1.1°
Graphite monochromatorh = 047
θ/2θ scansk = 010
5506 measured reflectionsl = 2020
5423 independent reflections3 standard reflections every 97 reflections
2754 reflections with I > 2σ(I) intensity decay: 3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.075P)2]
where P = (Fo2 + 2Fc2)/3
5423 reflections(Δ/σ)max < 0.001
344 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C14H17N3S·0.25C2H3NV = 5850 (2) Å3
Mr = 269.64Z = 16
Monoclinic, C2/cMo Kα radiation
a = 39.370 (8) ŵ = 0.21 mm1
b = 8.8800 (18) ÅT = 298 K
c = 17.056 (3) Å0.50 × 0.40 × 0.20 mm
β = 101.19 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.050
5506 measured reflections3 standard reflections every 97 reflections
5423 independent reflections intensity decay: 3%
2754 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 0.99Δρmax = 0.38 e Å3
5423 reflectionsΔρmin = 0.24 e Å3
344 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1A0.30718 (2)0.24174 (11)0.27209 (5)0.0478 (3)
N1A0.32656 (7)0.2712 (4)0.01178 (18)0.0536 (8)
N2A0.35114 (7)0.3122 (3)0.18127 (16)0.0512 (8)
H2AA0.35800.31480.13630.061*
H2AB0.36370.35130.22320.061*
N3A0.18347 (7)0.2138 (3)0.13861 (16)0.0453 (7)
C1A0.25282 (7)0.0149 (3)0.04174 (17)0.0338 (7)
C2A0.22709 (8)0.0820 (4)0.05954 (19)0.0419 (8)
H2AC0.22530.09530.11270.050*
C3A0.20450 (8)0.1576 (4)0.00131 (19)0.0419 (8)
H3AA0.18780.22010.01590.050*
C4A0.20615 (8)0.1424 (3)0.0792 (2)0.0394 (8)
C5A0.23241 (8)0.0470 (4)0.09762 (18)0.0425 (8)
H5AA0.23450.03520.15070.051*
C6A0.25474 (8)0.0280 (4)0.03933 (18)0.0398 (8)
H6AA0.27170.08930.05370.048*
C7A0.27457 (8)0.0913 (3)0.10672 (17)0.0351 (7)
H7AA0.26870.07350.15620.042*
C8A0.30202 (7)0.1846 (3)0.10968 (17)0.0318 (7)
C9A0.31473 (7)0.2292 (4)0.04067 (19)0.0366 (8)
C10A0.32134 (8)0.2480 (3)0.18593 (17)0.0351 (7)
C11A0.15694 (9)0.3130 (4)0.1196 (2)0.0538 (10)
H11B0.16640.36950.07170.065*
H11C0.15030.38440.16290.065*
C12A0.12486 (9)0.2282 (5)0.1065 (3)0.0697 (12)
H12A0.10780.29880.09590.105*
H12B0.11550.17100.15350.105*
H12C0.13100.16130.06170.105*
C13A0.18095 (9)0.1790 (4)0.2231 (2)0.0517 (9)
H13A0.18810.07560.22810.062*
H13B0.15690.18710.24980.062*
C14A0.20243 (10)0.2797 (5)0.2647 (2)0.0678 (12)
H14B0.19950.25070.31980.102*
H14C0.19510.38220.26130.102*
H14D0.22640.27050.23960.102*
S1B0.41456 (2)0.47668 (11)0.30624 (5)0.0500 (3)
N1B0.40596 (8)0.6653 (4)0.58260 (19)0.0717 (11)
N2B0.37145 (7)0.5157 (3)0.40298 (16)0.0463 (7)
H2BA0.36600.54840.44640.056*
H2BB0.35640.46900.36830.056*
N3B0.57131 (7)0.9542 (3)0.63859 (16)0.0446 (7)
C1B0.48736 (8)0.7335 (3)0.49443 (18)0.0364 (7)
C2B0.52112 (8)0.7223 (4)0.4801 (2)0.0445 (8)
H2BC0.52500.66430.43720.053*
C3B0.54872 (8)0.7935 (4)0.5268 (2)0.0456 (9)
H3BA0.57080.78060.51590.055*
C4B0.54420 (8)0.8859 (4)0.59123 (18)0.0383 (8)
C5B0.50987 (8)0.9042 (4)0.60238 (18)0.0407 (8)
H5BA0.50550.96910.64210.049*
C6B0.48296 (8)0.8299 (4)0.55692 (18)0.0400 (8)
H6BA0.46090.84320.56750.048*
C7B0.46041 (8)0.6522 (3)0.44399 (18)0.0368 (8)
H7BA0.46630.61580.39730.044*
C8B0.42750 (8)0.6185 (3)0.45210 (18)0.0348 (7)
C9B0.41600 (8)0.6480 (4)0.5246 (2)0.0427 (8)
C10B0.40321 (8)0.5375 (3)0.38965 (18)0.0357 (7)
C11B0.60725 (8)0.9184 (4)0.6357 (2)0.0531 (10)
H11A0.60840.81520.61790.064*
H11D0.62100.92520.68930.064*
C12B0.62301 (10)1.0190 (5)0.5817 (3)0.0750 (13)
H12D0.64640.98770.58210.113*
H12E0.62301.12110.60020.113*
H12F0.60981.01260.52830.113*
C13B0.56671 (9)1.0554 (4)0.7037 (2)0.0514 (9)
H13C0.54581.11410.68680.062*
H13D0.58611.12490.71460.062*
C14B0.56427 (11)0.9718 (5)0.7793 (2)0.0748 (13)
H14A0.56131.04250.82000.112*
H14E0.58510.91510.79690.112*
H14F0.54480.90450.76920.112*
N1S0.50000.7142 (8)0.25000.110 (2)
C1S0.50000.5886 (9)0.25000.0738 (18)
C2S0.50000.4252 (8)0.25000.130 (3)
H2SA0.51780.38910.29250.195*0.50
H2SB0.50430.38910.19980.195*0.50
H2SC0.47790.38910.25770.195*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0487 (5)0.0586 (6)0.0382 (5)0.0023 (5)0.0134 (4)0.0077 (4)
N1A0.0501 (18)0.062 (2)0.0504 (18)0.0092 (16)0.0147 (15)0.0046 (16)
N2A0.0421 (16)0.072 (2)0.0395 (16)0.0167 (16)0.0074 (13)0.0171 (15)
N3A0.0458 (16)0.0388 (17)0.0479 (17)0.0098 (14)0.0009 (13)0.0044 (14)
C1A0.0325 (17)0.0321 (18)0.0349 (18)0.0000 (15)0.0016 (13)0.0021 (15)
C2A0.045 (2)0.042 (2)0.0380 (18)0.0014 (17)0.0060 (15)0.0076 (16)
C3A0.0388 (19)0.036 (2)0.049 (2)0.0070 (16)0.0047 (16)0.0044 (16)
C4A0.0378 (18)0.0293 (18)0.048 (2)0.0005 (15)0.0003 (15)0.0012 (15)
C5A0.046 (2)0.042 (2)0.0362 (18)0.0026 (17)0.0015 (15)0.0008 (16)
C6A0.0393 (18)0.0347 (19)0.044 (2)0.0043 (16)0.0044 (15)0.0012 (16)
C7A0.0363 (18)0.0352 (19)0.0335 (17)0.0080 (15)0.0058 (14)0.0022 (15)
C8A0.0311 (16)0.0285 (17)0.0357 (17)0.0049 (14)0.0065 (13)0.0031 (14)
C9A0.0307 (17)0.0345 (19)0.0425 (19)0.0004 (15)0.0020 (15)0.0100 (16)
C10A0.0354 (17)0.0305 (17)0.0390 (18)0.0044 (15)0.0063 (13)0.0034 (15)
C11A0.053 (2)0.045 (2)0.059 (2)0.0105 (19)0.0020 (18)0.0079 (19)
C12A0.053 (2)0.077 (3)0.078 (3)0.005 (2)0.008 (2)0.012 (2)
C13A0.052 (2)0.045 (2)0.052 (2)0.0050 (18)0.0037 (18)0.0031 (18)
C14A0.083 (3)0.064 (3)0.054 (2)0.003 (2)0.007 (2)0.004 (2)
S1B0.0437 (5)0.0612 (6)0.0456 (5)0.0129 (5)0.0098 (4)0.0153 (5)
N1B0.056 (2)0.107 (3)0.056 (2)0.028 (2)0.0208 (17)0.022 (2)
N2B0.0386 (16)0.0543 (19)0.0455 (16)0.0096 (14)0.0072 (12)0.0101 (14)
N3B0.0406 (16)0.0371 (16)0.0520 (17)0.0047 (14)0.0012 (13)0.0032 (14)
C1B0.0372 (17)0.0312 (18)0.0400 (18)0.0016 (15)0.0054 (14)0.0017 (15)
C2B0.0408 (19)0.044 (2)0.049 (2)0.0027 (17)0.0105 (16)0.0077 (17)
C3B0.0345 (18)0.042 (2)0.061 (2)0.0035 (16)0.0118 (17)0.0035 (18)
C4B0.0382 (18)0.0311 (18)0.0439 (19)0.0045 (15)0.0033 (15)0.0037 (16)
C5B0.0395 (19)0.039 (2)0.0432 (19)0.0051 (16)0.0071 (15)0.0074 (16)
C6B0.0353 (17)0.040 (2)0.0444 (19)0.0032 (16)0.0072 (15)0.0022 (16)
C7B0.0439 (19)0.0305 (19)0.0347 (17)0.0037 (15)0.0045 (15)0.0001 (14)
C8B0.0345 (17)0.0324 (18)0.0378 (18)0.0013 (15)0.0074 (14)0.0017 (15)
C9B0.0344 (18)0.048 (2)0.044 (2)0.0106 (16)0.0021 (16)0.0048 (17)
C10B0.0342 (17)0.0295 (18)0.0422 (18)0.0005 (14)0.0042 (14)0.0086 (15)
C11B0.041 (2)0.038 (2)0.075 (3)0.0047 (17)0.0037 (18)0.0073 (19)
C12B0.058 (3)0.061 (3)0.111 (4)0.010 (2)0.029 (2)0.012 (3)
C13B0.051 (2)0.042 (2)0.057 (2)0.0123 (18)0.0014 (17)0.0069 (19)
C14B0.087 (3)0.078 (3)0.057 (2)0.015 (3)0.006 (2)0.003 (2)
N1S0.142 (6)0.074 (4)0.134 (6)0.0000.079 (5)0.000
C1S0.073 (4)0.081 (5)0.080 (4)0.0000.045 (3)0.000
C2S0.149 (8)0.060 (5)0.212 (10)0.0000.107 (7)0.000
Geometric parameters (Å, º) top
S1A—C10A1.671 (3)N2B—H2BA0.8600
N1A—C9A1.148 (4)N2B—H2BB0.8600
N2A—C10A1.320 (4)N3B—C4B1.351 (4)
N2A—H2AA0.8600N3B—C11B1.460 (4)
N2A—H2AB0.8600N3B—C13B1.467 (4)
N3A—C4A1.369 (4)C1B—C2B1.401 (4)
N3A—C11A1.451 (4)C1B—C6B1.404 (4)
N3A—C13A1.458 (4)C1B—C7B1.426 (4)
C1A—C6A1.404 (4)C2B—C3B1.371 (4)
C1A—C2A1.406 (4)C2B—H2BC0.9300
C1A—C7A1.433 (4)C3B—C4B1.410 (4)
C2A—C3A1.373 (4)C3B—H3BA0.9300
C2A—H2AC0.9300C4B—C5B1.410 (4)
C3A—C4A1.394 (4)C5B—C6B1.356 (4)
C3A—H3AA0.9300C5B—H5BA0.9300
C4A—C5A1.418 (4)C6B—H6BA0.9300
C5A—C6A1.366 (4)C7B—C8B1.363 (4)
C5A—H5AA0.9300C7B—H7BA0.9300
C6A—H6AA0.9300C8B—C9B1.422 (4)
C7A—C8A1.355 (4)C8B—C10B1.473 (4)
C7A—H7AA0.9300C11B—C12B1.500 (5)
C8A—C9A1.422 (4)C11B—H11A0.9700
C8A—C10A1.484 (4)C11B—H11D0.9700
C11A—C12A1.524 (5)C12B—H12D0.9600
C11A—H11B0.9700C12B—H12E0.9600
C11A—H11C0.9700C12B—H12F0.9600
C12A—H12A0.9600C13B—C14B1.508 (5)
C12A—H12B0.9600C13B—H13C0.9700
C12A—H12C0.9600C13B—H13D0.9700
C13A—C14A1.500 (5)C14B—H14A0.9600
C13A—H13A0.9700C14B—H14E0.9600
C13A—H13B0.9700C14B—H14F0.9600
C14A—H14B0.9600N1S—C1S1.116 (8)
C14A—H14C0.9600C1S—C2S1.451 (10)
C14A—H14D0.9600C2S—H2SA0.9600
S1B—C10B1.662 (3)C2S—H2SB0.9600
N1B—C9B1.144 (4)C2S—H2SC0.9600
N2B—C10B1.328 (4)
C10A—N2A—H2AA120.0C4B—N3B—C13B121.9 (3)
C10A—N2A—H2AB120.0C11B—N3B—C13B114.9 (3)
H2AA—N2A—H2AB120.0C2B—C1B—C6B115.9 (3)
C4A—N3A—C11A120.7 (3)C2B—C1B—C7B118.6 (3)
C4A—N3A—C13A122.9 (3)C6B—C1B—C7B125.4 (3)
C11A—N3A—C13A115.8 (3)C3B—C2B—C1B122.5 (3)
C6A—C1A—C2A116.2 (3)C3B—C2B—H2BC118.8
C6A—C1A—C7A125.7 (3)C1B—C2B—H2BC118.8
C2A—C1A—C7A118.0 (3)C2B—C3B—C4B121.1 (3)
C3A—C2A—C1A122.4 (3)C2B—C3B—H3BA119.5
C3A—C2A—H2AC118.8C4B—C3B—H3BA119.5
C1A—C2A—H2AC118.8N3B—C4B—C3B121.5 (3)
C2A—C3A—C4A121.2 (3)N3B—C4B—C5B122.3 (3)
C2A—C3A—H3AA119.4C3B—C4B—C5B116.2 (3)
C4A—C3A—H3AA119.4C6B—C5B—C4B122.0 (3)
N3A—C4A—C3A122.4 (3)C6B—C5B—H5BA119.0
N3A—C4A—C5A120.8 (3)C4B—C5B—H5BA119.0
C3A—C4A—C5A116.8 (3)C5B—C6B—C1B122.2 (3)
C6A—C5A—C4A121.6 (3)C5B—C6B—H6BA118.9
C6A—C5A—H5AA119.2C1B—C6B—H6BA118.9
C4A—C5A—H5AA119.2C8B—C7B—C1B131.4 (3)
C5A—C6A—C1A121.8 (3)C8B—C7B—H7BA114.3
C5A—C6A—H6AA119.1C1B—C7B—H7BA114.3
C1A—C6A—H6AA119.1C7B—C8B—C9B121.2 (3)
C8A—C7A—C1A132.1 (3)C7B—C8B—C10B122.0 (3)
C8A—C7A—H7AA113.9C9B—C8B—C10B116.6 (3)
C1A—C7A—H7AA113.9N1B—C9B—C8B176.8 (4)
C7A—C8A—C9A123.1 (3)N2B—C10B—C8B116.6 (3)
C7A—C8A—C10A122.3 (3)N2B—C10B—S1B121.2 (2)
C9A—C8A—C10A114.6 (3)C8B—C10B—S1B122.2 (2)
N1A—C9A—C8A175.4 (3)N3B—C11B—C12B114.2 (3)
N2A—C10A—C8A114.9 (3)N3B—C11B—H11A108.7
N2A—C10A—S1A121.3 (2)C12B—C11B—H11A108.7
C8A—C10A—S1A123.8 (2)N3B—C11B—H11D108.7
N3A—C11A—C12A112.7 (3)C12B—C11B—H11D108.7
N3A—C11A—H11B109.1H11A—C11B—H11D107.6
C12A—C11A—H11B109.1C11B—C12B—H12D109.5
N3A—C11A—H11C109.1C11B—C12B—H12E109.5
C12A—C11A—H11C109.1H12D—C12B—H12E109.5
H11B—C11A—H11C107.8C11B—C12B—H12F109.5
C11A—C12A—H12A109.5H12D—C12B—H12F109.5
C11A—C12A—H12B109.5H12E—C12B—H12F109.5
H12A—C12A—H12B109.5N3B—C13B—C14B112.5 (3)
C11A—C12A—H12C109.5N3B—C13B—H13C109.1
H12A—C12A—H12C109.5C14B—C13B—H13C109.1
H12B—C12A—H12C109.5N3B—C13B—H13D109.1
N3A—C13A—C14A113.9 (3)C14B—C13B—H13D109.1
N3A—C13A—H13A108.8H13C—C13B—H13D107.8
C14A—C13A—H13A108.8C13B—C14B—H14A109.5
N3A—C13A—H13B108.8C13B—C14B—H14E109.5
C14A—C13A—H13B108.8H14A—C14B—H14E109.5
H13A—C13A—H13B107.7C13B—C14B—H14F109.5
C13A—C14A—H14B109.5H14A—C14B—H14F109.5
C13A—C14A—H14C109.5H14E—C14B—H14F109.5
H14B—C14A—H14C109.5N1S—C1S—C2S180.000 (3)
C13A—C14A—H14D109.5C1S—C2S—H2SA109.5
H14B—C14A—H14D109.5C1S—C2S—H2SB109.5
H14C—C14A—H14D109.5H2SA—C2S—H2SB109.5
C10B—N2B—H2BA120.0C1S—C2S—H2SC109.5
C10B—N2B—H2BB120.0H2SA—C2S—H2SC109.5
H2BA—N2B—H2BB120.0H2SB—C2S—H2SC109.5
C4B—N3B—C11B122.7 (3)
C6A—C1A—C2A—C3A1.4 (5)C6B—C1B—C2B—C3B3.7 (5)
C7A—C1A—C2A—C3A178.5 (3)C7B—C1B—C2B—C3B178.3 (3)
C1A—C2A—C3A—C4A0.4 (5)C1B—C2B—C3B—C4B1.7 (5)
C11A—N3A—C4A—C3A1.7 (5)C11B—N3B—C4B—C3B10.5 (5)
C13A—N3A—C4A—C3A169.0 (3)C13B—N3B—C4B—C3B177.4 (3)
C11A—N3A—C4A—C5A179.1 (3)C11B—N3B—C4B—C5B170.3 (3)
C13A—N3A—C4A—C5A10.2 (5)C13B—N3B—C4B—C5B1.7 (5)
C2A—C3A—C4A—N3A178.5 (3)C2B—C3B—C4B—N3B178.7 (3)
C2A—C3A—C4A—C5A0.7 (5)C2B—C3B—C4B—C5B2.1 (5)
N3A—C4A—C5A—C6A178.4 (3)N3B—C4B—C5B—C6B176.9 (3)
C3A—C4A—C5A—C6A0.8 (5)C3B—C4B—C5B—C6B3.9 (5)
C4A—C5A—C6A—C1A0.2 (5)C4B—C5B—C6B—C1B1.9 (5)
C2A—C1A—C6A—C5A1.3 (5)C2B—C1B—C6B—C5B1.9 (5)
C7A—C1A—C6A—C5A178.6 (3)C7B—C1B—C6B—C5B179.8 (3)
C6A—C1A—C7A—C8A3.4 (5)C2B—C1B—C7B—C8B165.7 (3)
C2A—C1A—C7A—C8A176.7 (3)C6B—C1B—C7B—C8B16.5 (6)
C1A—C7A—C8A—C9A1.4 (5)C1B—C7B—C8B—C9B8.6 (5)
C1A—C7A—C8A—C10A178.3 (3)C1B—C7B—C8B—C10B177.1 (3)
C7A—C8A—C10A—N2A167.4 (3)C7B—C8B—C10B—N2B177.6 (3)
C9A—C8A—C10A—N2A12.4 (4)C9B—C8B—C10B—N2B7.9 (4)
C7A—C8A—C10A—S1A13.0 (4)C7B—C8B—C10B—S1B2.0 (4)
C9A—C8A—C10A—S1A167.3 (2)C9B—C8B—C10B—S1B172.5 (2)
C4A—N3A—C11A—C12A83.2 (4)C4B—N3B—C11B—C12B93.8 (4)
C13A—N3A—C11A—C12A88.2 (4)C13B—N3B—C11B—C12B93.7 (4)
C4A—N3A—C13A—C14A94.4 (4)C4B—N3B—C13B—C14B83.7 (4)
C11A—N3A—C13A—C14A94.5 (4)C11B—N3B—C13B—C14B88.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H2AA···N1Bi0.862.262.990 (4)143
N2A—H2AB···S1B0.862.483.293 (4)158
N2B—H2BA···N1Aii0.862.433.133 (4)139
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+1, z+1/2.

Experimental details

(Ia)(Ib)(Ic)
Crystal data
Chemical formulaC14H17N3SC14H17N3SC14H17N3S·0.25C2H3N
Mr259.38259.38269.64
Crystal system, space groupTriclinic, P1Monoclinic, P21/nMonoclinic, C2/c
Temperature (K)298295298
a, b, c (Å)8.753 (3), 8.890 (3), 10.830 (4)9.1670 (18), 13.023 (3), 12.172 (2)39.370 (8), 8.8800 (18), 17.056 (3)
α, β, γ (°)85.44 (3), 69.76 (2), 63.65 (3)90, 93.97 (3), 9090, 101.19 (3), 90
V3)705.8 (5)1449.6 (5)5850 (2)
Z2416
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.220.210.21
Crystal size (mm)0.50 × 0.40 × 0.200.50 × 0.35 × 0.250.50 × 0.40 × 0.20
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Enraf–Nonius CAD-4
diffractometer
Enraf–Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2639, 2465, 1811 3307, 3114, 2316 5506, 5423, 2754
Rint0.0160.0270.050
(sin θ/λ)max1)0.5960.6380.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.098, 1.00 0.038, 0.113, 1.03 0.050, 0.149, 0.99
No. of reflections246531145423
No. of parameters165165344
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.180.21, 0.150.38, 0.24

Computer programs: CAD-4 Software (Enraf–Nonuis, 1989), CAD-4 Software, SHELXTL-Plus (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus, SHELXL97.

Selected geometric parameters (Å, º) for (Ia) top
S1—C101.669 (2)C7—C81.358 (2)
N1—C91.145 (2)C8—C91.428 (3)
N2—C101.330 (2)C8—C101.476 (2)
N3—C41.361 (2)
C8—C7—C1131.08 (16)N1—C9—C8177.31 (18)
C2—C1—C7—C8167.98 (17)C9—C8—C10—N210.0 (2)
C1—C7—C8—C10177.86 (16)C7—C8—C10—S113.1 (2)
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.353.069 (2)141
N2—H2B···S1ii0.862.663.481 (2)160
Symmetry codes: (i) x+2, y+1, z; (ii) x+3, y, z.
Selected geometric parameters (Å, º) for (Ib) top
S1—C101.6723 (15)C7—C81.366 (2)
N1—C91.137 (2)C8—C91.433 (2)
N2—C101.3270 (19)C8—C101.467 (2)
N3—C41.362 (2)
C8—C7—C1132.68 (14)N1—C9—C8178.70 (18)
C2—C1—C7—C8170.58 (19)C9—C8—C10—N2164.83 (16)
C1—C7—C8—C10179.09 (17)C7—C8—C10—S1159.37 (13)
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.202.989 (2)152
N2—H2B···S1ii0.862.583.421 (2)167
Symmetry codes: (i) x+1/2, y+1/2, z+3/2; (ii) x, y+1, z+2.
Selected geometric parameters (Å, º) for (Ic) top
S1A—C10A1.671 (3)S1B—C10B1.662 (3)
N1A—C9A1.148 (4)N1B—C9B1.144 (4)
N2A—C10A1.320 (4)N2B—C10B1.328 (4)
N3A—C4A1.369 (4)N3B—C4B1.351 (4)
C7A—C8A1.355 (4)C7B—C8B1.363 (4)
C8A—C9A1.422 (4)C8B—C9B1.422 (4)
C8A—C10A1.484 (4)C8B—C10B1.473 (4)
C8A—C7A—C1A132.1 (3)C8B—C7B—C1B131.4 (3)
N1A—C9A—C8A175.4 (3)N1B—C9B—C8B176.8 (4)
C2A—C1A—C7A—C8A176.7 (3)C2B—C1B—C7B—C8B165.7 (3)
C1A—C7A—C8A—C10A178.3 (3)C1B—C7B—C8B—C10B177.1 (3)
C9A—C8A—C10A—N2A12.4 (4)C9B—C8B—C10B—N2B7.9 (4)
C7A—C8A—C10A—S1A13.0 (4)C7B—C8B—C10B—S1B2.0 (4)
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···AD—HH···AD···AD—H···A
N2A—H2AA···N1Bi0.862.262.990 (4)143
N2A—H2AB···S1B0.862.483.293 (4)158
N2B—H2BA···N1Aii0.862.433.133 (4)139
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+1, z+1/2.
 

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