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The title compounds, 3,4-dimethyl-N-[1-(1H-pyrrol-2-yl)ethyl­idene]aniline, C14H16N2, (I), and its analogue 3,4-dimethyl-N-[1-(1-thio­phen-2-yl)ethyl­idene]aniline, C14H15NS, (II), both have basic heterocyclic imino structures showing a planar backbone with similar features, but differing in the hetero­atoms of the five-membered heterocyclic rings, i.e. N in (I) and S in (II). The dihedral angles formed by the five-membered and benzene rings are 81.78 (8) and 75.89 (7)° for (I) and (II), respectively. In (I), centrosymmetric imino­pyrrole dimers are assembled by means of two inverted N—H...N hydrogen bonds and two inverted C—H...π inter­actions. In (II), however, mol­ecules are linked by nonclassical C—H...N hydrogen bonds in which the mol­ecules act as both hydrogen-bond donors and acceptors, resulting in one-dimensional supra­molecular chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113022142/cu3033sup1.cif
Contains datablocks I, II, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113022142/cu3033Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113022142/cu3033IIsup3.hkl
Contains datablock II

CCDC references: 964774; 964775

Introduction top

Late transition metal catalysts have attracted much attention in recent years because of their good anti­oxidant properties and outstanding catalytic activities for olefin polymerization (Small et al., 1998; Gibson et al., 1998; Britovsek et al., 2003; Su & Zhao., 2006). Nitro­gen-based ligands, acting as good electron donors, are usually employed as ligand precursors in the preparation of coordination compounds. Recently, the exploration of nitro­gen-based ligands has shifted to the alternative variants of typical bis­(imino)­pyridine, such as pyrimidine, pyrazine, triazine, pyrrole, carbazole, furan and thio­phene (Tenza et al., 2009), in which the central pyridine ring has been replaced by alternative heterocycles. In the research field of five-membered heterocyclic rings, in comparision with the considerable researches about the symmetric bis­(imino)­pyrrole, little attention has been paid to the asymmetric heterocyclic imino derivatives. To the best of our knowledge, only a limited number of mono(imino)­pyrrole compounds have been reported in the literature (Dawson et al., 2000; Anderson et al., 2006; Carabineiro et al., 2007; Pérez-Puente et al., 2008). The case is similar for mono(imino)­thio­phene compounds (Cuesta et al., 2011), in which most of the side arms of the heterocyclic rings were H atoms. To simulate the original structure of a bis­(imino)­pyridine ligand, we chose to replace an H atom with a methyl group and thus prepare new heterocyclic imino compounds. As part of our studies of heterocyclic imino ligands (Su et al., 2009a,b), we have reported the molecular structures of some mono(imino)­pyrrolyl compounds (Su, Li et al., 2012a,b; Su, Qin & Wang, 2012; Su, Qin, Jiao & Wang, 2012; Su et al., 2013).

Experimental top

Synthesis and crystallization top

For the synthesis of compound (I), 2-acetyl­pyrrole (0.2003 g, 1.8354 mmol) and 3,4-di­methyl­aniline (0.4432 g, 3.6574 mmol) were placed in a 50 ml flask. For the synthesis of compound (II), 2-acetyl­thio­phene (0.5966 g, 4.7282 mmol) and 3,4-di­methyl­aniline (1.1275 g, 9.3043 mmol) were placed in a 50 ml flask. A few drops of acetic acid were added and the mixture was subjected to irradiation in a 800 W microwave oven for 3 and 2 min for (I) and (II), respectively, on a medium–heat setting; the colours of both solutions changed from brown to black. The reactions were monitored by thin-layer chromatography (TLC), and the crude products were purified by silica-gel column chromatography (eluant petroleum ether–ethyl acetate, 5:1 v:v). The colourless crystals of (I) and yellow crystals of (II) were both obtained by recrystallization from ethanol and water [for (I), yield 0.1274 g, 32.69%; m.p. 386.6—388.3 K; for (II), yield 0.2962 g, 27.31%, m.p. 341.7—343.3 K]. Crystallization from ethanol and water gave crystals suitable for single-crystal X-ray diffraction.

The purity and the composition of compounds (I) and (II) were checked and characterized by IR spectroscopy, NMR, mass spectrometry and elemental analysis. Data for (I): νCN 1672 cm-1. 1H NMR (400 MHz, CDCl3): δ 7.13 (t, 2H, benzene ring aromatic H), 7.05 (m, 1H, benzene ring aromatic H), 6.68 (d, 1H, pyrrole ring aromatic H), 6.33 (s, 1H, pyrrole ring aromatic H), 6.17 (d, 1H, pyrrole ring aromatic H), 2.08 (s, 6H, benzene-CH3), 1.89 [s, 3H, –N C(CH3)–]. MS (EI): m/z 212 (M). Analysis calculated for C14H16N2: C 79.21, H 7.60, N 13.20%; found: C 79.05, H 7.49, N 12.91%. Data for (II), IR (KBr): νCN 1620 cm-1. 1H NMR (400 MHz, CDCl3): δ 7.43 (m, 2H, benzene ring aromatic H), 7.08 (m, 2H, thio­phene ring aromatic H), 6.62 (s, 1H, benzene ring aromatic H), 6.56 (s, 1H, thio­phene ring aromatic H), 2.23 (t, 6H, benzene-CH3), 2.19 [s, 3H, –NC(CH3)–]. MS (EI): m/z 230 (M + H). Analysis calculated for C14H15NS: C 73.32, H 6.59, N 6.11%; found: C 73.36, H 6.80, N 5.92%.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. For compounds (I) and (II), all H atoms, except for the N-bound H atoms in (I), were positioned geometrically and treated using a riding model, with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively. The displacement parameters of the H atoms were constrained to Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. For (I), the N-bound H atoms were located in difference electron-density maps and were refined freely. One reflection, which was clearly an outlier and failed to meet processing requirements, was omitted.

Results and discussion top

In this report, we present here the crystal structures of 3,4-di­methyl-N-[1-(1H-pyrrol-2-yl)ethyl­idene]aniline, (I), and its analogue 3,4-di­methyl-N-[1-(1-thio­phen-2-yl)ethyl­idene]aniline, (II). In both compounds, the meta and para positions of the benzene rings are substituted by methyl groups, the only difference between the two compounds being the heteroatoms in the five-membered rings, i.e. N in (I) and S in (II) (see Scheme). The corresponding molecular structures are depicted in Fig. 1. The sum of all the angles around atom C4 is ca 360° in both compounds, indicating the the C4—C5 bond and the five-membered rings are in the same plane. Likewise, the N1—C4—C5—N2 torsion angle of -3.3 (3)° in (I) and the S1—C4—C5—N1 torsion angle of -0.7 (3)° in (II) show that the five-membered rings and the –NC(CH3)– groups are nearly coplanar in both cases. For both (I) and (II), the planes of the aromatic substituents on the imine N atoms show dihedral angles of 81.78 (8) and 75.89 (7)° with respect to the plane of the five-membered ring in (I) and (II), respectively. These values are in keeping with the reported trend in our previous work (Su et al., 2013), which is that the benzene rings are rotated about the Nimine—Car bond, forming dihedral angles of approximately 80° with the plane of the five-membered ring.

Both (I) and (II) have the basic heterocyclic imino structure, showing a planar backbone with similar features. A brief analysis of the bond lengths and angles in these derivatives (Tables 2 and 3) reveals some noticeable differences in corresponding bond lengths and angles. The C4—C5 bond in (I) is substanti­ally shorter than that in (II), whereas the C5—N2 bond in (I) is obviously longer than the C5—N1 bond in (II). Even so, all the C4—C5 bond lengths, in the range 1.447 (3)–1.466 (3) Å, are slightly shorter than the normal value for a typical Csp2—Csp2 single bond (1.476 Å; Allen et al., 1987). Similarly, the C5—N2 and C5—N1 bond lengths, in the range 1.269 (3)–1.284 (3) Å, are slightly shorter than the normal value for a typical Csp2N double bonds (1.324 Å; Allen et al., 1987), all above facts reveal electron delocalization effects produced from both pyrrole and thio­phene rings towards the –NC(CH3)– substituent, in which the delocalization effect of pyrrole ring is relatively strong.

As has been reported before (Su, Li et al., 2012a,b; Su, Qin & Wang, 2012; Su, Qin, Jiao & Wang, 2012; Su et al., 2013), these types of organic derivatives assemble as imino­pyrrole dimers through the formation of two complementary hydrogen bonds between a pyrrole N—H group and the imine N atom belonging to the other molecule of the pair. Besides, the dimers are stabilized by a pair of inter­molecular C—H···π inter­actions between a C—H group bonded to pyrrolyl N atom and the benzene ring belonging to the other molecule of the pair. Accordingly, both inverted N—H···N hydrogen bonds and two inverted C—H···π inter­actions exist in compound (I), which join two molecules in a head-to-tail manner across crystallographic inversion centres to give dimers (Table 4 and Fig. 2). In C—H···π inter­actions, the H···Cg (Cg is the centroid of the benzene rings) distances are 2.76 Å, and the C—H···π angle is 142.2°, the angle of approach of the H···Cg vector to the plane of the aromatic ring is 80.5° and the perpendicular projection of the H atoms onto the pyrrole ring plane is 0.45 Å from the centroid of the ring. It is observed that the H atom lies above the centre of the benzene ring, but the C—H bond points towards a benzene ring C atom. This inter­actions belong to type III according to the classification of Malone et al. (1997). In contrast to the classical hydrogen bonds in (I), examination of the structure with PLATON (Spek, 2009) indicates that there are no classical hydrogen bonds in (II) due to the fact that there is no classical donor (N), whereas nonclassical C—H···Ni hydrogen bonds inter­actions are found in (II) [symmetry codes: (i) -x+1/2, y-1/2, -z+1/2; Table 5 and Fig. 3]. Molecules are linked by nonclassical C—H···N hydrogen bonds in which the molecules play both the roles of hydrogen bond donors and acceptors resulting in one-dimensional supra­molecular chains. Due to the supra­molecular inter­actions described above, the crystal packing shows a zigzag arrangement when viewed along a axis, as depicted in Fig. 3.

Related literature top

For related literature, see: Allen et al. (1987); Anderson et al. (2006); Britovsek et al. (2003); Carabineiro et al. (2007); Cuesta et al. (2011); Dawson et al. (2000); Gibson et al. (1998); Malone et al. (1997); Pérez-Puente, de Jesús, Flores & Gómez-Sal (2008); Small et al. (1998); Spek (2009); Su & Zhao (2006); Su et al. (2009a, 2009b, 2012a, 2012b, 2013); Tenza et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008) for (I); APEX2 (Bruker,2008) for (II). Cell refinement: SAINT (Bruker, 2008) for (I); SAINT (Bruker,2008) for (II). Data reduction: SAINT (Bruker, 2008 for (I); SAINT (Bruker,2008) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
Fig. 1. The molecular structures of (a) (I) and (b) (II), showing the atom-numbering schemes. Displacement ellipsiods are drawn at 40% probability level. H atoms are presented as a small spheres of arbitrary radius.

Fig. 2. A view of N—H···N and C—H···π interactions (dotted lines) in the crystal structure of (I). H atoms not involved in hydrogen bonding have been omitted for clarity. The largest spheres indicate the centroids of the C7–C11 rings (Cg1). [Symmetry code: (i) -x, -y+1, -z.]

Fig. 3. A view of the unit-cell packing in (II), view along a axis, with the C—H···N bonding scheme shown as dashed lines. H atoms not involved in C—H···N interactions have been omitted for clarity. [Symmetry code: (i) -x+1/2, y-1/2, -z+1/2.]
(I) 3,4-Dimethyl-N-[1-(1H-pyrrol-2-yl)ethylidene]aniline top
Crystal data top
C14H16N2F(000) = 456
Mr = 212.29Dx = 1.139 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 838 reflections
a = 13.013 (3) Åθ = 2.6–22.5°
b = 10.265 (2) ŵ = 0.07 mm1
c = 9.892 (2) ÅT = 296 K
β = 110.448 (4)°Block, colourless
V = 1238.2 (4) Å30.37 × 0.26 × 0.15 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
2603 independent reflections
Radiation source: fine-focus sealed tube1344 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ϕ and ω scansθmax = 26.9°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 167
Tmin = 0.975, Tmax = 0.990k = 1213
6774 measured reflectionsl = 1212
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
2603 reflections(Δ/σ)max = 0.001
151 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C14H16N2V = 1238.2 (4) Å3
Mr = 212.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.013 (3) ŵ = 0.07 mm1
b = 10.265 (2) ÅT = 296 K
c = 9.892 (2) Å0.37 × 0.26 × 0.15 mm
β = 110.448 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2603 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1344 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.990Rint = 0.047
6774 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.189H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.17 e Å3
2603 reflectionsΔρmin = 0.16 e Å3
151 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
N10.17111 (16)0.46605 (19)0.02161 (19)0.0606 (5)
H10.1169 (19)0.500 (2)0.040 (2)0.073*
N20.03340 (15)0.40619 (18)0.18907 (18)0.0643 (6)
C10.27753 (19)0.4720 (2)0.1073 (3)0.0723 (7)
H1A0.30550.51540.19510.087*
C20.3370 (2)0.4029 (3)0.0421 (3)0.0795 (8)
H20.41260.39110.07730.095*
C30.2642 (2)0.3534 (3)0.0862 (3)0.0748 (7)
H30.28240.30220.15210.090*
C40.15956 (18)0.3937 (2)0.0987 (2)0.0579 (6)
C50.0541 (2)0.3664 (2)0.2080 (2)0.0594 (6)
C60.0547 (2)0.2908 (3)0.3394 (3)0.0915 (9)
H6A0.02560.20510.33770.137*
H6B0.12860.28400.33840.137*
H6C0.01040.33530.42530.137*
C70.13719 (19)0.3741 (2)0.2936 (2)0.0601 (6)
C80.1881 (2)0.2577 (2)0.2830 (2)0.0744 (7)
H80.15320.19860.21020.089*
C90.2905 (2)0.2303 (3)0.3809 (3)0.0795 (8)
H90.32310.15140.37310.095*
C100.34727 (19)0.3147 (3)0.4904 (2)0.0689 (7)
C110.2978 (2)0.4342 (2)0.4993 (2)0.0642 (6)
C120.1935 (2)0.4612 (2)0.4006 (2)0.0648 (6)
H120.16080.54040.40690.078*
C130.4574 (2)0.2778 (3)0.5978 (3)0.0988 (9)
H13A0.47730.19260.57550.148*
H13B0.45380.27750.69310.148*
H13C0.51140.33980.59350.148*
C140.3561 (2)0.5324 (3)0.6135 (3)0.0956 (9)
H14A0.31300.61050.59920.143*
H14B0.42630.55210.60710.143*
H14C0.36600.49700.70710.143*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0576 (12)0.0699 (13)0.0547 (10)0.0015 (9)0.0201 (10)0.0055 (9)
N20.0624 (13)0.0724 (13)0.0543 (11)0.0006 (10)0.0154 (10)0.0119 (9)
C10.0597 (15)0.0922 (18)0.0584 (13)0.0008 (13)0.0123 (13)0.0062 (13)
C20.0620 (15)0.0979 (19)0.0698 (15)0.0160 (14)0.0120 (13)0.0005 (15)
C30.0743 (17)0.0842 (18)0.0658 (15)0.0177 (13)0.0245 (13)0.0011 (13)
C40.0655 (15)0.0582 (13)0.0489 (11)0.0062 (11)0.0187 (11)0.0007 (10)
C50.0715 (16)0.0552 (13)0.0500 (12)0.0038 (11)0.0193 (12)0.0020 (10)
C60.092 (2)0.109 (2)0.0698 (16)0.0110 (16)0.0233 (15)0.0271 (15)
C70.0669 (14)0.0634 (14)0.0488 (11)0.0009 (11)0.0187 (11)0.0093 (11)
C80.0840 (18)0.0665 (16)0.0613 (14)0.0064 (13)0.0112 (13)0.0031 (12)
C90.0881 (19)0.0778 (17)0.0681 (15)0.0203 (15)0.0217 (14)0.0013 (14)
C100.0673 (15)0.0826 (17)0.0557 (13)0.0089 (13)0.0203 (12)0.0057 (12)
C110.0722 (16)0.0750 (16)0.0448 (11)0.0082 (13)0.0196 (12)0.0034 (11)
C120.0788 (16)0.0639 (15)0.0514 (12)0.0074 (13)0.0225 (12)0.0066 (11)
C130.0736 (18)0.133 (3)0.0812 (18)0.0164 (17)0.0165 (15)0.0066 (18)
C140.117 (2)0.090 (2)0.0657 (15)0.0132 (17)0.0139 (16)0.0032 (14)
Geometric parameters (Å, º) top
N1—C11.349 (3)C7—C81.388 (3)
N1—C41.366 (3)C8—C91.375 (3)
N1—H10.86 (2)C8—H80.9300
N2—C51.284 (3)C9—C101.382 (3)
N2—C71.423 (3)C9—H90.9300
C1—C21.367 (3)C10—C111.403 (3)
C1—H1A0.9300C10—C131.505 (3)
C2—C31.387 (3)C11—C121.395 (3)
C2—H20.9300C11—C141.506 (3)
C3—C41.387 (3)C12—H120.9300
C3—H30.9300C13—H13A0.9600
C4—C51.447 (3)C13—H13B0.9600
C5—C61.517 (3)C13—H13C0.9600
C6—H6A0.9600C14—H14A0.9600
C6—H6B0.9600C14—H14B0.9600
C6—H6C0.9600C14—H14C0.9600
C7—C121.384 (3)
C1—N1—C4110.39 (19)C9—C8—C7119.6 (2)
C1—N1—H1126.0 (15)C9—C8—H8120.2
C4—N1—H1123.6 (15)C7—C8—H8120.2
C5—N2—C7119.03 (18)C8—C9—C10123.0 (2)
N1—C1—C2107.8 (2)C8—C9—H9118.5
N1—C1—H1A126.1C10—C9—H9118.5
C2—C1—H1A126.1C9—C10—C11117.8 (2)
C1—C2—C3107.7 (2)C9—C10—C13120.9 (2)
C1—C2—H2126.2C11—C10—C13121.4 (2)
C3—C2—H2126.2C12—C11—C10119.0 (2)
C2—C3—C4107.9 (2)C12—C11—C14120.3 (2)
C2—C3—H3126.0C10—C11—C14120.7 (2)
C4—C3—H3126.0C7—C12—C11122.2 (2)
N1—C4—C3106.2 (2)C7—C12—H12118.9
N1—C4—C5122.9 (2)C11—C12—H12118.9
C3—C4—C5130.9 (2)C10—C13—H13A109.5
N2—C5—C4119.17 (19)C10—C13—H13B109.5
N2—C5—C6124.0 (2)H13A—C13—H13B109.5
C4—C5—C6116.9 (2)C10—C13—H13C109.5
C5—C6—H6A109.5H13A—C13—H13C109.5
C5—C6—H6B109.5H13B—C13—H13C109.5
H6A—C6—H6B109.5C11—C14—H14A109.5
C5—C6—H6C109.5C11—C14—H14B109.5
H6A—C6—H6C109.5H14A—C14—H14B109.5
H6B—C6—H6C109.5C11—C14—H14C109.5
C12—C7—C8118.3 (2)H14A—C14—H14C109.5
C12—C7—N2121.4 (2)H14B—C14—H14C109.5
C8—C7—N2120.1 (2)
C4—N1—C1—C20.2 (3)C5—N2—C7—C887.4 (3)
N1—C1—C2—C30.3 (3)C12—C7—C8—C92.1 (3)
C1—C2—C3—C40.3 (3)N2—C7—C8—C9177.1 (2)
C1—N1—C4—C30.0 (3)C7—C8—C9—C100.8 (4)
C1—N1—C4—C5177.7 (2)C8—C9—C10—C111.0 (4)
C2—C3—C4—N10.1 (3)C8—C9—C10—C13177.8 (2)
C2—C3—C4—C5177.6 (2)C9—C10—C11—C121.5 (3)
C7—N2—C5—C4177.21 (18)C13—C10—C11—C12177.3 (2)
C7—N2—C5—C62.6 (3)C9—C10—C11—C14178.4 (2)
N1—C4—C5—N23.3 (3)C13—C10—C11—C142.7 (3)
C3—C4—C5—N2173.8 (2)C8—C7—C12—C111.6 (3)
N1—C4—C5—C6176.8 (2)N2—C7—C12—C11176.56 (19)
C3—C4—C5—C66.0 (4)C10—C11—C12—C70.2 (3)
C5—N2—C7—C1297.8 (3)C14—C11—C12—C7179.7 (2)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C7–C12 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.86 (2)2.33 (2)3.122 (3)154 (2)
C1—H1A···Cg1i0.932.763.537 (6)142
Symmetry code: (i) x, y+1, z.
(II) 3,4-Dimethyl-N-[1-(1-thiophen-2-yl)ethylidene]aniline top
Crystal data top
C14H15NSF(000) = 976
Mr = 229.33Dx = 1.170 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1387 reflections
a = 11.1481 (15) Åθ = 2.3–20.8°
b = 13.1309 (18) ŵ = 0.22 mm1
c = 17.839 (2) ÅT = 296 K
β = 94.474 (3)°Block, yellow
V = 2603.3 (6) Å30.37 × 0.30 × 0.27 mm
Z = 8
Data collection top
Bruker APEXII CCD
diffractometer
2292 independent reflections
Radiation source: fine-focus sealed tube1563 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 139
Tmin = 0.923, Tmax = 0.942k = 1515
6337 measured reflectionsl = 1821
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
2292 reflections(Δ/σ)max < 0.001
148 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C14H15NSV = 2603.3 (6) Å3
Mr = 229.33Z = 8
Monoclinic, C2/cMo Kα radiation
a = 11.1481 (15) ŵ = 0.22 mm1
b = 13.1309 (18) ÅT = 296 K
c = 17.839 (2) Å0.37 × 0.30 × 0.27 mm
β = 94.474 (3)°
Data collection top
Bruker APEXII CCD
diffractometer
2292 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1563 reflections with I > 2σ(I)
Tmin = 0.923, Tmax = 0.942Rint = 0.025
6337 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.173H-atom parameters constrained
S = 1.07Δρmax = 0.16 e Å3
2292 reflectionsΔρmin = 0.27 e Å3
148 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
S10.20232 (6)0.52375 (5)0.25492 (4)0.0871 (4)
N10.37976 (17)0.62611 (14)0.35887 (11)0.0678 (6)
C10.1665 (3)0.4120 (2)0.21001 (16)0.0882 (8)
H10.09890.40360.17660.106*
C20.2455 (3)0.3381 (2)0.22768 (16)0.0825 (8)
H20.23890.27260.20790.099*
C30.3407 (2)0.36991 (19)0.27980 (14)0.0727 (7)
H30.40310.32770.29830.087*
C40.3299 (2)0.47154 (17)0.29997 (12)0.0603 (6)
C50.40930 (19)0.53363 (16)0.35088 (12)0.0550 (5)
C60.5174 (2)0.48288 (19)0.38900 (16)0.0786 (8)
H6A0.55160.52580.42870.118*
H6B0.57590.47130.35320.118*
H6C0.49430.41890.40960.118*
C70.4550 (2)0.69472 (16)0.40323 (14)0.0617 (6)
C80.5569 (2)0.7354 (2)0.37574 (15)0.0752 (7)
H80.58090.71410.32950.090*
C90.6228 (2)0.8075 (2)0.41679 (16)0.0823 (8)
H90.69150.83380.39770.099*
C100.5907 (2)0.84183 (19)0.48493 (16)0.0737 (7)
C110.4879 (2)0.80154 (18)0.51412 (14)0.0695 (7)
C120.4204 (2)0.72907 (19)0.47157 (14)0.0679 (6)
H120.35060.70340.48970.082*
C130.6665 (3)0.9214 (2)0.5284 (2)0.1071 (10)
H13A0.73260.94070.50000.161*
H13B0.69690.89360.57590.161*
H13C0.61800.98010.53670.161*
C140.4467 (3)0.8354 (3)0.58840 (17)0.1086 (10)
H14A0.51000.82460.62720.163*
H14B0.37710.79680.59950.163*
H14C0.42650.90650.58590.163*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0852 (6)0.0742 (5)0.0967 (6)0.0026 (3)0.0258 (4)0.0070 (3)
N10.0632 (12)0.0535 (11)0.0835 (14)0.0011 (9)0.0147 (10)0.0011 (9)
C10.0889 (19)0.088 (2)0.0851 (19)0.0266 (17)0.0115 (15)0.0106 (15)
C20.0938 (19)0.0722 (17)0.0827 (18)0.0243 (16)0.0137 (15)0.0162 (14)
C30.0752 (16)0.0666 (15)0.0780 (16)0.0088 (13)0.0165 (14)0.0089 (12)
C40.0634 (14)0.0582 (14)0.0597 (14)0.0064 (11)0.0063 (11)0.0008 (10)
C50.0577 (13)0.0536 (13)0.0539 (12)0.0018 (10)0.0051 (10)0.0051 (9)
C60.0801 (17)0.0683 (16)0.0846 (18)0.0146 (13)0.0117 (14)0.0058 (13)
C70.0606 (13)0.0497 (12)0.0720 (15)0.0041 (10)0.0134 (11)0.0034 (11)
C80.0727 (16)0.0726 (16)0.0799 (16)0.0064 (13)0.0037 (13)0.0033 (13)
C90.0722 (16)0.0807 (18)0.094 (2)0.0173 (14)0.0038 (15)0.0009 (15)
C100.0702 (16)0.0661 (15)0.0812 (18)0.0008 (12)0.0180 (14)0.0057 (13)
C110.0748 (16)0.0634 (14)0.0677 (15)0.0129 (12)0.0110 (13)0.0021 (11)
C120.0620 (14)0.0647 (14)0.0752 (16)0.0027 (11)0.0063 (12)0.0112 (12)
C130.108 (2)0.087 (2)0.120 (2)0.0198 (18)0.0307 (19)0.0155 (17)
C140.124 (3)0.120 (3)0.081 (2)0.008 (2)0.0015 (18)0.0136 (18)
Geometric parameters (Å, º) top
S1—C11.704 (3)C7—C121.383 (3)
S1—C41.720 (2)C8—C91.374 (3)
N1—C51.269 (3)C8—H80.9300
N1—C71.428 (3)C9—C101.370 (4)
C1—C21.331 (4)C9—H90.9300
C1—H10.9300C10—C111.399 (4)
C2—C31.418 (4)C10—C131.518 (4)
C2—H20.9300C11—C121.399 (3)
C3—C41.390 (3)C11—C141.503 (4)
C3—H30.9300C12—H120.9300
C4—C51.466 (3)C13—H13A0.9600
C5—C61.494 (3)C13—H13B0.9600
C6—H6A0.9600C13—H13C0.9600
C6—H6B0.9600C14—H14A0.9600
C6—H6C0.9600C14—H14B0.9600
C7—C81.379 (3)C14—H14C0.9600
C1—S1—C491.79 (14)C9—C8—H8120.1
C5—N1—C7121.31 (19)C7—C8—H8120.1
C2—C1—S1112.9 (2)C10—C9—C8122.3 (2)
C2—C1—H1123.5C10—C9—H9118.9
S1—C1—H1123.5C8—C9—H9118.9
C1—C2—C3112.8 (2)C9—C10—C11118.9 (2)
C1—C2—H2123.6C9—C10—C13120.4 (3)
C3—C2—H2123.6C11—C10—C13120.7 (3)
C4—C3—C2112.1 (2)C10—C11—C12118.5 (2)
C4—C3—H3123.9C10—C11—C14122.1 (3)
C2—C3—H3123.9C12—C11—C14119.4 (3)
C3—C4—C5129.4 (2)C7—C12—C11121.7 (2)
C3—C4—S1110.30 (18)C7—C12—H12119.2
C5—C4—S1120.34 (17)C11—C12—H12119.2
N1—C5—C4116.9 (2)C10—C13—H13A109.5
N1—C5—C6125.7 (2)C10—C13—H13B109.5
C4—C5—C6117.4 (2)H13A—C13—H13B109.5
C5—C6—H6A109.5C10—C13—H13C109.5
C5—C6—H6B109.5H13A—C13—H13C109.5
H6A—C6—H6B109.5H13B—C13—H13C109.5
C5—C6—H6C109.5C11—C14—H14A109.5
H6A—C6—H6C109.5C11—C14—H14B109.5
H6B—C6—H6C109.5H14A—C14—H14B109.5
C8—C7—C12118.8 (2)C11—C14—H14C109.5
C8—C7—N1120.8 (2)H14A—C14—H14C109.5
C12—C7—N1120.2 (2)H14B—C14—H14C109.5
C9—C8—C7119.9 (2)
C4—S1—C1—C20.3 (2)C5—N1—C7—C12109.2 (3)
S1—C1—C2—C30.1 (3)C12—C7—C8—C91.0 (4)
C1—C2—C3—C40.5 (3)N1—C7—C8—C9174.8 (2)
C2—C3—C4—C5179.0 (2)C7—C8—C9—C100.4 (4)
C2—C3—C4—S10.7 (3)C8—C9—C10—C110.6 (4)
C1—S1—C4—C30.52 (19)C8—C9—C10—C13179.8 (2)
C1—S1—C4—C5179.16 (19)C9—C10—C11—C121.4 (3)
C7—N1—C5—C4175.8 (2)C13—C10—C11—C12179.4 (2)
C7—N1—C5—C64.4 (4)C9—C10—C11—C14179.9 (2)
C3—C4—C5—N1178.9 (2)C13—C10—C11—C140.9 (4)
S1—C4—C5—N10.7 (3)C8—C7—C12—C111.8 (3)
C3—C4—C5—C61.3 (3)N1—C7—C12—C11175.6 (2)
S1—C4—C5—C6179.07 (17)C10—C11—C12—C72.0 (3)
C5—N1—C7—C877.1 (3)C14—C11—C12—C7179.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N1i0.932.573.428 (3)153
Symmetry code: (i) x+1/2, y1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H16N2C14H15NS
Mr212.29229.33
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/c
Temperature (K)296296
a, b, c (Å)13.013 (3), 10.265 (2), 9.892 (2)11.1481 (15), 13.1309 (18), 17.839 (2)
β (°) 110.448 (4) 94.474 (3)
V3)1238.2 (4)2603.3 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.070.22
Crystal size (mm)0.37 × 0.26 × 0.150.37 × 0.30 × 0.27
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Bruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Multi-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.975, 0.9900.923, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
6774, 2603, 1344 6337, 2292, 1563
Rint0.0470.025
(sin θ/λ)max1)0.6360.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.189, 0.96 0.048, 0.173, 1.07
No. of reflections26032292
No. of parameters151148
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.160.16, 0.27

Computer programs: APEX2 (Bruker, 2008), APEX2 (Bruker,2008), SAINT (Bruker, 2008), SAINT (Bruker,2008), SAINT (Bruker, 2008, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) for (I) top
N1—C11.349 (3)C1—C21.367 (3)
N1—C41.366 (3)C2—C31.387 (3)
N2—C51.284 (3)C3—C41.387 (3)
N2—C71.423 (3)C4—C51.447 (3)
C1—N1—C4110.39 (19)N1—C4—C3106.2 (2)
N1—C1—C2107.8 (2)N1—C4—C5122.9 (2)
C1—C2—C3107.7 (2)C3—C4—C5130.9 (2)
C2—C3—C4107.9 (2)N2—C5—C4119.17 (19)
N1—C4—C5—N23.3 (3)C5—N2—C7—C887.4 (3)
Selected geometric parameters (Å, º) for (II) top
S1—C11.704 (3)C1—C21.331 (4)
S1—C41.720 (2)C2—C31.418 (4)
N1—C51.269 (3)C3—C41.390 (3)
N1—C71.428 (3)C4—C51.466 (3)
C1—S1—C491.79 (14)C3—C4—C5129.4 (2)
C2—C1—S1112.9 (2)C3—C4—S1110.30 (18)
C1—C2—C3112.8 (2)C5—C4—S1120.34 (17)
C4—C3—C2112.1 (2)N1—C5—C4116.9 (2)
S1—C4—C5—N10.7 (3)C5—N1—C7—C877.1 (3)
Hydrogen-bond geometry (Å, º) for (I) top
Cg1 is the centroid of the C7–C12 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.86 (2)2.33 (2)3.122 (3)154 (2)
C1—H1A···Cg1i0.932.763.537 (6)142.2
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N1i0.932.573.428 (3)152.7
Symmetry code: (i) x+1/2, y1/2, z+1/2.
 

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