Three polar derivatives of N-ethylcarbazole: materials for optical applications

Three N-ethyl­carbazole derivatives have been synthesized and tested for non-linear optical (NLO) properties. The compounds are 2-(9-ethyl-9H-carbazol-3-yl­methyl­ene)­malono­nitrile, C₁₈H₁₃N₃, (IIIa), 2-cyano-3-(9-ethyl-9H-carba­zol-3-yl)­thio­acryl­amide, C₁₈H₁₅N₃S, (IIIb), and 3-(9-ethyl-9H-carbazol-3-yl)-2-(4-phenyl-1,3-thia­zol-2-yl)­acrylo­nitrile, C₂₆H₁₉N₃S, (V). It was found that the mol­ecules of (IIIa) and (V) are nearly planar, while non-planarity is more pronounced for (IIIb). Molecules of (IIIa) and (V) exhibit herring-bone packing motifs. In (IIIb), the mol­ecules form layers coplanar with (01), within which they form centrosymmetric dimers via N—H...S hydrogen bonds.

S1. Comment

Polar organic molecules as components of NLO, electro-optical, photorefractive and optical-limiting materials have been under intensive investigation for the last two decades (e.g. Zyss, 1994; Nalwa & Miyata, 1997; Kuzyk & Dirk, 1998). Structural data, along with theoretical calculations and experimental measurements, help to reveal the nature of the relevant structure-property relationships. The present investigation is a continuation of our project which includes synthesis, structural studies and evaluation of properties of organic compounds for potential optical applications (Antipin et al., 1997, 1998, 2001; Timofeeva et al., 2000; Nesterov et al., 2000). To our knowledge, no structural information on NLO carbazole derivatives has previously been available. Recently, we have synthesized and characterized a series of N-ethylcarbazole derivatives, (IIIa), (IIIb) and (V), shown in the synthetic scheme below. \sch

In this paper we present the results of structural investigations and the evaluation of second-harmonic generation (SGH) in solution for compounds (IIIa), (IIIb) and (V). Recently, we investigated another polar N-ethylcarbazole derivative, namely (E)-4-(9-ethyl-9H-carbazol-3-ylvinyl)-N-methylpyridinium iodide, (VI) (Wang et al., 2001), and we will compare the molecular geometry parameters for all four of these compounds.

The polar molecules under investigation can be formally divided into three planar fragments: a donor part, D, comprising the N-ethylcarbazole moiety less the ethyl group, a bridging part, B [–CH═C< in (IIIa), (IIIb) and (V), but –CH═CH– in (VI)], and an acceptor part, A, which differs in each molecule. The geometric parameters for N-ethylcarbazole in (IIIa), (IIIb), (V) and in the two symmetrically independent molecules of (VI) are very similar and do not vary from the standard values for corresponding heterocyclic systems (Allen et al., 1987). The orientation of the N-ethyl substituents in all the molecules is almost perpendicular to the carbazole plane (Tables 1, 2 and 4). In all the molecules, the bridging part B has a C═C bond which is slightly longer than the standard value (Allen et al., 1987). As the attached single bonds are slightly shorter (Tables 1, 2 and 4), this is evidence of some delocalization in the bridging units of these molecules.

The geometric parameters of the dicyanovinyl acceptor fragment in molecule (IIIa) (Fig. 1) are standard (Timofeeva et al., 2000). Molecule (IIIa) is almost planar, the dihedral angle between the least-squares mean planes of the donor part D Is this change OK? and the dicyanovinyl group is 5.1 (1)°. This does not differ significantly from the results for the other dicyanovinylaromatic molecules (Timofeeva et al., 2000). Molecules of (IIIa) adopt a herring-bone packing motif.

The Cambridge Structural Database (CSD, Version?; Allen & Kennard, 1993) contains only one compound, namely trans,trans-2-cyano-5-(4-methoxyphenyl)penta-2,4-dienethioamide (Nesterov et al., 2000), which has mutually trans CN and S substituents and is suitable for direct comparison with the cyanovinylthioamide fragment found in (IIIb) (Fig. 2). In the other two known structures containing such fragments, the cyano and thio substituents are mutually cis (Brunskill at al., 1984; Nesterov et al., 1991).

The different relative orientations of the substituents do not significantly influence the bond lengths and angles in this fragment, and their values are very similar in all these molecules. Molecule (IIIb) is less planar than (IIIa); the dihedral angle between the D and B fragments is 15.5 (1)°, and between B and A it is 12.0 (2)°. The molecules pack in layers coplanar with (201). Within these layers, (IIIb) forms centrosymmetric dimers via N3—H3B···S1ⁱ hydrogen bonds [Table 3; symmetry code: (i) 1 - x, 1 - y, 2 - z].

In molecule (V) (Fig. 3), the values for the molecular geometry parameters of the phenylthiazole (Ph—T) substituents are similar to the other examples found in the CSD. The dihedral angles between planar fragments in (V) are D/B 6.3 (1), B/T 5.0 (1) and T/Ph 4.2 (1)°. Molecule (V) has a `bent' conformation and a mutually trans orientation of the S atom and C═C bridge (Fig. 3). We used molecular mechanics calculations to compare the relative energies of `bent' and `stretched' molecules of (V) having cis orientations of S and the double bond. Please explain `bent' and `stretched'. We found that the `stretched' conformation is favoured (the energy difference is 2.1 kcal mol^-1; 1kcal mol^-1 = 4.184 kJ mol^-1), and this suggests that under other circumstances (e.g. in solution or in other polymorph), molecule (V) might adopt a different conformation. Molecules of (V) exhibit a herring-bone pattern in their packing.

All crystalline samples investigated are centrosymmetric, so they cannot manifest SHG in their crystalline phases. X-ray powder diffraction has shown that for both (IIIb) and (V), the crystalline phase present in the powder samples and in single crystals is the same. In contrast, the powder diffraction pattern for compound (IIIa) shows the presence of another crystalline phase. Unfortunately, we have not been able to obtain single crystals of the second phase of (IIIa) by conventional methods, and we are currently investigating other approaches to growing single crystals suitable for X-ray investigation.

SHG in solution can be measured after orientation of the molecules by an electric field. Electric field-induced second harmonic generation (EFISH) measurements of hyperpolarizability β(ω) in solution give values of 42.5, 60.2 and 65.2 × 10^-30 esu for molecules (IIIa), (IIIb) and (V), respectively. These results suggest that materials incorporating molecules of (IIIb) or (V) might be as efficient as traditional cyanovinyl derivatives (Antipin et al., 1997), but their melting point and thermal stability would both be higher because of the presence of the N-ethylcarbazole moiety.

S2. Experimental

The title compounds (IIIa) and (IIIb) were obtained by the reaction of N-ethyl-3-carbazolealdehyde, (I) (1.115 g, 0.005 mol), with malononitrile, (IIa) (0.330 g, 0.005 mol), or 2-cyanothioacetamide, (IIb) (0.500 g, 0.005 mol), respectively, in the presence of a catalytic amount of morpholine in ethanol (20 ml) at room temperature. The precipitates which separated from the solutions were recrystallized from ethanol (30 ml) and acetonitrile (30 ml), respectively [m.p. 431 K, yield 1.018 g (75%) for (IIIa); m.p. 490 K, yield 1.176 g (77%) for (IIIb)]. Compound (V) was obtained by the reaction of (IIIb) (1.527 g, 0.005 mol) with 2-bromoacetophenone, (IV) (0.995 g, 0.005 mol), in dimethylformamide (20 ml) at room temperature. The precipitate which separated from the solution was recrystallized from acetonitrile (30 ml) [m.p. 428 K; yield 1.521 g (75%)]. Crystals were obtained by isothermal evaporation from ethanolic solutions of (IIIa) or (IIIb), or from a solution of (V) in acetonitrile.

S3. Refinement

Molecular mechanics calculations were carried out using MM3 (Allinger et al., 1989; Lii & Allinger, 1989). EFISH measurements of hyperpolarizability of the three compounds in solution were performed using the methods described by Sanghadasa et al. (1996) and Antipin et al. (1997). H atoms were placed geometrically; for (IIIa) and (V), those attached to sp², methyl and methylene C atoms were set at 0.95, 0.98 and 0.99 Å, respectively. For (IIIb), the corresponding distances were 0.93, 0.96 and 0.97 Å. For methyl H atoms, U_iso(H) = 1.5U_eq(C), for all others U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (IIIa), (IIIb); P3 (Siemens, 1989) for (V). Cell refinement: CAD-4 Software for (IIIa), (IIIb); P3 for (V). For all compounds, 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

	Fig. 1. A view of the molecule of (IIIa) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (IIIb) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A view of the molecule of (V) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(IIIa) 2-(9-ethyl-9H-carbazol-3-ylmethylene)malononitrile

Crystal data

C18H13N3	F(000) = 568
Mr = 271.31	Dx = 1.269 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.731 (3) Å	Cell parameters from 24 reflections
b = 4.2160 (8) Å	θ = 11–12°
c = 26.640 (5) Å	µ = 0.08 mm^−1
β = 96.87 (3)°	T = 298 K
V = 1419.6 (5) Å^3	Needle, yellow
Z = 4	0.5 × 0.1 × 0.1 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.5°
Graphite monochromator	h = 0→15
θ/2θ scans	k = 0→5
2575 measured reflections	l = −31→31
2458 independent reflections	3 standard reflections every 97 reflections
1280 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.062P)^2] where P = (Fo^2 + 2Fc^2)/3
2458 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.24263 (18)	0.2665 (6)	0.12782 (9)	0.0432 (7)
N2	0.7266 (3)	0.2384 (9)	0.01848 (13)	0.0812 (11)
N3	0.9166 (2)	−0.3603 (10)	0.12600 (12)	0.0877 (12)
C1	0.4002 (2)	0.2588 (8)	0.08033 (12)	0.0487 (9)
H1A	0.3686	0.3770	0.0521	0.058*
C2	0.5028 (2)	0.1540 (8)	0.08266 (11)	0.0502 (9)
H2A	0.5425	0.2047	0.0557	0.060*
C3	0.5512 (2)	−0.0260 (8)	0.12358 (11)	0.0447 (8)
C4	0.4921 (2)	−0.1046 (8)	0.16329 (11)	0.0452 (9)
H4A	0.5230	−0.2311	0.1907	0.054*
C5	0.3892 (2)	0.0020 (8)	0.16249 (10)	0.0418 (8)
C6	0.3086 (2)	−0.0295 (8)	0.19616 (11)	0.0416 (8)
C7	0.3045 (2)	−0.1738 (8)	0.24234 (12)	0.0497 (9)
H7A	0.3637	−0.2884	0.2581	0.060*
C8	0.2135 (3)	−0.1496 (9)	0.26530 (12)	0.0559 (9)
H8A	0.2103	−0.2450	0.2974	0.067*
C9	0.1260 (3)	0.0143 (9)	0.24167 (13)	0.0565 (10)
H9A	0.0635	0.0243	0.2579	0.068*
C10	0.1272 (2)	0.1612 (8)	0.19584 (12)	0.0495 (9)
H10A	0.0674	0.2727	0.1800	0.059*
C11	0.2202 (2)	0.1390 (8)	0.17366 (11)	0.0416 (8)
C12	0.1706 (2)	0.4617 (9)	0.09390 (12)	0.0533 (9)
H12A	0.2127	0.6077	0.0751	0.064*
H12B	0.1269	0.5921	0.1143	0.064*
C13	0.0992 (3)	0.2686 (10)	0.05679 (13)	0.0719 (12)
H13A	0.0530	0.4105	0.0349	0.108*
H13B	0.0559	0.1276	0.0751	0.108*
H13C	0.1420	0.1416	0.0361	0.108*
C14	0.3439 (2)	0.1862 (8)	0.12072 (11)	0.0415 (8)
C15	0.6578 (2)	−0.1410 (8)	0.12851 (12)	0.0513 (9)
H15A	0.6763	−0.2702	0.1574	0.062*
C16	0.7369 (2)	−0.0986 (8)	0.09939 (11)	0.0466 (9)
C17	0.7297 (2)	0.0886 (10)	0.05432 (14)	0.0563 (10)
C18	0.8373 (3)	−0.2418 (10)	0.11382 (13)	0.0595 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0349 (14)	0.0495 (18)	0.0444 (15)	0.0088 (13)	0.0006 (11)	0.0012 (14)
N2	0.076 (2)	0.101 (3)	0.069 (2)	0.019 (2)	0.0201 (18)	0.015 (2)
N3	0.0536 (19)	0.124 (3)	0.088 (2)	0.028 (2)	0.0153 (17)	0.017 (2)
C1	0.0421 (19)	0.059 (2)	0.0440 (18)	0.0069 (17)	0.0025 (14)	0.0087 (18)
C2	0.0402 (18)	0.063 (2)	0.0472 (19)	0.0058 (19)	0.0053 (14)	0.0010 (19)
C3	0.0355 (17)	0.052 (2)	0.0460 (18)	0.0026 (17)	0.0033 (14)	−0.0014 (17)
C4	0.0433 (19)	0.048 (2)	0.0413 (18)	0.0024 (17)	−0.0054 (14)	0.0005 (16)
C5	0.0359 (17)	0.045 (2)	0.0429 (18)	0.0005 (16)	−0.0008 (13)	−0.0013 (17)
C6	0.0392 (18)	0.045 (2)	0.0390 (17)	0.0020 (16)	−0.0007 (14)	−0.0013 (16)
C7	0.050 (2)	0.049 (2)	0.049 (2)	0.0031 (18)	0.0030 (15)	0.0026 (18)
C8	0.056 (2)	0.066 (3)	0.0459 (19)	−0.004 (2)	0.0076 (16)	0.0047 (19)
C9	0.047 (2)	0.068 (3)	0.057 (2)	−0.006 (2)	0.0145 (16)	−0.007 (2)
C10	0.0415 (18)	0.053 (2)	0.054 (2)	0.0055 (17)	0.0042 (15)	−0.0012 (18)
C11	0.0400 (17)	0.045 (2)	0.0394 (18)	0.0051 (16)	0.0040 (14)	−0.0034 (16)
C12	0.0494 (19)	0.057 (2)	0.0526 (19)	0.0165 (19)	0.0040 (15)	0.0107 (19)
C13	0.068 (2)	0.078 (3)	0.064 (2)	0.025 (2)	−0.0192 (19)	−0.001 (2)
C14	0.0347 (17)	0.045 (2)	0.0439 (18)	0.0042 (16)	−0.0014 (13)	−0.0045 (16)
C15	0.0411 (18)	0.063 (2)	0.0493 (19)	0.0054 (18)	0.0018 (15)	−0.0008 (18)
C16	0.0395 (18)	0.055 (2)	0.0452 (19)	0.0041 (17)	0.0038 (14)	−0.0072 (18)
C17	0.044 (2)	0.072 (3)	0.054 (2)	0.0055 (19)	0.0118 (17)	−0.002 (2)
C18	0.043 (2)	0.078 (3)	0.059 (2)	0.010 (2)	0.0114 (17)	0.007 (2)

Geometric parameters (Å, º)

N1—C11	1.395 (4)	C7—C8	1.377 (4)
N1—C12	1.461 (4)	C7—H7A	0.9500
N1—C14	1.368 (3)	C8—C9	1.396 (4)
N2—C17	1.142 (4)	C8—H8A	0.9500
N3—C18	1.138 (4)	C9—C10	1.371 (4)
C1—C2	1.372 (4)	C9—H9A	0.9500
C1—C14	1.396 (4)	C10—C11	1.387 (4)
C1—H1A	0.9500	C10—H10A	0.9500
C2—C3	1.408 (4)	C12—C13	1.501 (4)
C2—H2A	0.9500	C12—H12A	0.9900
C3—C4	1.409 (4)	C12—H12B	0.9900
C3—C15	1.432 (4)	C13—H13A	0.9800
C4—C5	1.383 (4)	C13—H13B	0.9800
C4—H4A	0.9500	C13—H13C	0.9800
C5—C14	1.421 (4)	C15—C16	1.355 (4)
C5—C6	1.448 (4)	C15—H15A	0.9500
C6—C7	1.379 (4)	C16—C18	1.424 (5)
C6—C11	1.403 (4)	C16—C17	1.431 (5)
C14—N1—C11	108.7 (2)	C9—C10—C11	116.8 (3)
C14—N1—C12	125.8 (3)	C9—C10—H10A	121.6
C11—N1—C12	125.4 (2)	C11—C10—H10A	121.6
C2—C1—C14	117.9 (3)	C10—C11—N1	128.4 (3)
C2—C1—H1A	121.1	C10—C11—C6	122.2 (3)
C14—C1—H1A	121.1	N1—C11—C6	109.3 (3)
C1—C2—C3	122.3 (3)	N1—C12—C13	112.8 (3)
C1—C2—H2A	118.9	N1—C12—H12A	109.0
C3—C2—H2A	118.9	C13—C12—H12A	109.0
C2—C3—C4	119.0 (3)	N1—C12—H12B	109.0
C2—C3—C15	125.1 (3)	C13—C12—H12B	109.0
C4—C3—C15	115.9 (3)	H12A—C12—H12B	107.8
C5—C4—C3	120.1 (3)	C12—C13—H13A	109.5
C5—C4—H4A	119.9	C12—C13—H13B	109.5
C3—C4—H4A	119.9	H13A—C13—H13B	109.5
C4—C5—C14	119.0 (3)	C12—C13—H13C	109.5
C4—C5—C6	134.5 (3)	H13A—C13—H13C	109.5
C14—C5—C6	106.5 (2)	H13B—C13—H13C	109.5
C7—C6—C11	119.4 (3)	N1—C14—C1	129.2 (3)
C7—C6—C5	134.3 (3)	N1—C14—C5	109.1 (3)
C11—C6—C5	106.3 (3)	C1—C14—C5	121.7 (3)
C8—C7—C6	119.1 (3)	C16—C15—C3	131.6 (3)
C8—C7—H7A	120.4	C16—C15—H15A	114.2
C6—C7—H7A	120.4	C3—C15—H15A	114.2
C7—C8—C9	120.4 (3)	C15—C16—C18	119.6 (3)
C7—C8—H8A	119.8	C15—C16—C17	125.2 (3)
C9—C8—H8A	119.8	C18—C16—C17	115.2 (3)
C10—C9—C8	122.1 (3)	N2—C17—C16	178.3 (4)
C10—C9—H9A	119.0	N3—C18—C16	178.6 (4)
C8—C9—H9A	119.0
C14—C1—C2—C3	1.1 (5)	C12—N1—C11—C6	−178.9 (3)
C1—C2—C3—C4	0.7 (5)	C7—C6—C11—C10	−1.3 (5)
C1—C2—C3—C15	−179.6 (3)	C5—C6—C11—C10	−179.7 (3)
C2—C3—C4—C5	−1.8 (5)	C7—C6—C11—N1	179.3 (3)
C15—C3—C4—C5	178.5 (3)	C5—C6—C11—N1	0.9 (4)
C3—C4—C5—C14	1.1 (5)	C14—N1—C12—C13	94.2 (4)
C3—C4—C5—C6	−179.2 (3)	C11—N1—C12—C13	−87.8 (4)
C4—C5—C6—C7	1.3 (7)	C11—N1—C14—C1	179.6 (3)
C14—C5—C6—C7	−178.9 (4)	C12—N1—C14—C1	−2.2 (5)
C4—C5—C6—C11	179.4 (4)	C11—N1—C14—C5	0.1 (3)
C14—C5—C6—C11	−0.8 (3)	C12—N1—C14—C5	178.4 (3)
C11—C6—C7—C8	0.1 (5)	C2—C1—C14—N1	178.8 (3)
C5—C6—C7—C8	178.0 (3)	C2—C1—C14—C5	−1.8 (5)
C6—C7—C8—C9	1.1 (5)	C4—C5—C14—N1	−179.8 (3)
C7—C8—C9—C10	−1.3 (5)	C6—C5—C14—N1	0.4 (3)
C8—C9—C10—C11	0.2 (5)	C4—C5—C14—C1	0.8 (5)
C9—C10—C11—N1	−179.6 (3)	C6—C5—C14—C1	−179.1 (3)
C9—C10—C11—C6	1.1 (5)	C2—C3—C15—C16	3.9 (6)
C14—N1—C11—C10	−180.0 (3)	C4—C3—C15—C16	−176.5 (3)
C12—N1—C11—C10	1.7 (5)	C3—C15—C16—C18	179.5 (4)
C14—N1—C11—C6	−0.7 (4)	C3—C15—C16—C17	0.9 (6)

(IIIb) 2-cyano-3-(9-ethyl-9H-carbazol-3-yl)thioacrylamide

Crystal data

C18H15N3S	Z = 2
Mr = 305.39	F(000) = 320
Triclinic, P1	Dx = 1.284 Mg m^−3
a = 8.4370 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7500 (17) Å	Cell parameters from 24 reflections
c = 12.300 (3) Å	θ = 11–12°
α = 79.82 (3)°	µ = 0.20 mm^−1
β = 76.82 (3)°	T = 298 K
γ = 63.76 (3)°	Parallelepiped prism, orange
V = 790.0 (3) Å^3	0.50 × 0.35 × 0.30 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.013
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.7°
Graphite monochromator	h = 0→10
θ/2θ scans	k = −9→10
2971 measured reflections	l = −14→14
2762 independent reflections	3 standard reflections every 97 reflections
2257 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.24P] where P = (Fo^2 + 2Fc^2)/3
2762 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.41428 (8)	0.37861 (7)	0.89386 (4)	0.0599 (2)
N1	0.0770 (2)	0.5525 (2)	0.26053 (12)	0.0453 (4)
N2	0.2878 (3)	0.9276 (3)	0.64142 (18)	0.0721 (6)
N3	0.4516 (2)	0.6662 (2)	0.85720 (13)	0.0565 (5)
H3A	0.4438	0.7603	0.8181	0.068*
H3B	0.4880	0.6413	0.9206	0.068*
C1	0.1080 (3)	0.7126 (2)	0.39735 (15)	0.0482 (4)
H1A	0.0477	0.8207	0.3629	0.058*
C2	0.1753 (3)	0.6928 (2)	0.49317 (15)	0.0475 (4)
H2A	0.1617	0.7895	0.5226	0.057*
C3	0.2644 (2)	0.5304 (2)	0.54832 (13)	0.0409 (4)
C4	0.2851 (2)	0.3853 (2)	0.50360 (14)	0.0414 (4)
H4A	0.3405	0.2775	0.5400	0.050*
C5	0.2230 (2)	0.4016 (2)	0.40500 (13)	0.0385 (4)
C6	0.2251 (2)	0.2815 (2)	0.33690 (14)	0.0420 (4)
C7	0.2969 (3)	0.1045 (3)	0.34141 (18)	0.0565 (5)
H7A	0.3554	0.0374	0.4001	0.068*
C8	0.2804 (4)	0.0297 (3)	0.2577 (2)	0.0702 (6)
H8A	0.3288	−0.0889	0.2597	0.084*
C9	0.1920 (4)	0.1294 (3)	0.1701 (2)	0.0707 (7)
H9A	0.1837	0.0755	0.1142	0.085*
C10	0.1163 (3)	0.3055 (3)	0.16378 (17)	0.0561 (5)
H10A	0.0557	0.3713	0.1057	0.067*
C11	0.1346 (2)	0.3806 (2)	0.24809 (14)	0.0427 (4)
C12	−0.0334 (3)	0.6954 (3)	0.19076 (17)	0.0569 (5)
H12A	−0.1117	0.7893	0.2364	0.068*
H12B	−0.1081	0.6606	0.1608	0.068*
C13	0.0772 (4)	0.7543 (4)	0.0971 (2)	0.0844 (8)
H13A	0.0004	0.8491	0.0535	0.127*
H13B	0.1522	0.6625	0.0505	0.127*
H13C	0.1508	0.7894	0.1265	0.127*
C14	0.1327 (2)	0.5660 (2)	0.35335 (14)	0.0402 (4)
C15	0.3292 (2)	0.5051 (2)	0.65209 (14)	0.0431 (4)
H15A	0.3658	0.3937	0.6856	0.052*
C16	0.3463 (2)	0.6140 (2)	0.70918 (14)	0.0426 (4)
C17	0.3106 (3)	0.7882 (3)	0.66844 (16)	0.0502 (5)
C18	0.4077 (2)	0.5594 (3)	0.81966 (14)	0.0445 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0807 (4)	0.0756 (4)	0.0394 (3)	−0.0425 (3)	−0.0283 (2)	0.0058 (2)
N1	0.0520 (9)	0.0510 (9)	0.0372 (8)	−0.0203 (7)	−0.0196 (7)	−0.0021 (6)
N2	0.0845 (14)	0.0540 (12)	0.0779 (13)	−0.0146 (10)	−0.0425 (11)	−0.0081 (9)
N3	0.0723 (11)	0.0784 (12)	0.0355 (8)	−0.0440 (10)	−0.0190 (8)	0.0010 (8)
C1	0.0533 (11)	0.0451 (10)	0.0448 (10)	−0.0132 (8)	−0.0228 (8)	−0.0019 (8)
C2	0.0527 (11)	0.0491 (10)	0.0427 (10)	−0.0161 (9)	−0.0188 (8)	−0.0089 (8)
C3	0.0401 (9)	0.0528 (10)	0.0296 (8)	−0.0185 (8)	−0.0083 (7)	−0.0031 (7)
C4	0.0452 (10)	0.0479 (10)	0.0308 (8)	−0.0198 (8)	−0.0092 (7)	0.0015 (7)
C5	0.0400 (9)	0.0472 (10)	0.0300 (8)	−0.0203 (8)	−0.0066 (7)	−0.0015 (7)
C6	0.0470 (10)	0.0510 (10)	0.0333 (9)	−0.0258 (8)	−0.0068 (7)	−0.0023 (7)
C7	0.0732 (14)	0.0504 (12)	0.0528 (11)	−0.0301 (10)	−0.0191 (10)	0.0013 (9)
C8	0.0951 (18)	0.0534 (13)	0.0728 (15)	−0.0348 (13)	−0.0231 (13)	−0.0099 (11)
C9	0.0991 (18)	0.0702 (15)	0.0619 (13)	−0.0448 (14)	−0.0225 (13)	−0.0156 (11)
C10	0.0708 (13)	0.0679 (13)	0.0434 (10)	−0.0363 (11)	−0.0200 (9)	−0.0052 (9)
C11	0.0461 (10)	0.0529 (11)	0.0351 (9)	−0.0252 (8)	−0.0083 (7)	−0.0048 (7)
C12	0.0641 (13)	0.0597 (12)	0.0519 (11)	−0.0215 (10)	−0.0300 (10)	−0.0026 (9)
C13	0.102 (2)	0.0909 (19)	0.0746 (17)	−0.0514 (17)	−0.0369 (15)	0.0167 (14)
C14	0.0398 (9)	0.0497 (10)	0.0326 (8)	−0.0181 (8)	−0.0117 (7)	−0.0019 (7)
C15	0.0424 (9)	0.0554 (11)	0.0306 (8)	−0.0189 (8)	−0.0088 (7)	−0.0026 (7)
C16	0.0372 (9)	0.0550 (11)	0.0321 (8)	−0.0147 (8)	−0.0077 (7)	−0.0056 (7)
C17	0.0480 (11)	0.0588 (13)	0.0422 (10)	−0.0128 (9)	−0.0179 (8)	−0.0135 (9)
C18	0.0384 (9)	0.0653 (12)	0.0315 (9)	−0.0212 (9)	−0.0064 (7)	−0.0094 (8)

Geometric parameters (Å, º)

S1—C18	1.665 (2)	C6—C11	1.410 (3)
N1—C11	1.387 (2)	C7—C8	1.375 (3)
N1—C12	1.457 (2)	C7—H7A	0.9300
N1—C14	1.371 (2)	C8—C9	1.392 (3)
N2—C17	1.146 (3)	C8—H8A	0.9300
N3—C18	1.327 (2)	C9—C10	1.378 (3)
N3—H3A	0.8600	C9—H9A	0.9300
N3—H3B	0.8600	C10—C11	1.391 (3)
C1—C2	1.374 (2)	C10—H10A	0.9300
C1—C14	1.393 (3)	C12—C13	1.480 (3)
C1—H1A	0.9300	C12—H12A	0.9700
C2—C3	1.411 (3)	C12—H12B	0.9700
C2—H2A	0.9300	C13—H13A	0.9600
C3—C4	1.397 (3)	C13—H13B	0.9600
C3—C15	1.445 (2)	C13—H13C	0.9600
C4—C5	1.388 (2)	C15—C16	1.351 (3)
C4—H4A	0.9300	C15—H15A	0.9300
C5—C14	1.408 (2)	C16—C17	1.435 (3)
C5—C6	1.447 (2)	C16—C18	1.488 (2)
C6—C7	1.387 (3)
C14—N1—C11	108.64 (15)	C8—C9—H9A	119.0
C14—N1—C12	125.48 (16)	C9—C10—C11	117.1 (2)
C11—N1—C12	125.79 (15)	C9—C10—H10A	121.4
C18—N3—H3A	120.0	C11—C10—H10A	121.4
C18—N3—H3B	120.0	N1—C11—C10	129.15 (18)
H3A—N3—H3B	120.0	N1—C11—C6	109.16 (15)
C2—C1—C14	118.06 (17)	C10—C11—C6	121.68 (18)
C2—C1—H1A	121.0	N1—C12—C13	111.69 (19)
C14—C1—H1A	121.0	N1—C12—H12A	109.3
C1—C2—C3	122.13 (17)	C13—C12—H12A	109.3
C1—C2—H2A	118.9	N1—C12—H12B	109.3
C3—C2—H2A	118.9	C13—C12—H12B	109.3
C4—C3—C2	118.78 (15)	H12A—C12—H12B	107.9
C4—C3—C15	117.50 (16)	C12—C13—H13A	109.5
C2—C3—C15	123.66 (17)	C12—C13—H13B	109.5
C5—C4—C3	120.19 (16)	H13A—C13—H13B	109.5
C5—C4—H4A	119.9	C12—C13—H13C	109.5
C3—C4—H4A	119.9	H13A—C13—H13C	109.5
C4—C5—C14	119.26 (16)	H13B—C13—H13C	109.5
C4—C5—C6	134.19 (17)	N1—C14—C1	128.98 (17)
C14—C5—C6	106.53 (15)	N1—C14—C5	109.49 (15)
C7—C6—C11	119.55 (17)	C1—C14—C5	121.53 (15)
C7—C6—C5	134.28 (17)	C16—C15—C3	131.64 (18)
C11—C6—C5	106.15 (16)	C16—C15—H15A	114.2
C8—C7—C6	118.9 (2)	C3—C15—H15A	114.2
C8—C7—H7A	120.5	C15—C16—C17	123.41 (16)
C6—C7—H7A	120.5	C15—C16—C18	121.76 (17)
C7—C8—C9	120.8 (2)	C17—C16—C18	114.82 (16)
C7—C8—H8A	119.6	N2—C17—C16	175.4 (2)
C9—C8—H8A	119.6	N3—C18—C16	115.93 (17)
C10—C9—C8	121.9 (2)	N3—C18—S1	121.89 (14)
C10—C9—H9A	119.0	C16—C18—S1	122.14 (14)
C14—C1—C2—C3	−1.2 (3)	C5—C6—C11—N1	−0.78 (19)
C1—C2—C3—C4	0.2 (3)	C7—C6—C11—C10	−0.5 (3)
C1—C2—C3—C15	−176.91 (18)	C5—C6—C11—C10	177.96 (17)
C2—C3—C4—C5	1.7 (3)	C14—N1—C12—C13	90.9 (2)
C15—C3—C4—C5	179.03 (15)	C11—N1—C12—C13	−93.0 (2)
C3—C4—C5—C14	−2.6 (3)	C11—N1—C14—C1	179.08 (18)
C3—C4—C5—C6	178.88 (17)	C12—N1—C14—C1	−4.3 (3)
C4—C5—C6—C7	−3.6 (4)	C11—N1—C14—C5	−1.9 (2)
C14—C5—C6—C7	177.8 (2)	C12—N1—C14—C5	174.73 (17)
C4—C5—C6—C11	178.26 (19)	C2—C1—C14—N1	179.17 (18)
C14—C5—C6—C11	−0.37 (19)	C2—C1—C14—C5	0.3 (3)
C11—C6—C7—C8	1.0 (3)	C4—C5—C14—N1	−177.47 (15)
C5—C6—C7—C8	−176.9 (2)	C6—C5—C14—N1	1.41 (19)
C6—C7—C8—C9	−0.5 (4)	C4—C5—C14—C1	1.6 (3)
C7—C8—C9—C10	−0.6 (4)	C6—C5—C14—C1	−179.51 (16)
C8—C9—C10—C11	1.1 (4)	C4—C3—C15—C16	172.01 (18)
C14—N1—C11—C10	−176.94 (19)	C2—C3—C15—C16	−10.9 (3)
C12—N1—C11—C10	6.4 (3)	C3—C15—C16—C17	−4.8 (3)
C14—N1—C11—C6	1.7 (2)	C3—C15—C16—C18	176.30 (17)
C12—N1—C11—C6	−174.96 (17)	C15—C16—C18—N3	167.64 (17)
C9—C10—C11—N1	177.9 (2)	C17—C16—C18—N3	−11.3 (2)
C9—C10—C11—C6	−0.5 (3)	C15—C16—C18—S1	−14.4 (2)
C7—C6—C11—N1	−179.26 (17)	C17—C16—C18—S1	166.67 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S1^i	0.86	2.55	3.402 (2)	170

Symmetry code: (i) −x+1, −y+1, −z+2.

(V) 3-(9-ethyl-9H-carbazol-3-yl)-2-(4-phenyl-1,3-thiazol-2-yl)acrylonitrile

Crystal data

C26H19N3S	F(000) = 848
Mr = 405.50	Dx = 1.299 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.384 (5) Å	Cell parameters from 24 reflections
b = 16.456 (4) Å	θ = 10–11°
c = 6.5323 (17) Å	µ = 0.17 mm^−1
β = 95.637 (19)°	T = 155 K
V = 2073.6 (9) Å^3	Parallelepiped prism, yellow
Z = 4	0.45 × 0.30 × 0.25 mm

Data collection

Syntex P21 diffractometer	Rint = 0.037
Radiation source: fine-focus sealed tube	θmax = 27.1°, θmin = 1.6°
Graphite monochromator	h = −24→24
θ/2θ scans	k = −21→1
4942 measured reflections	l = 0→8
4540 independent reflections	2 standard reflections every 98 reflections
3066 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 0.92	w = 1/[σ^2(Fo^2) + (0.068P)^2] where P = (Fo^2 + 2Fc^2)/3
4540 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.20194 (3)	0.31806 (3)	0.05188 (7)	0.02802 (13)
N1	0.12528 (8)	0.61215 (9)	1.2467 (2)	0.0254 (3)
N2	0.06157 (9)	0.38222 (11)	0.3266 (3)	0.0384 (4)
N3	0.30257 (8)	0.38962 (9)	0.2654 (2)	0.0248 (3)
C1	0.09224 (10)	0.53882 (11)	0.9157 (3)	0.0263 (4)
H1A	0.0436	0.5443	0.9202	0.032*
C2	0.11898 (9)	0.49900 (11)	0.7554 (3)	0.0250 (4)
H2A	0.0879	0.4766	0.6487	0.030*
C3	0.19116 (9)	0.49047 (10)	0.7449 (3)	0.0233 (4)
C4	0.23698 (9)	0.52376 (10)	0.9019 (3)	0.0222 (4)
H4A	0.2856	0.5190	0.8964	0.027*
C5	0.21125 (9)	0.56379 (10)	1.0661 (3)	0.0216 (4)
C6	0.24330 (9)	0.60339 (10)	1.2497 (3)	0.0229 (4)
C7	0.31150 (10)	0.61490 (11)	1.3325 (3)	0.0276 (4)
H7A	0.3489	0.5938	1.2653	0.033*
C8	0.32373 (10)	0.65775 (11)	1.5147 (3)	0.0313 (4)
H8A	0.3700	0.6662	1.5730	0.038*
C9	0.26847 (11)	0.68879 (11)	1.6141 (3)	0.0311 (4)
H9A	0.2782	0.7187	1.7380	0.037*
C10	0.20072 (11)	0.67714 (11)	1.5376 (3)	0.0289 (4)
H10A	0.1637	0.6980	1.6070	0.035*
C11	0.18801 (9)	0.63357 (10)	1.3541 (3)	0.0242 (4)
C12	0.05616 (9)	0.62479 (11)	1.3134 (3)	0.0281 (4)
H12A	0.0607	0.6353	1.4633	0.034*
H12B	0.0288	0.5744	1.2884	0.034*
C13	0.01729 (12)	0.69442 (14)	1.2049 (3)	0.0428 (5)
H13A	−0.0286	0.6993	1.2548	0.064*
H13B	0.0120	0.6842	1.0564	0.064*
H13C	0.0432	0.7450	1.2329	0.064*
C14	0.13916 (9)	0.57089 (10)	1.0716 (3)	0.0235 (4)
C15	0.22154 (9)	0.45043 (10)	0.5780 (3)	0.0230 (4)
H15A	0.2707	0.4538	0.5862	0.028*
C16	0.19238 (9)	0.40897 (10)	0.4118 (3)	0.0231 (4)
C17	0.11940 (10)	0.39494 (11)	0.3680 (3)	0.0267 (4)
C18	0.23587 (9)	0.37656 (10)	0.2586 (3)	0.0235 (4)
C19	0.28324 (10)	0.31182 (11)	−0.0283 (3)	0.0294 (4)
H19A	0.2941	0.2833	−0.1474	0.035*
C20	0.33026 (10)	0.35307 (11)	0.1013 (3)	0.0262 (4)
C21	0.40495 (10)	0.36253 (12)	0.0813 (3)	0.0305 (4)
C22	0.43695 (12)	0.32309 (16)	−0.0731 (4)	0.0494 (6)
H22A	0.4100	0.2901	−0.1699	0.059*
C23	0.50706 (13)	0.33114 (18)	−0.0876 (4)	0.0596 (7)
H23A	0.5279	0.3037	−0.1938	0.072*
C24	0.54709 (12)	0.37859 (17)	0.0506 (4)	0.0522 (6)
H24A	0.5956	0.3833	0.0416	0.063*
C25	0.51646 (12)	0.41932 (16)	0.2021 (4)	0.0509 (6)
H25A	0.5437	0.4533	0.2958	0.061*
C26	0.44613 (11)	0.41086 (13)	0.2182 (3)	0.0400 (5)
H26A	0.4257	0.4386	0.3246	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0328 (3)	0.0242 (2)	0.0271 (2)	−0.00163 (19)	0.00313 (18)	−0.00433 (19)
N1	0.0276 (8)	0.0254 (8)	0.0243 (8)	0.0004 (6)	0.0084 (6)	−0.0026 (6)
N2	0.0320 (10)	0.0438 (10)	0.0395 (10)	−0.0056 (8)	0.0040 (8)	−0.0111 (8)
N3	0.0303 (8)	0.0197 (7)	0.0250 (8)	0.0020 (6)	0.0050 (6)	−0.0011 (6)
C1	0.0243 (9)	0.0279 (9)	0.0271 (9)	−0.0015 (7)	0.0050 (7)	−0.0005 (8)
C2	0.0251 (9)	0.0256 (9)	0.0241 (9)	−0.0017 (7)	0.0012 (7)	−0.0008 (7)
C3	0.0271 (10)	0.0182 (8)	0.0250 (9)	−0.0005 (7)	0.0057 (7)	0.0026 (7)
C4	0.0222 (9)	0.0186 (8)	0.0263 (9)	0.0002 (7)	0.0054 (7)	0.0041 (7)
C5	0.0252 (9)	0.0168 (8)	0.0228 (9)	−0.0010 (7)	0.0028 (7)	0.0027 (7)
C6	0.0312 (10)	0.0154 (8)	0.0231 (9)	−0.0001 (7)	0.0067 (7)	0.0021 (7)
C7	0.0299 (10)	0.0220 (9)	0.0314 (10)	0.0004 (8)	0.0054 (8)	0.0012 (8)
C8	0.0339 (10)	0.0261 (10)	0.0326 (11)	−0.0029 (8)	−0.0031 (8)	0.0015 (8)
C9	0.0447 (12)	0.0213 (9)	0.0266 (10)	−0.0040 (8)	0.0006 (8)	−0.0010 (8)
C10	0.0408 (11)	0.0214 (9)	0.0257 (9)	0.0006 (8)	0.0084 (8)	−0.0013 (8)
C11	0.0302 (10)	0.0171 (8)	0.0261 (9)	−0.0002 (7)	0.0062 (8)	0.0034 (7)
C12	0.0281 (10)	0.0287 (9)	0.0287 (10)	0.0000 (8)	0.0094 (8)	−0.0008 (8)
C13	0.0451 (13)	0.0471 (13)	0.0376 (12)	0.0191 (10)	0.0115 (9)	0.0045 (10)
C14	0.0294 (10)	0.0185 (8)	0.0230 (9)	0.0007 (7)	0.0054 (7)	0.0007 (7)
C15	0.0238 (9)	0.0199 (8)	0.0259 (9)	−0.0003 (7)	0.0048 (7)	0.0026 (7)
C16	0.0279 (9)	0.0190 (8)	0.0231 (9)	0.0004 (7)	0.0059 (7)	0.0022 (7)
C17	0.0330 (11)	0.0229 (9)	0.0252 (10)	−0.0008 (8)	0.0075 (8)	−0.0045 (7)
C18	0.0310 (10)	0.0152 (8)	0.0245 (9)	0.0003 (7)	0.0040 (7)	−0.0008 (7)
C19	0.0381 (11)	0.0246 (9)	0.0266 (10)	0.0023 (8)	0.0079 (8)	−0.0033 (8)
C20	0.0311 (10)	0.0202 (8)	0.0283 (10)	0.0031 (7)	0.0076 (8)	0.0012 (7)
C21	0.0339 (10)	0.0289 (10)	0.0298 (10)	0.0056 (8)	0.0090 (8)	0.0021 (8)
C22	0.0428 (13)	0.0622 (16)	0.0456 (13)	−0.0008 (11)	0.0165 (11)	−0.0182 (12)
C23	0.0471 (15)	0.089 (2)	0.0461 (15)	0.0132 (14)	0.0202 (12)	−0.0094 (14)
C24	0.0348 (12)	0.0761 (18)	0.0477 (14)	0.0025 (12)	0.0135 (11)	0.0098 (13)
C25	0.0322 (12)	0.0656 (16)	0.0549 (15)	−0.0057 (11)	0.0033 (10)	−0.0062 (13)
C26	0.0366 (12)	0.0434 (12)	0.0406 (12)	0.0007 (9)	0.0069 (9)	−0.0078 (10)

Geometric parameters (Å, º)

S1—C18	1.7342 (18)	C10—C11	1.398 (3)
S1—C19	1.712 (2)	C10—H10A	0.9500
N1—C11	1.388 (2)	C12—C13	1.509 (3)
N1—C12	1.464 (2)	C12—H12A	0.9900
N1—C14	1.379 (2)	C12—H12B	0.9900
N2—C17	1.146 (2)	C13—H13A	0.9800
N3—C18	1.307 (2)	C13—H13B	0.9800
N3—C20	1.383 (2)	C13—H13C	0.9800
C1—C2	1.379 (3)	C15—C16	1.358 (2)
C1—C14	1.401 (3)	C15—H15A	0.9500
C1—H1A	0.9500	C16—C17	1.434 (3)
C2—C3	1.415 (2)	C16—C18	1.471 (2)
C2—H2A	0.9500	C19—C20	1.362 (3)
C3—C4	1.401 (3)	C19—H19A	0.9500
C3—C15	1.448 (2)	C20—C21	1.475 (3)
C4—C5	1.392 (2)	C21—C26	1.389 (3)
C4—H4A	0.9500	C21—C22	1.395 (3)
C5—C14	1.406 (2)	C22—C23	1.378 (3)
C5—C6	1.450 (2)	C22—H22A	0.9500
C6—C7	1.391 (3)	C23—C24	1.374 (4)
C6—C11	1.415 (2)	C23—H23A	0.9500
C7—C8	1.384 (3)	C24—C25	1.377 (3)
C7—H7A	0.9500	C24—H24A	0.9500
C8—C9	1.403 (3)	C25—C26	1.385 (3)
C8—H8A	0.9500	C25—H25A	0.9500
C9—C10	1.372 (3)	C26—H26A	0.9500
C9—H9A	0.9500
C18—S1—C19	88.93 (9)	C12—C13—H13A	109.5
C11—N1—C12	126.54 (15)	C12—C13—H13B	109.5
C11—N1—C14	108.14 (14)	H13A—C13—H13B	109.5
C12—N1—C14	125.15 (15)	C12—C13—H13C	109.5
C18—N3—C20	111.08 (15)	H13A—C13—H13C	109.5
C2—C1—C14	117.76 (17)	H13B—C13—H13C	109.5
C2—C1—H1A	121.1	N1—C14—C1	128.54 (17)
C14—C1—H1A	121.1	N1—C14—C5	109.72 (15)
C1—C2—C3	122.11 (17)	C1—C14—C5	121.74 (16)
C1—C2—H2A	118.9	C16—C15—C3	131.52 (17)
C3—C2—H2A	118.9	C16—C15—H15A	114.2
C4—C3—C2	118.98 (16)	C3—C15—H15A	114.2
C4—C3—C15	117.00 (16)	C15—C16—C17	124.43 (16)
C2—C3—C15	124.00 (16)	C15—C16—C18	120.34 (16)
C5—C4—C3	119.99 (16)	C17—C16—C18	115.21 (16)
C5—C4—H4A	120.0	N2—C17—C16	177.5 (2)
C3—C4—H4A	120.0	N3—C18—C16	123.25 (16)
C4—C5—C14	119.41 (16)	N3—C18—S1	114.59 (13)
C4—C5—C6	133.87 (16)	C16—C18—S1	122.16 (14)
C14—C5—C6	106.72 (15)	C20—C19—S1	111.09 (14)
C7—C6—C11	120.04 (17)	C20—C19—H19A	124.5
C7—C6—C5	134.13 (17)	S1—C19—H19A	124.5
C11—C6—C5	105.83 (16)	C19—C20—N3	114.30 (17)
C8—C7—C6	118.66 (17)	C19—C20—C21	126.89 (17)
C8—C7—H7A	120.7	N3—C20—C21	118.81 (17)
C6—C7—H7A	120.7	C26—C21—C22	117.6 (2)
C7—C8—C9	120.66 (18)	C26—C21—C20	120.70 (18)
C7—C8—H8A	119.7	C22—C21—C20	121.67 (19)
C9—C8—H8A	119.7	C23—C22—C21	121.1 (2)
C10—C9—C8	121.84 (18)	C23—C22—H22A	119.4
C10—C9—H9A	119.1	C21—C22—H22A	119.4
C8—C9—H9A	119.1	C24—C23—C22	120.4 (2)
C9—C10—C11	117.78 (18)	C24—C23—H23A	119.8
C9—C10—H10A	121.1	C22—C23—H23A	119.8
C11—C10—H10A	121.1	C23—C24—C25	119.5 (2)
N1—C11—C10	129.45 (17)	C23—C24—H24A	120.2
N1—C11—C6	109.55 (15)	C25—C24—H24A	120.2
C10—C11—C6	121.00 (17)	C24—C25—C26	120.2 (2)
N1—C12—C13	113.41 (16)	C24—C25—H25A	119.9
N1—C12—H12A	108.9	C26—C25—H25A	119.9
C13—C12—H12A	108.9	C25—C26—C21	121.1 (2)
N1—C12—H12B	108.9	C25—C26—H26A	119.5
C13—C12—H12B	108.9	C21—C26—H26A	119.5
H12A—C12—H12B	107.7
C14—C1—C2—C3	−0.4 (3)	C4—C5—C14—N1	179.80 (15)
C1—C2—C3—C4	−0.2 (3)	C6—C5—C14—N1	−0.06 (19)
C1—C2—C3—C15	−178.89 (17)	C4—C5—C14—C1	−0.1 (2)
C2—C3—C4—C5	0.6 (2)	C6—C5—C14—C1	−179.98 (16)
C15—C3—C4—C5	179.40 (15)	C4—C3—C15—C16	175.92 (18)
C3—C4—C5—C14	−0.5 (2)	C2—C3—C15—C16	−5.4 (3)
C3—C4—C5—C6	179.34 (17)	C3—C15—C16—C17	−0.9 (3)
C4—C5—C6—C7	−1.5 (3)	C3—C15—C16—C18	177.52 (17)
C14—C5—C6—C7	178.36 (19)	C20—N3—C18—C16	−179.18 (16)
C4—C5—C6—C11	179.14 (18)	C20—N3—C18—S1	0.39 (19)
C14—C5—C6—C11	−1.03 (18)	C15—C16—C18—N3	−4.4 (3)
C11—C6—C7—C8	−1.5 (3)	C17—C16—C18—N3	174.18 (16)
C5—C6—C7—C8	179.18 (18)	C15—C16—C18—S1	176.07 (13)
C6—C7—C8—C9	0.1 (3)	C17—C16—C18—S1	−5.4 (2)
C7—C8—C9—C10	1.0 (3)	C19—S1—C18—N3	−0.20 (14)
C8—C9—C10—C11	−0.6 (3)	C19—S1—C18—C16	179.38 (15)
C14—N1—C11—C10	178.64 (17)	C18—S1—C19—C20	−0.06 (15)
C12—N1—C11—C10	−5.9 (3)	S1—C19—C20—N3	0.3 (2)
C14—N1—C11—C6	−1.84 (19)	S1—C19—C20—C21	−178.99 (15)
C12—N1—C11—C6	173.61 (16)	C18—N3—C20—C19	−0.4 (2)
C9—C10—C11—N1	178.72 (17)	C18—N3—C20—C21	178.91 (16)
C9—C10—C11—C6	−0.8 (3)	C19—C20—C21—C26	175.8 (2)
C7—C6—C11—N1	−177.73 (15)	N3—C20—C21—C26	−3.4 (3)
C5—C6—C11—N1	1.76 (19)	C19—C20—C21—C22	−4.8 (3)
C7—C6—C11—C10	1.8 (3)	N3—C20—C21—C22	175.92 (19)
C5—C6—C11—C10	−178.67 (15)	C26—C21—C22—C23	0.7 (4)
C14—N1—C12—C13	−81.2 (2)	C20—C21—C22—C23	−178.7 (2)
C11—N1—C12—C13	104.1 (2)	C21—C22—C23—C24	−0.1 (4)
C11—N1—C14—C1	−178.92 (17)	C22—C23—C24—C25	−1.1 (4)
C12—N1—C14—C1	5.6 (3)	C23—C24—C25—C26	1.6 (4)
C11—N1—C14—C5	1.16 (19)	C24—C25—C26—C21	−1.0 (4)
C12—N1—C14—C5	−174.36 (15)	C22—C21—C26—C25	−0.2 (3)
C2—C1—C14—N1	−179.38 (17)	C20—C21—C26—C25	179.2 (2)
C2—C1—C14—C5	0.5 (3)