Indole- and carbazole-substituted pyridinium iodide salts: a rare case of conformational isomerism in crystals

A series of indole- and carbazole-substituted pyridinium iodide salts has been synthesized and characterized. X-ray analysis revealed that the iodide salt of the indole-substituted cation (E)-4-(1H-indol-3-yl­vinyl)-N-methyl­pyridinium (IMPE⁺), C₁₆H₁₅N₂⁺·I^-, (I), has two polymorphic modifications, (Ia) and (Ib), and a hemihydrate structure, C₁₆H₁₅N₂⁺·I^-·0.5H₂O, (II). Until now, only one crystal modi­fication has been identified for the (E)-4-(9-ethyl-9H-carbazol-3-yl­vinyl)-N-methyl­pyridinium (ECMPE⁺) iodide salt, C₂₂H₂₁N₂⁺·I^-, (III). Crystals of (Ia) and (Ib) comprise stacks of antiparallel cations with iodide anions located in the channels between the stacks. Due to the presence of the water mol­ecules, the packing in (II) is quite different to that found in (Ia) and (Ib), and positional disorder involving a statistical superposition of two rotamers of IMPE⁺, with different orientations of the indole fragment, was found. Crystals of (III) contain two independent ECMPE⁺ rotamers with different orientations of their carbazole substituents. The cations are packed in stacks, with the iodide anions located in the channels between the stacks. In (III), the iodide was found to be disordered over two sites, with occupancies of 0.83 and 0.17.

S1. Comment

In a search for potential non-linear optical (NLO) materials, we have carried out the synthesis and characterization of several indole- and carbazole-substituted pyridinium salts. In many cases, organic salts were found to be significantly more active as NLO materials than compounds containing neutral organic molecules. We plan to use long-tail analogues of the salts described in this paper in the preparation of Langmuir–Blodgett films. The NLO properties of several pyridinium and quinolinium salts which form Langmuir–Blodgett films have been described recently (Hu, 1993; Xu et al., 1997; Ashwell et al., 1998; Johal et al., 1999). To our knowledge, no pyridinium salts with indole or carbazole substituents have been previously structurally characterized.

Crystallization of (E)-4-(3-indolylvinyl)-N-methylpyridinium iodide (IMPE⁺·I^-) from dimethyl sulfoxide (DMSO) solution resulted in the formation of two types of crystals, namely orange square-prismatic crystals, (Ia), and thin yellow needles, (Ib). By crystallization of the same compound from ethanol, yellow hexagonal prismatic crystals of (E)-4-(3-indolylvinyl)-N-methylpyridinium iodide hemihydrate, (II), were obtained. Structural analysis revealed that (Ia) and (Ib) are triclinic and monoclinic polymorphs of IMPE⁺·I^-, respectively, while (II) is a monoclinic hemihydrate (IMPE⁺·I^-·0.5H₂O)of the same salt.

In all four structures, the cations are nearly planar (Table 1), the largest deviations from planarity being found for (II). The bond lengths and angles in the cation of (Ia) are close to standard values and to those found in (Ib), except for the bridging fragment C3—C6═C7—C8 (Figs. 1 and 2, and Table 1). The C6═C7 double bond in (Ib) [1.271 (8) Å] is considerably shorter not only than that in (Ia) [1.346 (8) Å] but also than the typical C═C bond length (1.34 Å; Allen et al., 1987). Moreover, the C3—C6 and C7—C8 bonds in (Ib) are elongated to 1.487 (8) and 1.497 (9) Å, respectively, compared with the corresponding bond lengths in (Ia) [1.465 (6) and 1.435 (7) Å]. Several similar examples, with a discussion of the reasons for the shortening of both the C═C and N═N bonds in trans-stilbene (Bernstein, 1975; Hoekstra et al., 1975), 2,2'-dimethylstilbene (Ogawa et al., 1988, 1992) and several substituted azobenzenes (Harada et al., 1997; Atroshchenko et al., 2000), have appeared in the literature. For instance, the X-ray investigation of (E)-2,2'-dimethylstilbene (Ogawa et al., 1988) reveals that the C═C bond at room temperature (1.281 Å) is significantly shorter than at 118 K (1.324 Å). Recent multi-temperature investigations of this phenomenon (Harada et al., 1995, 1997) led to the conclusion that shrinkage of the C═C double bonds is an artifact of torsion vibration of the C(or N)—Ph bonds. If the amplitude of the torsion vibration is large enough it gives rise to conformational interconversion and hence to dynamic disorder in the crystal. However, such dynamic disorder cannot usually be resolved in a routine experiment due to the low resolution of the X-ray data and the low population of one of the conformers (Harada et al., 1997). Therefore, the assumption is made that, even at 200 K, the unusual bond lengths in the bridging group of (Ib) are artifacts related to crystal disorder.

The crystal packing of (Ia) and (Ib) share some similar features. In both crystal phases, organic cations are packed in stacks. The stacks extend along [010] in (Ia) and along [100] in (Ib), by the inversion operations (-1 - x, 2 - y, 2 - z; -1 - x, 1 - y, 2 - z) and (-1 - x, 1 - y, -z; -x, 1 - y, -z), respectively (Figs. 3 and 4). The corresponding IMPE⁺ interplanar distances in these stacks are 3.36 (1) and 3.17 (1) Å for (Ia), and 3.31 (1) and 3.36 (1) Å for (Ib). In (Ia) (Fig. 3), stacks are packed in parallel and in (Ib) in a herring-bone manner (Fig. 4). The iodide anions are located in the channels between these stacks.

An alternative way to describe the packing in these polymorphs is by reference to a sheet [a structure-building motif according to Desiraju (1989, 1991)] of cations, and to the relative positions of the anions. It is possible to identify planar sheets of cations along [110] in (Ia) and slightly corrugated sheets along [101] in (Ib). We define a sheet plane as a plane that goes through the centers of mass of the corresponding molecules. The angles between the least-squares mean planes of the cations and the relevant crystal planes [110] and [101] are 6.3 and 11.5° in (Ia) and (Ib), respectively.

In (Ia), there is an alternation of intersheet distances, with separations of 3.09 and 3.33 Å. There are no iodides between the sheets with the shorter separation. In (Ia), all iodides are located between sheets with separations of 3.33 Å and their displacements from the nearest sheet are 0.898 Å. Four short contacts of the H···I type shorter than 3.18 Å have been found in (Ia) (Table 2). The sum of van der Waals radii of the I and H atoms is 3.18 Å (Bondi, 1964) and the length of the mean statistical H···I contact (3.13 Å; Rowland & Taylor, 1996) lies close to this value. In this structure, the iodide coordination environment within a sphere of 3.6 Å includes ten contacts of the types N—H···I and C—H ···I. All four short contacts are related to interaction of the anion with the same sheet of cations. The shortest contact is formed between an iodide and the acid H atom of the indole substituent (Table 2).

In (Ib), all intersheet distances are of 3.24 Å. Iodide anions are located between each pair of sheets, with a displacement from the sheet plane of 0.613 Å. There are nine I···H contacts in the environment of the anion within a sphere of 3.6 Å. Four of these are shorter than 3.18 Å, and the shortest H···I contact is of the same type as in (Ia). The iodide has one short contact (less than 3.18 Å) with one of the sheets, H16A···I1ⁱⁱ [symmetry code: (ii) -x, -y, -z], and three contacts with another adjacent sheet (Table 3).

Two crystallographically independent molecules (A and B) are found in (II) (Figs. 5a and 5 b). Organic cation A is equally disordered over two sites (Fig. 5a). The two cations forming `a disordered pair' are rotamers with the opposite orientation of the indole substituents around the C7—C8 bond (Fig. 5a). Corresponding torsion angles C6—C7—C8—C9 and C6'—C7'—C8'—C9' are -172 (1) and 13 (3)°, respectively. This type of disorder (Fig. 5a) is similar to that found in disordered diazabenzene or stilbene compounds. Although the disorder results in less precise geometry for cation A, bond lengths and valence angles for cation B in (II) do not differ considerably from the standard values (Allen et al., 1987), or from those in (Ia). Coplanar cations A and B form four-cation infinite stacks. Every such stack is surrounded by four others: within these the mean planes of the cations are oriented almost perpendicular to those in the reference pack (Fig. 6).

The water molecule is involved in the formation of an N—H···O hydrogen bond with the indole fragment of cation B. The quality of the X-ray data did not allow location of the H atoms of the water molecule. Nevertheless, the distances between the O atoms and iodide ions [I1···O1ⁱ 3.643 (7) Å and I1B···O1 3.398 (7) Å; symmetry code: (i) x - 1, -y + 1.5, z + 0.5] allow us to infer the presence of H···I interactions involving the water H atoms. Due to the complexity of the structure of (II), only those H···I contacts below 3.18 Å are listed in Table 4. Short H···I contacts (Table 4) with H atoms of the indole substituents involve both iodides in (II); these interactions are similar to those seen in (Ia) and (Ib).

In (III), there are also two independent ion pairs (A and B), for which different orientations of the carbazole moiety with respect to the C7—C8 bond are observed (Figs. 7a and 7 b, and Table 1). Moreover, the ethyl group has a different orientation in the two cations: the relevant torsion angles are -101.3 (3)° for C11—N2—C21—C22 in cation A and 85.1 (4)° for C11'-N2'-C21'-C22' in cation B. The distribution of bond lengths and angles is essentially the same as in (Ia), (Ib) and (II), and both cations in (III) are almost planar. R.m.s. deviations from the planes passing through all non-H atoms (except for the C atoms of the ethyl group) are 0.035 (for ion-pair A) and 0.043 Å (for ion-pair B). One of the iodides in (III) is statistically disordered over two sites, with occupancies of 0.83 and 0.17. The crystal packing of (III) is similar to that observed in (Ia) and (Ib). Cations in (III) form stacks along [100] and anions are located in channels between the stacks. Cations A and B alternate within these stacks, with interplanar distances of 3.31 (1) and 3.60 (1) Å. However, no sheets of cations are observed in (III). H···I short contacts of less than 3.18 Å are listed in Table 5.

The rare phenomenon of co-existence in one crystal of two conformers (rotamers) was observed the crystals of related compounds (II) and (III). While in (II), the second rotamer was found only as a part of `disordered pair', in (III), the two rotamers were observed in the asymmetric unit.

In spite of the drastic difference in molecular packing in polymorphs (Ia) and (Ib), hemihydrate (II) and carbazole derivative (III), in the majority of these structures [(Ia), (II) and (III)], the long axis of the molecules have a parallel orientation that is important for their potential application as liquid crystalline and/or Langmuir–Blodgett materials.

Related literature

For related literature, see: Ashwell et al. (1998); Atroshchenko et al. (2000); Bernstein (1975); Bondi (1964); Desiraju (1989, 1991); Harada et al. (1995, 1997); Hoekstra et al. (1975); Hu (1993); Johal et al. (1999); Marder et al. (1990, 1994); Ogawa et al. (1988, 1992); Rowland & Taylor (1996); Xu et al. (1997).

S2. Experimental

The salts IMPE⁺I^-, (I), and ECMPE⁺I^-, (III), were obtained by reaction of equimolar amounts of 1,4-dimethylpyridinium iodide (0.005 mol) with indole-3-carboxaldehyde [for the preparation of (I)] or N-ethyl-3-carbazolecarboxaldehyde (0.005 mol) [for the preparation of (III)] in the presence of catalytic amount of piperidine, in ethanol solution under reflux for 5 h (Marder et al., 1990, 1994). The precipitates were collected by vacuum filtration and recrystallized from acetonitrile. The yields of final products were: (I) 79%, m.p. 533 K; (III) 90%, m.p. 578 K. In (I), a trace amount of the cis isomer was found. Crystals of (Ia) and (Ib) were both grown from a DMSO solution of (I), while (II) was obtained from a solution in ethanol. [AUTHOR: supply details of how crystals of (3) were grown] Data for the trans isomer of compound (I): ¹H NMR (unisol): δ (p.p.m) 9.92 (s, HN), 8.62 (d, J = 6.62 Hz, HC1, HC5), 8.13 (d, J = 16.18 Hz, HC7), 8.03 (t, J = 4.05 Hz, HC14), 7.96 (d, J = 6.62 Hz, HC2, HC4), 7.83 (d, J = 2.94 Hz, HC9), 7.50 (dd, J = 4.42 Hz, HC13), 7.30–7.23 (m, HC11, HC12), 7.16 (d, J = 16.18 Hz, HC6), 4.28 (s, CH₃); ¹³C NMR (unisol): δ (p.p.m) 153.83 (C3), 142.47 (C1, C5), 136.72 (C15), 136.34 (C7), 131.51 (C10), 123.79 (C9), 122.02 (C2, C4), 120.72 (C6), 120.36 (C12), 119.14 (C13), 115.06 (C14), 112.72 (C8), 111.56 (C11), 45.36 (–CH₃); UV/vis (ethanol): λ_max 444 nm. Data for compound (III): ¹H NMR (unisol): δ (p.p.m) 8.80 (d, J = 6.62 Hz, HC1, HC5), 8.47 (s, HC13), 8.15 (d, J = 7.72 Hz, HC10), 8.09 (d, J = 6.98 Hz, HC2, HC4),8.03 (d, J = 7.73 Hz, HC18), 7.84 (d, J = 6.62 Hz, HC15), 7.53 (d, J = 16.18 Hz, HC7), 7.53 - 7.43 (m, HC16, HC17), 7.37 (d, J = 16.18 Hz, HC6), 7.32–7.21 (m, HC9), 4.46 (q, J = 7.72 Hz, H₂C21), 4.35 (s, H₃C20), 1.46 (t, H₃C22); ¹³C NMR (unisol): δ (p.p.m) 152.88, 125.41 (C9), 125.32 (C17), 125.18 (C12), 124.60 (C14), 122.13 (C13), 122.00 (C2, C4), 121.31 (C15), 119.33 (C6), 118.71 (C10), 117.94 (C16), 108.08 (C18), 45.75 (C20), 36.53 (C21), 12.64 (C22); UV/vis (ethanol): λ_max 442 nm.

S3. Refinement

The accuracy of structure (II) is limited by disorder; modelling of this required the applictaion of extensive distance restraints in the affected region. No sign of disorder was seen for the I and O atoms, for example, in the shapes of their ellipsoids. The residual density of 3.86 e Å^-3 suggests some further disorder not accommodated by the refinement model, but this peak is located very close (0.05 Å) to I1B. [Authors, please check and approve the following, added by co-editor] Methyl H atoms were located from difference Fourier syntheses and refined as a part of a rigid group which was allowed to rotate but not tip or distort, and with U_iso(H) = 1.5U_eq(C). Other H atoms were placed geometrically and refined using a riding model with U_iso(H) = 1.2U_eq(C,N). The following distance restraints were applied: in (Ia), N—H 0.86, C—H(methyl) 0.96, other C—H 0.93 Å; in (Ib) and (II), N—H 0.88, C—H(methyl) 0.98, other C—H 0.95 Å; in (III), C—H(methylene) 0.99, C—H(methyl) 0.98, other C—H 0.95 Å.

Computing details

Data collection: P3 (Siemens, 1989) for (Ia); SMART (Bruker, 1998) for (Ib), (II), (III). Cell refinement: P3 for (Ia); SMART for (Ib), (II), (III). Data reduction: XDISK (Siemens, 1991) for (Ia); SAINT (Bruker, 1998) for (Ib), (II), (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL97 (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL97.

Figures

	Fig. 1. View of (Ia) with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	Fig. 2. View of (Ib) with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	Fig. 3. Projection of the crystal packing of (Ia) along the b axis.
	Fig. 4. Projection of the crystal packing of (Ib) along the a axis.
	Fig. 5. View of ion pairs (a) A and (b) B of (II). Displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	Fig. 6. Projection of the crystal packing of (II) along the a axis. Only one molecule of a disordered pair is shown and, for clarity, all H atoms have been omitted. O atoms are shown as crossed-hatched circles and iodides are shown as shaded circles. Each infinite stack is surrounded by four others which are almost perpendicular to it.
	Fig. 7. View of ion pairs (a) A and (b) B of (III). Displacement ellipsoids for the non-H atoms drawn at the 50% probability level.

(Ia) (E)-4-(3-indolylvinyl)-N-methylpyridinium iodide

Crystal data

C16H15N2^+·I^−	Z = 2
Mr = 362.20	F(000) = 356
Triclinic, P1	Dx = 1.619 Mg m^−3
a = 8.097 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.223 (4) Å	Cell parameters from 24 reflections
c = 10.906 (4) Å	θ = 10–11°
α = 76.71 (3)°	µ = 2.14 mm^−1
β = 73.12 (3)°	T = 293 K
γ = 75.25 (3)°	Square prism, orange
V = 742.8 (5) Å^3	0.50 × 0.40 × 0.30 mm

Data collection

Siemens P3 diffractometer	2385 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 26.1°, θmin = 2.3°
θ/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.414, Tmax = 0.566	l = −12→13
3121 measured reflections	2 standard reflections every 98 reflections
2902 independent reflections	intensity decay: 3.2%

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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1081P)^2] where P = (Fo^2 + 2Fc^2)/3
2902 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 1.26 e Å^−3
0 restraints	Δρmin = −1.82 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.23207 (5)	0.38767 (4)	0.73216 (3)	0.0639 (2)
N1	0.3374 (5)	0.4479 (5)	1.2612 (4)	0.0486 (9)
N2	1.0015 (6)	−0.2343 (5)	0.7883 (5)	0.0581 (11)
H2N	1.0852	−0.3127	0.7775	0.070*
C1	0.2832 (7)	0.4668 (6)	1.1519 (5)	0.0511 (11)
H1	0.1880	0.5440	1.1376	0.061*
C2	0.3668 (7)	0.3734 (6)	1.0618 (4)	0.0488 (11)
H2	0.3262	0.3873	0.9876	0.059*
C3	0.5079 (7)	0.2609 (6)	1.0783 (5)	0.0496 (11)
C4	0.5595 (7)	0.2399 (6)	1.1952 (6)	0.0574 (12)
H4	0.6522	0.1615	1.2126	0.069*
C5	0.4721 (8)	0.3359 (6)	1.2829 (5)	0.0568 (12)
H5	0.5076	0.3227	1.3592	0.068*
C6	0.5943 (7)	0.1685 (6)	0.9758 (5)	0.0525 (11)
H6	0.5539	0.1970	0.9004	0.063*
C7	0.7266 (7)	0.0463 (6)	0.9805 (6)	0.0571 (12)
H7	0.7672	0.0180	1.0558	0.069*
C8	0.8110 (7)	−0.0443 (6)	0.8802 (5)	0.0514 (11)
C9	0.9432 (7)	−0.1677 (7)	0.8963 (6)	0.0618 (13)
H9	0.9868	−0.2012	0.9702	0.074*
C10	0.9068 (6)	−0.1576 (6)	0.6995 (5)	0.0498 (11)
C11	0.9193 (8)	−0.1870 (7)	0.5775 (6)	0.0640 (14)
H11	1.0033	−0.2670	0.5439	0.077*
C12	0.8042 (10)	−0.0947 (7)	0.5085 (6)	0.0725 (17)
H12	0.8076	−0.1131	0.4274	0.087*
C13	0.6794 (9)	0.0292 (7)	0.5600 (6)	0.0686 (15)
H13	0.6030	0.0920	0.5114	0.082*
C14	0.6701 (7)	0.0572 (6)	0.6789 (6)	0.0564 (12)
H14	0.5864	0.1377	0.7119	0.068*
C15	0.7849 (6)	−0.0338 (5)	0.7512 (5)	0.0460 (10)
C16	0.2450 (9)	0.5521 (7)	1.3553 (6)	0.0652 (15)
H16A	0.2265	0.4949	1.4419	0.098*
H16B	0.1333	0.6041	1.3378	0.098*
H16C	0.3150	0.6251	1.3474	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0626 (3)	0.0667 (3)	0.0612 (3)	0.01635 (17)	−0.02661 (18)	−0.02688 (18)
N1	0.051 (2)	0.056 (2)	0.0409 (19)	−0.0044 (18)	−0.0068 (17)	−0.0244 (17)
N2	0.043 (2)	0.050 (2)	0.081 (3)	0.0041 (17)	−0.011 (2)	−0.028 (2)
C1	0.055 (3)	0.055 (3)	0.041 (2)	−0.007 (2)	−0.009 (2)	−0.014 (2)
C2	0.056 (3)	0.057 (3)	0.037 (2)	−0.013 (2)	−0.007 (2)	−0.019 (2)
C3	0.052 (3)	0.051 (3)	0.051 (2)	−0.019 (2)	−0.004 (2)	−0.020 (2)
C4	0.055 (3)	0.053 (3)	0.067 (3)	−0.009 (2)	−0.019 (2)	−0.014 (2)
C5	0.068 (3)	0.058 (3)	0.053 (3)	−0.012 (2)	−0.024 (2)	−0.014 (2)
C6	0.053 (3)	0.054 (3)	0.053 (3)	−0.004 (2)	−0.015 (2)	−0.020 (2)
C7	0.055 (3)	0.062 (3)	0.061 (3)	−0.008 (2)	−0.014 (2)	−0.027 (2)
C8	0.051 (3)	0.045 (2)	0.064 (3)	−0.012 (2)	−0.009 (2)	−0.025 (2)
C9	0.049 (3)	0.074 (4)	0.067 (3)	0.000 (2)	−0.020 (2)	−0.027 (3)
C10	0.043 (2)	0.046 (2)	0.062 (3)	−0.003 (2)	−0.005 (2)	−0.028 (2)
C11	0.066 (3)	0.064 (3)	0.059 (3)	−0.015 (3)	0.005 (3)	−0.030 (3)
C12	0.104 (5)	0.065 (4)	0.055 (3)	−0.028 (4)	−0.016 (3)	−0.016 (3)
C13	0.087 (4)	0.055 (3)	0.066 (3)	−0.012 (3)	−0.028 (3)	−0.007 (3)
C14	0.059 (3)	0.042 (2)	0.067 (3)	−0.003 (2)	−0.015 (3)	−0.014 (2)
C15	0.041 (2)	0.038 (2)	0.060 (3)	−0.0065 (18)	−0.005 (2)	−0.020 (2)
C16	0.075 (4)	0.070 (3)	0.053 (3)	−0.007 (3)	−0.004 (3)	−0.037 (3)

Geometric parameters (Å, º)

N1—C1	1.347 (6)	C7—H7	0.9300
N1—C5	1.332 (7)	C8—C9	1.367 (8)
N1—C16	1.476 (6)	C8—C15	1.460 (7)
N2—C9	1.360 (7)	C9—H9	0.9300
N2—C10	1.366 (7)	C10—C11	1.388 (8)
N2—H2N	0.8600	C10—C15	1.412 (6)
C1—C2	1.368 (7)	C11—C12	1.367 (10)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.358 (8)	C12—C13	1.421 (10)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.411 (8)	C13—C14	1.358 (8)
C3—C6	1.465 (6)	C13—H13	0.9300
C4—C5	1.370 (8)	C14—C15	1.383 (7)
C4—H4	0.9300	C14—H14	0.9300
C5—H5	0.9300	C16—H16A	0.9600
C6—C7	1.346 (8)	C16—H16B	0.9600
C6—H6	0.9300	C16—H16C	0.9600
C7—C8	1.435 (7)
C5—N1—C1	119.8 (4)	C7—C8—C15	132.3 (5)
C5—N1—C16	121.3 (5)	N2—C9—C8	109.9 (5)
C1—N1—C16	118.9 (5)	N2—C9—H9	125.0
C9—N2—C10	109.7 (4)	C8—C9—H9	125.0
C9—N2—H2N	125.2	N2—C10—C11	129.3 (5)
C10—N2—H2N	125.2	N2—C10—C15	108.3 (4)
N1—C1—C2	120.6 (5)	C11—C10—C15	122.4 (5)
N1—C1—H1	119.7	C12—C11—C10	117.8 (5)
C2—C1—H1	119.7	C12—C11—H11	121.1
C3—C2—C1	121.5 (5)	C10—C11—H11	121.1
C3—C2—H2	119.3	C11—C12—C13	120.4 (6)
C1—C2—H2	119.3	C11—C12—H12	119.8
C2—C3—C4	117.1 (5)	C13—C12—H12	119.8
C2—C3—C6	118.4 (5)	C14—C13—C12	120.9 (6)
C4—C3—C6	124.5 (5)	C14—C13—H13	119.5
C5—C4—C3	119.5 (5)	C12—C13—H13	119.5
C5—C4—H4	120.3	C13—C14—C15	120.1 (5)
C3—C4—H4	120.3	C13—C14—H14	119.9
N1—C5—C4	121.5 (5)	C15—C14—H14	119.9
N1—C5—H5	119.2	C14—C15—C10	118.3 (5)
C4—C5—H5	119.2	C14—C15—C8	136.1 (5)
C7—C6—C3	126.1 (5)	C10—C15—C8	105.4 (4)
C7—C6—H6	117.0	N1—C16—H16A	109.5
C3—C6—H6	117.0	N1—C16—H16B	109.5
C6—C7—C8	126.1 (5)	H16A—C16—H16B	109.5
C6—C7—H7	117.0	N1—C16—H16C	109.5
C8—C7—H7	117.0	H16A—C16—H16C	109.5
C9—C8—C7	121.0 (5)	H16B—C16—H16C	109.5
C9—C8—C15	106.6 (4)
C5—N1—C1—C2	−1.0 (8)	C9—N2—C10—C11	−178.8 (6)
C16—N1—C1—C2	179.3 (5)	C9—N2—C10—C15	1.5 (6)
N1—C1—C2—C3	−1.0 (8)	N2—C10—C11—C12	178.0 (5)
C1—C2—C3—C4	2.8 (7)	C15—C10—C11—C12	−2.3 (8)
C1—C2—C3—C6	−178.1 (5)	C10—C11—C12—C13	1.5 (9)
C2—C3—C4—C5	−2.8 (7)	C11—C12—C13—C14	−0.9 (10)
C6—C3—C4—C5	178.2 (5)	C12—C13—C14—C15	1.1 (9)
C1—N1—C5—C4	1.0 (8)	C13—C14—C15—C10	−1.8 (8)
C16—N1—C5—C4	−179.3 (5)	C13—C14—C15—C8	−176.8 (5)
C3—C4—C5—N1	0.9 (8)	N2—C10—C15—C14	−177.8 (4)
C2—C3—C6—C7	−174.9 (5)	C11—C10—C15—C14	2.5 (7)
C4—C3—C6—C7	4.2 (8)	N2—C10—C15—C8	−1.4 (5)
C3—C6—C7—C8	179.8 (5)	C11—C10—C15—C8	178.9 (5)
C6—C7—C8—C9	−179.1 (6)	C9—C8—C15—C14	176.2 (6)
C6—C7—C8—C15	0.8 (9)	C7—C8—C15—C14	−3.7 (10)
C10—N2—C9—C8	−1.0 (6)	C9—C8—C15—C10	0.8 (5)
C7—C8—C9—N2	−179.9 (5)	C7—C8—C15—C10	−179.2 (5)
C15—C8—C9—N2	0.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···I1^i	0.86	2.81	3.609 (5)	155
C2—H2···I1	0.93	3.09	4.015 (5)	171
C14—H14···I1	0.93	3.18	4.040 (6)	155
C16—H16A···I1^ii	0.96	3.10	4.021 (6)	161

Symmetry codes: (i) x+1, y−1, z; (ii) x, y, z+1.

(Ib) (E)-4-(3-indolylvinyl)-N-methylpyridinium iodide

Crystal data

C16H15N2^+·I^−	F(000) = 712
Mr = 362.20	Dx = 1.605 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.3189 (17) Å	Cell parameters from 4500 reflections
b = 20.960 (5) Å	θ = 2–24°
c = 10.009 (2) Å	µ = 2.13 mm^−1
β = 102.597 (6)°	T = 200 K
V = 1498.5 (6) Å^3	Needle, yellow
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3248 independent reflections
Radiation source: fine-focus sealed tube	1571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→8
Tmin = 0.568, Tmax = 0.816	k = −25→26
8032 measured reflections	l = −12→9

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F^2) = 0.118	H-atom parameters constrained
S = 0.82	w = 1/[σ^2(Fo^2) + (0.0588P)^2] where P = (Fo^2 + 2Fc^2)/3
3248 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 1.02 e Å^−3
0 restraints	Δρmin = −0.55 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.

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.

The refinement of (Ib) was carried out using reflections with 2θ ≤ 54°, giving a ratio of observed/unique reflections of only 0.48. However, for reflections with 2θ ≤ 50° the aforementioned ratio is about 0.60. Therefore, we attribute the low ratio of observed reflections to the large fraction of weak reflections at high values of 2θ.

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

	x	y	z	Uiso*/Ueq
I1	0.02121 (6)	0.126956 (18)	0.17654 (4)	0.0682 (2)
N1	−0.0366 (6)	−0.1550 (2)	0.2561 (5)	0.0453 (10)
N2	0.6408 (6)	0.0780 (2)	0.9048 (5)	0.0563 (12)
H2N	0.7110	0.0812	0.9879	0.068*
C1	−0.0308 (8)	−0.0942 (3)	0.2200 (6)	0.0511 (13)
H1	−0.0946	−0.0823	0.1304	0.061*
C2	0.0593 (9)	−0.0488 (3)	0.3021 (7)	0.0607 (16)
H2	0.0581	−0.0060	0.2706	0.073*
C3	0.1511 (8)	−0.0636 (3)	0.4287 (7)	0.0598 (16)
C4	0.1474 (8)	−0.1279 (3)	0.4758 (6)	0.0626 (16)
H4	0.2081	−0.1398	0.5662	0.075*
C5	0.0517 (8)	−0.1716 (3)	0.3842 (6)	0.0527 (14)
H5	0.0476	−0.2148	0.4120	0.063*
C6	0.2525 (9)	−0.0113 (3)	0.5145 (7)	0.0728 (18)
H6	0.2392	0.0305	0.4772	0.087*
C7	0.3556 (9)	−0.0179 (4)	0.6335 (7)	0.0765 (19)
H7	0.3679	−0.0598	0.6709	0.092*
C8	0.4594 (9)	0.0344 (3)	0.7200 (7)	0.0622 (16)
C9	0.5680 (9)	0.0233 (3)	0.8468 (6)	0.0640 (16)
H9	0.5893	−0.0175	0.8884	0.077*
C10	0.5907 (7)	0.1283 (3)	0.8165 (5)	0.0480 (13)
C11	0.6386 (8)	0.1920 (3)	0.8342 (6)	0.0596 (16)
H11	0.7138	0.2076	0.9173	0.072*
C12	0.5709 (9)	0.2316 (3)	0.7242 (8)	0.0747 (19)
H12	0.6027	0.2757	0.7290	0.090*
C13	0.4546 (8)	0.2065 (4)	0.6048 (7)	0.076 (2)
H13	0.4081	0.2347	0.5310	0.091*
C14	0.4056 (8)	0.1442 (4)	0.5897 (7)	0.0694 (18)
H14	0.3260	0.1296	0.5074	0.083*
C15	0.4724 (7)	0.1020 (3)	0.6952 (5)	0.0588 (16)
C16	−0.1381 (8)	−0.2031 (3)	0.1614 (6)	0.0600 (16)
H16A	−0.1446	−0.1894	0.0668	0.090*
H16B	−0.2651	−0.2079	0.1767	0.090*
H16C	−0.0722	−0.2440	0.1774	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0955 (4)	0.0540 (3)	0.0505 (3)	−0.0047 (2)	0.0057 (2)	0.0019 (2)
N1	0.039 (2)	0.043 (3)	0.056 (3)	0.000 (2)	0.016 (2)	−0.002 (2)
N2	0.060 (3)	0.065 (3)	0.044 (3)	−0.017 (3)	0.011 (2)	−0.012 (2)
C1	0.049 (3)	0.041 (3)	0.067 (3)	0.009 (3)	0.021 (3)	0.006 (3)
C2	0.067 (4)	0.042 (3)	0.080 (5)	0.006 (3)	0.031 (4)	0.000 (3)
C3	0.059 (4)	0.049 (3)	0.081 (4)	−0.010 (3)	0.036 (3)	−0.023 (3)
C4	0.056 (4)	0.066 (4)	0.057 (3)	−0.001 (3)	−0.008 (3)	−0.003 (3)
C5	0.054 (3)	0.048 (3)	0.057 (3)	−0.001 (3)	0.016 (3)	−0.002 (3)
C6	0.063 (4)	0.082 (5)	0.080 (5)	0.010 (4)	0.030 (4)	−0.004 (4)
C7	0.066 (5)	0.102 (5)	0.068 (4)	0.002 (4)	0.028 (4)	−0.007 (4)
C8	0.051 (4)	0.073 (4)	0.064 (4)	−0.009 (3)	0.016 (3)	−0.022 (4)
C9	0.063 (4)	0.064 (4)	0.068 (4)	−0.005 (3)	0.021 (3)	−0.006 (3)
C10	0.037 (3)	0.063 (4)	0.045 (3)	−0.002 (3)	0.010 (2)	−0.005 (3)
C11	0.046 (4)	0.063 (4)	0.070 (4)	−0.002 (3)	0.010 (3)	−0.006 (3)
C12	0.061 (4)	0.064 (4)	0.099 (5)	0.005 (3)	0.017 (4)	0.003 (4)
C13	0.045 (4)	0.109 (6)	0.074 (5)	0.027 (4)	0.012 (3)	0.034 (4)
C14	0.040 (3)	0.102 (6)	0.067 (4)	0.001 (3)	0.013 (3)	−0.001 (4)
C15	0.034 (3)	0.101 (5)	0.043 (3)	0.007 (3)	0.013 (3)	0.001 (3)
C16	0.057 (4)	0.056 (3)	0.065 (4)	−0.007 (3)	0.010 (3)	−0.007 (3)

Geometric parameters (Å, º)

N1—C1	1.328 (7)	C7—H7	0.9500
N1—C5	1.350 (7)	C8—C9	1.362 (8)
N1—C16	1.469 (6)	C8—C15	1.445 (9)
N2—C9	1.341 (7)	C9—H9	0.9500
N2—C10	1.373 (6)	C10—C11	1.381 (7)
N2—H2N	0.8800	C10—C15	1.439 (7)
C1—C2	1.333 (7)	C11—C12	1.382 (8)
C1—H1	0.9500	C11—H11	0.9500
C2—C3	1.335 (8)	C12—C13	1.409 (10)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.430 (8)	C13—C14	1.354 (9)
C3—C6	1.487 (8)	C13—H13	0.9500
C4—C5	1.376 (7)	C14—C15	1.382 (9)
C4—H4	0.9500	C14—H14	0.9500
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.271 (8)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800
C7—C8	1.497 (9)
C1—N1—C5	118.0 (5)	C15—C8—C7	131.5 (6)
C1—N1—C16	121.7 (5)	N2—C9—C8	110.8 (6)
C5—N1—C16	120.4 (4)	N2—C9—H9	124.6
C9—N2—C10	110.6 (5)	C8—C9—H9	124.6
C9—N2—H2N	124.7	N2—C10—C11	129.4 (5)
C10—N2—H2N	124.7	N2—C10—C15	106.0 (5)
N1—C1—C2	123.9 (6)	C11—C10—C15	124.6 (6)
N1—C1—H1	118.0	C10—C11—C12	116.2 (6)
C2—C1—H1	118.0	C10—C11—H11	121.9
C1—C2—C3	119.9 (5)	C12—C11—H11	121.9
C1—C2—H2	120.1	C11—C12—C13	119.7 (6)
C3—C2—H2	120.1	C11—C12—H12	120.2
C2—C3—C4	119.4 (5)	C13—C12—H12	120.2
C2—C3—C6	117.5 (6)	C14—C13—C12	123.5 (6)
C4—C3—C6	123.1 (6)	C14—C13—H13	118.3
C5—C4—C3	116.9 (5)	C12—C13—H13	118.3
C5—C4—H4	121.6	C13—C14—C15	119.4 (6)
C3—C4—H4	121.6	C13—C14—H14	120.3
N1—C5—C4	122.0 (5)	C15—C14—H14	120.3
N1—C5—H5	119.0	C14—C15—C10	116.5 (6)
C4—C5—H5	119.0	C14—C15—C8	137.1 (6)
C7—C6—C3	125.5 (7)	C10—C15—C8	106.4 (5)
C7—C6—H6	117.3	N1—C16—H16A	109.5
C3—C6—H6	117.3	N1—C16—H16B	109.5
C6—C7—C8	125.8 (7)	H16A—C16—H16B	109.5
C6—C7—H7	117.1	N1—C16—H16C	109.5
C8—C7—H7	117.1	H16A—C16—H16C	109.5
C9—C8—C15	106.2 (5)	H16B—C16—H16C	109.5
C9—C8—C7	122.3 (6)
C5—N1—C1—C2	1.0 (8)	C9—N2—C10—C11	−178.4 (6)
C16—N1—C1—C2	−180.0 (5)	C9—N2—C10—C15	1.7 (6)
N1—C1—C2—C3	0.2 (9)	N2—C10—C11—C12	178.0 (5)
C1—C2—C3—C4	−1.7 (9)	C15—C10—C11—C12	−2.1 (9)
C1—C2—C3—C6	178.7 (5)	C10—C11—C12—C13	2.2 (9)
C2—C3—C4—C5	1.9 (9)	C11—C12—C13—C14	−1.0 (10)
C6—C3—C4—C5	−178.5 (5)	C12—C13—C14—C15	−0.5 (10)
C1—N1—C5—C4	−0.8 (8)	C13—C14—C15—C10	0.5 (8)
C16—N1—C5—C4	−179.7 (5)	C13—C14—C15—C8	−178.2 (7)
C3—C4—C5—N1	−0.7 (9)	N2—C10—C15—C14	−179.3 (5)
C2—C3—C6—C7	−175.5 (6)	C11—C10—C15—C14	0.8 (8)
C4—C3—C6—C7	4.8 (10)	N2—C10—C15—C8	−0.1 (6)
C3—C6—C7—C8	179.5 (6)	C11—C10—C15—C8	179.9 (5)
C6—C7—C8—C9	−179.7 (7)	C9—C8—C15—C14	177.5 (7)
C6—C7—C8—C15	−0.4 (11)	C7—C8—C15—C14	−1.9 (12)
C10—N2—C9—C8	−2.7 (7)	C9—C8—C15—C10	−1.4 (7)
C15—C8—C9—N2	2.5 (7)	C7—C8—C15—C10	179.2 (6)
C7—C8—C9—N2	−178.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···I1^i	0.88	2.79	3.592 (4)	153
C2—H2···I1	0.95	2.94	3.882 (6)	175
C16—H16A···I1^ii	0.98	3.07	3.997 (6)	158
C16—H16C···I1^iii	0.98	3.06	3.931 (6)	149

Symmetry codes: (i) x+1, y, z+1; (ii) −x, −y, −z; (iii) −x, y−1/2, −z+1/2.

(II) (E)-4-(3-indolylvinyl)-N-methylpyridinium iodide hemihydrate

Crystal data

C16H15N2^+·I^−·0.5H2O	F(000) = 1456
Mr = 370.20	Dx = 1.661 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.3795 (19) Å	Cell parameters from 765 reflections
b = 13.8324 (17) Å	θ = 2–24°
c = 14.1690 (17) Å	µ = 2.16 mm^−1
β = 100.816 (2)°	T = 110 K
V = 2960.7 (6) Å^3	Hexagonal prism, yellow
Z = 8	0.50 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6728 independent reflections
Radiation source: fine-focus sealed tube	5246 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −19→19
Tmin = 0.412, Tmax = 0.672	k = −17→17
30042 measured reflections	l = −18→17

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0966P)^2] where P = (Fo^2 + 2Fc^2)/3
6728 reflections	(Δ/σ)max = 0.002
517 parameters	Δρmax = 3.86 e Å^−3
38 restraints	Δρmin = −1.06 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.

Refinement. Distance restraints (Å) were applied between atoms in the disordered region as follows:

C15—C10 1.390 (2), C13—C14 1.390 (2), C15—C14 1.390 (2), C11—C12 1.390 (2), C11—C10 1.390 (2), C12'—C11' 1.390 (2), C12'—C13' 1.390 (2), N1'—C5' 1.350 (2), N2'—C9' 1.350 (2), N2—C9 1.350 (2), C4'—C5' 1.390 (2), C6'—C7' 1.340 (2), C6'—C3' 1.450 (2).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.56906 (2)	0.20173 (2)	0.57329 (2)	0.04168 (12)
N1	−0.1758 (12)	0.4242 (15)	0.6083 (17)	0.025 (4)	0.50
N2	0.3688 (9)	0.3180 (13)	0.5375 (15)	0.023 (3)	0.50
H2N	0.4102	0.2818	0.5202	0.027*	0.50
C1	−0.1191 (12)	0.4889 (13)	0.6588 (14)	0.030 (6)	0.50
H1	−0.1427	0.5351	0.6968	0.036*	0.50
C2	−0.0314 (12)	0.4921 (15)	0.6587 (17)	0.026 (3)	0.50
H2	0.0057	0.5365	0.6987	0.031*	0.50
C3	0.0035 (9)	0.4294 (8)	0.5992 (9)	0.023 (2)	0.50
C4	−0.0567 (10)	0.3644 (9)	0.5464 (10)	0.023 (2)	0.50
H4	−0.0357	0.3177	0.5069	0.028*	0.50
C5	−0.1435 (11)	0.3666 (16)	0.5502 (14)	0.032 (4)	0.50
H5	−0.1828	0.3248	0.5093	0.038*	0.50
C6	0.0942 (7)	0.4311 (6)	0.5987 (6)	0.0229 (18)	0.50
H6	0.1265	0.4836	0.6313	0.027*	0.50
C7	0.1410 (5)	0.3669 (6)	0.5571 (5)	0.0192 (13)	0.50
H7	0.1092	0.3153	0.5224	0.023*	0.50
C8	0.2369 (9)	0.3697 (10)	0.5608 (9)	0.019 (2)	0.50
C9	0.2821 (9)	0.2952 (13)	0.5266 (12)	0.028 (3)	0.50
H9	0.2562	0.2367	0.4994	0.033*	0.50
C10	0.3812 (11)	0.4058 (15)	0.580 (2)	0.022 (4)	0.50
C11	0.4581 (14)	0.4607 (12)	0.589 (2)	0.036 (8)	0.50
H11	0.5086	0.4380	0.5665	0.043*	0.50
C12	0.4581 (13)	0.5500 (17)	0.634 (2)	0.032 (5)	0.50
H12	0.5115	0.5855	0.6526	0.039*	0.50
C13	0.3768 (19)	0.587 (3)	0.652 (3)	0.065 (11)	0.50
H13	0.3790	0.6475	0.6847	0.078*	0.50
C14	0.294 (2)	0.5438 (14)	0.627 (2)	0.036 (6)	0.50
H14	0.2393	0.5736	0.6310	0.043*	0.50
C15	0.3040 (13)	0.4501 (13)	0.5951 (19)	0.032 (7)	0.50
C16	−0.2697 (12)	0.4208 (11)	0.6182 (12)	0.038 (3)	0.50
H16A	−0.2735	0.4029	0.6842	0.058*	0.50
H16B	−0.3012	0.3728	0.5736	0.058*	0.50
H16C	−0.2967	0.4846	0.6034	0.058*	0.50
N1'	−0.1941 (12)	0.4328 (18)	0.6149 (17)	0.031 (4)	0.50
N2'	0.3454 (11)	0.3293 (18)	0.537 (2)	0.048 (5)	0.50
H2'N	0.3793	0.2867	0.5149	0.057*	0.50
C1'	−0.1761 (12)	0.3592 (15)	0.5520 (13)	0.036 (4)	0.50
H1'	−0.2230	0.3187	0.5215	0.043*	0.50
C2'	−0.0944 (13)	0.3452 (13)	0.5343 (10)	0.040 (4)	0.50
H2'	−0.0857	0.2983	0.4881	0.048*	0.50
C3'	−0.0224 (8)	0.3972 (12)	0.5817 (10)	0.033 (3)	0.50
C4'	−0.0421 (12)	0.4680 (16)	0.6442 (18)	0.034 (4)	0.50
H4'	0.0048	0.5083	0.6749	0.040*	0.50
C5'	−0.1258 (11)	0.4837 (16)	0.6649 (19)	0.047 (8)	0.50
H5'	−0.1347	0.5288	0.7127	0.056*	0.50
C6'	0.0615 (5)	0.3685 (7)	0.5579 (7)	0.049 (2)	0.50
H6'	0.0637	0.3146	0.5168	0.058*	0.50
C7'	0.1359 (7)	0.4168 (9)	0.5931 (8)	0.042 (3)	0.50
H7'	0.1303	0.4712	0.6325	0.051*	0.50
C8'	0.2229 (12)	0.3950 (12)	0.5776 (12)	0.036 (4)	0.50
C9'	0.2591 (11)	0.3159 (12)	0.5405 (11)	0.035 (4)	0.50
H9'	0.2272	0.2585	0.5200	0.042*	0.50
C10'	0.3735 (15)	0.4218 (16)	0.573 (2)	0.032 (5)	0.50
C11'	0.4570 (14)	0.4679 (16)	0.596 (2)	0.037 (7)	0.50
H11'	0.5103	0.4353	0.5911	0.045*	0.50
C12'	0.4569 (17)	0.5634 (18)	0.627 (3)	0.056 (9)	0.50
H12'	0.5076	0.6032	0.6290	0.067*	0.50
C13'	0.3811 (14)	0.599 (2)	0.655 (2)	0.030 (5)	0.50
H13'	0.3818	0.6623	0.6814	0.036*	0.50
C14'	0.3077 (17)	0.5469 (17)	0.644 (2)	0.029 (5)	0.50
H14'	0.2597	0.5728	0.6695	0.035*	0.50
C15'	0.2944 (18)	0.4538 (17)	0.597 (2)	0.034 (7)	0.50
C16'	−0.2817 (10)	0.4519 (12)	0.6332 (14)	0.043 (4)	0.50
H16D	−0.2823	0.5151	0.6643	0.065*	0.50
H16E	−0.2979	0.4016	0.6754	0.065*	0.50
H16F	−0.3242	0.4520	0.5723	0.065*	0.50
I1B	0.209554 (18)	0.03931 (2)	0.59623 (2)	0.03807 (12)
N1B	0.4679 (3)	0.3739 (3)	0.8183 (2)	0.0424 (9)
N2B	−0.0902 (3)	0.3226 (4)	0.8488 (3)	0.0543 (11)
H2BN	−0.1347	0.3448	0.8735	0.065*
C1B	0.4370 (3)	0.2937 (3)	0.7709 (3)	0.0378 (9)
H1B	0.4756	0.2574	0.7395	0.045*
C2B	0.3529 (3)	0.2620 (3)	0.7658 (3)	0.0383 (9)
H2B	0.3351	0.2032	0.7332	0.046*
C3B	0.2919 (3)	0.3137 (3)	0.8072 (3)	0.0366 (9)
C4B	0.3250 (3)	0.3955 (4)	0.8586 (3)	0.0463 (11)
H4B	0.2873	0.4317	0.8914	0.056*
C5B	0.4117 (4)	0.4254 (4)	0.8633 (3)	0.0547 (14)
H5B	0.4323	0.4823	0.8982	0.066*
C6B	0.2002 (3)	0.2812 (3)	0.7935 (3)	0.0369 (9)
H6B	0.1831	0.2270	0.7531	0.044*
C7B	0.1392 (3)	0.3239 (4)	0.8349 (3)	0.0397 (10)
H7B	0.1595	0.3750	0.8782	0.048*
C8B	0.0475 (3)	0.3020 (3)	0.8220 (3)	0.0392 (10)
C9B	−0.0060 (4)	0.3508 (4)	0.8736 (3)	0.0480 (12)
H9B	0.0143	0.3984	0.9209	0.058*
C10B	−0.0960 (3)	0.2524 (3)	0.7774 (3)	0.0401 (10)
C11B	−0.1698 (3)	0.2054 (4)	0.7280 (4)	0.0520 (14)
H11B	−0.2269	0.2174	0.7417	0.062*
C12B	−0.1577 (3)	0.1404 (4)	0.6580 (4)	0.0535 (14)
H12B	−0.2067	0.1053	0.6238	0.064*
C13B	−0.0722 (3)	0.1259 (3)	0.6367 (4)	0.0463 (11)
H13B	−0.0653	0.0818	0.5873	0.056*
C14B	0.0001 (3)	0.1730 (3)	0.6850 (3)	0.0367 (9)
H14B	0.0567	0.1627	0.6690	0.044*
C15B	−0.0103 (2)	0.2375 (3)	0.7592 (3)	0.0312 (8)
C16B	0.5593 (4)	0.4070 (6)	0.8234 (4)	0.079 (2)
H16G	0.5811	0.3846	0.7665	0.119*
H16H	0.5968	0.3807	0.8813	0.119*
H16I	0.5611	0.4778	0.8259	0.119*
O1	0.2659 (5)	0.8039 (5)	0.5795 (6)	0.126 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0541 (2)	0.04020 (19)	0.03137 (18)	0.00772 (12)	0.00956 (13)	−0.00243 (11)
N1	0.016 (6)	0.025 (4)	0.034 (6)	0.011 (5)	0.006 (5)	0.010 (4)
N2	0.025 (5)	0.022 (6)	0.019 (4)	0.012 (5)	−0.001 (4)	−0.003 (4)
C1	0.060 (14)	0.017 (6)	0.011 (6)	−0.009 (6)	0.006 (6)	−0.008 (4)
C2	0.026 (6)	0.030 (8)	0.020 (7)	−0.007 (5)	−0.002 (5)	−0.008 (5)
C3	0.031 (6)	0.017 (5)	0.020 (5)	−0.008 (4)	0.000 (4)	0.004 (4)
C4	0.018 (8)	0.027 (6)	0.023 (6)	0.003 (5)	−0.002 (5)	−0.003 (4)
C5	0.031 (11)	0.031 (7)	0.030 (6)	−0.020 (7)	−0.005 (7)	0.005 (4)
C6	0.032 (5)	0.019 (4)	0.017 (4)	0.000 (4)	0.001 (4)	−0.001 (3)
C7	0.027 (4)	0.019 (3)	0.009 (3)	0.002 (3)	−0.003 (3)	0.000 (3)
C8	0.019 (5)	0.021 (6)	0.017 (5)	0.011 (4)	0.006 (3)	−0.005 (4)
C9	0.028 (6)	0.036 (8)	0.021 (5)	0.008 (5)	0.007 (4)	−0.010 (4)
C10	0.025 (5)	0.018 (7)	0.021 (6)	0.008 (4)	0.001 (4)	0.003 (5)
C11	0.053 (15)	0.017 (7)	0.041 (15)	0.009 (7)	0.018 (9)	0.012 (7)
C12	0.032 (6)	0.027 (8)	0.040 (8)	−0.009 (5)	0.011 (6)	0.008 (6)
C13	0.10 (2)	0.042 (16)	0.049 (15)	0.024 (14)	0.009 (16)	−0.006 (11)
C14	0.039 (9)	0.039 (9)	0.025 (13)	0.001 (6)	−0.007 (7)	0.010 (6)
C15	0.036 (13)	0.034 (10)	0.024 (9)	−0.013 (9)	0.003 (7)	0.001 (7)
C16	0.041 (8)	0.045 (8)	0.033 (6)	0.018 (6)	0.015 (5)	0.007 (5)
N1'	0.026 (9)	0.045 (7)	0.024 (5)	0.010 (6)	0.010 (6)	−0.001 (4)
N2'	0.066 (13)	0.034 (6)	0.042 (6)	0.035 (9)	0.006 (9)	0.000 (4)
C1'	0.055 (12)	0.028 (6)	0.021 (5)	−0.021 (8)	−0.003 (8)	0.004 (4)
C2'	0.049 (12)	0.045 (9)	0.021 (5)	0.018 (8)	−0.003 (7)	0.002 (5)
C3'	0.032 (9)	0.039 (10)	0.025 (7)	0.004 (6)	0.001 (6)	0.011 (6)
C4'	0.025 (6)	0.045 (12)	0.027 (9)	−0.016 (6)	−0.004 (6)	−0.006 (6)
C5'	0.029 (9)	0.065 (14)	0.052 (12)	0.020 (8)	0.022 (8)	0.021 (9)
C6'	0.069 (7)	0.038 (5)	0.038 (5)	0.012 (5)	0.008 (5)	0.005 (4)
C7'	0.054 (8)	0.042 (7)	0.030 (5)	0.004 (6)	0.008 (6)	0.014 (5)
C8'	0.041 (8)	0.036 (7)	0.031 (7)	0.023 (6)	0.008 (5)	−0.006 (5)
C9'	0.052 (10)	0.032 (9)	0.019 (7)	0.007 (7)	0.004 (6)	−0.002 (6)
C10'	0.060 (11)	0.018 (7)	0.022 (6)	0.019 (6)	0.013 (6)	0.013 (5)
C11'	0.029 (11)	0.064 (15)	0.021 (9)	0.000 (8)	0.010 (7)	−0.002 (8)
C12'	0.081 (14)	0.025 (8)	0.056 (13)	0.001 (7)	−0.001 (9)	0.013 (8)
C13'	0.048 (11)	0.015 (6)	0.028 (9)	−0.006 (6)	0.008 (8)	−0.001 (5)
C14'	0.030 (9)	0.047 (9)	0.010 (8)	0.015 (6)	0.002 (8)	−0.003 (4)
C15'	0.030 (8)	0.052 (12)	0.024 (9)	0.032 (8)	0.016 (6)	0.024 (7)
C16'	0.016 (5)	0.055 (10)	0.059 (10)	0.007 (6)	0.006 (5)	0.003 (7)
I1B	0.04182 (18)	0.04034 (19)	0.03536 (18)	−0.00218 (11)	0.01576 (12)	0.00060 (11)
N1B	0.045 (2)	0.058 (2)	0.0235 (17)	−0.0162 (18)	0.0026 (15)	0.0096 (17)
N2B	0.058 (3)	0.077 (3)	0.032 (2)	0.024 (2)	0.0199 (18)	0.008 (2)
C1B	0.035 (2)	0.051 (3)	0.028 (2)	−0.0006 (18)	0.0069 (16)	0.0063 (17)
C2B	0.041 (2)	0.041 (2)	0.033 (2)	−0.0012 (18)	0.0058 (17)	0.0076 (18)
C3B	0.036 (2)	0.044 (2)	0.030 (2)	0.0075 (17)	0.0073 (16)	0.0155 (17)
C4B	0.053 (3)	0.050 (3)	0.038 (2)	0.014 (2)	0.013 (2)	0.010 (2)
C5B	0.082 (4)	0.041 (3)	0.035 (2)	−0.013 (3)	−0.003 (2)	0.006 (2)
C6B	0.053 (3)	0.031 (2)	0.026 (2)	0.0002 (17)	0.0058 (18)	0.0049 (16)
C7B	0.039 (2)	0.047 (2)	0.032 (2)	−0.0002 (19)	0.0047 (18)	0.0076 (19)
C8B	0.043 (2)	0.042 (2)	0.029 (2)	0.0072 (18)	−0.0002 (18)	0.0109 (17)
C9B	0.062 (3)	0.057 (3)	0.025 (2)	0.017 (2)	0.008 (2)	−0.0013 (19)
C10B	0.037 (2)	0.047 (3)	0.038 (2)	0.0037 (19)	0.0128 (18)	0.018 (2)
C11B	0.028 (2)	0.069 (3)	0.061 (3)	0.004 (2)	0.015 (2)	0.033 (3)
C12B	0.051 (3)	0.042 (3)	0.061 (3)	−0.016 (2)	−0.007 (2)	0.023 (2)
C13B	0.054 (3)	0.034 (2)	0.048 (3)	0.0042 (19)	0.001 (2)	0.005 (2)
C14B	0.040 (2)	0.033 (2)	0.038 (2)	0.0101 (17)	0.0086 (17)	0.0066 (17)
C15B	0.0262 (18)	0.038 (2)	0.0292 (19)	0.0059 (15)	0.0040 (15)	0.0128 (16)
C16B	0.052 (3)	0.136 (6)	0.044 (3)	−0.051 (4)	−0.004 (2)	0.027 (3)
O1	0.129 (5)	0.127 (6)	0.134 (6)	−0.022 (4)	0.052 (5)	−0.012 (4)

Geometric parameters (Å, º)

N1—C1	1.356 (15)	C7'—H7'	0.9500
N1—C5	1.31 (3)	C8'—C15'	1.36 (3)
N1—C16	1.48 (2)	C8'—C9'	1.376 (15)
N2—C9	1.350 (2)	C9'—H9'	0.9500
N2—C10	1.35 (3)	C10'—C15'	1.39 (2)
N2—H2N	0.8800	C10'—C11'	1.417 (18)
C1—C2	1.350 (18)	C11'—C12'	1.390 (2)
C1—H1	0.9500	C11'—H11'	0.9500
C2—C3	1.39 (2)	C12'—C13'	1.390 (2)
C2—H2	0.9500	C12'—H12'	0.9500
C3—C6	1.396 (17)	C13'—C14'	1.33 (2)
C3—C4	1.402 (13)	C13'—H13'	0.9500
C4—C5	1.348 (16)	C14'—C15'	1.45 (2)
C4—H4	0.9500	C14'—H14'	0.9500
C5—H5	0.9500	C16'—H16D	0.9800
C6—C7	1.347 (10)	C16'—H16E	0.9800
C6—H6	0.9500	C16'—H16F	0.9800
C7—C8	1.466 (15)	N1B—C1B	1.337 (6)
C7—H7	0.9500	N1B—C5B	1.367 (7)
C8—C9	1.382 (13)	N1B—C16B	1.467 (6)
C8—C15	1.53 (2)	N2B—C9B	1.334 (7)
C9—H9	0.9500	N2B—C10B	1.394 (7)
C10—C11	1.390 (2)	N2B—H2BN	0.8800
C10—C15	1.390 (2)	C1B—C2B	1.355 (6)
C11—C12	1.390 (2)	C1B—H1B	0.9500
C11—H11	0.9500	C2B—C3B	1.394 (6)
C12—C13	1.42 (2)	C2B—H2B	0.9500
C12—H12	0.9500	C3B—C4B	1.389 (7)
C13—C14	1.390 (2)	C3B—C6B	1.457 (6)
C13—H13	0.9500	C4B—C5B	1.386 (8)
C14—C15	1.390 (2)	C4B—H4B	0.9500
C14—H14	0.9500	C5B—H5B	0.9500
C16—H16A	0.9800	C6B—C7B	1.335 (7)
C16—H16B	0.9800	C6B—H6B	0.9500
C16—H16C	0.9800	C7B—C8B	1.420 (6)
N1'—C1'	1.41 (3)	C7B—H7B	0.9500
N1'—C5'	1.350 (2)	C8B—C9B	1.375 (7)
N1'—C16'	1.44 (2)	C8B—C15B	1.443 (6)
N2'—C9'	1.350 (2)	C9B—H9B	0.9500
N2'—C10'	1.42 (3)	C10B—C11B	1.379 (7)
N2'—H2'N	0.8800	C10B—C15B	1.405 (6)
C1'—C2'	1.34 (2)	C11B—C12B	1.377 (8)
C1'—H1'	0.9500	C11B—H11B	0.9500
C2'—C3'	1.38 (2)	C12B—C13B	1.416 (8)
C2'—H2'	0.9500	C12B—H12B	0.9500
C3'—C4'	1.39 (2)	C13B—C14B	1.358 (7)
C3'—C6'	1.449 (2)	C13B—H13B	0.9500
C4'—C5'	1.390 (2)	C14B—C15B	1.410 (6)
C4'—H4'	0.9500	C14B—H14B	0.9500
C5'—H5'	0.9500	C16B—H16G	0.9800
C6'—C7'	1.339 (2)	C16B—H16H	0.9800
C6'—H6'	0.9500	C16B—H16I	0.9800
C7'—C8'	1.43 (2)
C5—N1—C1	116.9 (17)	C8'—C9'—H9'	123.9
C5—N1—C16	122.2 (17)	C15'—C10'—C11'	127 (2)
C1—N1—C16	120.9 (19)	C15'—C10'—N2'	98.9 (19)
C10—N2—C9	108.5 (14)	C11'—C10'—N2'	134 (2)
C10—N2—H2N	125.8	C12'—C11'—C10'	116 (2)
C9—N2—H2N	125.8	C12'—C11'—H11'	121.8
C2—C1—N1	124.4 (14)	C10'—C11'—H11'	121.8
C2—C1—H1	117.8	C11'—C12'—C13'	119 (3)
N1—C1—H1	117.8	C11'—C12'—H12'	120.7
C1—C2—C3	118.8 (12)	C13'—C12'—H12'	120.7
C1—C2—H2	120.6	C14'—C13'—C12'	121 (3)
C3—C2—H2	120.6	C14'—C13'—H13'	119.5
C2—C3—C6	119.6 (11)	C12'—C13'—H13'	119.5
C2—C3—C4	115.7 (12)	C13'—C14'—C15'	126 (2)
C6—C3—C4	124.6 (12)	C13'—C14'—H14'	117.2
C5—C4—C3	121.6 (14)	C15'—C14'—H14'	117.2
C5—C4—H4	119.2	C8'—C15'—C10'	118 (2)
C3—C4—H4	119.2	C8'—C15'—C14'	132 (2)
N1—C5—C4	122.3 (16)	C10'—C15'—C14'	110 (2)
N1—C5—H5	118.8	N1'—C16'—H16D	109.5
C4—C5—H5	118.8	N1'—C16'—H16E	109.5
C7—C6—C3	127.5 (9)	H16D—C16'—H16E	109.5
C7—C6—H6	116.3	N1'—C16'—H16F	109.5
C3—C6—H6	116.3	H16D—C16'—H16F	109.5
C6—C7—C8	125.7 (9)	H16E—C16'—H16F	109.5
C6—C7—H7	117.1	C1B—N1B—C5B	118.0 (4)
C8—C7—H7	117.1	C1B—N1B—C16B	122.1 (5)
C9—C8—C7	122.5 (11)	C5B—N1B—C16B	119.9 (5)
C9—C8—C15	107.4 (13)	C9B—N2B—C10B	108.7 (4)
C7—C8—C15	130.0 (13)	C9B—N2B—H2BN	125.6
N2—C9—C8	109.6 (12)	C10B—N2B—H2BN	125.6
N2—C9—H9	125.2	N1B—C1B—C2B	122.8 (4)
C8—C9—H9	125.2	N1B—C1B—H1B	118.6
N2—C10—C11	125.7 (18)	C2B—C1B—H1B	118.6
N2—C10—C15	114.4 (15)	C1B—C2B—C3B	121.5 (4)
C11—C10—C15	119 (2)	C1B—C2B—H2B	119.3
C10—C11—C12	117 (2)	C3B—C2B—H2B	119.3
C10—C11—H11	121.3	C4B—C3B—C2B	115.4 (4)
C12—C11—H11	121.3	C4B—C3B—C6B	124.9 (4)
C11—C12—C13	119 (2)	C2B—C3B—C6B	119.7 (4)
C11—C12—H12	120.7	C5B—C4B—C3B	121.6 (5)
C13—C12—H12	120.7	C5B—C4B—H4B	119.2
C14—C13—C12	126 (3)	C3B—C4B—H4B	119.2
C14—C13—H13	116.9	N1B—C5B—C4B	120.6 (5)
C12—C13—H13	116.9	N1B—C5B—H5B	119.7
C13—C14—C15	110 (3)	C4B—C5B—H5B	119.7
C13—C14—H14	125.2	C7B—C6B—C3B	123.2 (4)
C15—C14—H14	125.2	C7B—C6B—H6B	118.4
C10—C15—C14	128 (2)	C3B—C6B—H6B	118.4
C10—C15—C8	100.0 (14)	C6B—C7B—C8B	127.8 (5)
C14—C15—C8	132.1 (19)	C6B—C7B—H7B	116.1
C5'—N1'—C1'	118.7 (18)	C8B—C7B—H7B	116.1
C5'—N1'—C16'	118.1 (19)	C9B—C8B—C7B	120.4 (5)
C1'—N1'—C16'	123.1 (16)	C9B—C8B—C15B	105.7 (4)
C9'—N2'—C10'	110.1 (16)	C7B—C8B—C15B	133.8 (4)
C9'—N2'—H2'N	124.9	N2B—C9B—C8B	111.4 (4)
C10'—N2'—H2'N	124.9	N2B—C9B—H9B	124.3
C2'—C1'—N1'	121.6 (15)	C8B—C9B—H9B	124.3
C2'—C1'—H1'	119.2	C11B—C10B—N2B	129.2 (4)
N1'—C1'—H1'	119.2	C11B—C10B—C15B	123.2 (5)
C1'—C2'—C3'	121.8 (14)	N2B—C10B—C15B	107.5 (4)
C1'—C2'—H2'	119.1	C12B—C11B—C10B	117.6 (4)
C3'—C2'—H2'	119.1	C12B—C11B—H11B	121.2
C2'—C3'—C4'	115.1 (12)	C10B—C11B—H11B	121.2
C2'—C3'—C6'	114.2 (14)	C11B—C12B—C13B	120.1 (4)
C4'—C3'—C6'	130.6 (15)	C11B—C12B—H12B	119.9
C5'—C4'—C3'	124.4 (15)	C13B—C12B—H12B	119.9
C5'—C4'—H4'	117.8	C14B—C13B—C12B	122.0 (5)
C3'—C4'—H4'	117.8	C14B—C13B—H13B	119.0
N1'—C5'—C4'	117.9 (18)	C12B—C13B—H13B	119.0
N1'—C5'—H5'	121.0	C13B—C14B—C15B	118.8 (4)
C4'—C5'—H5'	121.0	C13B—C14B—H14B	120.6
C7'—C6'—C3'	120.8 (13)	C15B—C14B—H14B	120.6
C7'—C6'—H6'	119.6	C10B—C15B—C14B	118.1 (4)
C3'—C6'—H6'	119.6	C10B—C15B—C8B	106.6 (4)
C6'—C7'—C8'	126.6 (14)	C14B—C15B—C8B	135.1 (4)
C6'—C7'—H7'	116.7	N1B—C16B—H16G	109.5
C8'—C7'—H7'	116.7	N1B—C16B—H16H	109.5
C15'—C8'—C9'	100.6 (16)	H16G—C16B—H16H	109.5
C15'—C8'—C7'	126.1 (16)	N1B—C16B—H16I	109.5
C9'—C8'—C7'	133.3 (17)	H16G—C16B—H16I	109.5
N2'—C9'—C8'	112.2 (14)	H16H—C16B—H16I	109.5
N2'—C9'—H9'	123.9
C5—N1—C1—C2	−6 (4)	C9'—N2'—C10'—C15'	1 (3)
C16—N1—C1—C2	175 (2)	C9'—N2'—C10'—C11'	171 (3)
N1—C1—C2—C3	4 (4)	C15'—C10'—C11'—C12'	−15 (4)
C1—C2—C3—C6	−179.5 (17)	N2'—C10'—C11'—C12'	177 (3)
C1—C2—C3—C4	−3 (3)	C10'—C11'—C12'—C13'	15 (5)
C2—C3—C4—C5	3 (2)	C11'—C12'—C13'—C14'	−6 (5)
C6—C3—C4—C5	179.9 (14)	C12'—C13'—C14'—C15'	−6 (5)
C1—N1—C5—C4	6 (3)	C9'—C8'—C15'—C10'	2 (3)
C16—N1—C5—C4	−174.8 (18)	C7'—C8'—C15'—C10'	−177 (2)
C3—C4—C5—N1	−5 (3)	C9'—C8'—C15'—C14'	−175 (3)
C2—C3—C6—C7	169.3 (15)	C7'—C8'—C15'—C14'	6 (4)
C4—C3—C6—C7	−7.4 (17)	C11'—C10'—C15'—C8'	−173 (3)
C3—C6—C7—C8	−177.9 (10)	N2'—C10'—C15'—C8'	−2 (3)
C6—C7—C8—C9	171.9 (12)	C11'—C10'—C15'—C14'	4 (4)
C6—C7—C8—C15	−12 (2)	N2'—C10'—C15'—C14'	176 (2)
C10—N2—C9—C8	1 (2)	C13'—C14'—C15'—C8'	−177 (3)
C7—C8—C9—N2	178.8 (14)	C13'—C14'—C15'—C10'	6 (4)
C15—C8—C9—N2	2 (2)	C5B—N1B—C1B—C2B	0.1 (6)
C9—N2—C10—C11	−170 (2)	C16B—N1B—C1B—C2B	179.8 (4)
C9—N2—C10—C15	−3 (3)	N1B—C1B—C2B—C3B	2.4 (7)
N2—C10—C11—C12	180 (3)	C1B—C2B—C3B—C4B	−4.0 (6)
C15—C10—C11—C12	14 (4)	C1B—C2B—C3B—C6B	175.1 (4)
C10—C11—C12—C13	−11 (4)	C2B—C3B—C4B—C5B	3.4 (6)
C11—C12—C13—C14	−2 (6)	C6B—C3B—C4B—C5B	−175.7 (4)
C12—C13—C14—C15	10 (5)	C1B—N1B—C5B—C4B	−0.8 (6)
N2—C10—C15—C14	−173 (3)	C16B—N1B—C5B—C4B	179.6 (4)
C11—C10—C15—C14	−5 (5)	C3B—C4B—C5B—N1B	−1.1 (7)
N2—C10—C15—C8	4 (3)	C4B—C3B—C6B—C7B	−4.6 (7)
C11—C10—C15—C8	171 (2)	C2B—C3B—C6B—C7B	176.4 (4)
C13—C14—C15—C10	−6 (5)	C3B—C6B—C7B—C8B	175.9 (4)
C13—C14—C15—C8	178 (3)	C6B—C7B—C8B—C9B	177.3 (4)
C9—C8—C15—C10	−3 (2)	C6B—C7B—C8B—C15B	−6.0 (8)
C7—C8—C15—C10	179.9 (16)	C10B—N2B—C9B—C8B	−0.3 (5)
C9—C8—C15—C14	173 (3)	C7B—C8B—C9B—N2B	177.6 (4)
C7—C8—C15—C14	−4 (4)	C15B—C8B—C9B—N2B	0.1 (5)
C5'—N1'—C1'—C2'	−6 (3)	C9B—N2B—C10B—C11B	−177.4 (4)
C16'—N1'—C1'—C2'	178 (2)	C9B—N2B—C10B—C15B	0.4 (5)
N1'—C1'—C2'—C3'	5 (3)	N2B—C10B—C11B—C12B	178.0 (4)
C1'—C2'—C3'—C4'	−3 (2)	C15B—C10B—C11B—C12B	0.5 (7)
C1'—C2'—C3'—C6'	176.4 (14)	C10B—C11B—C12B—C13B	−1.9 (7)
C2'—C3'—C4'—C5'	4 (3)	C11B—C12B—C13B—C14B	1.4 (7)
C6'—C3'—C4'—C5'	−176 (2)	C12B—C13B—C14B—C15B	0.7 (7)
C1'—N1'—C5'—C4'	7 (4)	C11B—C10B—C15B—C14B	1.6 (6)
C16'—N1'—C5'—C4'	−177 (2)	N2B—C10B—C15B—C14B	−176.4 (4)
C3'—C4'—C5'—N1'	−6 (4)	C11B—C10B—C15B—C8B	177.6 (4)
C2'—C3'—C6'—C7'	175.3 (11)	N2B—C10B—C15B—C8B	−0.3 (4)
C4'—C3'—C6'—C7'	−5 (2)	C13B—C14B—C15B—C10B	−2.1 (6)
C3'—C6'—C7'—C8'	178.3 (12)	C13B—C14B—C15B—C8B	−176.8 (4)
C6'—C7'—C8'—C15'	166.1 (18)	C9B—C8B—C15B—C10B	0.2 (4)
C6'—C7'—C8'—C9'	−13 (3)	C7B—C8B—C15B—C10B	−176.9 (4)
C10'—N2'—C9'—C8'	0 (3)	C9B—C8B—C15B—C14B	175.3 (5)
C15'—C8'—C9'—N2'	−1 (2)	C7B—C8B—C15B—C14B	−1.8 (8)
C7'—C8'—C9'—N2'	178 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2B—H2BN···O1^i	0.88	2.31	3.072 (9)	145
N2—H2N···I1	0.88	2.66	3.427 (13)	146
N2′—H2′N···I1	0.88	3.11	3.814 (15)	138
N2B—H2BN···I1B^ii	0.88	2.99	3.674 (4)	136
C1B—H1B···I1	0.95	3.08	3.965 (5)	156
C5′—H5′···I1B^ii	0.95	3.14	3.92 (3)	140
C5B—H5B···I1^iii	0.95	3.06	3.924 (5)	151
C16′—H16E···I1^iv	0.98	3.58	4.152 (18)	120
C16B—H16H···I1^v	0.98	3.05	3.823 (6)	137

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x−1, y, z; (v) x, −y+1/2, z+1/2.

(III) (E)-4-(9-ethylcarbazol-3-ylvinyl)-N-methylpyridinium iodide

Crystal data

C22H21N2^+·I^−	Z = 4
Mr = 440.31	F(000) = 880
Triclinic, P1	Dx = 1.497 Mg m^−3
a = 7.554 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.046 (6) Å	Cell parameters from 547 reflections
c = 16.295 (5) Å	θ = 2–24°
α = 82.27 (3)°	µ = 1.65 mm^−1
β = 87.36 (2)°	T = 110 K
γ = 87.42 (3)°	Needle, yellow
V = 1953.5 (10) Å^3	0.50 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	8901 independent reflections
Radiation source: fine-focus sealed tube	6571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→9
Tmin = 0.493, Tmax = 0.853	k = −20→20
15654 measured reflections	l = −20→21

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F^2) = 0.096	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0531P)^2] where P = (Fo^2 + 2Fc^2)/3
8901 reflections	(Δ/σ)max = 0.002
464 parameters	Δρmax = 1.76 e Å^−3
0 restraints	Δρmin = −0.53 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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.36199 (3)	0.918785 (14)	0.184615 (12)	0.03059 (8)
N1	0.4388 (3)	0.71476 (17)	0.39461 (15)	0.0272 (6)
N2	−0.1844 (3)	0.81231 (17)	0.98128 (15)	0.0263 (6)
C1	0.4207 (4)	0.7963 (2)	0.40724 (19)	0.0291 (7)
H1	0.4585	0.8392	0.3650	0.035*
C2	0.3483 (4)	0.8174 (2)	0.48051 (19)	0.0293 (7)
H2	0.3377	0.8749	0.4889	0.035*
C3	0.2888 (4)	0.7545 (2)	0.54400 (18)	0.0279 (7)
C4	0.3133 (5)	0.6706 (2)	0.5288 (2)	0.0357 (8)
H4	0.2794	0.6262	0.5703	0.043*
C5	0.3864 (5)	0.6524 (2)	0.4540 (2)	0.0348 (8)
H5	0.4002	0.5955	0.4439	0.042*
C6	0.2083 (4)	0.7799 (2)	0.62021 (19)	0.0307 (7)
H6	0.2063	0.8381	0.6256	0.037*
C7	0.1366 (4)	0.7282 (2)	0.68358 (19)	0.0307 (7)
H7	0.1413	0.6698	0.6789	0.037*
C8	0.0518 (4)	0.7542 (2)	0.75929 (18)	0.0281 (7)
C9	0.0243 (4)	0.8404 (2)	0.76873 (19)	0.0308 (7)
H9	0.0606	0.8815	0.7244	0.037*
C10	−0.0531 (4)	0.8675 (2)	0.83980 (18)	0.0267 (7)
H10	−0.0713	0.9256	0.8448	0.032*
C11	−0.1035 (4)	0.8039 (2)	0.90449 (18)	0.0246 (6)
C12	−0.0778 (4)	0.7172 (2)	0.89690 (18)	0.0250 (7)
C13	−0.0023 (4)	0.6928 (2)	0.82357 (18)	0.0266 (7)
H13	0.0123	0.6348	0.8174	0.032*
C14	−0.1467 (4)	0.6707 (2)	0.97358 (18)	0.0262 (7)
C15	−0.1610 (5)	0.5847 (2)	1.0031 (2)	0.0329 (8)
H15	−0.1214	0.5431	0.9694	0.040*
C16	−0.2341 (5)	0.5613 (2)	1.0826 (2)	0.0360 (8)
H16	−0.2427	0.5034	1.1035	0.043*
C17	−0.2951 (5)	0.6230 (2)	1.1319 (2)	0.0344 (8)
H17	−0.3433	0.6058	1.1861	0.041*
C18	−0.2867 (4)	0.7090 (2)	1.10334 (19)	0.0303 (7)
H18	−0.3309	0.7504	1.1364	0.036*
C19	−0.2106 (4)	0.7316 (2)	1.02402 (18)	0.0241 (6)
C20	0.5187 (5)	0.6932 (2)	0.31522 (19)	0.0342 (8)
H20A	0.4655	0.6425	0.3015	0.051*
H20B	0.6468	0.6828	0.3204	0.051*
H20C	0.4967	0.7400	0.2712	0.051*
C21	−0.2402 (4)	0.8916 (2)	1.01209 (19)	0.0285 (7)
H21A	−0.3584	0.8853	1.0406	0.034*
H21B	−0.2513	0.9366	0.9645	0.034*
C22	−0.1095 (5)	0.9174 (2)	1.0720 (2)	0.0418 (9)
H22A	−0.1547	0.9690	1.0931	0.063*
H22B	0.0057	0.9274	1.0430	0.063*
H22C	−0.0955	0.8723	1.1185	0.063*
I1'	0.36709 (10)	0.47233 (4)	0.27656 (3)	0.06087 (17)	0.83
I1''	0.3110 (6)	0.4804 (2)	0.2392 (2)	0.0829 (11)	0.17
N1'	0.6971 (3)	0.28531 (18)	−0.02850 (15)	0.0291 (6)
N2'	0.0910 (4)	0.14567 (17)	0.58059 (16)	0.0291 (6)
C1'	0.6416 (5)	0.3492 (2)	0.0140 (2)	0.0338 (8)
H1'	0.6533	0.4056	−0.0113	0.041*
C2'	0.5696 (5)	0.3340 (2)	0.0920 (2)	0.0362 (8)
H2'	0.5325	0.3800	0.1207	0.043*
C3'	0.5489 (4)	0.2505 (2)	0.1316 (2)	0.0340 (8)
C4'	0.6063 (5)	0.1852 (2)	0.0863 (2)	0.0344 (8)
H4'	0.5942	0.1281	0.1097	0.041*
C5'	0.6810 (5)	0.2049 (2)	0.0070 (2)	0.0355 (8)
H5'	0.7220	0.1606	−0.0231	0.043*
C6'	0.4684 (5)	0.2398 (2)	0.2164 (2)	0.0377 (8)
H6'	0.4406	0.2897	0.2404	0.045*
C7'	0.4307 (5)	0.1679 (2)	0.2626 (2)	0.0360 (8)
H7'	0.4593	0.1171	0.2400	0.043*
C8'	0.3473 (5)	0.1613 (2)	0.3468 (2)	0.0356 (8)
C9'	0.3119 (5)	0.0810 (2)	0.3889 (2)	0.0372 (8)
H9'	0.3459	0.0331	0.3624	0.045*
C10'	0.2293 (4)	0.0684 (2)	0.4673 (2)	0.0324 (7)
H10'	0.2080	0.0135	0.4947	0.039*
C11'	0.1786 (4)	0.1405 (2)	0.50445 (19)	0.0302 (7)
C12'	0.2143 (4)	0.2226 (2)	0.46416 (19)	0.0300 (7)
C13'	0.2981 (4)	0.2325 (2)	0.3843 (2)	0.0334 (8)
H13'	0.3207	0.2871	0.3565	0.040*
C14'	0.1476 (4)	0.2809 (2)	0.5197 (2)	0.0309 (7)
C15'	0.1426 (5)	0.3687 (2)	0.5159 (2)	0.0386 (8)
H15'	0.1915	0.4028	0.4688	0.046*
C16'	0.0656 (5)	0.4047 (3)	0.5813 (3)	0.0472 (10)
H16'	0.0615	0.4642	0.5795	0.057*
C17'	−0.0084 (5)	0.3538 (3)	0.6521 (2)	0.0458 (10)
H17'	−0.0620	0.3805	0.6962	0.055*
C18'	−0.0045 (5)	0.2661 (3)	0.6588 (2)	0.0380 (8)
H18'	−0.0523	0.2324	0.7064	0.046*
C19'	0.0741 (4)	0.2308 (2)	0.5915 (2)	0.0304 (7)
C20'	0.7766 (5)	0.3055 (3)	−0.11310 (19)	0.0393 (9)
H20D	0.7685	0.2571	−0.1434	0.059*
H20E	0.9015	0.3184	−0.1097	0.059*
H20F	0.7126	0.3544	−0.1422	0.059*
C21'	0.0529 (4)	0.0743 (2)	0.64429 (19)	0.0319 (7)
H21C	0.0256	0.0249	0.6173	0.038*
H21D	−0.0524	0.0887	0.6788	0.038*
C22'	0.2115 (5)	0.0519 (2)	0.6996 (2)	0.0411 (9)
H22D	0.1777	0.0097	0.7462	0.062*
H22E	0.2481	0.1026	0.7207	0.062*
H22F	0.3103	0.0291	0.6671	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.03226 (12)	0.03371 (13)	0.02567 (12)	0.00207 (9)	0.00106 (8)	−0.00530 (8)
N1	0.0271 (14)	0.0343 (16)	0.0207 (13)	0.0004 (12)	−0.0003 (11)	−0.0058 (11)
N2	0.0288 (14)	0.0300 (15)	0.0205 (13)	−0.0016 (12)	0.0030 (10)	−0.0056 (11)
C1	0.0302 (17)	0.0340 (19)	0.0232 (16)	−0.0036 (14)	0.0002 (13)	−0.0044 (13)
C2	0.0299 (17)	0.0325 (19)	0.0263 (16)	−0.0006 (14)	0.0006 (13)	−0.0072 (13)
C3	0.0235 (16)	0.040 (2)	0.0216 (15)	−0.0011 (14)	−0.0009 (12)	−0.0071 (13)
C4	0.042 (2)	0.038 (2)	0.0258 (17)	−0.0054 (16)	0.0029 (14)	0.0007 (14)
C5	0.043 (2)	0.0309 (19)	0.0303 (18)	−0.0014 (16)	0.0019 (15)	−0.0033 (14)
C6	0.0289 (17)	0.038 (2)	0.0263 (17)	−0.0030 (15)	0.0001 (13)	−0.0068 (14)
C7	0.0290 (17)	0.040 (2)	0.0232 (16)	0.0021 (15)	−0.0010 (13)	−0.0054 (14)
C8	0.0255 (16)	0.0353 (19)	0.0230 (16)	−0.0012 (14)	−0.0015 (13)	−0.0020 (13)
C9	0.0295 (17)	0.038 (2)	0.0241 (16)	−0.0043 (15)	0.0002 (13)	−0.0023 (14)
C10	0.0260 (16)	0.0282 (17)	0.0255 (16)	−0.0015 (13)	−0.0009 (13)	−0.0025 (13)
C11	0.0212 (15)	0.0306 (18)	0.0218 (15)	−0.0019 (13)	0.0018 (12)	−0.0037 (12)
C12	0.0220 (15)	0.0300 (18)	0.0229 (15)	0.0025 (13)	−0.0012 (12)	−0.0037 (12)
C13	0.0257 (16)	0.0291 (17)	0.0248 (16)	0.0024 (13)	0.0016 (12)	−0.0046 (13)
C14	0.0224 (16)	0.0316 (18)	0.0243 (16)	0.0002 (13)	0.0020 (12)	−0.0036 (13)
C15	0.039 (2)	0.0305 (19)	0.0286 (17)	0.0038 (15)	0.0040 (14)	−0.0043 (14)
C16	0.044 (2)	0.0294 (19)	0.0317 (18)	−0.0006 (16)	0.0081 (15)	0.0016 (14)
C17	0.039 (2)	0.039 (2)	0.0237 (16)	−0.0053 (16)	0.0086 (14)	−0.0028 (14)
C18	0.0244 (16)	0.041 (2)	0.0255 (16)	0.0002 (14)	0.0074 (13)	−0.0079 (14)
C19	0.0220 (15)	0.0264 (17)	0.0240 (15)	0.0011 (13)	0.0001 (12)	−0.0045 (12)
C20	0.039 (2)	0.040 (2)	0.0242 (17)	−0.0001 (16)	0.0033 (14)	−0.0082 (14)
C21	0.0315 (17)	0.0267 (17)	0.0271 (16)	0.0019 (14)	0.0030 (13)	−0.0056 (13)
C22	0.046 (2)	0.042 (2)	0.040 (2)	−0.0030 (18)	−0.0045 (17)	−0.0151 (16)
I1'	0.0908 (4)	0.0245 (2)	0.0643 (4)	−0.0067 (2)	0.0415 (3)	−0.0082 (2)
I1''	0.121 (3)	0.0291 (12)	0.096 (3)	−0.0115 (15)	0.055 (2)	−0.0165 (17)
N1'	0.0270 (14)	0.0377 (17)	0.0232 (13)	−0.0004 (12)	0.0005 (11)	−0.0069 (11)
N2'	0.0265 (14)	0.0340 (16)	0.0262 (14)	−0.0029 (12)	0.0034 (11)	−0.0027 (11)
C1'	0.0356 (19)	0.034 (2)	0.0330 (18)	−0.0037 (15)	0.0017 (14)	−0.0089 (14)
C2'	0.0351 (19)	0.047 (2)	0.0285 (18)	−0.0022 (16)	0.0022 (14)	−0.0125 (15)
C3'	0.0250 (17)	0.051 (2)	0.0269 (17)	−0.0035 (16)	−0.0036 (13)	−0.0081 (15)
C4'	0.0340 (19)	0.0331 (19)	0.0343 (19)	−0.0053 (15)	−0.0087 (15)	0.0054 (14)
C5'	0.0348 (19)	0.037 (2)	0.0362 (19)	−0.0001 (16)	−0.0071 (15)	−0.0095 (15)
C6'	0.0332 (19)	0.041 (2)	0.041 (2)	−0.0011 (16)	−0.0046 (15)	−0.0101 (16)
C7'	0.0311 (18)	0.041 (2)	0.0377 (19)	−0.0021 (16)	−0.0068 (15)	−0.0087 (16)
C8'	0.0283 (18)	0.050 (2)	0.0292 (18)	−0.0049 (16)	−0.0025 (14)	−0.0081 (16)
C9'	0.0302 (18)	0.049 (2)	0.0342 (19)	−0.0033 (16)	−0.0008 (15)	−0.0126 (16)
C10'	0.0296 (18)	0.039 (2)	0.0293 (17)	−0.0028 (15)	0.0008 (14)	−0.0070 (14)
C11'	0.0222 (16)	0.043 (2)	0.0244 (16)	−0.0022 (14)	−0.0026 (13)	−0.0012 (14)
C12'	0.0220 (16)	0.040 (2)	0.0275 (17)	−0.0015 (14)	−0.0052 (13)	0.0003 (14)
C13'	0.0258 (17)	0.042 (2)	0.0296 (17)	−0.0060 (15)	−0.0046 (14)	0.0075 (15)
C14'	0.0247 (17)	0.0327 (19)	0.0336 (18)	−0.0005 (14)	−0.0032 (13)	0.0022 (14)
C15'	0.0310 (19)	0.039 (2)	0.045 (2)	−0.0006 (16)	0.0007 (16)	0.0000 (16)
C16'	0.041 (2)	0.033 (2)	0.068 (3)	0.0010 (17)	−0.010 (2)	−0.0048 (19)
C17'	0.036 (2)	0.052 (3)	0.051 (2)	0.0031 (19)	0.0004 (17)	−0.0155 (19)
C18'	0.0300 (18)	0.049 (2)	0.0357 (19)	0.0058 (16)	0.0001 (15)	−0.0104 (16)
C19'	0.0227 (16)	0.037 (2)	0.0315 (17)	0.0001 (14)	−0.0028 (13)	−0.0035 (14)
C20'	0.037 (2)	0.059 (3)	0.0225 (17)	−0.0070 (18)	0.0017 (14)	−0.0039 (16)
C21'	0.0288 (17)	0.041 (2)	0.0263 (17)	−0.0083 (15)	0.0028 (13)	−0.0043 (14)
C22'	0.052 (2)	0.042 (2)	0.0291 (18)	−0.0136 (18)	−0.0078 (16)	0.0037 (15)

Geometric parameters (Å, º)

N1—C1	1.351 (4)	N1'—C1'	1.353 (4)
N1—C5	1.355 (4)	N1'—C5'	1.349 (4)
N1—C20	1.479 (4)	N1'—C20'	1.479 (4)
N2—C11	1.387 (4)	N2'—C11'	1.389 (4)
N2—C19	1.404 (4)	N2'—C19'	1.400 (4)
N2—C21	1.467 (4)	N2'—C21'	1.468 (4)
C1—C2	1.368 (4)	C1'—C2'	1.355 (5)
C1—H1	0.9500	C1'—H1'	0.9500
C2—C3	1.417 (5)	C2'—C3'	1.419 (5)
C2—H2	0.9500	C2'—H2'	0.9500
C3—C4	1.405 (5)	C3'—C4'	1.403 (5)
C3—C6	1.457 (4)	C3'—C6'	1.475 (5)
C4—C5	1.376 (5)	C4'—C5'	1.389 (5)
C4—H4	0.9500	C4'—H4'	0.9500
C5—H5	0.9500	C5'—H5'	0.9500
C6—C7	1.344 (5)	C6'—C7'	1.325 (5)
C6—H6	0.9500	C6'—H6'	0.9500
C7—C8	1.466 (4)	C7'—C8'	1.476 (5)
C7—H7	0.9500	C7'—H7'	0.9500
C8—C13	1.398 (4)	C8'—C13'	1.395 (5)
C8—C9	1.417 (5)	C8'—C9'	1.406 (5)
C9—C10	1.386 (4)	C9'—C10'	1.390 (5)
C9—H9	0.9500	C9'—H9'	0.9500
C10—C11	1.417 (4)	C10'—C11'	1.407 (5)
C10—H10	0.9500	C10'—H10'	0.9500
C11—C12	1.417 (4)	C11'—C12'	1.421 (5)
C12—C13	1.396 (4)	C12'—C13'	1.413 (5)
C12—C14	1.454 (4)	C12'—C14'	1.447 (5)
C13—H13	0.9500	C13'—H13'	0.9500
C14—C15	1.406 (5)	C14'—C15'	1.400 (5)
C14—C19	1.415 (4)	C14'—C19'	1.432 (5)
C15—C16	1.394 (5)	C15'—C16'	1.374 (5)
C15—H15	0.9500	C15'—H15'	0.9500
C16—C17	1.407 (5)	C16'—C17'	1.428 (6)
C16—H16	0.9500	C16'—H16'	0.9500
C17—C18	1.399 (5)	C17'—C18'	1.395 (5)
C17—H17	0.9500	C17'—H17'	0.9500
C18—C19	1.399 (4)	C18'—C19'	1.399 (5)
C18—H18	0.9500	C18'—H18'	0.9500
C20—H20A	0.9800	C20'—H20D	0.9800
C20—H20B	0.9800	C20'—H20E	0.9800
C20—H20C	0.9800	C20'—H20F	0.9800
C21—C22	1.528 (4)	C21'—C22'	1.533 (5)
C21—H21A	0.9900	C21'—H21C	0.9900
C21—H21B	0.9900	C21'—H21D	0.9900
C22—H22A	0.9800	C22'—H22D	0.9800
C22—H22B	0.9800	C22'—H22E	0.9800
C22—H22C	0.9800	C22'—H22F	0.9800
C1—N1—C5	120.9 (3)	C5'—N1'—C1'	119.8 (3)
C1—N1—C20	119.6 (3)	C5'—N1'—C20'	121.3 (3)
C5—N1—C20	119.5 (3)	C1'—N1'—C20'	118.9 (3)
C11—N2—C19	108.4 (3)	C11'—N2'—C19'	107.7 (3)
C11—N2—C21	126.3 (3)	C11'—N2'—C21'	125.7 (3)
C19—N2—C21	125.2 (3)	C19'—N2'—C21'	125.7 (3)
N1—C1—C2	120.4 (3)	N1'—C1'—C2'	121.2 (3)
N1—C1—H1	119.8	N1'—C1'—H1'	119.4
C2—C1—H1	119.8	C2'—C1'—H1'	119.4
C1—C2—C3	120.8 (3)	C1'—C2'—C3'	121.0 (3)
C1—C2—H2	119.6	C1'—C2'—H2'	119.5
C3—C2—H2	119.6	C3'—C2'—H2'	119.5
C4—C3—C2	116.8 (3)	C4'—C3'—C2'	116.9 (3)
C4—C3—C6	124.2 (3)	C4'—C3'—C6'	125.6 (3)
C2—C3—C6	119.0 (3)	C2'—C3'—C6'	117.4 (3)
C5—C4—C3	120.3 (3)	C5'—C4'—C3'	119.3 (3)
C5—C4—H4	119.8	C5'—C4'—H4'	120.4
C3—C4—H4	119.8	C3'—C4'—H4'	120.4
N1—C5—C4	120.7 (3)	N1'—C5'—C4'	121.8 (3)
N1—C5—H5	119.6	N1'—C5'—H5'	119.1
C4—C5—H5	119.6	C4'—C5'—H5'	119.1
C7—C6—C3	125.8 (3)	C7'—C6'—C3'	127.0 (4)
C7—C6—H6	117.1	C7'—C6'—H6'	116.5
C3—C6—H6	117.1	C3'—C6'—H6'	116.5
C6—C7—C8	125.6 (3)	C6'—C7'—C8'	124.4 (4)
C6—C7—H7	117.2	C6'—C7'—H7'	117.8
C8—C7—H7	117.2	C8'—C7'—H7'	117.8
C13—C8—C9	119.4 (3)	C13'—C8'—C9'	119.5 (3)
C13—C8—C7	119.3 (3)	C13'—C8'—C7'	121.7 (3)
C9—C8—C7	121.3 (3)	C9'—C8'—C7'	118.8 (3)
C10—C9—C8	123.0 (3)	C10'—C9'—C8'	123.0 (3)
C10—C9—H9	118.5	C10'—C9'—H9'	118.5
C8—C9—H9	118.5	C8'—C9'—H9'	118.5
C9—C10—C11	116.4 (3)	C9'—C10'—C11'	117.2 (3)
C9—C10—H10	121.8	C9'—C10'—H10'	121.4
C11—C10—H10	121.8	C11'—C10'—H10'	121.4
N2—C11—C12	109.1 (3)	N2'—C11'—C10'	128.7 (3)
N2—C11—C10	128.9 (3)	N2'—C11'—C12'	110.0 (3)
C12—C11—C10	121.9 (3)	C10'—C11'—C12'	121.3 (3)
C13—C12—C11	119.7 (3)	C13'—C12'—C11'	119.7 (3)
C13—C12—C14	133.3 (3)	C13'—C12'—C14'	133.7 (3)
C11—C12—C14	107.0 (3)	C11'—C12'—C14'	106.6 (3)
C12—C13—C8	119.6 (3)	C8'—C13'—C12'	119.3 (3)
C12—C13—H13	120.2	C8'—C13'—H13'	120.3
C8—C13—H13	120.2	C12'—C13'—H13'	120.3
C15—C14—C19	119.5 (3)	C15'—C14'—C19'	119.6 (3)
C15—C14—C12	134.2 (3)	C15'—C14'—C12'	134.2 (3)
C19—C14—C12	106.2 (3)	C19'—C14'—C12'	106.2 (3)
C16—C15—C14	119.1 (3)	C16'—C15'—C14'	118.8 (3)
C16—C15—H15	120.5	C16'—C15'—H15'	120.6
C14—C15—H15	120.5	C14'—C15'—H15'	120.6
C15—C16—C17	120.4 (3)	C15'—C16'—C17'	120.8 (4)
C15—C16—H16	119.8	C15'—C16'—H16'	119.6
C17—C16—H16	119.8	C17'—C16'—H16'	119.6
C18—C17—C16	121.8 (3)	C18'—C17'—C16'	122.2 (4)
C18—C17—H17	119.1	C18'—C17'—H17'	118.9
C16—C17—H17	119.1	C16'—C17'—H17'	118.9
C19—C18—C17	117.2 (3)	C17'—C18'—C19'	116.1 (4)
C19—C18—H18	121.4	C17'—C18'—H18'	122.0
C17—C18—H18	121.4	C19'—C18'—H18'	122.0
C18—C19—N2	128.8 (3)	C18'—C19'—N2'	128.1 (3)
C18—C19—C14	122.0 (3)	C18'—C19'—C14'	122.5 (3)
N2—C19—C14	109.2 (3)	N2'—C19'—C14'	109.4 (3)
N1—C20—H20A	109.5	N1'—C20'—H20D	109.5
N1—C20—H20B	109.5	N1'—C20'—H20E	109.5
H20A—C20—H20B	109.5	H20D—C20'—H20E	109.5
N1—C20—H20C	109.5	N1'—C20'—H20F	109.5
H20A—C20—H20C	109.5	H20D—C20'—H20F	109.5
H20B—C20—H20C	109.5	H20E—C20'—H20F	109.5
N2—C21—C22	112.3 (3)	N2'—C21'—C22'	110.8 (3)
N2—C21—H21A	109.2	N2'—C21'—H21C	109.5
C22—C21—H21A	109.2	C22'—C21'—H21C	109.5
N2—C21—H21B	109.2	N2'—C21'—H21D	109.5
C22—C21—H21B	109.2	C22'—C21'—H21D	109.5
H21A—C21—H21B	107.9	H21C—C21'—H21D	108.1
C21—C22—H22A	109.5	C21'—C22'—H22D	109.5
C21—C22—H22B	109.5	C21'—C22'—H22E	109.5
H22A—C22—H22B	109.5	H22D—C22'—H22E	109.5
C21—C22—H22C	109.5	C21'—C22'—H22F	109.5
H22A—C22—H22C	109.5	H22D—C22'—H22F	109.5
H22B—C22—H22C	109.5	H22E—C22'—H22F	109.5
C5—N1—C1—C2	−0.2 (5)	C5'—N1'—C1'—C2'	0.0 (5)
C20—N1—C1—C2	−179.5 (3)	C20'—N1'—C1'—C2'	−179.3 (3)
N1—C1—C2—C3	−0.8 (5)	N1'—C1'—C2'—C3'	−0.5 (5)
C1—C2—C3—C4	2.0 (4)	C1'—C2'—C3'—C4'	0.1 (5)
C1—C2—C3—C6	−178.4 (3)	C1'—C2'—C3'—C6'	−179.7 (3)
C2—C3—C4—C5	−2.2 (5)	C2'—C3'—C4'—C5'	0.7 (5)
C6—C3—C4—C5	178.2 (3)	C6'—C3'—C4'—C5'	−179.5 (3)
C1—N1—C5—C4	0.0 (5)	C1'—N1'—C5'—C4'	0.9 (5)
C20—N1—C5—C4	179.3 (3)	C20'—N1'—C5'—C4'	−179.9 (3)
C3—C4—C5—N1	1.3 (5)	C3'—C4'—C5'—N1'	−1.2 (5)
C4—C3—C6—C7	−4.6 (5)	C4'—C3'—C6'—C7'	−2.7 (5)
C2—C3—C6—C7	175.9 (3)	C2'—C3'—C6'—C7'	177.0 (3)
C3—C6—C7—C8	−178.4 (3)	C3'—C6'—C7'—C8'	−179.0 (3)
C6—C7—C8—C13	−174.0 (3)	C6'—C7'—C8'—C13'	1.1 (5)
C6—C7—C8—C9	5.7 (5)	C6'—C7'—C8'—C9'	179.0 (3)
C13—C8—C9—C10	0.6 (5)	C13'—C8'—C9'—C10'	−0.1 (5)
C7—C8—C9—C10	−179.1 (3)	C7'—C8'—C9'—C10'	−178.2 (3)
C8—C9—C10—C11	0.5 (4)	C8'—C9'—C10'—C11'	0.7 (5)
C19—N2—C11—C12	0.3 (3)	C19'—N2'—C11'—C10'	178.5 (3)
C21—N2—C11—C12	−177.4 (3)	C21'—N2'—C11'—C10'	8.6 (5)
C19—N2—C11—C10	179.2 (3)	C19'—N2'—C11'—C12'	−1.8 (3)
C21—N2—C11—C10	1.4 (5)	C21'—N2'—C11'—C12'	−171.6 (3)
C9—C10—C11—N2	−179.3 (3)	C9'—C10'—C11'—N2'	178.3 (3)
C9—C10—C11—C12	−0.5 (4)	C9'—C10'—C11'—C12'	−1.5 (4)
N2—C11—C12—C13	178.3 (3)	N2'—C11'—C12'—C13'	−178.1 (3)
C10—C11—C12—C13	−0.7 (4)	C10'—C11'—C12'—C13'	1.7 (4)
N2—C11—C12—C14	−0.1 (3)	N2'—C11'—C12'—C14'	1.1 (3)
C10—C11—C12—C14	−179.1 (3)	C10'—C11'—C12'—C14'	−179.1 (3)
C11—C12—C13—C8	1.8 (4)	C9'—C8'—C13'—C12'	0.3 (5)
C14—C12—C13—C8	179.8 (3)	C7'—C8'—C13'—C12'	178.3 (3)
C9—C8—C13—C12	−1.8 (4)	C11'—C12'—C13'—C8'	−1.1 (4)
C7—C8—C13—C12	177.9 (3)	C14'—C12'—C13'—C8'	180.0 (3)
C13—C12—C14—C15	1.1 (6)	C13'—C12'—C14'—C15'	−0.9 (6)
C11—C12—C14—C15	179.3 (3)	C11'—C12'—C14'—C15'	−179.9 (3)
C13—C12—C14—C19	−178.3 (3)	C13'—C12'—C14'—C19'	179.0 (3)
C11—C12—C14—C19	−0.1 (3)	C11'—C12'—C14'—C19'	0.0 (3)
C19—C14—C15—C16	−1.6 (5)	C19'—C14'—C15'—C16'	−0.4 (5)
C12—C14—C15—C16	179.1 (3)	C12'—C14'—C15'—C16'	179.4 (3)
C14—C15—C16—C17	1.0 (5)	C14'—C15'—C16'—C17'	−0.1 (5)
C15—C16—C17—C18	0.7 (5)	C15'—C16'—C17'—C18'	0.8 (6)
C16—C17—C18—C19	−1.6 (5)	C16'—C17'—C18'—C19'	−0.9 (5)
C17—C18—C19—N2	−179.3 (3)	C17'—C18'—C19'—N2'	−177.9 (3)
C17—C18—C19—C14	0.9 (4)	C17'—C18'—C19'—C14'	0.4 (5)
C11—N2—C19—C18	179.8 (3)	C11'—N2'—C19'—C18'	−179.8 (3)
C21—N2—C19—C18	−2.4 (5)	C21'—N2'—C19'—C18'	−10.0 (5)
C11—N2—C19—C14	−0.4 (3)	C11'—N2'—C19'—C14'	1.7 (3)
C21—N2—C19—C14	177.4 (3)	C21'—N2'—C19'—C14'	171.6 (3)
C15—C14—C19—C18	0.6 (4)	C15'—C14'—C19'—C18'	0.3 (5)
C12—C14—C19—C18	−179.9 (3)	C12'—C14'—C19'—C18'	−179.6 (3)
C15—C14—C19—N2	−179.2 (3)	C15'—C14'—C19'—N2'	178.8 (3)
C12—C14—C19—N2	0.3 (3)	C12'—C14'—C19'—N2'	−1.1 (3)
C11—N2—C21—C22	−101.3 (3)	C11'—N2'—C21'—C22'	85.1 (4)
C19—N2—C21—C22	81.2 (4)	C19'—N2'—C21'—C22'	−83.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1	0.95	3.15	3.921 (3)	140
C20—H20C···I1	0.98	3.17	4.100 (4)	159
C5′—H5′···I1^i	0.95	3.17	3.951 (4)	140
C21′—H21D···I1^ii	0.99	3.15	4.105 (4)	163
C21—H21A···I1^iii	0.99	3.17	4.069 (3)	152
C20—H20A···I1′	0.98	2.95	3.911 (4)	168
C6′—H6′···I1′	0.95	3.09	4.017 (4)	166
C13′—H13′···I1′	0.95	3.11	4.055 (4)	174
C2′—H2′···I1′′	0.95	3.07	3.970 (5)	159
C6′—H6′···I1′′	0.95	3.17	4.049 (5)	155
C17′—H17′···I1′′^ii	0.95	3.11	3.973 (6)	151
C20′—H20F···I1′′^i	0.98	2.90	3.806 (5)	154

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z+1.