4-[2-(4-Cyano­phenyl)ethenyl]-N-methyl­pyridinium tetra­phenyl­borate

Jin, D.; Zhang, D.-C.

doi:10.1107/S010827010503060X

4-[2-(4-Cyanophenyl)ethenyl]-N-methylpyridinium tetraphenylborate

In the title compound, C₁₅H₁₃N₂⁺·C₂₄H₂₀B⁻, the pyridyl ring of the cation makes a dihedral angle of 1.6° with the benzene ring. Each is rotated in the same direction with respect to the central –C—CH=CH—C– linkage, by 3.8 and 5.3°, respectively. The anions have a slightly distorted tetrahedral geometry. Molecular packing analysis was carried out using the packing energy portioning scheme in the program OPEC. Around each anion in the crystal structure there are eight anions, which interact with the central anion through C—H

π interactions. The cations are hydrogen bonded in a head-to-tail fashion, forming chains along [10 $\overline{1}$ ].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010503060X/sf1010sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S010827010503060X/sf1010Isup2.hkl Contains datablock I

CCDC reference: 290579

Comment top

Considerable effort has been made to investigate organic salts with large second-order optical nonlinearities (Chemla & Zyss, 1987). Marder et al. (1994) have synthesized a number of stilbazolium salts with large powder second-harmonic generation (SHG) efficiencies. According to the organic `salt methodology' principle (Marder et al., 1989, 1994), Coulombic interactions in organic salts could override dipole–dipole interactions which are favoured for antiparallel centrosymmetric packing. During our systematic search for organic non-linear optical (NLO) materials, we isolated the title compound, (I), and describe its crystal structure here.

Compound (I) consists of a 4'-cyano-4-N-methylstilbazolium cation and a BPh₄⁻ anion. In the cation, which is nearly planar and in the trans form (Fig. 1), the pyridyl ring makes a dihedral angle of 1.6° with the phenyl ring. They are rotated in the same direction with respect to the central C—CH═CH—C linkage, by 3.8 and 5.3°, respectively. The anion takes a slightly distorted tetrahedral geometry. The B—C bond lengths are in the range 1.628 (6)–1.660 (6) Å, and the C—B—C bond angles are in the range 102.8 (4)–114.0 (2)° (Table 1).

The portioning scheme in the program OPEC (Gavezzotti, 1983) with largely improved parameters (Gavezzotti & Filippini, 1994) was used to analyse the packing mode for the cations and anions in the crystal structure of (I). Table 3 lists the most important C—H···π interactions (type I; Umezawa et al., 1998) in the title crystal. Table 4 lists the calculated packing energy (PE) between the fundamental molecule (FM) and its surrounding molecules (SMs) which most strongly interact with the FM. Although the absolute total PE calculated is not very accurate (about 2 kcal mol⁻¹; 1 kcal mol⁻¹ = 4.184 kJ mol⁻¹; Gavezzotti & Filippini, 1994), the relative order after portioning into the contributions for individual SMs is believed to be meaningful. According to Table 4, the anion in the FM most strongly interacts with the first eight anions in the SMs, or in this sense, it is surrounded by these eight anions. When comparing the SMs in both Tables 3 and 4, one can see that the interactions between the FM and SMs, particularly the anion–anion and cation–anion interactions, are C—H···π type (type I; Umezawa et al., 1998). On the other hand, the major cation–cation interaction is the hydrogen bond (line 1 in Table 2) between the N atom in CN and the C—H on the opposite side of the cation. This is therefore in a head-to-tail mode and forms chains along [101].

The organic salt methodology principle (Marder et al., 1989) suggested that the anion–cation interaction in organic salts could override the dipole–dipole interaction, which provides a strong driving force for centrosymmetric packing in dipolar crystals. Compound (I) crystallized in the noncentrosymmetric space group Cc, belonging to point group m, one of the favourable groups for SHG, and is therefore a potential SHG crystal. However, not all similar crystals are noncentrosymmetric. A search was carried out of the Cambridge Structural Database (CSD, Version?; Allen, 2002) for stilbazolium tetraphenylborates and resulted in three crystals. In order to estimate the relative contributions of the cation–cation, anion–anion and anion–cation interactions, packing energies were calculated on these three crystals and (I) using the program OPEC. The results are listed in Table 5. Although the data are very limited and the calculated absolute total PE value is not very accurate, we could tentatively state that the non-centrosymmetric packing of the title crystal is possibly due to the much stronger anion–cation interaction.

Experimental top

1,4-Dimethylpyridinium iodide (7.05 g, 30 mmol) (prepared from CH₃I and 1-methylpyridine), 4-cyanobenzaldehyde (6.42 g, 49 mmol) and piperidine (0.2 ml) in methanol (40 ml) were heated at 353 K with stirring for 8 h (Okada et al., 1990). The product was recrystallized twice from ethanol–water (2:1), dissolved in water (0.70 g in 100 ml) and treated with a saturated solution of sodium tetraphenylborate. The title compound was separated and recrystallized twice from ethanol–water (4:1). Yellow crystals of (I) (m.p. 489–490 K) were grown by slow evaporation at ambient temperature from N,N-dimethylformamide over a period of 18 d. Elemental analysis (Perkin–Elmer 240 C elemental analyzer): calculated for C₁₅H₁₃N₂⁺·BPh₄⁻: C 86.67, H 6.11, N 5.19%; found: C 87.09, H 6.27, N 4.85%. Spectroscopic analysis: IR (FT–IR spectrometer with KBr pellets, ν, cm⁻¹): 3050 (Ar—H), 2995 (–C—H), 2227 (cyano), 1644 (–CH═CH–), 1627 (–CH═N–), 1519 (ph), 1478 (ph), 1427 (ph), 1334 (–CH₃), 1188 (–CH═C—H), 1151 (–CH═C—H), 1031 (Ar—H), 972 (Ar—H), 955 (Ar—H), 848 (Ar—H), 733 (Ar—H), 711 (Ar—H); ¹H NMR (Bruker AV-400 NMR spectrometer, DMSO, 399.97 MHz, ambient temperature, δ, p.p.m.): 8.91 (d, 2H, pyridyl ring), 8.25 (d, 2H, pyridyl ring), 8.03 (d, 1H, –CH═ CH–), 7.97 (d, 2H, ph), 7.91 (d, 2H, ph), 7.32 (d, 1H, –CH═ CH–), 7.18 (s, 8H, ph), 6.94–6.90 (m, 8H, ph), 6.80–6.77 (m, 4H, ph), 2.50 (s, 3H, –CH₃).

Computing details top

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Please provide details; software used to prepare material for publication: Please provide details.

Figures top

	Fig. 1. A view of the molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I), viewed down the b axis.

4-[2-(4-Cyanophenyl)ethenyl]-N-methylpyridinium tetraphenylborate top

Crystal data top

C₁₅H₁₃N₂⁺·C₂₄H₂₀B⁻	F(000) = 1144
M_r = 540.48	D_x = 1.198 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: C -2yc	Cell parameters from 5327 reflections
a = 16.930 (3) Å	θ = 3.0–25.3°
b = 10.7694 (18) Å	µ = 0.07 mm⁻¹
c = 17.665 (3) Å	T = 193 K
β = 111.543 (5)°	Block, yellow
V = 2995.8 (9) Å³	0.50 × 0.19 × 0.11 mm
Z = 4

Data collection top

Rigaku Mercury diffractometer	2726 independent reflections
Radiation source: fine-focus sealed tube	2355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.0°
ω scans	h = −20→20
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
T_min = 0.966, T_max = 0.993	l = −20→21
14471 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0568P)² + 0.9638P] where P = (F_o² + 2F_c²)/3
2726 reflections	(Δ/σ)_max < 0.001
381 parameters	Δρ_max = 0.15 e Å⁻³
2 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₅H₁₃N₂⁺·C₂₄H₂₀B⁻	V = 2995.8 (9) Å³
M_r = 540.48	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 16.930 (3) Å	µ = 0.07 mm⁻¹
b = 10.7694 (18) Å	T = 193 K
c = 17.665 (3) Å	0.50 × 0.19 × 0.11 mm
β = 111.543 (5)°

Data collection top

Rigaku Mercury diffractometer	2726 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	2355 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.993	R_int = 0.047
14471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	2 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.11	Δρ_max = 0.15 e Å⁻³
2726 reflections	Δρ_min = −0.18 e Å⁻³
381 parameters

Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.4647 (2)	0.4662 (3)	0.2605 (2)	0.0435 (9)
N2	0.9400 (3)	−0.0179 (4)	−0.0027 (3)	0.0747 (12)
C1	0.4553 (3)	0.3487 (4)	0.2330 (3)	0.0500 (12)
H1	0.4088	0.3006	0.2344	0.060*
C2	0.5111 (3)	0.2977 (4)	0.2032 (3)	0.0475 (12)
H2	0.5031	0.2148	0.1835	0.057*
C3	0.5811 (3)	0.3668 (4)	0.2012 (3)	0.0377 (9)
C4	0.5896 (3)	0.4865 (4)	0.2316 (3)	0.0456 (11)
H4	0.6364	0.5359	0.2327	0.055*
C5	0.5309 (3)	0.5341 (4)	0.2602 (3)	0.0495 (12)
H5	0.5372	0.6168	0.2801	0.059*
C6	0.6439 (3)	0.3179 (4)	0.1711 (3)	0.0431 (11)
H6	0.6907	0.3703	0.1758	0.052*
C7	0.6425 (3)	0.2070 (4)	0.1377 (3)	0.0415 (11)
H7	0.5955	0.1547	0.1322	0.050*
C8	0.7070 (3)	0.1584 (4)	0.1085 (3)	0.0370 (9)
C9	0.7002 (3)	0.0375 (4)	0.0794 (3)	0.0410 (10)
H9	0.6536	−0.0124	0.0787	0.049*
C10	0.7594 (3)	−0.0112 (4)	0.0516 (3)	0.0448 (11)
H10	0.7551	−0.0950	0.0336	0.054*
C11	0.8256 (3)	0.0629 (4)	0.0501 (3)	0.0422 (10)
C12	0.8327 (3)	0.1849 (4)	0.0770 (3)	0.0451 (11)
H12	0.8779	0.2357	0.0752	0.054*
C13	0.7734 (3)	0.2319 (4)	0.1063 (3)	0.0423 (11)
H13	0.7782	0.3152	0.1251	0.051*
C14	0.4017 (3)	0.5208 (5)	0.2908 (3)	0.0613 (14)
H14A	0.4139	0.4935	0.3469	0.092*
H14B	0.3446	0.4934	0.2562	0.092*
H14C	0.4048	0.6116	0.2892	0.092*
C15	0.8883 (3)	0.0161 (4)	0.0200 (3)	0.0532 (12)
C16	0.8483 (2)	0.5763 (3)	0.3257 (2)	0.0292 (9)
C17	0.8391 (3)	0.5383 (4)	0.2467 (2)	0.0331 (9)
H17	0.8663	0.4638	0.2408	0.040*
C18	0.7929 (3)	0.6035 (4)	0.1777 (2)	0.0384 (10)
H18	0.7892	0.5739	0.1259	0.046*
C19	0.7517 (3)	0.7123 (4)	0.1835 (3)	0.0440 (11)
H19	0.7186	0.7567	0.1360	0.053*
C20	0.7598 (3)	0.7549 (4)	0.2598 (3)	0.0407 (10)
H20	0.7328	0.8301	0.2649	0.049*
C21	0.8071 (3)	0.6886 (3)	0.3289 (3)	0.0329 (9)
H21	0.8118	0.7203	0.3806	0.040*
C22	0.9388 (2)	0.5649 (3)	0.4899 (2)	0.0283 (8)
C23	0.9838 (3)	0.6748 (3)	0.4932 (2)	0.0322 (9)
H23	0.9800	0.7127	0.4435	0.039*
C24	1.0337 (2)	0.7315 (4)	0.5657 (3)	0.0361 (10)
H24	1.0639	0.8055	0.5649	0.043*
C25	1.0391 (3)	0.6794 (4)	0.6393 (3)	0.0400 (10)
H25	1.0728	0.7176	0.6891	0.048*
C26	0.9949 (3)	0.5709 (4)	0.6395 (3)	0.0378 (10)
H26	0.9978	0.5348	0.6895	0.045*
C27	0.9463 (2)	0.5154 (3)	0.5659 (2)	0.0312 (9)
H27	0.9170	0.4407	0.5671	0.037*
C28	0.8121 (3)	0.4040 (3)	0.4092 (2)	0.0316 (9)
C29	0.7566 (3)	0.4509 (4)	0.4453 (3)	0.0369 (10)
H29	0.7679	0.5305	0.4701	0.044*
C30	0.6864 (3)	0.3864 (4)	0.4463 (3)	0.0447 (11)
H30	0.6509	0.4210	0.4718	0.054*
C31	0.6685 (3)	0.2712 (5)	0.4098 (3)	0.0498 (12)
H31	0.6208	0.2256	0.4108	0.060*
C32	0.7191 (3)	0.2225 (4)	0.3721 (3)	0.0475 (12)
H32	0.7064	0.1434	0.3465	0.057*
C33	0.7899 (3)	0.2894 (4)	0.3713 (3)	0.0401 (10)
H33	0.8237	0.2552	0.3438	0.048*
C34	0.9709 (3)	0.4051 (3)	0.3984 (2)	0.0286 (9)
C35	0.9939 (3)	0.2889 (3)	0.4353 (2)	0.0336 (9)
H35	0.9591	0.2524	0.4610	0.040*
C36	1.0645 (3)	0.2251 (4)	0.4361 (3)	0.0436 (11)
H36	1.0771	0.1461	0.4617	0.052*
C37	1.1176 (3)	0.2748 (4)	0.4002 (3)	0.0424 (11)
H37	1.1663	0.2306	0.4004	0.051*
C38	1.0981 (3)	0.3900 (4)	0.3640 (3)	0.0383 (10)
H38	1.1339	0.4262	0.3393	0.046*
C39	1.0262 (2)	0.4535 (4)	0.3634 (2)	0.0324 (9)
H39	1.0142	0.5328	0.3383	0.039*
B1	0.8930 (4)	0.4878 (3)	0.4058 (3)	0.0287 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.037 (2)	0.044 (2)	0.049 (2)	−0.0032 (16)	0.0149 (18)	−0.0100 (17)
N2	0.086 (3)	0.059 (3)	0.097 (3)	−0.004 (2)	0.054 (3)	−0.021 (2)
C1	0.035 (3)	0.048 (3)	0.070 (3)	−0.010 (2)	0.022 (2)	−0.016 (2)
C2	0.039 (3)	0.035 (2)	0.069 (3)	−0.0112 (18)	0.020 (2)	−0.014 (2)
C3	0.037 (2)	0.039 (2)	0.038 (2)	−0.0072 (19)	0.0147 (19)	−0.0018 (18)
C4	0.053 (3)	0.042 (2)	0.048 (3)	−0.015 (2)	0.025 (2)	−0.007 (2)
C5	0.062 (3)	0.038 (2)	0.056 (3)	−0.012 (2)	0.030 (3)	−0.011 (2)
C6	0.031 (2)	0.052 (3)	0.048 (2)	−0.0093 (19)	0.016 (2)	−0.008 (2)
C7	0.035 (2)	0.043 (2)	0.046 (3)	−0.0116 (18)	0.014 (2)	−0.0036 (19)
C8	0.031 (2)	0.036 (2)	0.041 (2)	−0.0046 (17)	0.0104 (19)	−0.0006 (18)
C9	0.043 (3)	0.036 (2)	0.044 (2)	−0.0085 (19)	0.016 (2)	−0.0051 (19)
C10	0.053 (3)	0.035 (2)	0.047 (3)	−0.0085 (19)	0.019 (2)	−0.0063 (19)
C11	0.048 (3)	0.043 (2)	0.040 (2)	0.000 (2)	0.020 (2)	−0.0056 (19)
C12	0.042 (3)	0.040 (2)	0.055 (3)	−0.0098 (19)	0.021 (2)	−0.009 (2)
C13	0.040 (3)	0.036 (2)	0.055 (3)	−0.0089 (18)	0.022 (2)	−0.014 (2)
C14	0.052 (3)	0.064 (3)	0.077 (4)	−0.003 (2)	0.035 (3)	−0.020 (3)
C15	0.062 (3)	0.044 (3)	0.059 (3)	−0.004 (2)	0.029 (3)	−0.013 (2)
C16	0.022 (2)	0.0327 (19)	0.034 (2)	−0.0034 (16)	0.0119 (18)	−0.0019 (16)
C17	0.030 (2)	0.035 (2)	0.033 (2)	−0.0029 (16)	0.0103 (18)	−0.0013 (17)
C18	0.030 (2)	0.055 (3)	0.028 (2)	−0.0047 (18)	0.0089 (18)	0.0032 (18)
C19	0.031 (2)	0.050 (2)	0.047 (3)	0.0003 (19)	0.009 (2)	0.022 (2)
C20	0.026 (2)	0.042 (2)	0.055 (3)	0.0023 (16)	0.015 (2)	0.0094 (19)
C21	0.024 (2)	0.036 (2)	0.039 (2)	0.0016 (16)	0.0120 (18)	0.0058 (17)
C22	0.023 (2)	0.0309 (19)	0.030 (2)	0.0036 (16)	0.0087 (17)	−0.0002 (16)
C23	0.032 (2)	0.033 (2)	0.034 (2)	−0.0009 (16)	0.0149 (18)	−0.0005 (16)
C24	0.028 (2)	0.033 (2)	0.047 (2)	−0.0032 (15)	0.0128 (18)	−0.0063 (18)
C25	0.027 (2)	0.050 (2)	0.037 (2)	0.0004 (18)	0.0052 (18)	−0.0100 (19)
C26	0.036 (2)	0.042 (2)	0.033 (2)	0.0046 (17)	0.0093 (18)	0.0000 (17)
C27	0.027 (2)	0.0310 (19)	0.034 (2)	−0.0005 (15)	0.0104 (18)	−0.0002 (16)
C28	0.032 (2)	0.035 (2)	0.027 (2)	−0.0046 (16)	0.0100 (19)	0.0019 (16)
C29	0.033 (2)	0.043 (2)	0.035 (2)	0.0012 (18)	0.0139 (19)	0.0001 (18)
C30	0.027 (3)	0.064 (3)	0.044 (3)	0.002 (2)	0.014 (2)	0.013 (2)
C31	0.035 (3)	0.060 (3)	0.051 (3)	−0.014 (2)	0.011 (2)	0.013 (2)
C32	0.040 (3)	0.047 (3)	0.049 (3)	−0.012 (2)	0.009 (2)	0.003 (2)
C33	0.041 (3)	0.037 (2)	0.042 (2)	−0.0038 (19)	0.015 (2)	0.0001 (19)
C34	0.028 (2)	0.028 (2)	0.027 (2)	−0.0032 (15)	0.0075 (18)	−0.0045 (16)
C35	0.031 (2)	0.035 (2)	0.035 (2)	0.0025 (17)	0.0117 (19)	0.0004 (17)
C36	0.044 (3)	0.033 (2)	0.050 (3)	0.0089 (19)	0.014 (2)	0.0011 (19)
C37	0.029 (2)	0.050 (3)	0.045 (3)	0.0048 (19)	0.009 (2)	−0.010 (2)
C38	0.033 (3)	0.047 (2)	0.038 (2)	−0.0034 (18)	0.016 (2)	−0.007 (2)
C39	0.027 (2)	0.0328 (19)	0.034 (2)	0.0001 (16)	0.0078 (18)	−0.0035 (17)
B1	0.0270 (15)	0.0306 (18)	0.0292 (15)	0.000 (2)	0.0111 (13)	0.001 (2)

Geometric parameters (Å, º) top

N1—C5	1.339 (6)	C20—C21	1.387 (6)
N1—C1	1.344 (6)	C20—H20	0.9500
N1—C14	1.479 (6)	C21—H21	0.9500
N2—C15	1.148 (6)	C22—C23	1.397 (5)
C1—C2	1.355 (6)	C22—C27	1.406 (5)
C1—H1	0.9500	C22—B1	1.628 (6)
C2—C3	1.410 (6)	C23—C24	1.390 (6)
C2—H2	0.9500	C23—H23	0.9500
C3—C4	1.383 (6)	C24—C25	1.387 (6)
C3—C6	1.451 (6)	C24—H24	0.9500
C4—C5	1.369 (6)	C25—C26	1.388 (6)
C4—H4	0.9500	C25—H25	0.9500
C5—H5	0.9500	C26—C27	1.393 (6)
C6—C7	1.328 (5)	C26—H26	0.9500
C6—H6	0.9500	C27—H27	0.9500
C7—C8	1.464 (6)	C28—C33	1.389 (6)
C7—H7	0.9500	C28—C29	1.410 (6)
C8—C13	1.387 (6)	C28—B1	1.660 (6)
C8—C9	1.390 (6)	C29—C30	1.382 (6)
C9—C10	1.373 (6)	C29—H29	0.9500
C9—H9	0.9500	C30—C31	1.380 (7)
C10—C11	1.384 (6)	C30—H30	0.9500
C10—H10	0.9500	C31—C32	1.369 (7)
C11—C12	1.387 (6)	C31—H31	0.9500
C11—C15	1.443 (6)	C32—C33	1.403 (6)
C12—C13	1.384 (6)	C32—H32	0.9500
C12—H12	0.9500	C33—H33	0.9500
C13—H13	0.9500	C34—C39	1.397 (6)
C14—H14A	0.9800	C34—C35	1.398 (5)
C14—H14B	0.9800	C34—B1	1.635 (6)
C14—H14C	0.9800	C35—C36	1.375 (6)
C16—C17	1.407 (5)	C35—H35	0.9500
C16—C21	1.408 (5)	C36—C37	1.385 (7)
C16—B1	1.643 (6)	C36—H36	0.9500
C17—C18	1.375 (6)	C37—C38	1.379 (6)
C17—H17	0.9500	C37—H37	0.9500
C18—C19	1.387 (6)	C38—C39	1.394 (6)
C18—H18	0.9500	C38—H38	0.9500
C19—C20	1.382 (7)	C39—H39	0.9500
C19—H19	0.9500

C5—N1—C1	120.0 (4)	C20—C21—C16	122.7 (4)
C5—N1—C14	120.0 (4)	C20—C21—H21	118.6
C1—N1—C14	120.0 (4)	C16—C21—H21	118.6
N1—C1—C2	121.0 (4)	C23—C22—C27	115.1 (4)
N1—C1—H1	119.5	C23—C22—B1	122.7 (3)
C2—C1—H1	119.5	C27—C22—B1	121.6 (3)
C1—C2—C3	120.5 (4)	C24—C23—C22	123.3 (4)
C1—C2—H2	119.7	C24—C23—H23	118.4
C3—C2—H2	119.7	C22—C23—H23	118.4
C4—C3—C2	116.8 (4)	C25—C24—C23	119.6 (4)
C4—C3—C6	119.6 (4)	C25—C24—H24	120.2
C2—C3—C6	123.6 (4)	C23—C24—H24	120.2
C5—C4—C3	120.4 (4)	C24—C25—C26	119.6 (4)
C5—C4—H4	119.8	C24—C25—H25	120.2
C3—C4—H4	119.8	C26—C25—H25	120.2
N1—C5—C4	121.3 (4)	C25—C26—C27	119.5 (4)
N1—C5—H5	119.4	C25—C26—H26	120.2
C4—C5—H5	119.4	C27—C26—H26	120.2
C7—C6—C3	126.3 (3)	C26—C27—C22	123.0 (4)
C7—C6—H6	116.8	C26—C27—H27	118.5
C3—C6—H6	116.8	C22—C27—H27	118.5
C6—C7—C8	125.7 (3)	C33—C28—C29	115.4 (4)
C6—C7—H7	117.2	C33—C28—B1	123.1 (4)
C8—C7—H7	117.2	C29—C28—B1	121.2 (4)
C13—C8—C9	118.8 (4)	C30—C29—C28	123.1 (4)
C13—C8—C7	121.5 (4)	C30—C29—H29	118.5
C9—C8—C7	119.6 (4)	C28—C29—H29	118.5
C10—C9—C8	121.2 (4)	C31—C30—C29	119.2 (4)
C10—C9—H9	119.4	C31—C30—H30	120.4
C8—C9—H9	119.4	C29—C30—H30	120.4
C9—C10—C11	119.3 (4)	C32—C31—C30	120.2 (4)
C9—C10—H10	120.3	C32—C31—H31	119.9
C11—C10—H10	120.3	C30—C31—H31	119.9
C10—C11—C12	120.6 (4)	C31—C32—C33	119.8 (4)
C10—C11—C15	121.1 (4)	C31—C32—H32	120.1
C12—C11—C15	118.3 (4)	C33—C32—H32	120.1
C13—C12—C11	119.4 (4)	C28—C33—C32	122.2 (4)
C13—C12—H12	120.3	C28—C33—H33	118.9
C11—C12—H12	120.3	C32—C33—H33	118.9
C12—C13—C8	120.6 (4)	C39—C34—C35	115.1 (4)
C12—C13—H13	119.7	C39—C34—B1	121.5 (3)
C8—C13—H13	119.7	C35—C34—B1	123.0 (4)
N1—C14—H14A	109.5	C36—C35—C34	122.9 (4)
N1—C14—H14B	109.5	C36—C35—H35	118.5
H14A—C14—H14B	109.5	C34—C35—H35	118.5
N1—C14—H14C	109.5	C35—C36—C37	120.7 (4)
H14A—C14—H14C	109.5	C35—C36—H36	119.6
H14B—C14—H14C	109.5	C37—C36—H36	119.6
N2—C15—C11	177.7 (5)	C38—C37—C36	118.3 (4)
C17—C16—C21	114.5 (4)	C38—C37—H37	120.8
C17—C16—B1	122.2 (3)	C36—C37—H37	120.8
C21—C16—B1	122.8 (3)	C37—C38—C39	120.3 (4)
C18—C17—C16	123.4 (4)	C37—C38—H38	119.8
C18—C17—H17	118.3	C39—C38—H38	119.8
C16—C17—H17	118.3	C38—C39—C34	122.6 (4)
C17—C18—C19	120.3 (4)	C38—C39—H39	118.7
C17—C18—H18	119.9	C34—C39—H39	118.7
C19—C18—H18	119.9	C22—B1—C34	102.9 (4)
C20—C19—C18	118.7 (4)	C22—B1—C16	113.8 (2)
C20—C19—H19	120.6	C34—B1—C16	112.2 (4)
C18—C19—H19	120.6	C22—B1—C28	111.5 (4)
C19—C20—C21	120.4 (4)	C34—B1—C28	114.0 (2)
C19—C20—H20	119.8	C16—B1—C28	102.8 (4)
C21—C20—H20	119.8

C5—N1—C1—C2	−1.2 (8)	C33—C28—C29—C30	2.5 (6)
C14—N1—C1—C2	178.4 (5)	B1—C28—C29—C30	177.1 (4)
N1—C1—C2—C3	0.6 (8)	C28—C29—C30—C31	−0.7 (7)
C1—C2—C3—C4	0.7 (7)	C29—C30—C31—C32	−0.9 (7)
C1—C2—C3—C6	179.2 (5)	C30—C31—C32—C33	0.6 (7)
C2—C3—C4—C5	−1.5 (7)	C29—C28—C33—C32	−2.8 (6)
C6—C3—C4—C5	−180.0 (4)	B1—C28—C33—C32	−177.3 (4)
C1—N1—C5—C4	0.4 (7)	C31—C32—C33—C28	1.4 (7)
C14—N1—C5—C4	−179.1 (5)	C39—C34—C35—C36	−1.2 (6)
C3—C4—C5—N1	0.9 (8)	B1—C34—C35—C36	−173.1 (4)
C4—C3—C6—C7	−177.4 (4)	C34—C35—C36—C37	0.5 (7)
C2—C3—C6—C7	4.1 (7)	C35—C36—C37—C38	0.4 (7)
C3—C6—C7—C8	−179.2 (5)	C36—C37—C38—C39	−0.5 (7)
C6—C7—C8—C13	−6.5 (7)	C37—C38—C39—C34	−0.2 (7)
C6—C7—C8—C9	176.0 (4)	C35—C34—C39—C38	1.0 (6)
C13—C8—C9—C10	2.5 (7)	B1—C34—C39—C38	173.1 (4)
C7—C8—C9—C10	−180.0 (4)	C23—C22—B1—C34	83.1 (4)
C8—C9—C10—C11	−2.2 (7)	C27—C22—B1—C34	−87.2 (4)
C9—C10—C11—C12	0.5 (7)	C23—C22—B1—C16	−38.6 (6)
C9—C10—C11—C15	−178.8 (4)	C27—C22—B1—C16	151.1 (3)
C10—C11—C12—C13	0.7 (7)	C23—C22—B1—C28	−154.3 (3)
C15—C11—C12—C13	−179.9 (4)	C27—C22—B1—C28	35.4 (5)
C11—C12—C13—C8	−0.4 (7)	C39—C34—B1—C22	−84.8 (5)
C9—C8—C13—C12	−1.2 (7)	C35—C34—B1—C22	86.6 (4)
C7—C8—C13—C12	−178.7 (4)	C39—C34—B1—C16	38.0 (5)
C21—C16—C17—C18	−0.9 (6)	C35—C34—B1—C16	−150.6 (4)
B1—C16—C17—C18	171.7 (4)	C39—C34—B1—C28	154.3 (3)
C16—C17—C18—C19	−0.5 (6)	C35—C34—B1—C28	−34.3 (6)
C17—C18—C19—C20	1.5 (6)	C17—C16—B1—C22	151.5 (3)
C18—C19—C20—C21	−1.1 (7)	C21—C16—B1—C22	−36.5 (6)
C19—C20—C21—C16	−0.4 (7)	C17—C16—B1—C34	35.1 (5)
C17—C16—C21—C20	1.3 (6)	C21—C16—B1—C34	−152.9 (4)
B1—C16—C21—C20	−171.3 (4)	C17—C16—B1—C28	−87.8 (4)
C27—C22—C23—C24	0.9 (6)	C21—C16—B1—C28	84.2 (4)
B1—C22—C23—C24	−169.9 (4)	C33—C28—B1—C22	−146.2 (4)
C22—C23—C24—C25	−1.1 (6)	C29—C28—B1—C22	39.6 (5)
C23—C24—C25—C26	0.3 (6)	C33—C28—B1—C34	−30.2 (6)
C24—C25—C26—C27	0.5 (6)	C29—C28—B1—C34	155.6 (3)
C25—C26—C27—C22	−0.7 (6)	C33—C28—B1—C16	91.5 (4)
C23—C22—C27—C26	−0.1 (6)	C29—C28—B1—C16	−82.7 (5)
B1—C22—C27—C26	170.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14ⁱ—H14Aⁱ···N2	0.98	2.54	3.463 (7)	157
C35ⁱⁱ—H35ⁱⁱ···N2	0.95	2.65	3.359 (8)	131

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₂⁺·C₂₄H₂₀B⁻
M_r	540.48
Crystal system, space group	Monoclinic, Cc
Temperature (K)	193
a, b, c (Å)	16.930 (3), 10.7694 (18), 17.665 (3)
β (°)	111.543 (5)
V (Å³)	2995.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.19 × 0.11

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.966, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	14471, 2726, 2355
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.121, 1.11
No. of reflections	2726
No. of parameters	381
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18

Computer programs: CrystalClear (Rigaku, 1999), CrystalClear, CrystalStructure (Rigaku, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Please provide details.

Selected geometric parameters (Å, º) top

N1—C5	1.339 (6)	C7—C8	1.464 (6)
N1—C1	1.344 (6)	C11—C15	1.443 (6)
N1—C14	1.479 (6)	C16—B1	1.643 (6)
N2—C15	1.148 (6)	C22—B1	1.628 (6)
C3—C6	1.451 (6)	C28—B1	1.660 (6)
C6—C7	1.328 (5)	C34—B1	1.635 (6)

C5—N1—C1	120.0 (4)	C10—C11—C12	120.6 (4)
C5—N1—C14	120.0 (4)	C10—C11—C15	121.1 (4)
C1—N1—C14	120.0 (4)	C12—C11—C15	118.3 (4)
C4—C3—C2	116.8 (4)	N2—C15—C11	177.7 (5)
C4—C3—C6	119.6 (4)	C22—B1—C34	102.9 (4)
C2—C3—C6	123.6 (4)	C22—B1—C16	113.8 (2)
C7—C6—C3	126.3 (3)	C34—B1—C16	112.2 (4)
C6—C7—C8	125.7 (3)	C22—B1—C28	111.5 (4)
C13—C8—C9	118.8 (4)	C34—B1—C28	114.0 (2)
C13—C8—C7	121.5 (4)	C16—B1—C28	102.8 (4)
C9—C8—C7	119.6 (4)

C4—C3—C6—C7	−177.4 (4)	B1—C22—C23—C24	−169.9 (4)
C2—C3—C6—C7	4.1 (7)	B1—C22—C27—C26	170.9 (4)
C3—C6—C7—C8	−179.2 (5)	B1—C28—C29—C30	177.1 (4)
C6—C7—C8—C13	−6.5 (7)	B1—C28—C33—C32	−177.3 (4)
C6—C7—C8—C9	176.0 (4)	B1—C34—C35—C36	−173.1 (4)
B1—C16—C17—C18	171.7 (4)	B1—C34—C39—C38	173.1 (4)
B1—C16—C21—C20	−171.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14ⁱ—H14Aⁱ···N2	0.98	2.54	3.463 (7)	157
C35ⁱⁱ—H35ⁱⁱ···N2	0.95	2.65	3.359 (8)	131

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

C—H···π interactions in I (Å, °) top

C	H	Plane^a	d_HP^b	τ^c	Molecule^d
C4	H4	P4	2.88	13.3	FM
C12	H12	P5	2.46	20.9	3
C9	H9	P5	2.91	12.5	5
C1	H1	P4	2.53	16.6	7
C37	H37	P4	2.13	23.4	1
C37	H37	P6	2.27	30.9	1
C5	H5	P7	2.60	23.8	2
C18	H18	P6	2.51	30.5	3
C29	H29	P2	2.66	17.0	4
C26	H26	P7	2.27	20.7	4
C31	H31	P5	2.09	24.0	7
C31	H31	P7	2.27	29.5	7
C39	H39	P1	2.79	15.5	8

(a) The planes P1 (C1–C5/N1), P2 (C8–C13), P3 (C3/C6–C8), P4 (C16–C21), P5 (C22–C27), P6 (C28–C33) and P7 (C34–C39) in the fundamental molecule (FM). The C—H group is in a particular surrounding molecule (SM), specified by the code in the last column. (b) d_HP is the distance of the H atom from the plane. (c) τ is the angle formed by the vectors of C—H and the perpendicular line passing through the H atom to the plane. (d) The SMs which interact most strongly with the FM, numbered as in Table 4. The first four interactions are indicated in Fig. 2 by bold dotted lines, labelled L0–L3, respectively.

The packing energy (PE) portioning in (I) (kcal mol⁻¹) top

Molecule^a	PE^b	c–c^c	a–a^d	c–a^e	d_B···B^f	symmetry code
1	-12.1	-5.9	-2.6	-3.6	10.03	x − 1/2,y + 1/2,z
2	-12.1	-5.9	-2.6	-3.6	10.03	x + 1/2,y − 1/2,z
3	-10.2	-0.4	-4.4	-5.4	8.84	x,-y + 1,z + 1/2
4	-10.2	-0.4	-4.4	-5.4	8.84	x,-y + 1,z − 1/2
5	-10.0	-0.9	-0.7	-8.4	11.00	x + 1/2,-y + 1/2,z + 1/2
6	-10.0	-0.9	-0.7	-8.4	11.00	x − 1/2,-y + 1/2,z − 1/2
7	-7.2	-0.3	-2.6	-4.3	10.03	x + 1/2,y + 1/2, z
8	-7.2	-0.3	-2.6	-4.3	10.03	x − 1/2,y − 1/2,z
9	-4.1	-0.4		-3.7		x,-y,z + 1/2
10	-4.1	-0.4		-3.7		x,-y,z − 1/2
11	-3.5		-1.6	-1.9		x − 1/2,-y + 3/2,z − 1/2
12	-3.5		-1.6	-1.9		x + 1/2,-y + 2/3,z + 1/2
13	-2.6		-0.7	-1.9		x,y − 1,z
14	-2.6		-0.7	-1.9		x,y + 1,z
total	-123.7	-16.7	-25.9	-81.1

(a) Taking one molecule in the crystal as the fundamental molecule (FM), then all surrounding molecules (SMs) interact with the FM, each of which may correspond to a certain symmetry operator when the asymmetric unit consists of one or less than one molecule. (b) The packing energies, calculated using the program OPEC (Gavezzotti, 1983) with the improved set of parameters (Gavezzotti & Filippini, 1994). Value omitted if it is less than 1% of the total PE in the column. (c) The PE between the cation in the FM and that in the SM indicated by the symmetry code in the last column. (d) The PE between the anion in the FM and that in the SM indicated by the symmetry code in the last column. (e) The PE between the cation in the FM and the anion in the SM indicated by the symmetry code in the last column. (f) The distance between the central B atoms. Value omitted if it is greater than 11 A°.

Packing energies^a of some stilbazolium tetraphenylborates (kcal mol⁻¹) top

CSD refcode^b	total PE	Space group	(a–a)%	(c–a)%	µ^c	substituent
QOBDEQ	-235.73	P2₁/c	22.63	53.16	15.61	4-N(OCH₃)₂
WOCRAH	-257.22	P2₁/c	23.29	58.42	14.63	4-OCH₃
BOQKEX	-264.73	Cc	16.35	68.51	18.34	3,4-OCH₃
I	-258.74	Cc	20.97	65.51	18.85	4-CN

(a) Packing energies calculated using the program OPEC (Gavezzotti, 1983). (a–a)% is the percentage for the anion–anion interaction in the total PE. (c–a)% is the percentage for the cation–anion interaction in the total PE. (b) References: for QOBDEQ, Li et al. (2000a); for WOCRAH, Li et al. (2000b); for BOQKEX, Zhang et al. (1999); for (I), this study. (c) The dipole moment of the cation (Debye), calculated by the program MOPAC (Dewar et al., 1985) using the dipole moment summation method (Kurtz et al., 1990).

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4-[2-(4-Cyano­phenyl)ethenyl]-N-methyl­pyridinium tetra­phenyl­borate

Supporting information

4-[2-(4-Cyanophenyl)ethenyl]-N-methylpyridinium tetraphenylborate