4-[2-(3-Methoxy­phen­yl)ethen­yl]-N-methyl­pyridinium tetra­phenyl­borate

In the title compound, C₁₅H₁₆NO⁺·C₂₄H₂₀B^-, the pyridinium ring of the cation makes a dihedral angle of 4.3 (2)° with the benzene ring. Each is rotated in the same direction with respect to the central C-CH=CH-C linkage, by 10.0 (2) and 7.8 (2)°, respectively. The anions have a slightly distorted tetra­hedral geometry. The most inter­esting feature of the structure is that the anions form a honeycomb-like hexa­gonal structure down the b axis through C-H...[pi] inter­actions. The hexa­gon is constructed from six BPh₄^- anions. The cations inter­act in a head-to-tail fashion along [010], forming chains, and pack anti­parallel inside the above honeycomb-like structure through C-H...[pi] inter­actions.

S1. Comment

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. The organic `salt methodology' principle (Marder et al., 1989, 1994) claims that Coulombic interactions in organic salts could override dipole–dipole interactions which are favoured for antiparallel centrosymmetric packing [can this sentence be omitted since there is a similar statement below (move the 1994 reference to the later statement?)?]. During our systematic research for organic nonlinear optical materials, we isolated the title compound, (I), and describe its crystal structure here.

The title molecule (I) consists of a 3-methoxy-N-methyl-4-stilbazolium 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 4.3 (2)° with the phenyl ring. They are rotated in the same direction with respect to the central C—CH═CH—C linkage, by 10.0 (2) and 7.8 (2)°, respectively. The anion takes a slightly distorted tetrahedral geometry. The B—C bond lengths are in the range 1.640 (3)–1.652 (3) Å, and the bond angles of C—B—C are in the range 104.8 (2)–113.7 (2)°.

The most interesting feature in the crystal structure is that the anions form a honeycomb-like hexagonal structure along the b axis. Table 2 lists the most important C—H···π interactions (type I; Umezawa et al., 1998). We can see the interactions between the fundamental molecule (FM) and its surrounding molecules (SMs). In particular, the anion–anion and the cation–anion interactions are C—H···π type (type I; Umezawa et al., 1998). On the other hand, the cations interact in a head-to-tail fashion [through interactions C14—H14C···O1(x, y - 1, z) and C15—H15A···N1 (x, y + 1, z), which could be considered as very weak hydrogen bonding], forming chains along [010], and the chains are packed in an antiparallel fashion inside the above honeycomb-like structure (Fig. 2) through C—H···π interactions. In the crystal structure, a hexagon is constructed by the six BPh₄^- anions whose central B atoms are labeled B1–B6 in Fig. 2. The portioning scheme in the program OPEC (Gavezzotti, 1983) with largely improved parameters (Gavezzotti & Filippini, 1994) was used to analyse the packing mode. Table 3 lists the corresponding data. According to Table 3, these factors probably contribute to the macroscopic morphology of the crystal structure. Therefore, the crystal might have potential applications in a field other than SHG.

The organic salt methodology principle (Marder et al., 1989) suggests 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. However, compound (I) is crystallized in the centrosymmetric space group P2₁/c and shows no SHG effect. To analyse the reason for this, a search was carried out of the Cambridge Structural Datebase (CSD; Verson 5.26; Allen, 2002) for stilbazolium tetraphenylborates. The total packing energies for cation–cation, anion–anion and anion–cation interactions were calculated using OPEC. The results for the related structures found in the search are listed in Table 4. As shown by Table 4, the data are very limited and the calculated absolute total PE value is not very accurate, but we could tentatively state that the centrosymmetric packing of the title crystal is likely to be due to the much stronger anion–anion interaction.

Related literature

For related literature, see: Allen (2002); Chemla & Zyss (1987); Gavezzotti (1983); Gavezzotti & Filippini (1994); Marder et al. (1989, 1994); Okada et al. (1990); Umezawa et al. (1998).

S2. Experimental

1,4-Dimethylpyridinium iodide (7.05 g, 30 mmol), prepared from CH₃I and 1-methylpyridine [quantities?], 3-methoxybenzaldehyde (6.67 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, recrystallized twice from ethanol–water (4:1), and finally crystallized from ethanol/acetone (2:1). Brown–yellow crystals of (I) (m.p. 462–463 K) were grown by slow evaporation at ambient temperature for two weeks. Elemental analysis calculated for C₁₅H₁₆NO⁺·BPh₄^-: C 85.87, H 6.61, N 2.57%; found: C 85.97, H 6.84, N 2.47%. IR (KBr pellets, cm^-1): 3053 (Ar—H), 3001 (C—H), 1620 (–CH═CH–), 1579 (–CH═ N–), 1515 (Ph), 1467 (Ph), 1427 (Ph), 1250 (–CH₃), 1186 (–C—O–), 1032 (–CH═C—H), 953(–CH═C—H), 842 (Ar—H), 735 (Ar—H), 708 (Ar—H), 681 (Ar—H). ¹H NMR (DMSO, 399.97 MHz, ambient temperature): 8.85 (d, 2H, pyridyl ring), 8.20 (d, 2H, pyridyl ring), 7.94 (s, 1H, Ph), 7.53 (d, 1H, Ph), 7.40 (m, 1H, Ph), 7.32 (s, 2H, –CH═ CH–), 7.17 (s, 8H, Ph), 7.04 (d, 1H, Ph), 6.94–6.90 (m, 8H, Ph), 6.80–6.77 (m, 4H, Ph), 4.25 (s, 3H, –CH₃), 3.83 (s, 3H, –CH₃).

S3. Refinement

H atoms were positioned geometrically and treated as riding [C—H = 0.95–0.98 Å, and U_iso(H) = 1.2U_eq(C aromatic) or U_eq(H) = 1.5U_eq(C methyl)].

Computing details

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

Figures

	Fig. 1. 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. The packing for (I), viewed down the b axis. Key: L0: C1—H1···P7; L1: C13—H13···P7(1 - x, 1 - y, 1 - z); L2: C15—H15B···P5(x + 1, y - 1, z); L3: C14—H14A···P4(-x + 1, y + 1/2, -z + 3/2); L4: C5—H5···P5(x + 1,y, z). Table 3 lists the detailed geometric data.

4-[2-(3-Methoxyphenyl)ethenyl]-N-methylpyridinium tetraphenylborate

Crystal data

C15H16NO^+·C24H20B^−	F(000) = 1160
Mr = 545.50	Dx = 1.216 Mg m^−3
Monoclinic, P21/c	Melting point = 462–463 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 12.8417 (18) Å	Cell parameters from 8586 reflections
b = 10.8158 (16) Å	θ = 3.0–25.3°
c = 21.790 (4) Å	µ = 0.07 mm^−1
β = 100.106 (5)°	T = 193 K
V = 2979.5 (8) Å^3	Block, brown–yellow
Z = 4	0.35 × 0.30 × 0.11 mm

Data collection

Rigaku Mercury diffractometer	5440 independent reflections
Radiation source: fine-focus sealed tube	4141 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 7.31 pixels mm^-1	θmax = 25.4°, θmin = 3.2°
ω scans	h = −14→15
Absorption correction: multi-scan (Rigaku, 1999; Jacobson, 1998)	k = −11→13
Tmin = 0.98, Tmax = 0.99	l = −26→26
28897 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.7775P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
5440 reflections	Δρmax = 0.15 e Å^−3
383 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (6)

Special details

Experimental. Elemental analysis: Perkin-Elmer 240 C elemental analyser. IR: FT–IR spectrometer with KBr pellets. 1H NMR: Bruker AV-400 NMR Spectrometer, DMSO, 399.97MHZ, ambient temperature.

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
O1	0.05812 (16)	1.08994 (17)	0.60432 (9)	0.0618 (6)
N1	0.27962 (15)	0.26132 (18)	0.65459 (9)	0.0401 (5)
C1	0.31075 (19)	0.3168 (2)	0.60569 (12)	0.0424 (6)
H1	0.3560	0.2739	0.5829	0.051*
C2	0.27846 (19)	0.4337 (2)	0.58832 (12)	0.0429 (6)
H2	0.3007	0.4704	0.5532	0.051*
C3	0.21362 (18)	0.4999 (2)	0.62111 (11)	0.0394 (6)
C4	0.1797 (2)	0.4378 (2)	0.66999 (12)	0.0447 (6)
H4	0.1323	0.4775	0.6926	0.054*
C5	0.2135 (2)	0.3204 (2)	0.68599 (12)	0.0453 (6)
H5	0.1899	0.2801	0.7198	0.054*
C6	0.18382 (19)	0.6291 (2)	0.60871 (12)	0.0420 (6)
H6	0.1325	0.6640	0.6301	0.050*
C7	0.22426 (19)	0.7003 (2)	0.56937 (12)	0.0431 (6)
H7	0.2736	0.6620	0.5477	0.052*
C8	0.20200 (18)	0.8311 (2)	0.55529 (11)	0.0388 (6)
C9	0.1391 (2)	0.9033 (2)	0.58685 (11)	0.0434 (6)
H9	0.1108	0.8692	0.6206	0.052*
C10	0.1176 (2)	1.0249 (2)	0.56921 (12)	0.0425 (6)
C11	0.1585 (2)	1.0756 (2)	0.52016 (11)	0.0432 (6)
H11	0.1430	1.1587	0.5077	0.052*
C12	0.2219 (2)	1.0039 (2)	0.48977 (12)	0.0475 (7)
H12	0.2505	1.0384	0.4562	0.057*
C13	0.2445 (2)	0.8836 (2)	0.50694 (12)	0.0449 (6)
H13	0.2894	0.8360	0.4858	0.054*
C14	0.3220 (2)	0.1382 (3)	0.67540 (14)	0.0585 (8)
H14A	0.3913	0.1478	0.7021	0.088*
H14B	0.3294	0.0879	0.6390	0.088*
H14C	0.2733	0.0972	0.6989	0.088*
C15	0.0133 (2)	1.2038 (2)	0.57972 (14)	0.0533 (7)
H15A	0.0701	1.2624	0.5759	0.080*
H15B	−0.0312	1.2381	0.6078	0.080*
H15C	−0.0298	1.1895	0.5386	0.080*
C16	0.60673 (17)	0.3849 (2)	0.71217 (11)	0.0330 (5)
C17	0.51700 (18)	0.4612 (2)	0.70113 (12)	0.0392 (6)
H17	0.5021	0.5054	0.6629	0.047*
C18	0.44897 (19)	0.4748 (2)	0.74369 (13)	0.0458 (6)
H18	0.3905	0.5297	0.7349	0.055*
C19	0.4662 (2)	0.4087 (2)	0.79871 (13)	0.0475 (7)
H19	0.4189	0.4159	0.8275	0.057*
C20	0.5528 (2)	0.3323 (2)	0.81124 (12)	0.0484 (7)
H20	0.5656	0.2865	0.8490	0.058*
C21	0.6215 (2)	0.3218 (2)	0.76915 (11)	0.0404 (6)
H21	0.6814	0.2694	0.7794	0.048*
C22	0.78510 (17)	0.2787 (2)	0.68835 (11)	0.0339 (5)
C23	0.86382 (18)	0.3287 (2)	0.73445 (11)	0.0402 (6)
H23	0.8549	0.4106	0.7483	0.048*
C24	0.95351 (19)	0.2646 (2)	0.76065 (12)	0.0457 (6)
H24	1.0048	0.3034	0.7913	0.055*
C25	0.9693 (2)	0.1457 (3)	0.74284 (12)	0.0467 (7)
H25	1.0305	0.1010	0.7613	0.056*
C26	0.8942 (2)	0.0919 (2)	0.69751 (12)	0.0465 (7)
H26	0.9042	0.0098	0.6841	0.056*
C27	0.80436 (19)	0.1573 (2)	0.67142 (11)	0.0393 (6)
H27	0.7536	0.1178	0.6407	0.047*
C28	0.73423 (18)	0.4957 (2)	0.63876 (11)	0.0356 (5)
C29	0.8111 (2)	0.4889 (2)	0.60010 (12)	0.0471 (7)
H29	0.8271	0.4102	0.5847	0.057*
C30	0.8646 (2)	0.5914 (3)	0.58335 (13)	0.0553 (8)
H30	0.9163	0.5821	0.5574	0.066*
C31	0.8424 (2)	0.7068 (3)	0.60452 (13)	0.0541 (7)
H31	0.8794	0.7775	0.5938	0.065*
C32	0.7665 (2)	0.7186 (2)	0.64122 (13)	0.0494 (7)
H32	0.7499	0.7980	0.6555	0.059*
C33	0.71368 (19)	0.6147 (2)	0.65773 (11)	0.0399 (6)
H33	0.6613	0.6255	0.6831	0.048*
C34	0.60617 (17)	0.3031 (2)	0.59896 (11)	0.0333 (5)
C35	0.57591 (19)	0.3631 (2)	0.54181 (11)	0.0382 (6)
H35	0.6023	0.4439	0.5368	0.046*
C36	0.5087 (2)	0.3093 (2)	0.49193 (12)	0.0455 (6)
H36	0.4890	0.3542	0.4542	0.055*
C37	0.47069 (19)	0.1917 (2)	0.49700 (12)	0.0457 (7)
H37	0.4268	0.1537	0.4625	0.055*
C38	0.49710 (19)	0.1296 (2)	0.55270 (12)	0.0421 (6)
H38	0.4707	0.0485	0.5570	0.051*
C39	0.56214 (18)	0.1851 (2)	0.60260 (11)	0.0363 (6)
H39	0.5776	0.1414	0.6409	0.044*
B1	0.6824 (2)	0.3658 (2)	0.65958 (12)	0.0328 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0860 (14)	0.0495 (12)	0.0582 (12)	0.0209 (11)	0.0360 (11)	0.0076 (10)
N1	0.0426 (11)	0.0403 (12)	0.0357 (12)	0.0042 (10)	0.0023 (10)	0.0018 (9)
C1	0.0432 (14)	0.0466 (15)	0.0381 (15)	0.0086 (12)	0.0088 (12)	0.0000 (12)
C2	0.0481 (14)	0.0453 (15)	0.0365 (14)	0.0022 (12)	0.0110 (12)	0.0038 (12)
C3	0.0403 (13)	0.0375 (14)	0.0398 (14)	−0.0012 (11)	0.0055 (11)	−0.0032 (11)
C4	0.0488 (15)	0.0465 (16)	0.0416 (15)	0.0027 (12)	0.0156 (12)	−0.0028 (12)
C5	0.0528 (15)	0.0483 (16)	0.0358 (15)	0.0005 (13)	0.0103 (12)	0.0038 (12)
C6	0.0444 (14)	0.0419 (15)	0.0414 (15)	0.0037 (12)	0.0121 (12)	−0.0029 (12)
C7	0.0429 (14)	0.0461 (15)	0.0402 (15)	0.0016 (12)	0.0068 (12)	−0.0020 (12)
C8	0.0399 (13)	0.0384 (14)	0.0367 (14)	0.0002 (11)	0.0029 (11)	−0.0020 (11)
C9	0.0533 (15)	0.0429 (15)	0.0369 (14)	0.0006 (12)	0.0156 (12)	0.0037 (12)
C10	0.0509 (15)	0.0411 (14)	0.0362 (14)	0.0036 (12)	0.0095 (12)	−0.0002 (12)
C11	0.0544 (15)	0.0362 (14)	0.0382 (14)	−0.0004 (12)	0.0056 (12)	0.0024 (11)
C12	0.0571 (16)	0.0470 (16)	0.0415 (15)	−0.0039 (13)	0.0174 (13)	0.0017 (12)
C13	0.0485 (14)	0.0447 (15)	0.0436 (15)	0.0026 (12)	0.0141 (12)	0.0000 (12)
C14	0.0645 (18)	0.0539 (18)	0.0545 (18)	0.0173 (15)	0.0036 (15)	0.0141 (14)
C15	0.0530 (16)	0.0454 (16)	0.0626 (19)	0.0088 (13)	0.0135 (14)	0.0001 (14)
C16	0.0373 (12)	0.0278 (12)	0.0332 (13)	−0.0047 (10)	0.0046 (10)	−0.0029 (10)
C17	0.0403 (13)	0.0367 (13)	0.0394 (14)	−0.0014 (11)	0.0039 (11)	−0.0042 (11)
C18	0.0390 (13)	0.0411 (14)	0.0571 (18)	−0.0019 (11)	0.0082 (13)	−0.0135 (13)
C19	0.0496 (15)	0.0454 (15)	0.0525 (17)	−0.0115 (13)	0.0227 (13)	−0.0129 (13)
C20	0.0611 (17)	0.0466 (15)	0.0403 (16)	−0.0060 (14)	0.0171 (13)	0.0020 (12)
C21	0.0467 (14)	0.0360 (13)	0.0398 (15)	0.0011 (11)	0.0115 (12)	0.0021 (11)
C22	0.0364 (12)	0.0355 (13)	0.0310 (13)	−0.0019 (10)	0.0092 (10)	0.0026 (10)
C23	0.0415 (13)	0.0394 (14)	0.0399 (15)	0.0015 (11)	0.0077 (11)	0.0026 (12)
C24	0.0397 (14)	0.0535 (17)	0.0431 (16)	−0.0005 (12)	0.0052 (12)	0.0068 (13)
C25	0.0407 (14)	0.0557 (17)	0.0453 (16)	0.0126 (13)	0.0121 (13)	0.0149 (13)
C26	0.0541 (16)	0.0413 (15)	0.0466 (16)	0.0134 (13)	0.0155 (14)	0.0054 (13)
C27	0.0432 (13)	0.0387 (14)	0.0375 (14)	0.0024 (11)	0.0111 (11)	−0.0011 (11)
C28	0.0373 (12)	0.0358 (13)	0.0320 (13)	0.0008 (11)	0.0014 (10)	0.0018 (10)
C29	0.0513 (15)	0.0474 (16)	0.0445 (16)	0.0004 (13)	0.0137 (13)	0.0057 (12)
C30	0.0513 (16)	0.071 (2)	0.0447 (17)	−0.0091 (15)	0.0101 (13)	0.0164 (15)
C31	0.0607 (17)	0.0522 (18)	0.0442 (17)	−0.0205 (15)	−0.0053 (14)	0.0144 (14)
C32	0.0614 (17)	0.0391 (15)	0.0436 (16)	−0.0086 (13)	−0.0021 (14)	0.0062 (12)
C33	0.0452 (14)	0.0354 (14)	0.0374 (14)	−0.0024 (11)	0.0022 (11)	0.0034 (11)
C34	0.0356 (12)	0.0311 (12)	0.0347 (13)	0.0044 (10)	0.0106 (10)	−0.0020 (10)
C35	0.0460 (14)	0.0349 (13)	0.0337 (14)	0.0069 (11)	0.0072 (11)	−0.0009 (11)
C36	0.0497 (15)	0.0508 (17)	0.0346 (15)	0.0110 (13)	0.0038 (12)	−0.0027 (12)
C37	0.0464 (15)	0.0487 (17)	0.0404 (16)	0.0032 (12)	0.0031 (12)	−0.0145 (13)
C38	0.0435 (14)	0.0354 (14)	0.0491 (16)	−0.0020 (11)	0.0125 (12)	−0.0101 (12)
C39	0.0398 (13)	0.0347 (13)	0.0352 (14)	0.0023 (11)	0.0089 (11)	−0.0048 (11)
B1	0.0381 (14)	0.0282 (14)	0.0326 (15)	0.0012 (11)	0.0075 (12)	0.0013 (11)

Geometric parameters (Å, º)

O1—C10	1.367 (3)	C19—C20	1.374 (4)
O1—C15	1.424 (3)	C19—H19	0.9500
N1—C5	1.342 (3)	C20—C21	1.384 (3)
N1—C1	1.344 (3)	C20—H20	0.9500
N1—C14	1.480 (3)	C21—H21	0.9500
C1—C2	1.363 (3)	C22—C27	1.398 (3)
C1—H1	0.9500	C22—C23	1.402 (3)
C2—C3	1.387 (3)	C22—B1	1.652 (3)
C2—H2	0.9500	C23—C24	1.379 (3)
C3—C4	1.393 (3)	C23—H23	0.9500
C3—C6	1.461 (3)	C24—C25	1.369 (4)
C4—C5	1.367 (4)	C24—H24	0.9500
C4—H4	0.9500	C25—C26	1.381 (4)
C5—H5	0.9500	C25—H25	0.9500
C6—C7	1.325 (3)	C26—C27	1.387 (3)
C6—H6	0.9500	C26—H26	0.9500
C7—C8	1.465 (3)	C27—H27	0.9500
C7—H7	0.9500	C28—C33	1.390 (3)
C8—C9	1.390 (3)	C28—C29	1.408 (3)
C8—C13	1.390 (3)	C28—B1	1.652 (3)
C9—C10	1.385 (3)	C29—C30	1.386 (4)
C9—H9	0.9500	C29—H29	0.9500
C10—C11	1.384 (3)	C30—C31	1.378 (4)
C11—C12	1.375 (3)	C30—H30	0.9500
C11—H11	0.9500	C31—C32	1.371 (4)
C12—C13	1.372 (3)	C31—H31	0.9500
C12—H12	0.9500	C32—C33	1.392 (3)
C13—H13	0.9500	C32—H32	0.9500
C14—H14A	0.9800	C33—H33	0.9500
C14—H14B	0.9800	C34—C35	1.397 (3)
C14—H14C	0.9800	C34—C39	1.404 (3)
C15—H15A	0.9800	C34—B1	1.646 (4)
C15—H15B	0.9800	C35—C36	1.391 (3)
C15—H15C	0.9800	C35—H35	0.9500
C16—C21	1.400 (3)	C36—C37	1.375 (4)
C16—C17	1.403 (3)	C36—H36	0.9500
C16—B1	1.640 (3)	C37—C38	1.376 (4)
C17—C18	1.389 (3)	C37—H37	0.9500
C17—H17	0.9500	C38—C39	1.386 (3)
C18—C19	1.380 (4)	C38—H38	0.9500
C18—H18	0.9500	C39—H39	0.9500
C10—O1—C15	117.6 (2)	C19—C20—C21	120.4 (2)
C5—N1—C1	119.6 (2)	C19—C20—H20	119.8
C5—N1—C14	120.3 (2)	C21—C20—H20	119.8
C1—N1—C14	120.0 (2)	C20—C21—C16	123.0 (2)
N1—C1—C2	121.1 (2)	C20—C21—H21	118.5
N1—C1—H1	119.5	C16—C21—H21	118.5
C2—C1—H1	119.5	C27—C22—C23	114.3 (2)
C1—C2—C3	121.1 (2)	C27—C22—B1	127.0 (2)
C1—C2—H2	119.5	C23—C22—B1	118.6 (2)
C3—C2—H2	119.5	C24—C23—C22	123.2 (2)
C2—C3—C4	116.2 (2)	C24—C23—H23	118.4
C2—C3—C6	124.0 (2)	C22—C23—H23	118.4
C4—C3—C6	119.7 (2)	C25—C24—C23	120.6 (3)
C5—C4—C3	121.0 (2)	C25—C24—H24	119.7
C5—C4—H4	119.5	C23—C24—H24	119.7
C3—C4—H4	119.5	C24—C25—C26	118.6 (2)
N1—C5—C4	120.9 (2)	C24—C25—H25	120.7
N1—C5—H5	119.6	C26—C25—H25	120.7
C4—C5—H5	119.6	C25—C26—C27	120.3 (2)
C7—C6—C3	123.8 (2)	C25—C26—H26	119.8
C7—C6—H6	118.1	C27—C26—H26	119.8
C3—C6—H6	118.1	C26—C27—C22	122.9 (2)
C6—C7—C8	127.8 (2)	C26—C27—H27	118.5
C6—C7—H7	116.1	C22—C27—H27	118.5
C8—C7—H7	116.1	C33—C28—C29	114.6 (2)
C9—C8—C13	119.1 (2)	C33—C28—B1	126.8 (2)
C9—C8—C7	123.2 (2)	C29—C28—B1	118.6 (2)
C13—C8—C7	117.7 (2)	C30—C29—C28	123.2 (3)
C10—C9—C8	120.1 (2)	C30—C29—H29	118.4
C10—C9—H9	120.0	C28—C29—H29	118.4
C8—C9—H9	120.0	C31—C30—C29	119.7 (3)
O1—C10—C11	123.6 (2)	C31—C30—H30	120.1
O1—C10—C9	115.9 (2)	C29—C30—H30	120.1
C11—C10—C9	120.4 (2)	C32—C31—C30	119.2 (2)
C12—C11—C10	119.0 (2)	C32—C31—H31	120.4
C12—C11—H11	120.5	C30—C31—H31	120.4
C10—C11—H11	120.5	C31—C32—C33	120.3 (3)
C13—C12—C11	121.3 (2)	C31—C32—H32	119.8
C13—C12—H12	119.4	C33—C32—H32	119.8
C11—C12—H12	119.4	C28—C33—C32	122.9 (2)
C12—C13—C8	120.1 (2)	C28—C33—H33	118.5
C12—C13—H13	120.0	C32—C33—H33	118.5
C8—C13—H13	120.0	C35—C34—C39	114.9 (2)
N1—C14—H14A	109.5	C35—C34—B1	123.9 (2)
N1—C14—H14B	109.5	C39—C34—B1	121.2 (2)
H14A—C14—H14B	109.5	C36—C35—C34	122.7 (2)
N1—C14—H14C	109.5	C36—C35—H35	118.7
H14A—C14—H14C	109.5	C34—C35—H35	118.7
H14B—C14—H14C	109.5	C37—C36—C35	120.3 (2)
O1—C15—H15A	109.5	C37—C36—H36	119.8
O1—C15—H15B	109.5	C35—C36—H36	119.8
H15A—C15—H15B	109.5	C36—C37—C38	119.1 (2)
O1—C15—H15C	109.5	C36—C37—H37	120.4
H15A—C15—H15C	109.5	C38—C37—H37	120.4
H15B—C15—H15C	109.5	C37—C38—C39	120.1 (2)
C21—C16—C17	114.7 (2)	C37—C38—H38	120.0
C21—C16—B1	123.6 (2)	C39—C38—H38	120.0
C17—C16—B1	121.6 (2)	C38—C39—C34	122.9 (2)
C18—C17—C16	122.8 (2)	C38—C39—H39	118.6
C18—C17—H17	118.6	C34—C39—H39	118.6
C16—C17—H17	118.6	C16—B1—C34	105.71 (18)
C19—C18—C17	120.1 (2)	C16—B1—C28	113.67 (18)
C19—C18—H18	119.9	C34—B1—C28	109.98 (19)
C17—C18—H18	119.9	C16—B1—C22	109.75 (18)
C20—C19—C18	119.0 (2)	C34—B1—C22	113.10 (18)
C20—C19—H19	120.5	C28—B1—C22	104.83 (18)
C18—C19—H19	120.5
C5—N1—C1—C2	1.7 (4)	B1—C22—C27—C26	178.8 (2)
C14—N1—C1—C2	−175.5 (2)	C33—C28—C29—C30	1.7 (4)
N1—C1—C2—C3	1.0 (4)	B1—C28—C29—C30	−175.6 (2)
C1—C2—C3—C4	−3.3 (4)	C28—C29—C30—C31	−0.5 (4)
C1—C2—C3—C6	174.2 (2)	C29—C30—C31—C32	−0.9 (4)
C2—C3—C4—C5	3.2 (4)	C30—C31—C32—C33	1.0 (4)
C6—C3—C4—C5	−174.5 (2)	C29—C28—C33—C32	−1.5 (4)
C1—N1—C5—C4	−1.9 (4)	B1—C28—C33—C32	175.4 (2)
C14—N1—C5—C4	175.3 (2)	C31—C32—C33—C28	0.2 (4)
C3—C4—C5—N1	−0.7 (4)	C39—C34—C35—C36	−1.0 (3)
C2—C3—C6—C7	−7.3 (4)	B1—C34—C35—C36	−178.0 (2)
C4—C3—C6—C7	170.1 (2)	C34—C35—C36—C37	−1.3 (4)
C3—C6—C7—C8	−178.0 (2)	C35—C36—C37—C38	2.2 (3)
C6—C7—C8—C9	5.8 (4)	C36—C37—C38—C39	−0.7 (3)
C6—C7—C8—C13	−172.7 (3)	C37—C38—C39—C34	−1.8 (3)
C13—C8—C9—C10	1.4 (4)	C35—C34—C39—C38	2.6 (3)
C7—C8—C9—C10	−177.1 (2)	B1—C34—C39—C38	179.6 (2)
C15—O1—C10—C11	16.9 (4)	C21—C16—B1—C34	114.3 (2)
C15—O1—C10—C9	−165.5 (2)	C17—C16—B1—C34	−61.5 (3)
C8—C9—C10—O1	−177.8 (2)	C21—C16—B1—C28	−125.0 (2)
C8—C9—C10—C11	−0.1 (4)	C17—C16—B1—C28	59.3 (3)
O1—C10—C11—C12	176.7 (2)	C21—C16—B1—C22	−8.0 (3)
C9—C10—C11—C12	−0.8 (4)	C17—C16—B1—C22	176.3 (2)
C10—C11—C12—C13	0.4 (4)	C35—C34—B1—C16	112.6 (2)
C11—C12—C13—C8	1.0 (4)	C39—C34—B1—C16	−64.1 (2)
C9—C8—C13—C12	−1.8 (4)	C35—C34—B1—C28	−10.5 (3)
C7—C8—C13—C12	176.8 (2)	C39—C34—B1—C28	172.77 (19)
C21—C16—C17—C18	1.0 (3)	C35—C34—B1—C22	−127.3 (2)
B1—C16—C17—C18	177.1 (2)	C39—C34—B1—C22	56.0 (3)
C16—C17—C18—C19	−2.2 (4)	C33—C28—B1—C16	−5.0 (3)
C17—C18—C19—C20	1.7 (4)	C29—C28—B1—C16	171.9 (2)
C18—C19—C20—C21	−0.1 (4)	C33—C28—B1—C34	113.3 (3)
C19—C20—C21—C16	−1.1 (4)	C29—C28—B1—C34	−69.8 (3)
C17—C16—C21—C20	0.6 (3)	C33—C28—B1—C22	−124.8 (2)
B1—C16—C21—C20	−175.4 (2)	C29—C28—B1—C22	52.0 (3)
C27—C22—C23—C24	0.7 (3)	C27—C22—B1—C16	109.7 (2)
B1—C22—C23—C24	−178.8 (2)	C23—C22—B1—C16	−70.9 (2)
C22—C23—C24—C25	−0.9 (4)	C27—C22—B1—C34	−8.1 (3)
C23—C24—C25—C26	0.9 (4)	C23—C22—B1—C34	171.31 (19)
C24—C25—C26—C27	−0.8 (4)	C27—C22—B1—C28	−127.9 (2)
C25—C26—C27—C22	0.7 (4)	C23—C22—B1—C28	51.5 (3)
C23—C22—C27—C26	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···O1^i	0.98	3.14	3.509 (3)	104
C15—H15A···N1^ii	0.98	2.93	3.576 (3)	125

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