1,6-Interactions between di­methyl­amino and aldehyde groups in two bi­phenyl derivatives

The title compounds, 2-(di­methyl­amino)­bi­phenyl-2′-carbox­aldehyde, C₁₅H₁₅NO, and 2-(di­methyl­amino)­bi­phenyl-2′,6′-dicarbox­aldehyde, C₁₆H₁₅­NO₂, show similar 1,6-interactions [N...C=O 2.929 (3) to 3.029 (3) Å] between the di­methyl­amino and aldehyde groups located in the ortho positions of the two rings, which lie at 58.1 (1)–62.4 (1)° to each other.

S1. Comment

Interactions between amino groups and carbonyl groups in natural products such as (1) and (2) have been interpreted as representing different stages in the progress of the corresponding chemical reaction (Bürgi et al., 1973a). Decreasing N···C distances are accompanied by increasing C═ O bond lengths. 1,5-N···C interactions between dimethylamino groups and various carbonyl containing functional groups have been observed in peri-naphthalene systems (Schweizer et al., 1978; Clayden et al., 1999; Hodgson et al., 1999), though the shortest N···C distance observed is only 2.489 (5) Å, for interaction with an aldehyde group in (3). Nevertheless, shorter 1,5-interactions are observed when the electrophilic group is an electron-deficient alkene as in (4), N···C 2.413 (2) Å, and almost complete bond formation is observed in (5), N—C 1.651 (3) Å, (Bell & Wallis, 1999). The use of the N···C distances in such systems as an indicator of the through space electron attracting powers of the electrophilic groups has been proposed (O'Leary et al., 2001). In the naphthalene system, the peri groups are constrained to some degree by the bonding geometry of the ring system. We now report the structures of the biphenyls (6) and (7) which contain ortho dimethylamino and ortho aldehyde substituents on opposite rings such that they are capable of forming 1,6 N···C interactions, but are not compelled by the molecular framework to be near one another at all. The biphenyls were prepared by Suzuki and Stille coupling methodologies and their molecular structures were analysed by single-crystal X-ray diffraction at 150 K. \sch

The results of the crystal structure determinations are shown in Fig. 1, and relevant molecular geometries are summarized in Table 1. Biphenyl (7) contains two independent molecules in the asymmetric unit. The three molecular conformations of (6) and (7) are very similar. The phenyl rings lie at 58.1 (1)–62.4 (1)° to each other such that there is a close N···C contact between the amino N atom and a carbonyl C atom. The dimethylamino group adopts pyramidal geometry, with a N—CH₃ bond making a torsion angle of 13.2 (3)–15.0 (3)° to the C2—C3 bond of the phenyl ring and directed away from the second phenyl ring. The carbonyl group lies almost in its phenyl ring plane, with the carbonyl bond directed away from the second phenyl ring. The N···C contact distances 2.929 (3)–3.029 (3) Å are longer than in the related naphthalene (3). The N···C═O angles lie in the range 123.8 (2)–128.2 (2)°, and the theoretical directions of the amino N atom lone pairs lie ca 19–25° to the N····C(═O) vectors. The dimethylamino N atom in (6) is displaced out of the best plane through its phenyl ring by 0.042 (2) Å towards the carbonyl group, and the carbonyl C atom is displaced out of its phenyl ring plane by 0.066 Å away from the dimethylamino group. In the two conformations of (7), the out-of-plane displacements of the corresponding aldehyde carbon atoms are similar to those in (6), 0.071 and 0.064 Å, respectively, but the dimethylamino N atoms are not displaced significantly out of the planes of their phenyl groups. Indeed, the Me₂N—C bond lengths of 1.402 (3) and 1.410 (3) Å are slightly shorter than in (6), 1.422 (2) Å. These two effects might be ascribable to the through bond electron attracting power of the second carbonyl group, though there are no other significant bond length changes in the molecular skeletons. The second aldehyde group in (7) has little effect on the molecular conformation making only a van der Waals contact with atom H6 on the opposite phenyl ring, C16···H6: 2.86 (2) & 2.99 (2) Å. There are no particularly short intermolecular interactions in the two crystal structures. In (6), centrosymmetric C—H···O interactions, graph set R²₂(10) are present, C9···O1ⁱ 3.4818 (15) Å, C—H···Oⁱ 164.8 (12)°, (i = 1 - x, -y, -z) and in (7) chains form comprising C4_A/B···O2_A/Bⁱⁱ 3.253 (3), 3.336 (3) Å, with C—H···Oⁱⁱ 129 (2) and 159 (3)°, respectively, symmetry operator ii = 1/2 + x, -y, z (for A) and -1/2 + x, 1 - y, z (for B).

The observed Me₂N···C═O interactions are of similar lengths to the 1,5-Me₂N/ketone carbonyl interactions in methadone, 2.911 & 2.912 Å (Bürgi et al., 1973b; Bye, 1974) where also the two groups are not forced to be near to one another as they are in the peri-naphthalene series. However, when the ¹³C NMR spectrum of (6) was measured in DCl/D₂O the appearance of a new resonance at δ 90.2 indicated addition of the dimethylamino group to a protonated carbonyl group. There are no directly comparable biphenyl structures with 1,6-amino/carbonylinteractions in the CAmbridge Structural Database (CSD; Allen & Kennard, 1993). The two molecules of 2,2-bis(dimethylamino)biphenyl (Staab et al., 1988) adopt conformations with the phenyl rings at 56.1 and 59.0° such that the pyramidal dimethylamino groups are on opposite sides of the molecule. The 2-methoxybiphenyl-2'-carboxylic acid (Krygowski et al., 1989) adopts a conformation with the phenyl rings at 54.4 (1)° such that the methoxy oxygen lies 3.023 (5) Å from the carboxyl carbon atom. The methoxy group lies close to its phenyl ring's best plane, so that the unconjugated lone pair is not well aligned with the MeO···C═O vector. Studies in the naphthalene series have shown that 1,5-MeO···sp²C interaction distances are remarkably insensitive to the nature of the carbon-containing functional group. In general, biphenyls with one ortho substituent per phenyl ring tend to have their phenyl rings not far from perpendicular. Exceptions occur when the substituents are small as for fluoride or alkoxy e.g. BAWPUK (Jones & Brown, 1982), DECFDP (Neronova, 1968), NOZZOR, NOZZUX (Ferreira et al., 1998), or can hydrogen bond as in diols e.g. JUPTOD (Sartori et al., 1992), NUTSUQ (Byrne et al., 1998), a hydroxy ether JAVHIX (Lin et al., 1989) and the 2,2^'-diamine DABIPH (Ottersen, 1977) where interplanar angles are ca 40–55°. The structures of (6) and (7) are likely to be more reasonable models for intermolecular interactions between dialkyamino groups and aldehydes than the structure of the related naphthalene derivative (3).

S2. Experimental

2-(N,N-Dimethylamino)biphenyl-2'-carboxaldehyde (6): sodium carbonate (6.42 g, 60.6 mmol) dissolved in degassed water (30 ml) was added to a mixture of 2-(N,N-dimethylamino)phenylboronic acid (1.80 g), Pd(PPh₃)₄ (0.70 g, 0.61 mmol) and 2-bromobenzaldehyde (2.68 g, 14.5 mmol) in a mixture of dry ethanol (5 ml) and DME (100 ml) and the mixture heated at reflux for 48 h. The cooled solution was diluted with diethyl ether (200 ml), extracted with 1M NaOH (50 ml) and then 1M HCl (4 x 150 ml). The acidic phase was made basic (pH 14) with 6M NaOH and extracted with ether (3x150 ml). The dried (MgSO₄) organic solution yielded the crude product which was purified by flash chromatography on silica, eluting first with chloroform followed by ethyl acetate to yield the product as a pale yellow oil which solidified on standing (1.23 g, 85%), m.p. 348–351 K. ¹H NMR (CDCl₃) δ: 9.57 (1H, s, CHO), 7.92 (1H, d, J = 7.7), 7.65 (1H, t, J = 7.6), 7.47–7.31 (m, 4H), 7.14 (1H, t, J = 7.4), 7.06 (1H, d, J = 7.2), 2.38 (6H, s, (CH₃)₂N); ¹³C NMR (CDCl₃) δ: 190.7 (C═O), 151.5, 142.7, 133.8, 133.1, 131.1, 131.1, 130.0, 129.5, 127.5, 126.7, 123.0, 118.1, 42.2 [(CH₃)₂N]; ν_max(cm^-1) (KBr): 2832, 1689, 1594, 1492, 1450, 1247, 1193, 945, 770; HRMS (ES): Found: 226.1229 (M+H)⁺, C₁₅H₁₅NO requires: 226.1232 (M+H)⁺.

2-(N,N-Dimethylamino)biphenyl-2',6'-dicarboxaldehyde (7): 2-trimethylstannyl-N,N-dimethylaniline (0.66 g, 2.35 mmol) and 2-bromoisophthalaldehyde (0.50 g, 2.35 mmol) were refluxed in dry THF (25 ml) with Pd(PPh₃)₄ (0.14 g, 0.12 mmol) and CuI (0.03 g, 0.17 mmol). After 24 h the amounts of catalysts were doubled and the reaction refluxed for 48 h. The THF was removed on the rotary evaporator, ethyl acetate (50 ml) was added to the residue and the mixture was filtered through Celite. The filtrate was washed with water (3 x 30 ml) and brine (30 ml), dried over Na₂SO₄ and evaporated to yield a brown oil. Purification by flash chromatography (SiO₂, 2:1 cyclohexane:diethyl ether) yielded (7) as a yellow oil which solidified on standing (0.10 g, 17%), m.p. 371–374 K. ¹H NMR (CDCl₃) δ: 9.75 (1H, s, CHO), 9.74 (1H, s, CHO), 8.24 (2H, d, J = 7.7), 7.62 (1H, t, J = 7.7), 7.45 (1H, m), 7.15 (3H, m), 2.45 [6H, s, (CH₃)₂N]; ¹³C NMR (CDCl₃) δ: 191.2 (C═O), 152.4, 146.2, 133.9, 133.7, 132.6, 130.7, 128.0, 124.9, 122.3, 118.6, 42.5 [(CH₃)₂N]; ν_max(cm^-1) (KBr): 2859, 1681, 1491, 1456, 1386, 1234, 945, 922, 799, 770; HRMS (ES): Found: 254.1178 (M+H)⁺, C₁₆H₁₅NO₂ requires: 254.1181 (M+H)⁺.

S3. Refinement

All hydrogen atoms were located in difference Fourier maps and refined with individual isotropic displacement parameters. The C—H bond lengths are 0.947 (16)–1.033 (15) Å in (6) and 0.92 (3)–1.08 (2) Å in (7). For compound (7) reflection data include 1362 merged Friedel pairs (as the absolute structure was not determined).

Computing details

For both compounds, data collection: DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPIII (Johnson & Burnett, 1996) drawings of (6) and (7) with anisotropic displacement parameters drawn at the 50% level.

(VI) 2-(N,N-Dimethylamino)-biphenyl-2'-carboxaldehyde

Crystal data

C15H15NO	Dx = 1.233 Mg m^−3
Mr = 225.28	Melting point = 348–351 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.169 (2) Å	Cell parameters from 2931 reflections
b = 11.042 (3) Å	θ = 2.9–27.5°
c = 13.745 (4) Å	µ = 0.08 mm^−1
β = 101.89 (1)°	T = 150 K
V = 1213.1 (6) Å^3	Block, yellow
Z = 4	0.40 × 0.40 × 0.25 mm
F(000) = 480

Data collection

Kappa-CCD diffractometer	2783 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	2211 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ϕ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1995)	h = −10→10
Tmin = 0.906, Tmax = 0.983	k = −14→14
12528 measured reflections	l = −15→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	All H-atom parameters refined
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0776P)^2 + 0.0677P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.008
2783 reflections	Δρmax = 0.23 e Å^−3
214 parameters	Δρmin = −0.38 e Å^−3
0 restraints

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
O1	0.42227 (14)	0.12485 (9)	0.06615 (7)	0.0439 (3)
C7	0.56425 (14)	0.05279 (10)	0.32747 (9)	0.0213 (3)
C8	0.54862 (14)	0.04338 (10)	0.22396 (8)	0.0210 (3)
C9	0.63454 (14)	−0.04752 (11)	0.18415 (9)	0.0244 (3)
C10	0.73601 (15)	−0.12794 (11)	0.24583 (10)	0.0278 (3)
C11	0.75298 (16)	−0.11882 (11)	0.34807 (10)	0.0292 (3)
C12	0.66787 (15)	−0.02939 (11)	0.38835 (9)	0.0262 (3)
C15	0.44751 (15)	0.13117 (11)	0.15572 (9)	0.0246 (3)
N1	0.20131 (12)	0.07866 (9)	0.28372 (7)	0.0241 (3)
C1	0.47517 (15)	0.14762 (10)	0.37424 (9)	0.0218 (3)
C2	0.29921 (15)	0.15933 (10)	0.35281 (8)	0.0217 (3)
C3	0.22753 (17)	0.25411 (11)	0.39690 (9)	0.0281 (3)
C4	0.32549 (19)	0.33511 (11)	0.46071 (10)	0.0330 (3)
C5	0.49737 (18)	0.32245 (12)	0.48333 (10)	0.0326 (3)
C6	0.57074 (16)	0.22835 (11)	0.44111 (9)	0.0271 (3)
C13	0.20425 (17)	−0.04795 (11)	0.31544 (11)	0.0288 (3)
C14	0.03054 (16)	0.11710 (13)	0.24248 (11)	0.0324 (3)
H9	0.6203 (18)	−0.0522 (13)	0.1141 (12)	0.035 (4)*
H10	0.7969 (18)	−0.1918 (14)	0.2204 (11)	0.036 (4)*
H11	0.8247 (18)	−0.1752 (13)	0.3923 (11)	0.032 (4)*
H12	0.6787 (18)	−0.0250 (13)	0.4609 (12)	0.037 (4)*
H15	0.4016 (17)	0.2026 (13)	0.1863 (10)	0.029 (3)*
H3	0.1049 (19)	0.2629 (12)	0.3822 (10)	0.031 (4)*
H4	0.2765 (19)	0.4009 (16)	0.4897 (11)	0.045 (4)*
H5	0.5685 (18)	0.3803 (13)	0.5287 (11)	0.035 (4)*
H6	0.6931 (19)	0.2189 (12)	0.4568 (10)	0.028 (3)*
H13X	0.318 (2)	−0.0761 (14)	0.3438 (11)	0.036 (4)*
H13Y	0.1528 (17)	−0.0961 (13)	0.2544 (11)	0.033 (4)*
H13Z	0.1321 (19)	−0.0627 (13)	0.3654 (11)	0.035 (4)*
H14X	−0.0182 (18)	0.0609 (14)	0.1853 (11)	0.039 (4)*
H14Y	−0.0441 (18)	0.1154 (12)	0.2947 (11)	0.033 (4)*
H14Z	0.0307 (17)	0.1988 (13)	0.2156 (10)	0.032 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0557 (7)	0.0523 (6)	0.0205 (5)	0.0163 (5)	0.0005 (5)	−0.0001 (4)
C7	0.0190 (5)	0.0223 (6)	0.0233 (6)	−0.0038 (4)	0.0057 (5)	−0.0005 (4)
C8	0.0189 (5)	0.0219 (5)	0.0222 (6)	−0.0043 (4)	0.0041 (5)	−0.0013 (4)
C9	0.0239 (6)	0.0267 (6)	0.0234 (7)	−0.0055 (5)	0.0067 (5)	−0.0042 (5)
C10	0.0243 (6)	0.0247 (6)	0.0365 (8)	0.0014 (5)	0.0111 (5)	−0.0028 (5)
C11	0.0246 (6)	0.0289 (7)	0.0346 (7)	0.0038 (5)	0.0073 (5)	0.0074 (5)
C12	0.0253 (6)	0.0309 (6)	0.0226 (6)	0.0008 (5)	0.0053 (5)	0.0028 (5)
C15	0.0260 (6)	0.0253 (6)	0.0227 (7)	−0.0022 (5)	0.0050 (5)	−0.0006 (5)
N1	0.0227 (5)	0.0242 (5)	0.0249 (5)	−0.0013 (4)	0.0037 (4)	0.0005 (4)
C1	0.0269 (6)	0.0215 (5)	0.0179 (6)	−0.0011 (5)	0.0064 (5)	0.0022 (4)
C2	0.0266 (6)	0.0206 (5)	0.0185 (6)	0.0005 (5)	0.0063 (5)	0.0032 (4)
C3	0.0318 (7)	0.0264 (6)	0.0274 (7)	0.0045 (5)	0.0095 (5)	0.0026 (5)
C4	0.0482 (8)	0.0238 (6)	0.0302 (7)	0.0042 (6)	0.0151 (6)	−0.0034 (5)
C5	0.0439 (8)	0.0290 (6)	0.0250 (7)	−0.0071 (6)	0.0078 (6)	−0.0064 (5)
C6	0.0304 (7)	0.0298 (6)	0.0215 (6)	−0.0050 (5)	0.0063 (5)	−0.0009 (5)
C13	0.0288 (7)	0.0236 (6)	0.0338 (7)	−0.0036 (5)	0.0061 (6)	−0.0004 (5)
C14	0.0253 (7)	0.0369 (8)	0.0329 (8)	0.0009 (6)	0.0011 (6)	0.0046 (6)

Geometric parameters (Å, º)

O1—C15	1.2077 (15)	N1—C2	1.4220 (15)
C7—C12	1.3959 (17)	N1—C14	1.4566 (16)
C7—C8	1.4058 (16)	N1—C13	1.4632 (16)
C7—C1	1.4939 (16)	C1—C6	1.3975 (16)
C8—C9	1.3992 (17)	C1—C2	1.4124 (17)
C8—C15	1.4773 (17)	C2—C3	1.3970 (17)
C9—C10	1.3802 (18)	C3—C4	1.3858 (19)
C10—C11	1.3870 (19)	C4—C5	1.381 (2)
C11—C12	1.3869 (18)	C5—C6	1.3853 (18)
C12—C7—C8	118.43 (10)	C2—N1—C13	115.28 (10)
C12—C7—C1	119.12 (10)	C14—N1—C13	110.49 (10)
C8—C7—C1	122.45 (10)	C6—C1—C2	119.03 (10)
C9—C8—C7	120.04 (11)	C6—C1—C7	118.32 (10)
C9—C8—C15	118.83 (10)	C2—C1—C7	122.64 (10)
C7—C8—C15	121.09 (10)	C3—C2—C1	118.53 (11)
C10—C9—C8	120.49 (11)	C3—C2—N1	122.05 (11)
C9—C10—C11	119.85 (11)	C1—C2—N1	119.34 (10)
C12—C11—C10	120.16 (12)	C4—C3—C2	121.27 (12)
C11—C12—C7	121.03 (11)	C5—C4—C3	120.32 (12)
O1—C15—C8	124.40 (11)	C4—C5—C6	119.28 (12)
C2—N1—C14	116.05 (10)	C5—C6—C1	121.51 (12)

(VII) 2-(N,N-Dimethylamino)-biphenyl-2',6'-dicarboxaldehyde

Crystal data

C16H15NO2	Dx = 1.270 Mg m^−3
Mr = 253.29	Melting point = 371–374 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 4682 reflections
a = 14.161 (3) Å	θ = 2.9–27.5°
b = 27.913 (6) Å	µ = 0.08 mm^−1
c = 6.7018 (13) Å	T = 150 K
V = 2648.9 (9) Å^3	Block, yellow
Z = 8	0.25 × 0.20 × 0.08 mm
F(000) = 1072

Data collection

Kappa-CCD diffractometer	3238 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	2378 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1995)	h = −13→18
Tmin = 0.873, Tmax = 0.994	k = −28→36
14314 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	All H-atom parameters refined
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0635P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.005
3238 reflections	Δρmax = 0.18 e Å^−3
463 parameters	Δρmin = −0.23 e Å^−3
1 restraint

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
O1A	1.12718 (10)	0.23205 (7)	0.4931 (4)	0.0546 (6)
O2A	0.72984 (11)	0.07603 (6)	0.5447 (3)	0.0529 (5)
N1A	1.06585 (12)	0.13667 (7)	0.1260 (3)	0.0302 (5)
C1A	1.01583 (14)	0.09621 (8)	0.4294 (4)	0.0278 (5)
C2A	1.07268 (14)	0.09740 (8)	0.2556 (4)	0.0298 (5)
C3A	1.13679 (16)	0.05968 (9)	0.2256 (5)	0.0409 (6)
C4A	1.14278 (19)	0.02208 (10)	0.3580 (5)	0.0488 (7)
C5A	1.08540 (19)	0.02002 (9)	0.5217 (5)	0.0485 (7)
C6A	1.02182 (17)	0.05721 (9)	0.5557 (4)	0.0387 (6)
C7A	0.95345 (14)	0.13732 (8)	0.4848 (3)	0.0261 (5)
C8A	0.99097 (13)	0.18330 (8)	0.5139 (3)	0.0267 (5)
C9A	0.93380 (15)	0.22104 (8)	0.5725 (4)	0.0318 (5)
C10A	0.83864 (16)	0.21450 (9)	0.6068 (4)	0.0369 (6)
C11A	0.80072 (14)	0.16971 (9)	0.5799 (4)	0.0335 (5)
C12A	0.85651 (13)	0.13111 (8)	0.5200 (3)	0.0281 (5)
C13A	0.97380 (17)	0.14260 (10)	0.0301 (4)	0.0359 (6)
C14A	1.14186 (19)	0.14276 (11)	−0.0184 (5)	0.0458 (7)
C15A	1.09333 (15)	0.19288 (9)	0.4905 (4)	0.0337 (5)
C16A	0.80912 (15)	0.08452 (9)	0.4870 (4)	0.0371 (6)
O1B	0.87226 (10)	0.27234 (6)	0.0471 (4)	0.0487 (5)
O2B	1.28798 (11)	0.41073 (6)	−0.1302 (4)	0.0498 (5)
N1B	0.92034 (12)	0.36081 (7)	−0.3886 (3)	0.0304 (4)
C1B	0.99517 (14)	0.40097 (8)	−0.1089 (4)	0.0272 (5)
C2B	0.92619 (14)	0.40074 (8)	−0.2604 (4)	0.0286 (5)
C3B	0.86406 (16)	0.43981 (9)	−0.2708 (5)	0.0392 (6)
C4B	0.87156 (18)	0.47756 (9)	−0.1404 (5)	0.0463 (7)
C5B	0.94198 (18)	0.47893 (9)	0.0024 (5)	0.0453 (7)
C6B	1.00272 (16)	0.44032 (8)	0.0176 (4)	0.0341 (5)
C7B	1.05555 (14)	0.35821 (8)	−0.0697 (3)	0.0253 (5)
C8B	1.01485 (13)	0.31466 (8)	−0.0129 (3)	0.0260 (5)
C9B	1.07078 (14)	0.27558 (8)	0.0370 (4)	0.0313 (5)
C10B	1.16828 (15)	0.27873 (8)	0.0305 (4)	0.0356 (6)
C11B	1.20969 (15)	0.32101 (8)	−0.0282 (4)	0.0325 (5)
C12B	1.15495 (14)	0.36089 (8)	−0.0774 (4)	0.0294 (5)
C13B	1.00215 (17)	0.35483 (10)	−0.5187 (4)	0.0356 (6)
C14B	0.83354 (18)	0.35543 (11)	−0.5008 (5)	0.0479 (7)
C15B	0.91117 (14)	0.30930 (9)	0.0087 (4)	0.0309 (5)
C16B	1.20348 (16)	0.40478 (9)	−0.1464 (4)	0.0369 (6)
H9A	0.9599 (16)	0.2541 (10)	0.597 (5)	0.047 (7)*
H10A	0.7973 (15)	0.2422 (9)	0.649 (4)	0.041 (7)*
H11A	0.7353 (16)	0.1640 (8)	0.599 (4)	0.033 (6)*
H15A	1.1344 (15)	0.1632 (9)	0.474 (4)	0.034 (6)*
H16A	0.8510 (16)	0.0597 (8)	0.401 (4)	0.041 (7)*
H3A	1.177 (2)	0.0616 (11)	0.105 (5)	0.066 (9)*
H4A	1.1870 (17)	−0.0040 (10)	0.330 (5)	0.051 (8)*
H5A	1.0879 (17)	−0.0068 (10)	0.621 (5)	0.052 (8)*
H6A	0.9818 (17)	0.0572 (9)	0.676 (5)	0.044 (7)*
H13X	0.9665 (18)	0.1191 (10)	−0.069 (5)	0.043 (8)*
H13Y	0.9665 (17)	0.1750 (11)	−0.039 (5)	0.054 (8)*
H13Z	0.924 (2)	0.1368 (11)	0.116 (6)	0.067 (10)*
H14X	1.1349 (16)	0.1754 (10)	−0.081 (5)	0.041 (7)*
H14Y	1.2028 (19)	0.1411 (9)	0.052 (5)	0.047 (8)*
H14Z	1.1436 (18)	0.1159 (10)	−0.118 (5)	0.053 (8)*
H9B	1.0381 (16)	0.2455 (9)	0.083 (4)	0.041 (7)*
H10B	1.2065 (13)	0.2516 (8)	0.067 (4)	0.030 (6)*
H11B	1.2798 (16)	0.3260 (8)	−0.032 (4)	0.036 (6)*
H15B	0.8747 (15)	0.3400 (9)	−0.008 (4)	0.039 (7)*
H16B	1.1607 (16)	0.4315 (8)	−0.210 (4)	0.036 (6)*
H3B	0.8167 (18)	0.4380 (9)	−0.364 (4)	0.042 (7)*
H4B	0.833 (2)	0.5055 (12)	−0.149 (6)	0.079 (10)*
H5B	0.9456 (16)	0.5072 (10)	0.099 (5)	0.049 (8)*
H6B	1.0486 (17)	0.4379 (9)	0.123 (5)	0.045 (8)*
H13C	1.0055 (17)	0.3807 (9)	−0.621 (5)	0.046 (8)*
H13D	1.0027 (18)	0.3230 (11)	−0.578 (5)	0.055 (8)*
H13E	1.063 (2)	0.3582 (11)	−0.449 (6)	0.064 (10)*
H14C	0.8369 (17)	0.3218 (10)	−0.564 (5)	0.046 (7)*
H14D	0.8276 (19)	0.3823 (10)	−0.606 (5)	0.057 (9)*
H14E	0.777 (2)	0.3599 (10)	−0.409 (6)	0.063 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0351 (9)	0.0515 (11)	0.0772 (15)	−0.0196 (8)	0.0018 (10)	0.0031 (12)
O2A	0.0376 (9)	0.0544 (10)	0.0668 (14)	−0.0193 (8)	0.0138 (9)	−0.0123 (11)
N1A	0.0238 (9)	0.0358 (10)	0.0310 (11)	−0.0002 (7)	0.0043 (8)	−0.0007 (10)
C1A	0.0230 (10)	0.0299 (12)	0.0304 (13)	0.0016 (9)	−0.0040 (9)	−0.0009 (11)
C2A	0.0229 (11)	0.0311 (12)	0.0352 (13)	0.0021 (9)	−0.0044 (10)	−0.0024 (11)
C3A	0.0294 (12)	0.0443 (15)	0.0491 (16)	0.0093 (10)	−0.0008 (12)	−0.0114 (15)
C4A	0.0475 (15)	0.0396 (15)	0.0594 (19)	0.0182 (12)	−0.0133 (14)	−0.0060 (15)
C5A	0.0598 (16)	0.0334 (13)	0.0524 (19)	0.0091 (12)	−0.0141 (15)	0.0029 (15)
C6A	0.0426 (14)	0.0358 (13)	0.0376 (15)	0.0024 (10)	−0.0059 (11)	0.0045 (13)
C7A	0.0225 (10)	0.0312 (11)	0.0245 (11)	0.0004 (8)	−0.0018 (9)	0.0028 (10)
C8A	0.0220 (10)	0.0320 (11)	0.0262 (12)	−0.0018 (8)	−0.0018 (9)	0.0036 (11)
C9A	0.0323 (12)	0.0277 (11)	0.0353 (14)	−0.0019 (9)	−0.0007 (10)	−0.0005 (12)
C10A	0.0304 (12)	0.0374 (13)	0.0430 (15)	0.0034 (10)	−0.0001 (11)	−0.0035 (13)
C11A	0.0207 (11)	0.0421 (13)	0.0377 (13)	−0.0016 (10)	0.0026 (10)	−0.0017 (12)
C12A	0.0232 (10)	0.0344 (11)	0.0267 (11)	−0.0042 (8)	0.0011 (9)	−0.0024 (11)
C13A	0.0308 (13)	0.0472 (15)	0.0296 (13)	0.0005 (11)	−0.0043 (11)	0.0041 (14)
C14A	0.0377 (15)	0.0531 (17)	0.0466 (16)	−0.0054 (12)	0.0155 (13)	−0.0027 (17)
C15A	0.0249 (11)	0.0423 (14)	0.0338 (13)	−0.0046 (10)	−0.0014 (11)	−0.0016 (13)
C16A	0.0316 (12)	0.0398 (13)	0.0400 (14)	−0.0092 (10)	−0.0006 (11)	−0.0022 (12)
O1B	0.0282 (8)	0.0441 (10)	0.0739 (15)	−0.0109 (7)	0.0058 (9)	0.0018 (10)
O2B	0.0285 (9)	0.0460 (10)	0.0748 (15)	−0.0118 (7)	−0.0022 (9)	0.0043 (10)
N1B	0.0220 (9)	0.0402 (11)	0.0291 (10)	−0.0019 (7)	−0.0027 (8)	0.0000 (10)
C1B	0.0218 (10)	0.0292 (11)	0.0305 (12)	0.0024 (9)	0.0037 (9)	0.0000 (11)
C2B	0.0219 (10)	0.0323 (12)	0.0316 (13)	−0.0008 (9)	0.0040 (10)	0.0037 (11)
C3B	0.0265 (12)	0.0410 (14)	0.0501 (17)	0.0078 (10)	−0.0008 (12)	0.0098 (15)
C4B	0.0381 (14)	0.0367 (14)	0.064 (2)	0.0119 (11)	0.0121 (14)	0.0082 (15)
C5B	0.0511 (15)	0.0333 (13)	0.0515 (17)	0.0048 (11)	0.0109 (14)	−0.0020 (14)
C6B	0.0367 (12)	0.0303 (12)	0.0354 (14)	−0.0003 (10)	0.0016 (11)	−0.0041 (13)
C7B	0.0236 (10)	0.0288 (11)	0.0236 (11)	0.0006 (8)	−0.0015 (9)	−0.0043 (10)
C8B	0.0215 (10)	0.0298 (11)	0.0267 (11)	−0.0016 (8)	−0.0013 (9)	−0.0024 (11)
C9B	0.0267 (11)	0.0288 (11)	0.0383 (14)	−0.0020 (9)	0.0006 (10)	−0.0008 (12)
C10B	0.0274 (11)	0.0328 (12)	0.0467 (16)	0.0061 (10)	−0.0048 (11)	−0.0015 (12)
C11B	0.0192 (10)	0.0370 (12)	0.0412 (13)	0.0003 (9)	−0.0042 (10)	−0.0030 (12)
C12B	0.0227 (10)	0.0314 (11)	0.0341 (12)	−0.0026 (9)	−0.0024 (9)	−0.0009 (11)
C13B	0.0334 (13)	0.0420 (14)	0.0313 (13)	0.0009 (11)	0.0059 (11)	−0.0043 (13)
C14B	0.0332 (14)	0.0630 (18)	0.0475 (17)	−0.0030 (13)	−0.0127 (14)	−0.0029 (16)
C15B	0.0246 (10)	0.0365 (13)	0.0316 (13)	−0.0017 (10)	0.0027 (10)	−0.0016 (12)
C16B	0.0267 (12)	0.0377 (13)	0.0462 (15)	−0.0028 (10)	−0.0011 (11)	0.0015 (13)

Geometric parameters (Å, º)

O1A—C15A	1.194 (3)	O1B—C15B	1.198 (3)
O2A—C16A	1.211 (3)	O2B—C16B	1.213 (2)
N1A—C2A	1.402 (3)	N1B—C2B	1.410 (3)
N1A—C14A	1.458 (3)	N1B—C14B	1.448 (3)
N1A—C13A	1.463 (3)	N1B—C13B	1.459 (3)
C1A—C6A	1.382 (4)	C1B—C6B	1.392 (4)
C1A—C2A	1.416 (3)	C1B—C2B	1.409 (3)
C1A—C7A	1.495 (3)	C1B—C7B	1.492 (3)
C2A—C3A	1.405 (3)	C2B—C3B	1.403 (3)
C3A—C4A	1.377 (4)	C3B—C4B	1.373 (4)
C4A—C5A	1.366 (5)	C4B—C5B	1.383 (4)
C5A—C6A	1.393 (4)	C5B—C6B	1.383 (4)
C7A—C8A	1.403 (3)	C7B—C8B	1.398 (3)
C7A—C12A	1.404 (3)	C7B—C12B	1.410 (3)
C8A—C9A	1.386 (3)	C8B—C9B	1.389 (3)
C8A—C15A	1.482 (3)	C8B—C15B	1.483 (3)
C9A—C10A	1.379 (3)	C9B—C10B	1.384 (3)
C10A—C11A	1.373 (3)	C10B—C11B	1.375 (3)
C11A—C12A	1.395 (3)	C11B—C12B	1.396 (3)
C12A—C16A	1.480 (3)	C12B—C16B	1.479 (3)
C2A—N1A—C14A	116.85 (19)	C2B—N1B—C14B	116.61 (19)
C2A—N1A—C13A	114.98 (18)	C2B—N1B—C13B	114.08 (18)
C14A—N1A—C13A	110.7 (2)	C14B—N1B—C13B	110.6 (2)
C6A—C1A—C2A	119.2 (2)	C6B—C1B—C2B	119.7 (2)
C6A—C1A—C7A	119.3 (2)	C6B—C1B—C7B	118.7 (2)
C2A—C1A—C7A	121.5 (2)	C2B—C1B—C7B	121.4 (2)
N1A—C2A—C3A	122.8 (2)	C3B—C2B—C1B	117.8 (2)
N1A—C2A—C1A	119.24 (19)	C3B—C2B—N1B	123.2 (2)
C3A—C2A—C1A	117.9 (2)	C1B—C2B—N1B	118.92 (19)
C4A—C3A—C2A	121.3 (3)	C4B—C3B—C2B	121.1 (3)
C5A—C4A—C3A	120.8 (2)	C3B—C4B—C5B	121.2 (2)
C4A—C5A—C6A	119.0 (3)	C4B—C5B—C6B	118.6 (3)
C1A—C6A—C5A	121.8 (3)	C5B—C6B—C1B	121.5 (3)
C8A—C7A—C12A	117.40 (19)	C8B—C7B—C12B	117.88 (18)
C8A—C7A—C1A	120.87 (17)	C8B—C7B—C1B	120.49 (17)
C12A—C7A—C1A	121.65 (19)	C12B—C7B—C1B	121.53 (19)
C9A—C8A—C7A	120.91 (18)	C9B—C8B—C7B	120.88 (18)
C9A—C8A—C15A	117.6 (2)	C9B—C8B—C15B	117.52 (19)
C7A—C8A—C15A	121.40 (19)	C7B—C8B—C15B	121.49 (18)
C10A—C9A—C8A	121.2 (2)	C10B—C9B—C8B	120.8 (2)
C11A—C10A—C9A	118.7 (2)	C11B—C10B—C9B	119.3 (2)
C10A—C11A—C12A	121.31 (19)	C10B—C11B—C12B	121.01 (19)
C11A—C12A—C7A	120.5 (2)	C11B—C12B—C7B	120.2 (2)
C11A—C12A—C16A	117.70 (19)	C11B—C12B—C16B	118.45 (19)
C7A—C12A—C16A	121.8 (2)	C7B—C12B—C16B	121.29 (19)
O1A—C15A—C8A	123.8 (2)	O1B—C15B—C8B	124.3 (2)
O2A—C16A—C12A	123.0 (2)	O2B—C16B—C12B	123.0 (2)