Two crystal forms of mesogenic bis­(4'-cyano­biphenyl-4-yl) butane­dioate

The title compound, C₃₀H₂₀N₂O₄, exhibits a nematic phase in the wide temperature range between 498.5 and 538.6 K, in spite of the short linker moiety. Two crystal forms have been found. In both forms, the mol­ecule is centrosymmetric. Form I has a planar biphenyl group, while form II has a twisted biphenyl group with a twist angle of 34.75 (6)°. The packing modes are also different. In form I the long mol­ecular axes are tilted with respect to each other at about 30°, while in form II the long mol­ecular axes have an almost parallel arrangement.

S1. Comment

Dimeric liquid crystals have attracted considerable attention because they are regarded as model compounds for polymeric liquid crystals. Previously, we reported the crystal structures of two series, α,ω-bis(4-cyanobiphenyl-4'-yloxycarbonyl)propane and -hexane, and α,ω-bis(4-cyanobiphenyl-4'-yl)octane and -nonane (Hori et al. 2004). The inversion centres are located at the centres of the molecules of the ester compounds, while the molecular structures were asymmetric for the latter two compounds with alkyl chains as linkages.

In order to investigate the short limit of the linkage for liquid crystalline behaviour, we synthesized the title compound, (I), which exhibits the nematic phase in the wide temperature range between 498.5 and 538.6 K. We found two crystal forms, I and II. Form I, with an oval plate shape, was obtained predominantly, while form II, with a rod shape, was only obtained once. Both forms were apparently stable between 200 K and room temperature.

As shown in Fig. 1, the inversion centre is located in the middle of the molecules in both forms. The molecules are fully extended with trans conformations in the alkyl chain linkages. However, the biphenyl moieties are quite different, with an almost planar biphenyl moiety [dihedral angle 4.65 (10)°] in form I and a twisted biphenyl moiety [dihedral angle 34.75 (6)°] in form II.

The packing modes are also different. In form I, the long molecular axes are tilted with respect to each other at about 30°, as shown in Fig. 2. Here, the nearest groups for the CN group are the ester linkages: 3.189 (2) for N1···C14(x - 1, -y + 1/2, z + 1/2), 3.261 (2) for N1···O1(x - 1, -y + 1/2, z + 1/2), 3.356 (2) for O1···C1(-x, -y, -z + 1), 3.595 (2) for N1···O2(x - 1, -y + 1/2, z + 1/2) and 3.620 (2) Å for N1···O1(-x, -y, -z + 1).

On the other hand, the long molecular axes have an almost parallel arrangement in form II, as shown in Fig. 3. An antiparallel arrangement of CN groups, with distances of 3.260 (3) for N1···N1(-x + 2, -y, -z + 3) and 3.267 (2) Å for N1···C1(-x + 2, -y, -z + 3), is found in the sheet parallel to the ac plane. In addition, short distances are found between a CN group and an ester moiety: 3.1672 (18) for N1···O2(-x + 2, -y, -z + 2) and 3.5156 (19) Å for N1···C14(-x + 2, -y, -z + 2).

Differential scanning calorimetry (DSC) showed no phase transitions between room temperature and the melting point of for I of (I) at 498.5 K. Unfortunately, DSC could not be carried out for form II due to the very small number of crystals. Microscopic observation confirmed that form II showed no change until the melting point, which was 1–2 K lower than that of form I, meaning that form I is more stable throughout the temperature range from room temperature to the melting point. This result is in accordance with the density rule, stating that the most efficiently packed structure is the most stable form (Bernstein, 2002), a direct consequence of the closest packing principle (Kitaigorodsky, 1961).

For isolated molecules, the most stable conformation of the biphenyl moiety was obtained when the dihedral angle was 40° by AM1 calculation (MOPAC2002; Fujitsu, 2002). The heat of formation for the planar conformation was higher by 4.5 kcal mol^-1 (1 kcal mol^-1 = 4.184 kJ mol^-1). Thus, the disadvantage of the molecular stability of form I is compensated by the more efficient packing of its planar biphenyl moieties.

On melting, the nematic phase appeared, as confirmed by the Schlieren texture, and the material then transformed to the isotropic phase at 538.6 K. The transition enthalpies were 37.3 kJ mol^-1 for form I to nematic and 6.5 kJ mol^-1 for nematic to isotropic.

S2. Experimental

The title compound was synthesized as described previously (Hori et al. 2004). Three kinds of crystals, oval plate, needle and rod, were obtained by slow evaporation from dichloromethane with a small amount of methanol. Cell dimensions were the same for the oval plate and needle crystals and these were denoted form I. The rod-shaped crystals, obtained only once, had different cell dimensions and were denoted form II.

DSC was carried out on a DSC-22 C (Seiko) and microscopic observation was done on a POM microscope (Olympus) equipped with an FP-82 hot stage (Mettler).

S3. Refinement

H atoms were positioned geometrically and treated as riding, with C—H = 0.95–0.99 Å and with U_iso(H) = 1.2U_eq(C). [Please check added text]

Computing details

For both compounds, data collection: PROCESS (Rigaku, 1996); cell refinement: PROCESS (Rigaku, 1996); data reduction: PROCESS (Rigaku, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: TEXSAN (Molecular Structure Corporation & Rigaku, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structures of forms I (top?) and II (bottom?) of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal structure of form I of (I), viewed along the b (top) and c (bottom) axes. Black and grey molecules denote corresponding molecules in the two parts. Green lines denote the N1···C14 distance (3.189 Å) and red lines denote the O1···C1 distance (3.356 Å). H atoms have been omitted for clarity.
	Fig. 3. The crystal structure of form II of (I), viewed along the b (top) and a (bottom) axes. Black and grey molecules denote corresponding molecules in the two parts. Dashed lines denote the N1···C1 distance (3.267 Å), and dotted and dashed lines denote the N1···C14 distance (3.516 Å). H atoms have been omitted for clarity.

(I) bis(4'-cyanobiphenyl-4-yl) butanedioate

Crystal data

C30H20N2O4	F(000) = 492
Mr = 472.48	Dx = 1.381 Mg m^−3
Monoclinic, P21/c	Melting point: 498 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 10.478 (3) Å	Cell parameters from 25 reflections
b = 11.6064 (11) Å	θ = 22.5–25°
c = 9.590 (3) Å	µ = 0.75 mm^−1
β = 103.06 (2)°	T = 200 K
V = 1136.1 (5) Å^3	Oval plate, colourless
Z = 2	0.6 × 0.4 × 0.1 mm

Data collection

Rigaku AFC-7R diffractometer	1955 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.036
Graphite monochromator	θmax = 68.0°, θmin = 4.3°
2θ/ω scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→13
Tmin = 0.654, Tmax = 0.932	l = −11→4
2587 measured reflections	3 standard reflections every 150 reflections
2033 independent reflections	intensity decay: 0.3%

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)] = 0.047	H-atom parameters not refined
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0676P)^2 + 0.4554P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.004
2033 reflections	Δρmax = 0.35 e Å^−3
164 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0144 (15)

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

	x	y	z	Uiso*/Ueq
O1	0.34484 (10)	0.04546 (11)	0.22003 (12)	0.0347 (3)
O2	0.26457 (10)	0.05620 (11)	−0.01839 (12)	0.0361 (3)
N1	−0.53275 (16)	0.20929 (14)	0.64755 (19)	0.0483 (4)
C1	−0.44609 (16)	0.19595 (14)	0.59542 (18)	0.0351 (4)
C2	−0.33566 (15)	0.17836 (14)	0.53109 (16)	0.0293 (4)
C3	−0.33186 (16)	0.08356 (15)	0.44384 (17)	0.0337 (4)
H3	−0.4034	0.0313	0.4235	0.040*
C4	−0.22379 (15)	0.06533 (14)	0.38655 (17)	0.0324 (4)
H4	−0.2226	0.0006	0.3263	0.039*
C5	−0.11603 (13)	0.14006 (13)	0.41517 (15)	0.0254 (4)
C6	−0.12218 (15)	0.23470 (13)	0.50348 (17)	0.0309 (4)
H6	−0.0504	0.2867	0.5249	0.037*
C7	−0.23007 (16)	0.25447 (14)	0.56032 (17)	0.0328 (4)
H7	−0.2323	0.3199	0.6193	0.039*
C8	0.00057 (14)	0.11911 (13)	0.35395 (15)	0.0259 (4)
C9	0.01032 (15)	0.02110 (15)	0.27398 (18)	0.0339 (4)
H9	−0.0608	−0.0316	0.2540	0.041*
C10	0.12098 (16)	−0.00184 (15)	0.22256 (18)	0.0365 (4)
H10	0.1257	−0.0694	0.1680	0.044*
C11	0.22395 (14)	0.07437 (14)	0.25150 (16)	0.0298 (4)
C12	0.21658 (16)	0.17443 (15)	0.32509 (19)	0.0384 (4)
H12	0.2868	0.2281	0.3407	0.046*
C13	0.10565 (16)	0.19643 (15)	0.3765 (2)	0.0377 (4)
H13	0.1008	0.2655	0.4282	0.045*
C14	0.35332 (14)	0.03680 (13)	0.08143 (16)	0.0276 (4)
C15	0.48881 (14)	−0.00147 (14)	0.07518 (16)	0.0308 (4)
H15A	0.5031	−0.0809	0.1130	0.037*
H15B	0.5537	0.0492	0.1373	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0231 (6)	0.0505 (7)	0.0329 (6)	0.0073 (5)	0.0112 (4)	0.0012 (5)
O2	0.0265 (6)	0.0462 (7)	0.0358 (6)	0.0073 (5)	0.0076 (5)	0.0014 (5)
N1	0.0426 (9)	0.0467 (9)	0.0643 (10)	0.0064 (7)	0.0301 (8)	0.0022 (7)
C1	0.0351 (9)	0.0321 (9)	0.0412 (9)	0.0030 (7)	0.0148 (7)	0.0024 (7)
C2	0.0268 (8)	0.0313 (8)	0.0317 (8)	0.0038 (6)	0.0106 (6)	0.0033 (6)
C3	0.0286 (8)	0.0353 (9)	0.0398 (8)	−0.0061 (6)	0.0133 (6)	−0.0042 (7)
C4	0.0319 (8)	0.0318 (8)	0.0362 (8)	−0.0048 (6)	0.0131 (6)	−0.0082 (6)
C5	0.0242 (7)	0.0255 (8)	0.0270 (7)	0.0017 (6)	0.0065 (5)	0.0026 (6)
C6	0.0281 (8)	0.0285 (8)	0.0371 (8)	−0.0018 (6)	0.0095 (6)	−0.0030 (6)
C7	0.0341 (8)	0.0286 (8)	0.0382 (8)	0.0011 (6)	0.0133 (7)	−0.0055 (6)
C8	0.0239 (7)	0.0261 (8)	0.0282 (7)	0.0012 (6)	0.0067 (5)	0.0026 (6)
C9	0.0264 (8)	0.0350 (9)	0.0418 (9)	−0.0044 (6)	0.0110 (7)	−0.0094 (7)
C10	0.0322 (9)	0.0367 (9)	0.0432 (9)	−0.0010 (7)	0.0138 (7)	−0.0127 (7)
C11	0.0226 (7)	0.0385 (9)	0.0302 (7)	0.0049 (6)	0.0098 (6)	0.0031 (6)
C12	0.0293 (8)	0.0363 (9)	0.0534 (10)	−0.0072 (7)	0.0173 (7)	−0.0070 (7)
C13	0.0329 (9)	0.0310 (8)	0.0538 (10)	−0.0055 (7)	0.0196 (7)	−0.0117 (7)
C14	0.0259 (8)	0.0247 (7)	0.0340 (8)	0.0005 (6)	0.0107 (6)	0.0002 (6)
C15	0.0233 (7)	0.0351 (9)	0.0356 (9)	0.0056 (6)	0.0104 (6)	0.0021 (6)

Geometric parameters (Å, º)

O1—C14	1.3557 (19)	C7—H7	0.9500
O1—C11	1.4074 (18)	C8—C9	1.389 (2)
O2—C14	1.1956 (19)	C8—C13	1.399 (2)
N1—C1	1.142 (2)	C9—C10	1.385 (2)
C1—C2	1.443 (2)	C9—H9	0.9500
C2—C3	1.388 (2)	C10—C11	1.374 (2)
C2—C7	1.394 (2)	C10—H10	0.9500
C3—C4	1.382 (2)	C11—C12	1.370 (2)
C3—H3	0.9500	C12—C13	1.385 (2)
C4—C5	1.401 (2)	C12—H12	0.9500
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.397 (2)	C14—C15	1.502 (2)
C5—C8	1.490 (2)	C15—C15^i	1.513 (3)
C6—C7	1.381 (2)	C15—H15A	0.9900
C6—H6	0.9500	C15—H15B	0.9900
C14—O1—C11	119.30 (11)	C10—C9—H9	119.1
N1—C1—C2	179.29 (19)	C8—C9—H9	119.1
C3—C2—C7	119.60 (14)	C11—C10—C9	119.13 (15)
C3—C2—C1	120.31 (15)	C11—C10—H10	120.4
C7—C2—C1	120.05 (15)	C9—C10—H10	120.4
C4—C3—C2	119.91 (14)	C12—C11—C10	121.10 (14)
C4—C3—H3	120.0	C12—C11—O1	118.08 (14)
C2—C3—H3	120.0	C10—C11—O1	120.46 (14)
C3—C4—C5	121.58 (14)	C11—C12—C13	119.29 (15)
C3—C4—H4	119.2	C11—C12—H12	120.4
C5—C4—H4	119.2	C13—C12—H12	120.4
C6—C5—C4	117.39 (14)	C12—C13—C8	121.40 (15)
C6—C5—C8	121.41 (13)	C12—C13—H13	119.3
C4—C5—C8	121.20 (14)	C8—C13—H13	119.3
C7—C6—C5	121.59 (14)	O2—C14—O1	124.03 (14)
C7—C6—H6	119.2	O2—C14—C15	126.51 (14)
C5—C6—H6	119.2	O1—C14—C15	109.45 (12)
C6—C7—C2	119.91 (14)	C14—C15—C15^i	112.52 (15)
C6—C7—H7	120.0	C14—C15—H15A	109.1
C2—C7—H7	120.0	C15^i—C15—H15A	109.1
C9—C8—C13	117.23 (14)	C14—C15—H15B	109.1
C9—C8—C5	121.36 (14)	C15^i—C15—H15B	109.1
C13—C8—C5	121.40 (14)	H15A—C15—H15B	107.8
C10—C9—C8	121.75 (15)
C7—C2—C3—C4	−0.1 (2)	C5—C8—C9—C10	−176.81 (14)
C1—C2—C3—C4	−177.85 (15)	C8—C9—C10—C11	0.0 (3)
C2—C3—C4—C5	0.5 (3)	C9—C10—C11—C12	−2.7 (3)
C3—C4—C5—C6	−0.4 (2)	C9—C10—C11—O1	170.29 (14)
C3—C4—C5—C8	179.45 (14)	C14—O1—C11—C12	−118.01 (16)
C4—C5—C6—C7	−0.2 (2)	C14—O1—C11—C10	68.8 (2)
C8—C5—C6—C7	179.95 (14)	C10—C11—C12—C13	2.9 (3)
C5—C6—C7—C2	0.7 (2)	O1—C11—C12—C13	−170.23 (15)
C3—C2—C7—C6	−0.5 (2)	C11—C12—C13—C8	−0.5 (3)
C1—C2—C7—C6	177.27 (15)	C9—C8—C13—C12	−2.0 (3)
C6—C5—C8—C9	175.72 (15)	C5—C8—C13—C12	177.05 (15)
C4—C5—C8—C9	−4.2 (2)	C11—O1—C14—O2	2.7 (2)
C6—C5—C8—C13	−3.3 (2)	C11—O1—C14—C15	−176.67 (13)
C4—C5—C8—C13	176.86 (15)	O2—C14—C15—C15^i	7.9 (3)
C13—C8—C9—C10	2.2 (2)	O1—C14—C15—C15^i	−172.69 (16)

Symmetry code: (i) −x+1, −y, −z.

(II) bis(4'-cyanobiphenyl-4-yl) butanedioate

Crystal data

C30H20N2O4	F(000) = 492
Mr = 472.48	Dx = 1.353 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.9235 (11) Å	θ = 22.5–25°
b = 8.7879 (10) Å	µ = 0.74 mm^−1
c = 13.4152 (17) Å	T = 200 K
β = 97.452 (10)°	Rod, colourless
V = 1160.0 (2) Å^3	0.5 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku AFC-7R diffractometer	1928 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.044
Graphite monochromator	θmax = 68.0°, θmin = 4.5°
2θ/ω scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −10→0
Tmin = 0.819, Tmax = 0.929	l = −11→16
2846 measured reflections	3 standard reflections every 150 reflections
2097 independent reflections	intensity decay: −3.1%

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)] = 0.037	H-atom parameters not refined
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0512P)^2 + 0.3663P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2097 reflections	Δρmax = 0.27 e Å^−3
164 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (5)

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

	x	y	z	Uiso*/Ueq
O1	0.53710 (10)	−0.08728 (11)	0.71712 (7)	0.0361 (3)
O2	0.61269 (10)	0.13196 (11)	0.65649 (7)	0.0382 (3)
N1	1.14390 (14)	−0.0570 (2)	1.46662 (10)	0.0559 (4)
C1	1.08008 (14)	−0.04991 (18)	1.38933 (11)	0.0391 (3)
C2	1.00031 (13)	−0.04484 (15)	1.29165 (9)	0.0308 (3)
C3	0.87076 (14)	0.02009 (16)	1.27896 (9)	0.0322 (3)
H3	0.8352	0.0645	1.3346	0.039*
C4	0.79441 (13)	0.01957 (15)	1.18505 (9)	0.0302 (3)
H4	0.7071	0.0657	1.1764	0.036*
C5	0.84404 (13)	−0.04808 (14)	1.10257 (9)	0.0286 (3)
C6	0.97534 (14)	−0.10996 (16)	1.11679 (10)	0.0338 (3)
H6	1.0115	−0.1543	1.0613	0.041*
C7	1.05294 (13)	−0.10768 (16)	1.20969 (10)	0.0338 (3)
H7	1.1422	−0.1489	1.2178	0.041*
C8	0.76131 (13)	−0.05489 (14)	1.00228 (9)	0.0291 (3)
C9	0.67238 (14)	0.06198 (15)	0.96762 (9)	0.0317 (3)
H9	0.6626	0.1471	1.0097	0.038*
C10	0.59778 (14)	0.05626 (15)	0.87251 (10)	0.0332 (3)
H10	0.5378	0.1368	0.8494	0.040*
C11	0.61228 (14)	−0.06819 (15)	0.81233 (9)	0.0307 (3)
C12	0.69804 (16)	−0.18617 (16)	0.84508 (10)	0.0381 (3)
H12	0.7063	−0.2716	0.8029	0.046*
C13	0.77203 (15)	−0.17980 (16)	0.93971 (10)	0.0370 (3)
H13	0.8309	−0.2615	0.9624	0.044*
C14	0.55481 (12)	0.01303 (15)	0.64236 (9)	0.0276 (3)
C15	0.49264 (14)	−0.05225 (15)	0.54361 (9)	0.0322 (3)
H15A	0.3949	−0.0719	0.5463	0.039*
H15B	0.5367	−0.1508	0.5326	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0476 (6)	0.0360 (5)	0.0222 (5)	−0.0092 (4)	−0.0044 (4)	0.0013 (4)
O2	0.0483 (6)	0.0380 (5)	0.0272 (5)	−0.0115 (4)	0.0004 (4)	−0.0013 (4)
N1	0.0421 (7)	0.0909 (12)	0.0319 (7)	0.0151 (7)	−0.0055 (6)	−0.0103 (7)
C1	0.0335 (7)	0.0513 (9)	0.0315 (7)	0.0026 (6)	0.0008 (6)	−0.0043 (6)
C2	0.0331 (7)	0.0325 (7)	0.0256 (6)	−0.0046 (5)	−0.0013 (5)	0.0010 (5)
C3	0.0366 (7)	0.0359 (7)	0.0242 (6)	−0.0012 (5)	0.0037 (5)	−0.0017 (5)
C4	0.0314 (6)	0.0323 (7)	0.0265 (6)	0.0017 (5)	0.0014 (5)	0.0013 (5)
C5	0.0339 (7)	0.0269 (6)	0.0241 (6)	−0.0009 (5)	0.0004 (5)	0.0021 (5)
C6	0.0360 (7)	0.0374 (7)	0.0277 (6)	0.0047 (6)	0.0031 (5)	−0.0021 (5)
C7	0.0308 (6)	0.0369 (7)	0.0326 (7)	0.0026 (5)	0.0005 (5)	0.0000 (5)
C8	0.0327 (6)	0.0300 (6)	0.0243 (6)	−0.0004 (5)	0.0022 (5)	0.0015 (5)
C9	0.0386 (7)	0.0313 (7)	0.0242 (6)	0.0045 (5)	0.0006 (5)	−0.0027 (5)
C10	0.0383 (7)	0.0333 (7)	0.0267 (6)	0.0058 (5)	−0.0015 (5)	0.0010 (5)
C11	0.0365 (7)	0.0332 (7)	0.0210 (6)	−0.0045 (5)	−0.0018 (5)	0.0011 (5)
C12	0.0513 (8)	0.0306 (7)	0.0307 (7)	0.0032 (6)	−0.0007 (6)	−0.0059 (5)
C13	0.0458 (8)	0.0309 (7)	0.0319 (7)	0.0081 (6)	−0.0033 (6)	−0.0013 (5)
C14	0.0267 (6)	0.0321 (6)	0.0236 (6)	0.0008 (5)	0.0013 (5)	−0.0004 (5)
C15	0.0371 (7)	0.0348 (7)	0.0230 (6)	−0.0053 (5)	−0.0021 (5)	0.0000 (5)

Geometric parameters (Å, º)

O1—C14	1.3636 (16)	C7—H7	0.9500
O1—C11	1.4032 (14)	C8—C9	1.3941 (18)
O2—C14	1.1958 (16)	C8—C13	1.3943 (19)
N1—C1	1.1444 (18)	C9—C10	1.3904 (17)
C1—C2	1.4411 (18)	C9—H9	0.9500
C2—C7	1.3913 (19)	C10—C11	1.3780 (19)
C2—C3	1.3966 (19)	C10—H10	0.9500
C3—C4	1.3832 (17)	C11—C12	1.377 (2)
C3—H3	0.9500	C12—C13	1.3827 (19)
C4—C5	1.4006 (18)	C12—H12	0.9500
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.4018 (19)	C14—C15	1.5009 (17)
C5—C8	1.4837 (16)	C15—C15^i	1.509 (2)
C6—C7	1.3776 (18)	C15—H15A	0.9900
C6—H6	0.9500	C15—H15B	0.9900
C14—O1—C11	119.22 (10)	C10—C9—H9	119.4
N1—C1—C2	178.62 (17)	C8—C9—H9	119.4
C7—C2—C3	119.99 (12)	C11—C10—C9	118.86 (12)
C7—C2—C1	119.21 (12)	C11—C10—H10	120.6
C3—C2—C1	120.79 (12)	C9—C10—H10	120.6
C4—C3—C2	119.76 (12)	C12—C11—C10	121.20 (12)
C4—C3—H3	120.1	C12—C11—O1	115.73 (12)
C2—C3—H3	120.1	C10—C11—O1	123.00 (12)
C3—C4—C5	120.91 (12)	C11—C12—C13	119.68 (12)
C3—C4—H4	119.5	C11—C12—H12	120.2
C5—C4—H4	119.5	C13—C12—H12	120.2
C4—C5—C6	118.23 (11)	C12—C13—C8	120.77 (12)
C4—C5—C8	121.58 (11)	C12—C13—H13	119.6
C6—C5—C8	120.19 (12)	C8—C13—H13	119.6
C7—C6—C5	121.21 (12)	O2—C14—O1	123.60 (11)
C7—C6—H6	119.4	O2—C14—C15	127.45 (12)
C5—C6—H6	119.4	O1—C14—C15	108.94 (10)
C6—C7—C2	119.84 (12)	C14—C15—C15^i	112.44 (13)
C6—C7—H7	120.1	C14—C15—H15A	109.1
C2—C7—H7	120.1	C15^i—C15—H15A	109.1
C9—C8—C13	118.27 (12)	C14—C15—H15B	109.1
C9—C8—C5	121.64 (11)	C15^i—C15—H15B	109.1
C13—C8—C5	120.08 (11)	H15A—C15—H15B	107.8
C10—C9—C8	121.20 (12)
C7—C2—C3—C4	1.0 (2)	C5—C8—C9—C10	178.40 (12)
C1—C2—C3—C4	−178.05 (13)	C8—C9—C10—C11	0.4 (2)
C2—C3—C4—C5	1.3 (2)	C9—C10—C11—C12	0.5 (2)
C3—C4—C5—C6	−2.48 (19)	C9—C10—C11—O1	177.17 (12)
C3—C4—C5—C8	177.59 (12)	C14—O1—C11—C12	−118.60 (14)
C4—C5—C6—C7	1.4 (2)	C14—O1—C11—C10	64.53 (17)
C8—C5—C6—C7	−178.68 (12)	C10—C11—C12—C13	−0.5 (2)
C5—C6—C7—C2	0.8 (2)	O1—C11—C12—C13	−177.44 (12)
C3—C2—C7—C6	−2.0 (2)	C11—C12—C13—C8	−0.3 (2)
C1—C2—C7—C6	177.00 (13)	C9—C8—C13—C12	1.1 (2)
C4—C5—C8—C9	34.72 (19)	C5—C8—C13—C12	−178.45 (13)
C6—C5—C8—C9	−145.21 (14)	C11—O1—C14—O2	−13.53 (19)
C4—C5—C8—C13	−145.76 (14)	C11—O1—C14—C15	165.67 (11)
C6—C5—C8—C13	34.32 (18)	O2—C14—C15—C15^i	−1.0 (2)
C13—C8—C9—C10	−1.1 (2)	O1—C14—C15—C15^i	179.81 (14)

Symmetry code: (i) −x+1, −y, −z+1.