Crystal structure of dimethyl 3,3'-[(4-fluoro-phen-yl)methyl-ene]bis-(1H-indole-2-carboxyl-ate).

In the title compound, C27H21FN2O4, the mean planes of the indole ring systems (r.m.s. deviations = 0.0263 and 0.0160 Å) are approximately perpendic-ular to one another, making a dihedral angle of 84.0 (5)°; the fluoro-benzene ring is twisted with respect to the mean planes of the two indole ring systems at 89.5 (5) and 84.6 (3)°. In the crystal, pairs of N-H⋯O hydrogen bonds link the mol-ecules into inversion dimers, which are further linked by N-H⋯O hydrogen bonds into supra-molecular chains propagated along the b-axis direction. Weak C-H⋯π inter-actions are observed between neighbouring chains.

Chemical context

Bis(indol­yl)methane derivatives have been found widely in various terrestrial and marine natural resources (Porter et al., 1977 ▸; Sundberg, 1996 ▸), and have many applications in pharmaceuticals with diverse activities, such as anti­cancer, anti­leishmanial and anti­hyperlipidemic (Chang et al., 1999 ▸; Ge et al., 1999 ▸). Other, bis­(indoly)methane derivatives can also be used as a precursor for MRI contrast agents (Ni, 2008 ▸). In recent years, we have reported the synthesis and crystal structures of some similar compounds (Sun et al., 2012 ▸, 2013 ▸, 2014 ▸; Li et al., 2014 ▸; Lu et al., 2014 ▸). Now we report herein another bis­(indoly)methane compound.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1 ▸. The two indole ring systems are approximately planar, the maximum deviations being 0.049 (3) and 0.030 (2) Å; the mean planes of the two indole ring systems nearly perpen­dicular to each other [dihedral angle = 84.0 (5)°] while the benzene ring (C22–C27) is twisted to the N1/C2–C9 and N2/C12–C19 indole ring systems by dihedral angles of 89.5 (5) and 84.6 (3)°, respectively. The carboxyl groups are approximately co-planar with the attached indole ring systems, the dihedral angles between the carboxyl groups and the mean planes of attached indole ring systems are 10.8 (3) and 12.3 (4)°.

Figure 1

The mol­ecular structure of the title mol­ecule, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Supra­molecular features

In the crystal, pairs of N1—H1A⋯O4i [symmetry code: (i) x, y + 1, z] hydrogen bonds link the mol­ecules into inversion dimmers, which are further linked by N2—H2A⋯O2ii [symmetry code: (ii) 1 − x, 1 − y, 1 − z] hydrogen bonds into supra­molecular chains propagated along the b axis (Table 1 ▸ and Fig. 2 ▸). Weak C—H⋯π inter­actions are also observed between neighbouring chains.

Table 1

Hydrogen-bond geometry (, )

Cg1, Cg4 and Cg5 are the centroids of the N1-ring, C14-ring and C22-ring.

DHA	DH	HA	D A	DHA
N1H1AO4i	0.86	2.07	2.903(3)	162
N2H2AO2ii	0.86	2.07	2.892(3)	159
C4H4A Cg5	0.93	2.82	3.622(3)	146
C5H5B Cg4iii	0.93	2.84	3.705(3)	156
C26H26A Cg1iv	0.93	2.69	3.587(4)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 2

A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Database survey

Several similar structures have been reported previously, i.e. diethyl 3,3′-(phenyl­methyl­ene)bis­(1H-indole-2-carboxyl­ate) (Sun et al., 2012 ▸), dimethyl 3,3′-(phenyl­methyl­ene)bis­(1H-indole-2-carboxyl­ate) (Sun et al., 2013 ▸), dimethyl 3,3′-[(4-chloro­phen­yl) methyl­ene]bis­(1H-indole-2-carboxyl­ate) (Li et al., 2014 ▸), dimethyl 3,3′-[(3-nitro­phen­yl) methyl­ene]bis­(1H-indole-2-carboxyl­ate) ethanol monosolvate (Sun et al., 2014 ▸) and dimethyl 3,3′-[(3-fluoro­phen­yl)methyl­ene]bis­(1H-indole-2-carboxyl­ate) (Lu et al., 2014 ▸). In those structures, the two indole ring systems are also nearly perpendicular to each other, the dihedral angles being 82.0 (5), 84.5 (5), 79.5 (4), 89.3 (5) and 87.8 (5)°, respectively.

Synthesis and crystallization

Methyl indole-2-carboxyl­ate (17.5 g, 100 mmol) was dissolved in 200 ml methanol; commercially available 4-fluoro­benzaldehyde (6.2 g, 50 mmol) was added and the mixture was heated to reflux temperature. Concentrated HCl (3.7 ml) was added and the reaction was left for 1 h. After cooling the white product was filtered off and washed thoroughly with methanol. The reaction was monitored by TLC (CHCl3:hexane = 1:1). Yield was 90%. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a methanol solution. 1H NMR (300 MHz, DMSO) δ 11.81 (s, 2H), 7.59–7.36 (m, 3H), 7.13 (dd, J = 15.1, 7.2 Hz, 6H), 6.71 (t, J = 7.5 Hz, 2H), 6.60 (d, J = 8.3 Hz, 2H), 3.77 (s, 6H).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were positioned geometrically with N—H = 0.86 Å and C—H = 0.93–0.98 Å, and constrained to ride on their parent atoms. U iso(H) = xU eq(C,N), where x = 1.5 for methyl H atoms and 1.2 for the others.

Table 2

Experimental details

Crystal data
Chemical formula	C27H21FN2O4
M r	456.46
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c ()	9.7270(19), 10.122(2), 13.441(3)
, , ()	68.15(3), 73.69(3), 89.73(3)
V (3)	1171.4(4)
Z	2
Radiation type	Mo K
(mm1)	0.09
Crystal size (mm)	0.30 0.20 0.10
Data collection
Diffractometer	Nonius CAD-4 diffractometer
Absorption correction	scan (North et al., 1968 ▸)
T min, T max	0.973, 0.991
No. of measured, independent and observed [I > 2(I)] reflections	4587, 4311, 2756
R int	0.040
(sin /)max (1)	0.603
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.054, 0.147, 1.00
No. of reflections	4311
No. of parameters	307
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.16, 0.18

Computer programs: CAD-4 EXPRESS (EnrafNonius, 1994 ▸), XCAD4 (Harms Wocadlo, 1995 ▸), SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901501628X/xu5870sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901501628X/xu5870Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901501628X/xu5870Isup3.cml

CCDC reference: 1421585

Additional supporting information: crystallographic information; 3D view; checkCIF report

C27H21FN2O4	Z = 2
Mr = 456.46	F(000) = 476
Triclinic, P1	Dx = 1.294 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7270 (19) Å	Cell parameters from 25 reflections
b = 10.122 (2) Å	θ = 9–13°
c = 13.441 (3) Å	µ = 0.09 mm−1
α = 68.15 (3)°	T = 293 K
β = 73.69 (3)°	Block, colorless
γ = 89.73 (3)°	0.30 × 0.20 × 0.10 mm
V = 1171.4 (4) Å3

Nonius CAD-4 diffractometer	2756 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 25.4°, θmin = 1.7°
ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.973, Tmax = 0.991	l = −15→16
4587 measured reflections	3 standard reflections every 200 reflections
4311 independent reflections	intensity decay: 1%

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3
4311 reflections	(Δ/σ)max < 0.001
307 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.6800 (2)	1.1318 (2)	0.27546 (18)	0.0513 (6)
H1A	0.6727	1.1742	0.3213	0.062*
C1	0.7071 (2)	0.8060 (2)	0.20833 (19)	0.0382 (5)
H1B	0.7844	0.7680	0.2409	0.046*
O1	0.6875 (3)	0.9631 (2)	0.47878 (17)	0.0872 (7)
N2	0.4265 (2)	0.49916 (19)	0.39447 (16)	0.0465 (5)
H2A	0.3987	0.4100	0.4353	0.056*
O2	0.7270 (2)	0.77039 (17)	0.43616 (14)	0.0554 (5)
C2	0.6977 (2)	0.9558 (2)	0.2084 (2)	0.0386 (5)
O3	0.8103 (2)	0.52264 (18)	0.29747 (17)	0.0636 (5)
C3	0.6956 (2)	1.0904 (2)	0.1197 (2)	0.0395 (6)
O4	0.6464 (2)	0.32942 (17)	0.38907 (16)	0.0633 (5)
C4	0.7094 (3)	1.1362 (2)	0.0044 (2)	0.0479 (6)
H4A	0.7174	1.0699	−0.0292	0.058*
F	0.8690 (2)	0.7816 (2)	−0.22102 (14)	0.0854 (6)
C5	0.7110 (3)	1.2785 (3)	−0.0579 (2)	0.0559 (7)
H5B	0.7218	1.3084	−0.1342	0.067*
C6	0.6967 (3)	1.3798 (3)	−0.0089 (3)	0.0627 (8)
H6A	0.6972	1.4757	−0.0534	0.075*
C7	0.6819 (3)	1.3414 (3)	0.1023 (3)	0.0587 (7)
H7A	0.6717	1.4090	0.1348	0.070*
C8	0.6827 (3)	1.1961 (2)	0.1658 (2)	0.0464 (6)
C9	0.6911 (3)	0.9871 (2)	0.3010 (2)	0.0443 (6)
C10	0.7028 (3)	0.8940 (3)	0.4101 (2)	0.0485 (6)
C11	0.7075 (5)	0.8835 (4)	0.5877 (3)	0.1118 (15)
H11A	0.6940	0.9428	0.6304	0.168*
H11B	0.8033	0.8555	0.5773	0.168*
H11C	0.6386	0.7997	0.6272	0.168*
C12	0.5725 (3)	0.7045 (2)	0.28357 (19)	0.0384 (5)
C13	0.4254 (3)	0.7349 (2)	0.30284 (19)	0.0408 (6)
C14	0.3562 (3)	0.8584 (3)	0.2647 (2)	0.0502 (7)
H14A	0.4102	0.9463	0.2179	0.060*
C15	0.2095 (3)	0.8478 (3)	0.2971 (2)	0.0616 (8)
H15A	0.1641	0.9295	0.2720	0.074*
C16	0.1249 (3)	0.7167 (3)	0.3675 (3)	0.0649 (8)
H16A	0.0250	0.7130	0.3880	0.078*
C17	0.1881 (3)	0.5942 (3)	0.4064 (2)	0.0587 (7)
H17A	0.1327	0.5073	0.4538	0.070*
C18	0.3376 (3)	0.6042 (2)	0.37256 (19)	0.0441 (6)
C19	0.5672 (3)	0.5583 (2)	0.34119 (19)	0.0399 (6)
C20	0.6760 (3)	0.4588 (3)	0.3467 (2)	0.0460 (6)
C21	0.9232 (3)	0.4299 (3)	0.2909 (3)	0.0868 (11)
H21A	1.0152	0.4869	0.2540	0.130*
H21B	0.9091	0.3751	0.2490	0.130*
H21C	0.9203	0.3662	0.3653	0.130*
C22	0.7510 (2)	0.8014 (2)	0.09177 (19)	0.0386 (6)
C23	0.6484 (3)	0.7791 (3)	0.0436 (2)	0.0495 (6)
H23A	0.5512	0.7679	0.0834	0.059*
C24	0.6868 (3)	0.7731 (3)	−0.0611 (2)	0.0527 (7)
H24A	0.6170	0.7588	−0.0924	0.063*
C25	0.8294 (3)	0.7885 (3)	−0.1176 (2)	0.0543 (7)
C26	0.9337 (3)	0.8114 (3)	−0.0755 (3)	0.0698 (9)
H26A	1.0304	0.8225	−0.1164	0.084*
C27	0.8938 (3)	0.8180 (3)	0.0304 (2)	0.0581 (7)
H27A	0.9648	0.8339	0.0600	0.070*

	U11	U22	U33	U12	U13	U23
N1	0.0702 (15)	0.0321 (11)	0.0561 (14)	0.0069 (10)	−0.0203 (11)	−0.0209 (10)
C1	0.0363 (13)	0.0298 (12)	0.0485 (14)	0.0036 (10)	−0.0142 (11)	−0.0142 (10)
O1	0.158 (2)	0.0616 (13)	0.0675 (14)	0.0279 (14)	−0.0540 (15)	−0.0379 (12)
N2	0.0553 (13)	0.0267 (10)	0.0480 (12)	−0.0034 (9)	−0.0092 (10)	−0.0086 (9)
O2	0.0728 (13)	0.0346 (10)	0.0542 (11)	0.0024 (8)	−0.0202 (9)	−0.0113 (8)
C2	0.0337 (12)	0.0299 (12)	0.0494 (14)	0.0010 (9)	−0.0114 (11)	−0.0131 (11)
O3	0.0548 (12)	0.0421 (10)	0.0936 (15)	0.0147 (9)	−0.0217 (11)	−0.0262 (10)
C3	0.0353 (13)	0.0292 (12)	0.0511 (15)	0.0006 (10)	−0.0136 (11)	−0.0119 (11)
O4	0.0838 (14)	0.0297 (10)	0.0768 (13)	0.0119 (9)	−0.0245 (11)	−0.0209 (9)
C4	0.0477 (15)	0.0340 (13)	0.0594 (17)	−0.0002 (11)	−0.0175 (13)	−0.0139 (12)
F	0.0945 (14)	0.1087 (15)	0.0628 (11)	0.0344 (11)	−0.0181 (10)	−0.0482 (11)
C5	0.0586 (17)	0.0418 (15)	0.0601 (17)	−0.0014 (12)	−0.0234 (14)	−0.0074 (13)
C6	0.071 (2)	0.0319 (14)	0.078 (2)	0.0014 (13)	−0.0318 (17)	−0.0065 (14)
C7	0.076 (2)	0.0311 (13)	0.074 (2)	0.0059 (13)	−0.0321 (16)	−0.0184 (13)
C8	0.0462 (15)	0.0326 (13)	0.0599 (17)	0.0033 (11)	−0.0173 (12)	−0.0165 (12)
C9	0.0514 (15)	0.0285 (12)	0.0521 (15)	0.0017 (10)	−0.0146 (12)	−0.0152 (11)
C10	0.0569 (17)	0.0396 (14)	0.0511 (16)	−0.0015 (12)	−0.0172 (13)	−0.0190 (12)
C11	0.192 (5)	0.096 (3)	0.071 (2)	0.030 (3)	−0.064 (3)	−0.041 (2)
C12	0.0473 (14)	0.0292 (12)	0.0387 (13)	0.0027 (10)	−0.0115 (11)	−0.0142 (10)
C13	0.0462 (14)	0.0312 (12)	0.0402 (13)	−0.0007 (10)	−0.0068 (11)	−0.0128 (10)
C14	0.0493 (16)	0.0332 (13)	0.0606 (17)	0.0054 (11)	−0.0125 (13)	−0.0128 (12)
C15	0.0484 (17)	0.0472 (16)	0.080 (2)	0.0104 (13)	−0.0138 (15)	−0.0185 (15)
C16	0.0446 (16)	0.0591 (18)	0.075 (2)	0.0039 (13)	−0.0047 (14)	−0.0182 (16)
C17	0.0469 (17)	0.0479 (16)	0.0610 (18)	−0.0098 (13)	−0.0009 (13)	−0.0098 (13)
C18	0.0522 (16)	0.0342 (13)	0.0399 (14)	−0.0009 (11)	−0.0080 (12)	−0.0122 (11)
C19	0.0498 (15)	0.0288 (12)	0.0415 (13)	0.0022 (10)	−0.0135 (11)	−0.0141 (10)
C20	0.0596 (17)	0.0342 (13)	0.0483 (15)	0.0067 (12)	−0.0182 (13)	−0.0190 (11)
C21	0.066 (2)	0.073 (2)	0.130 (3)	0.0350 (18)	−0.033 (2)	−0.047 (2)
C22	0.0382 (13)	0.0279 (11)	0.0464 (14)	0.0021 (9)	−0.0085 (11)	−0.0137 (10)
C23	0.0410 (15)	0.0523 (15)	0.0546 (16)	0.0014 (12)	−0.0085 (12)	−0.0240 (13)
C24	0.0574 (18)	0.0510 (16)	0.0564 (17)	0.0068 (13)	−0.0199 (14)	−0.0259 (13)
C25	0.0631 (19)	0.0544 (16)	0.0486 (16)	0.0144 (13)	−0.0121 (14)	−0.0270 (13)
C26	0.0444 (17)	0.094 (2)	0.072 (2)	0.0155 (16)	−0.0050 (15)	−0.0420 (19)
C27	0.0397 (15)	0.0742 (19)	0.0661 (19)	0.0057 (13)	−0.0142 (14)	−0.0345 (16)

N1—C8	1.364 (3)	C11—H11A	0.9600
N1—C9	1.386 (3)	C11—H11B	0.9600
N1—H1A	0.8600	C11—H11C	0.9600
C1—C12	1.513 (3)	C12—C19	1.385 (3)
C1—C2	1.519 (3)	C12—C13	1.434 (3)
C1—C22	1.522 (3)	C13—C14	1.410 (3)
C1—H1B	0.9800	C13—C18	1.413 (3)
O1—C10	1.328 (3)	C14—C15	1.362 (4)
O1—C11	1.453 (4)	C14—H14A	0.9300
N2—C18	1.366 (3)	C15—C16	1.403 (4)
N2—C19	1.372 (3)	C15—H15A	0.9300
N2—H2A	0.8600	C16—C17	1.371 (4)
O2—C10	1.209 (3)	C16—H16A	0.9300
C2—C9	1.379 (3)	C17—C18	1.389 (4)
C2—C3	1.443 (3)	C17—H17A	0.9300
O3—C20	1.329 (3)	C19—C20	1.456 (3)
O3—C21	1.446 (3)	C21—H21A	0.9600
C3—C4	1.409 (3)	C21—H21B	0.9600
C3—C8	1.411 (3)	C21—H21C	0.9600
O4—C20	1.216 (3)	C22—C27	1.376 (3)
C4—C5	1.368 (3)	C22—C23	1.393 (3)
C4—H4A	0.9300	C23—C24	1.375 (3)
F—C25	1.363 (3)	C23—H23A	0.9300
C5—C6	1.398 (4)	C24—C25	1.359 (4)
C5—H5B	0.9300	C24—H24A	0.9300
C6—C7	1.362 (4)	C25—C26	1.351 (4)
C6—H6A	0.9300	C26—C27	1.393 (4)
C7—C8	1.400 (3)	C26—H26A	0.9300
C7—H7A	0.9300	C27—H27A	0.9300
C9—C10	1.454 (3)
C8—N1—C9	108.9 (2)	C13—C12—C1	128.2 (2)
C8—N1—H1A	125.6	C14—C13—C18	117.7 (2)
C9—N1—H1A	125.6	C14—C13—C12	134.8 (2)
C12—C1—C2	113.09 (19)	C18—C13—C12	107.4 (2)
C12—C1—C22	110.81 (18)	C15—C14—C13	119.3 (2)
C2—C1—C22	114.33 (18)	C15—C14—H14A	120.3
C12—C1—H1B	106.0	C13—C14—H14A	120.3
C2—C1—H1B	106.0	C14—C15—C16	121.7 (3)
C22—C1—H1B	106.0	C14—C15—H15A	119.1
C10—O1—C11	116.2 (2)	C16—C15—H15A	119.1
C18—N2—C19	109.29 (19)	C17—C16—C15	120.7 (3)
C18—N2—H2A	125.4	C17—C16—H16A	119.6
C19—N2—H2A	125.4	C15—C16—H16A	119.6
C9—C2—C3	105.93 (19)	C16—C17—C18	117.8 (2)
C9—C2—C1	123.5 (2)	C16—C17—H17A	121.1
C3—C2—C1	130.5 (2)	C18—C17—H17A	121.1
C20—O3—C21	116.5 (2)	N2—C18—C17	129.7 (2)
C4—C3—C8	117.4 (2)	N2—C18—C13	107.6 (2)
C4—C3—C2	135.5 (2)	C17—C18—C13	122.7 (2)
C8—C3—C2	107.1 (2)	N2—C19—C12	109.9 (2)
C5—C4—C3	119.7 (2)	N2—C19—C20	116.4 (2)
C5—C4—H4A	120.2	C12—C19—C20	133.4 (2)
C3—C4—H4A	120.2	O4—C20—O3	123.3 (2)
C4—C5—C6	121.3 (3)	O4—C20—C19	123.0 (2)
C4—C5—H5B	119.4	O3—C20—C19	113.7 (2)
C6—C5—H5B	119.4	O3—C21—H21A	109.5
C7—C6—C5	121.5 (2)	O3—C21—H21B	109.5
C7—C6—H6A	119.2	H21A—C21—H21B	109.5
C5—C6—H6A	119.2	O3—C21—H21C	109.5
C6—C7—C8	117.3 (3)	H21A—C21—H21C	109.5
C6—C7—H7A	121.4	H21B—C21—H21C	109.5
C8—C7—H7A	121.4	C27—C22—C23	117.5 (2)
N1—C8—C7	128.8 (2)	C27—C22—C1	121.2 (2)
N1—C8—C3	108.2 (2)	C23—C22—C1	121.4 (2)
C7—C8—C3	122.9 (2)	C24—C23—C22	121.9 (2)
C2—C9—N1	109.8 (2)	C24—C23—H23A	119.0
C2—C9—C10	129.3 (2)	C22—C23—H23A	119.0
N1—C9—C10	120.8 (2)	C25—C24—C23	118.2 (3)
O2—C10—O1	123.1 (2)	C25—C24—H24A	120.9
O2—C10—C9	125.4 (2)	C23—C24—H24A	120.9
O1—C10—C9	111.4 (2)	C26—C25—C24	122.6 (3)
O1—C11—H11A	109.5	C26—C25—F	118.6 (3)
O1—C11—H11B	109.5	C24—C25—F	118.8 (3)
H11A—C11—H11B	109.5	C25—C26—C27	118.8 (3)
O1—C11—H11C	109.5	C25—C26—H26A	120.6
H11A—C11—H11C	109.5	C27—C26—H26A	120.6
H11B—C11—H11C	109.5	C22—C27—C26	121.1 (3)
C19—C12—C13	105.8 (2)	C22—C27—H27A	119.5
C19—C12—C1	125.9 (2)	C26—C27—H27A	119.5
C12—C1—C2—C9	66.6 (3)	C1—C12—C13—C18	175.5 (2)
C22—C1—C2—C9	−165.3 (2)	C18—C13—C14—C15	0.8 (4)
C12—C1—C2—C3	−114.3 (3)	C12—C13—C14—C15	177.2 (3)
C22—C1—C2—C3	13.8 (3)	C13—C14—C15—C16	−0.1 (4)
C9—C2—C3—C4	174.6 (3)	C14—C15—C16—C17	0.1 (5)
C1—C2—C3—C4	−4.6 (4)	C15—C16—C17—C18	−0.8 (4)
C9—C2—C3—C8	−2.0 (3)	C19—N2—C18—C17	178.4 (3)
C1—C2—C3—C8	178.8 (2)	C19—N2—C18—C13	−0.1 (3)
C8—C3—C4—C5	0.5 (3)	C16—C17—C18—N2	−176.8 (3)
C2—C3—C4—C5	−175.8 (3)	C16—C17—C18—C13	1.6 (4)
C3—C4—C5—C6	−1.1 (4)	C14—C13—C18—N2	177.1 (2)
C4—C5—C6—C7	0.6 (4)	C12—C13—C18—N2	−0.2 (3)
C5—C6—C7—C8	0.5 (4)	C14—C13—C18—C17	−1.6 (4)
C9—N1—C8—C7	−176.3 (3)	C12—C13—C18—C17	−178.8 (2)
C9—N1—C8—C3	0.1 (3)	C18—N2—C19—C12	0.3 (3)
C6—C7—C8—N1	174.9 (3)	C18—N2—C19—C20	−174.2 (2)
C6—C7—C8—C3	−1.0 (4)	C13—C12—C19—N2	−0.4 (3)
C4—C3—C8—N1	−176.1 (2)	C1—C12—C19—N2	−175.7 (2)
C2—C3—C8—N1	1.2 (3)	C13—C12—C19—C20	172.8 (2)
C4—C3—C8—C7	0.6 (4)	C1—C12—C19—C20	−2.5 (4)
C2—C3—C8—C7	177.9 (2)	C21—O3—C20—O4	3.2 (4)
C3—C2—C9—N1	2.1 (3)	C21—O3—C20—C19	−174.6 (2)
C1—C2—C9—N1	−178.7 (2)	N2—C19—C20—O4	4.8 (4)
C3—C2—C9—C10	−173.9 (2)	C12—C19—C20—O4	−168.0 (3)
C1—C2—C9—C10	5.3 (4)	N2—C19—C20—O3	−177.5 (2)
C8—N1—C9—C2	−1.4 (3)	C12—C19—C20—O3	9.7 (4)
C8—N1—C9—C10	175.0 (2)	C12—C1—C22—C27	−145.7 (2)
C11—O1—C10—O2	2.5 (4)	C2—C1—C22—C27	85.1 (3)
C11—O1—C10—C9	−175.7 (3)	C12—C1—C22—C23	33.8 (3)
C2—C9—C10—O2	3.3 (4)	C2—C1—C22—C23	−95.4 (3)
N1—C9—C10—O2	−172.3 (2)	C27—C22—C23—C24	0.2 (4)
C2—C9—C10—O1	−178.5 (2)	C1—C22—C23—C24	−179.3 (2)
N1—C9—C10—O1	5.9 (3)	C22—C23—C24—C25	0.5 (4)
C2—C1—C12—C19	−148.6 (2)	C23—C24—C25—C26	−1.0 (4)
C22—C1—C12—C19	81.6 (3)	C23—C24—C25—F	179.4 (2)
C2—C1—C12—C13	37.2 (3)	C24—C25—C26—C27	0.6 (5)
C22—C1—C12—C13	−92.7 (3)	F—C25—C26—C27	−179.8 (2)
C19—C12—C13—C14	−176.2 (3)	C23—C22—C27—C26	−0.6 (4)
C1—C12—C13—C14	−1.1 (4)	C1—C22—C27—C26	178.9 (2)
C19—C12—C13—C18	0.4 (2)	C25—C26—C27—C22	0.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4i	0.86	2.07	2.903 (3)	162
N2—H2A···O2ii	0.86	2.07	2.892 (3)	159
C4—H4A···Cg5	0.93	2.82	3.622 (3)	146
C5—H5B···Cg4iii	0.93	2.84	3.705 (3)	156
C26—H26A···Cg1iv	0.93	2.69	3.587 (4)	161