Piperidinium 3-[(4-hydroxy-5,7-di­methyl-2-oxo-2H-chromen-3-yl)­phenyl­methyl]-5,7-di­methyl-2-oxo-2H-chromen-4-olate

In the title salt, C₅H₁₂N⁺·C₂₉H₂₃O₆^-, both benzo­pyran systems are planar. Intermolecular N-H...O hydrogen bonds and a short O-H...O intramolecular hydrogen bond are observed in the structure.

S1. Comment

The title compound, (I), is a derivative of 3,3'-benzylidenebis(4-hydroxycoumarin), also known as dicoumarol. Dicoumarol itself has received attention recently for its pronounced anti-HIV activity studied by various researchers (Thaisrivongs, 1994; Hong et al., 1996). In the present investigation, the X-ray structure analysis of (I) was carried out in order to to study its molecular conformation and hydrogen-bond characteristics.

In the molecule, both benzopyran rings are planar. The bond lengths C10—C4 1.464 (2), C4═C3 1.378 (2) and C3—C2 1.425 (2) Å in one ring system and the disyances C20—C14 1.469 (3), C14═C13 1.392 (2) and C13–C12 1.410 (2) Å in the other indicate conjugation (Alcock & Hough, 1972). A very short O4···O14 intramolecular hydrogen bond is observed. Because of this hydrogen bond, a chelate ring of eight atoms is formed comprised of O4, H4, O14, C14, C13, C21, C3 and C4. The plane of the phenyl ring is inclined at angles of 78.02 (7) and 77.2 (1)°, respectively, with respect to the benzopyran moieties. The dihedral angle between the two benzopyran moieties is 65.4 (1)°. The orientations of the benzopyran moieties about C21 may be described by the torsion angles C13—C21—C3—C4 of -88.7 (2)° and C3—C21—C13—C14 of 61.5 (2)°. The principal bond angles about C21 [113.6 (1), 114.5 (2) and 115.2 (1)°] are widened in comparison with normal tetrahedral values. Steric crowding about the C21 atom may be responsible for this (Valente & Eggleston, 1989). The catalytic piperidine molecule present in the structure is in chair conformation. N—H.·O-type intermolecular hydrogen bonds stabilize the structure.

S2. Experimental

4-Hydroxy-5,7-dimethylcoumarin (0.02 mol) in absolute ethanol (30 ml) was heated on a boiling water bath to produce a clear solution which was then filtered. Benzaldehyde (0.01 mol) was added and the resulting solution was refluxed for 15 h. Piperidine (8 to 10 drops) was then added as a catalyst. Excess solvent was distilled off and the solution was cooled gradually whereupon the title compound was obtained. The product was filtered off, dried and purified in ethanol (m.p. 548 K, yield 62%).

S3. Refinement

All H atoms were fixed and allowed to ride on their carrier atom. The O—H and N—H H atoms were located from difference Fourier maps and were included in the structure-factor calculations with isotropic displacement parameters equal to 1.1U_eq of the carrier atom and the parameters were not refined (N—H = 0.90 Å).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: MolEN (Fair, 1990); data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) showing 50% probabality displacement ellipsoids. H atoms have been omitted for clarity.

3,3'-Benzylidenebis(4-hydroxy-5,7-dimethyl-2H-chromen-2-one)piperidine(1:1) or 3, 3'-(phenylmethylene)bis[4-hydroxy-5,7-dimethyl-2H-1-benzopyran-2-one] piperidine(1:1) or 3, 3'-Benzylidenebis(5,7-dimethyl-4-hydroxycoumarin)

Crystal data

C5H12N^+·C29H23O6^−	Z = 2
Mr = 553.63	F(000) = 588
Triclinic, P1	Dx = 1.266 Mg m^−3
a = 9.568 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.567 (3) Å	Cell parameters from 25 reflections
c = 14.010 (4) Å	θ = 2–25°
α = 83.37 (2)°	µ = 0.09 mm^−1
β = 80.69 (5)°	T = 293 K
γ = 72.08 (3)°	Plate, colourless
V = 1452.3 (6) Å^3	0.25 × 0.20 × 0.12 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	4252 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 25.7°, θmin = 1.5°
ω–2θ scans	h = 0→11
Absorption correction: ψ scan ?	k = −13→14
Tmin = 0.977, Tmax = 0.993	l = −16→17
5659 measured reflections	2 standard reflections every 60 reflections
5305 independent reflections	intensity decay: none

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0654P)^2 + 0.4386P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5305 reflections	Δρmax = 0.25 e Å^−3
375 parameters	Δρmin = −0.23 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: 0.018 (2)

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	−0.48922 (14)	1.06828 (11)	0.82852 (9)	0.0547 (3)
O2	−0.30474 (15)	1.06020 (12)	0.71207 (11)	0.0627 (4)
C2	−0.38803 (19)	1.00487 (16)	0.75751 (13)	0.0488 (4)
C3	−0.38759 (18)	0.88470 (15)	0.74346 (12)	0.0458 (4)
O4	−0.46882 (14)	0.71501 (11)	0.80252 (10)	0.0556 (3)
C4	−0.47806 (19)	0.82968 (15)	0.80665 (13)	0.0458 (4)
C5	−0.6912 (2)	0.85488 (17)	0.94746 (13)	0.0535 (4)
C6	−0.7878 (2)	0.93324 (19)	1.01283 (14)	0.0594 (5)
H6	−0.8570	0.9047	1.0555	0.071*
C7	−0.7870 (2)	1.05248 (18)	1.01815 (13)	0.0560 (5)
C8	−0.6843 (2)	1.09424 (17)	0.95525 (14)	0.0565 (5)
H8	−0.6794	1.1728	0.9580	0.068*
C9	−0.58770 (19)	1.01835 (16)	0.88755 (13)	0.0486 (4)
C10	−0.58765 (18)	0.89898 (15)	0.88075 (12)	0.0461 (4)
O11	0.13161 (13)	0.72429 (12)	0.63824 (9)	0.0550 (3)
O12	−0.02042 (15)	0.87397 (12)	0.56102 (9)	0.0586 (4)
C12	−0.01064 (19)	0.78704 (15)	0.62314 (12)	0.0464 (4)
C13	−0.12942 (18)	0.75008 (15)	0.67682 (12)	0.0439 (4)
O14	−0.20607 (14)	0.60398 (11)	0.78583 (10)	0.0593 (4)
C14	−0.10298 (19)	0.64769 (15)	0.74178 (12)	0.0462 (4)
C15	0.0919 (2)	0.48774 (17)	0.83146 (14)	0.0565 (5)
C16	0.2403 (2)	0.43990 (18)	0.84071 (16)	0.0649 (5)
H16	0.2677	0.3759	0.8872	0.078*
C17	0.3520 (2)	0.48137 (18)	0.78483 (16)	0.0622 (5)
C18	0.3104 (2)	0.57758 (18)	0.71723 (15)	0.0591 (5)
H18	0.3814	0.6084	0.6788	0.071*
C19	0.1621 (2)	0.62780 (15)	0.70702 (13)	0.0482 (4)
C20	0.04966 (19)	0.58582 (15)	0.76094 (12)	0.0459 (4)
C21	−0.28369 (18)	0.82528 (15)	0.65615 (12)	0.0460 (4)
H21	−0.2667	0.8944	0.6135	0.055*
C22	−0.3565 (2)	0.76391 (17)	0.59524 (13)	0.0507 (4)
C23	−0.2925 (2)	0.6466 (2)	0.56593 (15)	0.0654 (5)
H23	−0.2050	0.5985	0.5882	0.079*
C24	−0.3579 (3)	0.6001 (3)	0.50353 (19)	0.0839 (7)
H24	−0.3143	0.5210	0.4850	0.101*
C25	−0.4852 (3)	0.6696 (3)	0.46942 (19)	0.0905 (8)
H25	−0.5273	0.6382	0.4269	0.109*
C26	−0.5507 (3)	0.7848 (3)	0.49753 (18)	0.0851 (7)
H26	−0.6382	0.8320	0.4747	0.102*
C27	−0.4870 (2)	0.8321 (2)	0.56035 (16)	0.0679 (6)
H27	−0.5328	0.9108	0.5793	0.081*
C28	−0.8937 (3)	1.1327 (2)	1.09173 (15)	0.0729 (6)
H281	−0.8732	1.2095	1.0875	0.109*
H282	−0.8827	1.0939	1.1556	0.109*
H283	−0.9933	1.1460	1.0790	0.109*
C29	−0.7000 (3)	0.7263 (2)	0.95098 (18)	0.0756 (7)
H291	−0.7730	0.7142	1.0037	0.113*
H292	−0.6052	0.6697	0.9605	0.113*
H293	−0.7274	0.7131	0.8911	0.113*
C30	0.5121 (3)	0.4237 (2)	0.7987 (2)	0.0895 (8)
H301	0.5737	0.4578	0.7498	0.134*
H302	0.5380	0.3374	0.7933	0.134*
H303	0.5268	0.4390	0.8617	0.134*
C31	−0.0186 (3)	0.4339 (2)	0.89599 (18)	0.0783 (7)
H311	0.0328	0.3688	0.9382	0.117*
H312	−0.0703	0.4028	0.8566	0.117*
H313	−0.0883	0.4958	0.9341	0.117*
C32	0.1463 (3)	1.2374 (2)	0.6908 (2)	0.0888 (8)
H321	0.2202	1.2802	0.6715	0.107*
H322	0.1226	1.2361	0.7608	0.107*
C33	0.0083 (3)	1.3033 (2)	0.6446 (2)	0.0917 (8)
H331	−0.0338	1.3839	0.6685	0.110*
H332	0.0348	1.3129	0.5750	0.110*
C34	−0.1059 (3)	1.2356 (2)	0.6663 (2)	0.0787 (7)
H341	−0.1421	1.2350	0.7351	0.094*
H342	−0.1891	1.2767	0.6313	0.094*
N35	−0.04112 (19)	1.10852 (15)	0.63760 (12)	0.0612 (4)
C36	0.0949 (3)	1.0421 (2)	0.68361 (18)	0.0753 (6)
H361	0.0688	1.0339	0.7534	0.090*
H362	0.1360	0.9611	0.6604	0.090*
C37	0.2075 (3)	1.1091 (2)	0.66003 (19)	0.0775 (6)
H371	0.2398	1.1109	0.5907	0.093*
H372	0.2930	1.0665	0.6925	0.093*
H4	−0.3454	0.6652	0.7866	0.050*
H351	−0.1124	1.0714	0.6551	0.055*
H352	−0.0160	1.1146	0.5729	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0585 (7)	0.0430 (6)	0.0608 (8)	−0.0165 (6)	0.0021 (6)	−0.0066 (6)
O2	0.0610 (8)	0.0516 (7)	0.0760 (9)	−0.0255 (6)	0.0035 (7)	0.0001 (6)
C2	0.0448 (9)	0.0451 (9)	0.0546 (10)	−0.0130 (7)	−0.0052 (8)	0.0012 (7)
C3	0.0425 (9)	0.0447 (9)	0.0479 (9)	−0.0114 (7)	−0.0038 (7)	−0.0014 (7)
O4	0.0519 (7)	0.0456 (7)	0.0685 (8)	−0.0196 (6)	0.0078 (6)	−0.0088 (6)
C4	0.0431 (9)	0.0449 (9)	0.0494 (9)	−0.0136 (7)	−0.0052 (7)	−0.0030 (7)
C5	0.0511 (10)	0.0583 (11)	0.0500 (10)	−0.0183 (8)	−0.0009 (8)	−0.0023 (8)
C6	0.0561 (11)	0.0688 (12)	0.0491 (10)	−0.0175 (9)	0.0039 (9)	−0.0054 (9)
C7	0.0550 (11)	0.0635 (11)	0.0434 (9)	−0.0075 (9)	−0.0061 (8)	−0.0075 (8)
C8	0.0627 (12)	0.0482 (10)	0.0539 (10)	−0.0080 (8)	−0.0083 (9)	−0.0074 (8)
C9	0.0474 (9)	0.0486 (9)	0.0477 (9)	−0.0123 (8)	−0.0059 (8)	−0.0006 (7)
C10	0.0439 (9)	0.0472 (9)	0.0459 (9)	−0.0116 (7)	−0.0056 (7)	−0.0026 (7)
O11	0.0462 (7)	0.0575 (7)	0.0573 (7)	−0.0178 (6)	0.0036 (6)	0.0045 (6)
O12	0.0617 (8)	0.0572 (8)	0.0529 (7)	−0.0216 (6)	0.0034 (6)	0.0075 (6)
C12	0.0495 (10)	0.0445 (9)	0.0438 (9)	−0.0152 (7)	0.0016 (7)	−0.0050 (7)
C13	0.0461 (9)	0.0435 (9)	0.0420 (8)	−0.0158 (7)	0.0004 (7)	−0.0047 (7)
O14	0.0502 (7)	0.0527 (7)	0.0704 (9)	−0.0194 (6)	0.0039 (6)	0.0091 (6)
C14	0.0497 (9)	0.0424 (9)	0.0454 (9)	−0.0153 (7)	0.0028 (7)	−0.0070 (7)
C15	0.0641 (12)	0.0455 (10)	0.0576 (11)	−0.0146 (9)	−0.0066 (9)	−0.0014 (8)
C16	0.0703 (13)	0.0487 (10)	0.0715 (13)	−0.0090 (9)	−0.0193 (11)	0.0028 (9)
C17	0.0569 (11)	0.0530 (11)	0.0751 (13)	−0.0084 (9)	−0.0139 (10)	−0.0126 (10)
C18	0.0506 (10)	0.0577 (11)	0.0677 (12)	−0.0152 (9)	−0.0011 (9)	−0.0115 (9)
C19	0.0503 (10)	0.0429 (9)	0.0502 (9)	−0.0127 (7)	−0.0010 (8)	−0.0086 (7)
C20	0.0512 (9)	0.0403 (8)	0.0449 (9)	−0.0130 (7)	−0.0002 (7)	−0.0081 (7)
C21	0.0450 (9)	0.0450 (9)	0.0470 (9)	−0.0159 (7)	−0.0009 (7)	0.0010 (7)
C22	0.0512 (10)	0.0599 (11)	0.0428 (9)	−0.0226 (8)	−0.0010 (8)	−0.0012 (8)
C23	0.0687 (13)	0.0680 (13)	0.0631 (12)	−0.0218 (10)	−0.0094 (10)	−0.0135 (10)
C24	0.0938 (18)	0.0917 (17)	0.0785 (16)	−0.0373 (15)	−0.0113 (14)	−0.0288 (13)
C25	0.096 (2)	0.126 (2)	0.0703 (15)	−0.0538 (19)	−0.0169 (14)	−0.0233 (16)
C26	0.0685 (14)	0.124 (2)	0.0703 (15)	−0.0338 (15)	−0.0218 (12)	−0.0049 (15)
C27	0.0600 (12)	0.0813 (15)	0.0604 (12)	−0.0166 (11)	−0.0121 (10)	−0.0035 (10)
C28	0.0739 (14)	0.0798 (15)	0.0545 (12)	−0.0067 (12)	−0.0002 (10)	−0.0175 (11)
C29	0.0784 (15)	0.0683 (13)	0.0791 (15)	−0.0366 (12)	0.0245 (12)	−0.0092 (11)
C30	0.0632 (14)	0.0779 (16)	0.121 (2)	−0.0039 (12)	−0.0271 (14)	−0.0057 (15)
C31	0.0850 (16)	0.0707 (14)	0.0729 (14)	−0.0251 (12)	−0.0090 (12)	0.0241 (11)
C32	0.0898 (18)	0.0888 (18)	0.103 (2)	−0.0420 (15)	−0.0182 (15)	−0.0174 (15)
C33	0.105 (2)	0.0591 (14)	0.115 (2)	−0.0268 (14)	−0.0162 (17)	−0.0116 (14)
C34	0.0621 (13)	0.0718 (14)	0.0960 (18)	−0.0118 (11)	0.0005 (12)	−0.0179 (13)
N35	0.0627 (10)	0.0629 (10)	0.0628 (10)	−0.0304 (8)	−0.0001 (8)	−0.0017 (8)
C36	0.0859 (16)	0.0625 (13)	0.0771 (15)	−0.0210 (12)	−0.0172 (13)	0.0037 (11)
C37	0.0649 (13)	0.0906 (17)	0.0765 (15)	−0.0198 (12)	−0.0128 (11)	−0.0081 (13)

Geometric parameters (Å, º)

O1—C9	1.370 (2)	C22—C27	1.387 (3)
O1—C2	1.373 (2)	C23—C24	1.392 (3)
O2—C2	1.227 (2)	C23—H23	0.93
C2—C3	1.425 (2)	C24—C25	1.362 (4)
C3—C4	1.378 (2)	C24—H24	0.93
C3—C21	1.529 (2)	C25—C26	1.361 (4)
O4—C4	1.309 (2)	C25—H25	0.93
O4—H4	1.14	C26—C27	1.391 (3)
C4—C10	1.464 (2)	C26—H26	0.93
C5—C6	1.385 (3)	C27—H27	0.93
C5—C10	1.420 (2)	C28—H281	0.96
C5—C29	1.510 (3)	C28—H282	0.96
C6—C7	1.392 (3)	C28—H283	0.96
C6—H6	0.93	C29—H291	0.96
C7—C8	1.375 (3)	C29—H292	0.96
C7—C28	1.505 (3)	C29—H293	0.96
C8—C9	1.390 (3)	C30—H301	0.96
C8—H8	0.93	C30—H302	0.96
C9—C10	1.395 (2)	C30—H303	0.96
O11—C12	1.369 (2)	C31—H311	0.96
O11—C19	1.379 (2)	C31—H312	0.96
O12—C12	1.243 (2)	C31—H313	0.96
C12—C13	1.410 (2)	C32—C37	1.505 (4)
C13—C14	1.392 (2)	C32—C33	1.512 (4)
C13—C21	1.520 (2)	C32—H321	0.97
O14—C14	1.283 (2)	C32—H322	0.97
O14—H4	1.30	C33—C34	1.505 (4)
C14—C20	1.469 (3)	C33—H331	0.97
C15—C16	1.377 (3)	C33—H332	0.97
C15—C20	1.419 (3)	C34—N35	1.483 (3)
C15—C31	1.513 (3)	C34—H341	0.97
C16—C17	1.394 (3)	C34—H342	0.97
C16—H16	0.93	N35—C36	1.497 (3)
C17—C18	1.378 (3)	N35—H351	0.90
C17—C30	1.506 (3)	N35—H352	0.90
C18—C19	1.382 (3)	C36—C37	1.486 (3)
C18—H18	0.93	C36—H361	0.97
C19—C20	1.392 (2)	C36—H362	0.97
C21—C22	1.534 (3)	C37—H371	0.97
C21—H21	0.98	C37—H372	0.97
C22—C23	1.386 (3)
C9—O1—C2	121.87 (14)	C25—C24—H24	119.7
O2—C2—O1	114.50 (16)	C23—C24—H24	119.7
O2—C2—C3	126.47 (17)	C26—C25—C24	119.9 (2)
O1—C2—C3	119.03 (15)	C26—C25—H25	120.0
C4—C3—C2	119.83 (16)	C24—C25—H25	120.0
C4—C3—C21	124.21 (15)	C25—C26—C27	120.1 (3)
C2—C3—C21	115.96 (15)	C25—C26—H26	120.0
C4—O4—H4	105.8	C27—C26—H26	120.0
O4—C4—C3	121.46 (16)	C22—C27—C26	121.2 (2)
O4—C4—C10	118.22 (15)	C22—C27—H27	119.4
C3—C4—C10	120.32 (16)	C26—C27—H27	119.4
C6—C5—C10	118.42 (18)	C7—C28—H281	109.5
C6—C5—C29	118.47 (17)	C7—C28—H282	109.5
C10—C5—C29	123.10 (17)	H281—C28—H282	109.5
C5—C6—C7	123.50 (18)	C7—C28—H283	109.5
C5—C6—H6	118.2	H281—C28—H283	109.5
C7—C6—H6	118.3	H282—C28—H283	109.5
C8—C7—C6	118.10 (17)	C5—C29—H291	109.5
C8—C7—C28	120.9 (2)	C5—C29—H292	109.5
C6—C7—C28	120.99 (19)	H291—C29—H292	109.5
C7—C8—C9	119.65 (18)	C5—C29—H293	109.5
C7—C8—H8	120.2	H291—C29—H293	109.5
C9—C8—H8	120.2	H292—C29—H293	109.5
O1—C9—C8	115.16 (16)	C17—C30—H301	109.5
O1—C9—C10	121.81 (16)	C17—C30—H302	109.5
C8—C9—C10	123.02 (17)	H301—C30—H302	109.5
C9—C10—C5	117.27 (16)	C17—C30—H303	109.5
C9—C10—C4	116.75 (15)	H301—C30—H303	109.5
C5—C10—C4	125.96 (16)	H302—C30—H303	109.5
C12—O11—C19	121.73 (14)	C15—C31—H311	109.5
O12—C12—O11	114.18 (15)	C15—C31—H312	109.5
O12—C12—C13	126.36 (17)	H311—C31—H312	109.5
O11—C12—C13	119.47 (15)	C15—C31—H313	109.5
C14—C13—C12	120.64 (16)	H311—C31—H313	109.5
C14—C13—C21	123.26 (15)	H312—C31—H313	109.5
C12—C13—C21	116.06 (15)	C37—C32—C33	110.1 (2)
C14—O14—H4	121.4	C37—C32—H321	109.6
O14—C14—C13	123.03 (16)	C33—C32—H321	109.6
O14—C14—C20	118.07 (15)	C37—C32—H322	109.6
C13—C14—C20	118.90 (15)	C33—C32—H322	109.6
C16—C15—C20	118.11 (18)	H321—C32—H322	108.2
C16—C15—C31	119.06 (18)	C34—C33—C32	111.8 (2)
C20—C15—C31	122.84 (18)	C34—C33—H331	109.3
C15—C16—C17	124.12 (19)	C32—C33—H331	109.3
C15—C16—H16	117.9	C34—C33—H332	109.3
C17—C16—H16	117.9	C32—C33—H332	109.3
C18—C17—C16	117.63 (19)	H331—C33—H332	107.9
C18—C17—C30	121.3 (2)	N35—C34—C33	110.55 (19)
C16—C17—C30	121.0 (2)	N35—C34—H341	109.5
C17—C18—C19	119.38 (19)	C33—C34—H341	109.5
C17—C18—H18	120.3	N35—C34—H342	109.5
C19—C18—H18	120.3	C33—C34—H342	109.5
O11—C19—C18	115.02 (16)	H341—C34—H342	108.1
O11—C19—C20	121.33 (16)	C34—N35—C36	112.41 (18)
C18—C19—C20	123.65 (17)	C34—N35—H351	106.7
C19—C20—C15	117.10 (17)	C36—N35—H351	111.0
C19—C20—C14	117.63 (16)	C34—N35—H352	105.6
C15—C20—C14	125.26 (16)	C36—N35—H352	108.8
C13—C21—C3	115.15 (14)	H351—N35—H352	112.2
C13—C21—C22	114.54 (15)	C37—C36—N35	110.52 (19)
C3—C21—C22	113.57 (14)	C37—C36—H361	109.5
C13—C21—H21	103.9	N35—C36—H361	109.5
C3—C21—H21	103.9	C37—C36—H362	109.5
C22—C21—H21	103.9	N35—C36—H362	109.5
C23—C22—C27	117.60 (19)	H361—C36—H362	108.1
C23—C22—C21	123.48 (18)	C36—C37—C32	111.4 (2)
C27—C22—C21	118.69 (18)	C36—C37—H371	109.3
C22—C23—C24	120.6 (2)	C32—C37—H371	109.3
C22—C23—H23	119.7	C36—C37—H372	109.3
C24—C23—H23	119.7	C32—C37—H372	109.3
C25—C24—C23	120.6 (3)	H371—C37—H372	108.0
C9—O1—C2—O2	−178.26 (16)	C15—C16—C17—C30	−179.5 (2)
C9—O1—C2—C3	1.4 (2)	C16—C17—C18—C19	−0.5 (3)
O2—C2—C3—C4	173.40 (18)	C30—C17—C18—C19	−180.0 (2)
O1—C2—C3—C4	−6.2 (3)	C12—O11—C19—C18	−176.84 (16)
O2—C2—C3—C21	−6.9 (3)	C12—O11—C19—C20	3.3 (2)
O1—C2—C3—C21	173.53 (15)	C17—C18—C19—O11	179.40 (17)
C2—C3—C4—O4	−172.33 (16)	C17—C18—C19—C20	−0.8 (3)
C21—C3—C4—O4	8.0 (3)	O11—C19—C20—C15	−178.66 (16)
C2—C3—C4—C10	7.6 (3)	C18—C19—C20—C15	1.5 (3)
C21—C3—C4—C10	−172.10 (16)	O11—C19—C20—C14	0.2 (2)
C10—C5—C6—C7	−1.4 (3)	C18—C19—C20—C14	−179.60 (16)
C29—C5—C6—C7	178.1 (2)	C16—C15—C20—C19	−1.0 (3)
C5—C6—C7—C8	−0.2 (3)	C31—C15—C20—C19	179.30 (19)
C5—C6—C7—C28	−179.21 (19)	C16—C15—C20—C14	−179.74 (17)
C6—C7—C8—C9	1.4 (3)	C31—C15—C20—C14	0.5 (3)
C28—C7—C8—C9	−179.54 (18)	O14—C14—C20—C19	174.88 (16)
C2—O1—C9—C8	−179.32 (16)	C13—C14—C20—C19	−4.8 (2)
C2—O1—C9—C10	2.0 (3)	O14—C14—C20—C15	−6.4 (3)
C7—C8—C9—O1	−179.74 (17)	C13—C14—C20—C15	173.93 (17)
C7—C8—C9—C10	−1.1 (3)	C14—C13—C21—C3	61.5 (2)
O1—C9—C10—C5	178.00 (16)	C12—C13—C21—C3	−120.79 (17)
C8—C9—C10—C5	−0.6 (3)	C14—C13—C21—C22	−72.9 (2)
O1—C9—C10—C4	−0.6 (3)	C12—C13—C21—C22	104.79 (17)
C8—C9—C10—C4	−179.19 (17)	C4—C3—C21—C13	−88.7 (2)
C6—C5—C10—C9	1.8 (3)	C2—C3—C21—C13	91.61 (18)
C29—C5—C10—C9	−177.7 (2)	C4—C3—C21—C22	46.2 (2)
C6—C5—C10—C4	−179.76 (18)	C2—C3—C21—C22	−133.53 (17)
C29—C5—C10—C4	0.7 (3)	C13—C21—C22—C23	3.9 (2)
O4—C4—C10—C9	175.71 (16)	C3—C21—C22—C23	−131.28 (18)
C3—C4—C10—C9	−4.2 (3)	C13—C21—C22—C27	−170.42 (16)
O4—C4—C10—C5	−2.8 (3)	C3—C21—C22—C27	54.4 (2)
C3—C4—C10—C5	177.31 (17)	C27—C22—C23—C24	0.1 (3)
C19—O11—C12—O12	177.77 (15)	C21—C22—C23—C24	−174.19 (19)
C19—O11—C12—C13	−2.1 (2)	C22—C23—C24—C25	0.6 (4)
O12—C12—C13—C14	177.41 (17)	C23—C24—C25—C26	−1.0 (4)
O11—C12—C13—C14	−2.7 (2)	C24—C25—C26—C27	0.6 (4)
O12—C12—C13—C21	−0.3 (3)	C23—C22—C27—C26	−0.6 (3)
O11—C12—C13—C21	179.54 (14)	C21—C22—C27—C26	174.06 (19)
C12—C13—C14—O14	−173.59 (16)	C25—C26—C27—C22	0.2 (4)
C21—C13—C14—O14	4.0 (3)	C37—C32—C33—C34	55.0 (3)
C12—C13—C14—C20	6.1 (2)	C32—C33—C34—N35	−54.5 (3)
C21—C13—C14—C20	−176.30 (15)	C33—C34—N35—C36	55.1 (3)
C20—C15—C16—C17	−0.3 (3)	C34—N35—C36—C37	−56.5 (3)
C31—C15—C16—C17	179.5 (2)	N35—C36—C37—C32	56.7 (3)
C15—C16—C17—C18	1.1 (3)	C33—C32—C37—C36	−56.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O14	1.14	1.30	2.432 (2)	169
N35—H351···O2	0.90	1.92	2.765 (3)	155
N35—H352···O12^i	0.90	1.85	2.747 (2)	175

Symmetry code: (i) −x, −y+2, −z+1.