[N,N'-(4-Methyl-4-azaheptane-1,7-diyl-[kappa]N)bis(4-methoxysalicylideniminato-[kappa]⁴O,N,N',O')]cobalt(II) ethanol hemisolvate

The title compound, [Co(C₂₃H₂₉N₃O₄)]·0.5C₂H₆O or [Co^II{(4-MeO-sal)₂Medpt}]·0.5CH₃CH₂OH [(4-MeO-sal)₂Medpt is N,N'-(4-methyl-4-aza­heptane-1,7-diyl)­bis(4-methoxysalicyl­iden­iminate)], obtained through the reaction of H₂[(4-MeO-sal)₂Medpt] and Co(CH₃COO)₂ in refluxing ethanol under an atmosphere of ultrapure nitro­gen, has the usual pseudo-trigonal-bipyramidal coordination arrangement previously found for this class of (sal)₂Rdpt compounds. The O-Co-O bond angle [120.4 (1)°] is significantly smaller than the corresponding values previously found for most non-O₂-bound [Co^II{(sal)₂Medpt}]-type mol­ecules (observed range 126.9-138.6°), whereas the equatorial Co-N bond [2.185 (3) Å] is relatively long.

S1. Comment

Cobalt compounds able to react reversibly with dioxygen have captured the attention of several research groups during the past three decades (Rybak-Akimova et al., 1997, and references therein) and many structural studies have been performed on the parent cobalt complexes, [CoL], as well as on some dioxygen adducts, [CoL(O₂)] (Cini & Orioli, 1983, 1981; Huie et al., 1979). The L ligand is a Schiff base in most cases and belongs to the H₂(sal)₂en or H₂(sal)₂Medpt families (Anderson et al., 1998; Boca et al., 1998; Kingma et al., 1993; Polishchuk et al., 1991; Ready & Jacobsen, 1999; Sato et al., 1999). It has been observed that small structural changes to the cobalt complexes upon oxygenation correspond to relatively low activation energies for dioxygen binding (Rybak-Akimova et al., 1997). On the other hand, it has been found that the penta-coordinate cobalt complexes from the (sal)₂Medpt family span a wide range of values for the O—Co—O bond angle, which measures the cavity through which the entering dioxygen molecule approaches the metal (Boca et al., 1998, and references therein; Cini & Orioli, 1983, 1982).

On the basis of this reasoning, and as a continuation of the synthetic work and structural studies performed by this group during the past two decades, single crystals of the title compound, (I), have been prepared from deaerated ethanol solutions and analysed via X-ray diffraction. Reported here is the structure of (I), whose reactivity with dioxyen in dimethylsulfoxide solution, as determined via electrochemical methods, was previously reported by Zanello et al. (1983). \sch

The complex molecule is represented in Fig. 1 and selected geometrical parameters are listed in Table 1. The coordination sphere has the usual trigonal bipyramidal arrangement found for this type of complex, where the oxygen donors from the sal moiety and the Nsp³ donor from the dtp chain are considered as occupying the equatorial positions, and the Nsp² donors are at the apical positions. The Co—O bond distances are equal to within one s.u. and average 1.977 (2) Å, in agreement with the values previously found for analogous complexes (Boca et al., 1998, and references therein). The axial Co-Nsp² bond lengths are also equal to within one s.u. and average 2.060 (3) Å, a value which compares well with the corresponding lengths for analogous complexes. The equatorial Co-Nsp³ bond length found in (I), 2.185 (3) Å, follows the trend already noted for this class of compounds, but it is the largest such value observed so far; the range found in the literature varies from 2.123 (2) Å (Boca et al., 1998) to 2.170 (9) Å (Cini & Orioli, 1982).

The N1—Co—N2 bond angle of 176.9 (1)° is close to the idealized value (180°) for the axial donors of a trigonal bipyramid. The bond angles which involve one equatorial and one axial donor are also close to the idealized value of 90°; the largest deviation in (I) is 1.9 (1)° for N2—Co—O1. These angles are in good agreement with the values previously reported for analogous complexes. Interestingly, the N3—Co—O1 [124.7 (1)°] and N3—Co—O2 [115.0 (1)°] bond angles differ by ca 10°. This fact has to be compared with the small value [120.4 (1)°] of the O1—Co—O2 bond angle.

It must be noted that the solid-state molecular structures of metal complexes of (sal)₂Medpt-type dianions usually show two distinct sets, of three atoms each, around the Nsp³ donor (Boca et al., 1998; Cini & Orioli, 1982; Cini, 1983, 1986). Once this type of disorder happens, the equatorial set of donors (atoms O1 and O2) has an almost strict C₂ symmetry around the N3—Co vector. By contrast, the present structure does not have any detectable disorder around N3, the equatorial set of donors is far from C₂ symmetry, the O1—Co—O2 bond angle is narrow and the Co—N3 bond distance is long. The only other example of an X-ray structure for a cobalt complex from the (sal)₂Medpt family which has no disorder around N3 is the non-dioxygenated molecule of [Co{(sal)₂Medpt}(O₂)][Co{(sal)₂Medpt}]·2C₆H₆ (Cini & Orioli, 1983), the O1—Co—O2 bond angle being narrow also for that molecule, at 120.4 (7)°.

In conclusion, it seems that once the Co—N3 bond becomes shorter, the ligand forces the O1—Co—O2 angle to open. Furthermore, a short Co—N3 vector and the disorder around N3 seem to be related. These effects on the geometrical parameters of cobalt complexes with the (sal)₂Rdpt-type dianions can be due to specific electronic contributions from the ligand itself (tuned by the substituents), or can arise from several types of intermolecular forces or from both these sources. Of course, much more work, both experimental and theoretical, is needed to clarify the matter.

The analysis of the crystal packing in (I) shows several short O···H—C contacts which can be considered hydrogen-bond type interactions (Table 2) (Taylor & Kennard, 1982). Selected examples are: C14—H14···O3(x, -y, z + 1/2) 2.71 Å, C12—H12···O4(1 - x, -y, 1 - z) 2.62 Å and C22—H22C···O1E(x + 1/2, y - 1/2, z) 2.46 Å.

S2. Experimental

Crystals of (I) were obtained as dark-brown prisms from an absolute ethanol solution under an atmosphere of ultrapure nitrogen, following the procedure previously reported by Zanello et al. (1983) and references therein.

S3. Refinement

All the H atoms of the complex molecule were set in their calculated positions and allowed to ride on their respective parent atoms during refinement, with U_iso(H) constrained to 1.2U_eq of the parent atom. The H atoms for the disordered solvent molecule were not included at all.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS and XEMP (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 (Farrugia, 1998); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of the [Co^II{(4-MeO-sal)2Medpt}] cation in (I) showing 30% probability displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii and the solvent has been omitted for clarity.

N,N'-(4-methyl-4-azaheptane-1,7-diyl-κN)bis(4-methoxysalicylideneiminato- κ⁴O,N,N',O')cobalt(II)] ethanol hemisolvate

Crystal data

[Co(C23H29N3O4)]·0.5C2H6O	F(000) = 2080
Mr = 493.46	Dx = 1.335 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.793 (1) Å	Cell parameters from 42 reflections
b = 13.685 (2) Å	θ = 5–18°
c = 21.244 (1) Å	µ = 0.74 mm^−1
β = 92.11 (1)°	T = 293 K
V = 4878.8 (8) Å^3	Prism, brown
Z = 8	0.4 × 0.3 × 0.2 mm

Data collection

Siemens P4 diffractometer	3250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 26.5°, θmin = 1.9°
ω scans	h = −1→21
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	k = −1→17
Tmin = 0.766, Tmax = 0.863	l = −26→26
6080 measured reflections	3 standard reflections every 97 reflections
5067 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.03	Calculated w = 1/[σ^2(Fo^2) + (0.0751P)^2 + 2.313P] where P = (Fo^2 + 2Fc^2)/3
5067 reflections	(Δ/σ)max < 0.001
308 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.24 e Å^−3

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.

Once all the atoms of the complex molecule had been located and their positional parameters refined at the isotropic stage, three new peaks were found in the difference Fourier map. These peaks were in the proximity of a crystallographic twofold axis and were interpreted as the O and two C atoms of a co-crystallized and disordered ethanol molecule. The three atoms (O1E, C1E and C2E) were given occupancy factors of 0.5 and were included in the subsequent cycles of refinement. The bond distances were restrained to 1.45 (1) Å (O1E—C1E) and 1.53 (1) Å (C1E—C2E).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.18833 (2)	0.25192 (3)	0.29477 (2)	0.03848 (16)
O1	0.14350 (15)	0.16026 (17)	0.23095 (10)	0.0455 (6)
O2	0.30122 (13)	0.24120 (17)	0.32415 (11)	0.0477 (6)
O3	0.1069 (2)	−0.0073 (2)	0.03548 (13)	0.0705 (8)
O4	0.53457 (17)	0.1040 (2)	0.42360 (16)	0.0797 (9)
N1	0.21703 (16)	0.3459 (2)	0.22320 (13)	0.0428 (7)
N2	0.15483 (16)	0.1634 (2)	0.36743 (13)	0.0437 (7)
N3	0.12212 (16)	0.3712 (2)	0.33687 (13)	0.0428 (7)
C1	0.18399 (19)	0.2381 (2)	0.13571 (15)	0.0404 (7)
C2	0.15150 (18)	0.1597 (2)	0.16966 (15)	0.0386 (7)
C3	0.1261 (2)	0.0765 (3)	0.13602 (16)	0.0426 (8)
H3	0.1056	0.0238	0.1578	0.051*
C4	0.1308 (2)	0.0709 (3)	0.07111 (17)	0.0479 (8)
C5	0.1615 (2)	0.1488 (3)	0.03763 (17)	0.0545 (10)
H5	0.1645	0.1456	−0.0059	0.065*
C6	0.1871 (2)	0.2298 (3)	0.06939 (17)	0.0515 (9)
H6	0.2074	0.2818	0.0467	0.062*
C7	0.2131 (2)	0.3272 (3)	0.16419 (16)	0.0456 (8)
H7	0.2306	0.3756	0.1373	0.055*
C8	0.2879 (2)	0.1137 (3)	0.40164 (15)	0.0432 (8)
C9	0.3329 (2)	0.1784 (2)	0.36486 (15)	0.0414 (8)
C10	0.4168 (2)	0.1749 (3)	0.37220 (17)	0.0491 (9)
H10	0.4477	0.2169	0.3489	0.059*
C11	0.4536 (2)	0.1096 (3)	0.41362 (19)	0.0547 (10)
C12	0.4095 (3)	0.0435 (3)	0.4478 (2)	0.0646 (12)
H12	0.4347	−0.0023	0.4740	0.077*
C13	0.3287 (2)	0.0476 (3)	0.44192 (17)	0.0545 (10)
H13	0.2991	0.0047	0.4656	0.065*
C14	0.2025 (2)	0.1131 (3)	0.40268 (15)	0.0451 (8)
H14	0.1797	0.0721	0.4319	0.054*
C15	0.2460 (2)	0.4419 (3)	0.24447 (18)	0.0516 (9)
H15A	0.2718	0.4745	0.2101	0.062*
H15B	0.2851	0.4335	0.2787	0.062*
C16	0.1782 (2)	0.5052 (3)	0.2665 (2)	0.0578 (10)
H16A	0.1606	0.5470	0.2319	0.069*
H16B	0.1988	0.5471	0.3002	0.069*
C17	0.1062 (2)	0.4507 (3)	0.29011 (18)	0.0521 (9)
H17A	0.0711	0.4980	0.3088	0.063*
H17B	0.0776	0.4226	0.2540	0.063*
C18	0.0695 (2)	0.1584 (3)	0.38000 (19)	0.0575 (10)
H18A	0.0605	0.1078	0.4109	0.069*
H18B	0.0397	0.1415	0.3415	0.069*
C19	0.0404 (2)	0.2548 (3)	0.4042 (2)	0.0622 (11)
H19A	0.0730	0.2730	0.4410	0.075*
H19B	−0.0138	0.2467	0.4175	0.075*
C20	0.0421 (2)	0.3380 (3)	0.35662 (19)	0.0580 (10)
H20A	0.0116	0.3179	0.3192	0.070*
H20B	0.0150	0.3937	0.3742	0.070*
C21	0.1695 (2)	0.4090 (3)	0.39172 (17)	0.0566 (10)
H21A	0.1794	0.3570	0.4214	0.085*
H21B	0.1405	0.4603	0.4115	0.085*
H21C	0.2193	0.4340	0.3779	0.085*
C22	0.5824 (3)	0.1774 (4)	0.3975 (3)	0.0925 (17)
H22A	0.6374	0.1644	0.4081	0.139*
H22B	0.5679	0.2399	0.4140	0.139*
H22C	0.5743	0.1777	0.3525	0.139*
C23	0.0749 (4)	−0.0903 (3)	0.0667 (2)	0.0881 (16)
H23A	0.0606	−0.1396	0.0361	0.132*
H23B	0.0284	−0.0711	0.0886	0.132*
H23C	0.1141	−0.1160	0.0962	0.132*
O1E	0.0849 (4)	0.7973 (5)	0.2668 (3)	0.0664 (16)	0.50
C1E	0.0445 (9)	0.8902 (7)	0.2677 (7)	0.271 (16)	0.50
C2E	0.0658 (5)	0.9947 (6)	0.2864 (4)	0.060 (2)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0348 (2)	0.0441 (3)	0.0362 (2)	−0.0004 (2)	−0.00251 (16)	0.0053 (2)
O1	0.0565 (14)	0.0449 (13)	0.0353 (12)	−0.0093 (12)	0.0019 (10)	0.0046 (10)
O2	0.0359 (12)	0.0542 (15)	0.0526 (14)	0.0025 (12)	−0.0039 (10)	0.0140 (12)
O3	0.107 (2)	0.0538 (17)	0.0502 (16)	−0.0112 (17)	0.0023 (16)	−0.0103 (13)
O4	0.0479 (16)	0.089 (2)	0.101 (2)	0.0135 (17)	−0.0175 (16)	0.002 (2)
N1	0.0419 (15)	0.0434 (16)	0.0427 (16)	−0.0060 (13)	−0.0029 (12)	0.0047 (13)
N2	0.0377 (15)	0.0511 (17)	0.0421 (15)	−0.0054 (13)	−0.0023 (12)	0.0107 (14)
N3	0.0354 (14)	0.0491 (17)	0.0435 (15)	0.0012 (13)	−0.0028 (12)	0.0016 (13)
C1	0.0354 (15)	0.048 (2)	0.0380 (16)	−0.0013 (16)	0.0052 (13)	0.0025 (15)
C2	0.0321 (16)	0.0447 (19)	0.0389 (17)	0.0012 (14)	0.0016 (13)	0.0041 (15)
C3	0.0423 (18)	0.0422 (19)	0.0433 (18)	0.0045 (15)	0.0010 (15)	0.0055 (15)
C4	0.052 (2)	0.048 (2)	0.0439 (19)	0.0042 (17)	0.0008 (16)	−0.0037 (17)
C5	0.062 (2)	0.064 (2)	0.0381 (19)	−0.001 (2)	0.0096 (17)	0.0000 (18)
C6	0.055 (2)	0.060 (3)	0.0402 (18)	−0.0084 (18)	0.0125 (16)	0.0083 (17)
C7	0.0437 (19)	0.049 (2)	0.0444 (19)	−0.0071 (16)	0.0047 (15)	0.0113 (17)
C8	0.050 (2)	0.0452 (19)	0.0339 (16)	0.0061 (16)	−0.0052 (15)	0.0007 (15)
C9	0.0412 (18)	0.0429 (18)	0.0398 (17)	0.0044 (15)	−0.0035 (14)	−0.0048 (15)
C10	0.0424 (19)	0.052 (2)	0.052 (2)	0.0043 (17)	−0.0041 (16)	−0.0081 (18)
C11	0.045 (2)	0.059 (2)	0.060 (2)	0.0148 (19)	−0.0138 (18)	−0.010 (2)
C12	0.061 (3)	0.074 (3)	0.057 (2)	0.018 (2)	−0.014 (2)	0.007 (2)
C13	0.063 (3)	0.056 (2)	0.044 (2)	0.008 (2)	−0.0052 (18)	0.0045 (18)
C14	0.052 (2)	0.048 (2)	0.0349 (17)	−0.0034 (17)	0.0023 (15)	0.0064 (16)
C15	0.052 (2)	0.051 (2)	0.051 (2)	−0.0146 (18)	−0.0053 (17)	0.0042 (18)
C16	0.067 (3)	0.044 (2)	0.062 (2)	−0.0036 (19)	−0.006 (2)	0.0059 (19)
C17	0.049 (2)	0.047 (2)	0.060 (2)	0.0056 (18)	−0.0073 (18)	0.0039 (18)
C18	0.043 (2)	0.070 (3)	0.060 (2)	−0.010 (2)	0.0022 (18)	0.017 (2)
C19	0.0383 (18)	0.083 (3)	0.066 (2)	0.000 (2)	0.0112 (17)	0.016 (2)
C20	0.039 (2)	0.070 (3)	0.066 (2)	0.0058 (19)	0.0056 (18)	0.007 (2)
C21	0.055 (2)	0.066 (3)	0.048 (2)	0.001 (2)	−0.0059 (18)	−0.0061 (19)
C22	0.051 (3)	0.083 (4)	0.141 (5)	0.008 (3)	−0.023 (3)	−0.012 (4)
C23	0.140 (5)	0.054 (3)	0.070 (3)	−0.027 (3)	−0.006 (3)	−0.006 (2)
O1E	0.059 (4)	0.065 (4)	0.077 (4)	0.006 (3)	0.026 (3)	−0.003 (3)
C1E	0.174 (19)	0.55 (5)	0.093 (13)	−0.16 (2)	0.074 (14)	0.00 (2)
C2E	0.050 (4)	0.046 (4)	0.085 (6)	−0.014 (4)	0.026 (4)	−0.013 (4)

Geometric parameters (Å, º)

Co1—O1	1.976 (2)	C10—H10	0.9300
Co1—O2	1.979 (2)	C11—C12	1.389 (6)
Co1—N2	2.057 (3)	C12—C13	1.359 (5)
Co1—N1	2.062 (3)	C12—H12	0.9300
Co1—N3	2.185 (3)	C13—H13	0.9300
O1—C2	1.314 (4)	C14—H14	0.9300
O2—C9	1.318 (4)	C15—C16	1.517 (5)
O3—C4	1.362 (4)	C15—H15A	0.9700
O3—C23	1.430 (5)	C15—H15B	0.9700
O4—C11	1.371 (5)	C16—C17	1.521 (5)
O4—C22	1.412 (6)	C16—H16A	0.9700
N1—C7	1.279 (4)	C16—H16B	0.9700
N1—C15	1.467 (4)	C17—H17A	0.9700
N2—C14	1.277 (4)	C17—H17B	0.9700
N2—C18	1.469 (4)	C18—C19	1.505 (5)
N3—C21	1.479 (4)	C18—H18A	0.9700
N3—C17	1.490 (4)	C18—H18B	0.9700
N3—C20	1.493 (4)	C19—C20	1.524 (5)
C1—C6	1.416 (5)	C19—H19A	0.9700
C1—C2	1.413 (4)	C19—H19B	0.9700
C1—C7	1.439 (5)	C20—H20A	0.9700
C2—C3	1.403 (5)	C20—H20B	0.9700
C3—C4	1.386 (5)	C21—H21A	0.9600
C3—H3	0.9300	C21—H21B	0.9600
C4—C5	1.392 (5)	C21—H21C	0.9600
C5—C6	1.359 (5)	C22—H22A	0.9600
C5—H5	0.9300	C22—H22B	0.9600
C6—H6	0.9300	C22—H22C	0.9600
C7—H7	0.9300	C23—H23A	0.9600
C8—C13	1.407 (5)	C23—H23B	0.9600
C8—C9	1.417 (5)	C23—H23C	0.9600
C8—C14	1.435 (5)	O1E—C1E	1.441 (9)
C9—C10	1.413 (5)	C1E—C2E	1.523 (9)
C10—C11	1.384 (5)	C1E—C1E^i	1.65 (3)
O1—Co1—O2	120.38 (10)	C12—C13—H13	118.5
O1—Co1—N2	91.91 (10)	C8—C13—H13	118.5
O2—Co1—N2	90.28 (10)	N2—C14—C8	126.4 (3)
O1—Co1—N1	89.05 (10)	N2—C14—H14	116.8
O2—Co1—N1	91.81 (10)	C8—C14—H14	116.8
N2—Co1—N1	176.87 (11)	N1—C15—C16	111.3 (3)
O1—Co1—N3	124.65 (10)	N1—C15—H15A	109.4
O2—Co1—N3	114.97 (10)	C16—C15—H15A	109.4
N2—Co1—N3	88.59 (11)	N1—C15—H15B	109.4
N1—Co1—N3	88.41 (11)	C16—C15—H15B	109.4
C2—O1—Co1	129.3 (2)	H15A—C15—H15B	108.0
C9—O2—Co1	127.9 (2)	C15—C16—C17	115.9 (3)
C4—O3—C23	118.3 (3)	C15—C16—H16A	108.3
C11—O4—C22	118.4 (3)	C17—C16—H16A	108.3
C7—N1—C15	119.0 (3)	C15—C16—H16B	108.3
C7—N1—Co1	126.4 (2)	C17—C16—H16B	108.3
C15—N1—Co1	114.5 (2)	H16A—C16—H16B	107.4
C14—N2—C18	117.6 (3)	N3—C17—C16	116.9 (3)
C14—N2—Co1	125.1 (2)	N3—C17—H17A	108.1
C18—N2—Co1	117.3 (2)	C16—C17—H17A	108.1
C21—N3—C17	110.4 (3)	N3—C17—H17B	108.1
C21—N3—C20	110.4 (3)	C16—C17—H17B	108.1
C17—N3—C20	105.6 (3)	H17A—C17—H17B	107.3
C21—N3—Co1	108.4 (2)	N2—C18—C19	110.7 (3)
C17—N3—Co1	110.7 (2)	N2—C18—H18A	109.5
C20—N3—Co1	111.4 (2)	C19—C18—H18A	109.5
C6—C1—C2	118.4 (3)	N2—C18—H18B	109.5
C6—C1—C7	117.5 (3)	C19—C18—H18B	109.5
C2—C1—C7	124.1 (3)	H18A—C18—H18B	108.1
O1—C2—C3	118.0 (3)	C18—C19—C20	114.4 (3)
O1—C2—C1	123.9 (3)	C18—C19—H19A	108.7
C3—C2—C1	118.2 (3)	C20—C19—H19A	108.7
C4—C3—C2	121.6 (3)	C18—C19—H19B	108.7
C4—C3—H3	119.2	C20—C19—H19B	108.7
C2—C3—H3	119.2	H19A—C19—H19B	107.6
O3—C4—C3	124.8 (3)	N3—C20—C19	117.0 (3)
O3—C4—C5	115.2 (3)	N3—C20—H20A	108.1
C3—C4—C5	120.1 (3)	C19—C20—H20A	108.1
C6—C5—C4	119.2 (3)	N3—C20—H20B	108.1
C6—C5—H5	120.4	C19—C20—H20B	108.1
C4—C5—H5	120.4	H20A—C20—H20B	107.3
C5—C6—C1	122.4 (3)	N3—C21—H21A	109.5
C5—C6—H6	118.8	N3—C21—H21B	109.5
C1—C6—H6	118.8	H21A—C21—H21B	109.5
N1—C7—C1	125.9 (3)	N3—C21—H21C	109.5
N1—C7—H7	117.1	H21A—C21—H21C	109.5
C1—C7—H7	117.1	H21B—C21—H21C	109.5
C13—C8—C9	118.6 (3)	O4—C22—H22A	109.5
C13—C8—C14	116.9 (3)	O4—C22—H22B	109.5
C9—C8—C14	124.5 (3)	H22A—C22—H22B	109.5
O2—C9—C10	118.1 (3)	O4—C22—H22C	109.5
O2—C9—C8	124.0 (3)	H22A—C22—H22C	109.5
C10—C9—C8	117.9 (3)	H22B—C22—H22C	109.5
C11—C10—C9	120.8 (4)	O3—C23—H23A	109.5
C11—C10—H10	119.6	O3—C23—H23B	109.5
C9—C10—H10	119.6	H23A—C23—H23B	109.5
O4—C11—C10	123.4 (4)	O3—C23—H23C	109.5
O4—C11—C12	115.3 (4)	H23A—C23—H23C	109.5
C10—C11—C12	121.2 (4)	H23B—C23—H23C	109.5
C13—C12—C11	118.4 (4)	O1E—C1E—C2E	136.5 (12)
C13—C12—H12	120.8	O1E—C1E—C1E^i	114.4 (8)
C11—C12—H12	120.8	C2E—C1E—C1E^i	108.6 (7)
C12—C13—C8	123.0 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O3^ii	0.93	2.71	3.601 (7)	162
C12—H12···O4^iii	0.93	2.62	3.498 (7)	158
C21—H21B···O4^iv	0.96	2.67	3.582 (7)	159
C22—H22C···O1E^v	0.96	2.46	3.226 (9)	137

Symmetry codes: (ii) x, −y, z+1/2; (iii) −x+1, −y, −z+1; (iv) x−1/2, y+1/2, z; (v) x+1/2, y−1/2, z.