The cyclic vanadylacetate (C₂₄H₂₀P)[V₄O₈(C₂H₃O₂)₄(NO₃)]

In the title complex, tetraphenylphosphonium μ₄-nitrato-κ⁴O-cyclo-tetrakis(μ-acetato-O:O′)tetra-μ-oxo-tetrakis[oxovana-dium(V)], the anion lies about a twofold axis and consists of the cyclic [V₄O₈] unit coordinated by four acetato ligands with interatomic V...V distances of 3.269 (1) and 3.273 (1) Å. The double-bonded O atom [N=O 1.102 (6) and N—O 1.268 (4) Å] of the nitrato ligand links the four V atoms with V—O bond distances of 2.613 (2) and 2.813 (2) Å. The negative charge of the complex is balanced by tetraphenyl­phosphonium cations occupying the Na positions in the NaCl-type ionic packing of the structure.

S1. Comment

Our attempts to synthesize (PPh₄)[VO₂(NO₃)₂] resulted in the formation of the title compound, (PPh₄)[V^V₄O₈(CH₃COO)₄(NO₃)], (I). Similar cyclic oxovanadium carboxylate complexes were previously described by Rehder (1994) and Priebsch et al. (1991) in [V^V₃V^IVO₇OH(t-BuCH₂COO)₄K][tBuCH₂COO].2 t-BuCH₂COOH and by Heinrich et al. (1989) in the compound (NEt₄)₂[V^V₃V^IVO₈(tca)₄(NO₃)]·H₂O (tca⁻ = thiophene-2-carboxylate). Furthermore, the [V₄O₈] moiety was observed as a building unit in the oxovanadium phosphonates (NBu₄)₂[(V^V₄O₈)₂OV^IV(H₂O)₄(PhPO₃)₈Cl₂]. 2Et₂O·2MeOH·4H₂O (Chen & Zubieta, 1994), the [V₅O₉] group of compounds (NEt₄)₂[V^VV^IV₄O₉(tca)₄Cl]·MeCN (Heinrich et al., 1989) and (Me₂NH₂)₅(NH₄)[(V^VV^IV₄O₉)V^IV₂O₄(H₂O)₂(PhPO₃)₈ (2NH₄Cl)]·5H₂O·4DMF (Müller et al., 1992) and the isopolyvanadates Cs₉[H₄V^IV₁₈O₄₂X].12H₂O (X = Br⁻ or I⁻) (Müller et al., 1990). The complex vanadate ion [V^V₄O₈(CH₃COO)₄(NO₃)]⁻ reported here is the first example of a non-reduced cyclic vanadyl carboxylate ion. Its partly reduced counterpart [V^V₃V^IVO₈(tca)₄(NO₃)]²⁻, investigated by Heinrich et al. (1989), indicates the capability of this type of compound to participate in reversible redox reactions.

The structure of (I) (Fig. 1) consists of two crystallographically different phosphonium cations, P6 and P7, occupying special positions with site symmetry 4 (Wyckoff b and a, respectively). The cyclic anions are placed in the resulting gaps with site symmetry 2 (Wyckoff e) with the twofold axis of the C_2v symmetry of the anion coinciding with the fourfold screw axis of the crystal symmetry. Four V atoms in square pyramidal coordination are corner-connected to form a cyclic tetramer. The two lower basal O atoms of the [OVO₄] pyramids belong to acetato ligands, each of them linking two metal centres. Bond distances and angles (Table 1) agree with the data of the compounds described by Heinrich et al. (1989), Priebsch et al. (1991) and Chen & Zubieta (1994) (V═O 1.54–1.65, V—O 1.77–2.07 and V···O 2.02–2.79 Å). Mean plane calculations yield a mean distance of 0.37 (2) Å for the metal atoms above the basal plane of the square pyramids (atoms used for V1 were O21, O31, O23 and O24ⁱ and for V2 O21ⁱ, O31, O13 and O14). Valence sum calculations (Brese & O'Keeffe, 1991) clearly revealed the valence of +5 for both symmetry independent V atoms.

The two different V···O bond distances of 2.613 (2) (× 2) and 2.813 (2) Å (× 2) to the double-bonded O atom of the central nitrate anion [N═O 1.102 (6) and N—O 1.268 (4) Å], which reflect the local C_2v symmetry of the [V₄O₈(Ac)₄(NO₃)]⁻ anion, (Fig. 1) are remarkable. This low symmetry is in good agreement with the observations of Heinrich et al. (1989) for [V₄O₈(tca)₄(NO₃)]²⁻ [V···O 2.564 (13)–2.793 (14) Å]. Calculations of the angles between the least-squares basal planes of opposing [OVO₄] pyramids yielded 60.41 (5) and 78.31 (5)° for V1/V1ⁱ and V2/V2ⁱ, consistent with the C_2v symmetry.

S2. Experimental

Compound (I) was obtained by reacting (Ph₄P)[VO₂Cl₂] with AgNO₃ in acetonitrile under anαerobic conditions. On slow evaporation of the filtered solution, red cube-shaped crystals up to 2 mm in diameter were obtained, which were stable in air (yield: 70% based on V). It is assumed that the acetato ligands are formed by acid hydrolysis of the acetonitrile solvent caused by traces of water.

S3. Refinement

The difference Fourier synthesis showed the methyl groups to be disordered. Therefore, the H atoms were placed in accordance with two methyl groups in a staggered orientation. The geometrically restrained refinement was performed with isotropic displacement parameters and free C—H bond distances.

Computing details

Data collection: IPDS (Stoe & Cie, 1996); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ZORTEP (Zsolnai, 1994); software used to prepare material for publication: SHELXL93.

Figures

Fig. 1. The structure of the cyclic anion of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. Bonds between V and O atoms are shown by heavy lines.

tetraphenylphosphonium µ₄-nitrato-κ⁴O-cyclo- tetrakis(µ-acetato-κO:κO')tetra-µ-oxo-tetrakis[oxovanadium(V)]

Crystal data

(C24H20P)[V4O8(C2H3O2)4(NO3)]	Dx = 1.721 Mg m^−3
Mr = 969.32	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 5000 reflections
Hall symbol: -I 4ad	θ = 8.1–20.7°
a = 15.856 (2) Å	µ = 1.10 mm^−1
c = 29.753 (5) Å	T = 200 K
V = 7480.3 (18) Å^3	Prism, dark red
Z = 8	0.23 × 0.23 × 0.15 mm
F(000) = 3920

Data collection

Stoe IPDS diffractometer	3685 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
Detector resolution: 6.67 pixels mm^-1	θmax = 26.1°, θmin = 2.3°
oscillation scans	h = −13→13
Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983)	k = 0→19
Tmin = 0.547, Tmax = 0.867	l = 0→36
32401 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.02	Calculated w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 2.7778P] where P = (Fo^2 + 2Fc^2)/3
3309 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.75 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 on F² for ALL reflections except for 376 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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	Occ. (<1)
V1	0.43804 (3)	0.37781 (3)	0.10358 (2)	0.0271 (2)
O11	0.39943 (13)	0.45712 (13)	0.07856 (7)	0.0317 (5)
O21	0.38597 (13)	0.29100 (13)	0.07629 (7)	0.0297 (5)
O31	0.53999 (13)	0.36437 (13)	0.07606 (7)	0.0302 (5)
V2	0.63420 (3)	0.31484 (3)	0.09685 (2)	0.0314 (2)
O12	0.70589 (14)	0.34932 (15)	0.06478 (8)	0.0423 (6)
C23	0.5777 (2)	0.4455 (2)	0.16236 (10)	0.0290 (7)
O13	0.63637 (13)	0.40452 (13)	0.14377 (7)	0.0347 (5)
O23	0.50058 (13)	0.43955 (13)	0.15293 (7)	0.0325 (5)
C13	0.6027 (2)	0.5050 (2)	0.19885 (11)	0.0421 (8)
H13A	0.6648 (15)	0.5034 (2)	0.2028 (2)	0.063*	0.19 (3)
H13B	0.5749 (7)	0.4881 (4)	0.2274 (7)	0.063*	0.19 (3)
H13C	0.5849 (5)	0.5630 (14)	0.1907 (2)	0.063*	0.19 (3)
H13D	0.5516 (12)	0.5329 (7)	0.2111 (3)	0.063*	0.81 (3)
H13E	0.6415 (10)	0.5483 (11)	0.1865 (3)	0.063*	0.81 (3)
H13F	0.6315 (7)	0.4733 (8)	0.2232 (6)	0.063*	0.81 (3)
C24	0.6978 (2)	0.1888 (2)	0.16351 (10)	0.0295 (7)
O14	0.70448 (14)	0.25896 (14)	0.14434 (7)	0.0357 (5)
O24	0.64552 (13)	0.13147 (13)	0.15352 (6)	0.0309 (5)
C14	0.7567 (2)	0.1700 (2)	0.20183 (11)	0.0408 (8)
H14A	0.7453 (3)	0.1156 (14)	0.2132 (3)	0.061*	0.19 (3)
H14B	0.7489 (3)	0.2103 (10)	0.2248 (6)	0.061*	0.19 (3)
H14C	0.8130 (14)	0.1723 (2)	0.1915 (3)	0.061*	0.19 (3)
H14D	0.7928 (9)	0.2165 (11)	0.2065 (2)	0.061*	0.81 (3)
H14E	0.7892 (8)	0.1218 (12)	0.1949 (2)	0.061*	0.81 (3)
H14F	0.7251 (8)	0.1599 (3)	0.2282 (7)	0.061*	0.81 (3)
N5	0.5000	0.2500	0.1852 (2)	0.0517 (12)
O15	0.5000	0.2500	0.14813 (13)	0.0341 (7)
O25	0.4388 (2)	0.2209 (2)	0.20781 (8)	0.0580 (7)
P6	0.5000	0.7500	0.1250	0.0236 (3)
C16	0.4480 (2)	0.8253 (2)	0.08975 (9)	0.0254 (6)
C26	0.3709 (2)	0.8596 (2)	0.10246 (10)	0.0312 (7)
H26	0.3434 (11)	0.8404 (8)	0.1286 (10)	0.037*
C36	0.3350 (2)	0.9222 (2)	0.07653 (11)	0.0391 (8)
H36	0.289 (2)	0.9433 (10)	0.0840 (4)	0.047*
C46	0.3753 (2)	0.9496 (2)	0.03808 (11)	0.0385 (8)
H46	0.3541 (11)	0.9882 (19)	0.0231 (7)	0.046*
C56	0.4496 (2)	0.9142 (2)	0.02427 (10)	0.0364 (7)
H56	0.4760 (10)	0.9326 (7)	−0.0037 (11)	0.044*
C66	0.4871 (2)	0.8522 (2)	0.05013 (10)	0.0309 (7)
H66	0.537 (2)	0.8287 (9)	0.0413 (4)	0.037*
P7	0.0000	0.2500	0.1250	0.0240 (3)
C17	0.0764 (2)	0.3030 (2)	0.09078 (9)	0.0251 (6)
C27	0.1156 (2)	0.3750 (2)	0.10787 (11)	0.0296 (6)
H27	0.0997 (7)	0.3959 (9)	0.1332 (11)	0.036*
C37	0.1800 (2)	0.4126 (2)	0.08392 (11)	0.0362 (7)
H37	0.2058 (11)	0.4582 (19)	0.0950 (5)	0.043*
C47	0.2044 (2)	0.3802 (2)	0.04315 (11)	0.0395 (8)
H47	0.2498 (19)	0.4061 (11)	0.0270 (7)	0.047*
C57	0.1646 (2)	0.3114 (2)	0.02531 (11)	0.0413 (8)
H57	0.1802 (7)	0.2915 (9)	−0.0028 (12)	0.050*
C67	0.1012 (2)	0.2712 (2)	0.04904 (10)	0.0352 (7)
H67	0.0772 (11)	0.2271 (19)	0.0382 (5)	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0321 (3)	0.0254 (3)	0.0239 (3)	0.0034 (2)	0.0012 (2)	0.0015 (2)
O11	0.0370 (12)	0.0279 (11)	0.0301 (11)	0.0043 (9)	0.0019 (9)	0.0015 (9)
O21	0.0318 (11)	0.0310 (11)	0.0264 (10)	0.0036 (9)	−0.0015 (8)	0.0007 (8)
O31	0.0348 (12)	0.0278 (11)	0.0281 (11)	0.0007 (9)	0.0019 (8)	0.0007 (8)
V2	0.0286 (3)	0.0298 (3)	0.0357 (3)	−0.0013 (2)	0.0030 (2)	−0.0003 (2)
O12	0.0354 (13)	0.0369 (13)	0.0546 (14)	−0.0007 (10)	0.0129 (11)	0.0041 (11)
C23	0.033 (2)	0.027 (2)	0.0279 (15)	−0.0059 (13)	−0.0017 (12)	0.0032 (12)
O13	0.0287 (12)	0.0302 (12)	0.0452 (12)	−0.0007 (9)	−0.0004 (10)	−0.0043 (10)
O23	0.0320 (12)	0.0364 (12)	0.0291 (11)	−0.0007 (9)	0.0009 (9)	−0.0013 (9)
C13	0.044 (2)	0.044 (2)	0.039 (2)	−0.009 (2)	−0.0026 (15)	−0.008 (2)
C24	0.024 (2)	0.037 (2)	0.0273 (15)	0.0008 (13)	0.0025 (12)	−0.0047 (13)
O14	0.0305 (12)	0.0324 (12)	0.0442 (12)	−0.0017 (9)	−0.0019 (10)	−0.0002 (10)
O24	0.0328 (12)	0.0319 (12)	0.0279 (10)	−0.0035 (10)	−0.0014 (9)	0.0006 (9)
C14	0.038 (2)	0.052 (2)	0.033 (2)	−0.004 (2)	−0.0047 (14)	−0.0017 (15)
N5	0.024 (2)	0.028 (2)	0.103 (4)	−0.002 (2)	0.000	0.000
O15	0.032 (2)	0.019 (2)	0.051 (2)	0.0069 (12)	0.000	0.000
O25	0.059 (2)	0.074 (2)	0.0419 (14)	−0.0034 (15)	−0.0019 (12)	0.0014 (13)
P6	0.0251 (5)	0.0251 (5)	0.0207 (7)	0.000	0.000	0.000
C16	0.029 (2)	0.0265 (15)	0.0204 (13)	−0.0017 (12)	−0.0016 (11)	0.0007 (11)
C26	0.029 (2)	0.036 (2)	0.029 (2)	−0.0009 (13)	−0.0001 (13)	−0.0009 (13)
C36	0.032 (2)	0.041 (2)	0.044 (2)	0.0076 (15)	−0.0066 (14)	−0.0007 (15)
C46	0.048 (2)	0.030 (2)	0.037 (2)	0.000 (2)	−0.020 (2)	0.0036 (14)
C56	0.048 (2)	0.035 (2)	0.026 (2)	−0.008 (2)	−0.0068 (14)	0.0054 (13)
C66	0.031 (2)	0.036 (2)	0.0263 (15)	−0.0004 (13)	−0.0003 (12)	0.0027 (13)
P7	0.0247 (5)	0.0247 (5)	0.0228 (7)	0.000	0.000	0.000
C17	0.0249 (15)	0.0263 (15)	0.0239 (14)	0.0005 (12)	−0.0019 (11)	0.0018 (11)
C27	0.032 (2)	0.028 (2)	0.0293 (14)	0.0037 (13)	−0.0012 (12)	−0.0011 (12)
C37	0.033 (2)	0.028 (2)	0.048 (2)	−0.0058 (14)	0.0006 (14)	0.0030 (14)
C47	0.035 (2)	0.038 (2)	0.046 (2)	−0.0014 (15)	0.0102 (15)	0.010 (2)
C57	0.049 (2)	0.044 (2)	0.031 (2)	0.002 (2)	0.0139 (15)	0.0008 (14)
C67	0.042 (2)	0.032 (2)	0.031 (2)	−0.0049 (14)	0.0067 (14)	−0.0046 (13)

Geometric parameters (Å, º)

V1—O11	1.584 (2)	N5—O25	1.268 (4)
V1—O21	1.799 (2)	O15—V1^i	2.613 (2)
V1—O31	1.825 (2)	O15—V2^i	2.813 (2)
V1—O24^i	1.996 (2)	P6—C16^ii	1.791 (3)
V1—O23	2.024 (2)	P6—C16^iii	1.791 (3)
V1—O15	2.613 (2)	P6—C16	1.791 (3)
O21—V2^i	1.815 (2)	P6—C16^iv	1.791 (3)
V2—O12	1.582 (2)	C16—C26	1.390 (4)
V2—O31	1.797 (2)	C16—C66	1.399 (4)
V2—O21^i	1.815 (2)	C26—C36	1.379 (5)
V2—O13	1.993 (2)	C26—H26	0.94 (4)
V2—O14	2.006 (2)	C36—C46	1.381 (5)
V2—O15	2.813 (2)	C36—H36	0.83 (4)
C23—O23	1.258 (4)	C46—C56	1.367 (5)
C23—O13	1.262 (4)	C46—H46	0.83 (4)
C23—C13	1.492 (4)	C56—C66	1.383 (4)
C13—H13A	0.99 (2)	C56—H56	0.98 (4)
C13—H13B	0.99 (2)	C66—H66	0.92 (3)
C13—H13C	0.99 (2)	P7—C17^v	1.792 (3)
C13—H13D	0.99 (2)	P7—C17^vi	1.792 (3)
C13—H13E	0.99 (2)	P7—C17	1.792 (3)
C13—H13F	0.99 (2)	P7—C17^vii	1.792 (3)
C24—O14	1.255 (4)	C17—C27	1.396 (4)
C24—O24	1.265 (4)	C17—C67	1.397 (4)
C24—C14	1.503 (4)	C27—C37	1.380 (4)
O24—V1^i	1.996 (2)	C27—H27	0.86 (4)
C14—H14A	0.94 (2)	C37—C47	1.373 (5)
C14—H14B	0.94 (2)	C37—H37	0.89 (4)
C14—H14C	0.94 (2)	C47—C57	1.368 (5)
C14—H14D	0.94 (2)	C47—H47	0.96 (4)
C14—H14E	0.94 (2)	C57—C67	1.383 (5)
C14—H14F	0.94 (2)	C57—H57	0.93 (4)
N5—O15	1.102 (6)	C67—H67	0.86 (4)
N5—O25^i	1.268 (4)
O11—V1—O21	102.58 (10)	C24—C14—H14E	109.5 (2)
O11—V1—O31	102.95 (10)	H14A—C14—H14E	56.3
O21—V1—O31	96.58 (9)	H14B—C14—H14E	141.1
O11—V1—O24^i	98.73 (10)	H14C—C14—H14E	56.3
O21—V1—O24^i	88.56 (9)	H14D—C14—H14E	109.5
O31—V1—O24^i	155.99 (9)	C24—C14—H14F	109.5 (2)
O11—V1—O23	98.41 (10)	H14A—C14—H14F	56.3
O21—V1—O23	157.27 (9)	H14B—C14—H14F	56.3
O31—V1—O23	87.02 (9)	H14C—C14—H14F	141.1
O24^i—V1—O23	79.69 (8)	H14D—C14—H14F	109.5
O11—V1—O15	177.55 (10)	H14E—C14—H14F	109.5
O21—V1—O15	78.94 (8)	O15—N5—O25^i	122.1 (3)
O31—V1—O15	78.69 (8)	O15—N5—O25	122.1 (3)
O24^i—V1—O15	79.33 (8)	O25^i—N5—O25	115.9 (6)
O23—V1—O15	79.80 (8)	N5—O15—V1^i	120.48 (7)
O12—V2—O31	103.81 (11)	N5—O15—V1	120.48 (7)
O12—V2—O21^i	104.06 (11)	V1^i—O15—V1	119.04 (14)
O31—V2—O21^i	98.14 (9)	N5—O15—V2^i	122.85 (7)
O12—V2—O13	99.41 (11)	V1^i—O15—V2^i	74.09 (7)
O31—V2—O13	86.77 (9)	V1—O15—V2^i	73.98 (7)
O21^i—V2—O13	154.03 (9)	N5—O15—V2	122.85 (7)
O12—V2—O14	100.27 (11)	V1^i—O15—V2	73.98 (7)
O31—V2—O14	153.78 (9)	V1—O15—V2	74.09 (7)
O21^i—V2—O14	85.80 (9)	V2^i—O15—V2	114.31 (13)
O13—V2—O14	79.18 (9)	C16^ii—P6—C16^iii	110.06 (9)
O12—V2—O15	175.74 (12)	C16^ii—P6—C16	110.06 (9)
O31—V2—O15	73.60 (8)	C16^iii—P6—C16	108.3 (2)
O21^i—V2—O15	73.23 (8)	C16^ii—P6—C16^iv	108.3 (2)
O13—V2—O15	83.91 (8)	C16^iii—P6—C16^iv	110.06 (9)
O14—V2—O15	82.92 (8)	C16—P6—C16^iv	110.06 (9)
V1—O21—V2^i	129.52 (11)	C26—C16—C66	120.0 (3)
V2—O31—V1	129.27 (12)	C26—C16—P6	120.4 (2)
O23—C23—O13	125.4 (3)	C66—C16—P6	119.5 (2)
O23—C23—C13	117.9 (3)	C36—C26—C16	119.5 (3)
O13—C23—C13	116.7 (3)	C36—C26—H26	120.3 (2)
C23—O13—V2	131.4 (2)	C16—C26—H26	120.3 (2)
C23—O23—V1	132.4 (2)	C26—C36—C46	119.9 (3)
C23—C13—H13A	109.5 (2)	C26—C36—H36	120.0 (2)
C23—C13—H13B	109.5 (2)	C46—C36—H36	120.0 (2)
H13A—C13—H13B	109.5	C56—C46—C36	121.2 (3)
C23—C13—H13C	109.5 (2)	C56—C46—H46	119.4 (2)
H13A—C13—H13C	109.5	C36—C46—H46	119.4 (2)
H13B—C13—H13C	109.5	C46—C56—C66	119.7 (3)
C23—C13—H13D	109.5 (2)	C46—C56—H56	120.2 (2)
H13A—C13—H13D	141.1	C66—C56—H56	120.2 (2)
H13B—C13—H13D	56.3	C56—C66—C16	119.6 (3)
H13C—C13—H13D	56.3	C56—C66—H66	120.2 (2)
C23—C13—H13E	109.5 (2)	C16—C66—H66	120.2 (2)
H13A—C13—H13E	56.3	C17^v—P7—C17^vi	108.84 (9)
H13B—C13—H13E	141.1	C17^v—P7—C17	108.84 (9)
H13C—C13—H13E	56.3	C17^vi—P7—C17	110.7 (2)
H13D—C13—H13E	109.5	C17^v—P7—C17^vii	110.7 (2)
C23—C13—H13F	109.5 (2)	C17^vi—P7—C17^vii	108.84 (9)
H13A—C13—H13F	56.3	C17—P7—C17^vii	108.84 (9)
H13B—C13—H13F	56.3	C27—C17—C67	119.6 (3)
H13C—C13—H13F	141.1	C27—C17—P7	118.5 (2)
H13D—C13—H13F	109.5	C67—C17—P7	121.8 (2)
H13E—C13—H13F	109.5	C37—C27—C17	119.6 (3)
O14—C24—O24	125.8 (3)	C37—C27—H27	120.2 (2)
O14—C24—C14	117.9 (3)	C17—C27—H27	120.2 (2)
O24—C24—C14	116.3 (3)	C47—C37—C27	120.2 (3)
C24—O14—V2	131.7 (2)	C47—C37—H37	119.9 (2)
C24—O24—V1^i	131.5 (2)	C27—C37—H37	119.9 (2)
C24—C14—H14A	109.5 (2)	C57—C47—C37	120.7 (3)
C24—C14—H14B	109.5 (2)	C57—C47—H47	119.6 (2)
H14A—C14—H14B	109.5	C37—C47—H47	119.6 (2)
C24—C14—H14C	109.5 (2)	C47—C57—C67	120.3 (3)
H14A—C14—H14C	109.5	C47—C57—H57	119.9 (2)
H14B—C14—H14C	109.5	C67—C57—H57	119.9 (2)
C24—C14—H14D	109.5 (2)	C57—C67—C17	119.5 (3)
H14A—C14—H14D	141.1	C57—C67—H67	120.3 (2)
H14B—C14—H14D	56.3	C17—C67—H67	120.3 (2)
H14C—C14—H14D	56.3

Symmetry codes: (i) −x+1, −y+1/2, z; (ii) y−1/4, −x+5/4, −z+1/4; (iii) −x+1, −y+3/2, z; (iv) −y+5/4, x+1/4, −z+1/4; (v) −y+1/4, x+1/4, −z+1/4; (vi) −x, −y+1/2, z; (vii) y−1/4, −x+1/4, −z+1/4.