One-dimensional chains in sodium tetraphenylphosphonium bis(2-mercapto-4-methylphenolato-O,S)oxovanadate(IV)

The title compound, Na(C₂₄H₂₀P)[V(C₇H₆OS)₂O], contains oxovanadium(IV) in a square-pyramidal coordination geometry with a basal plane consisting of a cis-S₂O₂ donor group. The [VO(mmp)₂]^2- (mmpH₂ = 2-mercapto-4-methyl­phenol) units are linked into infinite chains by the sodium ions.

S1. Comment

The controlled linking of discrete molecular building blocks into supramolecular aggregates can be achieved through utilizing a number of different kinds of inter-subunit interactions. For oxovanadium(IV) compounds, solid state and solution structures have been stabilized by specific interactions including (i) V═O—V═O linkages (Zheng et al., 1995; Aiello et al., 1997; Sáez-Puche et al., 1998), (ii) hydrogen bonds (Wen et al., 1998), (iii) bridging ligands (Salta et al., 1996) and (iv) alkali or alkaline earth ions functioning in a bridging mode (Garcia-Jaca et al., 1993). We have reported (Klich et al., 1996) the vanadyl(IV) complex Na(Ph₄P)[VO(mp)₂]·Et₂O containing the mixed O,S donor ligand mp^2- [mpH₂ = 2-mercaptophenol, C₆H₄(OH)(SH)]. In this solid, a pair of [VO(mp)₂]^2- anions are linked together through a pair of Na⁺ ions into a centrosymmetric dimer. Each sodium ion is bonded to two ligand O atoms from one [VO(mp)₂]^2- unit and to one ligand O atom plus the vanadyl O atom from the other. In the course of these studies we also prepared the related compound Na(Ph₄P)[VO(mmp)₂] (mmpH₂ = 2-mercapto-4-methylphenol), (I), which crystallized in a structure with anionic chains [NaVO(mmp)₂^-]_∞. We report herein upon this structure. \sch

The square-pyramidal anion, [VO(mmp)₂]^2-, contains an apical O atom with a V═O bond length of 1.619 (2) Å, and an O₂S₂ basal plane with the two five-membered chelate rings V—O—C—C—S in a cis configuration (Fig. 1). This cis configuration has been seen in the other four structurally characterized oxovanadium(IV) complexes with an O₂S₂ donor set (Higes-Rolando et al., 1994; Tsagkalidis et al., 1994; Preuss et al., 1990; Klich et al., 1996; Wen et al., 1998). The V(O₂S₂) core thus displays pseudo-C_s symmetry with the σ plane passing through the V—O3 bond and bisecting the O1—O2 and S1—S2 vectors. The vanadium atom is displaced 0.598 (1) Å from the O₂S₂ least-squares plane, giving a slightly flatter pyramid than in [VO(mp)₂]^2- where the corresponding displacement is 0.638 Å. The V—S and V—O basal plane bond lengths average to 2.375 and 1.963 Å, respectively, and are very similar to those in [VO(mp)₂]^2- (2.365 and 1.959 Å, respectively) and the other three VO(OS)₂ complexes. The two five-membered chelate rings are folded about the O—S vector, with the aromatic rings bending toward the apical O and making angles of 24.54 (9) and 12.60 (8)° with the O1—V—S1 and O2—V—S2 planes, respectively. While this bending is also observed in the related complexes [VO(mp)₂]^2- (Klich et al., 1996) and VO(Hmpp)₂ (Wen et al., 1998) it is more pronounced in the title compound.

The [VO(mmp)₂]^2- ions are linked through sodium ions into one-dimensional polymeric chains (Fig. 2). Each Na⁺ bridges two [VO(mmp)₂]^2- ions, coordinating through the two ligand O atoms from one unit and the ligand S atom plus the vanadyl O atom from the other. The chains run parallel to the b axis, along the crystallographic twofold screw, so that each [VO(mp)₂]^2- unit is rotated 180° to the next. The chains are well isolated from each other, being separated by Ph₄P⁺ ions. The sodium ions are four-coordinate, with no solvent molecules attached, in contrast to the dimeric units in Na(Ph₄P)[VO(mp)₂]·Et₂O, where a molecule of ether completes the five-coordination of each sodium. In the title compound a phenyl ring from Ph₄P⁺ blocks one side of each Na⁺ where a solvent molecule might otherwise have been located. The Na—O bond lengths are significantly shorter in the title compound than in Na(Ph₄P)[VO(mp)₂]·Et₂O, probably reflecting an opening up of the dimeric structure relative to the infinite chain due to close proximity of the Na⁺ ions held between pairs of [VO(mp)₂]^2- ions.

S2. Experimental

Na(Ph₄P)[VO(mmp)₂] was prepared under an atmosphere of pre-purified N₂. To a stirred suspension of VO(acac)₂ (0.76 g, 2.9 mmol) in EtOH (35 ml) was added a solution of Na₂mmp in MeOH (15 ml) [prepared from reaction of 2-mercapto-4-methylphenol (1.0 g, 7.1 mmol) with NaOMe in MeOH]. The VO(acac)₂ dissolved in the reaction mixture and an olive-green solution resulted. After 2 h of stirring at ambient temperature the mixture was filtered to remove small amounts of undissolved material, and Ph₄PCl was added. Some pale solid (NaCl) precipitated and was removed by filtration. Addition of a small amount of diethylether to the green filtrate and subsequent standing led to formation of well formed green crystals, which were isolated by filtration. The IR spectrum showed a strong band at 951 cm^-1 indicative of the presence of the V═O group.

S3. Refinement

A peak representing 0.76 e/Å^e was observed in the final difference map at a distance of 1.32 Å from V, 1.92 Å from O1, 2.28 Å from O2, 2.14 Å from S1 and 2.43 Å from S2. However, in a refinement carried out on another data set on the smae crystal, collected using a Bruker 1 K CCd detector, the peak was not observed. The 20 highest peaks in the diffrence map were all found in the vicinity of the aromatic rings of the ligands and the tetraphenylphosphonium cation, with none greater than 0.41 e/ų. It was concluded that the peak near V was spurious. The H-atom isotropic displacement parameters were fixed at either 1.5 (methyl) or 1.2 (aryl) times the equivalent isotropic displacement parameters

Computing details

Data collection: P3/P4-PC (Siemens, 1991a); cell refinement: P3/P4-PC; data reduction: XDISK (Siemens, 1991b); program(s) used to solve structure: XS (Siemens, 1994); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL93.

Figures

	Fig. 1. Structure of the [VO(mmp)2]^2- dianion. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the [NaVO(mmp)2^-]∞ chains down the a axis. The chains can be seen running parallel to b. C and H atoms have been omitted for clarity.

sodium tetraphenylphosphonium bis(2-mercapto-4- methylphenolato)oxovanadate(IV)]

Crystal data

Na(C24H20P)[V(C7H6OS)2O]	F(000) = 1460
Mr = 705.66	Dx = 1.381 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.888 (3) Å	Cell parameters from 30 reflections
b = 10.947 (2) Å	θ = 20.8–28.9°
c = 22.330 (5) Å	µ = 0.51 mm^−1
β = 90.01 (2)°	T = 129 K
V = 3394.9 (13) Å^3	Block, green
Z = 4	0.42 × 0.38 × 0.28 mm

Data collection

Syntex P21 diffractometer	4301 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω scans	h = −16→16
Absorption correction: ψ scan (North et al., 1968)	k = −1→13
Tmin = 0.789, Tmax = 0.841	l = −26→26
13312 measured reflections	3 standard reflections every 97 reflections
5977 independent reflections	intensity decay: <2%

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.00	Calculated w = 1/[σ^2(Fo^2) + (0.0295P)^2] where P = (Fo^2 + 2Fc^2)/3
5977 reflections	(Δ/σ)max = −0.008
417 parameters	Δρmax = 0.77 e Å^−3
0 restraints	Δρmin = −0.38 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 0 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.

All H atoms were placed in calculated positions and refined using a riding model. The two methyl groups were treated as rigid rotors by refining their torsion angles so as to maximize the sum of the electron density calculated at the three hydrogen atom positions.

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

	x	y	z	Uiso*/Ueq
V	0.65993 (3)	0.54295 (4)	0.21782 (2)	0.01605 (10)
Na	0.68926 (6)	0.82949 (8)	0.24921 (4)	0.0222 (2)
S1	0.73781 (5)	0.43502 (6)	0.13868 (3)	0.0236 (2)
S2	0.51155 (4)	0.44553 (6)	0.19729 (3)	0.02245 (15)
O1	0.74978 (10)	0.67348 (14)	0.19462 (7)	0.0174 (4)
O2	0.57844 (10)	0.67921 (14)	0.24365 (7)	0.0173 (4)
O3	0.70306 (10)	0.47735 (14)	0.27704 (6)	0.0182 (4)
C1	0.8408 (2)	0.5300 (2)	0.13837 (10)	0.0186 (5)
C2	0.8328 (2)	0.6438 (2)	0.16657 (10)	0.0159 (5)
C3	0.9112 (2)	0.7227 (2)	0.16681 (10)	0.0181 (5)
H3	0.9061 (2)	0.8004 (2)	0.18542 (10)	0.022*
C4	0.9978 (2)	0.6876 (2)	0.13965 (11)	0.0234 (6)
H4	1.0512 (2)	0.7418 (2)	0.14033 (11)	0.028*
C5	1.0068 (2)	0.5747 (2)	0.11170 (11)	0.0278 (6)
C6	0.9278 (2)	0.4965 (2)	0.11120 (10)	0.0262 (6)
H6	0.9330 (2)	0.4192 (2)	0.09213 (10)	0.031*
C7	1.1008 (2)	0.5358 (3)	0.08260 (14)	0.0469 (8)
H7A	1.1547 (2)	0.5774 (13)	0.1024 (6)	0.070*
H7B	1.0998 (6)	0.5578 (16)	0.0401 (2)	0.070*
H7C	1.1086 (7)	0.4472 (4)	0.0866 (7)	0.070*
C8	0.4400 (2)	0.5532 (2)	0.23543 (10)	0.0189 (5)
C9	0.4839 (2)	0.6618 (2)	0.25481 (10)	0.0170 (5)
C10	0.4293 (2)	0.7499 (2)	0.28388 (10)	0.0196 (5)
H10	0.4589 (2)	0.8228 (2)	0.29784 (10)	0.024*
C11	0.3305 (2)	0.7312 (2)	0.29262 (10)	0.0239 (6)
H11	0.2935 (2)	0.7921 (2)	0.31239 (10)	0.029*
C12	0.2859 (2)	0.6256 (3)	0.27293 (10)	0.0255 (6)
C13	0.3418 (2)	0.5374 (2)	0.24489 (10)	0.0236 (6)
H13	0.3120 (2)	0.4639 (2)	0.23178 (10)	0.028*
C14	0.1780 (2)	0.6075 (3)	0.27907 (12)	0.0361 (7)
H14A	0.1480 (2)	0.6842 (5)	0.2919 (7)	0.054*
H14B	0.1652 (2)	0.5439 (11)	0.3089 (6)	0.054*
H14C	0.1510 (3)	0.5827 (16)	0.2404 (2)	0.054*
P	0.71640 (4)	1.02550 (6)	0.02564 (3)	0.01600 (14)
C15	0.7062 (2)	0.8749 (2)	−0.00567 (10)	0.0172 (5)
C16	0.7547 (2)	0.7781 (2)	0.02163 (11)	0.0223 (6)
H16	0.7969 (2)	0.7934 (2)	0.05426 (11)	0.027*
C17	0.7414 (2)	0.6602 (2)	0.00126 (11)	0.0278 (6)
H17	0.7741 (2)	0.5943 (2)	0.02007 (11)	0.033*
C18	0.6807 (2)	0.6382 (2)	−0.04637 (12)	0.0303 (6)
H18	0.6722 (2)	0.5571 (2)	−0.06046 (12)	0.036*
C19	0.6324 (2)	0.7327 (2)	−0.07372 (11)	0.0277 (6)
H19	0.5912 (2)	0.7163 (2)	−0.10670 (11)	0.033*
C20	0.6435 (2)	0.8519 (2)	−0.05344 (10)	0.0223 (6)
H20	0.6090 (2)	0.9169 (2)	−0.07174 (10)	0.027*
C21	0.65173 (15)	1.0271 (2)	0.09516 (9)	0.0141 (5)
C22	0.5925 (2)	0.9313 (2)	0.11212 (10)	0.0177 (5)
H22	0.5855 (2)	0.8618 (2)	0.08700 (10)	0.021*
C23	0.5434 (2)	0.9380 (2)	0.16642 (10)	0.0188 (5)
H23	0.5031 (2)	0.8726 (2)	0.17878 (10)	0.023*
C24	0.55359 (15)	1.0404 (2)	0.20237 (10)	0.0186 (5)
H24	0.52029 (15)	1.0445 (2)	0.23948 (10)	0.022*
C25	0.6115 (2)	1.1365 (2)	0.18491 (10)	0.0186 (5)
H25	0.6169 (2)	1.2070 (2)	0.20950 (10)	0.022*
C26	0.6617 (2)	1.1298 (2)	0.13141 (10)	0.0185 (5)
H26	0.7027 (2)	1.1950 (2)	0.11951 (10)	0.022*
C27	0.8392 (2)	1.0667 (2)	0.04167 (9)	0.0178 (5)
C28	0.8819 (2)	1.0197 (2)	0.09313 (10)	0.0207 (6)
H28	0.8463 (2)	0.9677 (2)	0.11903 (10)	0.025*
C29	0.9766 (2)	1.0493 (2)	0.10642 (10)	0.0256 (6)
H29	1.0064 (2)	1.0168 (2)	0.14126 (10)	0.031*
C30	1.0277 (2)	1.1262 (2)	0.06883 (11)	0.0269 (6)
H30	1.0924 (2)	1.1466 (2)	0.07824 (11)	0.032*
C31	0.9858 (2)	1.1734 (2)	0.01799 (11)	0.0276 (6)
H31	1.0216 (2)	1.2260 (2)	−0.00750 (11)	0.033*
C32	0.8912 (2)	1.1443 (2)	0.00400 (10)	0.0226 (6)
H32	0.8620 (2)	1.1769 (2)	−0.03098 (10)	0.027*
C33	0.6662 (2)	1.1363 (2)	−0.02472 (10)	0.0207 (6)
C34	0.5990 (2)	1.2203 (2)	−0.00404 (11)	0.0247 (6)
H34	0.5770 (2)	1.2160 (2)	0.03617 (11)	0.030*
C35	0.5640 (2)	1.3104 (2)	−0.04192 (12)	0.0330 (7)
H35	0.5180 (2)	1.3678 (2)	−0.02773 (12)	0.040*
C36	0.5961 (2)	1.3164 (3)	−0.10009 (12)	0.0352 (7)
H36	0.5726 (2)	1.3786 (3)	−0.12587 (12)	0.042*
C37	0.6622 (2)	1.2331 (3)	−0.12140 (11)	0.0308 (7)
H37	0.6839 (2)	1.2381 (3)	−0.16168 (11)	0.037*
C38	0.6972 (2)	1.1420 (2)	−0.08422 (10)	0.0254 (6)
H38	0.7419 (2)	1.0837 (2)	−0.09906 (10)	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V	0.0161 (2)	0.0129 (2)	0.0191 (2)	0.0002 (2)	−0.0020 (2)	0.0010 (2)
Na	0.0177 (5)	0.0173 (5)	0.0314 (6)	−0.0031 (4)	0.0018 (4)	−0.0039 (4)
S1	0.0323 (4)	0.0163 (3)	0.0220 (3)	−0.0047 (3)	0.0030 (3)	−0.0035 (3)
S2	0.0201 (3)	0.0163 (3)	0.0310 (3)	−0.0022 (3)	−0.0077 (3)	−0.0020 (3)
O1	0.0155 (8)	0.0134 (8)	0.0232 (9)	0.0008 (7)	0.0022 (7)	−0.0006 (7)
O2	0.0118 (8)	0.0138 (9)	0.0262 (9)	−0.0006 (7)	0.0004 (7)	−0.0007 (7)
O3	0.0180 (8)	0.0178 (9)	0.0190 (8)	0.0013 (7)	−0.0013 (6)	0.0009 (7)
C1	0.0247 (13)	0.0148 (13)	0.0164 (12)	0.0007 (11)	0.0024 (10)	0.0022 (11)
C2	0.0172 (12)	0.0162 (13)	0.0144 (12)	0.0041 (11)	0.0006 (9)	0.0044 (10)
C3	0.0222 (13)	0.0146 (13)	0.0175 (12)	0.0031 (11)	0.0022 (10)	0.0009 (11)
C4	0.0211 (13)	0.0237 (14)	0.0253 (14)	0.0000 (12)	0.0059 (11)	0.0066 (12)
C5	0.0262 (14)	0.029 (2)	0.0279 (14)	0.0079 (12)	0.0106 (11)	0.0044 (13)
C6	0.037 (2)	0.0177 (14)	0.0237 (13)	0.0046 (12)	0.0100 (11)	−0.0029 (12)
C7	0.036 (2)	0.041 (2)	0.063 (2)	0.009 (2)	0.026 (2)	−0.004 (2)
C8	0.0201 (12)	0.0181 (13)	0.0185 (12)	−0.0018 (11)	−0.0055 (10)	0.0043 (11)
C9	0.0143 (12)	0.0191 (13)	0.0175 (12)	−0.0009 (10)	−0.0036 (9)	0.0079 (11)
C10	0.0172 (13)	0.0184 (13)	0.0233 (13)	−0.0013 (11)	−0.0005 (10)	0.0046 (11)
C11	0.0193 (13)	0.033 (2)	0.0193 (13)	0.0042 (12)	0.0032 (10)	0.0050 (12)
C12	0.0164 (13)	0.040 (2)	0.0200 (13)	−0.0056 (13)	0.0004 (10)	0.0051 (13)
C13	0.0224 (13)	0.0264 (15)	0.0219 (13)	−0.0113 (12)	−0.0040 (10)	0.0045 (12)
C14	0.0187 (14)	0.057 (2)	0.033 (2)	−0.0064 (14)	0.0028 (12)	0.0021 (15)
P	0.0188 (3)	0.0159 (3)	0.0133 (3)	−0.0027 (3)	0.0002 (2)	0.0002 (3)
C15	0.0178 (12)	0.0193 (13)	0.0144 (12)	−0.0014 (11)	0.0063 (10)	−0.0020 (11)
C16	0.0254 (14)	0.0230 (14)	0.0186 (13)	−0.0006 (12)	0.0016 (11)	−0.0018 (11)
C17	0.0314 (15)	0.0218 (15)	0.030 (2)	0.0037 (12)	0.0064 (12)	−0.0003 (12)
C18	0.036 (2)	0.0197 (14)	0.035 (2)	−0.0072 (13)	0.0123 (13)	−0.0105 (13)
C19	0.0294 (15)	0.030 (2)	0.0236 (14)	−0.0084 (13)	0.0013 (11)	−0.0080 (13)
C20	0.0251 (14)	0.0234 (14)	0.0184 (13)	−0.0020 (12)	−0.0006 (10)	−0.0009 (12)
C21	0.0146 (11)	0.0137 (12)	0.0140 (11)	0.0017 (10)	−0.0012 (9)	0.0020 (10)
C22	0.0181 (12)	0.0173 (13)	0.0176 (12)	0.0008 (11)	−0.0041 (10)	−0.0018 (11)
C23	0.0132 (12)	0.0212 (14)	0.0221 (13)	−0.0022 (11)	0.0000 (10)	0.0041 (11)
C24	0.0119 (11)	0.0294 (14)	0.0146 (12)	0.0064 (11)	0.0010 (9)	0.0008 (11)
C25	0.0189 (12)	0.0179 (13)	0.0191 (12)	0.0056 (11)	−0.0036 (10)	−0.0040 (11)
C26	0.0183 (12)	0.0144 (13)	0.0229 (13)	−0.0010 (11)	−0.0004 (10)	0.0032 (11)
C27	0.0214 (12)	0.0171 (13)	0.0149 (12)	−0.0035 (11)	0.0014 (10)	−0.0041 (11)
C28	0.0231 (13)	0.0241 (14)	0.0149 (12)	−0.0011 (11)	0.0025 (10)	−0.0030 (11)
C29	0.0250 (13)	0.034 (2)	0.0179 (13)	0.0024 (13)	−0.0048 (10)	−0.0075 (12)
C30	0.0169 (13)	0.035 (2)	0.0289 (15)	−0.0023 (12)	0.0024 (11)	−0.0117 (13)
C31	0.0241 (14)	0.0265 (15)	0.032 (2)	−0.0097 (12)	0.0072 (11)	−0.0030 (13)
C32	0.0246 (13)	0.0244 (14)	0.0187 (13)	−0.0048 (12)	0.0005 (10)	0.0004 (11)
C33	0.0227 (13)	0.0203 (13)	0.0191 (13)	−0.0087 (11)	−0.0061 (10)	0.0039 (11)
C34	0.0282 (14)	0.0210 (14)	0.0248 (14)	−0.0009 (12)	−0.0049 (11)	0.0026 (12)
C35	0.037 (2)	0.0225 (15)	0.039 (2)	0.0008 (13)	−0.0126 (13)	0.0035 (13)
C36	0.047 (2)	0.024 (2)	0.035 (2)	−0.0086 (14)	−0.0177 (14)	0.0116 (13)
C37	0.040 (2)	0.034 (2)	0.0190 (14)	−0.0165 (14)	−0.0083 (12)	0.0074 (13)
C38	0.0309 (15)	0.0251 (15)	0.0202 (13)	−0.0086 (12)	−0.0051 (11)	0.0021 (12)

Geometric parameters (Å, º)

V—O3	1.6194 (15)	C12—C13	1.389 (3)
V—O2	1.959 (2)	C12—C14	1.518 (3)
V—O1	1.967 (2)	P—C15	1.796 (2)
V—S2	2.3652 (8)	P—C21	1.794 (2)
V—S1	2.3853 (8)	P—C27	1.800 (2)
V—Na^i	3.2232 (11)	P—C33	1.795 (2)
V—Na	3.2398 (12)	C15—C20	1.400 (3)
Na—O2	2.256 (2)	C15—C16	1.395 (3)
Na—O1	2.260 (2)	C16—C17	1.381 (3)
Na—O3^ii	2.281 (2)	C17—C18	1.378 (4)
Na—S1^ii	2.9371 (12)	C18—C19	1.376 (4)
Na—C23	2.988 (2)	C19—C20	1.390 (3)
Na—V^ii	3.2232 (11)	C21—C22	1.386 (3)
S1—C1	1.768 (2)	C21—C26	1.393 (3)
S1—Na^i	2.9371 (12)	C22—C23	1.393 (3)
S2—C8	1.761 (2)	C23—C24	1.386 (3)
O1—C2	1.352 (2)	C24—C25	1.381 (3)
O2—C9	1.350 (3)	C25—C26	1.385 (3)
O3—Na^i	2.281 (2)	C27—C28	1.391 (3)
C1—C6	1.402 (3)	C27—C32	1.397 (3)
C1—C2	1.401 (3)	C28—C29	1.387 (3)
C2—C3	1.390 (3)	C29—C30	1.384 (3)
C3—C4	1.401 (3)	C30—C31	1.377 (3)
C4—C5	1.390 (3)	C31—C32	1.387 (3)
C5—C6	1.392 (3)	C33—C34	1.389 (3)
C5—C7	1.519 (3)	C33—C38	1.398 (3)
C8—C13	1.392 (3)	C34—C35	1.388 (3)
C8—C9	1.405 (3)	C35—C36	1.375 (4)
C9—C10	1.388 (3)	C36—C37	1.379 (4)
C10—C11	1.401 (3)	C37—C38	1.385 (3)
C11—C12	1.383 (4)
O3—V—O2	108.11 (7)	C2—C3—C4	120.1 (2)
O3—V—O1	107.62 (7)	C5—C4—C3	121.0 (2)
O2—V—O1	83.74 (6)	C4—C5—C6	118.6 (2)
O3—V—S2	106.29 (6)	C4—C5—C7	121.2 (2)
O2—V—S2	84.09 (5)	C6—C5—C7	120.1 (2)
O1—V—S2	146.04 (5)	C5—C6—C1	121.1 (2)
O3—V—S1	102.57 (6)	C13—C8—C9	118.9 (2)
O2—V—S1	149.01 (5)	C13—C8—S2	122.9 (2)
O1—V—S1	82.93 (5)	C9—C8—S2	118.1 (2)
S2—V—S1	91.61 (3)	O2—C9—C10	121.4 (2)
O3—V—Na^i	41.57 (6)	O2—C9—C8	119.0 (2)
O2—V—Na^i	149.33 (5)	C10—C9—C8	119.7 (2)
O1—V—Na^i	100.06 (5)	C9—C10—C11	120.0 (2)
S2—V—Na^i	106.47 (3)	C12—C11—C10	121.1 (2)
S1—V—Na^i	61.01 (3)	C13—C12—C11	118.3 (2)
O3—V—Na	101.90 (6)	C13—C12—C14	120.1 (2)
O2—V—Na	43.27 (5)	C11—C12—C14	121.5 (2)
O1—V—Na	43.43 (5)	C12—C13—C8	122.0 (2)
S2—V—Na	126.01 (3)	C15—P—C21	107.84 (11)
S1—V—Na	125.65 (3)	C15—P—C27	112.42 (11)
Na^i—V—Na	124.81 (2)	C21—P—C27	107.47 (10)
O2—Na—O1	70.92 (6)	C15—P—C33	110.24 (11)
O2—Na—O3^ii	161.95 (7)	C21—P—C33	109.94 (11)
O1—Na—O3^ii	98.84 (6)	C27—P—C33	108.87 (11)
O2—Na—S1^ii	124.67 (6)	C20—C15—C16	119.8 (2)
O1—Na—S1^ii	128.95 (5)	C20—C15—P	120.7 (2)
O3^ii—Na—S1^ii	73.37 (5)	C16—C15—P	119.3 (2)
O2—Na—C23	78.09 (7)	C17—C16—C15	120.1 (2)
O1—Na—C23	102.64 (7)	C18—C17—C16	119.9 (3)
O3^ii—Na—C23	90.18 (7)	C19—C18—C17	120.6 (2)
S1^ii—Na—C23	127.20 (6)	C18—C19—C20	120.5 (2)
O2—Na—V^ii	169.88 (6)	C15—C20—C19	119.0 (2)
O1—Na—V^ii	115.42 (5)	C22—C21—C26	120.8 (2)
O3^ii—Na—V^ii	28.11 (4)	C22—C21—P	121.8 (2)
S1^ii—Na—V^ii	45.27 (2)	C26—C21—P	117.5 (2)
C23—Na—V^ii	107.06 (6)	C21—C22—C23	119.2 (2)
O2—Na—V	36.53 (4)	C24—C23—C22	119.8 (2)
O1—Na—V	36.73 (4)	C24—C23—Na	83.93 (13)
O3^ii—Na—V	135.56 (5)	C22—C23—Na	100.71 (14)
S1^ii—Na—V	127.48 (3)	C25—C24—C23	120.8 (2)
C23—Na—V	99.55 (5)	C26—C25—C24	119.8 (2)
V^ii—Na—V	146.41 (3)	C25—C26—C21	119.6 (2)
C1—S1—V	94.50 (8)	C28—C27—C32	120.1 (2)
C1—S1—Na^i	87.47 (8)	C28—C27—P	118.4 (2)
V—S1—Na^i	73.72 (3)	C32—C27—P	121.5 (2)
C8—S2—V	95.52 (8)	C29—C28—C27	119.6 (2)
C2—O1—V	119.26 (14)	C28—C29—C30	119.9 (2)
C2—O1—Na	138.47 (14)	C31—C30—C29	120.8 (2)
V—O1—Na	99.84 (7)	C30—C31—C32	120.0 (2)
C9—O2—V	120.61 (14)	C31—C32—C27	119.6 (2)
C9—O2—Na	139.11 (14)	C34—C33—C38	119.6 (2)
V—O2—Na	100.21 (7)	C34—C33—P	120.0 (2)
V—O3—Na^i	110.32 (8)	C38—C33—P	120.4 (2)
C6—C1—C2	119.7 (2)	C33—C34—C35	120.2 (2)
C6—C1—S1	123.1 (2)	C36—C35—C34	119.7 (3)
C2—C1—S1	117.2 (2)	C35—C36—C37	120.7 (3)
O1—C2—C3	121.2 (2)	C36—C37—C38	120.2 (2)
O1—C2—C1	119.3 (2)	C37—C38—C33	119.6 (3)
C3—C2—C1	119.5 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.