Crystal structure of an ordered [WOF5]− salt: (1,10-phen-H)[WOF5] (1,10-phen = 1,10-phenanthroline)

Turnbull, D.; Gerken, M.

doi:10.1107/S2056989020009767

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ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1345-1348

https://doi.org/10.1107/S2056989020009767

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Crystal structure of an ordered [WOF₅]⁻ salt: (1,10-phen-H)[WOF₅] (1,10-phen = 1,10-phenanthroline)

Douglas Turnbull ^a and Michael Gerken ^a ^*

^aCanadian Centre for Research in Advanced Fluorine Technologies, Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, Alberta, Canada, T1K 3M4
^*Correspondence e-mail: michael.gerken@uleth.ca

Edited by A. M. Chippindale, University of Reading, England (Received 9 July 2020; accepted 16 July 2020; online 24 July 2020)

Crystals of 1,10-phenanthrolinium pentafluoridooxidotungstate(VI), (1,10-phen-H)[WOF₅] (1,10-phen = 1,10-phenanthroline, C₁₂H₈N₂), were obtained upon hydrolysis of WF₆(1,10-phen) in CH₃CN at 193 K. The (1,10-phen-H)[WOF₅] salt contains a rare example of a [WOF₅]⁻ anion in which the oxygen and fluorine atoms are ordered. This ordering was verified by bond-valence determinations and structural comparisons with [Xe₂F₁₁][WOF₅] and Lewis acid-base adducts of WOF₄ with main-group donor ligands. The crystal packing is controlled by N—H⋯F hydrogen bonding that is directed exclusively to the axial F atom as a result of its increased basicity caused by the trans influence of the oxido ligand.

Keywords: tungsten; fluoride; oxide; crystal structure; O/F ordered anion.

CCDC reference: 2016898

1. Chemical context

The crystal structure of tetrameric, fluorine-bridged WOF₄ (Edwards & Jones, 1968 ), as well as those of various fluorido-oxidotungstates(VI) of the form [WO_nF_6–n]ⁿ⁻ (n = 1–3), are characterized by extensive disorder between the oxido and fluorido ligands (Voit et al., 2006 ). Such disorder complications originally led to the incorrect assumption that WOF₄ existed as an oxygen-bridged species. This was later disproved by vibrational spectroscopic studies of WOF₄ that revealed exclusively terminal W=O bonds (Bennett et al., 1972 ; Asprey et al., 1972 ). In [WO_nF_6–n]ⁿ⁻ anions, the nature of the O/F disorder can be controlled by the properties of the counter-cations. For example, Na[WO₂F₄] is ordered (Vlasse et al., 1982 ; Chaminade et al., 1986 ), whereas Rb[WO₂F₄] (Udovenko & Laptash, 2008a ) and Cs[WO₂F₄] (Srivastava et al., 1992 ) are statically disordered, and [NH₄]₂[WO₂F₄] exhibits simultaneous static and dynamic disorder, both of which are quenched below 201 K to reveal an ordered structure (Udovenko & Laptash, 2008b ). In addition, the double salt, [HNC₆H₆OH]₂[Cu(NC₅H₅)₄][WO₂F₄]₂, exhibits ordered [WO₂F₄]²⁻ anions at 153 K as a result of H⋯F and Cu⋯O secondary-bonding interactions (Welk et al., 2001 ). An ordered [WO₃F₃]³⁻ fragment was identified within Pb₅W₃O₉F₁₀ (Abrahams et al., 1987 ) and, despite extensive dynamic disorder within [NH₄]₃[WO₃F₃] (Voit et al., 2006), the stereochemistry could be resolved from the observed displacement of the tungsten atoms from their octahedral symmetry centres (Udovenko & Laptash, 2008a). In all cases, mutual cis arrangements of the oxido ligands are preferred (i.e., cis-[WO₂F₄]²⁻ and fac-[WO₃F₃]³⁻). A trans influence from the oxido ligands results in increased electron density on the effected fluorido ligands, and it is these fluorido ligands that participate in fluorine bridging within multinuclear systems, such as in WOF₄ and in various [W₂O₂F₉]⁻ salts with different counterions {[H₃O]⁺(Hoskins et al., 1987 ); [WF₄(2,2′-bipy)₂]²⁺(Arnaudet et al., 1992 ); [Os₃(CO)₁₂H]⁺ (Crossman et al., 1996 ); [XeF₅]⁺(Bortolus et al., 2020 ); Li–Cs⁺ (Stene et al., 2020 )}, and in [W₂O₄F₆]²⁻ (Wollert et al., 1991 ).

Crystallographically characterized [WOF₅]⁻ salts with a range of counterions {[As(C₆H₅)₄]⁺ (Massa et al., 1982 ); [Cs(15-crown-5)₂]⁺ (Nuszhär et al., 1992 ); Ag²⁺ (Mazej et al., 2017 ); [WF₄(1,2-{P(CH₃)₂}₂C₆H₄)]²⁺ (Levason et al., 2018 )} have exhibited some degree of O/F disorder in the anion, obfuscating the W=O and W—F bond lengths. Recently, however, [Xe₂F₁₁][WOF₅] and [XeF₅][WOF₅]·XeOF₄ were reported to contain [WOF₅]⁻ anions that are ordered as a consequence of multiple Xe⋯F—W interactions (Bortolus et al., 2020). Herein, we report a new ordered [WOF₅]⁻ salt in the form of (1,10-phen-H)[WOF₅] (Fig. 1), obtained during an attempted crystallization of WF₆(1,10-phen) (Turnbull et al., 2019a ).

Figure 1
Displacement ellipsoid plot (50% probability level) of (1,10-phen-H)[WOF₅].

2. Structural commentary

The W=O bond length in (1,10-phen-H)[WOF₅] [1.698 (2) Å] is indistinguishable from those in [Xe₂F₁₁][WOF₅] [1.698 (3) Å; Bortolus et al., 2020), WOF₄{OP(C₆H₅)₃} [1.682 (5) Å; Levason et al., 2016 ] and WOF₄(NC₅H₅) [1.690 (3) Å; Turnbull et al., 2019b ]. The W—F_eq bond lengths [1.8677 (15)–1.8809 (15) Å] are also insignificantly different from those in WOF₄{OP(C₆H₅)₃} [1.857 (3)–1.871 (3) Å; Levason et al., 2016] and WOF₄(NC₅H₅) [1.859 (3)–1.868 (3) Å; Turnbull et al., 2019b]. The W—F_eq bonds in [Xe₂F₁₁][WOF₅] (Bortolus et al., 2020) are also of similar lengths to those in the title compound, although one terminal W—F_eq bond [1.848 (2) Å] is significantly shorter in the [Xe₂F₁₁]⁺ salt, and one bridging bond significantly longer [1.900 (2) Å].

The W—F_ax bond length of (1,10-phen-H)[WOF₅] [2.0048 (15) Å] is slightly shorter than those in [Xe₂F₁₁][WOF₅] [2.047 (2) Å; Bortolus et al., 2020] and [C₅H₅NH][W(NC₆F₅)F₅] [2.0212 (13) Å; Turnbull et al., 2017 ]. In the latter compound, the N1—H1⋯F1 interaction resulted in significant elongation of the W—F_ax bond with respect to that observed in [N(CH₃)₄][W(NC₆F₅)F₅] [1.973 (3) Å; Turnbull et al., 2017]. Gas-phase geometry optimizations of the [Xe₂F₁₁][WOF₅] ion pair and free [WOF₅]⁻ corroborated a significant elongation of the W—F_ax bond in the former anion compared to the latter (2.148 vs 1.972 Å, respectively) arising from cation–anion interactions (Bortolus et al., 2020).

The individual bond valences of the [WOF₅]⁻ anion in (1,10-phen-H)[WOF₅] (Table 1) reveal that the W=O bond (ν = 1.81) is approximately double the strength of the W—F_eq bonds (ν = 0.87–0.90), indicating complete O/F ordering; in a disordered anion, the W=O bond valence is artificially decreased due to averaging with the W—F single bonds. The F1 atom possesses a valence sum significantly less than unity (V = 0.81) because of the trans influence of the oxido ligand and N1—H1⋯F1 hydrogen-bonding interaction substantially polarizing that bond.

Table 1
Bond valences and sums of the [WOF₅]⁻ anion in (1,10-phen-H)[WOF₅]

	ν_i^a		V^b
		W	5.98
W=O	1.81	O	1.88
W—F1	0.62	F1	0.81
W—F2	0.89	F2	0.95
W—F3	0.88	F3	0.94
W—F4	0.90	F4	0.97
W—F5	0.87	F5	0.95
Notes: (a) Defined as ν_i = exp [R_o − R/b], where R is the observed bond length (in Å) and R_o and b are empirical parameters (Brown & Altermatt, 1985 ; Brese & O'Keeffe, 1991 ; Brown, 2002 ; Adams et al., 2004 ). (b) Defined as V = Σ(ν_i). Only secondary contacts within the sum of the van der Waals radii (Bondi, 1964 ) were considered.

3. Supramolecular features

Besides the N1—H1⋯F1 hydrogen-bonding interactions, there also exist weak intermolecular C5⋯O [3.163 (3) Å] and C3⋯C10 [3.204 (4) Å] interactions that result in the formation of columns of cations and anions running parallel to the a axis (Fig. 2) in the packed crystal. The crystal packing, however, appears to be dominated by the N1—H1⋯F1 hydrogen bonds (Table 2) and other intermolecular interactions, such as π–π stacking interactions between cations, are absent.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯F1	0.89 (3)	1.88 (3)	2.704 (3)	154 (3)

Figure 2
Crystal packing of (1,10-phen-H)[WOF₅] viewed along the a axis.

4. Synthesis and crystallization

In the dry box, a 1/4"-o.d. FEP reactor, equipped with a 316-stainless-steel valve and pre-passivated with F₂ (100%, Linde Gas), was charged with WF₆(1,10-phen) (ca 0.01 g), prepared as described previously (Turnbull et al., 2019a). Acetonitrile (ca 0.1 mL), dried as previously described (Winfield, 1984 ), was distilled into the reactor through a glass vacuum line equipped with grease-free PTFE stopcocks (J. Young). The reactor was heated to 353 K in a hot-water bath and allowed to cool to ambient temperature over 16 h. The reactor was then cooled rapidly to 233 K and the solvent was removed under dynamic vacuum at that temperature, resulting in the formation of colourless needles of (1,10-phen-H)[WOF₅], together with an off-white microcrystalline material that was not further characterized, but is presumed to contain WF₆(1,10-phen) and (1,10-phen-H)[WOF₅].

The reactor was cut open and the crystals transferred onto an aluminium trough cooled to 193 K under a constant stream of liquid-N₂-cooled, dry N₂. The selected crystal was affixed to a Nylon cryo-loop submerged in perfluorinated polyether oil (Fomblin Z-25) and quickly transferred to the goniometer to minimize exposure to air.

5. Refinement details

Crystallographic data collection and refinement parameters are summarized in Table 3. All the hydrogen atoms were located in difference Fourier maps and were refined using a riding model, with the exception of H1, the position of which was refined freely (Table 2).

Table 3
Experimental details

Crystal data
Chemical formula	(C₁₂H₉N₂)[WOF₅]
M_r	476.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	112
a, b, c (Å)	7.1664 (2), 15.5088 (4), 11.6516 (4)
β (°)	101.202 (3)
V (Å³)	1270.31 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	9.16
Crystal size (mm)	0.27 × 0.12 × 0.06

Data collection
Diffractometer	Rigaku SuperNova, Dual source (Mo and Cu), Pilatus 200/300K
Absorption correction	Analytical [numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995 ) implemented in CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Oxford, England.]$ ). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK]
T_min, T_max	0.447, 0.645
No. of measured, independent and observed [I > 2σ(I)] reflections	15835, 2908, 2652
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.038, 1.06
No. of reflections	2908
No. of parameters	194
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.83
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Oxford, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), XP (Sheldrick, 2008 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2016898

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009767/cq2038sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009767/cq2038Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

1,10-Phenanthrolinium pentafluoridooxidotungstate(VI) top

Crystal data top

(C₁₂H₉N₂)[WOF₅]	F(000) = 888
M_r = 476.06	D_x = 2.489 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.1664 (2) Å	Cell parameters from 8493 reflections
b = 15.5088 (4) Å	θ = 3.6–31.4°
c = 11.6516 (4) Å	µ = 9.15 mm⁻¹
β = 101.202 (3)°	T = 112 K
V = 1270.31 (7) Å³	Needle, clear colourless
Z = 4	0.27 × 0.12 × 0.06 mm

Data collection top

Rigaku SuperNova, Dual source (Mo and Cu), Pilatus 200/300K diffractometer	2908 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2652 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: analytical [Numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995) implemented in CrysAlisPro (Rigaku OD, 2015). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK]	h = −9→9
T_min = 0.447, T_max = 0.645	k = −19→20
15835 measured reflections	l = −15→13

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.038	w = 1/[σ²(F_o²) + (0.0179P)² + 0.7231P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
2908 reflections	Δρ_max = 0.97 e Å⁻³
194 parameters	Δρ_min = −0.83 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
W1	0.45262 (2)	0.57004 (2)	0.26707 (2)	0.01171 (4)
F1	0.4234 (2)	0.44319 (10)	0.29168 (15)	0.0209 (3)
F2	0.4618 (2)	0.57848 (10)	0.42837 (14)	0.0226 (4)
F3	0.7145 (2)	0.54615 (11)	0.29703 (15)	0.0222 (3)
F4	0.4359 (2)	0.53785 (11)	0.11094 (13)	0.0233 (3)
F5	0.1857 (2)	0.56900 (10)	0.24578 (15)	0.0202 (3)
O1	0.4729 (3)	0.67755 (13)	0.24458 (18)	0.0242 (4)
N1	0.1998 (3)	0.35275 (14)	0.41042 (18)	0.0134 (4)
H1	0.286 (4)	0.3659 (19)	0.368 (2)	0.014 (7)*
N2	0.4933 (3)	0.24312 (14)	0.39891 (19)	0.0154 (4)
C1	0.0520 (4)	0.40604 (17)	0.4040 (2)	0.0172 (5)
H1A	0.041718	0.455156	0.354409	0.021*
C2	−0.0870 (4)	0.39002 (18)	0.4694 (2)	0.0198 (6)
H2	−0.195569	0.426242	0.462155	0.024*
C3	−0.0649 (4)	0.32076 (17)	0.5449 (2)	0.0170 (5)
H3	−0.156152	0.310602	0.592588	0.020*
C4	0.0917 (4)	0.26498 (17)	0.5518 (2)	0.0151 (5)
C5	0.2231 (3)	0.28172 (16)	0.4800 (2)	0.0129 (5)
C6	0.3802 (3)	0.22474 (16)	0.4765 (2)	0.0133 (5)
C7	0.4049 (3)	0.15380 (17)	0.5530 (2)	0.0153 (5)
C8	0.5628 (4)	0.10033 (18)	0.5500 (2)	0.0189 (5)
H8	0.588937	0.052531	0.601602	0.023*
C9	0.6790 (4)	0.11795 (18)	0.4715 (2)	0.0204 (6)
H9	0.785780	0.082457	0.467828	0.024*
C10	0.6365 (4)	0.18924 (17)	0.3973 (2)	0.0190 (5)
H10	0.715470	0.199719	0.342053	0.023*
C11	0.1198 (4)	0.19063 (17)	0.6274 (2)	0.0181 (5)
H11	0.032761	0.178632	0.677319	0.022*
C12	0.2702 (4)	0.13793 (18)	0.6272 (2)	0.0187 (5)
H12	0.287124	0.089145	0.677491	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01223 (6)	0.01049 (6)	0.01259 (6)	−0.00060 (3)	0.00287 (4)	0.00057 (4)
F1	0.0272 (8)	0.0131 (8)	0.0256 (8)	−0.0023 (6)	0.0129 (7)	−0.0004 (6)
F2	0.0277 (9)	0.0254 (9)	0.0147 (8)	−0.0001 (7)	0.0044 (7)	−0.0030 (6)
F3	0.0153 (8)	0.0213 (8)	0.0298 (9)	0.0018 (6)	0.0037 (7)	0.0017 (7)
F4	0.0282 (9)	0.0284 (9)	0.0145 (7)	−0.0049 (7)	0.0071 (6)	−0.0014 (7)
F5	0.0121 (7)	0.0233 (9)	0.0249 (8)	0.0003 (6)	0.0027 (6)	−0.0025 (6)
O1	0.0249 (10)	0.0152 (10)	0.0320 (11)	−0.0003 (8)	0.0043 (9)	0.0021 (8)
N1	0.0137 (10)	0.0133 (10)	0.0140 (10)	−0.0023 (8)	0.0051 (9)	−0.0005 (8)
N2	0.0162 (10)	0.0131 (11)	0.0179 (11)	−0.0016 (8)	0.0058 (9)	0.0000 (9)
C1	0.0209 (13)	0.0119 (12)	0.0185 (13)	0.0018 (10)	0.0029 (11)	0.0012 (10)
C2	0.0179 (13)	0.0183 (14)	0.0238 (14)	0.0031 (11)	0.0056 (11)	−0.0047 (11)
C3	0.0167 (12)	0.0166 (12)	0.0191 (13)	−0.0019 (10)	0.0065 (10)	−0.0060 (10)
C4	0.0151 (12)	0.0154 (13)	0.0143 (12)	−0.0044 (10)	0.0017 (10)	−0.0038 (10)
C5	0.0131 (11)	0.0107 (12)	0.0142 (11)	−0.0015 (9)	0.0007 (9)	−0.0036 (10)
C6	0.0127 (11)	0.0126 (12)	0.0143 (11)	−0.0022 (9)	0.0018 (9)	−0.0027 (9)
C7	0.0158 (12)	0.0133 (12)	0.0151 (12)	−0.0025 (10)	−0.0011 (10)	−0.0013 (10)
C8	0.0210 (13)	0.0139 (12)	0.0189 (13)	0.0024 (11)	−0.0035 (11)	0.0010 (11)
C9	0.0185 (13)	0.0168 (14)	0.0250 (14)	0.0034 (10)	0.0023 (11)	−0.0042 (11)
C10	0.0152 (12)	0.0200 (14)	0.0231 (13)	−0.0010 (10)	0.0072 (11)	−0.0036 (11)
C11	0.0220 (13)	0.0174 (13)	0.0167 (12)	−0.0040 (10)	0.0083 (11)	−0.0001 (10)
C12	0.0232 (13)	0.0176 (13)	0.0143 (12)	−0.0047 (11)	0.0008 (10)	0.0018 (10)

Geometric parameters (Å, º) top

W1—F1	2.0048 (15)	C3—C4	1.407 (4)
W1—F2	1.8724 (16)	C4—C5	1.400 (4)
W1—F3	1.8779 (15)	C4—C11	1.441 (4)
W1—F4	1.8677 (15)	C5—C6	1.438 (4)
W1—F5	1.8809 (15)	C6—C7	1.405 (4)
W1—O1	1.698 (2)	C7—C8	1.409 (4)
N1—H1	0.89 (3)	C7—C12	1.437 (4)
N1—C1	1.334 (3)	C8—H8	0.9500
N1—C5	1.359 (3)	C8—C9	1.379 (4)
N2—C6	1.357 (3)	C9—H9	0.9500
N2—C10	1.326 (3)	C9—C10	1.400 (4)
C1—H1A	0.9500	C10—H10	0.9500
C1—C2	1.389 (4)	C11—H11	0.9500
C2—H2	0.9500	C11—C12	1.353 (4)
C2—C3	1.378 (4)	C12—H12	0.9500
C3—H3	0.9500

F2—W1—F1	84.80 (7)	C3—C4—C11	122.8 (2)
F2—W1—F3	89.33 (7)	C5—C4—C3	118.3 (2)
F2—W1—F5	88.24 (7)	C5—C4—C11	118.9 (2)
F3—W1—F1	84.73 (7)	N1—C5—C4	119.2 (2)
F3—W1—F5	167.69 (7)	N1—C5—C6	119.2 (2)
F4—W1—F1	83.59 (7)	C4—C5—C6	121.6 (2)
F4—W1—F2	168.37 (7)	N2—C6—C5	117.5 (2)
F4—W1—F3	90.06 (7)	N2—C6—C7	124.7 (2)
F4—W1—F5	89.89 (7)	C7—C6—C5	117.7 (2)
F5—W1—F1	83.04 (7)	C6—C7—C8	116.6 (2)
O1—W1—F1	178.86 (8)	C6—C7—C12	120.0 (2)
O1—W1—F2	95.67 (8)	C8—C7—C12	123.5 (2)
O1—W1—F3	96.31 (8)	C7—C8—H8	120.3
O1—W1—F4	95.93 (9)	C9—C8—C7	119.5 (2)
O1—W1—F5	95.94 (8)	C9—C8—H8	120.3
C1—N1—H1	117.1 (19)	C8—C9—H9	120.7
C1—N1—C5	122.7 (2)	C8—C9—C10	118.6 (2)
C5—N1—H1	120.1 (19)	C10—C9—H9	120.7
C10—N2—C6	116.2 (2)	N2—C10—C9	124.4 (2)
N1—C1—H1A	119.9	N2—C10—H10	117.8
N1—C1—C2	120.3 (2)	C9—C10—H10	117.8
C2—C1—H1A	119.9	C4—C11—H11	120.0
C1—C2—H2	120.5	C12—C11—C4	119.9 (2)
C3—C2—C1	119.0 (3)	C12—C11—H11	120.0
C3—C2—H2	120.5	C7—C12—H12	119.1
C2—C3—H3	119.8	C11—C12—C7	121.7 (2)
C2—C3—C4	120.5 (2)	C11—C12—H12	119.1
C4—C3—H3	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F1	0.89 (3)	1.88 (3)	2.704 (3)	154 (3)

Bond valences and sums of the [WOF₅]^- anion in (1,10-phen-H)[WOF₅] top

	ν_i^a		V^b
		W	5.98
W═O	1.81	O	1.88
W—F1	0.62	F1	0.81
W—F2	0.89	F2	0.95
W—F3	0.88	F3	0.94
W—F4	0.90	F4	0.97
W—F5	0.87	F5	0.95

Notes: (a) Defined as ν_i = exp[R_o - R/b], where R is the observed bond length (in Å) and R_o and b are empirical parameters (Brown & Altermatt, 1985; Brese & O'Keeffe, 1991; Brown, 2002; Adams et al., 2004). (b) Defined as V = Σ(ν_i). Only secondary contacts within the sum of the van der Waals' radii (Bondi, 1964) were considered.

Acknowledgements

We thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for awarding a Discovery grant to MG as well as CGS-M and PGS-D scholarships to DT. In addition, we would like to thank the University of Lethbridge for awarding the SGS Dean's Scholarship and Tuition Award to DT and supporting this work.

Funding information

Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada (grant No. 261340-2013 to Michael Gerken; scholarship to Douglas Turnbull).

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