(Hexa­fluoro­silicato-[kappa]²F,F')bis­(1,10-phenanthroline-[kappa]²N,N')zinc(II) methanol monosolvate

The title compound, [Zn(SiF₆)(C₁₂H₈N₂)₂]·CH₃OH, contains a neutral heteroleptic tris-chelate Zn^II complex, viz. [Zn(SiF₆)(phen)₂] (phen is 1,10-phenanthroline), exhibiting approximate mol­ecular C₂ point-group symmetry. The Zn^II cation adopts a severely distorted octa­hedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn^II complex bearing a bidentate-bound hexa­fluoro­silicate ligand. A density functional theory study of the isolated [Zn(SiF₆)(phen)₂] complex was undertaken to reveal the influence of crystal packing on the mol­ecular structure of the complex. In the crystal structure, the methanol solvent mol­ecule forms a hydrogen bond to one F atom of the hexa­fluoro­silicate ligand. The hydrogen-bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).

S1. Introduction

In this contribution, we report the molecular structure of [Zn(SiF₆)(phen)₂] (phen is 1,10-phenanthroline) and the crystal structure of its methanol monosolvate, the title compound, (I). To the best of our knowledge and based on a search of the Cambridge Structural Database (CSD; Version 5.34, with updates to May 2013; Allen, 2002), (I) represents the first crystallographically characterized example of a Zn^II complex containing a bidentate-bound hexa­fluoro­silicate ligand. This is of particular inter­est considering that linear [Zn(µ-SiF₆)]_n pillars, formed through the bridging of Zn^II cations by the F atoms in axial positions, are often exploited as building blocks in the construction of coordination networks (Larpent et al., 2013, and references therein). Examples of structurally characterized complexes containing a hexa­fluoro­silicate ligand in a chelate binding mode for other metal ions are also scarce (Fleming et al., 1998; Lehaire et al., 2002).

Compound (I) was obtained unintentionally during our systematic crystal-engineering studies of discrete and polymeric metallo­supra­molecular assemblies formed from labile cis-preconfigured precursor complexes and the bent 4,4'-di­thiodi­pyridine bridging ligand (Seidel, Goddard & Oppel, 2013). To this end, we used phen as a cis-protecting ligand. While we succeeded in preparing a metallamacrocycle and a one-dimensional coordination polymer, consisting of 4,4'-di­thiodi­pyridine as bridging ligands and [Cu(phen)]²⁺ and [Cd(phen)]²⁺ as corner units, respectively (Seidel et al., 2011a), our attempts to combine [Zn(phen)]²⁺ units with 4,4'-di­thiodi­pyridine have so far been unsuccessful (Seidel et al., 2011b, 2012; Seidel, Dietz et al., 2013). When equimolar amounts of Zn^II, phen and 4,4'-di­thiodi­pyridine were mixed in methanol in the presence of weakly coordinating tetra­fluoro­borate counter-ions, in the hope of obtaining a metallamacrocycle or a coordination polymer consisting of [Zn(phen)]²⁺ units joined by 4,4'-di­thiodi­pyridine, colourless crystals of (I) were found after prolonged standing at ambient temperature. X-ray analysis revealed the structure of (I). It has been documented in the literature that hexa­fluoro­silicate ions can occur in crystallization samples containing tetra­fluoro­borate, because trace amounts of hydro­fluoric acid from partial hydrolysis of tetra­fluoro­borate react with the surface of the glassware (van Konigsbruggen et al., 1993; Fleming et al., 1998).

S2. Experimental

S2.1. Synthesis and crystallization

All starting materials were purchased commercially and used as received. Solvents were of reagent grade. The IR spectrum in the range 4000–400 cm^-1 was recorded on a Nicolet Impact 400D FT–IR spectrometer with a resolution of 2 cm^-1, using the KBr pellet technique. The intensities are abbreviated as follows: s = strong, m = medium and w = weak.

A solution of AgBF₄ (17 mg, 0.088 mmol) in methanol (0.5 ml) was added to a solution of ZnCl₂ (6 mg, 0.044 mmol) in methanol (2 ml). After stirring for 15 min in the dark, the white precipitate which formed was removed by centrifugation and a solution of phen monohydrate (9 mg, 0.044 mmol) in methanol (1 ml) was added to the resulting clear solution with stirring. The solution so obtained was layered carefully onto a solution of 4,4'-di­thiodi­pyridine (10 mg, 0.044 mmol) in di­chloro­methane (3 ml). After standing at room temperature for a couple of months, colourless crystals of (I) suitable for X-ray diffraction were found. IR (KBr, ν, cm^-1): 3377 (m, broad band), 3234 (w, broad band), 3113 (w), 3098 (w), 3075 (w), 3053 (w), 2477 (w), 2467 (w), 2361 (w), 2328 (w), 1637 (w), 1591 (s), 1550 (m), 1519 (w), 1483 (m), 1417 (s), 1385 (w), 1319 (w), 1221 (m), 1149 (w), 1144 (w), 1101 (m), 1061 (s), 1041 (w), 1024 (m), 1004 (w), 987 (w), 860 (m), 818 (m), 812 (m), 781 (s), 750 (m), 727 (m), 717 (s), 679 (m), 654 (s), 607 (m, broad band), 496 (m), 482 (m), 444 (w), 434 (w), 426 (w).

The DFT quantum-chemical calculations for an isolated molecule of [Zn(SiF₆)(phen)₂] were performed at the dispersion-corrected (Grimme, 2006) B3LYP level of theory (Becke, 1993; Lee et al., 1988) using the GAUSSIAN09 program package (Frisch et al., 2010). The Zn atom was described by a small-core relativistic pseudopotential (Figgen et al., 2005) in conjunction with a correlation-consistent polarized valence triple-zeta basis set (Peterson & Puzzarini, 2005). For the remaining atoms, all-electron basis sets of analogous quality [Si: cc-pV(T+d)Z; C, N, F and H: cc-pVTZ] were employed (Dunning et al., 2001; Dunning, 1989). Basis sets, as well as the pseudopotential of Zn, were obtained from the EMSL basis-set library using the Basis Set Exchange web portal (Feller, 1996; Schuchardt et al., 2007). The geometry of [Zn(SiF₆)(phen)₂] was optimized under C₂ point-group symmetry, starting from the structure determined by single-crystal X-ray analysis. The subsequent harmonic vibrational analysis revealed the stationary point to be a minimum on the potential energy surface. The optimized structure in MOL2 format is available in the Supplementary materials.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms of the phen ligands were placed in geometrically calculated positions and refined with the appropriate riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The positions of the methyl H atoms were determined using an initial circular Fourier search and subsequent refinement of the torsion angle of the methyl group while maintaining the tetra­hedral geometry, with C—H = 0.98 Å. The hy­droxy H atom was located in a difference Fourier map and the O—H distance was subsequently restrained to a target value of 0.84 (2) Å. U_iso(H) values were set at 1.5U_eq(C,O) for the methanol molecule.

S3. Results and discussion

In the title complex, (I), the phen chelate ligands are arranged in a cis manner and two cis F atoms of the bidentate-bound hexa­fluoro­silicate ligand occupy the remaining two cis coordination sites of Zn^II. The complex exhibits approximate molecular C₂ point-group symmetry, with the twofold rotation axis passing through the Zn^II and Si atoms, and is thus chiral. The chemical diagram and the displacement ellipsoid plot (Fig. 1) depict the right-handed Δ form, but the centrosymmetric crystal structure contains both enanti­omers. Table 2 compares selected bond lengths and angles for [Zn(SiF₆)(phen)₂] from the X-ray analysis of (I) and the density functional theory (DFT) structure optimization of an isolated molecule.

The coordination of atom Zn1 represents a severely distorted o­cta­hedron formed by two hexa­fluoro­silicate F atoms and four phen N atoms. The deviation from regular o­cta­hedral geometry can be primarily attributed to the chelate angles of the bidentate hexa­fluoro­silicate ligand and the phen ligands, which are, respectively, 65.47 (5) and 78.5 (4)° (average). In (I), the Zn1—F1 and Zn1—F2 distances [2.1070 (12) and 2.2135 (13) Å, respectively] are shorter than the Cu—F distances [2.203 (3) and 2.355 (3) Å] in the [1,3-bis­{[(3-(pyridin-2-yl)pyrazol-1-yl]methyl}­benzene](hexa­fluoro­silicato-κ²F,F')copper(I) cation (CSD refcode NUSKAN; Fleming et al., 1998), while the corresponding F1—Zn1—F2 angle is larger than that in NUSKAN [61.84 (9)°]. A notable feature of (I) is the large variation in the Si—F distances in the SiF₆^2- anion. The Si1—F1 and Si1—F2 bonds, which take part in the SiF₂Zn four-membered ring, at 1.73 (2) Å (average), are significantly elongated compared with the other Si—F bonds, which are similar in length to the average Si—F bond of the noncoordinating SiF₆^2- anion in 251 crystal structures taken from the CSD [1.672 (3) Å].

Fig. 2 shows a superposition of the structure of [Zn(SiF₆)(phen)₂] in (I) in the crystal structure and that calculated for the free complex. As expected, the Zn—N bond lengths and chelate angles of the phen ligands in the DFT-calculated structure are essentially comparable. Most noticeable is the difference in the orientation of the phen ligands and the positions of the axial F atoms in the SiF₆^2- anion. The former is most likely due to effects of crystal packing, since the N20—Zn1—N10 bond angle, in particular, reveals that the coordination of atom Zn1 deviates much less from regular o­cta­hedral geometry in the DFT-calculated structure than in the crystal. Moreover, the significantly larger angle between the mean planes of the phen ligands in the DFT-calculated structure of 78.88°, compared with 47.32 (2)° in the crystal, is consistent with the assumption that the mutual orientation of the phen ligands is mainly determined by steric repulsion for an isolated molecule, but is affected by packing of the molecules in the solid state. In this connection, it is inter­esting to note that the packing coefficient of (I) at 74.1% (calculated using PLATON; Spek, 2009) is high for a molecular crystal, which suggests that (I) exhibits an efficient crystal packing. Packing coefficients are usually in the range of 65–77% (Kitajgorodskij, 1973).

In the crystal structure of (I), the methanol solvent molecule forms an O—H···F hydrogen bond to a noncoordinating hexa­fluoro­silicate F atom (Table 3). There are no strong polymeric inter­molecular inter­actions but only C—H···F, C—H···O and π–π contacts between adjacent molecules. Fig. 3 shows a layer of (I) parallel to (010), revealing a dove-tailed molecular packing of O—H···F hydrogen-bonded assemblies.

In the DFT-calculated structure, the Zn—F bond lengths are shorter than in the solid state, while the F—Zn—F angle is larger. Whereas the F5—Si1—F6 bond angle in the crystal is almost linear at 177.19 (8)°, in the DFT-calculated structure it is remarkably smaller at 166.19°, suggesting a slight contribution from the SiF₄.ZnF₂(phen)₂ canonical form in the free complex. Conversely, it would appear that distortion of the phen ligands about Zn^II caused by crystal packing results in some stabilization of the SiF₆^2- anion contribution. In this regard, it is perhaps worth noting that attempts to optimize the structure of the Zn(SiF₆-κF,F') subunit alone by DFT-calculations were unsuccessful. Instead, such a geometry optimization led to the structures of the dissociation products, ZnF₂ and SiF₄.

Related literature

For related literature, see: Allen (2002); Becke (1993); Dunning (1989); Dunning et al. (2001); Feller (1996); Figgen et al. (2005); Fleming et al. (1998); Frisch (2010); Grimme (2006); Kitajgorodskij (1973); Konigsbruggen et al. (1993); Larpent et al. (2013); Lee et al. (1988); Lehaire et al. (2002); Peterson & Puzzarini (2005); Schuchardt et al. (2007); Seidel et al. (2011a, 2011b, 2012); Seidel, Dietz, Goddard & Oppel (2013); Seidel, Goddard & Oppel (2013); Spek (2009).

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: DIAMOND (Brandenburg, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. (a) The asymmetric unit of (I) and (b) a top view of the [Zn(SiF6)(phen)2] complex in (I) along the Si1···Zn1 axis, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only methanol H atoms are shown, for clarity. The O1—H1···F3 hydrogen bond is illustrated by a dashed line.
	Fig. 2. An overlay diagram of [Zn(SiF6)(phen)2] in (I) (blue in the electronic version of the paper) with the DFT-optimized structure (red). For the sake of clarity, H atoms have been omitted.
	Fig. 3. A packing diagram for (I), showing a molecular layer viewed down the crystallographic b axis. Zn atoms are represented by small spheres and methanol molecules are in space-filling representation. H atoms of the phen ligands have been omitted for clarity.

(Hexafluorosilicato-κ²F,F')bis(1,10-phenanthroline-κ²N,N')zinc(II) methanol monosolvate

Crystal data

[Zn(SiF6)(C12H8N2)2]·CH4O	F(000) = 1216
Mr = 599.91	Dx = 1.722 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.3701 (3) Å	Cell parameters from 7125 reflections
b = 12.7057 (3) Å	θ = 2.8–26.5°
c = 16.3139 (4) Å	µ = 1.19 mm^−1
β = 100.896 (2)°	T = 110 K
V = 2314.3 (1) Å^3	Prism, colourless
Z = 4	0.36 × 0.25 × 0.16 mm

Data collection

Agilent Xcalibur2 diffractometer	4819 independent reflections
Radiation source: sealed X-ray tube	3856 reflections with I > 2σ(I)
Detector resolution: 8.4171 pixels mm^-1	Rint = 0.047
ω scans	θmax = 26.6°, θmin = 2.9°
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Agilent, 2012)	h = −14→14
Tmin = 0.809, Tmax = 1.000	k = −15→15
24589 measured reflections	l = −20→20

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0292P)^2 + 1.4015P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4819 reflections	Δρmax = 0.39 e Å^−3
347 parameters	Δρmin = −0.33 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.

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

	x	y	z	Uiso*/Ueq
Zn1	0.91420 (2)	0.36534 (2)	0.73955 (2)	0.01224 (8)
N1	0.86409 (15)	0.45870 (14)	0.63137 (11)	0.0132 (4)
N2	0.98631 (15)	0.26411 (14)	0.83994 (11)	0.0137 (4)
N10	0.98048 (15)	0.27293 (14)	0.64708 (11)	0.0147 (4)
N20	1.02377 (16)	0.47050 (14)	0.82026 (11)	0.0135 (4)
C1A	0.88539 (18)	0.41246 (17)	0.56050 (13)	0.0133 (4)
C2	0.80828 (19)	0.55115 (17)	0.62480 (14)	0.0156 (5)
H2	0.7939	0.5843	0.6742	0.019*
C2A	1.05413 (18)	0.31603 (17)	0.90496 (13)	0.0132 (4)
C3	0.7698 (2)	0.60163 (18)	0.54814 (15)	0.0187 (5)
H3	0.7310	0.6681	0.5460	0.022*
C4A	0.84844 (19)	0.45720 (18)	0.48095 (13)	0.0157 (5)
C4	0.7886 (2)	0.55431 (18)	0.47628 (14)	0.0184 (5)
H4	0.7613	0.5869	0.4237	0.022*
C5	0.8744 (2)	0.40294 (19)	0.40913 (14)	0.0198 (5)
H5	0.8490	0.4325	0.3552	0.024*
C6	0.9342 (2)	0.31073 (19)	0.41699 (14)	0.0201 (5)
H6	0.9515	0.2771	0.3686	0.024*
C6A	0.97215 (19)	0.26265 (18)	0.49728 (14)	0.0162 (5)
C7	1.0330 (2)	0.16581 (18)	0.50840 (15)	0.0208 (5)
H7	1.0514	0.1289	0.4618	0.025*
C8	1.0653 (2)	0.12552 (19)	0.58708 (15)	0.0213 (5)
H8	1.1059	0.0600	0.5956	0.026*
C9	1.0380 (2)	0.18155 (18)	0.65505 (15)	0.0187 (5)
H9	1.0618	0.1528	0.7094	0.022*
C10A	0.94727 (18)	0.31330 (17)	0.56861 (13)	0.0139 (4)
C12	0.96903 (19)	0.16127 (17)	0.84794 (14)	0.0154 (5)
H12	0.9219	0.1244	0.8027	0.019*
C13	1.01751 (19)	0.10537 (18)	0.92024 (14)	0.0172 (5)
H13	1.0047	0.0317	0.9232	0.021*
C14	1.08365 (19)	0.15758 (18)	0.98694 (14)	0.0170 (5)
H14	1.1154	0.1207	1.0369	0.020*
C14A	1.10401 (19)	0.26640 (17)	0.98072 (13)	0.0147 (5)
C15	1.1708 (2)	0.32788 (18)	1.04710 (14)	0.0177 (5)
H15	1.2043	0.2947	1.0984	0.021*
C16	1.1871 (2)	0.43214 (18)	1.03806 (14)	0.0185 (5)
H16	1.2324	0.4711	1.0828	0.022*
C16A	1.13677 (19)	0.48493 (17)	0.96177 (13)	0.0152 (5)
C17	1.1461 (2)	0.59422 (19)	0.95024 (15)	0.0187 (5)
H17	1.1876	0.6371	0.9940	0.022*
C18	1.09486 (19)	0.63824 (18)	0.87546 (14)	0.0190 (5)
H18	1.0999	0.7120	0.8671	0.023*
C19	1.03502 (19)	0.57379 (17)	0.81135 (14)	0.0169 (5)
H19	1.0011	0.6051	0.7594	0.020*
C20A	1.07201 (18)	0.42661 (17)	0.89491 (13)	0.0130 (4)
Si1	0.65646 (5)	0.36606 (5)	0.77480 (4)	0.01211 (13)
F1	0.75094 (10)	0.28379 (9)	0.73078 (8)	0.0155 (3)
F2	0.77198 (11)	0.45464 (10)	0.78483 (8)	0.0173 (3)
F3	0.57288 (11)	0.45166 (10)	0.81725 (8)	0.0219 (3)
F4	0.55058 (11)	0.27485 (10)	0.76277 (8)	0.0220 (3)
F5	0.71643 (12)	0.31890 (11)	0.86860 (8)	0.0225 (3)
F6	0.60314 (12)	0.41378 (10)	0.67982 (8)	0.0223 (3)
O1	0.33588 (17)	0.46237 (18)	0.73023 (15)	0.0473 (6)
H1	0.4092 (17)	0.453 (3)	0.745 (2)	0.071*
C1	0.2801 (2)	0.3765 (2)	0.76105 (17)	0.0335 (6)
H1A	0.2954	0.3791	0.8222	0.050*
H1B	0.3123	0.3108	0.7428	0.050*
H1C	0.1936	0.3795	0.7397	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01307 (13)	0.01362 (13)	0.00961 (13)	−0.00022 (10)	0.00103 (9)	−0.00006 (10)
N1	0.0127 (9)	0.0151 (9)	0.0118 (9)	−0.0028 (7)	0.0024 (7)	−0.0019 (8)
N2	0.0125 (9)	0.0152 (9)	0.0135 (9)	−0.0005 (7)	0.0028 (7)	−0.0014 (8)
N10	0.0138 (9)	0.0164 (10)	0.0142 (9)	0.0001 (8)	0.0030 (7)	−0.0006 (8)
N20	0.0131 (9)	0.0147 (9)	0.0122 (9)	−0.0002 (7)	0.0016 (7)	−0.0002 (8)
C1A	0.0114 (10)	0.0159 (11)	0.0123 (11)	−0.0039 (9)	0.0018 (8)	−0.0013 (9)
C2	0.0151 (11)	0.0165 (11)	0.0161 (11)	−0.0027 (9)	0.0050 (9)	−0.0022 (9)
C2A	0.0113 (10)	0.0167 (11)	0.0119 (11)	0.0013 (9)	0.0026 (8)	−0.0012 (9)
C3	0.0174 (11)	0.0169 (11)	0.0215 (12)	−0.0007 (9)	0.0031 (9)	0.0026 (10)
C4A	0.0133 (10)	0.0204 (12)	0.0137 (11)	−0.0043 (9)	0.0034 (9)	0.0010 (10)
C4	0.0176 (11)	0.0200 (12)	0.0167 (12)	−0.0023 (10)	0.0009 (9)	0.0068 (10)
C5	0.0213 (12)	0.0265 (12)	0.0121 (11)	−0.0042 (10)	0.0039 (9)	0.0013 (10)
C6	0.0223 (12)	0.0256 (13)	0.0137 (11)	−0.0045 (10)	0.0068 (9)	−0.0053 (10)
C6A	0.0145 (11)	0.0181 (11)	0.0169 (11)	−0.0045 (9)	0.0053 (9)	−0.0028 (9)
C7	0.0215 (12)	0.0211 (12)	0.0222 (13)	−0.0027 (10)	0.0104 (10)	−0.0058 (10)
C8	0.0213 (12)	0.0184 (12)	0.0266 (13)	0.0040 (10)	0.0105 (10)	0.0011 (10)
C9	0.0200 (12)	0.0182 (12)	0.0186 (12)	0.0018 (10)	0.0055 (9)	0.0023 (10)
C10A	0.0117 (10)	0.0178 (11)	0.0129 (11)	−0.0044 (9)	0.0041 (8)	−0.0017 (9)
C12	0.0148 (11)	0.0174 (12)	0.0148 (11)	−0.0022 (9)	0.0045 (9)	−0.0028 (9)
C13	0.0167 (11)	0.0142 (11)	0.0212 (12)	0.0001 (9)	0.0052 (9)	0.0032 (9)
C14	0.0148 (11)	0.0199 (12)	0.0164 (11)	0.0033 (9)	0.0033 (9)	0.0046 (9)
C14A	0.0116 (10)	0.0190 (11)	0.0142 (11)	0.0014 (9)	0.0041 (8)	0.0017 (9)
C15	0.0175 (11)	0.0248 (12)	0.0102 (11)	0.0021 (10)	0.0014 (9)	0.0023 (9)
C16	0.0152 (11)	0.0243 (13)	0.0151 (11)	−0.0013 (9)	0.0009 (9)	−0.0036 (10)
C16A	0.0143 (11)	0.0189 (12)	0.0132 (11)	−0.0002 (9)	0.0042 (9)	−0.0017 (9)
C17	0.0169 (11)	0.0206 (12)	0.0186 (12)	−0.0035 (10)	0.0032 (9)	−0.0069 (10)
C18	0.0191 (11)	0.0143 (11)	0.0237 (12)	−0.0015 (10)	0.0038 (10)	−0.0014 (10)
C19	0.0158 (11)	0.0149 (12)	0.0197 (12)	0.0004 (9)	0.0024 (9)	0.0024 (9)
C20A	0.0115 (10)	0.0156 (11)	0.0125 (11)	0.0010 (9)	0.0041 (8)	−0.0005 (9)
Si1	0.0133 (3)	0.0122 (3)	0.0109 (3)	−0.0013 (2)	0.0026 (2)	−0.0008 (2)
F1	0.0154 (6)	0.0140 (6)	0.0169 (6)	−0.0007 (5)	0.0027 (5)	−0.0035 (5)
F2	0.0191 (7)	0.0159 (6)	0.0179 (7)	−0.0064 (5)	0.0063 (5)	−0.0058 (5)
F3	0.0195 (7)	0.0201 (7)	0.0279 (8)	−0.0010 (6)	0.0092 (6)	−0.0086 (6)
F4	0.0216 (7)	0.0187 (7)	0.0273 (8)	−0.0083 (6)	0.0089 (6)	−0.0062 (6)
F5	0.0302 (8)	0.0249 (7)	0.0117 (6)	0.0005 (6)	0.0023 (6)	0.0033 (6)
F6	0.0254 (7)	0.0222 (7)	0.0169 (7)	0.0037 (6)	−0.0022 (6)	0.0034 (6)
O1	0.0246 (10)	0.0479 (13)	0.0621 (15)	0.0023 (10)	−0.0107 (10)	0.0161 (11)
C1	0.0264 (14)	0.0420 (17)	0.0327 (15)	0.0090 (13)	0.0076 (12)	−0.0005 (14)

Geometric parameters (Å, º)

Zn1—F1	2.1070 (12)	C8—C9	1.401 (3)
Zn1—N20	2.1097 (18)	C8—H8	0.9500
Zn1—N1	2.1134 (18)	C9—H9	0.9500
Zn1—N2	2.1216 (18)	C12—C13	1.398 (3)
Zn1—N10	2.1569 (18)	C12—H12	0.9500
Zn1—F2	2.2135 (13)	C13—C14	1.371 (3)
N1—C2	1.330 (3)	C13—H13	0.9500
N1—C1A	1.359 (3)	C14—C14A	1.409 (3)
N2—C12	1.331 (3)	C14—H14	0.9500
N2—C2A	1.358 (3)	C14A—C15	1.431 (3)
N10—C9	1.327 (3)	C15—C16	1.349 (3)
N10—C10A	1.364 (3)	C15—H15	0.9500
N20—C19	1.329 (3)	C16—C16A	1.434 (3)
N20—C20A	1.357 (3)	C16—H16	0.9500
C1A—C4A	1.406 (3)	C16A—C20A	1.406 (3)
C1A—C10A	1.437 (3)	C16A—C17	1.408 (3)
C2—C3	1.400 (3)	C17—C18	1.368 (3)
C2—H2	0.9500	C17—H17	0.9500
C2A—C14A	1.408 (3)	C18—C19	1.399 (3)
C2A—C20A	1.433 (3)	C18—H18	0.9500
C3—C4	1.370 (3)	C19—H19	0.9500
C3—H3	0.9500	Si1—F4	1.6557 (14)
C4A—C4	1.404 (3)	Si1—F5	1.6646 (14)
C4A—C5	1.437 (3)	Si1—F6	1.6677 (14)
C4—H4	0.9500	Si1—F3	1.6778 (14)
C5—C6	1.348 (3)	Si1—F2	1.7138 (13)
C5—H5	0.9500	Si1—F1	1.7475 (13)
C6—C6A	1.436 (3)	O1—C1	1.402 (3)
C6—H6	0.9500	O1—H1	0.830 (18)
C6A—C10A	1.405 (3)	C1—H1A	0.9800
C6A—C7	1.406 (3)	C1—H1B	0.9800
C7—C8	1.366 (3)	C1—H1C	0.9800
C7—H7	0.9500
F1—Zn1—N20	139.69 (6)	C8—C9—H9	118.5
F1—Zn1—N1	97.14 (6)	N10—C10A—C6A	122.8 (2)
N20—Zn1—N1	101.53 (7)	N10—C10A—C1A	117.37 (19)
F1—Zn1—N2	87.78 (6)	C6A—C10A—C1A	119.8 (2)
N20—Zn1—N2	78.79 (7)	N2—C12—C13	122.6 (2)
N1—Zn1—N2	171.41 (7)	N2—C12—H12	118.7
F1—Zn1—N10	96.01 (6)	C13—C12—H12	118.7
N20—Zn1—N10	122.56 (7)	C14—C13—C12	119.6 (2)
N1—Zn1—N10	78.24 (7)	C14—C13—H13	120.2
N2—Zn1—N10	94.29 (7)	C12—C13—H13	120.2
F1—Zn1—F2	65.47 (5)	C13—C14—C14A	119.4 (2)
N20—Zn1—F2	81.35 (6)	C13—C14—H14	120.3
N1—Zn1—F2	83.82 (6)	C14A—C14—H14	120.3
N2—Zn1—F2	104.67 (6)	C2A—C14A—C14	117.3 (2)
N10—Zn1—F2	152.42 (6)	C2A—C14A—C15	119.2 (2)
C2—N1—C1A	118.20 (19)	C14—C14A—C15	123.5 (2)
C2—N1—Zn1	127.75 (15)	C16—C15—C14A	121.1 (2)
C1A—N1—Zn1	113.87 (14)	C16—C15—H15	119.4
C12—N2—C2A	118.20 (19)	C14A—C15—H15	119.4
C12—N2—Zn1	128.90 (15)	C15—C16—C16A	120.9 (2)
C2A—N2—Zn1	112.82 (14)	C15—C16—H16	119.5
C9—N10—C10A	117.69 (19)	C16A—C16—H16	119.5
C9—N10—Zn1	129.70 (15)	C20A—C16A—C17	117.2 (2)
C10A—N10—Zn1	112.35 (14)	C20A—C16A—C16	119.4 (2)
C19—N20—C20A	118.22 (19)	C17—C16A—C16	123.3 (2)
C19—N20—Zn1	127.93 (15)	C18—C17—C16A	119.5 (2)
C20A—N20—Zn1	112.99 (14)	C18—C17—H17	120.3
N1—C1A—C4A	122.7 (2)	C16A—C17—H17	120.3
N1—C1A—C10A	117.63 (19)	C17—C18—C19	119.5 (2)
C4A—C1A—C10A	119.7 (2)	C17—C18—H18	120.3
N1—C2—C3	122.7 (2)	C19—C18—H18	120.3
N1—C2—H2	118.6	N20—C19—C18	122.6 (2)
C3—C2—H2	118.6	N20—C19—H19	118.7
N2—C2A—C14A	122.9 (2)	C18—C19—H19	118.7
N2—C2A—C20A	117.29 (19)	N20—C20A—C16A	122.9 (2)
C14A—C2A—C20A	119.8 (2)	N20—C20A—C2A	117.60 (19)
C4—C3—C2	119.4 (2)	C16A—C20A—C2A	119.5 (2)
C4—C3—H3	120.3	F4—Si1—F5	91.11 (7)
C2—C3—H3	120.3	F4—Si1—F6	90.91 (7)
C4—C4A—C1A	117.5 (2)	F5—Si1—F6	177.19 (8)
C4—C4A—C5	123.3 (2)	F4—Si1—F3	92.68 (7)
C1A—C4A—C5	119.1 (2)	F5—Si1—F3	91.11 (7)
C3—C4—C4A	119.5 (2)	F6—Si1—F3	90.74 (7)
C3—C4—H4	120.3	F4—Si1—F2	176.25 (7)
C4A—C4—H4	120.3	F5—Si1—F2	88.58 (7)
C6—C5—C4A	121.1 (2)	F6—Si1—F2	89.28 (7)
C6—C5—H5	119.4	F3—Si1—F2	91.06 (7)
C4A—C5—H5	119.4	F4—Si1—F1	91.28 (7)
C5—C6—C6A	121.0 (2)	F5—Si1—F1	89.18 (7)
C5—C6—H6	119.5	F6—Si1—F1	88.82 (7)
C6A—C6—H6	119.5	F3—Si1—F1	176.02 (7)
C10A—C6A—C7	117.7 (2)	F2—Si1—F1	84.98 (6)
C10A—C6A—C6	119.2 (2)	Si1—F1—Zn1	106.26 (6)
C7—C6A—C6	123.1 (2)	Si1—F2—Zn1	103.09 (6)
C8—C7—C6A	119.2 (2)	C1—O1—H1	107 (3)
C8—C7—H7	120.4	O1—C1—H1A	109.5
C6A—C7—H7	120.4	O1—C1—H1B	109.5
C7—C8—C9	119.5 (2)	H1A—C1—H1B	109.5
C7—C8—H8	120.2	O1—C1—H1C	109.5
C9—C8—H8	120.2	H1A—C1—H1C	109.5
N10—C9—C8	123.1 (2)	H1B—C1—H1C	109.5
N10—C9—H9	118.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···F3	0.83 (2)	2.01 (2)	2.802 (2)	160 (4)