Crystal structures of three copper(II)–2,2′-bi­pyridine (bpy) compounds, [Cu(bpy)2(H2O)][SiF6]·4H2O, [Cu(bpy)2(TaF6)2] and [Cu(bpy)3][TaF6]2 and a related coordination polymer, [Cu(bpy)(H2O)2SnF6]n

Nisbet, M.L.; Hiralal, E.; Poeppelmeier, K.R.

doi:10.1107/S2056989021000633

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 158-164

https://doi.org/10.1107/S2056989021000633

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Crystal structures of three copper(II)–2,2′-bipyridine (bpy) compounds, [Cu(bpy)₂(H₂O)][SiF₆]·4H₂O, [Cu(bpy)₂(TaF₆)₂] and [Cu(bpy)₃][TaF₆]₂ and a related coordination polymer, [Cu(bpy)(H₂O)₂SnF₆]_n

Matthew L. Nisbet,^a Emily Hiralal ^a and Kenneth R. Poeppelmeier ^a ^*

^a2145 Sheridan Road, Evanston, IL 60208, USA
^*Correspondence e-mail: krp@northwestern.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 December 2020; accepted 19 January 2021; online 26 January 2021)

We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ²N,N′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy)₂(H₂O)][SiF₆]·4H₂O (bpy is 2,2′-bipyridine, C₁₀H₈N₂), (I), bis(2,2′-bipyridine-3κ²N,N′)-di-μ-fluorido-1:3κ²F:F;2:3κ²F:F-decafluorido-1κ⁵F,2κ⁵F-ditantalum(V)copper(II), [Cu(bpy)₂(TaF₆)₂], (II), tris(2,2′-bipyridine-κ²N,N′)copper(II) bis[hexafluoridotantalate(V)], [Cu(bpy)₃][TaF₆]₂, (III), and catena-poly[[diaqua(2,2′-bipyridine-κ²N,N′)copper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H₂O)₂SnF₆]_n, (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C₂, D₂, and D₃ symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H⋯F and O—H⋯O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin.

Keywords: crystal structure; hydrothermal synthesis; racemic compounds; copper; main group; d⁰ early transition metal.

CCDC references: 2048914; 2048918; 2048917; 2048915

1. Chemical context

Copper(II) complexes of 2,2′-bipyridine (bpy) adopt a wide range of coordination geometries, including square pyramidal, trigonal bipyramidal and octahedral, depending on experimental conditions such as the ligand-to-metal ratio and pH (Garribba et al., 2000 ). Previous studies have shown that racemic combinations of chiral [Cu(bpy)₂(H₂O)]²⁺ can crystallize in polar structures in the presence of early transition metal fluorides MF₆^2–, (M = Ti, Zr, Hf) (Gautier et al., 2012 ; Nisbet et al., 2020 ).

Here, we investigate the influence of the anion on the speciation of the copper(II) complex and the arrangement of the ions in the crystal structure in a series of compounds based on copper(II)–2,2′-bipyridine cations and SiF₆^2–, SnF₆^2– and TaF₆⁻ anions. Among these hydrothermally prepared structures we observe three distinct locally chiral copper-bipyridine complexes: C₂-symmetric cations in [Cu(bpy)₂(H₂O)][SiF₆]·4H₂O, (I), D₂-symmetric Cu(bpy)₂(TaF₆)₂ molecules, (II) and D₃-symmetric cations in [Cu(bpy)₃][TaF₆]₂, (III). We also report the structure of a coordination polymer based on Cu(bpy)(H₂O)₂²⁺ cations and SnF₆^2– anions, (IV), that forms under similar conditions.

2. Structural commentary

Compound (I) has the formula [Cu(bpy)₂(H₂O)][SiF₆]·4H₂O and crystallizes in space group C2/c. The structure features isolated C₂-symmetric Δ- and Λ-[Cu(bpy)₂(H₂O)]²⁺ cations and octahedral SiF₆^2– anions (Fig. 1). The five-coordinate Cu²⁺ ion has a slightly distorted trigonal–bipyramidal coordination environment (τ = 0.77), as described by the parameter τ = (β − α)/60, where β and α are the two largest angles of the complex (τ = 1 corresponds to an ideal trigonal bipyramid and τ = 0 corresponds to an ideal square pyramid) (Melnic et al., 2014 ). The average Cu—N bond length and the Cu—OH₂ bond distance in (I) are in agreement with the reported distances in other known [Cu(bpy)₂(H₂O)]²⁺ complexes (Gautier et al., 2012; Nisbet et al., 2020; Shi et al., 2010 ; Yu et al., 2007 ).

Figure 1
The molecular structure of (I)

. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å. [Symmetry code: (i) $[1\over2]$ + x, $[1\over2]$ − y, $[1\over2]$ + z.]

Compound (II) has the formula Cu(bpy)₂(TaF₆)₂ and crystallizes in space group P $[\overline{1}]$ . The structure is comprised of molecular Δ- and Λ- Cu(bpy)₂(TaF₆)₂ complexes with local D₂ symmetry. Each Cu^II center is equatorially coordinated by two bpy ligands and axially coordinated by two TaF₆⁻ groups. Two independent Cu(bpy)₂(TaF₆)₂ units with the same handedness are present within the arbitrarily chosen asymmetric unit (Fig. 2). These complexes differ in their Cu—F bond lengths and F—Cu—F angles: Cu1—F1 = 2.537 (3), Cu1—F7 = 2.987 (3) Å, F1—Cu1—F7 = 161.46 (9)°; Cu2—F13 = 2.706 (3), Cu2—F19 = 2.775 (3) Å, F13—Cu2—F19 = 168.21 (10)°. The observed Cu—F distances fall above the upper quartile of the distribution of known Cu—F bond distances among structures in the Cambridge Structural Database (mean = 2.240 Å, standard deviation = 0.270 Å). The Cu—N and Cu—F distances in (II) are in reasonable agreement with the bond distances reported in the complex (6,6′′′-dimethyl-2,2′:6′,2′′:6′′,2′′′-quaterpyridine)bis(tetrafluoroborate)copper(II) (CSD refcode: UZELOC; Adamski et al., 2017 ).

Figure 2
The molecular structure of one of the two independent molecules in (II)

. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å.

Compound (III) has the formula [Cu(bpy)₃][TaF₆]₂ and crystallizes in the enantiomorphous space group P3₂. The structure of (III) contains D₃-symmetric Λ-Cu(bpy)₃²⁺ cations with Cu^II in an octahedral CuN₆ coordination environment. The Cu—N distances are in agreement with those of the Cu(bpy)₃²⁺ cations in [Cu(bpy)₃][PF₆]₂ (CSD refcode: REZJAI; Wang et al., 2007 ) and [Cu(bpy)₃][BF₄]₂ (CSD refcode: RIGTEH; Chamayou et al., 2007 ). Two distinct octahedral TaF₆⁻ anions are present in the asymmetric unit (Fig. 3).

Figure 3
The molecular structure of (III)

. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å.

Compound (IV) has the formula Cu(bpy)(H₂O)₂SnF₆ and crystallizes in space group P2/n. The structure is composed of one-dimensional coordination chains propagating in the [101] direction that can be described as alternating Cu(bpy)(H₂O)₂²⁺ cations (Cu site symmetry 2) and SnF₆²⁻ anions catenated through bridging Cu—F—Sn linkages. The Sn⁴⁺ ion occupies a crystallographic inversion center. Intramolecular hydrogen bonding is present along the chains via O1—H1A⋯F2 and O1—H1B⋯F3 contacts (Fig. 4; Table 2). The Cu—F bond distance of 2.3830 (10) Å is in agreement with those found in the reported compound Cu(4,4′-bipyridine)₂SiF₆ (CSD refcode: PETWES; Nugent et al., 2013 ).

Table 2
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F2ⁱ	0.88 (3)	1.79 (3)	2.6444 (17)	165 (3)
O1—H1B⋯F3ⁱⁱ	0.81 (3)	1.84 (4)	2.6293 (17)	164 (4)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ ; (ii) .

Figure 4
The molecular structure of (IV)

. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å. [Symmetry code: (i) $[1\over2]$ − x, y, $[3\over2]$ − z.]

3. Supramolecular features

In the extended structure of (I), the Cu(bpy)₂(H₂O)²⁺ and SiF₆²⁻ groups are linked via O—H⋯F hydrogen bonding between the apical water molecule and two SiF₆²⁻ ions (Table 1). The Δ/Λ-Cu(bpy)₂(H₂O)²⁺ units participate in displaced heterochiral π–π stacking interactions between the N1/C1–C5 and N2/C6–C10 rings with an interplanar angle of 1.11 (11)°, centroid–centroid distance of 3.8774 (12) Å, and a slippage distance of 1.490 Å to form Δup–Λdown–Δup–Λdown and Δdown–Λup–Δdown–Λup chains (up/down refers to the orientation of the Cu—O bond vector in the +a or –a direction). The water molecules of hydration are involved in O—H⋯F hydrogen bonding interactions with the SiF₆²⁻ anion as well as O—H⋯O bonds with other water molecules (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F3	0.76 (3)	1.91 (3)	2.6616 (14)	177 (3)
O1—H1B⋯F6ⁱ	0.78 (2)	1.93 (2)	2.7053 (14)	170 (2)
O2—H2A⋯F1	0.75 (2)	1.94 (2)	2.6677 (17)	164 (2)
O2—H2B⋯F4ⁱ	0.79 (3)	2.00 (3)	2.7807 (17)	167 (2)
O3—H3A⋯F5ⁱⁱ	0.77 (3)	1.99 (3)	2.7607 (18)	177 (3)
O3—H3B⋯O5ⁱⁱⁱ	0.73 (3)	2.06 (3)	2.779 (2)	171 (3)
O4—H4A⋯O3	0.72 (2)	2.05 (2)	2.749 (2)	162 (2)
O4—H4B⋯F4	0.77 (3)	1.98 (3)	2.7462 (16)	170 (2)
O5—H5A⋯O4	0.69 (2)	2.13 (2)	2.779 (2)	158 (2)
O5—H5B⋯O2^iv	0.81 (3)	1.99 (3)	2.786 (2)	169 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 5
Packing diagram for (I)

: yellow polyhedra represent Cu(bpy)₂(H₂O)²⁺ cations and pink polyhedra represent SiF₆²⁻ anions.

The neutral Cu(bpy)₂(TaF₆)₂ complexes in (II) form homochiral chains in which the F—Cu—F bond axes of adjacent complexes are aligned along the a + b or b – a directions, as shown in Fig. 6. Along the c-axis direction, each chain is neighbored by a chain with the opposite chirality and same orientation on one side and a chain with the same chirality and opposite orientation on the other.

Figure 6
Packing diagram for (II)

: yellow polyhedra represent Cu(bpy)₂²⁺ cations and green polyhedra represent TaF₆⁻ anions.

In (III), the Λ-Cu(bpy)₃²⁺ complexes participate in displaced π–π stacking interactions propagating along the 3₂ screw axes with an interplanar angle of 13.9 (2)°, centroid–centroid distance of 3.933 (2) Å between adjacent N1/C1–C5 and N5/C21–C25 pyridine rings, and a horizontal shift distance of 1.970 Å. Each Λ-Cu(bpy)₃²⁺ cation is surrounded by six TaF₆⁻ anions (Fig. 7).

Figure 7
Packing diagram for (III)

: yellow polyhedra represent Cu(bpy)₃²⁺ cations and green polyhedra represent TaF₆⁻ anions.

The one-dimensional coordination chains in (IV) pack in a brickwork arrangement via parallel displaced π–π stacking interactions (Fig. 8). One of the stacking interactions involves parallel N1/C1–C5 pyridine rings at a centroid–centroid distance of 3.8133 (12) Å and a shift distance 1.676 Å, while the other stacking interaction involves nonparallel N1/C1–C5 pyridine rings with an interplanar angle of 3.54 (11)°, centroid–centroid distance of 3.5830 (14) Å and a shift distance of 1.072 Å.

Figure 8
Packing diagram for (IV)

: Yellow polyhedra represent Cu(bpy)(H₂O)₂²⁺ cations and magenta polyhedra represent SnF₆²⁻ anions.

4. Database survey

A survey of structures related to (I) reported in the Cambridge Structural Database (CSD, version 2020.2.0 from September 2020; Groom et al., 2016 ) produced five other compounds based on [Cu(bpy)₂(H₂O)]²⁺ complexes and fluorinated inorganic anions: [Cu(bpy)₂(H₂O)][BF₄]₂ (CSD refcode: VIKDOJ; Yu et al., 2007), [Cu(bpy)₂(H₂O)][PF₆]₂ (CSD refcode: EQIQOL; Shi et al., 2010), and [Cu(bpy)₂(H₂O)][MF₆] (M = Ti, Zr, Hf; CSD refcodes: GESHOD, YUGYEH, YUGYIL, YUGYOR; Gautier et al., 2012; Nisbet et al., 2020). These compounds display a variety of packing architectures, with compounds based on singly charged PF₆⁻ and BF₄⁻ anions displaying hydrogen-bonded clusters composed of two anions and one cation while compounds based on doubly charged MF₆²⁻ anions form extended hydrogen-bonded networks. The hydrogen-bonding interactions in (I) differ from the analogous compounds based on early transition-metal fluorides in that the MF₆²⁻ anions hydrogen bonded to the [Cu(bpy)₂(H₂O)]²⁺ complex are both hydrogen bonded to the same pair of [Cu(bpy)₂)(H₂O)]²⁺ complexes in the ETM case, whereas they are bound to two different complexes in the SiF₆²⁻ case. Further, while the [Cu(bpy)₂(H₂O)][MF₆] (M = Ti, Zr, Hf) compounds display both face-to-face and displaced π–π stacking interactions, (I) has only displaced stacking interactions.

A search of the CSD for structures related to (II) revealed no other known octahedral bis(2,2′-bipyridine)copper(II) complexes with two fluorinated anions coordinated in the apical positions. The most similar example known to the authors is (6,6′′′-dimethyl-2,2′:6′,2′′:6′′,2′′′-quaterpyridine)bis(tetrafluoroborate)copper(II) (CSD refcode: UZELOC; Adamski et al., 2017). This structure features copper(II) complexes arranged such that the F—Cu—F axis of each complex is oriented along the a-axis direction. Additionally, these complexes participate in heterochiral π–π stacking interactions.

Compound (III) is a new member of the family of compounds that includes [A(bpy)₃][PF₆] (A = Mn, Co, Ni, Cu, Zn, Ru, and Cd; CSD refcodes: YEGLUR, VUMTEE, WOTSAZ01, REZJAI, WOTSON, BPYRUG, XEFNOM, respectively; (Deisenroth et al., 2001 ); Breu et al., 2000 ; Björemark et al., 2015 ; Wang et al., 2007; Kundu et al., 2005 ), Zn(bpy)₃][TaF₆]₂ (CSD refcode: HAHFII; Gautier & Poeppelmeier, 2016 ), and [Zn(bpy)₃][NbF₆]₂ (CSD refcode: HAHFUU; Gautier & Poeppelmeier, 2016). These compounds include either Δ- or Λ-Cu(bpy)₃²⁺ cations arranged along 3₁ or 3₂ screw axes depending on the handedness of the Cu(bpy)₃²⁺ complexes.

Compound (IV) is isostructural to the coordination polymer Cu(bpy)(H₂O)HfF₆ (CSD refcode: YUGXOQ; Nisbet et al., 2020). These compounds share identical connectivity with a series of coordination polymers with the formula M′(bpy)(H₂O)₂MO_xF_6–x compounds (M′/M = Cu/Ti, Cu/V, Cu/Nb, Cu/Mo, Zn/Mo, and Zn/W), which display polar zigzag chains (Gautier & Poeppelmeier, 2013 ).

5. Synthesis and crystallization

The compounds reported here were synthesized by the hydrothermal pouch method (Harrison et al., 1993 ). In each reaction, reagents were heat sealed in Teflon pouches. Groups of six pouches were then placed into a 125 ml Parr autoclave with 40 ml distilled water as backfill. The autoclave was heated at a rate of 5°C min⁻¹ to 150°C and held at 150°C for 24 h. The autoclaves were allowed to cool to room temperature at a rate of 6°C h⁻¹ and the solid products were recovered by vacuum filtration. Compound (I) was synthesized in a pouch containing 1.9 mmol of Cu(NO₃)₂·H₂O, 5 mmol of 2,2′-bipyridine, 1.5 mmol of (NH₄)₂SiF₆ and 1ml of deionized H₂O. Compound (II) was synthesized in a pouch containing 1.7 mmol of CuO, 2.5 mmol of 2,2′-bipyridine, 0.85 mmol of Ta₂O₅, 0.8 ml HF(aq), and 0.3 ml of deionized H₂O. Compound (III) was synthesized in a pouch containing 1.7 mmol of CuO, 5.1 mmol of 2,2′-bipyridine, 0.85 mmol Ta₂O₅, 1 ml of HF(aq) and 0.1 ml of deionized H₂O. Compound (IV) was synthesized in a pouch containing 1.9 mmol of Cu(NO₃)₂·H₂O, 1.3 mmol of 2,2′-bipyridine, 1.7 mmol of (NH₄)₂SnF₆ and 1 ml of deionized H₂O.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atom positions were assigned from difference map peaks and their positions freely refined with the exception of C—H hydrogen atoms of 2,2′-bipyridine, which were constrained to ride at distances of 0.95 Å from the associated C atoms with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	[Cu(C₁₀H₈N₂)₂(H₂O)][SiF₆]·4H₂O	[CuTa₂F₁₂(C₁₀H₈N₂)₂]	[Cu(C₁₀H₈N₂)₃][TaF₆]₂	[CuSnF₆(C₁₀H₈N₂)(H₂O)₂]
M_r	608.08	965.81	1121.99	488.45
Crystal system, space group	Monoclinic, C2/c	Triclinic, P $[\overline{1}]$	Trigonal, P3₂	Monoclinic, P2/n
Temperature (K)	100	100	100	100
a, b, c (Å)	25.4971 (16), 13.3573 (9), 18.944 (2)	9.5465 (1), 10.5102 (1), 25.9853 (4)	10.5172 (10), 10.5172 (10), 26.288 (2)	6.2590 (2), 9.2167 (3), 12.1648 (3)
α, β, γ (°)	90, 131.949 (1), 90	96.723 (1), 100.256 (1), 96.672 (1)	90, 90, 120	90, 90.734 (2), 90
V (Å³)	4798.5 (7)	2522.78 (5)	2518.2 (5)	701.70 (4)
Z	8	4	3	2
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	1.05	9.60	7.23	3.37
Crystal size (mm)	0.30 × 0.26 × 0.15	0.52 × 0.32 × 0.22	0.22 × 0.16 × 0.12	0.20 × 0.13 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD	Rigaku Oxford Diffraction XtaLAB Synergy, Single source at offset/far, HyPix	Bruker Kappa APEX CCD area detector	Rigaku Oxford Diffraction XtaLAB Synergy, Single source at offset/far, HyPix
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Gaussian CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )	Multi-scan (SADABS; Bruker, 2016)	Gaussian CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )
T_min, T_max	0.694, 0.746	0.035, 0.414	0.559, 0.746	0.732, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	57770, 6660, 5863	93570, 18263, 15170	148130, 12260, 12121	22131, 3686, 3251
R_int	0.050	0.060	0.050	0.055
(sin θ/λ)_max (Å⁻¹)	0.693	0.785	0.761	0.870

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.04	0.037, 0.088, 1.05	0.016, 0.031, 1.03	0.029, 0.067, 1.07
No. of reflections	6660	18263	12260	3686
No. of parameters	374	704	462	110
No. of restraints	0	0	1	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.25	1.67, −3.53	0.96, −0.85	2.05, −0.85
Absolute structure	–	–	Flack x determined using 5861 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	–
Absolute structure parameter	–	–	0.5036 (7)	–
Computer programs: APEX2 (Bruker, 2017 ), SAINT (Bruker, 2016), CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

The measured crystal of (III) is a class II twin by merohedry about a twofold axis along the [110] direction to give apparent Laue symmetry of $[\overline{3}]$ m1. The twinning occurs with a BASF of 0.5, suggesting that both the P3₁ and P3₂ configurations are present in equal proportions within the sample.

Supporting information

CCDC references: 2048914; 2048918; 2048917; 2048915

Crystal structure: contains datablocks global, II, III, IV, I. DOI: https://doi.org/10.1107/S2056989021000633/hb7957sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2017) for (I), (III); CrysAlis PRO (Rigaku OD, 2020) for (II), (IV). Cell refinement: SAINT (Bruker, 2016) for (I), (III); CrysAlis PRO (Rigaku OD, 2020) for (II), (IV). Data reduction: SAINT (Bruker, 2016) for (I), (III); CrysAlis PRO (Rigaku OD, 2020) for (II), (IV). For all structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Aquabis(2,2'-bipyridine-κ²N,N')copper(II) hexafluoridosilicate tetrahydrate (I) top

Crystal data top

[Cu(C₁₀H₈N₂)₂(H₂O)][SiF₆]·4H₂O	F(000) = 2488
M_r = 608.08	D_x = 1.683 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.4971 (16) Å	Cell parameters from 9731 reflections
b = 13.3573 (9) Å	θ = 2.8–29.4°
c = 18.944 (2) Å	µ = 1.05 mm⁻¹
β = 131.949 (1)°	T = 100 K
V = 4798.5 (7) Å³	Block, blue
Z = 8	0.30 × 0.26 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	6660 independent reflections
Radiation source: sealed tube	5863 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.050
Detector resolution: 8 pixels mm^-1	θ_max = 29.5°, θ_min = 1.9°
φ and ω scans	h = −35→34
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −18→18
T_min = 0.694, T_max = 0.746	l = −24→26
57770 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0277P)² + 6.982P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
6660 reflections	Δρ_max = 0.79 e Å⁻³
374 parameters	Δρ_min = −0.24 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
Cu1	0.38373 (2)	0.37571 (2)	0.22886 (2)	0.01115 (5)
O1	0.30718 (6)	0.41614 (9)	0.23571 (8)	0.0177 (2)
H1A	0.3036 (13)	0.3839 (18)	0.2650 (17)	0.035 (6)*
H1B	0.3081 (12)	0.4726 (19)	0.2479 (16)	0.033 (6)*
N1	0.37806 (6)	0.26410 (8)	0.15033 (8)	0.0120 (2)
N3	0.46003 (6)	0.48439 (9)	0.31770 (8)	0.0122 (2)
N4	0.44106 (6)	0.30358 (8)	0.35115 (8)	0.0124 (2)
N2	0.32619 (6)	0.44426 (9)	0.10503 (8)	0.0124 (2)
C6	0.31103 (7)	0.39110 (10)	0.03265 (9)	0.0117 (2)
C16	0.49954 (7)	0.35110 (10)	0.42717 (9)	0.0122 (2)
C15	0.51060 (7)	0.45257 (10)	0.40829 (9)	0.0120 (2)
C17	0.54345 (8)	0.30770 (11)	0.51640 (10)	0.0164 (3)
H17	0.584712	0.341450	0.569103	0.020*
C4	0.33051 (8)	0.22242 (11)	−0.00601 (10)	0.0166 (3)
H4	0.303744	0.241407	−0.070316	0.020*
C5	0.34040 (7)	0.28885 (10)	0.05837 (9)	0.0120 (2)
C11	0.46479 (8)	0.57742 (10)	0.29641 (10)	0.0156 (3)
H11	0.429070	0.600245	0.233009	0.019*
C18	0.52625 (8)	0.21425 (11)	0.52759 (10)	0.0181 (3)
H18	0.555859	0.183054	0.588184	0.022*
C12	0.51911 (8)	0.64187 (11)	0.36212 (11)	0.0177 (3)
H12	0.520466	0.707626	0.344271	0.021*
C20	0.42436 (8)	0.21398 (10)	0.36308 (10)	0.0149 (3)
H20	0.382534	0.181730	0.309805	0.018*
C14	0.56701 (8)	0.51293 (11)	0.47781 (10)	0.0168 (3)
H14	0.602223	0.488785	0.540838	0.020*
C19	0.46602 (8)	0.16686 (11)	0.45043 (10)	0.0165 (3)
H19	0.453313	0.103009	0.457052	0.020*
C10	0.30008 (8)	0.53675 (10)	0.08876 (10)	0.0151 (3)
H10	0.309292	0.572663	0.139338	0.018*
C3	0.36042 (9)	0.12784 (11)	0.02521 (11)	0.0197 (3)
H3	0.353934	0.080777	−0.017661	0.024*
C2	0.39978 (9)	0.10290 (11)	0.11951 (11)	0.0192 (3)
H2	0.421146	0.038806	0.142568	0.023*
C9	0.26007 (8)	0.58174 (11)	0.00054 (10)	0.0165 (3)
H9	0.242705	0.647922	−0.009131	0.020*
C13	0.57152 (8)	0.60901 (11)	0.45437 (11)	0.0187 (3)
H13	0.609914	0.651426	0.500877	0.022*
C7	0.27095 (8)	0.43169 (11)	−0.05742 (10)	0.0159 (3)
H7	0.260819	0.393583	−0.107643	0.019*
C1	0.40748 (8)	0.17297 (10)	0.17963 (10)	0.0158 (3)
H1	0.434783	0.155761	0.244450	0.019*
C8	0.24582 (8)	0.52859 (11)	−0.07328 (10)	0.0178 (3)
H8	0.219083	0.558236	−0.134231	0.021*
Si1	0.23943 (2)	0.20875 (3)	0.28568 (3)	0.01040 (8)
F4	0.30094 (5)	0.12511 (7)	0.36761 (6)	0.02014 (19)
F2	0.26224 (5)	0.18737 (8)	0.22236 (6)	0.0246 (2)
F6	0.17998 (5)	0.11481 (6)	0.22816 (6)	0.02098 (19)
F3	0.30005 (5)	0.30181 (7)	0.34414 (6)	0.01928 (18)
F5	0.21850 (6)	0.23088 (7)	0.35102 (8)	0.0248 (2)
F1	0.17872 (5)	0.29058 (7)	0.20409 (7)	0.0281 (2)
O2	0.14362 (8)	0.48395 (10)	0.17503 (12)	0.0332 (3)
H2A	0.1591 (11)	0.4330 (17)	0.1834 (15)	0.023 (5)*
H2B	0.1657 (13)	0.5213 (19)	0.1710 (17)	0.036 (6)*
O3	0.39995 (8)	0.19743 (10)	0.68756 (10)	0.0252 (3)
H3A	0.3668 (14)	0.2152 (18)	0.6774 (17)	0.037 (7)*
H3B	0.4124 (14)	0.156 (2)	0.7206 (19)	0.046 (8)*
O4	0.41008 (7)	0.12569 (10)	0.56108 (9)	0.0246 (3)
H4A	0.3995 (12)	0.1479 (17)	0.5847 (16)	0.028 (6)*
H4B	0.3776 (14)	0.1313 (17)	0.5077 (19)	0.036 (7)*
O5	0.54187 (8)	0.03556 (10)	0.68866 (10)	0.0267 (3)
H5A	0.5100 (11)	0.0531 (15)	0.6479 (15)	0.013 (5)*
H5B	0.5669 (13)	0.0274 (18)	0.6773 (17)	0.040 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01351 (9)	0.00970 (8)	0.00754 (8)	0.00123 (6)	0.00592 (7)	0.00124 (5)
O1	0.0241 (6)	0.0120 (5)	0.0260 (6)	0.0011 (4)	0.0205 (5)	0.0028 (4)
N1	0.0122 (6)	0.0115 (5)	0.0113 (5)	0.0010 (4)	0.0075 (5)	0.0002 (4)
N3	0.0126 (6)	0.0127 (5)	0.0104 (5)	−0.0005 (4)	0.0074 (5)	0.0006 (4)
N4	0.0132 (6)	0.0124 (5)	0.0110 (5)	0.0015 (4)	0.0078 (5)	0.0019 (4)
N2	0.0138 (6)	0.0115 (5)	0.0103 (5)	0.0019 (4)	0.0074 (5)	0.0009 (4)
C6	0.0118 (6)	0.0125 (6)	0.0107 (6)	−0.0002 (5)	0.0074 (5)	0.0001 (5)
C16	0.0122 (6)	0.0132 (6)	0.0121 (6)	0.0020 (5)	0.0085 (5)	0.0014 (5)
C15	0.0117 (6)	0.0136 (6)	0.0115 (6)	0.0010 (5)	0.0080 (5)	0.0006 (5)
C17	0.0128 (7)	0.0194 (7)	0.0114 (6)	0.0012 (5)	0.0058 (6)	0.0015 (5)
C4	0.0212 (8)	0.0165 (6)	0.0141 (6)	0.0005 (5)	0.0126 (6)	−0.0010 (5)
C5	0.0116 (6)	0.0122 (6)	0.0118 (6)	0.0000 (5)	0.0078 (5)	0.0004 (5)
C11	0.0179 (7)	0.0141 (6)	0.0144 (6)	−0.0008 (5)	0.0105 (6)	0.0016 (5)
C18	0.0171 (7)	0.0211 (7)	0.0134 (6)	0.0056 (5)	0.0090 (6)	0.0078 (5)
C12	0.0206 (7)	0.0137 (6)	0.0201 (7)	−0.0039 (5)	0.0141 (6)	−0.0014 (5)
C20	0.0151 (7)	0.0151 (6)	0.0142 (6)	0.0003 (5)	0.0097 (6)	0.0015 (5)
C14	0.0145 (7)	0.0189 (7)	0.0130 (6)	−0.0010 (5)	0.0075 (6)	−0.0011 (5)
C19	0.0193 (7)	0.0146 (6)	0.0191 (7)	0.0033 (5)	0.0142 (6)	0.0049 (5)
C10	0.0170 (7)	0.0129 (6)	0.0138 (6)	0.0017 (5)	0.0097 (6)	0.0004 (5)
C3	0.0268 (8)	0.0155 (6)	0.0216 (7)	0.0002 (6)	0.0181 (7)	−0.0038 (5)
C2	0.0240 (8)	0.0133 (6)	0.0241 (7)	0.0044 (5)	0.0177 (7)	0.0011 (5)
C9	0.0169 (7)	0.0136 (6)	0.0144 (6)	0.0041 (5)	0.0085 (6)	0.0037 (5)
C13	0.0166 (7)	0.0188 (7)	0.0181 (7)	−0.0049 (5)	0.0105 (6)	−0.0053 (5)
C7	0.0167 (7)	0.0179 (6)	0.0103 (6)	0.0007 (5)	0.0078 (6)	0.0006 (5)
C1	0.0178 (7)	0.0133 (6)	0.0159 (6)	0.0037 (5)	0.0111 (6)	0.0029 (5)
C8	0.0177 (7)	0.0183 (7)	0.0123 (6)	0.0033 (5)	0.0080 (6)	0.0047 (5)
Si1	0.01073 (18)	0.00884 (15)	0.00999 (16)	0.00026 (13)	0.00624 (15)	0.00056 (12)
F4	0.0190 (5)	0.0192 (4)	0.0132 (4)	0.0048 (3)	0.0070 (4)	0.0019 (3)
F2	0.0299 (5)	0.0312 (5)	0.0166 (4)	−0.0035 (4)	0.0171 (4)	−0.0048 (4)
F6	0.0171 (4)	0.0126 (4)	0.0194 (4)	−0.0030 (3)	0.0065 (4)	0.0002 (3)
F3	0.0205 (5)	0.0198 (4)	0.0144 (4)	−0.0078 (3)	0.0103 (4)	−0.0032 (3)
F5	0.0360 (6)	0.0175 (4)	0.0397 (6)	−0.0025 (4)	0.0331 (5)	−0.0043 (4)
F1	0.0198 (5)	0.0147 (4)	0.0271 (5)	0.0010 (4)	0.0063 (4)	0.0065 (4)
O2	0.0311 (7)	0.0166 (6)	0.0643 (10)	0.0028 (5)	0.0371 (8)	0.0061 (6)
O3	0.0239 (7)	0.0252 (6)	0.0312 (7)	−0.0023 (5)	0.0204 (6)	−0.0025 (5)
O4	0.0253 (7)	0.0281 (6)	0.0154 (6)	−0.0004 (5)	0.0116 (6)	0.0012 (5)
O5	0.0242 (7)	0.0280 (6)	0.0323 (7)	0.0018 (5)	0.0207 (7)	0.0037 (5)

Geometric parameters (Å, º) top

Cu1—O1	2.1112 (11)	C20—C19	1.3831 (19)
Cu1—N1	2.0419 (12)	C14—H14	0.9500
Cu1—N3	2.0849 (12)	C14—C13	1.388 (2)
Cu1—N4	1.9760 (11)	C19—H19	0.9500
Cu1—N2	1.9730 (11)	C10—H10	0.9500
O1—H1A	0.76 (3)	C10—C9	1.3841 (19)
O1—H1B	0.78 (2)	C3—H3	0.9500
N1—C5	1.3527 (17)	C3—C2	1.383 (2)
N1—C1	1.3401 (17)	C2—H2	0.9500
N3—C15	1.3528 (17)	C2—C1	1.383 (2)
N3—C11	1.3368 (17)	C9—H9	0.9500
N4—C16	1.3525 (18)	C9—C8	1.383 (2)
N4—C20	1.3392 (18)	C13—H13	0.9500
N2—C6	1.3510 (17)	C7—H7	0.9500
N2—C10	1.3379 (18)	C7—C8	1.385 (2)
C6—C5	1.4749 (18)	C1—H1	0.9500
C6—C7	1.3852 (18)	C8—H8	0.9500
C16—C15	1.4761 (19)	Si1—F4	1.6918 (9)
C16—C17	1.3845 (19)	Si1—F2	1.6708 (10)
C15—C14	1.3860 (19)	Si1—F6	1.6886 (9)
C17—H17	0.9500	Si1—F3	1.6947 (9)
C17—C18	1.386 (2)	Si1—F5	1.6695 (10)
C4—H4	0.9500	Si1—F1	1.6677 (10)
C4—C5	1.3883 (19)	O2—H2A	0.75 (2)
C4—C3	1.387 (2)	O2—H2B	0.79 (3)
C11—H11	0.9500	O3—H3A	0.77 (3)
C11—C12	1.380 (2)	O3—H3B	0.73 (3)
C18—H18	0.9500	O4—H4A	0.72 (2)
C18—C19	1.376 (2)	O4—H4B	0.77 (3)
C12—H12	0.9500	O5—H5A	0.69 (2)
C12—C13	1.382 (2)	O5—H5B	0.81 (3)
C20—H20	0.9500

N1—Cu1—O1	127.84 (5)	N4—C20—H20	118.9
N1—Cu1—N3	132.07 (5)	N4—C20—C19	122.15 (14)
N3—Cu1—O1	100.04 (5)	C19—C20—H20	118.9
N4—Cu1—O1	92.43 (5)	C15—C14—H14	120.4
N4—Cu1—N1	97.75 (5)	C15—C14—C13	119.29 (13)
N4—Cu1—N3	80.40 (5)	C13—C14—H14	120.4
N2—Cu1—O1	88.34 (5)	C18—C19—C20	118.74 (13)
N2—Cu1—N1	80.70 (5)	C18—C19—H19	120.6
N2—Cu1—N3	100.81 (5)	C20—C19—H19	120.6
N2—Cu1—N4	178.43 (5)	N2—C10—H10	119.0
Cu1—O1—H1A	118.2 (18)	N2—C10—C9	122.06 (13)
Cu1—O1—H1B	114.6 (17)	C9—C10—H10	119.0
H1A—O1—H1B	109 (2)	C4—C3—H3	120.4
C5—N1—Cu1	113.79 (9)	C2—C3—C4	119.18 (13)
C1—N1—Cu1	127.88 (10)	C2—C3—H3	120.4
C1—N1—C5	118.32 (12)	C3—C2—H2	120.6
C15—N3—Cu1	112.90 (9)	C1—C2—C3	118.80 (14)
C11—N3—Cu1	128.87 (10)	C1—C2—H2	120.6
C11—N3—C15	118.23 (12)	C10—C9—H9	120.6
C16—N4—Cu1	116.39 (9)	C8—C9—C10	118.78 (13)
C20—N4—Cu1	124.34 (10)	C8—C9—H9	120.6
C20—N4—C16	119.23 (12)	C12—C13—C14	118.78 (14)
C6—N2—Cu1	116.33 (9)	C12—C13—H13	120.6
C10—N2—Cu1	124.23 (9)	C14—C13—H13	120.6
C10—N2—C6	119.40 (12)	C6—C7—H7	120.4
N2—C6—C5	114.45 (11)	C6—C7—C8	119.10 (13)
N2—C6—C7	121.29 (12)	C8—C7—H7	120.4
C7—C6—C5	124.26 (12)	N1—C1—C2	122.79 (13)
N4—C16—C15	115.22 (12)	N1—C1—H1	118.6
N4—C16—C17	121.31 (13)	C2—C1—H1	118.6
C17—C16—C15	123.42 (13)	C9—C8—C7	119.32 (13)
N3—C15—C16	114.92 (12)	C9—C8—H8	120.3
N3—C15—C14	121.76 (13)	C7—C8—H8	120.3
C14—C15—C16	123.29 (12)	F4—Si1—F3	90.21 (5)
C16—C17—H17	120.5	F2—Si1—F4	89.52 (5)
C16—C17—C18	118.93 (14)	F2—Si1—F6	90.16 (5)
C18—C17—H17	120.5	F2—Si1—F3	89.51 (5)
C5—C4—H4	120.6	F6—Si1—F4	89.03 (5)
C3—C4—H4	120.6	F6—Si1—F3	179.18 (5)
C3—C4—C5	118.83 (13)	F5—Si1—F4	89.80 (5)
N1—C5—C6	114.73 (11)	F5—Si1—F2	178.71 (6)
N1—C5—C4	122.06 (13)	F5—Si1—F6	90.92 (5)
C4—C5—C6	123.21 (12)	F5—Si1—F3	89.40 (5)
N3—C11—H11	118.4	F1—Si1—F4	179.43 (6)
N3—C11—C12	123.13 (13)	F1—Si1—F2	89.97 (6)
C12—C11—H11	118.4	F1—Si1—F6	90.70 (5)
C17—C18—H18	120.2	F1—Si1—F3	90.05 (5)
C19—C18—C17	119.62 (13)	F1—Si1—F5	90.71 (6)
C19—C18—H18	120.2	H2A—O2—H2B	106 (2)
C11—C12—H12	120.6	H3A—O3—H3B	103 (3)
C11—C12—C13	118.79 (13)	H4A—O4—H4B	105 (2)
C13—C12—H12	120.6	H5A—O5—H5B	107 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F3	0.76 (3)	1.91 (3)	2.6616 (14)	177 (3)
O1—H1B···F6ⁱ	0.78 (2)	1.93 (2)	2.7053 (14)	170 (2)
O2—H2A···F1	0.75 (2)	1.94 (2)	2.6677 (17)	164 (2)
O2—H2B···F4ⁱ	0.79 (3)	2.00 (3)	2.7807 (17)	167 (2)
O3—H3A···F5ⁱⁱ	0.77 (3)	1.99 (3)	2.7607 (18)	177 (3)
O3—H3B···O5ⁱⁱⁱ	0.73 (3)	2.06 (3)	2.779 (2)	171 (3)
O4—H4A···O3	0.72 (2)	2.05 (2)	2.749 (2)	162 (2)
O4—H4B···F4	0.77 (3)	1.98 (3)	2.7462 (16)	170 (2)
O5—H5A···O4	0.69 (2)	2.13 (2)	2.779 (2)	158 (2)
O5—H5B···O2^iv	0.81 (3)	1.99 (3)	2.786 (2)	169 (2)

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

Bis(2,2'-bipyridine-3κ²N,N')-di-µ-fluorido-1:3κ²F:F;2:3κ²F:F-decafluorido-1κ⁵F,2κ⁵F-copper(II)ditantalum(V) (II) top

Crystal data top

[CuTa₂F₁₂(C₁₀H₈N₂)₂]	Z = 4
M_r = 965.81	F(000) = 1788
Triclinic, P1	D_x = 2.543 Mg m⁻³
a = 9.5465 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5102 (1) Å	Cell parameters from 52090 reflections
c = 25.9853 (4) Å	θ = 2.1–33.9°
α = 96.723 (1)°	µ = 9.60 mm⁻¹
β = 100.256 (1)°	T = 100 K
γ = 96.672 (1)°	Plate, blue
V = 2522.78 (5) Å³	0.52 × 0.32 × 0.22 mm

Data collection top

Rigaku Oxford Diffraction XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	18263 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	15170 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.060
Detector resolution: 10.0000 pixels mm^-1	θ_max = 33.9°, θ_min = 2.0°
ω scans	h = −14→13
Absorption correction: gaussian Crysalispro (Rigaku OD, 2020)	k = −16→16
T_min = 0.035, T_max = 0.414	l = −40→39
93570 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0409P)² + 5.1565P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max = 0.002
S = 1.05	Δρ_max = 1.67 e Å⁻³
18263 reflections	Δρ_min = −3.53 e Å⁻³
704 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00034 (4)

Special details top

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

	x	y	z	U_iso*/U_eq
Ta2	0.98596 (2)	1.10178 (2)	0.12906 (2)	0.01573 (4)
Ta1	0.41338 (2)	0.45975 (2)	0.10819 (2)	0.01761 (4)
Cu1	0.68618 (5)	0.78568 (5)	0.13192 (2)	0.01516 (9)
F9	0.9510 (3)	1.1887 (3)	0.19295 (10)	0.0252 (5)
F5	0.2489 (3)	0.4552 (3)	0.14002 (11)	0.0267 (6)
F8	0.7872 (3)	1.0564 (3)	0.10038 (11)	0.0260 (6)
F12	1.0286 (3)	1.0247 (3)	0.06509 (10)	0.0239 (5)
F11	1.1860 (3)	1.1389 (3)	0.15719 (11)	0.0262 (6)
F3	0.5185 (3)	0.4088 (3)	0.16953 (11)	0.0247 (5)
F7	0.9770 (3)	0.9436 (3)	0.15757 (11)	0.0294 (6)
F4	0.3621 (3)	0.2852 (3)	0.07704 (12)	0.0305 (6)
F10	0.9810 (3)	1.2592 (2)	0.10011 (11)	0.0256 (6)
F2	0.5792 (3)	0.4746 (3)	0.07763 (12)	0.0331 (6)
F6	0.3068 (3)	0.5133 (3)	0.04785 (11)	0.0270 (6)
F1	0.4651 (3)	0.6364 (2)	0.14024 (11)	0.0269 (6)
N3	0.7804 (4)	0.6735 (3)	0.17963 (14)	0.0160 (6)
N1	0.5349 (3)	0.8408 (3)	0.08062 (14)	0.0157 (6)
N4	0.8057 (4)	0.7153 (3)	0.08444 (14)	0.0152 (6)
N2	0.6440 (4)	0.9307 (3)	0.17981 (14)	0.0157 (6)
C2	0.3580 (5)	0.8158 (4)	0.00134 (18)	0.0216 (8)
H2	0.319847	0.772106	−0.033323	0.026*
C20	0.8274 (4)	0.7603 (4)	0.04025 (17)	0.0175 (7)
H20	0.767028	0.818420	0.025928	0.021*
C17	0.9999 (5)	0.5935 (4)	0.08156 (18)	0.0215 (8)
H17	1.057912	0.534030	0.096134	0.026*
C5	0.4765 (4)	0.9423 (4)	0.10083 (16)	0.0152 (7)
C7	0.5236 (4)	1.1185 (4)	0.17918 (17)	0.0185 (8)
H7	0.455457	1.165969	0.161648	0.022*
C6	0.5475 (4)	1.0002 (4)	0.15501 (16)	0.0162 (7)
C11	0.7482 (4)	0.6497 (4)	0.22631 (17)	0.0189 (8)
H11	0.688936	0.702667	0.242198	0.023*
C12	0.7986 (5)	0.5507 (4)	0.25202 (17)	0.0200 (8)
H12	0.777478	0.537798	0.285559	0.024*
C15	0.8624 (4)	0.5978 (4)	0.15622 (16)	0.0157 (7)
C8	0.6014 (5)	1.1659 (4)	0.22958 (17)	0.0206 (8)
H8	0.588245	1.247440	0.246647	0.025*
C19	0.9357 (5)	0.7250 (4)	0.01437 (17)	0.0208 (8)
H19	0.948827	0.757597	−0.017295	0.025*
C9	0.6985 (5)	1.0938 (4)	0.25498 (18)	0.0211 (8)
H9	0.750625	1.123962	0.289801	0.025*
C3	0.2968 (4)	0.9182 (4)	0.02197 (17)	0.0207 (8)
H3	0.214765	0.944598	0.001826	0.025*
C16	0.8910 (4)	0.6331 (4)	0.10567 (16)	0.0158 (7)
C1	0.4762 (4)	0.7779 (4)	0.03212 (16)	0.0182 (7)
H1	0.516609	0.705646	0.018558	0.022*
C14	0.9133 (4)	0.4946 (4)	0.17934 (17)	0.0197 (8)
H14	0.969857	0.440928	0.162279	0.024*
C4	0.3562 (4)	0.9825 (4)	0.07255 (17)	0.0184 (8)
H4	0.315036	1.052700	0.087389	0.022*
C18	1.0233 (5)	0.6418 (4)	0.03578 (18)	0.0230 (8)
H18	1.099428	0.617504	0.019383	0.028*
C10	0.7175 (4)	0.9771 (4)	0.22842 (16)	0.0179 (7)
H10	0.785232	0.928262	0.245294	0.021*
C13	0.8803 (5)	0.4712 (4)	0.22762 (18)	0.0216 (8)
H13	0.913687	0.400990	0.243799	0.026*
Ta3	−0.00635 (2)	0.33576 (2)	0.38898 (2)	0.02034 (4)
Ta4	0.63142 (2)	−0.13811 (2)	0.36861 (2)	0.02023 (4)
Cu2	0.29152 (6)	0.10318 (5)	0.36059 (2)	0.01799 (10)
F21	0.8047 (3)	−0.0728 (3)	0.34984 (13)	0.0329 (7)
F13	0.0337 (3)	0.1905 (3)	0.34529 (12)	0.0312 (6)
F23	0.5569 (3)	−0.2131 (3)	0.29738 (11)	0.0307 (6)
F16	−0.0387 (3)	0.4811 (3)	0.43312 (13)	0.0359 (7)
F24	0.4541 (3)	−0.2063 (4)	0.38472 (13)	0.0458 (9)
F15	−0.1820 (3)	0.3384 (3)	0.34261 (12)	0.0359 (7)
F19	0.5514 (3)	0.0146 (3)	0.35417 (13)	0.0383 (7)
F22	0.7064 (3)	−0.2934 (3)	0.38108 (16)	0.0460 (9)
F14	−0.0971 (4)	0.2243 (3)	0.42789 (14)	0.0484 (9)
F20	0.6966 (4)	−0.0686 (4)	0.44044 (13)	0.0504 (9)
N7	0.1943 (4)	−0.0253 (3)	0.39661 (14)	0.0170 (6)
F17	0.0823 (4)	0.4475 (3)	0.34739 (15)	0.0440 (8)
N5	0.3281 (4)	0.2525 (3)	0.32378 (14)	0.0182 (7)
N6	0.4368 (4)	0.2126 (3)	0.41895 (14)	0.0181 (7)
N8	0.2405 (4)	−0.0415 (3)	0.29996 (15)	0.0191 (7)
F18	0.1739 (4)	0.3349 (4)	0.43259 (17)	0.0627 (12)
C39	0.2640 (5)	−0.1563 (4)	0.21782 (18)	0.0218 (8)
H39	0.291350	−0.154459	0.184489	0.026*
C26	0.4974 (4)	0.3223 (4)	0.40414 (17)	0.0178 (7)
C23	0.3995 (5)	0.4718 (4)	0.2798 (2)	0.0259 (9)
H23	0.426235	0.545695	0.264082	0.031*
C35	0.1492 (4)	−0.1430 (4)	0.36712 (16)	0.0168 (7)
C33	0.0475 (5)	−0.2200 (4)	0.43722 (18)	0.0221 (8)
H33	−0.002722	−0.287185	0.451181	0.027*
C37	0.1677 (4)	−0.2708 (4)	0.28085 (17)	0.0199 (8)
H37	0.129683	−0.348965	0.291495	0.024*
C22	0.2878 (5)	0.3774 (4)	0.25324 (18)	0.0233 (8)
H22	0.234903	0.387033	0.219656	0.028*
C31	0.1648 (4)	−0.0038 (4)	0.44524 (17)	0.0202 (8)
H31	0.192692	0.080082	0.465036	0.024*
C34	0.0740 (5)	−0.2408 (4)	0.38662 (18)	0.0212 (8)
H34	0.040589	−0.322079	0.365254	0.025*
C27	0.6082 (5)	0.4046 (5)	0.43749 (19)	0.0254 (9)
H27	0.649078	0.480936	0.426353	0.030*
C32	0.0950 (5)	−0.1001 (4)	0.46741 (18)	0.0217 (8)
H32	0.079950	−0.084253	0.502625	0.026*
C36	0.1841 (4)	−0.1539 (4)	0.31391 (16)	0.0166 (7)
C29	0.5970 (5)	0.2631 (5)	0.50230 (19)	0.0272 (9)
H29	0.629406	0.241474	0.536481	0.033*
C21	0.2552 (5)	0.2689 (4)	0.27675 (17)	0.0214 (8)
H21	0.178536	0.204241	0.258864	0.026*
C25	0.4332 (4)	0.3463 (4)	0.35056 (17)	0.0180 (7)
C24	0.4716 (5)	0.4571 (4)	0.32964 (18)	0.0226 (8)
H24	0.545932	0.522120	0.348967	0.027*
C38	0.2078 (5)	−0.2715 (4)	0.23199 (19)	0.0232 (9)
H38	0.196865	−0.350143	0.208612	0.028*
C30	0.4876 (5)	0.1833 (4)	0.46724 (17)	0.0215 (8)
H30	0.447016	0.105492	0.477449	0.026*
C40	0.2796 (5)	−0.0435 (4)	0.25308 (17)	0.0215 (8)
H40	0.319631	0.035248	0.243508	0.026*
C28	0.6592 (5)	0.3750 (5)	0.4873 (2)	0.0293 (10)
H28	0.735536	0.430406	0.510793	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ta2	0.01384 (7)	0.01637 (7)	0.01688 (8)	0.00172 (5)	0.00301 (6)	0.00224 (6)
Ta1	0.01627 (8)	0.01625 (8)	0.02005 (8)	0.00161 (6)	0.00173 (6)	0.00487 (6)
Cu1	0.0163 (2)	0.0154 (2)	0.0156 (2)	0.00803 (17)	0.00351 (17)	0.00329 (17)
F9	0.0252 (13)	0.0316 (14)	0.0196 (13)	0.0051 (11)	0.0082 (10)	0.0003 (10)
F5	0.0206 (12)	0.0359 (15)	0.0268 (14)	0.0074 (11)	0.0059 (10)	0.0120 (12)
F8	0.0158 (11)	0.0372 (15)	0.0237 (13)	−0.0007 (10)	0.0022 (10)	0.0056 (11)
F12	0.0263 (13)	0.0245 (13)	0.0211 (13)	0.0048 (10)	0.0066 (10)	−0.0008 (10)
F11	0.0153 (11)	0.0350 (15)	0.0263 (14)	0.0025 (10)	0.0027 (10)	−0.0012 (11)
F3	0.0234 (12)	0.0226 (12)	0.0267 (14)	0.0041 (10)	−0.0023 (10)	0.0076 (10)
F7	0.0364 (15)	0.0221 (13)	0.0290 (15)	0.0037 (11)	0.0015 (12)	0.0091 (11)
F4	0.0407 (16)	0.0173 (12)	0.0287 (15)	0.0020 (11)	−0.0023 (12)	0.0000 (11)
F10	0.0352 (15)	0.0184 (12)	0.0280 (14)	0.0070 (10)	0.0140 (11)	0.0069 (10)
F2	0.0247 (14)	0.0439 (17)	0.0319 (16)	0.0030 (12)	0.0093 (12)	0.0062 (13)
F6	0.0278 (13)	0.0303 (14)	0.0227 (13)	0.0026 (11)	0.0000 (11)	0.0117 (11)
F1	0.0296 (14)	0.0183 (12)	0.0300 (15)	0.0009 (10)	0.0004 (11)	0.0029 (10)
N3	0.0158 (15)	0.0143 (14)	0.0187 (16)	0.0053 (12)	0.0041 (12)	0.0016 (12)
N1	0.0146 (14)	0.0137 (14)	0.0202 (17)	0.0051 (11)	0.0038 (12)	0.0038 (12)
N4	0.0160 (15)	0.0129 (14)	0.0174 (16)	0.0022 (11)	0.0033 (12)	0.0038 (12)
N2	0.0160 (15)	0.0150 (14)	0.0175 (16)	0.0050 (12)	0.0046 (12)	0.0029 (12)
C2	0.0221 (19)	0.0216 (19)	0.020 (2)	0.0054 (15)	−0.0001 (16)	0.0030 (16)
C20	0.0166 (17)	0.0168 (17)	0.0206 (19)	0.0036 (14)	0.0042 (15)	0.0069 (14)
C17	0.0194 (19)	0.022 (2)	0.024 (2)	0.0082 (15)	0.0056 (16)	0.0004 (16)
C5	0.0154 (16)	0.0151 (16)	0.0179 (18)	0.0046 (13)	0.0060 (14)	0.0066 (14)
C7	0.0164 (17)	0.0166 (17)	0.024 (2)	0.0054 (14)	0.0058 (15)	0.0023 (15)
C6	0.0149 (17)	0.0159 (17)	0.0205 (19)	0.0054 (13)	0.0062 (14)	0.0061 (14)
C11	0.0187 (18)	0.0192 (18)	0.0190 (19)	0.0046 (14)	0.0036 (15)	0.0022 (15)
C12	0.0231 (19)	0.0213 (19)	0.0171 (19)	0.0032 (15)	0.0043 (15)	0.0082 (15)
C15	0.0139 (16)	0.0158 (17)	0.0175 (18)	0.0043 (13)	0.0022 (14)	0.0016 (14)
C8	0.0221 (19)	0.0179 (18)	0.022 (2)	0.0032 (15)	0.0071 (16)	−0.0005 (15)
C19	0.0218 (19)	0.0219 (19)	0.020 (2)	0.0021 (15)	0.0085 (16)	0.0030 (15)
C9	0.0214 (19)	0.0197 (19)	0.021 (2)	0.0008 (15)	0.0043 (16)	−0.0010 (15)
C3	0.0170 (18)	0.024 (2)	0.021 (2)	0.0066 (15)	0.0005 (15)	0.0056 (16)
C16	0.0163 (17)	0.0135 (16)	0.0176 (18)	0.0029 (13)	0.0032 (14)	0.0013 (13)
C1	0.0207 (18)	0.0179 (18)	0.0177 (19)	0.0067 (15)	0.0046 (15)	0.0032 (14)
C14	0.0188 (18)	0.0176 (18)	0.023 (2)	0.0048 (14)	0.0033 (15)	0.0016 (15)
C4	0.0164 (17)	0.0169 (17)	0.024 (2)	0.0069 (14)	0.0039 (15)	0.0047 (15)
C18	0.021 (2)	0.025 (2)	0.025 (2)	0.0069 (16)	0.0092 (17)	0.0003 (17)
C10	0.0192 (18)	0.0190 (18)	0.0163 (18)	0.0045 (14)	0.0037 (14)	0.0033 (14)
C13	0.023 (2)	0.0180 (18)	0.023 (2)	0.0063 (15)	−0.0007 (16)	0.0056 (15)
Ta3	0.02110 (8)	0.01596 (8)	0.02421 (9)	0.00380 (6)	0.00382 (6)	0.00350 (6)
Ta4	0.01788 (8)	0.02380 (9)	0.01855 (9)	0.00452 (6)	0.00136 (6)	0.00287 (6)
Cu2	0.0231 (2)	0.0138 (2)	0.0162 (2)	−0.00050 (18)	0.00276 (19)	0.00333 (17)
F21	0.0188 (13)	0.0342 (15)	0.0464 (18)	0.0008 (11)	0.0027 (12)	0.0167 (14)
F13	0.0352 (15)	0.0216 (13)	0.0429 (18)	0.0083 (11)	0.0209 (13)	0.0048 (12)
F23	0.0284 (14)	0.0391 (16)	0.0215 (14)	0.0037 (12)	0.0046 (11)	−0.0073 (12)
F16	0.0457 (18)	0.0243 (14)	0.0370 (17)	0.0067 (13)	0.0116 (14)	−0.0048 (12)
F24	0.0234 (14)	0.084 (3)	0.0337 (18)	0.0028 (16)	0.0096 (13)	0.0226 (17)
F15	0.0379 (16)	0.0344 (16)	0.0317 (16)	0.0131 (13)	−0.0044 (13)	−0.0014 (13)
F19	0.0375 (16)	0.0310 (16)	0.0461 (19)	0.0211 (13)	0.0008 (14)	−0.0011 (14)
F22	0.0273 (15)	0.0263 (15)	0.078 (3)	0.0024 (12)	−0.0137 (16)	0.0199 (16)
F14	0.078 (3)	0.0344 (17)	0.049 (2)	0.0158 (17)	0.0395 (19)	0.0197 (15)
F20	0.065 (2)	0.057 (2)	0.0195 (15)	−0.0035 (18)	−0.0066 (15)	−0.0008 (14)
N7	0.0184 (15)	0.0156 (15)	0.0169 (16)	0.0031 (12)	0.0034 (12)	0.0013 (12)
F17	0.057 (2)	0.0232 (14)	0.059 (2)	−0.0018 (14)	0.0350 (18)	0.0055 (14)
N5	0.0195 (16)	0.0171 (15)	0.0180 (16)	0.0004 (12)	0.0040 (13)	0.0043 (12)
N6	0.0187 (16)	0.0181 (16)	0.0180 (16)	0.0049 (13)	0.0036 (13)	0.0018 (13)
N8	0.0195 (16)	0.0139 (15)	0.0237 (18)	0.0016 (12)	0.0044 (13)	0.0026 (13)
F18	0.041 (2)	0.071 (3)	0.064 (3)	0.0237 (19)	−0.0188 (18)	−0.012 (2)
C39	0.0202 (19)	0.025 (2)	0.019 (2)	0.0033 (16)	0.0034 (15)	−0.0007 (16)
C26	0.0147 (17)	0.0155 (17)	0.023 (2)	0.0020 (13)	0.0037 (15)	0.0021 (14)
C23	0.030 (2)	0.020 (2)	0.031 (2)	0.0057 (17)	0.0095 (19)	0.0116 (17)
C35	0.0135 (16)	0.0165 (17)	0.0200 (19)	0.0014 (13)	0.0018 (14)	0.0037 (14)
C33	0.0183 (18)	0.022 (2)	0.028 (2)	0.0023 (15)	0.0066 (16)	0.0101 (17)
C37	0.0213 (19)	0.0141 (17)	0.023 (2)	0.0011 (14)	0.0027 (16)	0.0014 (15)
C22	0.026 (2)	0.024 (2)	0.022 (2)	0.0052 (17)	0.0053 (17)	0.0082 (16)
C31	0.0211 (19)	0.0186 (18)	0.022 (2)	0.0045 (15)	0.0045 (16)	0.0049 (15)
C34	0.0204 (19)	0.0154 (18)	0.028 (2)	0.0007 (15)	0.0048 (16)	0.0053 (16)
C27	0.020 (2)	0.027 (2)	0.027 (2)	−0.0026 (16)	0.0034 (17)	0.0016 (18)
C32	0.0207 (19)	0.023 (2)	0.025 (2)	0.0065 (16)	0.0071 (16)	0.0086 (16)
C36	0.0125 (16)	0.0164 (17)	0.0197 (19)	0.0006 (13)	0.0008 (14)	0.0032 (14)
C29	0.020 (2)	0.039 (3)	0.022 (2)	0.0058 (18)	0.0002 (17)	0.0043 (19)
C21	0.0223 (19)	0.0221 (19)	0.020 (2)	0.0009 (16)	0.0050 (16)	0.0050 (16)
C25	0.0167 (17)	0.0158 (17)	0.022 (2)	0.0039 (14)	0.0047 (15)	0.0036 (15)
C24	0.024 (2)	0.0172 (18)	0.026 (2)	−0.0018 (15)	0.0049 (17)	0.0045 (16)
C38	0.0195 (19)	0.021 (2)	0.027 (2)	0.0038 (15)	0.0021 (16)	−0.0019 (16)
C30	0.0205 (19)	0.025 (2)	0.019 (2)	0.0028 (16)	0.0031 (15)	0.0041 (16)
C40	0.026 (2)	0.0195 (19)	0.019 (2)	0.0031 (16)	0.0027 (16)	0.0043 (15)
C28	0.022 (2)	0.036 (3)	0.026 (2)	−0.0040 (18)	0.0003 (18)	0.0021 (19)

Geometric parameters (Å, º) top

Ta2—F9	1.902 (3)	Ta3—F13	1.910 (3)
Ta2—F8	1.893 (2)	Ta3—F16	1.889 (3)
Ta2—F12	1.894 (3)	Ta3—F15	1.887 (3)
Ta2—F11	1.896 (2)	Ta3—F14	1.870 (3)
Ta2—F7	1.897 (3)	Ta3—F17	1.912 (3)
Ta2—F10	1.898 (3)	Ta3—F18	1.886 (3)
Ta1—F5	1.899 (3)	Ta4—F21	1.883 (3)
Ta1—F3	1.894 (3)	Ta4—F23	1.901 (3)
Ta1—F4	1.888 (3)	Ta4—F24	1.896 (3)
Ta1—F2	1.892 (3)	Ta4—F19	1.903 (3)
Ta1—F6	1.893 (3)	Ta4—F22	1.895 (3)
Ta1—F1	1.913 (3)	Ta4—F20	1.889 (3)
Cu1—F7	2.987 (3)	Cu2—F13	2.706 (3)
Cu1—F1	2.537 (3)	Cu2—F19	2.775 (3)
Cu1—N3	1.982 (3)	Cu2—N7	1.968 (3)
Cu1—N1	1.972 (3)	Cu2—N5	1.960 (3)
Cu1—N4	1.964 (3)	Cu2—N6	2.005 (4)
Cu1—N2	1.977 (3)	Cu2—N8	2.006 (4)
N3—C11	1.347 (5)	N7—C35	1.356 (5)
N3—C15	1.348 (5)	N7—C31	1.342 (5)
N1—C5	1.354 (5)	N5—C21	1.335 (6)
N1—C1	1.344 (5)	N5—C25	1.351 (5)
N4—C20	1.332 (5)	N6—C26	1.356 (5)
N4—C16	1.353 (5)	N6—C30	1.346 (6)
N2—C6	1.362 (5)	N8—C36	1.356 (5)
N2—C10	1.337 (5)	N8—C40	1.335 (6)
C2—H2	0.9500	C39—H39	0.9500
C2—C3	1.382 (6)	C39—C38	1.383 (6)
C2—C1	1.390 (6)	C39—C40	1.386 (6)
C20—H20	0.9500	C26—C27	1.379 (6)
C20—C19	1.392 (6)	C26—C25	1.481 (6)
C17—H17	0.9500	C23—H23	0.9500
C17—C16	1.385 (6)	C23—C22	1.389 (7)
C17—C18	1.390 (6)	C23—C24	1.388 (7)
C5—C6	1.475 (6)	C35—C34	1.382 (6)
C5—C4	1.387 (5)	C35—C36	1.474 (6)
C7—H7	0.9500	C33—H33	0.9500
C7—C6	1.388 (5)	C33—C34	1.380 (6)
C7—C8	1.389 (6)	C33—C32	1.385 (6)
C11—H11	0.9500	C37—H37	0.9500
C11—C12	1.388 (6)	C37—C36	1.390 (6)
C12—H12	0.9500	C37—C38	1.389 (6)
C12—C13	1.383 (6)	C22—H22	0.9500
C15—C16	1.468 (6)	C22—C21	1.385 (6)
C15—C14	1.395 (6)	C31—H31	0.9500
C8—H8	0.9500	C31—C32	1.385 (6)
C8—C9	1.390 (6)	C34—H34	0.9500
C19—H19	0.9500	C27—H27	0.9500
C19—C18	1.375 (6)	C27—C28	1.384 (7)
C9—H9	0.9500	C32—H32	0.9500
C9—C10	1.382 (6)	C29—H29	0.9500
C3—H3	0.9500	C29—C30	1.380 (6)
C3—C4	1.394 (6)	C29—C28	1.383 (7)
C1—H1	0.9500	C21—H21	0.9500
C14—H14	0.9500	C25—C24	1.381 (6)
C14—C13	1.389 (6)	C24—H24	0.9500
C4—H4	0.9500	C38—H38	0.9500
C18—H18	0.9500	C30—H30	0.9500
C10—H10	0.9500	C40—H40	0.9500
C13—H13	0.9500	C28—H28	0.9500

F8—Ta2—F9	92.66 (12)	F13—Ta3—F17	89.01 (13)
F8—Ta2—F12	89.58 (12)	F16—Ta3—F13	177.92 (14)
F8—Ta2—F11	177.33 (12)	F16—Ta3—F17	90.17 (14)
F8—Ta2—F7	87.35 (12)	F15—Ta3—F13	91.30 (13)
F8—Ta2—F10	88.94 (12)	F15—Ta3—F16	90.58 (14)
F12—Ta2—F9	176.38 (11)	F15—Ta3—F17	87.30 (16)
F12—Ta2—F11	88.98 (12)	F14—Ta3—F13	90.20 (13)
F12—Ta2—F7	92.89 (12)	F14—Ta3—F16	90.66 (14)
F12—Ta2—F10	88.43 (11)	F14—Ta3—F15	91.22 (17)
F11—Ta2—F9	88.88 (11)	F14—Ta3—F17	178.31 (17)
F11—Ta2—F7	90.47 (12)	F14—Ta3—F18	91.3 (2)
F11—Ta2—F10	93.28 (12)	F18—Ta3—F13	87.43 (16)
F7—Ta2—F9	90.05 (12)	F18—Ta3—F16	90.66 (16)
F7—Ta2—F10	176.05 (12)	F18—Ta3—F15	177.17 (18)
F10—Ta2—F9	88.78 (12)	F18—Ta3—F17	90.2 (2)
F5—Ta1—F1	87.61 (12)	F21—Ta4—F23	90.32 (13)
F3—Ta1—F5	89.44 (12)	F21—Ta4—F24	177.79 (14)
F3—Ta1—F1	89.06 (11)	F21—Ta4—F19	90.96 (14)
F4—Ta1—F5	92.10 (13)	F21—Ta4—F22	89.84 (14)
F4—Ta1—F3	90.64 (12)	F21—Ta4—F20	92.80 (16)
F4—Ta1—F2	91.12 (14)	F23—Ta4—F19	89.22 (14)
F4—Ta1—F6	90.26 (12)	F24—Ta4—F23	87.48 (14)
F4—Ta1—F1	179.59 (13)	F24—Ta4—F19	88.86 (16)
F2—Ta1—F5	176.73 (13)	F22—Ta4—F23	89.03 (15)
F2—Ta1—F3	91.08 (13)	F22—Ta4—F24	90.27 (16)
F2—Ta1—F6	89.72 (13)	F22—Ta4—F19	178.08 (14)
F2—Ta1—F1	89.17 (13)	F20—Ta4—F23	176.84 (15)
F6—Ta1—F5	89.71 (12)	F20—Ta4—F24	89.40 (16)
F6—Ta1—F3	178.79 (12)	F20—Ta4—F19	91.22 (16)
F6—Ta1—F1	90.04 (12)	F20—Ta4—F22	90.48 (17)
F1—Cu1—F7	161.46 (9)	F13—Cu2—F19	168.21 (10)
N3—Cu1—F7	83.17 (11)	N7—Cu2—F13	83.91 (12)
N3—Cu1—F1	81.03 (12)	N7—Cu2—F19	103.51 (12)
N1—Cu1—F7	118.40 (11)	N7—Cu2—N6	103.87 (14)
N1—Cu1—F1	78.18 (12)	N7—Cu2—N8	82.29 (14)
N1—Cu1—N3	158.21 (14)	N5—Cu2—F13	77.43 (12)
N1—Cu1—N2	83.13 (14)	N5—Cu2—F19	95.18 (13)
N4—Cu1—F7	70.99 (11)	N5—Cu2—N7	161.27 (15)
N4—Cu1—F1	116.26 (12)	N5—Cu2—N6	82.25 (15)
N4—Cu1—N3	82.84 (14)	N5—Cu2—N8	101.20 (15)
N4—Cu1—N1	100.59 (14)	N6—Cu2—F13	113.10 (12)
N4—Cu1—N2	150.27 (14)	N6—Cu2—F19	74.40 (12)
N2—Cu1—F7	81.24 (11)	N6—Cu2—N8	150.51 (14)
N2—Cu1—F1	93.43 (12)	N8—Cu2—F13	96.12 (12)
N2—Cu1—N3	104.65 (14)	N8—Cu2—F19	76.12 (12)
Ta2—F7—Cu1	114.17 (12)	Ta3—F13—Cu2	122.63 (14)
Ta1—F1—Cu1	125.65 (14)	Ta4—F19—Cu2	135.07 (17)
C11—N3—Cu1	126.4 (3)	C35—N7—Cu2	114.6 (3)
C11—N3—C15	119.5 (3)	C31—N7—Cu2	125.9 (3)
C15—N3—Cu1	112.8 (3)	C31—N7—C35	119.4 (4)
C5—N1—Cu1	113.7 (3)	C21—N5—Cu2	125.5 (3)
C1—N1—Cu1	126.0 (3)	C21—N5—C25	119.5 (4)
C1—N1—C5	119.8 (3)	C25—N5—Cu2	115.0 (3)
C20—N4—Cu1	125.2 (3)	C26—N6—Cu2	113.1 (3)
C20—N4—C16	119.9 (3)	C30—N6—Cu2	127.7 (3)
C16—N4—Cu1	113.6 (3)	C30—N6—C26	118.8 (4)
C6—N2—Cu1	112.9 (3)	C36—N8—Cu2	112.8 (3)
C10—N2—Cu1	126.5 (3)	C40—N8—Cu2	127.0 (3)
C10—N2—C6	119.5 (3)	C40—N8—C36	118.9 (4)
C3—C2—H2	120.5	C38—C39—H39	120.6
C3—C2—C1	118.9 (4)	C38—C39—C40	118.9 (4)
C1—C2—H2	120.5	C40—C39—H39	120.6
N4—C20—H20	118.9	N6—C26—C27	121.6 (4)
N4—C20—C19	122.2 (4)	N6—C26—C25	114.7 (3)
C19—C20—H20	118.9	C27—C26—C25	123.7 (4)
C16—C17—H17	120.4	C22—C23—H23	120.3
C16—C17—C18	119.3 (4)	C24—C23—H23	120.3
C18—C17—H17	120.4	C24—C23—C22	119.4 (4)
N1—C5—C6	114.6 (3)	N7—C35—C34	120.8 (4)
N1—C5—C4	121.3 (4)	N7—C35—C36	114.5 (3)
C4—C5—C6	124.1 (4)	C34—C35—C36	124.7 (4)
C6—C7—H7	120.7	C34—C33—H33	120.4
C6—C7—C8	118.5 (4)	C34—C33—C32	119.2 (4)
C8—C7—H7	120.7	C32—C33—H33	120.4
N2—C6—C5	114.9 (3)	C36—C37—H37	120.5
N2—C6—C7	121.4 (4)	C38—C37—H37	120.5
C7—C6—C5	123.7 (4)	C38—C37—C36	118.9 (4)
N3—C11—H11	118.9	C23—C22—H22	120.7
N3—C11—C12	122.3 (4)	C21—C22—C23	118.6 (4)
C12—C11—H11	118.9	C21—C22—H22	120.7
C11—C12—H12	120.8	N7—C31—H31	119.0
C13—C12—C11	118.4 (4)	N7—C31—C32	121.9 (4)
C13—C12—H12	120.8	C32—C31—H31	119.0
N3—C15—C16	114.7 (3)	C35—C34—H34	120.1
N3—C15—C14	121.0 (4)	C33—C34—C35	119.8 (4)
C14—C15—C16	124.3 (4)	C33—C34—H34	120.1
C7—C8—H8	120.1	C26—C27—H27	120.3
C7—C8—C9	119.9 (4)	C26—C27—C28	119.5 (4)
C9—C8—H8	120.1	C28—C27—H27	120.3
C20—C19—H19	120.8	C33—C32—H32	120.6
C18—C19—C20	118.4 (4)	C31—C32—C33	118.7 (4)
C18—C19—H19	120.8	C31—C32—H32	120.6
C8—C9—H9	120.8	N8—C36—C35	115.0 (3)
C10—C9—C8	118.5 (4)	N8—C36—C37	121.6 (4)
C10—C9—H9	120.8	C37—C36—C35	123.3 (4)
C2—C3—H3	120.2	C30—C29—H29	120.2
C2—C3—C4	119.5 (4)	C30—C29—C28	119.5 (4)
C4—C3—H3	120.2	C28—C29—H29	120.2
N4—C16—C17	120.7 (4)	N5—C21—C22	122.0 (4)
N4—C16—C15	114.5 (3)	N5—C21—H21	119.0
C17—C16—C15	124.7 (4)	C22—C21—H21	119.0
N1—C1—C2	121.6 (4)	N5—C25—C26	114.5 (3)
N1—C1—H1	119.2	N5—C25—C24	121.7 (4)
C2—C1—H1	119.2	C24—C25—C26	123.8 (4)
C15—C14—H14	120.4	C23—C24—H24	120.6
C13—C14—C15	119.1 (4)	C25—C24—C23	118.7 (4)
C13—C14—H14	120.4	C25—C24—H24	120.6
C5—C4—C3	118.9 (4)	C39—C38—C37	119.2 (4)
C5—C4—H4	120.6	C39—C38—H38	120.4
C3—C4—H4	120.6	C37—C38—H38	120.4
C17—C18—H18	120.2	N6—C30—C29	121.8 (4)
C19—C18—C17	119.6 (4)	N6—C30—H30	119.1
C19—C18—H18	120.2	C29—C30—H30	119.1
N2—C10—C9	122.3 (4)	N8—C40—C39	122.5 (4)
N2—C10—H10	118.9	N8—C40—H40	118.8
C9—C10—H10	118.9	C39—C40—H40	118.8
C12—C13—C14	119.7 (4)	C27—C28—H28	120.6
C12—C13—H13	120.2	C29—C28—C27	118.8 (4)
C14—C13—H13	120.2	C29—C28—H28	120.6

Tris(2,2'-bipyridine-κ²N,N')copper(II) bis[hexafluoridotantalate(V)] (III) top

Crystal data top

[Cu(C₁₀H₈N₂)₃][TaF₆]₂	D_x = 2.220 Mg m⁻³
M_r = 1121.99	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₂	Cell parameters from 9702 reflections
a = 10.5172 (10) Å	θ = 2.2–32.5°
c = 26.288 (2) Å	µ = 7.23 mm⁻¹
V = 2518.2 (5) Å³	T = 100 K
Z = 3	Block, blue
F(000) = 1587	0.22 × 0.16 × 0.12 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	12260 independent reflections
Radiation source: sealed tube	12121 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.050
Detector resolution: 8 pixels mm^-1	θ_max = 32.7°, θ_min = 1.6°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −15→15
T_min = 0.559, T_max = 0.746	l = −38→39
148130 measured reflections

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0106P)² + 0.1438P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.016	(Δ/σ)_max = 0.002
wR(F²) = 0.031	Δρ_max = 0.96 e Å⁻³
S = 1.03	Δρ_min = −0.85 e Å⁻³
12260 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
462 parameters	Extinction coefficient: 0.00031 (3)
1 restraint	Absolute structure: Flack x determined using 5861 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Hydrogen site location: inferred from neighbouring sites	Absolute structure parameter: 0.5036 (7)

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Ta2	0.00684 (3)	−0.03219 (2)	0.32198 (2)	0.01774 (4)
Ta1	0.70686 (2)	1.36139 (2)	0.47151 (2)	0.01986 (4)
Cu1	0.32411 (6)	0.64362 (5)	0.57036 (2)	0.01228 (8)
F2	0.5183 (3)	1.2403 (5)	0.44310 (13)	0.0633 (12)
F4	0.7724 (4)	1.2402 (3)	0.44119 (10)	0.0408 (7)
C17	−0.0981 (5)	0.5633 (6)	0.6138 (2)	0.0188 (9)
H17	−0.153152	0.611150	0.608263	0.023*
F8	−0.1759 (3)	−0.0847 (3)	0.35333 (9)	0.0300 (6)
N4	0.1166 (4)	0.5474 (4)	0.59777 (12)	0.0126 (6)
F5	0.9006 (3)	1.4788 (3)	0.49516 (10)	0.0347 (6)
F12	0.0952 (3)	0.0141 (3)	0.38681 (9)	0.0402 (7)
F6	0.6515 (4)	1.2435 (3)	0.53047 (10)	0.0494 (9)
C16	0.0368 (5)	0.6141 (5)	0.59049 (14)	0.0130 (8)
C18	−0.1519 (4)	0.4417 (5)	0.64542 (14)	0.0220 (7)
H18	−0.243559	0.406714	0.662085	0.026*
F9	−0.0912 (3)	−0.0756 (3)	0.25849 (8)	0.0268 (5)
N3	0.2459 (3)	0.8080 (3)	0.54816 (11)	0.0142 (5)
F3	0.7575 (3)	1.4716 (3)	0.41088 (10)	0.0428 (7)
F10	−0.0341 (3)	−0.2286 (3)	0.32783 (10)	0.0295 (6)
F11	0.1857 (3)	0.0098 (3)	0.29071 (10)	0.0305 (6)
F7	0.0551 (3)	0.1672 (3)	0.31516 (9)	0.0283 (5)
F1	0.6482 (4)	1.4867 (4)	0.50135 (13)	0.0455 (8)
C15	0.1004 (4)	0.7442 (4)	0.55624 (12)	0.0138 (6)
C19	−0.0715 (5)	0.3711 (4)	0.65269 (15)	0.0194 (7)
H19	−0.107200	0.286719	0.673773	0.023*
N2	0.5147 (4)	0.7648 (4)	0.53243 (12)	0.0135 (7)
N5	0.4063 (3)	0.7268 (3)	0.64157 (10)	0.0152 (5)
C9	0.7449 (6)	0.9811 (6)	0.51576 (17)	0.0206 (10)
H9	0.823892	1.071865	0.527435	0.025*
C6	0.5147 (4)	0.7167 (4)	0.48464 (13)	0.0138 (6)
C23	0.5294 (5)	0.8446 (5)	0.73468 (18)	0.0230 (10)
H23	0.573816	0.885667	0.766493	0.028*
C24	0.5230 (4)	0.7175 (5)	0.71745 (14)	0.0216 (8)
H24	0.562435	0.670166	0.737466	0.026*
C10	0.6291 (5)	0.8936 (5)	0.54776 (16)	0.0171 (9)
H10	0.630309	0.925531	0.581658	0.021*
C22	0.4708 (5)	0.9115 (4)	0.70528 (14)	0.0216 (7)
H22	0.471689	0.997549	0.716782	0.026*
C11	0.3105 (5)	0.9276 (4)	0.51831 (14)	0.0180 (7)
H11	0.413500	0.974026	0.512970	0.022*
C21	0.4108 (4)	0.8499 (4)	0.65868 (14)	0.0191 (8)
H21	0.371299	0.895865	0.637984	0.023*
C20	0.0634 (4)	0.4284 (4)	0.62794 (13)	0.0157 (7)
H20	0.119861	0.381628	0.632587	0.019*
N1	0.2704 (3)	0.5298 (3)	0.50323 (10)	0.0130 (5)
C5	0.3856 (4)	0.5755 (4)	0.47127 (12)	0.0135 (6)
C7	0.6286 (4)	0.7992 (4)	0.45095 (14)	0.0205 (8)
H7	0.627957	0.763870	0.417631	0.025*
N6	0.3922 (4)	0.4832 (4)	0.60312 (12)	0.0180 (6)
C26	0.4437 (4)	0.5196 (4)	0.65109 (13)	0.0164 (6)
C8	0.7437 (5)	0.9345 (5)	0.46684 (15)	0.0240 (8)
H8	0.820854	0.994029	0.444011	0.029*
C13	0.0833 (4)	0.9178 (4)	0.50245 (13)	0.0196 (7)
H13	0.027481	0.954984	0.486504	0.023*
C25	0.4586 (4)	0.6591 (4)	0.67064 (13)	0.0150 (6)
C14	0.0144 (4)	0.7946 (4)	0.53329 (13)	0.0179 (7)
H14	−0.088668	0.745881	0.538648	0.022*
C12	0.2327 (4)	0.9860 (4)	0.49499 (14)	0.0185 (7)
H12	0.281469	1.071236	0.474305	0.022*
C27	0.4749 (5)	0.4294 (5)	0.68023 (15)	0.0241 (9)
H27	0.510287	0.456347	0.714018	0.029*
C2	0.1346 (5)	0.3167 (4)	0.45214 (16)	0.0225 (8)
H2	0.045309	0.228062	0.445925	0.027*
C1	0.1471 (4)	0.4030 (4)	0.49352 (14)	0.0174 (7)
H1	0.065657	0.371517	0.515813	0.021*
C30	0.3758 (4)	0.3587 (4)	0.58279 (15)	0.0201 (7)
H30	0.343309	0.335632	0.548553	0.024*
C3	0.2530 (5)	0.3601 (4)	0.41977 (15)	0.0250 (8)
H3	0.247427	0.300756	0.391649	0.030*
C4	0.3810 (5)	0.4932 (4)	0.42942 (14)	0.0218 (8)
H4	0.463614	0.526892	0.407591	0.026*
C28	0.4537 (5)	0.2983 (5)	0.65946 (16)	0.0272 (9)
H28	0.472935	0.234061	0.679147	0.033*
C29	0.4043 (5)	0.2626 (5)	0.60978 (16)	0.0234 (8)
H29	0.390410	0.174533	0.594640	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ta2	0.01698 (8)	0.01449 (10)	0.01536 (7)	0.00308 (8)	−0.00052 (7)	0.00018 (7)
Ta1	0.01754 (9)	0.01929 (10)	0.01742 (7)	0.00521 (9)	0.00037 (7)	0.00145 (8)
Cu1	0.01235 (18)	0.0136 (2)	0.0094 (2)	0.00535 (17)	0.00046 (17)	−0.00043 (14)
F2	0.0201 (13)	0.077 (3)	0.0550 (18)	−0.0039 (17)	−0.0002 (12)	−0.019 (2)
F4	0.056 (2)	0.0339 (17)	0.0316 (14)	0.0220 (16)	0.0046 (14)	−0.0086 (12)
C17	0.018 (2)	0.019 (2)	0.0220 (19)	0.0108 (17)	0.0047 (18)	−0.0006 (18)
F8	0.0297 (12)	0.0280 (14)	0.0236 (11)	0.0079 (11)	0.0091 (9)	0.0002 (10)
N4	0.0142 (14)	0.0117 (15)	0.0106 (13)	0.0056 (12)	0.0025 (10)	0.0018 (11)
F5	0.0275 (12)	0.0382 (16)	0.0390 (14)	0.0169 (13)	−0.0148 (11)	−0.0190 (13)
F12	0.0493 (17)	0.0341 (15)	0.0229 (12)	0.0100 (14)	−0.0170 (12)	−0.0010 (11)
F6	0.074 (3)	0.0418 (16)	0.0303 (13)	0.0279 (18)	0.0220 (15)	0.0169 (12)
C16	0.0189 (19)	0.0114 (16)	0.0080 (16)	0.0071 (15)	0.0001 (13)	0.0001 (13)
C18	0.0182 (16)	0.0188 (18)	0.0262 (18)	0.0071 (16)	0.0076 (14)	0.0031 (16)
F9	0.0312 (12)	0.0345 (13)	0.0178 (10)	0.0188 (11)	−0.0044 (9)	−0.0056 (10)
N3	0.0130 (13)	0.0128 (14)	0.0144 (13)	0.0045 (11)	−0.0013 (11)	−0.0010 (11)
F3	0.0340 (17)	0.0616 (19)	0.0311 (13)	0.0226 (15)	0.0034 (13)	0.0225 (13)
F10	0.0232 (13)	0.0193 (11)	0.0406 (14)	0.0065 (10)	0.0020 (11)	0.0039 (11)
F11	0.0199 (12)	0.0248 (13)	0.0441 (15)	0.0091 (10)	0.0035 (11)	0.0046 (12)
F7	0.0343 (15)	0.0190 (11)	0.0296 (12)	0.0117 (11)	0.0006 (11)	−0.0009 (9)
F1	0.0452 (19)	0.052 (2)	0.0562 (18)	0.0374 (18)	0.0084 (15)	0.0021 (16)
C15	0.0157 (15)	0.0154 (15)	0.0112 (15)	0.0085 (13)	0.0001 (12)	−0.0002 (12)
C19	0.0216 (18)	0.0149 (16)	0.0203 (18)	0.0081 (15)	0.0078 (15)	0.0069 (14)
N2	0.0127 (14)	0.0116 (14)	0.0140 (14)	0.0045 (12)	−0.0019 (10)	−0.0008 (12)
N5	0.0169 (12)	0.0146 (13)	0.0135 (12)	0.0073 (11)	0.0019 (10)	0.0012 (10)
C9	0.017 (2)	0.018 (2)	0.022 (2)	0.0049 (17)	−0.0038 (17)	−0.0039 (18)
C6	0.0152 (14)	0.0142 (16)	0.0128 (14)	0.0079 (13)	0.0014 (11)	−0.0009 (13)
C23	0.026 (2)	0.025 (2)	0.0129 (19)	0.0091 (16)	−0.0027 (17)	−0.0043 (18)
C24	0.0247 (18)	0.025 (2)	0.0124 (16)	0.0105 (16)	−0.0056 (14)	−0.0019 (14)
C10	0.0132 (17)	0.020 (2)	0.0144 (18)	0.0050 (15)	−0.0033 (14)	−0.0005 (15)
C22	0.0217 (19)	0.0186 (15)	0.0183 (16)	0.0054 (16)	−0.0012 (16)	−0.0064 (13)
C11	0.0213 (18)	0.0138 (16)	0.0163 (18)	0.0070 (14)	0.0013 (14)	−0.0006 (13)
C21	0.025 (2)	0.0173 (15)	0.0147 (15)	0.0105 (15)	0.0009 (14)	−0.0006 (12)
C20	0.0182 (17)	0.0139 (15)	0.0159 (16)	0.0087 (14)	0.0017 (13)	0.0016 (13)
N1	0.0131 (13)	0.0134 (12)	0.0130 (12)	0.0069 (11)	−0.0012 (11)	−0.0007 (9)
C5	0.0149 (16)	0.0146 (16)	0.0107 (13)	0.0071 (12)	−0.0003 (12)	−0.0007 (12)
C7	0.0176 (16)	0.0226 (19)	0.0143 (16)	0.0047 (15)	0.0020 (13)	−0.0016 (14)
N6	0.0201 (16)	0.0217 (15)	0.0157 (14)	0.0129 (13)	0.0011 (12)	−0.0002 (12)
C26	0.0128 (16)	0.0210 (19)	0.0147 (15)	0.0078 (14)	0.0021 (14)	0.0025 (14)
C8	0.0173 (18)	0.023 (2)	0.0217 (19)	0.0022 (16)	0.0042 (14)	0.0046 (16)
C13	0.027 (2)	0.0222 (18)	0.0170 (15)	0.0175 (16)	0.0036 (14)	0.0070 (14)
C25	0.0143 (15)	0.0166 (16)	0.0115 (14)	0.0056 (13)	−0.0006 (12)	0.0000 (12)
C14	0.0193 (17)	0.0213 (18)	0.0181 (17)	0.0137 (15)	0.0038 (14)	0.0025 (14)
C12	0.0248 (19)	0.0169 (17)	0.0134 (17)	0.0102 (15)	0.0014 (15)	0.0042 (14)
C27	0.032 (2)	0.033 (2)	0.0150 (17)	0.022 (2)	−0.0067 (16)	−0.0010 (16)
C2	0.0179 (18)	0.0167 (16)	0.0276 (19)	0.0048 (16)	−0.0019 (16)	−0.0068 (14)
C1	0.0173 (17)	0.0141 (15)	0.0170 (16)	0.0050 (13)	0.0002 (14)	−0.0006 (13)
C30	0.0221 (18)	0.0204 (18)	0.0195 (17)	0.0118 (15)	−0.0023 (15)	−0.0033 (15)
C3	0.030 (2)	0.0204 (18)	0.0198 (18)	0.0088 (17)	−0.0024 (17)	−0.0088 (15)
C4	0.0222 (19)	0.0203 (18)	0.0161 (16)	0.0055 (15)	0.0037 (15)	−0.0032 (14)
C28	0.036 (2)	0.033 (2)	0.0241 (19)	0.025 (2)	−0.0039 (18)	0.0042 (18)
C29	0.027 (2)	0.0218 (19)	0.028 (2)	0.0166 (17)	0.0006 (16)	−0.0019 (16)

Geometric parameters (Å, º) top

Ta2—F8	1.901 (2)	C23—C24	1.381 (7)
Ta2—F12	1.885 (2)	C23—C22	1.381 (6)
Ta2—F9	1.894 (2)	C24—H24	0.9500
Ta2—F10	1.893 (3)	C24—C25	1.391 (5)
Ta2—F11	1.892 (3)	C10—H10	0.9500
Ta2—F7	1.903 (2)	C22—H22	0.9500
Ta1—F2	1.894 (3)	C22—C21	1.382 (5)
Ta1—F4	1.901 (3)	C11—H11	0.9500
Ta1—F5	1.883 (2)	C11—C12	1.388 (5)
Ta1—F6	1.886 (3)	C21—H21	0.9500
Ta1—F3	1.884 (2)	C20—H20	0.9500
Ta1—F1	1.883 (3)	N1—C5	1.350 (4)
Cu1—N4	2.024 (3)	N1—C1	1.341 (5)
Cu1—N3	2.330 (3)	C5—C4	1.385 (5)
Cu1—N2	2.020 (3)	C7—H7	0.9500
Cu1—N5	2.064 (3)	C7—C8	1.394 (5)
Cu1—N1	2.047 (3)	N6—C26	1.350 (5)
Cu1—N6	2.305 (3)	N6—C30	1.343 (5)
C17—H17	0.9500	C26—C25	1.487 (5)
C17—C16	1.384 (6)	C26—C27	1.380 (5)
C17—C18	1.386 (6)	C8—H8	0.9500
N4—C16	1.350 (6)	C13—H13	0.9500
N4—C20	1.344 (5)	C13—C14	1.386 (5)
C16—C15	1.488 (5)	C13—C12	1.377 (5)
C18—H18	0.9500	C14—H14	0.9500
C18—C19	1.389 (6)	C12—H12	0.9500
N3—C15	1.346 (5)	C27—H27	0.9500
N3—C11	1.343 (5)	C27—C28	1.393 (6)
C15—C14	1.393 (5)	C2—H2	0.9500
C19—H19	0.9500	C2—C1	1.380 (5)
C19—C20	1.394 (5)	C2—C3	1.384 (6)
N2—C6	1.354 (5)	C1—H1	0.9500
N2—C10	1.348 (6)	C30—H30	0.9500
N5—C21	1.349 (4)	C30—C29	1.385 (5)
N5—C25	1.336 (4)	C3—H3	0.9500
C9—H9	0.9500	C3—C4	1.397 (6)
C9—C10	1.384 (7)	C4—H4	0.9500
C9—C8	1.374 (6)	C28—H28	0.9500
C6—C5	1.469 (5)	C28—C29	1.386 (6)
C6—C7	1.390 (5)	C29—H29	0.9500
C23—H23	0.9500

F8—Ta2—F7	92.03 (12)	C7—C6—C5	123.4 (3)
F12—Ta2—F8	88.82 (12)	C24—C23—H23	120.3
F12—Ta2—F9	176.22 (13)	C22—C23—H23	120.3
F12—Ta2—F10	91.26 (13)	C22—C23—C24	119.5 (4)
F12—Ta2—F11	91.61 (13)	C23—C24—H24	120.2
F12—Ta2—F7	88.58 (12)	C23—C24—C25	119.7 (4)
F9—Ta2—F8	87.85 (10)	C25—C24—H24	120.2
F9—Ta2—F7	89.75 (11)	N2—C10—C9	122.2 (4)
F10—Ta2—F8	90.12 (12)	N2—C10—H10	118.9
F10—Ta2—F9	90.53 (11)	C9—C10—H10	118.9
F10—Ta2—F7	177.84 (12)	C23—C22—H22	120.9
F11—Ta2—F8	177.08 (12)	C23—C22—C21	118.2 (4)
F11—Ta2—F9	91.81 (11)	C21—C22—H22	120.9
F11—Ta2—F10	86.98 (12)	N3—C11—H11	118.7
F11—Ta2—F7	90.87 (12)	N3—C11—C12	122.6 (4)
F2—Ta1—F4	89.58 (16)	C12—C11—H11	118.7
F5—Ta1—F2	175.49 (14)	N5—C21—C22	122.2 (4)
F5—Ta1—F4	86.68 (13)	N5—C21—H21	118.9
F5—Ta1—F6	92.12 (14)	C22—C21—H21	118.9
F5—Ta1—F3	89.74 (13)	N4—C20—C19	122.5 (4)
F6—Ta1—F2	90.39 (16)	N4—C20—H20	118.7
F6—Ta1—F4	90.02 (13)	C19—C20—H20	118.7
F3—Ta1—F2	87.64 (16)	C5—N1—Cu1	113.1 (2)
F3—Ta1—F4	88.41 (14)	C1—N1—Cu1	126.3 (2)
F3—Ta1—F6	177.48 (15)	C1—N1—C5	119.0 (3)
F1—Ta1—F2	92.03 (18)	N1—C5—C6	115.0 (3)
F1—Ta1—F4	178.14 (16)	N1—C5—C4	121.8 (3)
F1—Ta1—F5	91.67 (14)	C4—C5—C6	123.2 (3)
F1—Ta1—F6	90.91 (14)	C6—C7—H7	120.5
F1—Ta1—F3	90.72 (14)	C6—C7—C8	118.9 (3)
N4—Cu1—N3	76.58 (13)	C8—C7—H7	120.5
N4—Cu1—N5	90.44 (12)	C26—N6—Cu1	111.6 (2)
N4—Cu1—N1	95.81 (13)	C30—N6—Cu1	129.0 (3)
N4—Cu1—N6	98.80 (14)	C30—N6—C26	119.1 (3)
N2—Cu1—N4	166.58 (14)	N6—C26—C25	115.6 (3)
N2—Cu1—N3	90.89 (13)	N6—C26—C27	121.5 (4)
N2—Cu1—N5	96.14 (12)	C27—C26—C25	122.8 (3)
N2—Cu1—N1	80.79 (13)	C9—C8—C7	119.5 (4)
N2—Cu1—N6	94.16 (13)	C9—C8—H8	120.2
N5—Cu1—N3	98.11 (11)	C7—C8—H8	120.2
N5—Cu1—N6	75.75 (12)	C14—C13—H13	120.1
N1—Cu1—N3	96.98 (11)	C12—C13—H13	120.1
N1—Cu1—N5	164.65 (12)	C12—C13—C14	119.8 (3)
N1—Cu1—N6	89.41 (11)	N5—C25—C24	120.7 (4)
N6—Cu1—N3	172.42 (10)	N5—C25—C26	117.4 (3)
C16—C17—H17	120.4	C24—C25—C26	121.9 (3)
C16—C17—C18	119.3 (5)	C15—C14—H14	120.9
C18—C17—H17	120.4	C13—C14—C15	118.3 (4)
C16—N4—Cu1	119.0 (3)	C13—C14—H14	120.9
C20—N4—Cu1	121.2 (3)	C11—C12—H12	120.7
C20—N4—C16	119.3 (3)	C13—C12—C11	118.6 (3)
C17—C16—C15	121.7 (4)	C13—C12—H12	120.7
N4—C16—C17	121.3 (4)	C26—C27—H27	120.4
N4—C16—C15	117.0 (4)	C26—C27—C28	119.1 (4)
C17—C18—H18	120.0	C28—C27—H27	120.4
C17—C18—C19	119.9 (4)	C1—C2—H2	120.2
C19—C18—H18	120.0	C1—C2—C3	119.6 (4)
C15—N3—Cu1	109.0 (2)	C3—C2—H2	120.2
C11—N3—Cu1	129.8 (3)	N1—C1—C2	122.0 (4)
C11—N3—C15	118.4 (3)	N1—C1—H1	119.0
N3—C15—C16	115.5 (3)	C2—C1—H1	119.0
N3—C15—C14	122.3 (3)	N6—C30—H30	118.7
C14—C15—C16	122.2 (4)	N6—C30—C29	122.6 (4)
C18—C19—H19	121.2	C29—C30—H30	118.7
C18—C19—C20	117.7 (3)	C2—C3—H3	120.8
C20—C19—H19	121.2	C2—C3—C4	118.4 (4)
C6—N2—Cu1	114.0 (3)	C4—C3—H3	120.8
C10—N2—Cu1	126.3 (3)	C5—C4—C3	119.1 (4)
C10—N2—C6	119.1 (3)	C5—C4—H4	120.5
C21—N5—Cu1	121.0 (2)	C3—C4—H4	120.5
C25—N5—Cu1	119.3 (2)	C27—C28—H28	120.3
C25—N5—C21	119.7 (3)	C29—C28—C27	119.4 (4)
C10—C9—H9	120.5	C29—C28—H28	120.3
C8—C9—H9	120.5	C30—C29—C28	118.3 (4)
C8—C9—C10	118.9 (5)	C30—C29—H29	120.9
N2—C6—C5	115.3 (3)	C28—C29—H29	120.9
N2—C6—C7	121.3 (3)

catena-Poly[[diaqua(2,2'-bipyridine-κ²N,N')copper(II)]-µ-fluorido-tetrafluoridotin-µ-fluorido] (IV) top

Crystal data top

[CuSnF₆(C₁₀H₈N₂)(H₂O)₂]	F(000) = 470
M_r = 488.45	D_x = 2.312 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.2590 (2) Å	Cell parameters from 9773 reflections
b = 9.2167 (3) Å	θ = 2.2–37.7°
c = 12.1648 (3) Å	µ = 3.37 mm⁻¹
β = 90.734 (2)°	T = 100 K
V = 701.70 (4) Å³	Block, blue
Z = 2	0.20 × 0.13 × 0.12 mm

Data collection top

Rigaku Oxford Diffraction XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	3686 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	3251 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.055
Detector resolution: 10.0000 pixels mm^-1	θ_max = 38.2°, θ_min = 2.2°
ω scans	h = −10→10
Absorption correction: gaussian CrysalisPro (Rigaku OD, 2020)	k = −15→15
T_min = 0.732, T_max = 1.000	l = −20→21
22131 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0285P)² + 0.1262P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3686 reflections	Δρ_max = 2.05 e Å⁻³
110 parameters	Δρ_min = −0.85 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Sn1	0.500000	1.000000	0.500000	0.00931 (4)
Cu1	0.250000	0.78803 (3)	0.750000	0.00868 (5)
F1	0.42425 (17)	0.82052 (11)	0.57872 (8)	0.01353 (18)
F2	0.78470 (17)	0.92222 (12)	0.46961 (9)	0.0184 (2)
F3	0.39654 (19)	0.91649 (12)	0.36083 (8)	0.0183 (2)
O1	0.4565 (2)	0.93265 (14)	0.80535 (10)	0.0147 (2)
N1	0.0722 (2)	0.62522 (16)	0.69309 (12)	0.0136 (3)
C5	0.1508 (4)	0.49153 (18)	0.71618 (16)	0.0184 (3)
C1	−0.1085 (3)	0.6393 (3)	0.63416 (16)	0.0223 (4)
H1	−0.162552	0.733418	0.618476	0.027*
C4	0.0467 (5)	0.3679 (2)	0.6778 (2)	0.0339 (6)
H4	0.103791	0.274557	0.693689	0.041*
C2	−0.2186 (4)	0.5178 (3)	0.5954 (2)	0.0357 (6)
H2	−0.347822	0.529058	0.554473	0.043*
C3	−0.1386 (5)	0.3807 (3)	0.6169 (2)	0.0438 (8)
H3	−0.210607	0.296937	0.590073	0.053*
H1A	0.424 (6)	0.983 (3)	0.864 (3)	0.037 (9)*
H1B	0.518 (6)	0.985 (3)	0.763 (3)	0.040 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01216 (7)	0.00790 (7)	0.00789 (6)	−0.00206 (4)	0.00114 (5)	0.00053 (4)
Cu1	0.00956 (11)	0.00682 (11)	0.00964 (11)	0.000	−0.00066 (9)	0.000
F1	0.0188 (5)	0.0100 (4)	0.0119 (4)	−0.0018 (3)	0.0028 (4)	0.0013 (3)
F2	0.0162 (5)	0.0176 (5)	0.0215 (5)	0.0034 (4)	0.0055 (4)	0.0071 (4)
F3	0.0284 (6)	0.0160 (5)	0.0103 (4)	−0.0102 (4)	−0.0013 (4)	−0.0008 (4)
O1	0.0188 (6)	0.0145 (6)	0.0110 (5)	−0.0075 (4)	0.0021 (4)	−0.0025 (4)
N1	0.0151 (6)	0.0130 (6)	0.0128 (6)	−0.0055 (5)	0.0019 (5)	−0.0024 (5)
C5	0.0299 (10)	0.0091 (7)	0.0166 (8)	−0.0056 (6)	0.0097 (7)	−0.0022 (5)
C1	0.0154 (8)	0.0346 (11)	0.0169 (8)	−0.0093 (7)	−0.0004 (6)	−0.0036 (7)
C4	0.0571 (16)	0.0153 (9)	0.0297 (11)	−0.0190 (9)	0.0126 (11)	−0.0078 (8)
C2	0.0306 (12)	0.0541 (16)	0.0223 (10)	−0.0294 (11)	0.0024 (9)	−0.0094 (10)
C3	0.0595 (18)	0.0433 (15)	0.0288 (11)	−0.0414 (14)	0.0116 (12)	−0.0150 (11)

Geometric parameters (Å, º) top

Sn1—F1	1.9723 (10)	O1—H1B	0.81 (3)
Sn1—F1ⁱ	1.9723 (10)	N1—C5	1.355 (2)
Sn1—F2	1.9603 (11)	N1—C1	1.337 (2)
Sn1—F2ⁱ	1.9603 (11)	C5—C5ⁱⁱ	1.481 (5)
Sn1—F3ⁱ	1.9621 (10)	C5—C4	1.390 (3)
Sn1—F3	1.9621 (10)	C1—H1	0.9500
Cu1—F1	2.3830 (10)	C1—C2	1.394 (3)
Cu1—F1ⁱⁱ	2.3830 (10)	C4—H4	0.9500
Cu1—O1ⁱⁱ	1.9695 (12)	C4—C3	1.374 (4)
Cu1—O1	1.9695 (12)	C2—H2	0.9500
Cu1—N1ⁱⁱ	1.9875 (14)	C2—C3	1.382 (4)
Cu1—N1	1.9875 (14)	C3—H3	0.9500
O1—H1A	0.88 (3)

F1—Sn1—F1ⁱ	180.0	N1ⁱⁱ—Cu1—F1	97.98 (5)
F2—Sn1—F1ⁱ	89.45 (4)	N1—Cu1—F1	92.92 (5)
F2ⁱ—Sn1—F1	89.45 (4)	N1—Cu1—F1ⁱⁱ	97.98 (5)
F2ⁱ—Sn1—F1ⁱ	90.55 (4)	N1ⁱⁱ—Cu1—N1	81.95 (9)
F2—Sn1—F1	90.55 (4)	Sn1—F1—Cu1	130.20 (5)
F2ⁱ—Sn1—F2	180.0	Cu1—O1—H1A	118 (2)
F2—Sn1—F3	89.12 (5)	Cu1—O1—H1B	120 (3)
F2ⁱ—Sn1—F3	90.88 (5)	H1A—O1—H1B	109 (3)
F2ⁱ—Sn1—F3ⁱ	89.12 (5)	C5—N1—Cu1	114.47 (13)
F2—Sn1—F3ⁱ	90.88 (5)	C1—N1—Cu1	125.42 (14)
F3ⁱ—Sn1—F1ⁱ	90.64 (4)	C1—N1—C5	120.09 (17)
F3ⁱ—Sn1—F1	89.36 (4)	N1—C5—C5ⁱⁱ	114.51 (11)
F3—Sn1—F1ⁱ	89.36 (4)	N1—C5—C4	120.6 (2)
F3—Sn1—F1	90.64 (4)	C4—C5—C5ⁱⁱ	124.91 (16)
F3ⁱ—Sn1—F3	180.0	N1—C1—H1	119.5
F1—Cu1—F1ⁱⁱ	165.56 (5)	N1—C1—C2	121.0 (2)
O1ⁱⁱ—Cu1—F1ⁱⁱ	84.73 (5)	C2—C1—H1	119.5
O1—Cu1—F1	84.73 (5)	C5—C4—H4	120.0
O1ⁱⁱ—Cu1—F1	85.51 (5)	C3—C4—C5	119.9 (2)
O1—Cu1—F1ⁱⁱ	85.51 (5)	C3—C4—H4	120.0
O1—Cu1—O1ⁱⁱ	94.81 (8)	C1—C2—H2	120.2
O1—Cu1—N1	172.88 (6)	C3—C2—C1	119.6 (2)
O1ⁱⁱ—Cu1—N1ⁱⁱ	172.88 (6)	C3—C2—H2	120.2
O1—Cu1—N1ⁱⁱ	91.70 (6)	C4—C3—C2	118.8 (2)
O1ⁱⁱ—Cu1—N1	91.70 (6)	C4—C3—H3	120.6
N1ⁱⁱ—Cu1—F1ⁱⁱ	92.92 (5)	C2—C3—H3	120.6

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F2ⁱⁱⁱ	0.88 (3)	1.79 (3)	2.6444 (17)	165 (3)
O1—H1B···F3ⁱ	0.81 (3)	1.84 (4)	2.6293 (17)	164 (4)

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

Acknowledgements

Single-crystal X-ray diffraction data were acquired at IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN).

Funding information

Funding for this research was provided by: National Science Foundation (grant No. DMR-1904701); Office of Undergraduate Research at Northwestern University (Summer Undergraduate Research Grant No. 1041SUMMER1917662).

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Volume 77| Part 2| February 2021| Pages 158-164

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