Crystal structures of [Cu(phen)(H2O)3(MF6)]·H2O (M = Ti, Zr, Hf) and [Cu(phen)(H2O)2F]2[HfF6]·H2O

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

doi:10.1107/S2056989021000645

research communications

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ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 165-170

https://doi.org/10.1107/S2056989021000645

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Crystal structures of [Cu(phen)(H₂O)₃(MF₆)]·H₂O (M = Ti, Zr, Hf) and [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O

Matthew L. Nisbet ^a and Kenneth R. Poeppelmeier ^a ^*

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

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 23 December 2020; accepted 19 January 2021; online 26 January 2021)

The crystal structures of three bridged bimetallic molecular compounds, namely, triaqua-2κ³O-μ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N′)copper(II)titanium(IV) monohydrate, [Cu(TiF₆)(phen)(H₂O)₃]·H₂O (phen is 1,10-phenanthroline, C₁₂H₈N₂), (I), triaqua-2κ³O-μ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N′)copper(II)zirconium(IV) monohydrate, [Cu(ZrF₆)(phen)(H₂O)₃]·H₂O, (II), and triaqua-2κ³O-μ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N′)copper(II)hafnium(IV) monohydrate, [Cu(HfF₆)(phen)(H₂O)₃]·H₂O, (III), and one molecular salt, bis[diaquafluorido(1,10-phenanthroline-κ²N,N′)copper(II)] hexafluoridohafnate(IV) dihydrate, [CuF(phen)(H₂O)₂]₂[HfF₆]·2H₂O, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octahedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and intermolecular hydrogen bonds and intermolecular π–π stacking. The salt compound [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O displays an isolated square-pyramidal Cu(phen)(H₂O)₂F⁺ complex linked to other cationic complexes and isolated HfF₆²⁻ anions through intermolecular hydrogen-bonding interactions.

Keywords: crystal structures; lambda (Λ)-shapes; d⁰ early transition metals; hydrothermal synthesis.

CCDC references: 2045776; 2045775; 2045774; 2045773

1. Chemical context

Lambda (Λ)-shaped molecules have been demonstrated as efficient building blocks in the synthesis of non-centrosymmetric (NCS) materials via arrangement into head-to-tail and accordion (head-to-head, tail-to-tail) structures (Yamamoto et al., 1992 ; Tao et al., 1994 , 1995 ; Ostroverkhov et al., 2001 ; Chang et al., 2009 ). Although this concept was first applied to organic Λ-shaped molecules in crystalline materials and polymers, recently NCS compounds based on inorganic bimetallic Λ-shapes have been reported, namely K₁₀(Mo₂O₄F₇)₃X (X = Cl, ([Br₃][Br])_1/2, ([I₃][I])_1/2), K₁₀(Nb₂O₂F₉)₃X (X = Br, ([Br₃][Br])_1/2, ([I₃][I])_1/2), and [Cu(H₂O)₅(VOF₄(H₂O))]·H₂O (Donakowski et al., 2012 ; Holland et al., 2014 ). Here, we report the structures of three centrosymmetric compounds based on inorganic bimetallic Λ-shapes with the formula [Cu(phen)(H₂O)₃(MF₆)]·H₂O (M = Ti, Zr, Hf; phen = 1,10-phenanthroline). Although these compounds crystallize with inversion symmetry, the novel molecular building units are potential targets of future studies aimed to perturb their packing arrangement to form NCS structures. The salt compound [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O provides a point of comparison as an unbridged analogue of [Cu(phen)(H₂O)₃(HfF₆)]·H₂O.

2. Structural commentary

Compound (I) has the formula [Cu(phen)(H₂O)₃(TiF₆)]·H₂O and crystallizes in the orthorhombic space group Pbca (Fig. 1). The structure of compound (I) features Cu1 in a tetragonally distorted octahedral environment with elongated axial Cu1—F1 [2.3643 (12) Å] and Cu1—O1 [2.2794 (17) Å] bonds owing to the Jahn–Teller effect of copper(II). The Cu1 center is linked to the TiF₆²⁻ anion through the bridging F1 ligand. The octahedral coordination environment of Ti1 is slightly distorted, with Ti1—F bond lengths ranging from 1.8395 (13) to 1.9035 (13) Å. The Λ-shape, indicated by the Cu1—F1—Ti1 bond angle of 134.93 (6)°, is enforced by the two intramolecular O2—H2B⋯F5 and O3—H3B⋯F6 hydrogen bonds (Table 1).

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F2ⁱ	0.70 (4)	2.08 (4)	2.775 (2)	175 (4)
O1—H1B⋯F4ⁱⁱ	0.77 (4)	1.96 (4)	2.726 (2)	174 (3)
O2—H2A⋯O4	0.83 (3)	1.83 (3)	2.654 (2)	175 (3)
O2—H2B⋯F5	0.83 (4)	1.85 (4)	2.666 (2)	167 (3)
O3—H3A⋯F3ⁱ	0.84 (4)	1.85 (4)	2.683 (2)	171 (4)
O3—H3B⋯F6	0.90 (4)	1.81 (4)	2.683 (2)	163 (3)
O4—H4A⋯F3ⁱⁱⁱ	0.75 (4)	2.00 (4)	2.718 (2)	163 (4)
O4—H4B⋯F2ⁱ	0.77 (3)	1.96 (3)	2.691 (2)	156 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 1
Molecular structure of compound (I)

, [Cu(phen)(H₂O)₃(TiF₆)]·H₂O. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å.

Compound (II) has the formula [Cu(phen)(H₂O)₃(ZrF₆)]·H₂O and crystallizes in the monoclinic space group P2₁/n (Fig. 2). The structure of compound (II) features Cu1 in a tetragonally distorted octahedral environment with elongated axial Cu1—F1 [2.5184 (6) Å] and Cu—O1 [2.2758 (7) Å] bonds owing to the Jahn–Teller effect of copper(II). The Cu1 center is linked to the ZrF₆²⁻ anion through the bridging F1 ligand. The octahedral coordination environment of Zr1 is slightly distorted, with Zr1—F bond lengths ranging from 1.9910 (6) to 2.0430 (6) Å. The Λ-shape, indicated by the Cu1—F1—Zr1 bond angle of 132.59 (3)°, is enforced by an intramolecular O2—H2B⋯F6 hydrogen bond (Table 2). The single intramolecular hydrogen bond in compound (II) tilts the ZrF₆²⁻ group significantly relative to the TiF₆²⁻ group in compound (I), which is depicted in Fig. 5 and reflected in the F1—Cu1—N1 bond angle of 77.75 (3)° angle in compound (II) compared to 89.45 (6)° in compound (I).

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F5ⁱ	0.794 (18)	1.944 (18)	2.7338 (9)	173.5 (18)
O1—H1B⋯F4ⁱⁱ	0.78 (2)	1.93 (2)	2.7147 (10)	179 (2)
O2—H2A⋯F3ⁱ	0.79 (2)	1.85 (2)	2.6324 (10)	171 (2)
O2—H2B⋯F6	0.82 (2)	1.87 (2)	2.6491 (10)	159.2 (19)
O3—H3A⋯F2ⁱⁱⁱ	0.79 (2)	1.85 (2)	2.6327 (10)	177.5 (19)
O3—H3B⋯O4^iv	0.79 (2)	1.87 (2)	2.6481 (12)	170 (2)
O4—H4A⋯F3	0.799 (19)	2.002 (19)	2.7691 (10)	160.9 (18)
O4—H4B⋯F5^v	0.78 (2)	2.02 (2)	2.7449 (11)	155 (2)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) ; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Molecular structure of compound (II)

, [Cu(phen)(H₂O)₃(ZrF₆)]·H₂O. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å.

Figure 5
Comparison of the molecular structures of (a) compound (I)

and (b) compound (III)

Compound (III) has the formula [Cu(phen)(H₂O)₃(HfF₆)]·H₂O and crystallizes in the monoclinic space group P2₁/n (Fig. 3). Compound (III) is isostructural to compound (II).

Figure 3
Molecular structure of compound (III)

, [Cu(phen)(H₂O)₃(HfF₆)]·H₂O. 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(phen)(H₂O)₂F]₂[HfF₆]·H₂O and crystallizes in the monoclinic space group P2₁/n (Fig. 4). The structure of compound (IV) features isolated square pyramidal Cu(phen)(H₂O)₂F⁺ cations and octahedral HfF₆²⁻ anions. The free HfF₆²⁻ octahedron occupies an inversion center with three distinct bond lengths ranging between 1.9863 (10) and 1.9957 (9) Å.

Figure 4
Molecular structure of compound (IV)

, [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O. Ellipsoids of non-H atoms are drawn at 50% probability. H atoms are drawn with an atomic radius of 0.135 Å.

3. Supramolecular features

The Λ-shaped building units in compounds (I)–(III) are arranged in head-to-tail chains via intermolecular hydrogen bonding with multiple hydrogen-bonding interactions and π–π stacking contacts to adjacent chains.

Each [Cu(phen)(H₂O)₃(TiF₆)] complex in compound (I) participates in hydrogen bonding with four other [Cu(phen)(H₂O)₃(TiF₆)] complexes and three free water molecules (Fig. 6, Table 1). The complexes pack with both face-to-face and displaced π–π stacking interactions (Table 5).

Table 5
π–π stacking interactions in compounds (I)–(IV)

Compound number	type	d_{phenyl–pyridine}	d_{pyridine–pyridine}	d_{phenyl–phenyl}	interplanar angle
(I)	face-to-face	3.699	4.162	3.583	0
(I)	displaced	6.042	4.128	8.111	8.68
(II)/(III)	parallel displaced	4.469	3.407	6.324	0
(II)/(III)	parallel displaced	3.510	4.472	4.035	0
(IV)	face-to-face	3.664	3.48	4.07	0
(IV)	parallel displaced	3.508	3.881	4.604	0

Figure 6
Packing diagrams of compound (I)

, [Cu(phen)(H₂O)₃(TiF₆)]·H₂O. Yellow polyhedra represent Cu(phen)(H₂O)₃²⁺ cations and purple polyhedra represent TiF₆²⁻ anions.

The [Cu(phen)(H₂O)₃(MF₆)] (M = Zr, Hf) units in compound (II) and compound (III) are involved in five hydrogen-bonding contacts to adjacent [Cu(phen)(H₂O)₃(MF₆)] complexes and three contacts to hydrating water molecules (Fig. 7, Table 2, and Table 3). The [Cu(phen)(H₂O)₃(MF₆)] complexes participate in parallel displaced π–π stacking interactions (Table 5).

Table 3
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F5ⁱ	0.80 (3)	1.94 (3)	2.7359 (13)	172 (3)
O1—H1B⋯F4ⁱⁱ	0.77 (3)	1.95 (3)	2.7135 (13)	176 (3)
O2—H2A⋯F6	0.86 (3)	1.85 (3)	2.6456 (14)	154 (3)
O2—H2B⋯F3ⁱ	0.77 (3)	1.87 (3)	2.6362 (14)	171 (3)
O3—H3A⋯O4ⁱⁱⁱ	0.81 (3)	1.85 (3)	2.6529 (17)	173 (3)
O3—H3B⋯F2^iv	0.77 (3)	1.86 (3)	2.6330 (15)	176 (3)
O4—H4A⋯F5^v	0.81 (3)	2.00 (3)	2.7429 (15)	154 (3)
O4—H4B⋯F3	0.81 (3)	2.01 (3)	2.7702 (14)	156 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 7
Packing diagrams of compound (II)

, [Cu(phen)(H₂O)₃(ZrF₆)]·H₂O, and compound (III)

, [Cu(phen)(H₂O)₃(HfF₆)]·H₂O. Yellow polyhedra represent Cu(phen)(H₂O)₃²⁺ cations and green polyhedra represent ZrF₆²⁻ or HfF₆²⁻ anions.

In compound (IV), each fluoride ligand forms two hydrogen bonds with the water ligands of adjacent Cu(phen)(H₂O)₂F⁺ complexes (Fig. 8). The equatorial water ligands form O1—H1A⋯F1 hydrogen bonds with adjacent Cu(phen)(H₂O)₂F⁺ complexes and O1—H1B⋯F4 hydrogen bonds with HfF₆²⁻ groups (Table 4). The apical water molecule forms an O2—H2B⋯F1 hydrogen bond to an adjacent Cu(phen)(H₂O)₂F⁺ complex and a O2—H2A⋯O3 hydrogen bond with a free water molecule (Table 4). Each MF₆²⁻ group forms hydrogen bonds with four free water molecules and two Cu(phen)(H₂O)₂F⁺ complexes. The Cu(phen)(H₂O)₂F⁺ complexes pack with both face-to-face and parallel displaced π–π stacking interactions (Table 5).

Table 4
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F4	0.81 (3)	1.78 (3)	2.5926 (14)	176 (3)
O1—H1B⋯F1ⁱ	0.74 (3)	1.85 (3)	2.5861 (13)	172 (3)
O2—H2A⋯O3	0.74 (3)	1.95 (3)	2.6906 (15)	176 (3)
O2—H2B⋯F1ⁱⁱ	0.80 (3)	1.83 (3)	2.6255 (13)	175 (2)
O3—H3A⋯F2	0.78 (3)	1.94 (3)	2.7270 (17)	176 (3)
O3—H3B⋯F3ⁱⁱⁱ	0.75 (3)	1.96 (3)	2.7020 (15)	173 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) .

Figure 8
Packing diagrams of compound (IV)

, [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O. Yellow polyhedra represent Cu(phen)(H₂O)₂F⁺ cations and green polyhedra represent HfF₆²⁻ anions.

4. Database survey

Aside from compounds (I), (II), and (III), the compound [Cu(H₂O)₅(VO(H₂O)F₄)]·H₂O (Donakowski et al., 2012) is the only example of a molecular inorganic Λ-shape known to the authors. [Cu(H₂O)₅(VOF₄(H₂O))]·H₂O contains a molecular Λ-shaped [Cu(H₂O)₅(VOF₄(H₂O))] molecule that is bridged via the Cu1—O8—V1 linkage with a bond angle of 142.88°. The Λ-shape of this complex is supported by a single intramolecular hydrogen bond as well as two hydrogen-bonding interactions with a free water molecule that serves as an intermolecular `bridging molecule'. In contrast, the hydrating water molecules in compounds (I), (II), and (III) bridge between adjacent complexes rather than the same complex. The smallest O8—Cu—O bond angle in [Cu(H₂O)₅(VOF₄(H₂O))]·H₂O is 88.42°, meaning that the complex has a small tilt similar to compound (I).

The Λ-shapes in [Cu(H₂O)₅(VO(H₂O)F₄)]·H₂O are arranged in a polar NCS lattice containing head-to-head/tail-to-tail chains in which the polar moments of the Λ-shaped complexes are partially aligned perpendicular to the chain direction, with head-to-tail orientations between chains. In contrast, the Λ-shapes found in compounds (I), (II), and (III) are arranged in non-polar head-to-tail chains in which the polar moments of the Λ-shaped complexes are arranged in an antiparallel fashion within the chain, with a head-to-tail arrangement between chains.

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 of distilled water as backfill. The autoclave was heated at a rate of 5 K min⁻¹ to 423 K and held at 423 K for 24 h. The autoclaves were allowed to cool to room temperature at a rate of 6 K h⁻¹. Solid products were recovered by vacuum filtration. Compound (I) was synthesized in a pouch containing 1.69 mmol of CuO, 1.69 mmol of TiO₂, 2.56 mmol of 1,10-phenanthroline, 1.0 mL (27.6 mmol) of HF(aq) (48%), and 0.1 mL (5.5 mmol) of deionized H₂O. Compound (II) was synthesized in a pouch containing 1.69 mmol of CuO, 1.69 mmol of ZrO₂, 2.56 mmol of phen, 1.0 mL (27.6 mmol) of HF(aq) (48%), and 0.1 mL (5.5 mmol) of deionized H₂O. Compound (III) was synthesized in a pouch containing 1.69 mmol of CuO, 1.69 mmol of HfO₂, 2.56 mmol of phen, 1.0 mL (27.6 mmol) of HF(aq) (48%), and 0.1 mL (5.5 mmol) of deionized H₂O. Compound (IV) was synthesized in a pouch containing 1.69 mmol of CuO, 1.69 mmol of HfO₂, 2.56 mmol of phen, 0.4 mL (11.03 mmol) of HF(aq) (48%), and 0.7 mL (38.85 mmol) of deionized H₂O.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. Non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen-atom positions were assigned from difference map peaks with the exception of C—H hydrogen atoms of 1,10-phenanthroline, which were constrained to ride at distances of 0.95 Å from the associated C atoms with U_iso(H) = 1.2U_eq(C) within OLEX2 (Dolomanov et al., 2009).

Table 6
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	[CuTiF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	[CuZrF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	[CuHfF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	[CuF(C₁₂H₈N₂)(H₂O)₂]₂[HfF₆]·2H₂O
M_r	477.71	521.03	608.30	926.07
Crystal system, space group	Orthorhombic, Pbca	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	100	100	101	100
a, b, c (Å)	13.3603 (3), 14.1385 (3), 17.7895 (4)	9.9486 (4), 17.3006 (7), 10.0022 (4)	9.9411 (3), 17.2733 (4), 9.9972 (2)	13.6451 (2), 7.1161 (1), 15.7457 (3)
α, β, γ (°)	90, 90, 90	90, 95.1335 (18), 90	90, 95.116 (1), 90	90, 99.691 (1), 90
V (Å³)	3360.34 (13)	1714.64 (12)	1709.84 (7)	1507.09 (4)
Z	8	4	4	2
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	1.83	1.93	7.39	4.93
Crystal size (mm)	0.09 × 0.07 × 0.05	0.24 × 0.12 × 0.11	0.17 × 0.12 × 0.05	0.16 × 0.16 × 0.10

Data collection
Diffractometer	Bruker Kappa APEX CCD area detector	Bruker Kappa APEX CCD area detector	Bruker Kappa APEX CCD area detector	Bruker Kappa APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Multi-scan (SADABS; Bruker, 2016)	Multi-scan (SADABS; Bruker, 2016)	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.668, 0.746	0.683, 0.747	0.480, 0.747	0.489, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	36860, 4534, 3928	87607, 7546, 7052	43322, 8248, 7980	123138, 5034, 4982
R_int	0.043	0.031	0.026	0.033
(sin θ/λ)_max (Å⁻¹)	0.686	0.807	0.835	0.737

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.071, 1.10	0.018, 0.047, 1.04	0.015, 0.036, 1.13	0.014, 0.035, 1.15
No. of reflections	4534	7546	8248	5034
No. of parameters	267	267	267	230
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.45	0.57, −0.67	1.03, −0.98	0.67, −0.70
Computer programs: APEX2 and SAINT (Bruker, 2017 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2045776; 2045775; 2045774; 2045773

Crystal structure: contains datablocks I, II, III, IV, I, II, III, IV. DOI: https://doi.org/10.1107/S2056989021000645/tx2034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021000645/tx2034Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021000645/tx2034IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989021000645/tx2034IIIsup4.hkl

Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989021000645/tx2034IVsup5.hkl

checkCIF report

Computing details top

For all structures, data collection: APEX2(Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); 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).

Triaqua-2κ³O-µ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N')copper(II)titanium(IV) monohydrate (I) top

Crystal data top

[CuTiF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	D_x = 1.889 Mg m⁻³
M_r = 477.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9952 reflections
a = 13.3603 (3) Å	θ = 2.8–29.1°
b = 14.1385 (3) Å	µ = 1.83 mm⁻¹
c = 17.7895 (4) Å	T = 100 K
V = 3360.34 (13) Å³	Block, blue
Z = 8	0.09 × 0.07 × 0.05 mm
F(000) = 1912

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	4534 independent reflections
Radiation source: sealed tube	3928 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.043
Detector resolution: 8 pixels mm^-1	θ_max = 29.2°, θ_min = 2.3°
ω and φ scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −19→19
T_min = 0.668, T_max = 0.746	l = −23→24
36860 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.0163P)² + 6.5495P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
4534 reflections	Δρ_max = 0.46 e Å⁻³
267 parameters	Δρ_min = −0.45 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	0.56746 (2)	0.74025 (2)	0.36021 (2)	0.01008 (7)
Ti1	0.53873 (3)	0.60258 (3)	0.17156 (2)	0.00930 (8)
F1	0.53330 (10)	0.61607 (9)	0.27499 (7)	0.0133 (2)
F2	0.41521 (9)	0.54030 (9)	0.17056 (7)	0.0160 (3)
F3	0.59857 (10)	0.48206 (9)	0.18751 (7)	0.0146 (3)
F4	0.54844 (10)	0.58432 (9)	0.06857 (7)	0.0170 (3)
F5	0.66406 (10)	0.65896 (10)	0.17257 (8)	0.0194 (3)
F6	0.47531 (11)	0.71718 (9)	0.16027 (7)	0.0180 (3)
O1	0.58746 (13)	0.88113 (12)	0.42069 (10)	0.0153 (3)
H1A	0.586 (3)	0.923 (3)	0.400 (2)	0.036 (11)*
H1B	0.578 (2)	0.894 (2)	0.462 (2)	0.033 (9)*
O2	0.68191 (13)	0.76878 (12)	0.29363 (9)	0.0163 (3)
H2A	0.702 (2)	0.824 (2)	0.2876 (17)	0.025 (8)*
H2B	0.679 (3)	0.742 (2)	0.252 (2)	0.042 (10)*
O3	0.46639 (13)	0.80398 (12)	0.29423 (9)	0.0160 (3)
H3A	0.451 (3)	0.861 (3)	0.297 (2)	0.042 (10)*
H3B	0.468 (3)	0.787 (2)	0.246 (2)	0.040 (10)*
N1	0.46103 (13)	0.69042 (12)	0.42847 (10)	0.0105 (3)
N2	0.65702 (13)	0.66919 (12)	0.43147 (10)	0.0109 (3)
C1	0.36234 (16)	0.69370 (15)	0.42054 (12)	0.0129 (4)
H1	0.334951	0.722036	0.376706	0.015*
C2	0.29739 (16)	0.65669 (15)	0.47477 (13)	0.0149 (4)
H2	0.227049	0.659406	0.467260	0.018*
C3	0.33568 (17)	0.61635 (15)	0.53897 (13)	0.0150 (4)
H3	0.292095	0.593534	0.577071	0.018*
C4	0.44001 (17)	0.60926 (15)	0.54763 (12)	0.0136 (4)
C5	0.49937 (16)	0.64734 (14)	0.48989 (12)	0.0105 (4)
C6	0.48834 (18)	0.56371 (16)	0.60994 (13)	0.0166 (4)
H6	0.449007	0.539269	0.649962	0.020*
C7	0.58924 (18)	0.55511 (15)	0.61248 (12)	0.0166 (4)
H7	0.619530	0.524951	0.654432	0.020*
C8	0.65119 (17)	0.59062 (15)	0.55310 (12)	0.0146 (4)
C9	0.60562 (16)	0.63669 (14)	0.49233 (12)	0.0109 (4)
C10	0.75608 (18)	0.57771 (16)	0.54860 (13)	0.0176 (4)
H10	0.791122	0.547634	0.588454	0.021*
C11	0.80665 (17)	0.60883 (16)	0.48648 (14)	0.0179 (4)
H11	0.876860	0.599295	0.482704	0.022*
C12	0.75501 (16)	0.65480 (15)	0.42832 (13)	0.0145 (4)
H12	0.791179	0.676164	0.385595	0.017*
O4	0.74837 (14)	0.94525 (12)	0.28380 (11)	0.0194 (3)
H4A	0.782 (3)	0.961 (2)	0.253 (2)	0.036 (10)*
H4B	0.708 (2)	0.984 (2)	0.2893 (17)	0.026 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01007 (12)	0.01075 (12)	0.00941 (12)	0.00031 (9)	0.00038 (9)	0.00084 (9)
Ti1	0.00972 (17)	0.00994 (16)	0.00822 (16)	−0.00046 (13)	0.00042 (13)	−0.00037 (13)
F1	0.0171 (6)	0.0134 (6)	0.0092 (6)	−0.0008 (5)	0.0015 (5)	−0.0002 (4)
F2	0.0106 (6)	0.0187 (6)	0.0188 (7)	−0.0023 (5)	0.0008 (5)	−0.0042 (5)
F3	0.0143 (6)	0.0134 (6)	0.0161 (6)	0.0024 (5)	−0.0012 (5)	−0.0010 (5)
F4	0.0198 (7)	0.0222 (7)	0.0088 (6)	0.0007 (5)	0.0013 (5)	−0.0017 (5)
F5	0.0159 (6)	0.0246 (7)	0.0176 (7)	−0.0090 (5)	0.0053 (5)	−0.0060 (5)
F6	0.0273 (7)	0.0125 (6)	0.0143 (6)	0.0049 (5)	−0.0031 (5)	0.0002 (5)
O1	0.0225 (9)	0.0130 (8)	0.0103 (8)	0.0006 (6)	0.0004 (6)	−0.0001 (6)
O2	0.0184 (8)	0.0168 (8)	0.0137 (8)	−0.0046 (6)	0.0044 (6)	−0.0022 (6)
O3	0.0212 (8)	0.0135 (8)	0.0132 (8)	0.0053 (6)	−0.0026 (6)	−0.0013 (6)
N1	0.0105 (8)	0.0103 (8)	0.0105 (8)	−0.0002 (6)	0.0007 (6)	−0.0008 (6)
N2	0.0097 (8)	0.0105 (8)	0.0126 (8)	0.0014 (6)	−0.0002 (6)	−0.0018 (6)
C1	0.0115 (10)	0.0145 (9)	0.0127 (10)	0.0011 (8)	−0.0016 (8)	−0.0021 (8)
C2	0.0106 (10)	0.0143 (10)	0.0198 (11)	−0.0003 (8)	0.0008 (8)	−0.0024 (8)
C3	0.0159 (10)	0.0143 (10)	0.0149 (10)	−0.0025 (8)	0.0051 (8)	−0.0035 (8)
C4	0.0169 (10)	0.0112 (9)	0.0126 (10)	−0.0005 (8)	0.0010 (8)	−0.0026 (7)
C5	0.0116 (9)	0.0095 (9)	0.0103 (9)	0.0001 (7)	−0.0004 (7)	−0.0018 (7)
C6	0.0244 (12)	0.0137 (10)	0.0116 (10)	−0.0007 (8)	0.0020 (9)	0.0006 (8)
C7	0.0250 (12)	0.0131 (10)	0.0116 (10)	0.0015 (8)	−0.0053 (9)	0.0015 (8)
C8	0.0179 (11)	0.0120 (9)	0.0138 (10)	0.0020 (8)	−0.0054 (8)	−0.0023 (8)
C9	0.0126 (10)	0.0088 (9)	0.0111 (9)	0.0010 (7)	−0.0007 (8)	−0.0018 (7)
C10	0.0178 (11)	0.0153 (10)	0.0196 (11)	0.0037 (8)	−0.0091 (9)	−0.0029 (8)
C11	0.0119 (10)	0.0175 (10)	0.0245 (12)	0.0042 (8)	−0.0043 (9)	−0.0032 (9)
C12	0.0121 (10)	0.0133 (9)	0.0180 (10)	−0.0001 (8)	−0.0003 (8)	−0.0046 (8)
O4	0.0165 (8)	0.0163 (8)	0.0255 (9)	0.0008 (7)	0.0078 (7)	0.0021 (7)

Geometric parameters (Å, º) top

Cu1—F1	2.3643 (12)	C1—H1	0.9500
Cu1—O1	2.2794 (17)	C1—C2	1.399 (3)
Cu1—O2	1.9758 (16)	C2—H2	0.9500
Cu1—O3	2.0032 (16)	C2—C3	1.375 (3)
Cu1—N1	1.9981 (18)	C3—H3	0.9500
Cu1—N2	2.0120 (18)	C3—C4	1.406 (3)
Ti1—F1	1.8511 (13)	C4—C5	1.405 (3)
Ti1—F2	1.8706 (13)	C4—C6	1.435 (3)
Ti1—F3	1.9035 (13)	C5—C9	1.428 (3)
Ti1—F4	1.8548 (13)	C6—H6	0.9500
Ti1—F5	1.8545 (13)	C6—C7	1.354 (3)
Ti1—F6	1.8395 (13)	C7—H7	0.9500
O1—H1A	0.70 (4)	C7—C8	1.433 (3)
O1—H1B	0.77 (4)	C8—C9	1.401 (3)
O2—H2A	0.83 (3)	C8—C10	1.416 (3)
O2—H2B	0.83 (4)	C10—H10	0.9500
O3—H3A	0.84 (4)	C10—C11	1.368 (3)
O3—H3B	0.90 (4)	C11—H11	0.9500
N1—C1	1.327 (3)	C11—C12	1.403 (3)
N1—C5	1.352 (3)	C12—H12	0.9500
N2—C9	1.362 (3)	O4—H4A	0.75 (4)
N2—C12	1.326 (3)	O4—H4B	0.77 (3)

O1—Cu1—F1	166.96 (6)	C5—N1—Cu1	112.35 (14)
O2—Cu1—F1	85.21 (6)	C9—N2—Cu1	111.68 (14)
O2—Cu1—O1	90.79 (7)	C12—N2—Cu1	129.58 (15)
O2—Cu1—O3	94.51 (7)	C12—N2—C9	118.66 (19)
O2—Cu1—N1	170.75 (7)	N1—C1—H1	119.0
O2—Cu1—N2	91.11 (7)	N1—C1—C2	122.0 (2)
O3—Cu1—F1	80.11 (6)	C2—C1—H1	119.0
O3—Cu1—O1	87.85 (7)	C1—C2—H2	120.1
O3—Cu1—N2	174.07 (7)	C3—C2—C1	119.8 (2)
N1—Cu1—F1	89.45 (6)	C3—C2—H2	120.1
N1—Cu1—O1	96.01 (7)	C2—C3—H3	120.4
N1—Cu1—O3	92.01 (7)	C2—C3—C4	119.3 (2)
N1—Cu1—N2	82.20 (7)	C4—C3—H3	120.4
N2—Cu1—F1	98.51 (6)	C3—C4—C6	124.2 (2)
N2—Cu1—O1	93.97 (7)	C5—C4—C3	116.9 (2)
F1—Ti1—F2	91.34 (6)	C5—C4—C6	118.8 (2)
F1—Ti1—F3	87.74 (6)	N1—C5—C4	123.3 (2)
F1—Ti1—F4	177.26 (6)	N1—C5—C9	116.67 (19)
F1—Ti1—F5	88.94 (6)	C4—C5—C9	119.90 (19)
F2—Ti1—F3	87.17 (6)	C4—C6—H6	119.5
F4—Ti1—F2	89.24 (6)	C7—C6—C4	120.9 (2)
F4—Ti1—F3	89.61 (6)	C7—C6—H6	119.5
F5—Ti1—F2	177.38 (6)	C6—C7—H7	119.4
F5—Ti1—F3	90.24 (6)	C6—C7—C8	121.3 (2)
F5—Ti1—F4	90.36 (6)	C8—C7—H7	119.4
F6—Ti1—F1	89.99 (6)	C9—C8—C7	118.7 (2)
F6—Ti1—F2	90.41 (6)	C9—C8—C10	116.5 (2)
F6—Ti1—F3	176.64 (6)	C10—C8—C7	124.6 (2)
F6—Ti1—F4	92.69 (6)	N2—C9—C5	116.19 (18)
F6—Ti1—F5	92.20 (7)	N2—C9—C8	123.4 (2)
Ti1—F1—Cu1	134.93 (6)	C8—C9—C5	120.3 (2)
Cu1—O1—H1A	119 (3)	C8—C10—H10	120.2
Cu1—O1—H1B	130 (2)	C11—C10—C8	119.5 (2)
H1A—O1—H1B	107 (4)	C11—C10—H10	120.2
Cu1—O2—H2A	122 (2)	C10—C11—H11	119.9
Cu1—O2—H2B	113 (2)	C10—C11—C12	120.1 (2)
H2A—O2—H2B	109 (3)	C12—C11—H11	119.9
Cu1—O3—H3A	125 (2)	N2—C12—C11	121.7 (2)
Cu1—O3—H3B	115 (2)	N2—C12—H12	119.2
H3A—O3—H3B	109 (3)	C11—C12—H12	119.2
C1—N1—Cu1	129.07 (15)	H4A—O4—H4B	107 (3)
C1—N1—C5	118.57 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F2ⁱ	0.70 (4)	2.08 (4)	2.775 (2)	175 (4)
O1—H1B···F4ⁱⁱ	0.77 (4)	1.96 (4)	2.726 (2)	174 (3)
O2—H2A···O4	0.83 (3)	1.83 (3)	2.654 (2)	175 (3)
O2—H2B···F5	0.83 (4)	1.85 (4)	2.666 (2)	167 (3)
O3—H3A···F3ⁱ	0.84 (4)	1.85 (4)	2.683 (2)	171 (4)
O3—H3B···F6	0.90 (4)	1.81 (4)	2.683 (2)	163 (3)
O4—H4A···F3ⁱⁱⁱ	0.75 (4)	2.00 (4)	2.718 (2)	163 (4)
O4—H4B···F2ⁱ	0.77 (3)	1.96 (3)	2.691 (2)	156 (3)

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

Triaqua-2κ³O-µ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N')copper(II)zirconium(IV) monohydrate (II) top

Crystal data top

[CuZrF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	F(000) = 1028
M_r = 521.03	D_x = 2.018 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.9486 (4) Å	Cell parameters from 9425 reflections
b = 17.3006 (7) Å	θ = 3.0–34.9°
c = 10.0022 (4) Å	µ = 1.93 mm⁻¹
β = 95.1335 (18)°	T = 100 K
V = 1714.64 (12) Å³	Cuboid, blue
Z = 4	0.24 × 0.12 × 0.11 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	7546 independent reflections
Radiation source: sealed tube	7052 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.031
Detector resolution: 8 pixels mm^-1	θ_max = 35.0°, θ_min = 2.4°
ω and φ scans	h = −15→16
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −27→27
T_min = 0.683, T_max = 0.747	l = −16→16
87607 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.0222P)² + 0.6601P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
7546 reflections	Δρ_max = 0.57 e Å⁻³
267 parameters	Δρ_min = −0.67 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
Zr1	0.47531 (2)	0.17833 (2)	0.18511 (2)	0.00928 (2)
Cu1	0.23490 (2)	0.36879 (2)	0.23859 (2)	0.01147 (3)
F1	0.40575 (7)	0.28382 (3)	0.13913 (6)	0.01738 (11)
F2	0.55807 (7)	0.20897 (4)	0.36687 (6)	0.02055 (12)
F3	0.65583 (6)	0.20677 (4)	0.11564 (6)	0.01671 (11)
F4	0.53575 (7)	0.06931 (3)	0.22042 (7)	0.01918 (11)
F5	0.41618 (6)	0.14484 (4)	−0.00414 (6)	0.01543 (10)
F6	0.29772 (6)	0.15382 (4)	0.25277 (6)	0.01807 (11)
O1	0.09615 (8)	0.43805 (4)	0.36235 (8)	0.01672 (13)
H1A	0.0425 (17)	0.4171 (10)	0.4041 (17)	0.028 (4)*
H1B	0.0583 (19)	0.4762 (12)	0.3397 (19)	0.039 (5)*
O2	0.22635 (9)	0.28333 (4)	0.36875 (8)	0.02195 (15)
H2A	0.198 (2)	0.2842 (11)	0.440 (2)	0.043 (5)*
H2B	0.2341 (19)	0.2387 (11)	0.3444 (19)	0.039 (5)*
O3	0.08658 (9)	0.32098 (6)	0.12593 (9)	0.02716 (19)
H3A	0.0786 (18)	0.3133 (10)	0.048 (2)	0.034 (5)*
H3B	0.019 (2)	0.3082 (11)	0.155 (2)	0.040 (5)*
N1	0.40931 (8)	0.40912 (4)	0.32659 (8)	0.01241 (12)
N2	0.25539 (8)	0.45780 (4)	0.11410 (7)	0.01176 (12)
C1	0.48666 (10)	0.38078 (6)	0.42972 (10)	0.01668 (16)
H1	0.456184	0.336879	0.475402	0.020*
C2	0.61195 (11)	0.41331 (6)	0.47385 (10)	0.02059 (19)
H2	0.665231	0.391295	0.547766	0.025*
C3	0.65728 (10)	0.47718 (7)	0.40963 (11)	0.02061 (19)
H3	0.742169	0.499549	0.438437	0.025*
C4	0.57629 (9)	0.50917 (6)	0.30041 (10)	0.01582 (16)
C5	0.45370 (9)	0.47190 (5)	0.26198 (9)	0.01215 (14)
C6	0.61134 (10)	0.57674 (6)	0.22755 (11)	0.02057 (18)
H6	0.693485	0.602912	0.253555	0.025*
C7	0.52933 (11)	0.60382 (6)	0.12238 (11)	0.01943 (18)
H7	0.554529	0.648907	0.076505	0.023*
C8	0.40516 (10)	0.56548 (5)	0.07928 (9)	0.01432 (15)
C9	0.36882 (9)	0.49938 (5)	0.14917 (9)	0.01139 (13)
C10	0.31652 (11)	0.58914 (6)	−0.03080 (10)	0.01766 (17)
H10	0.336075	0.633809	−0.080793	0.021*
C11	0.20132 (11)	0.54697 (6)	−0.06530 (10)	0.01771 (16)
H11	0.140492	0.562526	−0.139020	0.021*
C12	0.17425 (9)	0.48094 (6)	0.00892 (9)	0.01485 (15)
H12	0.095257	0.451756	−0.016796	0.018*
O4	0.86608 (9)	0.29013 (6)	0.24604 (9)	0.02461 (17)
H4A	0.8042 (19)	0.2617 (10)	0.2257 (18)	0.031 (4)*
H4B	0.864 (2)	0.2988 (12)	0.322 (2)	0.042 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.01037 (4)	0.00955 (4)	0.00795 (4)	−0.00034 (2)	0.00102 (3)	−0.00012 (2)
Cu1	0.01226 (5)	0.01299 (5)	0.00913 (5)	−0.00278 (3)	0.00070 (4)	0.00011 (3)
F1	0.0245 (3)	0.0125 (2)	0.0153 (2)	0.0038 (2)	0.0034 (2)	0.00169 (19)
F2	0.0276 (3)	0.0226 (3)	0.0105 (2)	−0.0005 (2)	−0.0032 (2)	−0.0021 (2)
F3	0.0134 (2)	0.0231 (3)	0.0138 (2)	−0.0050 (2)	0.0024 (2)	−0.0008 (2)
F4	0.0211 (3)	0.0117 (2)	0.0239 (3)	0.0020 (2)	−0.0028 (2)	0.0013 (2)
F5	0.0146 (2)	0.0202 (3)	0.0111 (2)	0.0012 (2)	−0.00087 (19)	−0.00385 (19)
F6	0.0169 (3)	0.0176 (3)	0.0209 (3)	−0.0025 (2)	0.0084 (2)	−0.0003 (2)
O1	0.0169 (3)	0.0148 (3)	0.0194 (3)	0.0016 (2)	0.0069 (3)	0.0026 (2)
O2	0.0385 (5)	0.0138 (3)	0.0155 (3)	0.0005 (3)	0.0134 (3)	0.0004 (2)
O3	0.0223 (4)	0.0459 (5)	0.0138 (3)	−0.0194 (4)	0.0047 (3)	−0.0101 (3)
N1	0.0129 (3)	0.0130 (3)	0.0111 (3)	0.0020 (2)	−0.0005 (2)	−0.0016 (2)
N2	0.0099 (3)	0.0147 (3)	0.0107 (3)	−0.0003 (2)	0.0012 (2)	0.0001 (2)
C1	0.0184 (4)	0.0180 (4)	0.0130 (4)	0.0059 (3)	−0.0024 (3)	−0.0022 (3)
C2	0.0165 (4)	0.0273 (5)	0.0167 (4)	0.0079 (4)	−0.0055 (3)	−0.0057 (4)
C3	0.0118 (4)	0.0282 (5)	0.0209 (4)	0.0019 (3)	−0.0030 (3)	−0.0099 (4)
C4	0.0110 (4)	0.0187 (4)	0.0177 (4)	−0.0007 (3)	0.0011 (3)	−0.0068 (3)
C5	0.0104 (3)	0.0136 (3)	0.0124 (3)	0.0002 (3)	0.0006 (3)	−0.0034 (3)
C6	0.0149 (4)	0.0201 (4)	0.0273 (5)	−0.0064 (3)	0.0053 (4)	−0.0079 (4)
C7	0.0193 (4)	0.0153 (4)	0.0248 (5)	−0.0050 (3)	0.0083 (4)	−0.0034 (3)
C8	0.0161 (4)	0.0118 (3)	0.0157 (4)	−0.0007 (3)	0.0054 (3)	−0.0014 (3)
C9	0.0103 (3)	0.0125 (3)	0.0116 (3)	0.0002 (2)	0.0023 (3)	−0.0013 (3)
C10	0.0238 (5)	0.0140 (4)	0.0159 (4)	0.0026 (3)	0.0058 (3)	0.0021 (3)
C11	0.0208 (4)	0.0189 (4)	0.0133 (4)	0.0051 (3)	0.0007 (3)	0.0030 (3)
C12	0.0129 (4)	0.0188 (4)	0.0125 (3)	0.0017 (3)	−0.0005 (3)	0.0011 (3)
O4	0.0210 (4)	0.0353 (4)	0.0176 (3)	−0.0141 (3)	0.0026 (3)	−0.0055 (3)

Geometric parameters (Å, º) top

Zr1—F1	1.9910 (6)	C1—H1	0.9500
Zr1—F2	1.9991 (6)	C1—C2	1.4023 (15)
Zr1—F3	2.0430 (6)	C2—H2	0.9500
Zr1—F4	2.0014 (6)	C2—C3	1.3744 (17)
Zr1—F5	2.0163 (6)	C3—H3	0.9500
Zr1—F6	1.9933 (6)	C3—C4	1.4111 (15)
Cu1—F1	2.5184 (6)	C4—C5	1.4025 (13)
Cu1—O1	2.2758 (7)	C4—C6	1.4369 (15)
Cu1—O2	1.9768 (8)	C5—C9	1.4288 (13)
Cu1—O3	1.9580 (8)	C6—H6	0.9500
Cu1—N1	1.9997 (8)	C6—C7	1.3558 (17)
Cu1—N2	2.0021 (8)	C7—H7	0.9500
O1—H1A	0.794 (18)	C7—C8	1.4341 (14)
O1—H1B	0.78 (2)	C8—C9	1.4044 (12)
O2—H2A	0.79 (2)	C8—C10	1.4085 (14)
O2—H2B	0.82 (2)	C10—H10	0.9500
O3—H3A	0.79 (2)	C10—C11	1.3762 (15)
O3—H3B	0.79 (2)	C11—H11	0.9500
N1—C1	1.3245 (12)	C11—C12	1.4015 (13)
N1—C5	1.3577 (12)	C12—H12	0.9500
N2—C9	1.3577 (11)	O4—H4A	0.799 (19)
N2—C12	1.3292 (12)	O4—H4B	0.78 (2)

F1—Zr1—F2	94.21 (3)	C5—N1—Cu1	112.08 (6)
F1—Zr1—F3	89.92 (3)	C9—N2—Cu1	112.05 (6)
F1—Zr1—F4	175.79 (3)	C12—N2—Cu1	129.46 (6)
F1—Zr1—F5	88.87 (3)	C12—N2—C9	118.47 (8)
F1—Zr1—F6	88.46 (3)	N1—C1—H1	118.8
F2—Zr1—F3	86.70 (3)	N1—C1—C2	122.32 (10)
F2—Zr1—F4	89.81 (3)	C2—C1—H1	118.8
F2—Zr1—F5	172.66 (3)	C1—C2—H2	120.2
F4—Zr1—F3	91.58 (3)	C3—C2—C1	119.67 (9)
F4—Zr1—F5	87.29 (3)	C3—C2—H2	120.2
F5—Zr1—F3	86.64 (2)	C2—C3—H3	120.4
F6—Zr1—F2	93.04 (3)	C2—C3—C4	119.25 (9)
F6—Zr1—F3	178.34 (3)	C4—C3—H3	120.4
F6—Zr1—F4	90.06 (3)	C3—C4—C6	124.33 (9)
F6—Zr1—F5	93.71 (3)	C5—C4—C3	117.02 (9)
O1—Cu1—F1	170.35 (2)	C5—C4—C6	118.65 (9)
O2—Cu1—F1	83.91 (3)	N1—C5—C4	123.31 (9)
O2—Cu1—O1	88.37 (3)	N1—C5—C9	116.59 (8)
O2—Cu1—N1	93.32 (4)	C4—C5—C9	120.10 (8)
O2—Cu1—N2	176.00 (4)	C4—C6—H6	119.4
O3—Cu1—F1	91.52 (3)	C7—C6—C4	121.21 (9)
O3—Cu1—O1	94.18 (3)	C7—C6—H6	119.4
O3—Cu1—O2	89.34 (4)	C6—C7—H7	119.5
O3—Cu1—N1	168.59 (3)	C6—C7—C8	121.05 (9)
O3—Cu1—N2	94.61 (4)	C8—C7—H7	119.5
N1—Cu1—F1	77.75 (3)	C9—C8—C7	118.70 (9)
N1—Cu1—O1	96.98 (3)	C9—C8—C10	117.05 (9)
N1—Cu1—N2	82.69 (3)	C10—C8—C7	124.25 (9)
N2—Cu1—F1	95.36 (3)	N2—C9—C5	116.52 (8)
N2—Cu1—O1	91.94 (3)	N2—C9—C8	123.22 (8)
Zr1—F1—Cu1	132.59 (3)	C8—C9—C5	120.25 (8)
Cu1—O1—H1A	121.0 (13)	C8—C10—H10	120.3
Cu1—O1—H1B	125.9 (14)	C11—C10—C8	119.41 (9)
H1A—O1—H1B	102.0 (18)	C11—C10—H10	120.3
Cu1—O2—H2A	128.2 (14)	C10—C11—H11	120.2
Cu1—O2—H2B	120.1 (13)	C10—C11—C12	119.63 (9)
H2A—O2—H2B	109.8 (19)	C12—C11—H11	120.2
Cu1—O3—H3A	130.1 (13)	N2—C12—C11	122.20 (9)
Cu1—O3—H3B	122.1 (15)	N2—C12—H12	118.9
H3A—O3—H3B	107.6 (19)	C11—C12—H12	118.9
C1—N1—Cu1	129.37 (7)	H4A—O4—H4B	106.4 (19)
C1—N1—C5	118.41 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F5ⁱ	0.794 (18)	1.944 (18)	2.7338 (9)	173.5 (18)
O1—H1B···F4ⁱⁱ	0.78 (2)	1.93 (2)	2.7147 (10)	179 (2)
O2—H2A···F3ⁱ	0.79 (2)	1.85 (2)	2.6324 (10)	171 (2)
O2—H2B···F6	0.82 (2)	1.87 (2)	2.6491 (10)	159.2 (19)
O3—H3A···F2ⁱⁱⁱ	0.79 (2)	1.85 (2)	2.6327 (10)	177.5 (19)
O3—H3B···O4^iv	0.79 (2)	1.87 (2)	2.6481 (12)	170 (2)
O4—H4A···F3	0.799 (19)	2.002 (19)	2.7691 (10)	160.9 (18)
O4—H4B···F5^v	0.78 (2)	2.02 (2)	2.7449 (11)	155 (2)

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

Triaqua-2κ³O-µ-fluorido-pentafluorido-1κ⁵F-(1,10-phenanthroline-2κ²N,N')copper(II)hafnium(IV) monohydrate (III) top

Crystal data top

[CuHfF₆(C₁₂H₈N₂)(H₂O)₃]·H₂O	F(000) = 1156
M_r = 608.30	D_x = 2.363 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.9411 (3) Å	Cell parameters from 9921 reflections
b = 17.2733 (4) Å	θ = 2.4–36.4°
c = 9.9972 (2) Å	µ = 7.39 mm⁻¹
β = 95.116 (1)°	T = 101 K
V = 1709.84 (7) Å³	Rodlike, blue
Z = 4	0.17 × 0.12 × 0.05 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	8248 independent reflections
Radiation source: sealed tube	7980 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.026
Detector resolution: 8 pixels mm^-1	θ_max = 36.4°, θ_min = 2.4°
ω and φ scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −28→28
T_min = 0.480, T_max = 0.747	l = −13→16
43322 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.015	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.036	w = 1/[σ²(F_o²) + (0.0108P)² + 0.940P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.005
8248 reflections	Δρ_max = 1.03 e Å⁻³
267 parameters	Δρ_min = −0.98 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
Hf1	0.52483 (2)	0.82180 (2)	0.31483 (2)	0.00816 (1)
Cu1	0.76520 (2)	0.63146 (2)	0.26150 (2)	0.01043 (2)
F1	0.59437 (9)	0.71639 (5)	0.36048 (9)	0.01579 (14)
F2	0.44315 (10)	0.79101 (5)	0.13341 (9)	0.01846 (15)
F3	0.34510 (8)	0.79333 (5)	0.38379 (9)	0.01545 (13)
F4	0.46393 (9)	0.93051 (5)	0.27960 (10)	0.01710 (15)
F5	0.58415 (8)	0.85522 (5)	0.50333 (8)	0.01413 (13)
F6	0.70198 (9)	0.84641 (5)	0.24732 (9)	0.01652 (14)
O1	0.90410 (10)	0.56191 (6)	0.13766 (11)	0.01534 (16)
H1A	0.952 (3)	0.5850 (18)	0.092 (3)	0.043 (8)*
H1B	0.944 (3)	0.5250 (18)	0.158 (3)	0.038 (8)*
O2	0.77370 (14)	0.71712 (6)	0.13085 (11)	0.0204 (2)
H2A	0.770 (3)	0.7646 (16)	0.155 (3)	0.039 (8)*
H2B	0.794 (3)	0.7190 (18)	0.058 (3)	0.041 (8)*
O3	0.91370 (13)	0.67963 (8)	0.37400 (13)	0.0258 (3)
H3A	0.982 (3)	0.6915 (16)	0.342 (3)	0.036 (8)*
H3B	0.923 (3)	0.6862 (16)	0.451 (3)	0.036 (8)*
N1	0.59097 (11)	0.59097 (6)	0.17348 (10)	0.01118 (15)
N2	0.74478 (10)	0.54241 (6)	0.38597 (10)	0.01065 (14)
C1	0.51346 (13)	0.61947 (7)	0.07036 (13)	0.01500 (19)
H1	0.543886	0.663510	0.024768	0.018*
C2	0.38773 (14)	0.58678 (9)	0.02611 (15)	0.0187 (2)
H2	0.334281	0.608849	−0.047718	0.022*
C3	0.34248 (13)	0.52246 (9)	0.09056 (15)	0.0185 (2)
H3	0.257713	0.499831	0.061741	0.022*
C4	0.42372 (12)	0.49081 (7)	0.19968 (14)	0.01433 (19)
C5	0.38832 (14)	0.42310 (8)	0.27286 (16)	0.0186 (2)
H5	0.305923	0.397016	0.247140	0.022*
C6	0.47075 (14)	0.39590 (8)	0.37801 (15)	0.0175 (2)
H6	0.445833	0.350595	0.423706	0.021*
C7	0.59489 (13)	0.43449 (7)	0.42121 (13)	0.01293 (18)
C8	0.63154 (11)	0.50068 (6)	0.35078 (12)	0.01037 (16)
C9	0.54650 (11)	0.52808 (7)	0.23831 (12)	0.01084 (16)
C10	0.68394 (14)	0.41075 (7)	0.53102 (14)	0.0160 (2)
H10	0.664685	0.365860	0.580801	0.019*
C11	0.79903 (14)	0.45307 (7)	0.56563 (14)	0.0159 (2)
H11	0.859827	0.437608	0.639508	0.019*
C12	0.82601 (12)	0.51916 (7)	0.49119 (13)	0.01334 (18)
H12	0.905102	0.548379	0.516812	0.016*
O4	0.13489 (12)	0.70967 (8)	0.25315 (12)	0.0224 (2)
H4A	0.143 (3)	0.6980 (16)	0.176 (3)	0.030 (7)*
H4B	0.200 (3)	0.7376 (18)	0.269 (3)	0.043 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hf1	0.00935 (2)	0.00804 (2)	0.00717 (2)	−0.00036 (1)	0.00110 (1)	−0.00014 (1)
Cu1	0.01135 (5)	0.01143 (5)	0.00851 (6)	−0.00251 (4)	0.00096 (4)	0.00007 (4)
F1	0.0220 (4)	0.0106 (3)	0.0152 (3)	0.0038 (3)	0.0040 (3)	0.0018 (2)
F2	0.0247 (4)	0.0205 (4)	0.0095 (3)	−0.0001 (3)	−0.0024 (3)	−0.0022 (3)
F3	0.0121 (3)	0.0211 (4)	0.0134 (3)	−0.0043 (3)	0.0027 (2)	−0.0008 (3)
F4	0.0185 (4)	0.0101 (3)	0.0220 (4)	0.0021 (2)	−0.0022 (3)	0.0012 (3)
F5	0.0138 (3)	0.0182 (3)	0.0101 (3)	0.0009 (2)	−0.0005 (2)	−0.0036 (2)
F6	0.0154 (3)	0.0159 (3)	0.0195 (4)	−0.0027 (3)	0.0086 (3)	−0.0005 (3)
O1	0.0153 (4)	0.0138 (4)	0.0177 (4)	0.0018 (3)	0.0062 (3)	0.0026 (3)
O2	0.0361 (6)	0.0122 (4)	0.0147 (4)	0.0008 (4)	0.0127 (4)	0.0002 (3)
O3	0.0208 (5)	0.0440 (7)	0.0132 (5)	−0.0190 (5)	0.0050 (4)	−0.0095 (4)
N1	0.0121 (4)	0.0118 (4)	0.0094 (4)	0.0016 (3)	−0.0002 (3)	−0.0011 (3)
N2	0.0094 (3)	0.0127 (4)	0.0098 (4)	−0.0003 (3)	0.0005 (3)	0.0000 (3)
C1	0.0168 (5)	0.0155 (5)	0.0120 (5)	0.0052 (4)	−0.0023 (4)	−0.0018 (3)
C2	0.0141 (5)	0.0248 (6)	0.0160 (5)	0.0063 (4)	−0.0045 (4)	−0.0049 (4)
C3	0.0112 (4)	0.0253 (6)	0.0183 (6)	0.0016 (4)	−0.0025 (4)	−0.0082 (4)
C4	0.0103 (4)	0.0164 (5)	0.0162 (5)	−0.0012 (3)	0.0009 (3)	−0.0056 (4)
C5	0.0137 (5)	0.0184 (5)	0.0242 (6)	−0.0060 (4)	0.0052 (4)	−0.0060 (4)
C6	0.0178 (5)	0.0138 (5)	0.0221 (6)	−0.0052 (4)	0.0073 (4)	−0.0030 (4)
C7	0.0152 (4)	0.0100 (4)	0.0143 (5)	−0.0003 (3)	0.0051 (4)	−0.0007 (3)
C8	0.0096 (4)	0.0105 (4)	0.0113 (4)	−0.0008 (3)	0.0025 (3)	−0.0011 (3)
C9	0.0090 (4)	0.0123 (4)	0.0111 (4)	0.0002 (3)	0.0007 (3)	−0.0026 (3)
C10	0.0212 (5)	0.0127 (4)	0.0148 (5)	0.0024 (4)	0.0053 (4)	0.0022 (4)
C11	0.0190 (5)	0.0158 (5)	0.0129 (5)	0.0038 (4)	0.0008 (4)	0.0032 (4)
C12	0.0121 (4)	0.0166 (5)	0.0110 (4)	0.0010 (3)	−0.0004 (3)	0.0012 (3)
O4	0.0190 (4)	0.0316 (6)	0.0167 (5)	−0.0120 (4)	0.0027 (3)	−0.0048 (4)

Geometric parameters (Å, º) top

Hf1—F1	1.9863 (8)	C1—H1	0.9500
Hf1—F2	1.9922 (9)	C1—C2	1.4065 (19)
Hf1—F3	2.0320 (8)	C2—H2	0.9500
Hf1—F4	1.9946 (8)	C2—C3	1.380 (2)
Hf1—F5	2.0085 (8)	C3—H3	0.9500
Hf1—F6	1.9873 (8)	C3—C4	1.409 (2)
Cu1—F1	2.5130 (9)	C4—C5	1.440 (2)
Cu1—O1	2.2776 (10)	C4—C9	1.4033 (16)
Cu1—O2	1.9804 (11)	C5—H5	0.9500
Cu1—O3	1.9597 (11)	C5—C6	1.358 (2)
Cu1—N1	1.9979 (11)	C6—H6	0.9500
Cu1—N2	2.0002 (10)	C6—C7	1.4348 (18)
O1—H1A	0.80 (3)	C7—C8	1.4076 (17)
O1—H1B	0.77 (3)	C7—C10	1.4085 (19)
O2—H2A	0.86 (3)	C8—C9	1.4259 (17)
O2—H2B	0.77 (3)	C10—H10	0.9500
O3—H3A	0.81 (3)	C10—C11	1.376 (2)
O3—H3B	0.77 (3)	C11—H11	0.9500
N1—C1	1.3256 (16)	C11—C12	1.4016 (18)
N1—C9	1.3590 (16)	C12—H12	0.9500
N2—C8	1.3565 (15)	O4—H4A	0.81 (3)
N2—C12	1.3298 (16)	O4—H4B	0.81 (3)

F1—Hf1—F2	94.00 (4)	C9—N1—Cu1	112.08 (8)
F1—Hf1—F3	89.93 (4)	C8—N2—Cu1	112.04 (8)
F1—Hf1—F4	175.95 (4)	C12—N2—Cu1	129.51 (8)
F1—Hf1—F5	88.90 (4)	C12—N2—C8	118.43 (10)
F1—Hf1—F6	88.47 (4)	N1—C1—H1	118.9
F2—Hf1—F3	86.85 (4)	N1—C1—C2	122.28 (13)
F2—Hf1—F4	89.88 (4)	C2—C1—H1	118.9
F2—Hf1—F5	173.04 (4)	C1—C2—H2	120.2
F4—Hf1—F3	91.46 (4)	C3—C2—C1	119.61 (12)
F4—Hf1—F5	87.38 (4)	C3—C2—H2	120.2
F5—Hf1—F3	86.83 (3)	C2—C3—H3	120.5
F6—Hf1—F2	92.84 (4)	C2—C3—C4	119.07 (12)
F6—Hf1—F3	178.34 (4)	C4—C3—H3	120.5
F6—Hf1—F4	90.17 (4)	C3—C4—C5	124.03 (12)
F6—Hf1—F5	93.57 (4)	C9—C4—C3	117.37 (12)
O1—Cu1—F1	170.30 (3)	C9—C4—C5	118.61 (12)
O2—Cu1—F1	83.89 (4)	C4—C5—H5	119.4
O2—Cu1—O1	88.40 (4)	C6—C5—C4	121.10 (12)
O2—Cu1—N1	93.29 (5)	C6—C5—H5	119.4
O2—Cu1—N2	175.97 (5)	C5—C6—H6	119.5
O3—Cu1—F1	91.55 (5)	C5—C6—C7	121.04 (12)
O3—Cu1—O1	94.23 (5)	C7—C6—H6	119.5
O3—Cu1—O2	89.26 (6)	C8—C7—C6	118.74 (12)
O3—Cu1—N1	168.66 (5)	C8—C7—C10	116.98 (11)
O3—Cu1—N2	94.73 (5)	C10—C7—C6	124.28 (12)
N1—Cu1—F1	77.76 (4)	N2—C8—C7	123.21 (11)
N1—Cu1—O1	96.88 (4)	N2—C8—C9	116.62 (10)
N1—Cu1—N2	82.69 (4)	C7—C8—C9	120.16 (10)
N2—Cu1—F1	95.41 (4)	N1—C9—C4	123.19 (11)
N2—Cu1—O1	91.87 (4)	N1—C9—C8	116.50 (10)
Hf1—F1—Cu1	132.71 (4)	C4—C9—C8	120.31 (11)
Cu1—O1—H1A	118 (2)	C7—C10—H10	120.3
Cu1—O1—H1B	128 (2)	C11—C10—C7	119.48 (12)
H1A—O1—H1B	104 (3)	C11—C10—H10	120.3
Cu1—O2—H2A	121 (2)	C10—C11—H11	120.2
Cu1—O2—H2B	133 (2)	C10—C11—C12	119.57 (12)
H2A—O2—H2B	104 (3)	C12—C11—H11	120.2
Cu1—O3—H3A	120 (2)	N2—C12—C11	122.31 (12)
Cu1—O3—H3B	131 (2)	N2—C12—H12	118.8
H3A—O3—H3B	109 (3)	C11—C12—H12	118.8
C1—N1—Cu1	129.31 (9)	H4A—O4—H4B	101 (3)
C1—N1—C9	118.46 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F5ⁱ	0.80 (3)	1.94 (3)	2.7359 (13)	172 (3)
O1—H1B···F4ⁱⁱ	0.77 (3)	1.95 (3)	2.7135 (13)	176 (3)
O2—H2A···F6	0.86 (3)	1.85 (3)	2.6456 (14)	154 (3)
O2—H2B···F3ⁱ	0.77 (3)	1.87 (3)	2.6362 (14)	171 (3)
O3—H3A···O4ⁱⁱⁱ	0.81 (3)	1.85 (3)	2.6529 (17)	173 (3)
O3—H3B···F2^iv	0.77 (3)	1.86 (3)	2.6330 (15)	176 (3)
O4—H4A···F5^v	0.81 (3)	2.00 (3)	2.7429 (15)	154 (3)
O4—H4B···F3	0.81 (3)	2.01 (3)	2.7702 (14)	156 (3)

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

Bis[diaquafluorido(1,10-phenanthroline-κ²N,N')copper(II)] hexafluoridohafnate(IV) dihydrate (IV) top

Crystal data top

[CuF(C₁₂H₈N₂)(H₂O)₂]₂[HfF₆]·2H₂O	F(000) = 900
M_r = 926.07	D_x = 2.041 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.6451 (2) Å	Cell parameters from 9864 reflections
b = 7.1161 (1) Å	θ = 3.2–31.6°
c = 15.7457 (3) Å	µ = 4.93 mm⁻¹
β = 99.691 (1)°	T = 100 K
V = 1507.09 (4) Å³	Block, blue
Z = 2	0.16 × 0.16 × 0.10 mm

Data collection top

Bruker Kappa APEX CCD area detector diffractometer	5034 independent reflections
Radiation source: sealed tube	4982 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.033
Detector resolution: 8 pixels mm^-1	θ_max = 31.6°, θ_min = 1.8°
ω and φ scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −10→10
T_min = 0.489, T_max = 0.746	l = −23→23
123138 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.014	w = 1/[σ²(F_o²) + (0.0117P)² + 1.360P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.035	(Δ/σ)_max = 0.002
S = 1.15	Δρ_max = 0.67 e Å⁻³
5034 reflections	Δρ_min = −0.70 e Å⁻³
230 parameters	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00177 (14)
Primary atom site location: dual

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.62127 (2)	0.64187 (2)	0.68925 (2)	0.01005 (3)
F1	0.76115 (6)	0.65941 (11)	0.70156 (5)	0.01498 (14)
O1	0.62607 (8)	0.45374 (15)	0.78219 (7)	0.01690 (18)
H1A	0.624 (2)	0.491 (3)	0.8306 (18)	0.038 (7)*
H1B	0.6623 (18)	0.375 (4)	0.7848 (15)	0.031 (6)*
O2	0.61132 (8)	0.88111 (16)	0.76902 (8)	0.0210 (2)
H2A	0.5660 (19)	0.907 (4)	0.7866 (16)	0.035 (6)*
H2B	0.6525 (18)	0.961 (3)	0.7795 (15)	0.028 (6)*
N1	0.47279 (8)	0.62122 (15)	0.66010 (7)	0.01255 (18)
N2	0.60647 (8)	0.72932 (15)	0.56647 (7)	0.01210 (18)
C1	0.40802 (10)	0.5731 (2)	0.71056 (9)	0.0173 (2)
H1	0.431969	0.536685	0.768377	0.021*
C2	0.30508 (11)	0.5746 (2)	0.68062 (10)	0.0229 (3)
H2	0.260252	0.542670	0.718419	0.027*
C3	0.26932 (10)	0.6223 (2)	0.59655 (11)	0.0227 (3)
H3	0.199828	0.621543	0.575619	0.027*
C4	0.33664 (10)	0.67219 (19)	0.54175 (9)	0.0169 (2)
C5	0.43786 (9)	0.67246 (17)	0.57741 (8)	0.0125 (2)
C6	0.30786 (11)	0.7249 (2)	0.45299 (10)	0.0218 (3)
H6	0.239621	0.721580	0.427555	0.026*
C7	0.37640 (12)	0.7791 (2)	0.40497 (9)	0.0212 (3)
H7	0.355271	0.814434	0.346577	0.025*
C8	0.48019 (11)	0.78432 (18)	0.44052 (8)	0.0161 (2)
C9	0.51006 (9)	0.72954 (17)	0.52666 (8)	0.0122 (2)
C10	0.55590 (12)	0.84042 (19)	0.39478 (9)	0.0204 (3)
H10	0.539638	0.879121	0.336361	0.024*
C11	0.65340 (12)	0.8386 (2)	0.43549 (9)	0.0206 (3)
H11	0.704981	0.875387	0.405306	0.025*
C12	0.67606 (10)	0.78186 (19)	0.52197 (8)	0.0162 (2)
H12	0.743579	0.781115	0.549530	0.019*
Hf1	0.500000	0.500000	1.000000	0.01221 (3)
F2	0.41065 (9)	0.67878 (17)	0.92652 (8)	0.0399 (3)
F3	0.54442 (8)	0.69971 (16)	1.08602 (7)	0.0347 (3)
F4	0.61050 (7)	0.56285 (16)	0.93645 (6)	0.0286 (2)
O3	0.44170 (9)	0.97485 (17)	0.82435 (8)	0.0211 (2)
H3A	0.4338 (19)	0.893 (4)	0.8558 (17)	0.044 (7)*
H3B	0.4502 (18)	1.063 (4)	0.8509 (16)	0.034 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00921 (6)	0.01226 (7)	0.00874 (6)	0.00025 (5)	0.00170 (5)	0.00021 (5)
F1	0.0105 (3)	0.0159 (4)	0.0182 (4)	0.0005 (3)	0.0014 (3)	−0.0001 (3)
O1	0.0223 (5)	0.0169 (4)	0.0126 (4)	0.0065 (4)	0.0061 (4)	0.0035 (3)
O2	0.0179 (5)	0.0181 (5)	0.0301 (5)	−0.0050 (4)	0.0127 (4)	−0.0111 (4)
N1	0.0116 (4)	0.0135 (5)	0.0128 (4)	−0.0001 (4)	0.0027 (3)	−0.0023 (4)
N2	0.0146 (4)	0.0112 (4)	0.0107 (4)	−0.0009 (4)	0.0028 (3)	−0.0007 (3)
C1	0.0155 (5)	0.0213 (6)	0.0166 (6)	−0.0021 (5)	0.0070 (4)	−0.0041 (5)
C2	0.0147 (6)	0.0280 (7)	0.0281 (7)	−0.0020 (5)	0.0099 (5)	−0.0065 (6)
C3	0.0117 (5)	0.0253 (7)	0.0305 (7)	0.0023 (5)	0.0024 (5)	−0.0074 (6)
C4	0.0136 (5)	0.0146 (5)	0.0210 (6)	0.0034 (4)	−0.0014 (4)	−0.0046 (5)
C5	0.0127 (5)	0.0107 (5)	0.0134 (5)	0.0020 (4)	0.0001 (4)	−0.0026 (4)
C6	0.0203 (6)	0.0179 (6)	0.0230 (6)	0.0072 (5)	−0.0084 (5)	−0.0047 (5)
C7	0.0291 (7)	0.0151 (6)	0.0157 (6)	0.0074 (5)	−0.0075 (5)	−0.0020 (5)
C8	0.0256 (6)	0.0104 (5)	0.0108 (5)	0.0033 (5)	−0.0008 (4)	−0.0006 (4)
C9	0.0161 (5)	0.0089 (5)	0.0109 (5)	0.0014 (4)	0.0004 (4)	−0.0012 (4)
C10	0.0371 (8)	0.0129 (5)	0.0112 (5)	0.0010 (5)	0.0044 (5)	0.0012 (4)
C11	0.0323 (7)	0.0161 (6)	0.0156 (6)	−0.0021 (5)	0.0104 (5)	0.0006 (5)
C12	0.0206 (6)	0.0149 (5)	0.0144 (5)	−0.0029 (5)	0.0064 (4)	−0.0013 (4)
Hf1	0.01420 (4)	0.01322 (4)	0.01094 (4)	−0.00344 (2)	0.00713 (2)	−0.00266 (2)
F2	0.0325 (6)	0.0375 (6)	0.0482 (7)	0.0045 (5)	0.0029 (5)	0.0185 (5)
F3	0.0321 (5)	0.0372 (6)	0.0387 (6)	−0.0155 (4)	0.0174 (4)	−0.0263 (5)
F4	0.0268 (5)	0.0418 (6)	0.0213 (4)	−0.0156 (4)	0.0165 (4)	−0.0086 (4)
O3	0.0212 (5)	0.0188 (5)	0.0250 (5)	−0.0002 (4)	0.0093 (4)	−0.0061 (4)

Geometric parameters (Å, º) top

Cu1—F1	1.8899 (8)	C5—C9	1.4279 (18)
Cu1—O1	1.9763 (10)	C6—H6	0.9500
Cu1—O2	2.1335 (11)	C6—C7	1.354 (2)
Cu1—N1	2.0060 (11)	C7—H7	0.9500
Cu1—N2	2.0085 (11)	C7—C8	1.433 (2)
O1—H1A	0.81 (3)	C8—C9	1.4042 (17)
O1—H1B	0.74 (3)	C8—C10	1.413 (2)
O2—H2A	0.74 (3)	C10—H10	0.9500
O2—H2B	0.80 (3)	C10—C11	1.376 (2)
N1—C1	1.3290 (16)	C11—H11	0.9500
N1—C5	1.3588 (16)	C11—C12	1.4039 (19)
N2—C9	1.3586 (16)	C12—H12	0.9500
N2—C12	1.3254 (16)	Hf1—F2	1.9922 (11)
C1—H1	0.9500	Hf1—F2ⁱ	1.9921 (11)
C1—C2	1.4044 (19)	Hf1—F3	1.9863 (10)
C2—H2	0.9500	Hf1—F3ⁱ	1.9863 (10)
C2—C3	1.374 (2)	Hf1—F4	1.9957 (9)
C3—H3	0.9500	Hf1—F4ⁱ	1.9957 (9)
C3—C4	1.408 (2)	O3—H3A	0.78 (3)
C4—C5	1.4006 (17)	O3—H3B	0.75 (3)
C4—C6	1.436 (2)

F1—Cu1—O1	93.54 (4)	C4—C6—H6	119.5
F1—Cu1—O2	92.88 (4)	C7—C6—C4	121.08 (13)
F1—Cu1—N1	172.75 (4)	C7—C6—H6	119.5
F1—Cu1—N2	90.83 (4)	C6—C7—H7	119.4
O1—Cu1—O2	95.86 (5)	C6—C7—C8	121.29 (13)
O1—Cu1—N1	91.49 (5)	C8—C7—H7	119.4
O1—Cu1—N2	155.24 (5)	C9—C8—C7	118.50 (13)
N1—Cu1—O2	91.79 (4)	C9—C8—C10	116.91 (13)
N1—Cu1—N2	82.44 (4)	C10—C8—C7	124.59 (13)
N2—Cu1—O2	108.26 (5)	N2—C9—C5	116.56 (11)
Cu1—O1—H1A	118.1 (17)	N2—C9—C8	123.16 (12)
Cu1—O1—H1B	119.3 (18)	C8—C9—C5	120.27 (12)
H1A—O1—H1B	109 (2)	C8—C10—H10	120.2
Cu1—O2—H2A	124 (2)	C11—C10—C8	119.50 (12)
Cu1—O2—H2B	125.3 (17)	C11—C10—H10	120.2
H2A—O2—H2B	110 (3)	C10—C11—H11	120.3
C1—N1—Cu1	129.04 (9)	C10—C11—C12	119.49 (13)
C1—N1—C5	118.73 (11)	C12—C11—H11	120.3
C5—N1—Cu1	112.17 (8)	N2—C12—C11	122.24 (13)
C9—N2—Cu1	112.16 (8)	N2—C12—H12	118.9
C12—N2—Cu1	129.15 (9)	C11—C12—H12	118.9
C12—N2—C9	118.69 (11)	F2ⁱ—Hf1—F2	180.0
N1—C1—H1	119.1	F2—Hf1—F4	90.34 (5)
N1—C1—C2	121.71 (13)	F2—Hf1—F4ⁱ	89.66 (5)
C2—C1—H1	119.1	F2ⁱ—Hf1—F4ⁱ	90.34 (5)
C1—C2—H2	120.1	F2ⁱ—Hf1—F4	89.66 (5)
C3—C2—C1	119.88 (13)	F3ⁱ—Hf1—F2ⁱ	91.48 (6)
C3—C2—H2	120.1	F3ⁱ—Hf1—F2	88.52 (6)
C2—C3—H3	120.3	F3—Hf1—F2ⁱ	88.52 (6)
C2—C3—C4	119.36 (13)	F3—Hf1—F2	91.48 (6)
C4—C3—H3	120.3	F3ⁱ—Hf1—F3	180.0
C3—C4—C6	124.23 (13)	F3—Hf1—F4	90.69 (4)
C5—C4—C3	117.12 (13)	F3ⁱ—Hf1—F4ⁱ	90.69 (4)
C5—C4—C6	118.64 (13)	F3ⁱ—Hf1—F4	89.31 (4)
N1—C5—C4	123.15 (12)	F3—Hf1—F4ⁱ	89.31 (4)
N1—C5—C9	116.67 (11)	F4ⁱ—Hf1—F4	180.0
C4—C5—C9	120.18 (12)	H3A—O3—H3B	107 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F4	0.81 (3)	1.78 (3)	2.5926 (14)	176 (3)
O1—H1B···F1ⁱⁱ	0.74 (3)	1.85 (3)	2.5861 (13)	172 (3)
O2—H2A···O3	0.74 (3)	1.95 (3)	2.6906 (15)	176 (3)
O2—H2B···F1ⁱⁱⁱ	0.80 (3)	1.83 (3)	2.6255 (13)	175 (2)
O3—H3A···F2	0.78 (3)	1.94 (3)	2.7270 (17)	176 (3)
O3—H3B···F3^iv	0.75 (3)	1.96 (3)	2.7020 (15)	173 (3)

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

π–π stacking interactions in compounds (I)–(IV) top

Compound number	type	d_{phenyl–pyridine}	d_{pyridine–pyridine}	d_{phenyl–phenyl}	interplanar angle
(I)	face-to-face	3.699	4.162	3.583	0
(I)	displaced	6.042	4.128	8.111	8.68
(II)/(III)	parallel displaced	4.469	3.407	6.324	0
(II)/(III)	parallel displaced	3.510	4.472	4.035	0
(IV)	face to face	3.664	3.48	4.07	0
(IV)	parallel displaced	3.508	3.881	4.604	0

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 (award No. DMR-1904701).

References

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Volume 77| Part 2| February 2021| Pages 165-170

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