The syntheses and crystal structures of two bimetallic molecular compounds, namely, bis(6,6′-dimethyl-2,2′-bipyridine)copper(I) hexafluoridozirconate(IV) 1.134-hydrate, [Cu(dmbpy)2]2[ZrF6]·1.134H2O (dmbpy = 6,6′-dimethyl-2,2′-bipyridyl, C12H12N2), (I), and bis(6,6′-dimethyl-2,2′-bipyridine)copper(I) hexafluoridohafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]·0.671H2O, (II), are reported. Apart from a slight site occupancy difference for the water molecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetrahedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octahedral anions of fluorinated early transition metals.
Keywords: crystal structures, CuI complex, d 0 early transition metals, hydrothermal synthesis
Abstract
The syntheses and crystal structures of two bimetallic molecular compounds, namely, bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate, [Cu(dmbpy)2]2[ZrF6]·1.134H2O (dmbpy = 6,6′-dimethyl-2,2′-bipyridyl, C12H12N2), (I), and bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]·0.671H2O, (II), are reported. Apart from a slight site occupany difference for the water molecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetrahedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octahedral anions of fluorinated early transition metals. The tetrahedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic interactions between cations and anions and π–π stacking interactions between heterochiral Δ- and Λ-[Cu(dmbpy)2]+ complexes. A comparison between the title compounds and other [Cu(dmbpy)2]+ compounds with monovalent and bivalent anions reveals a significant influence of the cation-to-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetrahedral copper compounds.
Chemical context
Copper(I) complexes with distorted tetrahedral environments have been studied as catalytic active sites in electron-transfer reactions and are found in a number of proteins that contain copper (Vallee & Williams, 1968 ▸; Colman et al., 1978 ▸; Adman et al., 1978 ▸). The realization of significantly distorted tetrahedral geometry requires sufficient steric hindrance between the ligands. The methyl groups of the 6,6′-dimethyl-2,2′-bipyridyl (C12H12N2; dmbpy) ligand create a large steric hindrance upon coordination, and, consequently, a common strategy to form distorted tetrahedral complexes is to use dmbpy or its derivatives as ligands (McKenzie et al., 1971 ▸; Burke et al., 1980 ▸). Previously, compounds with distorted tetrahedral [Cu(dmbpy)2]+ cations have been reported, namely [Cu(dmbpy)2]X (X = [BF4]−, [ClO4]−, [PF6]−), [Cu(dmbpy)2][C16H9O8]·H2O (C16H9O8 = 2′,3,3′-tricarboxybiphenyl-2-carboxylate) and [Cu(dmbpy)2]X
2 (X = [BF4]−, [ClO4]−). (Burke et al., 1980 ▸; Cui et al., 2005 ▸; Itoh et al., 2005 ▸; Mei et al., 2011 ▸; Bozic-Weber et al., 2012 ▸; Li et al., 2017 ▸) Here, we report two structures with [MF6]2− (M = Zr, Hf), which are the first known distorted tetrahedral copper compounds with bivalent anions.
Structural commentary
Compound (I) has the formula [Cu(dmbpy)2]2[ZrF6]·1.134H2O and crystallizes in the triclinic space group P
(Fig. 1 ▸). The structure of compound (I) features isolated tetrahedral [Cu(dmbpy)2]+ cations and octahedral ZrF6
2− anions (Zr site symmetry
). The coordination geometry of Cu1 and its donor N atoms deviates from an ideal tetrahedron, as demonstrated by the 83.33 (10)° angle between the least squares planes containing Cu1 and each ligand (Table 1 ▸). To quantify the deviation from Td
symmetry in [Cu(dmbpy)2]+ cations, the τ4’ parameter is employed and it gives a value of 0.66 for compound (I) (Okuniewski et al., 2015 ▸). The distorted tetrahedral geometry of [Cu(dmbpy)2]+ in compound (I) is consistent with other reported compounds containing [Cu(dmbpy)2]+ cations (Burke et al., 1980 ▸; Cui et al., 2005 ▸; Mei et al., 2011 ▸; Bozic-Weber et al., 2012 ▸). Moreover, the dmbpy ligands in (I) are non-planar and are slightly twisted on the 2,2′ carbon bond to give a dihedral angle of 8.68 (10)° between the N1/C1–C5 and N2/C6–C10 rings and 7.44 (11)° between the N3/C13–C17 and N4/C18–C22 rings. The distorted tetrahedral environment and non-planar ligand geometry give the [Cu(dmbpy)2]+ cations a C
2 symmetry, and enantiomeric Δ- and Λ-[Cu(dmbpy)2]+ pairs are related across inversion centers. The octahedral coordination environment of Zr1 is slightly distorted, with Zr1—F bond lengths ranging from 1.9955 (13) to 2.0183 (12) Å (Table 1 ▸). The minor distortion of the ZrF6
2− anion may arise due to hydrogen-bonding interactions between water molecules of crystallization and fluorine atoms on the trans position of the ZrF6
2− anions [see O1—H1B⋯F2 (Table 2 ▸)].
Figure 1.
The molecular structure of (I) showing 50% displacement ellipsoids. Symmetry code: (i) −x, 2 − y, 2 − z.
Table 1. Selected geometric parameters (Å, °) for (I) .
| Cu1—N1 | 2.0208 (16) | Zr1—F1 | 2.0113 (15) |
| Cu1—N2 | 2.0348 (17) | Zr1—F2 | 2.0183 (12) |
| Cu1—N3 | 2.0123 (17) | Zr1—F3 | 1.9955 (13) |
| Cu1—N4 | 2.0616 (18) | ||
| N1—Cu1—N2 | 81.40 (7) | N3—Cu1—N1 | 136.29 (7) |
| N1—Cu1—N4 | 116.24 (7) | N3—Cu1—N2 | 126.16 (7) |
| N2—Cu1—N4 | 120.45 (7) | N3—Cu1—N4 | 81.05 (7) |
Table 2. Hydrogen-bond geometry (Å, °) for (I) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1B⋯F2 | 0.87 | 1.47 | 2.337 (4) | 177 |
Compound (II) has the formula [Cu(dmbpy)2]2[HfF6]·0.671H2O and crystallizes in the triclinic space group P
(Fig. 2 ▸). Compound (II) is isostructural to compound (I), therefore, the [Cu(dmbpy)2]+ cations also have C
2 symmetry, with the angle between the least squares planes containing Cu1 and each ligand being 84.14 (8)° (Table 3 ▸) and the τ4’ parameter being 0.66, and the dmbpy ligands are slightly twisted on the 2,2′ carbon bond to give an angle of 9.69 (7)° between the N1/C1–C5 and N2/C6–C10 rings and 7.97 (8)° between the N3/C13–C17 and N4/C18–C22 rings. Moreover, the octahedral coordination environment of Hf1 is also slightly distorted, with Hf1—F bond lengths ranging from 1.9945 (10) to 2.0111 (11) Å. Like in compound (I), hydrogen-bonding interactions are present between the water molecule of crystallization and fluorine atoms on the trans position of HfF6
2− anions, but the geometry of the hydrogen bond is slightly different from that in compound (I) [see O1—H1B⋯F2 (Table 4 ▸)].
Figure 2.
The molecular structure of (II) showing 50% displacement ellipsoids. Symmetry code: (i) (i) −x, 2 − y, 2 − z.
Table 3. Selected geometric parameters (Å, °) for (II) .
| Cu1—N1 | 2.0229 (12) | Hf1—F1 | 2.0111 (11) |
| Cu1—N2 | 2.0414 (12) | Hf1—F2 | 2.0033 (9) |
| Cu1—N3 | 2.0121 (12) | Hf1—F3 | 1.9945 (10) |
| Cu1—N4 | 2.0659 (13) | ||
| N1—Cu1—N2 | 81.22 (5) | N3—Cu1—N1 | 136.20 (5) |
| N1—Cu1—N4 | 116.52 (5) | N3—Cu1—N2 | 126.39 (5) |
| N2—Cu1—N4 | 120.35 (5) | N3—Cu1—N4 | 80.94 (5) |
Table 4. Hydrogen-bond geometry (Å, °) for (II) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1B—H1B⋯F2 | 0.87 | 1.50 | 2.328 (4) | 156 |
Supramolecular features
In the extended structures of compounds (I) and (II), the [Cu(dmbpy)2]+ cations and octahedral MF6 2− anions are closely packed via Coulombic interactions (Fig. 3 ▸). The Δ/Λ-[Cu(dmbpy)2]+ cations stack into racemic pairs along the c-axis direction via a heterochiral face-to-face π–π interaction between the N1/C1–C5 and N2/C6–C10 rings with an interplanar angle of 0°, interplanar distances of 3.347 and 3.355 Å, and centroid–centroid distances (d py–py) of 3.6967 (12) and 3.7016 (8) Å, for compounds (I) and (II), respectively (Tables 5 ▸ and 6 ▸). Next, Δ/Λ-[Cu(dmbpy)2]+ pairs pack into racemic chains along the c-axis direction with heterochiral parallel displaced π–π interactions between the N3/C13–C17 and N4/C18–C22 rings with an interplanar angle of 0°, interplanar distances of 3.708 and 3.678 Å, and centroid–centroid distances (d py–py) of 5.3726 (13) and 5.3777 (11) Å, for compounds (I) and (II), respectively. The MF6 2− anions with hydrogen-bonded water molecules are interlaced between the racemic chains to form the extended three-dimensional structure. Compared to other molecular compounds with MF6 2− anions in an extended and complicated hydrogen network (Gautier et al., 2012 ▸; Nisbet et al., 2020 ▸, 2021 ▸), the MF6 2− anions in (I) and (II) experience less distortion because the hydrogen-bonding contacts are less extensive and only occur along the same axis due to the site symmetry of hydrogen-bonding interactions (Kunz & Brown, 1995 ▸; Halasyamani, 2004 ▸).
Figure 3.
The packing for (I) viewed (a) down [100] and (b) down [001], with the copper and zirconium coordination environments represented by yellow/orange and green polyhedra, respectively.
Table 5. Aromatic π–π stacking interactions (Å, °) in (I).
| Description | type | d py–py | interplanar angle | interplanar distance |
|---|---|---|---|---|
| Heterochiral | face-to-face | 3.6967 (12) | 0 | 3.347 |
| Heterochiral | parallel displaced | 5.3726 (13) | 0 | 3.708 |
Table 6. Aromatic π–π stacking interactions (Å, °) in (II).
| Description | type | d py–py | interplanar angle | interplanar distance |
|---|---|---|---|---|
| Heterochiral | face-to-face | 3.7016 (8) | 0 | 3.355 |
| Heterochiral | parallel displaced | 5.3777 (11) | 0 | 3.678 |
Database survey
A survey of compounds related to compounds (I) and (II) reported in the Cambridge Structural Database (CSD version 2020.1 from April 2020; Groom et al., 2016 ▸) produced four other compounds based on [Cu(dmbpy)2]+ complexes: [Cu(dmbpy)2][BF4] (CSD refcode: MPYRCU; Burke et al., 1980 ▸), [Cu(dmbpy)2][PF6] (REFSUS; Bozic-Weber et al., 2012 ▸), [Cu(dmbpy)2][ClO4] (FAXLAS; Cui et al., 2005 ▸), and [Cu(dmbpy)2][C16H9O8]·H2O (C16H9O8 = 2′,3,3′-tricarboxybiphenyl-2-carboxylate) (ABIYER; Mei et al., 2011 ▸). All these structures have distorted tetrahedral [Cu(dmbpy)2]+ cations with C 2 symmetry, with a range of the angle between the least-squares planes containing the metal ion and each ligand being from 75.06 to 86.74°. Moreover, τ4’ parameters for these structures range from 0.70 to 0.74, whereas for both compound (I) and (II) the parameter is 0.66 (Okuniewski et al., 2015 ▸).
Unlike compound (I) and (II), which have bivalent anions MF6 2−, the compounds reported in the CSD are charge-balanced by monovalent anions and display two different types of packing architectures distinct from those of the title compounds: [Cu(dmbpy)2][BF4], [Cu(dmbpy)2][PF6], and [Cu(dmbpy)2][ClO4] are isostructural, crystallizing in space group P21/c. Compared to compounds (I) and (II), the ratio of cations-to-anions is smaller in these monovalent-anion compounds. Instead of racemic chains, homochiral chains are observed with homochiral displaced π–π interactions between the ligands with an interplanar angle of around 30°. No local or extended hydrogen-bond networks are observed because these structures do not contain water molecules of crystallization.
Another type of packing architecture is found in [Cu(dmbpy)2][C16H9O8]·H2O, which crystallizes in space group P
. Unlike the aforementioned five compounds with [Cu(dmbpy)2]+ cations, π–π interactions in the compound [Cu(dmbpy)2][C16H9O8]·H2O are dominant between [Cu(dmbpy)2]+ cations and [C16H9O8]− anions instead of between [Cu(dmbpy)2]+ cations. In this compound, the [Cu(dmbpy)2]+ cations and [C16H9O8]− anions are packed into charge-neutral chains via Coulombic interactions and π–π interactions along c axis and inversion centers are present between the chains. Additionally, the [C16H9O8]− anions and free water molecules generate a three-dimensional network via O—H⋯O hydrogen bonding interactions, resulting in a different architecture.
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 45 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. Orangish red solid products were recovered by vacuum filtration with a moderate yield. Compound (I) was synthesized in a pouch containing 0.4195 mmol of CuO, 0.4195 mmol of ZrO2, 0.835 mmol of 6,6′-dimethyl-2,2′-bipyridyl, 0.15 ml (4.14 mmol) of HF (aq) (48%), and 0.1 ml (5.5 mmol) of deionized H2O. Compound (II) was synthesized in a pouch containing 0.4195 mmol of CuO, 0.4195 mmol of HfO2, 0.835 mmol of 6,6′-dimethyl-2,2′-bipyridyl, 0.05 ml (1.38 mmol) of HF (aq) (48%), and 0.2 ml (11 mmol) of deionized H2O.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 7 ▸. Hydrogen-atom positions were assigned from difference map peaks with the exception of the C—H hydrogen atoms of dmbpy, 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 ▸). The water occupancies in both structures are refined freely. Four reflections showing very poor agreement were omitted from the final refinement for compound (I).
Table 7. Experimental details.
| (I) | (II) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | [Cu(C12H12N2)2]2[ZrF6]·1.134H2O | [Cu(C12H12N2)2]2[HfF6]·0.671H2O |
| M r | 1089.61 | 1168.58 |
| Crystal system, space group | Triclinic, P\overline{1} | Triclinic, P\overline{1} |
| Temperature (K) | 100 | 100 |
| a, b, c (Å) | 8.6219 (3), 10.8064 (3), 12.9992 (4) | 8.5737 (1), 10.7967 (2), 13.0183 (2) |
| α, β, γ (°) | 103.078 (2), 104.013 (3), 98.863 (2) | 103.273 (1), 103.662 (1), 98.785 (1) |
| V (Å3) | 1116.33 (6) | 1112.07 (3) |
| Z | 1 | 1 |
| Radiation type | Mo Kα | Mo Kα |
| μ (mm−1) | 1.25 | 3.35 |
| Crystal size (mm) | 0.98 × 0.13 × 0.05 | 0.3 × 0.17 × 0.08 |
| Data collection | ||
| Diffractometer | Rigaku Saturn724+ (2x2 bin mode) | Rigaku Saturn724+ (2x2 bin mode) |
| Absorption correction | Gaussian (CrysAlis PRO; Rigaku OD, 2020 ▸) | Gaussian (CrysAlis PRO; Rigaku OD, 2020 ▸) |
| T min, T max | 0.376, 1.000 | 0.433, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16573, 5673, 4588 | 40796, 8003, 7235 |
| R int | 0.039 | 0.032 |
| (sin θ/λ)max (Å−1) | 0.722 | 0.784 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.035, 0.088, 1.07 | 0.023, 0.056, 1.08 |
| No. of reflections | 5673 | 8003 |
| No. of parameters | 312 | 312 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.59, −0.54 | 0.48, −0.73 |
Supplementary Material
Crystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989021007295/hb7977sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021007295/hb7977Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989021007295/hb7977IIsup3.hkl
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
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). We thank Ms Charlotte Stern for helpful discussions.
supplementary crystallographic information
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Crystal data
| [Cu(C12H12N2)2]2[ZrF6]·1.134H2O | Z = 1 |
| Mr = 1089.61 | F(000) = 555 |
| Triclinic, P1 | Dx = 1.621 Mg m−3 |
| a = 8.6219 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 10.8064 (3) Å | Cell parameters from 10429 reflections |
| c = 12.9992 (4) Å | θ = 2.2–30.6° |
| α = 103.078 (2)° | µ = 1.25 mm−1 |
| β = 104.013 (3)° | T = 100 K |
| γ = 98.863 (2)° | Needle, clear orangish red |
| V = 1116.33 (6) Å3 | 0.98 × 0.13 × 0.05 mm |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Data collection
| Rigaku Saturn724+ (2x2 bin mode) diffractometer | 5673 independent reflections |
| Radiation source: Rotating Anode, Rotating Anode | 4588 reflections with I > 2σ(I) |
| Confocal monochromator | Rint = 0.039 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 30.9°, θmin = 2.0° |
| profile data from ω–scans | h = −11→11 |
| Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2020) | k = −14→15 |
| Tmin = 0.376, Tmax = 1.000 | l = −16→18 |
| 16573 measured reflections |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0397P)2 + 0.3898P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 5673 reflections | Δρmax = 0.59 e Å−3 |
| 312 parameters | Δρmin = −0.54 e Å−3 |
| 0 restraints |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Special details
| 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. |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Cu1 | 0.30548 (3) | 0.35420 (2) | 0.69756 (2) | 0.02018 (8) | |
| N1 | 0.4953 (2) | 0.36543 (16) | 0.82845 (13) | 0.0174 (3) | |
| C1 | 0.5623 (3) | 0.26739 (19) | 0.85293 (17) | 0.0207 (4) | |
| N2 | 0.3424 (2) | 0.54652 (16) | 0.77601 (14) | 0.0195 (3) | |
| C2 | 0.7120 (3) | 0.2905 (2) | 0.93235 (17) | 0.0212 (4) | |
| H2 | 0.756689 | 0.219858 | 0.948974 | 0.025* | |
| N3 | 0.0873 (2) | 0.23159 (15) | 0.61598 (14) | 0.0190 (3) | |
| C3 | 0.7947 (3) | 0.4174 (2) | 0.98671 (17) | 0.0230 (4) | |
| H3 | 0.898128 | 0.435022 | 1.040244 | 0.028* | |
| N4 | 0.3423 (2) | 0.29725 (16) | 0.54450 (14) | 0.0211 (4) | |
| C4 | 0.7257 (2) | 0.5187 (2) | 0.96256 (17) | 0.0210 (4) | |
| H4 | 0.780962 | 0.606656 | 0.999235 | 0.025* | |
| C5 | 0.5745 (2) | 0.48980 (18) | 0.88392 (16) | 0.0160 (4) | |
| C6 | 0.4869 (2) | 0.59134 (18) | 0.85644 (16) | 0.0166 (4) | |
| C7 | 0.5450 (3) | 0.72317 (19) | 0.91116 (17) | 0.0202 (4) | |
| H7 | 0.649798 | 0.753655 | 0.964086 | 0.024* | |
| C8 | 0.4472 (3) | 0.8091 (2) | 0.88699 (18) | 0.0237 (4) | |
| H8 | 0.484553 | 0.899537 | 0.923175 | 0.028* | |
| C9 | 0.2955 (3) | 0.7627 (2) | 0.81024 (19) | 0.0251 (4) | |
| H9 | 0.224458 | 0.819860 | 0.796195 | 0.030* | |
| C10 | 0.2476 (3) | 0.6306 (2) | 0.75341 (19) | 0.0247 (4) | |
| C11 | 0.4653 (3) | 0.1315 (2) | 0.7923 (2) | 0.0325 (5) | |
| H11A | 0.374488 | 0.110516 | 0.822909 | 0.049* | |
| H11B | 0.536537 | 0.069734 | 0.800414 | 0.049* | |
| H11C | 0.421624 | 0.125560 | 0.713932 | 0.049* | |
| C12 | 0.0897 (3) | 0.5747 (3) | 0.6624 (3) | 0.0505 (8) | |
| H12A | 0.113803 | 0.542757 | 0.592501 | 0.076* | |
| H12B | 0.027094 | 0.642511 | 0.656716 | 0.076* | |
| H12C | 0.025358 | 0.502569 | 0.678793 | 0.076* | |
| C13 | −0.0357 (3) | 0.20374 (19) | 0.65956 (18) | 0.0222 (4) | |
| C14 | −0.1902 (3) | 0.1331 (2) | 0.5926 (2) | 0.0299 (5) | |
| H14 | −0.276649 | 0.114742 | 0.624100 | 0.036* | |
| C15 | −0.2168 (3) | 0.0899 (2) | 0.4802 (2) | 0.0331 (6) | |
| H15 | −0.322268 | 0.042926 | 0.433723 | 0.040* | |
| C16 | −0.0896 (3) | 0.1152 (2) | 0.43557 (19) | 0.0286 (5) | |
| H16 | −0.105281 | 0.084169 | 0.358515 | 0.034* | |
| C17 | 0.0622 (3) | 0.18722 (18) | 0.50567 (17) | 0.0209 (4) | |
| C18 | 0.2076 (3) | 0.2182 (2) | 0.46677 (17) | 0.0228 (4) | |
| C19 | 0.2083 (3) | 0.1682 (2) | 0.35859 (18) | 0.0297 (5) | |
| H19 | 0.112010 | 0.114338 | 0.304771 | 0.036* | |
| C20 | 0.3513 (4) | 0.1981 (2) | 0.3308 (2) | 0.0356 (6) | |
| H20 | 0.354850 | 0.164937 | 0.257431 | 0.043* | |
| C21 | 0.4888 (3) | 0.2767 (2) | 0.4105 (2) | 0.0344 (5) | |
| H21 | 0.588640 | 0.296366 | 0.392590 | 0.041* | |
| C22 | 0.4816 (3) | 0.3270 (2) | 0.51691 (19) | 0.0260 (5) | |
| C23 | 0.0017 (3) | 0.2514 (2) | 0.78169 (19) | 0.0308 (5) | |
| H23A | 0.106137 | 0.232552 | 0.816790 | 0.046* | |
| H23B | −0.085860 | 0.207350 | 0.805470 | 0.046* | |
| H23C | 0.009325 | 0.345593 | 0.803131 | 0.046* | |
| C24 | 0.6265 (3) | 0.4151 (2) | 0.6065 (2) | 0.0325 (5) | |
| H24A | 0.593595 | 0.492033 | 0.643469 | 0.049* | |
| H24B | 0.713290 | 0.442318 | 0.574399 | 0.049* | |
| H24C | 0.667181 | 0.368394 | 0.660221 | 0.049* | |
| Zr1 | 0.000000 | 1.000000 | 1.000000 | 0.02476 (9) | |
| F1 | 0.09081 (18) | 0.99518 (14) | 0.87082 (13) | 0.0384 (3) | |
| F2 | −0.05473 (16) | 0.80350 (12) | 0.95926 (12) | 0.0322 (3) | |
| F3 | 0.22027 (15) | 1.00042 (12) | 1.09456 (13) | 0.0346 (3) | |
| O1 | −0.1062 (4) | 0.6247 (3) | 0.8061 (3) | 0.0369 (11) | 0.567 (6) |
| H1A | −0.045474 | 0.641036 | 0.764081 | 0.055* | 0.567 (6) |
| H1B | −0.087438 | 0.692874 | 0.861724 | 0.055* | 0.567 (6) |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.02111 (14) | 0.01747 (13) | 0.01614 (13) | 0.00081 (10) | −0.00092 (10) | 0.00225 (9) |
| N1 | 0.0200 (8) | 0.0173 (8) | 0.0128 (8) | 0.0026 (7) | 0.0022 (6) | 0.0033 (6) |
| C1 | 0.0253 (10) | 0.0205 (10) | 0.0184 (10) | 0.0078 (8) | 0.0073 (8) | 0.0065 (8) |
| N2 | 0.0193 (8) | 0.0167 (8) | 0.0198 (9) | 0.0029 (7) | 0.0016 (7) | 0.0051 (6) |
| C2 | 0.0232 (10) | 0.0255 (10) | 0.0205 (10) | 0.0114 (8) | 0.0095 (8) | 0.0100 (8) |
| N3 | 0.0226 (9) | 0.0142 (8) | 0.0175 (8) | 0.0038 (7) | 0.0022 (7) | 0.0029 (6) |
| C3 | 0.0168 (9) | 0.0325 (11) | 0.0204 (10) | 0.0052 (8) | 0.0036 (8) | 0.0109 (9) |
| N4 | 0.0251 (9) | 0.0206 (8) | 0.0191 (9) | 0.0049 (7) | 0.0066 (7) | 0.0082 (7) |
| C4 | 0.0180 (10) | 0.0206 (10) | 0.0203 (10) | 0.0007 (8) | 0.0023 (8) | 0.0039 (8) |
| C5 | 0.0165 (9) | 0.0167 (9) | 0.0148 (9) | 0.0033 (7) | 0.0051 (7) | 0.0040 (7) |
| C6 | 0.0169 (9) | 0.0174 (9) | 0.0160 (9) | 0.0031 (7) | 0.0058 (7) | 0.0048 (7) |
| C7 | 0.0211 (10) | 0.0188 (9) | 0.0194 (10) | 0.0008 (8) | 0.0064 (8) | 0.0043 (8) |
| C8 | 0.0334 (12) | 0.0168 (9) | 0.0224 (11) | 0.0039 (9) | 0.0123 (9) | 0.0048 (8) |
| C9 | 0.0289 (11) | 0.0222 (10) | 0.0311 (12) | 0.0102 (9) | 0.0128 (9) | 0.0131 (9) |
| C10 | 0.0223 (10) | 0.0231 (10) | 0.0293 (12) | 0.0045 (8) | 0.0037 (9) | 0.0125 (9) |
| C11 | 0.0456 (14) | 0.0190 (10) | 0.0265 (12) | 0.0104 (10) | −0.0010 (10) | 0.0033 (9) |
| C12 | 0.0333 (14) | 0.0281 (13) | 0.073 (2) | 0.0029 (11) | −0.0190 (14) | 0.0192 (13) |
| C13 | 0.0230 (10) | 0.0173 (9) | 0.0245 (11) | 0.0053 (8) | 0.0055 (8) | 0.0031 (8) |
| C14 | 0.0234 (11) | 0.0204 (10) | 0.0428 (14) | 0.0019 (9) | 0.0087 (10) | 0.0057 (10) |
| C15 | 0.0247 (12) | 0.0217 (11) | 0.0382 (14) | 0.0006 (9) | −0.0059 (10) | −0.0017 (10) |
| C16 | 0.0335 (12) | 0.0195 (10) | 0.0227 (11) | 0.0050 (9) | −0.0054 (9) | 0.0007 (8) |
| C17 | 0.0276 (11) | 0.0148 (9) | 0.0170 (10) | 0.0062 (8) | −0.0007 (8) | 0.0044 (7) |
| C18 | 0.0315 (11) | 0.0196 (10) | 0.0166 (10) | 0.0070 (9) | 0.0021 (8) | 0.0077 (8) |
| C19 | 0.0473 (14) | 0.0226 (11) | 0.0180 (11) | 0.0090 (10) | 0.0056 (10) | 0.0065 (9) |
| C20 | 0.0602 (17) | 0.0319 (12) | 0.0245 (12) | 0.0163 (12) | 0.0222 (12) | 0.0118 (10) |
| C21 | 0.0465 (15) | 0.0345 (13) | 0.0357 (14) | 0.0170 (11) | 0.0239 (12) | 0.0178 (11) |
| C22 | 0.0304 (11) | 0.0239 (10) | 0.0310 (12) | 0.0107 (9) | 0.0132 (9) | 0.0137 (9) |
| C23 | 0.0309 (12) | 0.0341 (12) | 0.0278 (12) | 0.0045 (10) | 0.0122 (10) | 0.0068 (10) |
| C24 | 0.0258 (12) | 0.0367 (13) | 0.0384 (14) | 0.0034 (10) | 0.0134 (10) | 0.0147 (11) |
| Zr1 | 0.01462 (14) | 0.02394 (15) | 0.03837 (19) | 0.00405 (11) | 0.00458 (12) | 0.01715 (13) |
| F1 | 0.0390 (8) | 0.0355 (8) | 0.0507 (9) | 0.0129 (6) | 0.0198 (7) | 0.0209 (7) |
| F2 | 0.0256 (7) | 0.0188 (6) | 0.0479 (9) | 0.0022 (5) | 0.0034 (6) | 0.0104 (6) |
| F3 | 0.0207 (6) | 0.0230 (6) | 0.0511 (9) | 0.0052 (5) | −0.0042 (6) | 0.0081 (6) |
| O1 | 0.041 (2) | 0.0389 (19) | 0.0244 (17) | 0.0009 (14) | 0.0117 (14) | 0.0001 (13) |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Geometric parameters (Å, º)
| Cu1—N1 | 2.0208 (16) | C12—H12B | 0.9800 |
| Cu1—N2 | 2.0348 (17) | C12—H12C | 0.9800 |
| Cu1—N3 | 2.0123 (17) | C13—C14 | 1.392 (3) |
| Cu1—N4 | 2.0616 (18) | C13—C23 | 1.490 (3) |
| N1—C1 | 1.346 (3) | C14—H14 | 0.9500 |
| N1—C5 | 1.354 (2) | C14—C15 | 1.379 (4) |
| C1—C2 | 1.390 (3) | C15—H15 | 0.9500 |
| C1—C11 | 1.502 (3) | C15—C16 | 1.379 (4) |
| N2—C6 | 1.355 (2) | C16—H16 | 0.9500 |
| N2—C10 | 1.346 (3) | C16—C17 | 1.392 (3) |
| C2—H2 | 0.9500 | C17—C18 | 1.481 (3) |
| C2—C3 | 1.380 (3) | C18—C19 | 1.390 (3) |
| N3—C13 | 1.344 (3) | C19—H19 | 0.9500 |
| N3—C17 | 1.356 (3) | C19—C20 | 1.379 (4) |
| C3—H3 | 0.9500 | C20—H20 | 0.9500 |
| C3—C4 | 1.385 (3) | C20—C21 | 1.377 (4) |
| N4—C18 | 1.355 (3) | C21—H21 | 0.9500 |
| N4—C22 | 1.347 (3) | C21—C22 | 1.388 (3) |
| C4—H4 | 0.9500 | C22—C24 | 1.500 (3) |
| C4—C5 | 1.388 (3) | C23—H23A | 0.9800 |
| C5—C6 | 1.485 (3) | C23—H23B | 0.9800 |
| C6—C7 | 1.391 (3) | C23—H23C | 0.9800 |
| C7—H7 | 0.9500 | C24—H24A | 0.9800 |
| C7—C8 | 1.384 (3) | C24—H24B | 0.9800 |
| C8—H8 | 0.9500 | C24—H24C | 0.9800 |
| C8—C9 | 1.378 (3) | Zr1—F1 | 2.0113 (15) |
| C9—H9 | 0.9500 | Zr1—F1i | 2.0113 (15) |
| C9—C10 | 1.396 (3) | Zr1—F2i | 2.0183 (12) |
| C10—C12 | 1.503 (3) | Zr1—F2 | 2.0183 (12) |
| C11—H11A | 0.9800 | Zr1—F3 | 1.9955 (13) |
| C11—H11B | 0.9800 | Zr1—F3i | 1.9955 (13) |
| C11—H11C | 0.9800 | O1—H1A | 0.8699 |
| C12—H12A | 0.9800 | O1—H1B | 0.8703 |
| N1—Cu1—N2 | 81.40 (7) | H12B—C12—H12C | 109.5 |
| N1—Cu1—N4 | 116.24 (7) | N3—C13—C14 | 120.9 (2) |
| N2—Cu1—N4 | 120.45 (7) | N3—C13—C23 | 116.93 (18) |
| N3—Cu1—N1 | 136.29 (7) | C14—C13—C23 | 122.2 (2) |
| N3—Cu1—N2 | 126.16 (7) | C13—C14—H14 | 120.2 |
| N3—Cu1—N4 | 81.05 (7) | C15—C14—C13 | 119.6 (2) |
| C1—N1—Cu1 | 127.37 (14) | C15—C14—H14 | 120.2 |
| C1—N1—C5 | 119.06 (17) | C14—C15—H15 | 120.2 |
| C5—N1—Cu1 | 112.61 (13) | C14—C15—C16 | 119.7 (2) |
| N1—C1—C2 | 121.76 (18) | C16—C15—H15 | 120.2 |
| N1—C1—C11 | 116.67 (19) | C15—C16—H16 | 120.7 |
| C2—C1—C11 | 121.55 (19) | C15—C16—C17 | 118.7 (2) |
| C6—N2—Cu1 | 112.50 (13) | C17—C16—H16 | 120.7 |
| C10—N2—Cu1 | 128.32 (14) | N3—C17—C16 | 121.5 (2) |
| C10—N2—C6 | 119.07 (17) | N3—C17—C18 | 115.35 (18) |
| C1—C2—H2 | 120.5 | C16—C17—C18 | 123.1 (2) |
| C3—C2—C1 | 119.10 (19) | N4—C18—C17 | 115.47 (18) |
| C3—C2—H2 | 120.5 | N4—C18—C19 | 121.7 (2) |
| C13—N3—Cu1 | 125.56 (14) | C19—C18—C17 | 122.8 (2) |
| C13—N3—C17 | 119.66 (18) | C18—C19—H19 | 120.6 |
| C17—N3—Cu1 | 114.36 (14) | C20—C19—C18 | 118.8 (2) |
| C2—C3—H3 | 120.3 | C20—C19—H19 | 120.6 |
| C2—C3—C4 | 119.43 (19) | C19—C20—H20 | 120.3 |
| C4—C3—H3 | 120.3 | C21—C20—C19 | 119.4 (2) |
| C18—N4—Cu1 | 113.01 (14) | C21—C20—H20 | 120.3 |
| C22—N4—Cu1 | 127.62 (15) | C20—C21—H21 | 120.0 |
| C22—N4—C18 | 119.34 (19) | C20—C21—C22 | 119.9 (2) |
| C3—C4—H4 | 120.5 | C22—C21—H21 | 120.0 |
| C3—C4—C5 | 118.94 (18) | N4—C22—C21 | 120.8 (2) |
| C5—C4—H4 | 120.5 | N4—C22—C24 | 116.8 (2) |
| N1—C5—C4 | 121.67 (18) | C21—C22—C24 | 122.3 (2) |
| N1—C5—C6 | 115.42 (17) | C13—C23—H23A | 109.5 |
| C4—C5—C6 | 122.90 (17) | C13—C23—H23B | 109.5 |
| N2—C6—C5 | 115.28 (16) | C13—C23—H23C | 109.5 |
| N2—C6—C7 | 121.72 (18) | H23A—C23—H23B | 109.5 |
| C7—C6—C5 | 122.97 (18) | H23A—C23—H23C | 109.5 |
| C6—C7—H7 | 120.6 | H23B—C23—H23C | 109.5 |
| C8—C7—C6 | 118.70 (19) | C22—C24—H24A | 109.5 |
| C8—C7—H7 | 120.6 | C22—C24—H24B | 109.5 |
| C7—C8—H8 | 120.1 | C22—C24—H24C | 109.5 |
| C9—C8—C7 | 119.71 (19) | H24A—C24—H24B | 109.5 |
| C9—C8—H8 | 120.1 | H24A—C24—H24C | 109.5 |
| C8—C9—H9 | 120.5 | H24B—C24—H24C | 109.5 |
| C8—C9—C10 | 119.0 (2) | F1i—Zr1—F1 | 180.00 (9) |
| C10—C9—H9 | 120.5 | F1—Zr1—F2i | 89.69 (6) |
| N2—C10—C9 | 121.56 (19) | F1—Zr1—F2 | 90.31 (6) |
| N2—C10—C12 | 116.3 (2) | F1i—Zr1—F2 | 89.69 (6) |
| C9—C10—C12 | 122.1 (2) | F1i—Zr1—F2i | 90.31 (6) |
| C1—C11—H11A | 109.5 | F2—Zr1—F2i | 180.0 |
| C1—C11—H11B | 109.5 | F3i—Zr1—F1 | 89.90 (6) |
| C1—C11—H11C | 109.5 | F3—Zr1—F1i | 89.90 (6) |
| H11A—C11—H11B | 109.5 | F3—Zr1—F1 | 90.10 (6) |
| H11A—C11—H11C | 109.5 | F3i—Zr1—F1i | 90.10 (6) |
| H11B—C11—H11C | 109.5 | F3i—Zr1—F2i | 89.43 (5) |
| C10—C12—H12A | 109.5 | F3—Zr1—F2 | 89.43 (5) |
| C10—C12—H12B | 109.5 | F3—Zr1—F2i | 90.57 (5) |
| C10—C12—H12C | 109.5 | F3i—Zr1—F2 | 90.57 (5) |
| H12A—C12—H12B | 109.5 | F3i—Zr1—F3 | 180.0 |
| H12A—C12—H12C | 109.5 | H1A—O1—H1B | 109.5 |
| Cu1—N1—C1—C2 | 166.88 (15) | C5—N1—C1—C2 | −1.0 (3) |
| Cu1—N1—C1—C11 | −14.7 (3) | C5—N1—C1—C11 | 177.37 (19) |
| Cu1—N1—C5—C4 | −167.35 (15) | C5—C6—C7—C8 | −173.85 (19) |
| Cu1—N1—C5—C6 | 14.0 (2) | C6—N2—C10—C9 | 0.5 (3) |
| Cu1—N2—C6—C5 | −9.8 (2) | C6—N2—C10—C12 | 179.4 (2) |
| Cu1—N2—C6—C7 | 172.18 (15) | C6—C7—C8—C9 | 0.2 (3) |
| Cu1—N2—C10—C9 | −175.40 (16) | C7—C8—C9—C10 | −3.8 (3) |
| Cu1—N2—C10—C12 | 3.4 (3) | C8—C9—C10—N2 | 3.6 (3) |
| Cu1—N3—C13—C14 | 170.26 (16) | C8—C9—C10—C12 | −175.2 (2) |
| Cu1—N3—C13—C23 | −10.0 (3) | C10—N2—C6—C5 | 173.65 (18) |
| Cu1—N3—C17—C16 | −171.70 (16) | C10—N2—C6—C7 | −4.4 (3) |
| Cu1—N3—C17—C18 | 9.7 (2) | C11—C1—C2—C3 | −179.0 (2) |
| Cu1—N4—C18—C17 | −0.4 (2) | C13—N3—C17—C16 | 1.3 (3) |
| Cu1—N4—C18—C19 | −179.26 (16) | C13—N3—C17—C18 | −177.34 (18) |
| Cu1—N4—C22—C21 | 177.41 (16) | C13—C14—C15—C16 | 1.1 (4) |
| Cu1—N4—C22—C24 | −1.9 (3) | C14—C15—C16—C17 | −1.7 (3) |
| N1—C1—C2—C3 | −0.7 (3) | C15—C16—C17—N3 | 0.5 (3) |
| N1—C5—C6—N2 | −2.7 (3) | C15—C16—C17—C18 | 179.0 (2) |
| N1—C5—C6—C7 | 175.24 (18) | C16—C17—C18—N4 | 175.31 (19) |
| C1—N1—C5—C4 | 2.3 (3) | C16—C17—C18—C19 | −5.9 (3) |
| C1—N1—C5—C6 | −176.43 (18) | C17—N3—C13—C14 | −1.9 (3) |
| C1—C2—C3—C4 | 1.2 (3) | C17—N3—C13—C23 | 177.87 (19) |
| N2—C6—C7—C8 | 4.0 (3) | C17—C18—C19—C20 | −177.4 (2) |
| C2—C3—C4—C5 | 0.0 (3) | C18—N4—C22—C21 | −0.7 (3) |
| N3—C13—C14—C15 | 0.7 (3) | C18—N4—C22—C24 | 179.95 (19) |
| N3—C17—C18—N4 | −6.1 (3) | C18—C19—C20—C21 | −0.2 (3) |
| N3—C17—C18—C19 | 172.72 (19) | C19—C20—C21—C22 | −1.4 (4) |
| C3—C4—C5—N1 | −1.7 (3) | C20—C21—C22—N4 | 1.8 (3) |
| C3—C4—C5—C6 | 176.86 (19) | C20—C21—C22—C24 | −178.8 (2) |
| N4—C18—C19—C20 | 1.3 (3) | C22—N4—C18—C17 | 177.93 (18) |
| C4—C5—C6—N2 | 178.58 (18) | C22—N4—C18—C19 | −0.9 (3) |
| C4—C5—C6—C7 | −3.4 (3) | C23—C13—C14—C15 | −179.0 (2) |
Symmetry code: (i) −x, −y+2, −z+2.
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I). Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1B···F2 | 0.87 | 1.47 | 2.337 (4) | 177 |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Crystal data
| [Cu(C12H12N2)2]2[HfF6]·0.671H2O | Z = 1 |
| Mr = 1168.58 | F(000) = 583 |
| Triclinic, P1 | Dx = 1.745 Mg m−3 |
| a = 8.5737 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 10.7967 (2) Å | Cell parameters from 31642 reflections |
| c = 13.0183 (2) Å | θ = 2.2–33.9° |
| α = 103.273 (1)° | µ = 3.35 mm−1 |
| β = 103.662 (1)° | T = 100 K |
| γ = 98.785 (1)° | Plate, clear orangish red |
| V = 1112.07 (3) Å3 | 0.3 × 0.17 × 0.08 mm |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Data collection
| Rigaku Saturn724+ (2x2 bin mode) diffractometer | 8003 independent reflections |
| Radiation source: Rotating Anode, Rotating Anode | 7235 reflections with I > 2σ(I) |
| Confocal monochromator | Rint = 0.032 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 33.9°, θmin = 2.0° |
| profile data from ω–scans | h = −13→13 |
| Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2020) | k = −16→16 |
| Tmin = 0.433, Tmax = 1.000 | l = −19→19 |
| 40796 measured reflections |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
| wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.029P)2 + 0.1688P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max = 0.002 |
| 8003 reflections | Δρmax = 0.48 e Å−3 |
| 312 parameters | Δρmin = −0.73 e Å−3 |
| 0 restraints |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Special details
| 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. |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Cu1 | 0.30255 (2) | 0.35382 (2) | 0.69812 (2) | 0.01849 (4) | |
| N1 | 0.49323 (15) | 0.36487 (11) | 0.82812 (9) | 0.0157 (2) | |
| C1 | 0.55897 (18) | 0.26589 (14) | 0.85279 (11) | 0.0184 (3) | |
| N2 | 0.33991 (15) | 0.54691 (12) | 0.77752 (10) | 0.0187 (2) | |
| C2 | 0.70930 (18) | 0.28901 (15) | 0.93195 (12) | 0.0200 (3) | |
| H2 | 0.752847 | 0.218202 | 0.949428 | 0.024* | |
| N3 | 0.08393 (15) | 0.23090 (11) | 0.61730 (10) | 0.0173 (2) | |
| C3 | 0.79431 (18) | 0.41592 (16) | 0.98475 (12) | 0.0218 (3) | |
| H3 | 0.898138 | 0.433093 | 1.037654 | 0.026* | |
| N4 | 0.33880 (17) | 0.29739 (13) | 0.54432 (11) | 0.0211 (2) | |
| C4 | 0.72716 (18) | 0.51810 (15) | 0.96003 (12) | 0.0206 (3) | |
| H4 | 0.784176 | 0.605989 | 0.995319 | 0.025* | |
| C5 | 0.57452 (16) | 0.48929 (13) | 0.88246 (11) | 0.0157 (2) | |
| C6 | 0.48691 (17) | 0.59126 (13) | 0.85563 (11) | 0.0159 (2) | |
| C7 | 0.54737 (18) | 0.72313 (14) | 0.90906 (12) | 0.0196 (3) | |
| H7 | 0.653940 | 0.753278 | 0.959803 | 0.024* | |
| C8 | 0.4488 (2) | 0.81009 (14) | 0.88679 (13) | 0.0222 (3) | |
| H8 | 0.487246 | 0.900700 | 0.922570 | 0.027* | |
| C9 | 0.2948 (2) | 0.76402 (15) | 0.81239 (13) | 0.0240 (3) | |
| H9 | 0.223979 | 0.821769 | 0.799097 | 0.029* | |
| C10 | 0.24454 (19) | 0.63174 (15) | 0.75708 (14) | 0.0247 (3) | |
| C11 | 0.4606 (2) | 0.13042 (15) | 0.79400 (14) | 0.0287 (3) | |
| H11A | 0.374850 | 0.108709 | 0.829125 | 0.043* | |
| H11B | 0.533164 | 0.068661 | 0.797454 | 0.043* | |
| H11C | 0.409525 | 0.125179 | 0.716942 | 0.043* | |
| C12 | 0.0821 (3) | 0.5765 (2) | 0.6712 (2) | 0.0523 (7) | |
| H12A | 0.100542 | 0.546189 | 0.599023 | 0.078* | |
| H12B | 0.017881 | 0.644134 | 0.669871 | 0.078* | |
| H12C | 0.021671 | 0.503124 | 0.688661 | 0.078* | |
| C13 | −0.03848 (19) | 0.20159 (14) | 0.66175 (13) | 0.0217 (3) | |
| C14 | −0.1938 (2) | 0.13117 (16) | 0.59615 (16) | 0.0294 (3) | |
| H14 | −0.279577 | 0.111864 | 0.628577 | 0.035* | |
| C15 | −0.2222 (2) | 0.08956 (17) | 0.48344 (16) | 0.0331 (4) | |
| H15 | −0.328350 | 0.042958 | 0.437675 | 0.040* | |
| C16 | −0.0952 (2) | 0.11615 (16) | 0.43760 (14) | 0.0279 (3) | |
| H16 | −0.112119 | 0.086313 | 0.360420 | 0.034* | |
| C17 | 0.05785 (19) | 0.18743 (14) | 0.50662 (12) | 0.0196 (3) | |
| C18 | 0.2030 (2) | 0.21916 (14) | 0.46699 (12) | 0.0215 (3) | |
| C19 | 0.2026 (3) | 0.16910 (16) | 0.35783 (13) | 0.0293 (3) | |
| H19 | 0.105673 | 0.115925 | 0.304363 | 0.035* | |
| C20 | 0.3465 (3) | 0.19880 (19) | 0.32964 (15) | 0.0370 (4) | |
| H20 | 0.349867 | 0.165652 | 0.256178 | 0.044* | |
| C21 | 0.4854 (3) | 0.27688 (19) | 0.40872 (16) | 0.0348 (4) | |
| H21 | 0.585269 | 0.296727 | 0.390165 | 0.042* | |
| C22 | 0.4786 (2) | 0.32667 (16) | 0.51629 (14) | 0.0265 (3) | |
| C23 | 0.0002 (2) | 0.24806 (18) | 0.78440 (14) | 0.0296 (3) | |
| H23A | 0.107943 | 0.232844 | 0.818103 | 0.044* | |
| H23B | −0.084204 | 0.200229 | 0.808740 | 0.044* | |
| H23C | 0.002281 | 0.341524 | 0.806634 | 0.044* | |
| C24 | 0.6249 (2) | 0.41315 (19) | 0.60455 (16) | 0.0332 (4) | |
| H24A | 0.593380 | 0.490705 | 0.642476 | 0.050* | |
| H24B | 0.711624 | 0.439691 | 0.571619 | 0.050* | |
| H24C | 0.665684 | 0.365753 | 0.657414 | 0.050* | |
| Hf1 | 0.000000 | 1.000000 | 1.000000 | 0.02373 (3) | |
| F1 | 0.09274 (14) | 0.99551 (11) | 0.87132 (10) | 0.0369 (2) | |
| F2 | −0.05307 (12) | 0.80472 (9) | 0.95921 (9) | 0.0312 (2) | |
| F3 | 0.22038 (12) | 1.00043 (10) | 1.09439 (10) | 0.0341 (2) | |
| O1 | −0.1061 (5) | 0.6264 (4) | 0.8063 (3) | 0.0338 (12) | 0.336 (5) |
| H1A | −0.014695 | 0.600372 | 0.823726 | 0.051* | 0.336 (5) |
| H1B | −0.097233 | 0.702606 | 0.850509 | 0.051* | 0.336 (5) |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.01904 (8) | 0.01683 (8) | 0.01581 (8) | 0.00282 (6) | −0.00052 (6) | 0.00350 (6) |
| N1 | 0.0167 (5) | 0.0146 (5) | 0.0154 (5) | 0.0047 (4) | 0.0031 (4) | 0.0040 (4) |
| C1 | 0.0211 (6) | 0.0187 (6) | 0.0178 (6) | 0.0077 (5) | 0.0063 (5) | 0.0067 (5) |
| N2 | 0.0177 (5) | 0.0158 (5) | 0.0213 (6) | 0.0045 (4) | 0.0018 (4) | 0.0058 (4) |
| C2 | 0.0208 (6) | 0.0249 (7) | 0.0215 (7) | 0.0115 (5) | 0.0098 (5) | 0.0119 (5) |
| N3 | 0.0197 (5) | 0.0142 (5) | 0.0161 (5) | 0.0046 (4) | 0.0013 (4) | 0.0035 (4) |
| C3 | 0.0148 (6) | 0.0293 (7) | 0.0227 (7) | 0.0063 (5) | 0.0039 (5) | 0.0105 (6) |
| N4 | 0.0247 (6) | 0.0214 (6) | 0.0215 (6) | 0.0094 (5) | 0.0074 (5) | 0.0106 (5) |
| C4 | 0.0159 (6) | 0.0207 (7) | 0.0214 (7) | 0.0025 (5) | 0.0015 (5) | 0.0032 (5) |
| C5 | 0.0144 (6) | 0.0165 (6) | 0.0169 (6) | 0.0044 (4) | 0.0051 (5) | 0.0044 (5) |
| C6 | 0.0159 (6) | 0.0154 (6) | 0.0180 (6) | 0.0043 (4) | 0.0063 (5) | 0.0054 (5) |
| C7 | 0.0200 (6) | 0.0163 (6) | 0.0220 (7) | 0.0022 (5) | 0.0071 (5) | 0.0041 (5) |
| C8 | 0.0320 (8) | 0.0141 (6) | 0.0246 (7) | 0.0061 (5) | 0.0142 (6) | 0.0061 (5) |
| C9 | 0.0280 (7) | 0.0199 (7) | 0.0328 (8) | 0.0125 (6) | 0.0136 (6) | 0.0145 (6) |
| C10 | 0.0219 (7) | 0.0203 (7) | 0.0332 (8) | 0.0067 (5) | 0.0037 (6) | 0.0125 (6) |
| C11 | 0.0364 (9) | 0.0170 (7) | 0.0280 (8) | 0.0082 (6) | −0.0004 (7) | 0.0053 (6) |
| C12 | 0.0307 (10) | 0.0317 (10) | 0.0783 (16) | 0.0056 (8) | −0.0207 (10) | 0.0220 (10) |
| C13 | 0.0216 (7) | 0.0166 (6) | 0.0263 (7) | 0.0054 (5) | 0.0059 (6) | 0.0049 (5) |
| C14 | 0.0206 (7) | 0.0206 (7) | 0.0439 (10) | 0.0028 (6) | 0.0077 (7) | 0.0053 (7) |
| C15 | 0.0228 (7) | 0.0220 (8) | 0.0402 (10) | 0.0018 (6) | −0.0064 (7) | −0.0012 (7) |
| C16 | 0.0306 (8) | 0.0215 (7) | 0.0219 (7) | 0.0053 (6) | −0.0062 (6) | 0.0012 (6) |
| C17 | 0.0249 (7) | 0.0149 (6) | 0.0167 (6) | 0.0070 (5) | 0.0000 (5) | 0.0041 (5) |
| C18 | 0.0308 (8) | 0.0182 (6) | 0.0162 (6) | 0.0092 (6) | 0.0036 (6) | 0.0071 (5) |
| C19 | 0.0483 (10) | 0.0248 (8) | 0.0169 (7) | 0.0136 (7) | 0.0084 (7) | 0.0073 (6) |
| C20 | 0.0652 (13) | 0.0345 (9) | 0.0250 (8) | 0.0232 (9) | 0.0248 (9) | 0.0139 (7) |
| C21 | 0.0474 (11) | 0.0339 (9) | 0.0380 (10) | 0.0185 (8) | 0.0264 (9) | 0.0177 (8) |
| C22 | 0.0308 (8) | 0.0270 (8) | 0.0318 (8) | 0.0131 (6) | 0.0155 (7) | 0.0162 (6) |
| C23 | 0.0297 (8) | 0.0349 (9) | 0.0272 (8) | 0.0077 (7) | 0.0141 (7) | 0.0077 (7) |
| C24 | 0.0258 (8) | 0.0366 (9) | 0.0427 (10) | 0.0071 (7) | 0.0154 (7) | 0.0154 (8) |
| Hf1 | 0.01372 (4) | 0.02043 (5) | 0.04096 (6) | 0.00568 (3) | 0.00576 (3) | 0.01683 (4) |
| F1 | 0.0372 (6) | 0.0331 (6) | 0.0534 (7) | 0.0157 (5) | 0.0229 (5) | 0.0215 (5) |
| F2 | 0.0218 (5) | 0.0179 (4) | 0.0518 (6) | 0.0039 (3) | 0.0038 (4) | 0.0125 (4) |
| F3 | 0.0193 (4) | 0.0218 (5) | 0.0541 (7) | 0.0064 (4) | −0.0039 (4) | 0.0100 (4) |
| O1 | 0.036 (2) | 0.035 (2) | 0.0227 (19) | 0.0034 (16) | 0.0075 (15) | −0.0029 (15) |
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Geometric parameters (Å, º)
| Cu1—N1 | 2.0229 (12) | C12—H12B | 0.9800 |
| Cu1—N2 | 2.0414 (12) | C12—H12C | 0.9800 |
| Cu1—N3 | 2.0121 (12) | C13—C14 | 1.391 (2) |
| Cu1—N4 | 2.0659 (13) | C13—C23 | 1.497 (2) |
| N1—C1 | 1.3487 (17) | C14—H14 | 0.9500 |
| N1—C5 | 1.3548 (18) | C14—C15 | 1.382 (3) |
| C1—C2 | 1.393 (2) | C15—H15 | 0.9500 |
| C1—C11 | 1.497 (2) | C15—C16 | 1.384 (3) |
| N2—C6 | 1.3558 (18) | C16—H16 | 0.9500 |
| N2—C10 | 1.3476 (19) | C16—C17 | 1.392 (2) |
| C2—H2 | 0.9500 | C17—C18 | 1.479 (2) |
| C2—C3 | 1.381 (2) | C18—C19 | 1.399 (2) |
| N3—C13 | 1.344 (2) | C19—H19 | 0.9500 |
| N3—C17 | 1.3607 (19) | C19—C20 | 1.381 (3) |
| C3—H3 | 0.9500 | C20—H20 | 0.9500 |
| C3—C4 | 1.386 (2) | C20—C21 | 1.380 (3) |
| N4—C18 | 1.356 (2) | C21—H21 | 0.9500 |
| N4—C22 | 1.347 (2) | C21—C22 | 1.399 (2) |
| C4—H4 | 0.9500 | C22—C24 | 1.495 (3) |
| C4—C5 | 1.3915 (19) | C23—H23A | 0.9800 |
| C5—C6 | 1.4845 (19) | C23—H23B | 0.9800 |
| C6—C7 | 1.389 (2) | C23—H23C | 0.9800 |
| C7—H7 | 0.9500 | C24—H24A | 0.9800 |
| C7—C8 | 1.390 (2) | C24—H24B | 0.9800 |
| C8—H8 | 0.9500 | C24—H24C | 0.9800 |
| C8—C9 | 1.380 (2) | Hf1—F1i | 2.0111 (11) |
| C9—H9 | 0.9500 | Hf1—F1 | 2.0111 (11) |
| C9—C10 | 1.392 (2) | Hf1—F2i | 2.0033 (9) |
| C10—C12 | 1.500 (2) | Hf1—F2 | 2.0033 (9) |
| C11—H11A | 0.9800 | Hf1—F3i | 1.9945 (10) |
| C11—H11B | 0.9800 | Hf1—F3 | 1.9945 (10) |
| C11—H11C | 0.9800 | O1—H1A | 0.8700 |
| C12—H12A | 0.9800 | O1—H1B | 0.8699 |
| N1—Cu1—N2 | 81.22 (5) | H12B—C12—H12C | 109.5 |
| N1—Cu1—N4 | 116.52 (5) | N3—C13—C14 | 121.15 (15) |
| N2—Cu1—N4 | 120.35 (5) | N3—C13—C23 | 116.98 (14) |
| N3—Cu1—N1 | 136.20 (5) | C14—C13—C23 | 121.87 (15) |
| N3—Cu1—N2 | 126.39 (5) | C13—C14—H14 | 120.3 |
| N3—Cu1—N4 | 80.94 (5) | C15—C14—C13 | 119.42 (17) |
| C1—N1—Cu1 | 127.24 (10) | C15—C14—H14 | 120.3 |
| C1—N1—C5 | 119.15 (12) | C14—C15—H15 | 120.2 |
| C5—N1—Cu1 | 112.66 (9) | C14—C15—C16 | 119.63 (15) |
| N1—C1—C2 | 121.40 (13) | C16—C15—H15 | 120.2 |
| N1—C1—C11 | 116.99 (13) | C15—C16—H16 | 120.6 |
| C2—C1—C11 | 121.58 (13) | C15—C16—C17 | 118.80 (15) |
| C6—N2—Cu1 | 112.15 (9) | C17—C16—H16 | 120.6 |
| C10—N2—Cu1 | 128.64 (10) | N3—C17—C16 | 121.28 (15) |
| C10—N2—C6 | 119.08 (13) | N3—C17—C18 | 115.28 (13) |
| C1—C2—H2 | 120.3 | C16—C17—C18 | 123.44 (14) |
| C3—C2—C1 | 119.31 (13) | N4—C18—C17 | 115.53 (13) |
| C3—C2—H2 | 120.3 | N4—C18—C19 | 121.93 (16) |
| C13—N3—Cu1 | 125.50 (10) | C19—C18—C17 | 122.51 (15) |
| C13—N3—C17 | 119.68 (13) | C18—C19—H19 | 120.8 |
| C17—N3—Cu1 | 114.43 (10) | C20—C19—C18 | 118.41 (17) |
| C2—C3—H3 | 120.2 | C20—C19—H19 | 120.8 |
| C2—C3—C4 | 119.57 (13) | C19—C20—H20 | 120.2 |
| C4—C3—H3 | 120.2 | C21—C20—C19 | 119.67 (16) |
| C18—N4—Cu1 | 113.01 (10) | C21—C20—H20 | 120.2 |
| C22—N4—Cu1 | 127.54 (11) | C20—C21—H21 | 120.1 |
| C22—N4—C18 | 119.43 (14) | C20—C21—C22 | 119.72 (18) |
| C3—C4—H4 | 120.7 | C22—C21—H21 | 120.1 |
| C3—C4—C5 | 118.63 (13) | N4—C22—C21 | 120.82 (17) |
| C5—C4—H4 | 120.7 | N4—C22—C24 | 117.38 (15) |
| N1—C5—C4 | 121.89 (13) | C21—C22—C24 | 121.80 (16) |
| N1—C5—C6 | 115.22 (12) | C13—C23—H23A | 109.5 |
| C4—C5—C6 | 122.86 (13) | C13—C23—H23B | 109.5 |
| N2—C6—C5 | 115.48 (12) | C13—C23—H23C | 109.5 |
| N2—C6—C7 | 121.72 (13) | H23A—C23—H23B | 109.5 |
| C7—C6—C5 | 122.77 (13) | H23A—C23—H23C | 109.5 |
| C6—C7—H7 | 120.7 | H23B—C23—H23C | 109.5 |
| C6—C7—C8 | 118.65 (14) | C22—C24—H24A | 109.5 |
| C8—C7—H7 | 120.7 | C22—C24—H24B | 109.5 |
| C7—C8—H8 | 120.2 | C22—C24—H24C | 109.5 |
| C9—C8—C7 | 119.60 (14) | H24A—C24—H24B | 109.5 |
| C9—C8—H8 | 120.2 | H24A—C24—H24C | 109.5 |
| C8—C9—H9 | 120.5 | H24B—C24—H24C | 109.5 |
| C8—C9—C10 | 119.06 (14) | F1i—Hf1—F1 | 180.00 (7) |
| C10—C9—H9 | 120.5 | F2i—Hf1—F1 | 89.79 (5) |
| N2—C10—C9 | 121.66 (14) | F2—Hf1—F1 | 90.21 (5) |
| N2—C10—C12 | 116.62 (15) | F2—Hf1—F1i | 89.79 (5) |
| C9—C10—C12 | 121.71 (15) | F2i—Hf1—F1i | 90.21 (5) |
| C1—C11—H11A | 109.5 | F2—Hf1—F2i | 180.0 |
| C1—C11—H11B | 109.5 | F3—Hf1—F1 | 90.15 (5) |
| C1—C11—H11C | 109.5 | F3—Hf1—F1i | 89.85 (5) |
| H11A—C11—H11B | 109.5 | F3i—Hf1—F1i | 90.15 (5) |
| H11A—C11—H11C | 109.5 | F3i—Hf1—F1 | 89.85 (5) |
| H11B—C11—H11C | 109.5 | F3—Hf1—F2 | 89.27 (4) |
| C10—C12—H12A | 109.5 | F3i—Hf1—F2i | 89.26 (4) |
| C10—C12—H12B | 109.5 | F3i—Hf1—F2 | 90.74 (4) |
| C10—C12—H12C | 109.5 | F3—Hf1—F2i | 90.73 (4) |
| H12A—C12—H12B | 109.5 | F3—Hf1—F3i | 180.0 |
| H12A—C12—H12C | 109.5 | H1A—O1—H1B | 109.5 |
| Cu1—N1—C1—C2 | 167.25 (11) | C5—N1—C1—C2 | −0.7 (2) |
| Cu1—N1—C1—C11 | −14.69 (19) | C5—N1—C1—C11 | 177.33 (13) |
| Cu1—N1—C5—C4 | −167.08 (11) | C5—C6—C7—C8 | −173.20 (13) |
| Cu1—N1—C5—C6 | 14.67 (15) | C6—N2—C10—C9 | 1.4 (2) |
| Cu1—N2—C6—C5 | −11.14 (15) | C6—N2—C10—C12 | −178.95 (17) |
| Cu1—N2—C6—C7 | 171.02 (11) | C6—C7—C8—C9 | −0.3 (2) |
| Cu1—N2—C10—C9 | −173.90 (12) | C7—C8—C9—C10 | −3.1 (2) |
| Cu1—N2—C10—C12 | 5.7 (2) | C8—C9—C10—N2 | 2.6 (2) |
| Cu1—N3—C13—C14 | 170.17 (12) | C8—C9—C10—C12 | −176.97 (18) |
| Cu1—N3—C13—C23 | −9.84 (19) | C10—N2—C6—C5 | 172.79 (13) |
| Cu1—N3—C17—C16 | −171.27 (11) | C10—N2—C6—C7 | −5.1 (2) |
| Cu1—N3—C17—C18 | 9.88 (15) | C11—C1—C2—C3 | −179.25 (14) |
| Cu1—N4—C18—C17 | −1.01 (15) | C13—N3—C17—C16 | 2.0 (2) |
| Cu1—N4—C18—C19 | −179.23 (12) | C13—N3—C17—C18 | −176.87 (12) |
| Cu1—N4—C22—C21 | 177.63 (12) | C13—C14—C15—C16 | 1.3 (3) |
| Cu1—N4—C22—C24 | −2.0 (2) | C14—C15—C16—C17 | −1.6 (2) |
| N1—C1—C2—C3 | −1.3 (2) | C15—C16—C17—N3 | 0.0 (2) |
| N1—C5—C6—N2 | −2.27 (18) | C15—C16—C17—C18 | 178.70 (15) |
| N1—C5—C6—C7 | 175.55 (13) | C16—C17—C18—N4 | 175.36 (14) |
| C1—N1—C5—C4 | 2.6 (2) | C16—C17—C18—C19 | −6.4 (2) |
| C1—N1—C5—C6 | −175.69 (12) | C17—N3—C13—C14 | −2.3 (2) |
| C1—C2—C3—C4 | 1.5 (2) | C17—N3—C13—C23 | 177.72 (13) |
| N2—C6—C7—C8 | 4.5 (2) | C17—C18—C19—C20 | −176.75 (14) |
| C2—C3—C4—C5 | 0.3 (2) | C18—N4—C22—C21 | −0.3 (2) |
| N3—C13—C14—C15 | 0.6 (2) | C18—N4—C22—C24 | −179.92 (14) |
| N3—C17—C18—N4 | −5.82 (18) | C18—C19—C20—C21 | −0.4 (3) |
| N3—C17—C18—C19 | 172.39 (13) | C19—C20—C21—C22 | −0.9 (3) |
| C3—C4—C5—N1 | −2.3 (2) | C20—C21—C22—N4 | 1.3 (3) |
| C3—C4—C5—C6 | 175.77 (13) | C20—C21—C22—C24 | −179.15 (16) |
| N4—C18—C19—C20 | 1.4 (2) | C22—N4—C18—C17 | 177.22 (13) |
| C4—C5—C6—N2 | 179.49 (13) | C22—N4—C18—C19 | −1.0 (2) |
| C4—C5—C6—C7 | −2.7 (2) | C23—C13—C14—C15 | −179.34 (16) |
Symmetry code: (i) −x, −y+2, −z+2.
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II). Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1B—H1B···F2 | 0.87 | 1.50 | 2.328 (4) | 156 |
Coordination geometry (Å, °) of Cu(dmbpy)2+ cations in (I)
| N—Cu—N | N—Cu | Cu—N | N—Cu—N |
| N1—Cu1—N2 | 2.0208 (16) | 2.0348 (17) | 81.40 (7) |
| N1—Cu1—N3 | 2.0123 (17) | 136.29 (7) | |
| N1—Cu1—N4 | 2.0616 (18) | 116.24 (7) | |
| N2—Cu1—N3 | 126.17 (7) | ||
| N2—Cu1—N4 | 120.45 (7) | ||
| N3—Cu1—N4 | 81.05 (7) |
Bond distances (Å) of ZrF62– in (I)
| Zr—F | Distance (Å) |
| Zr—F1 | 2.0113 (15) |
| Zr—F2 | 2.0183 (12) |
| Zr—F3 | 1.9955 (13) |
Hydrogen-bond geometry (Å, °) for (I)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1B···F2 | 0.870 (3) | 1.4674 (14) | 2.337 (3) | 177.1 (2) |
Coordination geometry (Å, °) of Cu(dmbpy)2+ cations in (II)
| N—Cu—N | N—Cu | Cu—N | N—Cu—N |
| N1—Cu1—N2 | 2.0229 (12) | 2.0414 (12) | 81.22 (5) |
| N1—Cu1—N3 | 2.0121 (12) | 136.20 (5) | |
| N1—Cu1—N4 | 2.0659 (13) | 116.52 (5) | |
| N2—Cu1—N3 | 126.39 (5) | ||
| N2—Cu1—N4 | 120.35 (5) | ||
| N3—Cu1—N4 | 80.94 (5) |
Bond distances (Å) of HfF62– in (II)
| Hf—F | Distance (Å) |
| Hf—F1 | 2.0111 (11) |
| Hf—F2 | 2.0033 (9) |
| Hf—F3 | 1.9945 (10) |
Hydrogen-bond geometry (Å, °) for (II)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1B···F2 | 0.870 (4) | 1.5048 (11) | 2.328 (4) | 156.4 (3) |
Funding Statement
This work was funded by National Science Foundation grant No. DMR-1904701.
References
- Adman, E. T., Stenkamp, R. E., Sieker, L. C. & Jensen, L. H. (1978). J. Mol. Biol. 123, 35–47. [DOI] [PubMed]
- Bozic-Weber, B., Chaurin, V., Constable, E. C., Housecroft, C. E., Meuwly, M., Neuburger, M., Rudd, J. A., Schönhofer, E. & Siegfried, L. (2012). Dalton Trans. 41, 14157–14169. [DOI] [PubMed]
- Burke, P. J., McMillin, D. R. & Robinson, W. R. (1980). Inorg. Chem. 19, 1211–1214.
- Colman, P. M., Freeman, H. C., Guss, J. M., Murata, M., Norris, V. A., Ramshaw, J. A. M. & Venkatappa, M. P. (1978). Nature, 272, 319–324.
- Cui, G. H., Li, J. R., Gao, D. & Ng, S. W. (2005). Acta Cryst. E61, m72–m73.
- Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
- Gautier, R., Norquist, A. J. & Poeppelmeier, K. R. (2012). Cryst. Growth Des. 12, 6267–6271.
- Halasyamani, P. S. (2004). Chem. Mater. 16, 3586–3592.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Harrison, W. T. A., Nenoff, T. M., Gier, T. E. & Stucky, G. D. (1993). Inorg. Chem. 32, 2437–2441.
- Itoh, S., Kishikawa, N., Suzuki, T. & Takagi, H. D. (2005). Dalton Trans. pp. 1066–1078. [DOI] [PubMed]
- Kunz, M. & Brown, I. D. (1995). J. Solid State Chem. 115, 395–406.
- Li, J., Yang, X., Yu, Z., Gurzadyan, G. G., Cheng, M., Zhang, F., Cong, J., Wang, W., Wang, H., Li, X., Kloo, L., Wang, M. & Sun, L. (2017). RSC Adv. 7, 4611–4615.
- McKenzie, E. D. (1971). Coord. Chem. Rev. 6, 187–216.
- Mei, C., Wang, J. & Shan, W. (2011). Jiegou Huaxue, 30, 1194.
- Nisbet, M. L., Pendleton, I. M., Nolis, G. M., Griffith, K. J., Schrier, J., Cabana, J., Norquist, A. J. & Poeppelmeier, K. R. (2020). J. Am. Chem. Soc. 142, 7555–7566. [DOI] [PubMed]
- Nisbet, M. L., Wang, Y. & Poeppelmeier, K. R. (2021). Cryst. Growth Des. 21, 552–562.
- Okuniewski, A., Rosiak, D., Chojnacki, J. & Becker, B. (2015). Polyhedron, 90, 47–57.
- Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
- Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
- Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
- Vallee, B. L. & Williams, R. (1968). PNAS USA 59, 498–505. [DOI] [PMC free article] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989021007295/hb7977sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021007295/hb7977Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989021007295/hb7977IIsup3.hkl
Additional supporting information: crystallographic information; 3D view; checkCIF report