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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989021007295/hb7977sup1.cif
Contains datablocks I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989021007295/hb7977Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989021007295/hb7977IIsup3.hkl
Contains datablock II

CCDC references: 2096336; 2096335

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • Mean [sigma](C-C) = 0.002 Å
  • Disorder in solvent or counterion
  • R factor = 0.035
  • wR factor = 0.088
  • Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT415_ALERT_2_A Short Inter D-H..H-X H1A ..H12B . 1.66 Ang. x,y,z = 1_555 Check
Alert level B PLAT415_ALERT_2_B Short Inter D-H..H-X H1A ..H12C . 1.92 Ang. x,y,z = 1_555 Check PLAT420_ALERT_2_B D-H Bond Without Acceptor O1 --H1A . Please Check
Alert level C PLAT077_ALERT_4_C Unitcell Contains Non-integer Number of Atoms .. Please Check PLAT220_ALERT_2_C NonSolvent Resd 1 C Ueq(max)/Ueq(min) Range 3.2 Ratio PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 2 Report PLAT977_ALERT_2_C Check Negative Difference Density on H23B -0.36 eA-3
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT063_ALERT_4_G Crystal Size Possibly too Large for Beam Size .. 0.98 mm PLAT068_ALERT_1_G Reported F000 Differs from Calcd (or Missing)... Please Check PLAT233_ALERT_4_G Hirshfeld (M-X Solvent) Zr1 --F2 . 6.0 s.u. PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd 3 ) 100% Note PLAT304_ALERT_4_G Non-Integer Number of Atoms in ..... (Resd 3 ) 1.70 Check PLAT432_ALERT_2_G Short Inter X...Y Contact O1 ..C12 2.83 Ang. x,y,z = 1_555 Check PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 3 Note H2 O PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 1323 Note PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 4 Note PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 7 Info
1 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 12 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 7 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Alert level B PLAT415_ALERT_2_B Short Inter D-H..H-X H3 ..H1A . 1.99 Ang. 1-x,1-y,2-z = 2_667 Check PLAT415_ALERT_2_B Short Inter D-H..H-X H12C ..H1A . 1.95 Ang. x,y,z = 1_555 Check
Alert level C PLAT077_ALERT_4_C Unitcell Contains Non-integer Number of Atoms .. Please Check PLAT220_ALERT_2_C NonSolvent Resd 1 C Ueq(max)/Ueq(min) Range 3.3 Ratio
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT042_ALERT_1_G Calc. and Reported Moiety Formula Strings Differ Please Check PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note) 0.001 Degree PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd 3 ) 100% Note PLAT432_ALERT_2_G Short Inter X...Y Contact O1 ..C12 2.68 Ang. x,y,z = 1_555 Check PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 3 Note H2 O PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 967 Note PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 2 Note PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 11 Info
0 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT2014/5 (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).

Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate (I) top
Crystal data top
[Cu(C12H12N2)2]2[ZrF6]·1.134H2OZ = 1
Mr = 1089.61F(000) = 555
Triclinic, P1Dx = 1.621 Mg m3
a = 8.6219 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.8064 (3) ÅCell parameters from 10429 reflections
c = 12.9992 (4) Åθ = 2.2–30.6°
α = 103.078 (2)°µ = 1.25 mm1
β = 104.013 (3)°T = 100 K
γ = 98.863 (2)°Needle, clear orangish red
V = 1116.33 (6) Å30.98 × 0.13 × 0.05 mm
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
5673 independent reflections
Radiation source: Rotating Anode, Rotating Anode4588 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.039
Detector resolution: 28.5714 pixels mm-1θmax = 30.9°, θmin = 2.0°
profile data from ω–scansh = 1111
Absorption correction: gaussian
(CrysAlisPro; Rigaku OD, 2020)
k = 1415
Tmin = 0.376, Tmax = 1.000l = 1618
16573 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.035H-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 reflectionsΔρmax = 0.59 e Å3
312 parametersΔρmin = 0.54 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cu10.30548 (3)0.35420 (2)0.69756 (2)0.02018 (8)
N10.4953 (2)0.36543 (16)0.82845 (13)0.0174 (3)
C10.5623 (3)0.26739 (19)0.85293 (17)0.0207 (4)
N20.3424 (2)0.54652 (16)0.77601 (14)0.0195 (3)
C20.7120 (3)0.2905 (2)0.93235 (17)0.0212 (4)
H20.7566890.2198580.9489740.025*
N30.0873 (2)0.23159 (15)0.61598 (14)0.0190 (3)
C30.7947 (3)0.4174 (2)0.98671 (17)0.0230 (4)
H30.8981280.4350221.0402440.028*
N40.3423 (2)0.29725 (16)0.54450 (14)0.0211 (4)
C40.7257 (2)0.5187 (2)0.96256 (17)0.0210 (4)
H40.7809620.6066560.9992350.025*
C50.5745 (2)0.48980 (18)0.88392 (16)0.0160 (4)
C60.4869 (2)0.59134 (18)0.85644 (16)0.0166 (4)
C70.5450 (3)0.72317 (19)0.91116 (17)0.0202 (4)
H70.6497980.7536550.9640860.024*
C80.4472 (3)0.8091 (2)0.88699 (18)0.0237 (4)
H80.4845530.8995370.9231750.028*
C90.2955 (3)0.7627 (2)0.81024 (19)0.0251 (4)
H90.2244580.8198600.7961950.030*
C100.2476 (3)0.6306 (2)0.75341 (19)0.0247 (4)
C110.4653 (3)0.1315 (2)0.7923 (2)0.0325 (5)
H11A0.3744880.1105160.8229090.049*
H11B0.5365370.0697340.8004140.049*
H11C0.4216240.1255600.7139320.049*
C120.0897 (3)0.5747 (3)0.6624 (3)0.0505 (8)
H12A0.1138030.5427570.5925010.076*
H12B0.0270940.6425110.6567160.076*
H12C0.0253580.5025690.6787930.076*
C130.0357 (3)0.20374 (19)0.65956 (18)0.0222 (4)
C140.1902 (3)0.1331 (2)0.5926 (2)0.0299 (5)
H140.2766490.1147420.6241000.036*
C150.2168 (3)0.0899 (2)0.4802 (2)0.0331 (6)
H150.3222680.0429260.4337230.040*
C160.0896 (3)0.1152 (2)0.43557 (19)0.0286 (5)
H160.1052810.0841690.3585150.034*
C170.0622 (3)0.18722 (18)0.50567 (17)0.0209 (4)
C180.2076 (3)0.2182 (2)0.46677 (17)0.0228 (4)
C190.2083 (3)0.1682 (2)0.35859 (18)0.0297 (5)
H190.1120100.1143380.3047710.036*
C200.3513 (4)0.1981 (2)0.3308 (2)0.0356 (6)
H200.3548500.1649370.2574310.043*
C210.4888 (3)0.2767 (2)0.4105 (2)0.0344 (5)
H210.5886400.2963660.3925900.041*
C220.4816 (3)0.3270 (2)0.51691 (19)0.0260 (5)
C230.0017 (3)0.2514 (2)0.78169 (19)0.0308 (5)
H23A0.1061370.2325520.8167900.046*
H23B0.0858600.2073500.8054700.046*
H23C0.0093250.3455930.8031310.046*
C240.6265 (3)0.4151 (2)0.6065 (2)0.0325 (5)
H24A0.5935950.4920330.6434690.049*
H24B0.7132900.4423180.5743990.049*
H24C0.6671810.3683940.6602210.049*
Zr10.0000001.0000001.0000000.02476 (9)
F10.09081 (18)0.99518 (14)0.87082 (13)0.0384 (3)
F20.05473 (16)0.80350 (12)0.95926 (12)0.0322 (3)
F30.22027 (15)1.00042 (12)1.09456 (13)0.0346 (3)
O10.1062 (4)0.6247 (3)0.8061 (3)0.0369 (11)0.567 (6)
H1A0.0454740.6410360.7640810.055*0.567 (6)
H1B0.0874380.6928740.8617240.055*0.567 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02111 (14)0.01747 (13)0.01614 (13)0.00081 (10)0.00092 (10)0.00225 (9)
N10.0200 (8)0.0173 (8)0.0128 (8)0.0026 (7)0.0022 (6)0.0033 (6)
C10.0253 (10)0.0205 (10)0.0184 (10)0.0078 (8)0.0073 (8)0.0065 (8)
N20.0193 (8)0.0167 (8)0.0198 (9)0.0029 (7)0.0016 (7)0.0051 (6)
C20.0232 (10)0.0255 (10)0.0205 (10)0.0114 (8)0.0095 (8)0.0100 (8)
N30.0226 (9)0.0142 (8)0.0175 (8)0.0038 (7)0.0022 (7)0.0029 (6)
C30.0168 (9)0.0325 (11)0.0204 (10)0.0052 (8)0.0036 (8)0.0109 (9)
N40.0251 (9)0.0206 (8)0.0191 (9)0.0049 (7)0.0066 (7)0.0082 (7)
C40.0180 (10)0.0206 (10)0.0203 (10)0.0007 (8)0.0023 (8)0.0039 (8)
C50.0165 (9)0.0167 (9)0.0148 (9)0.0033 (7)0.0051 (7)0.0040 (7)
C60.0169 (9)0.0174 (9)0.0160 (9)0.0031 (7)0.0058 (7)0.0048 (7)
C70.0211 (10)0.0188 (9)0.0194 (10)0.0008 (8)0.0064 (8)0.0043 (8)
C80.0334 (12)0.0168 (9)0.0224 (11)0.0039 (9)0.0123 (9)0.0048 (8)
C90.0289 (11)0.0222 (10)0.0311 (12)0.0102 (9)0.0128 (9)0.0131 (9)
C100.0223 (10)0.0231 (10)0.0293 (12)0.0045 (8)0.0037 (9)0.0125 (9)
C110.0456 (14)0.0190 (10)0.0265 (12)0.0104 (10)0.0010 (10)0.0033 (9)
C120.0333 (14)0.0281 (13)0.073 (2)0.0029 (11)0.0190 (14)0.0192 (13)
C130.0230 (10)0.0173 (9)0.0245 (11)0.0053 (8)0.0055 (8)0.0031 (8)
C140.0234 (11)0.0204 (10)0.0428 (14)0.0019 (9)0.0087 (10)0.0057 (10)
C150.0247 (12)0.0217 (11)0.0382 (14)0.0006 (9)0.0059 (10)0.0017 (10)
C160.0335 (12)0.0195 (10)0.0227 (11)0.0050 (9)0.0054 (9)0.0007 (8)
C170.0276 (11)0.0148 (9)0.0170 (10)0.0062 (8)0.0007 (8)0.0044 (7)
C180.0315 (11)0.0196 (10)0.0166 (10)0.0070 (9)0.0021 (8)0.0077 (8)
C190.0473 (14)0.0226 (11)0.0180 (11)0.0090 (10)0.0056 (10)0.0065 (9)
C200.0602 (17)0.0319 (12)0.0245 (12)0.0163 (12)0.0222 (12)0.0118 (10)
C210.0465 (15)0.0345 (13)0.0357 (14)0.0170 (11)0.0239 (12)0.0178 (11)
C220.0304 (11)0.0239 (10)0.0310 (12)0.0107 (9)0.0132 (9)0.0137 (9)
C230.0309 (12)0.0341 (12)0.0278 (12)0.0045 (10)0.0122 (10)0.0068 (10)
C240.0258 (12)0.0367 (13)0.0384 (14)0.0034 (10)0.0134 (10)0.0147 (11)
Zr10.01462 (14)0.02394 (15)0.03837 (19)0.00405 (11)0.00458 (12)0.01715 (13)
F10.0390 (8)0.0355 (8)0.0507 (9)0.0129 (6)0.0198 (7)0.0209 (7)
F20.0256 (7)0.0188 (6)0.0479 (9)0.0022 (5)0.0034 (6)0.0104 (6)
F30.0207 (6)0.0230 (6)0.0511 (9)0.0052 (5)0.0042 (6)0.0081 (6)
O10.041 (2)0.0389 (19)0.0244 (17)0.0009 (14)0.0117 (14)0.0001 (13)
Geometric parameters (Å, º) top
Cu1—N12.0208 (16)C12—H12B0.9800
Cu1—N22.0348 (17)C12—H12C0.9800
Cu1—N32.0123 (17)C13—C141.392 (3)
Cu1—N42.0616 (18)C13—C231.490 (3)
N1—C11.346 (3)C14—H140.9500
N1—C51.354 (2)C14—C151.379 (4)
C1—C21.390 (3)C15—H150.9500
C1—C111.502 (3)C15—C161.379 (4)
N2—C61.355 (2)C16—H160.9500
N2—C101.346 (3)C16—C171.392 (3)
C2—H20.9500C17—C181.481 (3)
C2—C31.380 (3)C18—C191.390 (3)
N3—C131.344 (3)C19—H190.9500
N3—C171.356 (3)C19—C201.379 (4)
C3—H30.9500C20—H200.9500
C3—C41.385 (3)C20—C211.377 (4)
N4—C181.355 (3)C21—H210.9500
N4—C221.347 (3)C21—C221.388 (3)
C4—H40.9500C22—C241.500 (3)
C4—C51.388 (3)C23—H23A0.9800
C5—C61.485 (3)C23—H23B0.9800
C6—C71.391 (3)C23—H23C0.9800
C7—H70.9500C24—H24A0.9800
C7—C81.384 (3)C24—H24B0.9800
C8—H80.9500C24—H24C0.9800
C8—C91.378 (3)Zr1—F12.0113 (15)
C9—H90.9500Zr1—F1i2.0113 (15)
C9—C101.396 (3)Zr1—F2i2.0183 (12)
C10—C121.503 (3)Zr1—F22.0183 (12)
C11—H11A0.9800Zr1—F31.9955 (13)
C11—H11B0.9800Zr1—F3i1.9955 (13)
C11—H11C0.9800O1—H1A0.8699
C12—H12A0.9800O1—H1B0.8703
N1—Cu1—N281.40 (7)H12B—C12—H12C109.5
N1—Cu1—N4116.24 (7)N3—C13—C14120.9 (2)
N2—Cu1—N4120.45 (7)N3—C13—C23116.93 (18)
N3—Cu1—N1136.29 (7)C14—C13—C23122.2 (2)
N3—Cu1—N2126.16 (7)C13—C14—H14120.2
N3—Cu1—N481.05 (7)C15—C14—C13119.6 (2)
C1—N1—Cu1127.37 (14)C15—C14—H14120.2
C1—N1—C5119.06 (17)C14—C15—H15120.2
C5—N1—Cu1112.61 (13)C14—C15—C16119.7 (2)
N1—C1—C2121.76 (18)C16—C15—H15120.2
N1—C1—C11116.67 (19)C15—C16—H16120.7
C2—C1—C11121.55 (19)C15—C16—C17118.7 (2)
C6—N2—Cu1112.50 (13)C17—C16—H16120.7
C10—N2—Cu1128.32 (14)N3—C17—C16121.5 (2)
C10—N2—C6119.07 (17)N3—C17—C18115.35 (18)
C1—C2—H2120.5C16—C17—C18123.1 (2)
C3—C2—C1119.10 (19)N4—C18—C17115.47 (18)
C3—C2—H2120.5N4—C18—C19121.7 (2)
C13—N3—Cu1125.56 (14)C19—C18—C17122.8 (2)
C13—N3—C17119.66 (18)C18—C19—H19120.6
C17—N3—Cu1114.36 (14)C20—C19—C18118.8 (2)
C2—C3—H3120.3C20—C19—H19120.6
C2—C3—C4119.43 (19)C19—C20—H20120.3
C4—C3—H3120.3C21—C20—C19119.4 (2)
C18—N4—Cu1113.01 (14)C21—C20—H20120.3
C22—N4—Cu1127.62 (15)C20—C21—H21120.0
C22—N4—C18119.34 (19)C20—C21—C22119.9 (2)
C3—C4—H4120.5C22—C21—H21120.0
C3—C4—C5118.94 (18)N4—C22—C21120.8 (2)
C5—C4—H4120.5N4—C22—C24116.8 (2)
N1—C5—C4121.67 (18)C21—C22—C24122.3 (2)
N1—C5—C6115.42 (17)C13—C23—H23A109.5
C4—C5—C6122.90 (17)C13—C23—H23B109.5
N2—C6—C5115.28 (16)C13—C23—H23C109.5
N2—C6—C7121.72 (18)H23A—C23—H23B109.5
C7—C6—C5122.97 (18)H23A—C23—H23C109.5
C6—C7—H7120.6H23B—C23—H23C109.5
C8—C7—C6118.70 (19)C22—C24—H24A109.5
C8—C7—H7120.6C22—C24—H24B109.5
C7—C8—H8120.1C22—C24—H24C109.5
C9—C8—C7119.71 (19)H24A—C24—H24B109.5
C9—C8—H8120.1H24A—C24—H24C109.5
C8—C9—H9120.5H24B—C24—H24C109.5
C8—C9—C10119.0 (2)F1i—Zr1—F1180.00 (9)
C10—C9—H9120.5F1—Zr1—F2i89.69 (6)
N2—C10—C9121.56 (19)F1—Zr1—F290.31 (6)
N2—C10—C12116.3 (2)F1i—Zr1—F289.69 (6)
C9—C10—C12122.1 (2)F1i—Zr1—F2i90.31 (6)
C1—C11—H11A109.5F2—Zr1—F2i180.0
C1—C11—H11B109.5F3i—Zr1—F189.90 (6)
C1—C11—H11C109.5F3—Zr1—F1i89.90 (6)
H11A—C11—H11B109.5F3—Zr1—F190.10 (6)
H11A—C11—H11C109.5F3i—Zr1—F1i90.10 (6)
H11B—C11—H11C109.5F3i—Zr1—F2i89.43 (5)
C10—C12—H12A109.5F3—Zr1—F289.43 (5)
C10—C12—H12B109.5F3—Zr1—F2i90.57 (5)
C10—C12—H12C109.5F3i—Zr1—F290.57 (5)
H12A—C12—H12B109.5F3i—Zr1—F3180.0
H12A—C12—H12C109.5H1A—O1—H1B109.5
Cu1—N1—C1—C2166.88 (15)C5—N1—C1—C21.0 (3)
Cu1—N1—C1—C1114.7 (3)C5—N1—C1—C11177.37 (19)
Cu1—N1—C5—C4167.35 (15)C5—C6—C7—C8173.85 (19)
Cu1—N1—C5—C614.0 (2)C6—N2—C10—C90.5 (3)
Cu1—N2—C6—C59.8 (2)C6—N2—C10—C12179.4 (2)
Cu1—N2—C6—C7172.18 (15)C6—C7—C8—C90.2 (3)
Cu1—N2—C10—C9175.40 (16)C7—C8—C9—C103.8 (3)
Cu1—N2—C10—C123.4 (3)C8—C9—C10—N23.6 (3)
Cu1—N3—C13—C14170.26 (16)C8—C9—C10—C12175.2 (2)
Cu1—N3—C13—C2310.0 (3)C10—N2—C6—C5173.65 (18)
Cu1—N3—C17—C16171.70 (16)C10—N2—C6—C74.4 (3)
Cu1—N3—C17—C189.7 (2)C11—C1—C2—C3179.0 (2)
Cu1—N4—C18—C170.4 (2)C13—N3—C17—C161.3 (3)
Cu1—N4—C18—C19179.26 (16)C13—N3—C17—C18177.34 (18)
Cu1—N4—C22—C21177.41 (16)C13—C14—C15—C161.1 (4)
Cu1—N4—C22—C241.9 (3)C14—C15—C16—C171.7 (3)
N1—C1—C2—C30.7 (3)C15—C16—C17—N30.5 (3)
N1—C5—C6—N22.7 (3)C15—C16—C17—C18179.0 (2)
N1—C5—C6—C7175.24 (18)C16—C17—C18—N4175.31 (19)
C1—N1—C5—C42.3 (3)C16—C17—C18—C195.9 (3)
C1—N1—C5—C6176.43 (18)C17—N3—C13—C141.9 (3)
C1—C2—C3—C41.2 (3)C17—N3—C13—C23177.87 (19)
N2—C6—C7—C84.0 (3)C17—C18—C19—C20177.4 (2)
C2—C3—C4—C50.0 (3)C18—N4—C22—C210.7 (3)
N3—C13—C14—C150.7 (3)C18—N4—C22—C24179.95 (19)
N3—C17—C18—N46.1 (3)C18—C19—C20—C210.2 (3)
N3—C17—C18—C19172.72 (19)C19—C20—C21—C221.4 (4)
C3—C4—C5—N11.7 (3)C20—C21—C22—N41.8 (3)
C3—C4—C5—C6176.86 (19)C20—C21—C22—C24178.8 (2)
N4—C18—C19—C201.3 (3)C22—N4—C18—C17177.93 (18)
C4—C5—C6—N2178.58 (18)C22—N4—C18—C190.9 (3)
C4—C5—C6—C73.4 (3)C23—C13—C14—C15179.0 (2)
Symmetry code: (i) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···F20.871.472.337 (4)177
Bis[bis(6,6'-dimethyl-2,2'-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate (II) top
Crystal data top
[Cu(C12H12N2)2]2[HfF6]·0.671H2OZ = 1
Mr = 1168.58F(000) = 583
Triclinic, P1Dx = 1.745 Mg m3
a = 8.5737 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.7967 (2) ÅCell parameters from 31642 reflections
c = 13.0183 (2) Åθ = 2.2–33.9°
α = 103.273 (1)°µ = 3.35 mm1
β = 103.662 (1)°T = 100 K
γ = 98.785 (1)°Plate, clear orangish red
V = 1112.07 (3) Å30.3 × 0.17 × 0.08 mm
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
8003 independent reflections
Radiation source: Rotating Anode, Rotating Anode7235 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.032
Detector resolution: 28.5714 pixels mm-1θmax = 33.9°, θmin = 2.0°
profile data from ω–scansh = 1313
Absorption correction: gaussian
(CrysAlisPro; Rigaku OD, 2020)
k = 1616
Tmin = 0.433, Tmax = 1.000l = 1919
40796 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.023H-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 reflectionsΔρmax = 0.48 e Å3
312 parametersΔρmin = 0.73 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cu10.30255 (2)0.35382 (2)0.69812 (2)0.01849 (4)
N10.49323 (15)0.36487 (11)0.82812 (9)0.0157 (2)
C10.55897 (18)0.26589 (14)0.85279 (11)0.0184 (3)
N20.33991 (15)0.54691 (12)0.77752 (10)0.0187 (2)
C20.70930 (18)0.28901 (15)0.93195 (12)0.0200 (3)
H20.7528470.2182020.9494280.024*
N30.08393 (15)0.23090 (11)0.61730 (10)0.0173 (2)
C30.79431 (18)0.41592 (16)0.98475 (12)0.0218 (3)
H30.8981380.4330931.0376540.026*
N40.33880 (17)0.29739 (13)0.54432 (11)0.0211 (2)
C40.72716 (18)0.51810 (15)0.96003 (12)0.0206 (3)
H40.7841760.6059890.9953190.025*
C50.57452 (16)0.48929 (13)0.88246 (11)0.0157 (2)
C60.48691 (17)0.59126 (13)0.85563 (11)0.0159 (2)
C70.54737 (18)0.72313 (14)0.90906 (12)0.0196 (3)
H70.6539400.7532780.9598030.024*
C80.4488 (2)0.81009 (14)0.88679 (13)0.0222 (3)
H80.4872460.9007000.9225700.027*
C90.2948 (2)0.76402 (15)0.81239 (13)0.0240 (3)
H90.2239790.8217690.7990970.029*
C100.24454 (19)0.63174 (15)0.75708 (14)0.0247 (3)
C110.4606 (2)0.13042 (15)0.79400 (14)0.0287 (3)
H11A0.3748500.1087090.8291250.043*
H11B0.5331640.0686610.7974540.043*
H11C0.4095250.1251790.7169420.043*
C120.0821 (3)0.5765 (2)0.6712 (2)0.0523 (7)
H12A0.1005420.5461890.5990230.078*
H12B0.0178810.6441340.6698710.078*
H12C0.0216710.5031240.6886610.078*
C130.03848 (19)0.20159 (14)0.66175 (13)0.0217 (3)
C140.1938 (2)0.13117 (16)0.59615 (16)0.0294 (3)
H140.2795770.1118640.6285770.035*
C150.2222 (2)0.08956 (17)0.48344 (16)0.0331 (4)
H150.3283500.0429580.4376750.040*
C160.0952 (2)0.11615 (16)0.43760 (14)0.0279 (3)
H160.1121190.0863130.3604200.034*
C170.05785 (19)0.18743 (14)0.50662 (12)0.0196 (3)
C180.2030 (2)0.21916 (14)0.46699 (12)0.0215 (3)
C190.2026 (3)0.16910 (16)0.35783 (13)0.0293 (3)
H190.1056730.1159250.3043630.035*
C200.3465 (3)0.19880 (19)0.32964 (15)0.0370 (4)
H200.3498670.1656520.2561780.044*
C210.4854 (3)0.27688 (19)0.40872 (16)0.0348 (4)
H210.5852690.2967270.3901650.042*
C220.4786 (2)0.32667 (16)0.51629 (14)0.0265 (3)
C230.0002 (2)0.24806 (18)0.78440 (14)0.0296 (3)
H23A0.1079430.2328440.8181030.044*
H23B0.0842040.2002290.8087400.044*
H23C0.0022810.3415240.8066340.044*
C240.6249 (2)0.41315 (19)0.60455 (16)0.0332 (4)
H24A0.5933800.4907050.6424760.050*
H24B0.7116240.4396910.5716190.050*
H24C0.6656840.3657530.6574140.050*
Hf10.0000001.0000001.0000000.02373 (3)
F10.09274 (14)0.99551 (11)0.87132 (10)0.0369 (2)
F20.05307 (12)0.80472 (9)0.95921 (9)0.0312 (2)
F30.22038 (12)1.00043 (10)1.09439 (10)0.0341 (2)
O10.1061 (5)0.6264 (4)0.8063 (3)0.0338 (12)0.336 (5)
H1A0.0146950.6003720.8237260.051*0.336 (5)
H1B0.0972330.7026060.8505090.051*0.336 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01904 (8)0.01683 (8)0.01581 (8)0.00282 (6)0.00052 (6)0.00350 (6)
N10.0167 (5)0.0146 (5)0.0154 (5)0.0047 (4)0.0031 (4)0.0040 (4)
C10.0211 (6)0.0187 (6)0.0178 (6)0.0077 (5)0.0063 (5)0.0067 (5)
N20.0177 (5)0.0158 (5)0.0213 (6)0.0045 (4)0.0018 (4)0.0058 (4)
C20.0208 (6)0.0249 (7)0.0215 (7)0.0115 (5)0.0098 (5)0.0119 (5)
N30.0197 (5)0.0142 (5)0.0161 (5)0.0046 (4)0.0013 (4)0.0035 (4)
C30.0148 (6)0.0293 (7)0.0227 (7)0.0063 (5)0.0039 (5)0.0105 (6)
N40.0247 (6)0.0214 (6)0.0215 (6)0.0094 (5)0.0074 (5)0.0106 (5)
C40.0159 (6)0.0207 (7)0.0214 (7)0.0025 (5)0.0015 (5)0.0032 (5)
C50.0144 (6)0.0165 (6)0.0169 (6)0.0044 (4)0.0051 (5)0.0044 (5)
C60.0159 (6)0.0154 (6)0.0180 (6)0.0043 (4)0.0063 (5)0.0054 (5)
C70.0200 (6)0.0163 (6)0.0220 (7)0.0022 (5)0.0071 (5)0.0041 (5)
C80.0320 (8)0.0141 (6)0.0246 (7)0.0061 (5)0.0142 (6)0.0061 (5)
C90.0280 (7)0.0199 (7)0.0328 (8)0.0125 (6)0.0136 (6)0.0145 (6)
C100.0219 (7)0.0203 (7)0.0332 (8)0.0067 (5)0.0037 (6)0.0125 (6)
C110.0364 (9)0.0170 (7)0.0280 (8)0.0082 (6)0.0004 (7)0.0053 (6)
C120.0307 (10)0.0317 (10)0.0783 (16)0.0056 (8)0.0207 (10)0.0220 (10)
C130.0216 (7)0.0166 (6)0.0263 (7)0.0054 (5)0.0059 (6)0.0049 (5)
C140.0206 (7)0.0206 (7)0.0439 (10)0.0028 (6)0.0077 (7)0.0053 (7)
C150.0228 (7)0.0220 (8)0.0402 (10)0.0018 (6)0.0064 (7)0.0012 (7)
C160.0306 (8)0.0215 (7)0.0219 (7)0.0053 (6)0.0062 (6)0.0012 (6)
C170.0249 (7)0.0149 (6)0.0167 (6)0.0070 (5)0.0000 (5)0.0041 (5)
C180.0308 (8)0.0182 (6)0.0162 (6)0.0092 (6)0.0036 (6)0.0071 (5)
C190.0483 (10)0.0248 (8)0.0169 (7)0.0136 (7)0.0084 (7)0.0073 (6)
C200.0652 (13)0.0345 (9)0.0250 (8)0.0232 (9)0.0248 (9)0.0139 (7)
C210.0474 (11)0.0339 (9)0.0380 (10)0.0185 (8)0.0264 (9)0.0177 (8)
C220.0308 (8)0.0270 (8)0.0318 (8)0.0131 (6)0.0155 (7)0.0162 (6)
C230.0297 (8)0.0349 (9)0.0272 (8)0.0077 (7)0.0141 (7)0.0077 (7)
C240.0258 (8)0.0366 (9)0.0427 (10)0.0071 (7)0.0154 (7)0.0154 (8)
Hf10.01372 (4)0.02043 (5)0.04096 (6)0.00568 (3)0.00576 (3)0.01683 (4)
F10.0372 (6)0.0331 (6)0.0534 (7)0.0157 (5)0.0229 (5)0.0215 (5)
F20.0218 (5)0.0179 (4)0.0518 (6)0.0039 (3)0.0038 (4)0.0125 (4)
F30.0193 (4)0.0218 (5)0.0541 (7)0.0064 (4)0.0039 (4)0.0100 (4)
O10.036 (2)0.035 (2)0.0227 (19)0.0034 (16)0.0075 (15)0.0029 (15)
Geometric parameters (Å, º) top
Cu1—N12.0229 (12)C12—H12B0.9800
Cu1—N22.0414 (12)C12—H12C0.9800
Cu1—N32.0121 (12)C13—C141.391 (2)
Cu1—N42.0659 (13)C13—C231.497 (2)
N1—C11.3487 (17)C14—H140.9500
N1—C51.3548 (18)C14—C151.382 (3)
C1—C21.393 (2)C15—H150.9500
C1—C111.497 (2)C15—C161.384 (3)
N2—C61.3558 (18)C16—H160.9500
N2—C101.3476 (19)C16—C171.392 (2)
C2—H20.9500C17—C181.479 (2)
C2—C31.381 (2)C18—C191.399 (2)
N3—C131.344 (2)C19—H190.9500
N3—C171.3607 (19)C19—C201.381 (3)
C3—H30.9500C20—H200.9500
C3—C41.386 (2)C20—C211.380 (3)
N4—C181.356 (2)C21—H210.9500
N4—C221.347 (2)C21—C221.399 (2)
C4—H40.9500C22—C241.495 (3)
C4—C51.3915 (19)C23—H23A0.9800
C5—C61.4845 (19)C23—H23B0.9800
C6—C71.389 (2)C23—H23C0.9800
C7—H70.9500C24—H24A0.9800
C7—C81.390 (2)C24—H24B0.9800
C8—H80.9500C24—H24C0.9800
C8—C91.380 (2)Hf1—F1i2.0111 (11)
C9—H90.9500Hf1—F12.0111 (11)
C9—C101.392 (2)Hf1—F2i2.0033 (9)
C10—C121.500 (2)Hf1—F22.0033 (9)
C11—H11A0.9800Hf1—F3i1.9945 (10)
C11—H11B0.9800Hf1—F31.9945 (10)
C11—H11C0.9800O1—H1A0.8700
C12—H12A0.9800O1—H1B0.8699
N1—Cu1—N281.22 (5)H12B—C12—H12C109.5
N1—Cu1—N4116.52 (5)N3—C13—C14121.15 (15)
N2—Cu1—N4120.35 (5)N3—C13—C23116.98 (14)
N3—Cu1—N1136.20 (5)C14—C13—C23121.87 (15)
N3—Cu1—N2126.39 (5)C13—C14—H14120.3
N3—Cu1—N480.94 (5)C15—C14—C13119.42 (17)
C1—N1—Cu1127.24 (10)C15—C14—H14120.3
C1—N1—C5119.15 (12)C14—C15—H15120.2
C5—N1—Cu1112.66 (9)C14—C15—C16119.63 (15)
N1—C1—C2121.40 (13)C16—C15—H15120.2
N1—C1—C11116.99 (13)C15—C16—H16120.6
C2—C1—C11121.58 (13)C15—C16—C17118.80 (15)
C6—N2—Cu1112.15 (9)C17—C16—H16120.6
C10—N2—Cu1128.64 (10)N3—C17—C16121.28 (15)
C10—N2—C6119.08 (13)N3—C17—C18115.28 (13)
C1—C2—H2120.3C16—C17—C18123.44 (14)
C3—C2—C1119.31 (13)N4—C18—C17115.53 (13)
C3—C2—H2120.3N4—C18—C19121.93 (16)
C13—N3—Cu1125.50 (10)C19—C18—C17122.51 (15)
C13—N3—C17119.68 (13)C18—C19—H19120.8
C17—N3—Cu1114.43 (10)C20—C19—C18118.41 (17)
C2—C3—H3120.2C20—C19—H19120.8
C2—C3—C4119.57 (13)C19—C20—H20120.2
C4—C3—H3120.2C21—C20—C19119.67 (16)
C18—N4—Cu1113.01 (10)C21—C20—H20120.2
C22—N4—Cu1127.54 (11)C20—C21—H21120.1
C22—N4—C18119.43 (14)C20—C21—C22119.72 (18)
C3—C4—H4120.7C22—C21—H21120.1
C3—C4—C5118.63 (13)N4—C22—C21120.82 (17)
C5—C4—H4120.7N4—C22—C24117.38 (15)
N1—C5—C4121.89 (13)C21—C22—C24121.80 (16)
N1—C5—C6115.22 (12)C13—C23—H23A109.5
C4—C5—C6122.86 (13)C13—C23—H23B109.5
N2—C6—C5115.48 (12)C13—C23—H23C109.5
N2—C6—C7121.72 (13)H23A—C23—H23B109.5
C7—C6—C5122.77 (13)H23A—C23—H23C109.5
C6—C7—H7120.7H23B—C23—H23C109.5
C6—C7—C8118.65 (14)C22—C24—H24A109.5
C8—C7—H7120.7C22—C24—H24B109.5
C7—C8—H8120.2C22—C24—H24C109.5
C9—C8—C7119.60 (14)H24A—C24—H24B109.5
C9—C8—H8120.2H24A—C24—H24C109.5
C8—C9—H9120.5H24B—C24—H24C109.5
C8—C9—C10119.06 (14)F1i—Hf1—F1180.00 (7)
C10—C9—H9120.5F2i—Hf1—F189.79 (5)
N2—C10—C9121.66 (14)F2—Hf1—F190.21 (5)
N2—C10—C12116.62 (15)F2—Hf1—F1i89.79 (5)
C9—C10—C12121.71 (15)F2i—Hf1—F1i90.21 (5)
C1—C11—H11A109.5F2—Hf1—F2i180.0
C1—C11—H11B109.5F3—Hf1—F190.15 (5)
C1—C11—H11C109.5F3—Hf1—F1i89.85 (5)
H11A—C11—H11B109.5F3i—Hf1—F1i90.15 (5)
H11A—C11—H11C109.5F3i—Hf1—F189.85 (5)
H11B—C11—H11C109.5F3—Hf1—F289.27 (4)
C10—C12—H12A109.5F3i—Hf1—F2i89.26 (4)
C10—C12—H12B109.5F3i—Hf1—F290.74 (4)
C10—C12—H12C109.5F3—Hf1—F2i90.73 (4)
H12A—C12—H12B109.5F3—Hf1—F3i180.0
H12A—C12—H12C109.5H1A—O1—H1B109.5
Cu1—N1—C1—C2167.25 (11)C5—N1—C1—C20.7 (2)
Cu1—N1—C1—C1114.69 (19)C5—N1—C1—C11177.33 (13)
Cu1—N1—C5—C4167.08 (11)C5—C6—C7—C8173.20 (13)
Cu1—N1—C5—C614.67 (15)C6—N2—C10—C91.4 (2)
Cu1—N2—C6—C511.14 (15)C6—N2—C10—C12178.95 (17)
Cu1—N2—C6—C7171.02 (11)C6—C7—C8—C90.3 (2)
Cu1—N2—C10—C9173.90 (12)C7—C8—C9—C103.1 (2)
Cu1—N2—C10—C125.7 (2)C8—C9—C10—N22.6 (2)
Cu1—N3—C13—C14170.17 (12)C8—C9—C10—C12176.97 (18)
Cu1—N3—C13—C239.84 (19)C10—N2—C6—C5172.79 (13)
Cu1—N3—C17—C16171.27 (11)C10—N2—C6—C75.1 (2)
Cu1—N3—C17—C189.88 (15)C11—C1—C2—C3179.25 (14)
Cu1—N4—C18—C171.01 (15)C13—N3—C17—C162.0 (2)
Cu1—N4—C18—C19179.23 (12)C13—N3—C17—C18176.87 (12)
Cu1—N4—C22—C21177.63 (12)C13—C14—C15—C161.3 (3)
Cu1—N4—C22—C242.0 (2)C14—C15—C16—C171.6 (2)
N1—C1—C2—C31.3 (2)C15—C16—C17—N30.0 (2)
N1—C5—C6—N22.27 (18)C15—C16—C17—C18178.70 (15)
N1—C5—C6—C7175.55 (13)C16—C17—C18—N4175.36 (14)
C1—N1—C5—C42.6 (2)C16—C17—C18—C196.4 (2)
C1—N1—C5—C6175.69 (12)C17—N3—C13—C142.3 (2)
C1—C2—C3—C41.5 (2)C17—N3—C13—C23177.72 (13)
N2—C6—C7—C84.5 (2)C17—C18—C19—C20176.75 (14)
C2—C3—C4—C50.3 (2)C18—N4—C22—C210.3 (2)
N3—C13—C14—C150.6 (2)C18—N4—C22—C24179.92 (14)
N3—C17—C18—N45.82 (18)C18—C19—C20—C210.4 (3)
N3—C17—C18—C19172.39 (13)C19—C20—C21—C220.9 (3)
C3—C4—C5—N12.3 (2)C20—C21—C22—N41.3 (3)
C3—C4—C5—C6175.77 (13)C20—C21—C22—C24179.15 (16)
N4—C18—C19—C201.4 (2)C22—N4—C18—C17177.22 (13)
C4—C5—C6—N2179.49 (13)C22—N4—C18—C191.0 (2)
C4—C5—C6—C72.7 (2)C23—C13—C14—C15179.34 (16)
Symmetry code: (i) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···F20.871.502.328 (4)156
Aromatic ππ stacking interactions (Å, °) in (I) top
Descriptiontypedpy–pyinterplanar angleinterplanar distance
Heterochiralface-to-face3.6967 (12)03.347
Heterochiralparallel displaced5.3726 (13)03.708
Aromatic ππ stacking interactions (Å, °) in (II) top
Descriptiontypedpy–pyinterplanar angleinterplanar distance
Heterochiralface-to-face3.7016 (8)03.355
Heterochiralparallel displaced5.3777 (11)03.678
Coordination geometry (Å, °) of Cu(dmbpy)2+ cations in (I) top
N—Cu—NN—CuCu—NN—Cu—N
N1—Cu1—N22.0208 (16)2.0348 (17)81.40 (7)
N1—Cu1—N32.0123 (17)136.29 (7)
N1—Cu1—N42.0616 (18)116.24 (7)
N2—Cu1—N3126.17 (7)
N2—Cu1—N4120.45 (7)
N3—Cu1—N481.05 (7)
Bond distances (Å) of ZrF62– in (I) top
Zr—FDistance (Å)
Zr—F12.0113 (15)
Zr—F22.0183 (12)
Zr—F31.9955 (13)
Hydrogen-bond geometry (Å, °) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···F20.870 (3)1.4674 (14)2.337 (3)177.1 (2)
Coordination geometry (Å, °) of Cu(dmbpy)2+ cations in (II) top
N—Cu—NN—CuCu—NN—Cu—N
N1—Cu1—N22.0229 (12)2.0414 (12)81.22 (5)
N1—Cu1—N32.0121 (12)136.20 (5)
N1—Cu1—N42.0659 (13)116.52 (5)
N2—Cu1—N3126.39 (5)
N2—Cu1—N4120.35 (5)
N3—Cu1—N480.94 (5)
Bond distances (Å) of HfF62– in (II) top
Hf—FDistance (Å)
Hf—F12.0111 (11)
Hf—F22.0033 (9)
Hf—F31.9945 (10)
Hydrogen-bond geometry (Å, °) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···F20.870 (4)1.5048 (11)2.328 (4)156.4 (3)

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