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

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

Crystal structures of three compounds with the formula [Cu(phen)(H₂O)₃(MF₆)]·H₂O (M = Ti, Zr, Hf) based on bimetallic Λ-shaped molecules and a related salt with the formula [Cu(phen)(H₂O)₂F]₂[HfF₆]·H₂O are reported.

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

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989021000645/tx2034sup1.cif Contains datablocks I, II, III, IV, I, II, III, IV
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989021000645/tx2034Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989021000645/tx2034IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989021000645/tx2034IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989021000645/tx2034IVsup5.hkl Contains datablock IV

CCDC references: 2045776; 2045775; 2045774; 2045773

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
Mean (C-C) = 0.001 Å
Mean (C-C) = 0.002 Å
Mean (C-C) = 0.002 Å
R factor = 0.030
wR factor = 0.071
Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT354_ALERT_3_C Short  O-H (X0.82,N0.98A)  O1       - H1A      .       0.70 Ang.

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       6.55 Why ?
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.19 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Ti1       (IV)      .       4.56 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        Hf1 Check

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zr1      --F1       .        7.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zr1      --F3       .        7.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zr1      --F5       .        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zr1      --F6       .        5.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --O2       .        5.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        7.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N2       .        7.0 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Zr1       (IV)      .       3.88 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.22 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check




Datablock: III



Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        Hf1 Check

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        5.2 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Hf1       (IV)      .       4.00 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.22 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check




Datablock: IV


Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        Hf1 Check

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N2       .        5.2 s.u.
PLAT233_ALERT_4_G Hirshfeld (M-X Solvent)    Hf1      --F2       .        5.2 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Hf1       (IV)      .       4.09 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.19 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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

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