Channels with ordered water and bipyridine mol­ecules in the porous coordination polymer {[Cu(SiF6)(C10H8N2)2]·2C10N2H8·5H2O}n

Aubert, E.; Doudouh, A.; Peluso, P.; Mamane, V.

doi:10.1107/S2056989016016686

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 11| November 2016| Pages 1654-1658

https://doi.org/10.1107/S2056989016016686

Open

access

Channels with ordered water and bipyridine molecules in the porous coordination polymer {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}_n

Emmanuel Aubert,^a ^* Abdelatif Doudouh,^a Paola Peluso ^b and Victor Mamane ^c

^aCristallographie, Résonance Magnétique et Modélisations (CRM2), UMR CNRS, 7036, Université de Lorraine, BP 70239, Bd des Aiguillettes, 54506, Vandoeuvre-les-Nancy, France, ^bIstituto di Chimica Biomolecolare ICB CNR - Sede Secondaria di Sassari, Traversa La Crucca 3, Regione Baldinca, I-07100 Li Punti - Sassari, Italy, and ^cInstitut de Chimie de Strasbourg, UMR 7177, Equipe LASYROC, 1 rue Blaise Pascal, BP 296 R8, 67008 Strasbourg Cedex, France
^*Correspondence e-mail: emmanuel.aubert@univ-lorraine.fr

Edited by A. Van der Lee, Université de Montpellier II, France (Received 6 October 2016; accepted 18 October 2016; online 25 October 2016)

The coordination polymer {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀H₈N₂·5H₂O}_n, systematic name: poly[[bis(μ₂-4,4′-bipyridine)(μ₂-hexafluoridosilicato)copper(II)] 4,4′-bipyridine disolvate pentahydrate], contains pores which are filled with water and 4,4′-bipyridine molecules. As a result of the presence of these ordered species, the framework changes its symmetry from P4/mmm to P2₁/c. The 4,4′-bipyridine guest molecules form chains inside the 6.5 × 6.9 Å pores parallel to [100] in which the molecules interact through π–π stacking. Ordered water molecules form infinite hydrogen-bonded chains inside a second pore system (1.6 × 5.3 Å free aperture) perpendicular to the 4,4′-bipyridine channels.

Keywords: Porous coordination polymer; adsorption; hydrogen bonding; π–π stacking; copper(II); 4,4′-bipyridine; crystal structure.

CCDC reference: 1510381

1. Chemical context

The title compound was obtained in an attempt to reproduce the synthesis of [Cu(μ-4,4′-bipy)(H₂O)₂(BF₄)₂]·4,4′-bipy (Blake et al., 1997 ). A contamination with SiF₆²⁻ is, however, at the origin of the formation of {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}_n, whose framework was previously described by Noro et al. (2000 , 2002 ). This framework has shown interesting gas adsorption properties in recent years (Burd et al., 2012 ; Yu et al., 2012 ; Fan et al., 2013 ). Several structures based on this porous framework have been published since its discovery [CSD refcodes: GORWUF (Noro et al., 2000), AFEKAX (Noro et al., 2002), HAPKOA (Burd et al., 2012)]. However, these structures which are reported in the tetragonal space group type P4/mmm are disordered: the framework bipyridines are disordered by symmetry whereas solvent molecules are not clearly identified within the pores. In this article, we show that this porous coordination polymer is capable of firmly stabilizing guest entities such as 4,4′-bipyridine and water molecules within its channels. The synthesis conditions thus seem a key factor in producing the ordering of guest molecules within this porous material.

2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) contains two copper(II) atoms, both lying on inversion centers; each of these two atoms is coordinated by N atoms of four symmetrically related 4,4′-bipyridine molecules (with one independent bipyridine for each copper atom), forming slightly distorted two-dimensional square grids parallel to (100). The copper(II) atoms are both at the center of elongated octahedra (Table 1).

Table 1
Selected geometric parameters (Å, °)

Cu1—N1ⁱ	2.0156 (11)	Cu2—N19^vi	2.0494 (11)
Cu1—N1	2.0156 (11)	Cu2—F2	2.4109 (9)
Cu1—N7ⁱⁱ	2.0467 (11)	Cu2—F2^iv	2.4109 (9)
Cu1—N7ⁱⁱⁱ	2.0467 (11)	Si1—F6	1.6534 (11)
Cu1—F1ⁱ	2.3585 (9)	Si1—F5	1.6806 (10)
Cu1—F1	2.3585 (9)	Si1—F3	1.6823 (10)
Cu2—N13^iv	2.0170 (11)	Si1—F4	1.6855 (11)
Cu2—N13	2.0170 (11)	Si1—F2	1.7120 (10)
Cu2—N19^v	2.0494 (11)	Si1—F1	1.7145 (10)

N1ⁱ—Cu1—N1	180.00 (6)	N19^v—Cu2—F2	90.67 (4)
N1ⁱ—Cu1—N7ⁱⁱ	91.58 (5)	N19^vi—Cu2—F2	89.33 (4)
N1—Cu1—N7ⁱⁱ	88.42 (5)	N13^iv—Cu2—F2^iv	89.41 (4)
N1ⁱ—Cu1—N7ⁱⁱⁱ	88.42 (5)	N13—Cu2—F2^iv	90.59 (4)
N1—Cu1—N7ⁱⁱⁱ	91.58 (5)	N19^v—Cu2—F2^iv	89.33 (4)
N7ⁱⁱ—Cu1—N7ⁱⁱⁱ	180.0	N19^vi—Cu2—F2^iv	90.67 (4)
N1ⁱ—Cu1—F1ⁱ	90.65 (4)	F2—Cu2—F2^iv	180.0
N1—Cu1—F1ⁱ	89.35 (4)	F6—Si1—F5	90.80 (6)
N7ⁱⁱ—Cu1—F1ⁱ	89.60 (4)	F6—Si1—F3	89.64 (6)
N7ⁱⁱⁱ—Cu1—F1ⁱ	90.40 (4)	F5—Si1—F3	179.55 (6)
N1ⁱ—Cu1—F1	89.35 (4)	F6—Si1—F4	178.87 (6)
N1—Cu1—F1	90.65 (4)	F5—Si1—F4	90.12 (6)
N7ⁱⁱ—Cu1—F1	90.40 (4)	F3—Si1—F4	89.44 (6)
N7ⁱⁱⁱ—Cu1—F1	89.60 (4)	F6—Si1—F2	91.01 (4)
F1ⁱ—Cu1—F1	180.0	F5—Si1—F2	89.67 (5)
N13^iv—Cu2—N13	180.0	F3—Si1—F2	90.41 (5)
N13^iv—Cu2—N19^v	90.73 (5)	F4—Si1—F2	89.64 (4)
N13—Cu2—N19^v	89.27 (5)	F6—Si1—F1	90.89 (4)
N13^iv—Cu2—N19^vi	89.27 (5)	F5—Si1—F1	90.35 (5)
N13—Cu2—N19^vi	90.73 (5)	F3—Si1—F1	89.56 (5)
N19^v—Cu2—N19^vi	180.0	F4—Si1—F1	88.45 (4)
N13^iv—Cu2—F2	90.59 (4)	F2—Si1—F1	178.09 (4)
N13—Cu2—F2	89.41 (4)	Si1—F1—Cu1	178.36 (5)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

The basal plane is composed of four nitrogen atoms coming from the 4,4′-bipyridine molecules, whereas the apical positions are occupied by fluorine atoms belonging to the SiF₆²⁻ anions pillaring the structure (Fig. 2).

Figure 2
View along [011]; the atoms belonging to the framework are shown as space-filling, whereas the molecules adsorbed inside the pores are shown as capped sticks.

The 2D coordination grids are stacked along the [100] direction through the SiF₆²⁻ anions, leading to a three-dimensional coordination polymer, which displays channels having a free aperture of 6.5 × 6.9 Å parallel to [100] and smaller pores of 1.6 × 5.3 Å along the [011] direction (as measured in projection in the plane perpendicular to the channels and using van der Waals radii). These interconnected pores are filled with two other 4,4′-bipyridine molecules and five water molecules (Figs. 3 and 4). In comparison, the previously reported structures with this framework are described in the P4/mmm space group type, implying a squared Cu grid and channels; here, the Cu–Cu–Cu grid angle significantly deviates from 90° (96.62°) and this may be related to the fact that, in the present compound, guest molecules fill the pores and interact significantly with the framework atoms (see below).

Figure 3
View along [100]; the atoms belonging to the framework are shown as space-filling, whereas the molecules inside the pores are shown as capped sticks.

Figure 4
ORTEP-style plot of the title compound showing the coordination about the two inequivalent copper atoms. Hydrogen atoms, adsorbed 4,4′-bipyridine and water molecules are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.

The Si—F bond lengths in SiF₆²⁻ show some variations (Table 1), ranging from 1.6534 (11) to 1.7145 (10) Å. The two longest bond lengths are associated with opposite fluorine atoms bounded to a Cu^II metal atom. Among the four remaining fluorine atoms, three of them form short hydrogen bonds with water molecules and display longer bond lengths than the last one, which only forms a weaker hydrogen-bonding interaction with a 4,4′-bipyridine molecule (Table 2). A search for SiF₆²⁻ anions within the Cambridge Structural Database (CSD Version 5.36; Groom et al., 2016 ) leads to 241 hits (using options `not disordered'" and `no errors'); the reported Si—F bond lengths range from 1.577 to 1.748 Å with a mean of 1.684 Å and a standard deviation of 0.022 Å.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N31^vii	0.95	2.34	3.2849 (19)	170
C20—H20⋯F2ⁱⁱ	0.95	2.32	3.0341 (16)	131
C20—H20⋯F5ⁱⁱ	0.95	2.53	3.4305 (17)	159
C18—H18⋯F2^iv	0.95	2.52	3.1085 (16)	120
C9—H9⋯O52	0.95	2.50	3.4223 (18)	163
C3—H3⋯N37^viii	0.95	2.54	3.4803 (19)	173
C21—H21⋯O52ⁱⁱ	0.95	2.56	3.4294 (18)	152
C14—H14⋯F2	0.95	2.43	3.0497 (16)	123
C14—H14⋯F4	0.95	2.55	3.4519 (17)	158
C8—H8⋯F1^v	0.95	2.33	3.0205 (16)	129
C8—H8⋯F4^v	0.95	2.51	3.3524 (18)	148
C5—H5⋯O52	0.95	2.43	3.2916 (18)	151
C24—H24⋯F2^vii	0.95	2.29	2.9997 (16)	131
C24—H24⋯F3^vii	0.95	2.55	3.4609 (17)	161
C11—H11⋯N37^viii	0.95	2.61	3.4358 (19)	145
C12—H12⋯F1^viii	0.95	2.26	2.9662 (16)	131
C12—H12⋯F6^viii	0.95	2.49	3.4040 (16)	161
C2—H2⋯F1ⁱ	0.95	2.52	3.0708 (16)	117
C2—H2⋯F3ⁱ	0.95	2.45	3.3364 (17)	156
C45—H45⋯O50^ix	0.95	2.44	3.376 (2)	167
C6—H6⋯F1	0.95	2.46	3.0691 (16)	122
C6—H6⋯F4	0.95	2.60	3.5313 (17)	166
C38—H38⋯F6	0.95	2.41	3.1240 (19)	132
C48—H48⋯O51^iv	0.95	2.50	3.330 (2)	146
O53—H53B⋯F3^v	0.78 (2)	1.96 (3)	2.7228 (17)	166 (2)
O52—H52B⋯O53	0.90 (3)	1.83 (3)	2.7227 (18)	170 (2)
O53—H53A⋯N43^iv	0.85 (3)	2.05 (3)	2.8666 (19)	161 (3)
O52—H52A⋯O51	0.90 (3)	1.84 (3)	2.726 (2)	172 (2)
O50—H50A⋯O49	1.05 (3)	1.72 (3)	2.741 (2)	163 (2)
O49—H49B⋯F5ⁱⁱ	0.96 (3)	1.82 (3)	2.7716 (18)	173 (3)
O50—H50B⋯N25ⁱ	0.96 (3)	1.86 (3)	2.816 (2)	173 (3)
O49—H49A⋯O52ⁱⁱ	1.00 (4)	1.81 (4)	2.798 (2)	169 (3)
O51—H51B⋯F4	0.91 (3)	1.88 (3)	2.7029 (18)	149 (2)
O51—H51A⋯O50	1.00 (4)	1.76 (4)	2.719 (2)	158 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (viii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ix) x, y+1, z.

3. Supramolecular features

Four of the five water molecules (O49 to O52) form infinite C₄⁴(2) chains running in the [001] direction throughout the pores (Fig. 5). The fifth water molecule (O53) interacts with these chains and several hydrogen bonds anchor these water molecules to the coordination polymer framework (Table 2). The 4,4′-bipyridine molecules filling the [100] channels form chains through π–π stacking (Fig. 6; Table 3), and are connected to three of the water molecules (O50, O51 and O53) and framework fluorine and aromatic hydrogen atoms by hydrogen bonds (Table 2); these intermolecular interactions induce different dihedral angles within the two symmetry-independent 4,4′-bipyridine molecules [bipy_(N25–N31): 45.29 (7)°; bipy_(N37–N43): 30.31 (7)°]. Whereas the 4,4′-bipyridine molecules belonging to the coordination network are rather rigid between the metal atoms [average U_eq = 0.014 (2) Å² as calculated on C,N atoms], the adsorbed 4,4′-bipyridine molecules display significantly larger atomic displacement parameters [U_eq = 0.025 (5) Å²].

Table 3
Geometrical parameters (Å, °) for the π–π stacking of the 4,4′-bipyridine molecules within the pores

Cg(I) is the centroid of the atoms defining plane I: Cg(N25) = N25/C26–C30; Cg(N31) = N31/C32–C36; Cg(N43) = N43/C44–7-C48 and Cg(N37) = N37/C38–C42. d_Cg–Cg is the distance between Cg(I) and Cg(J). α is the dihedral angle between planes I and J. β is the angle between the Cg(I)→Cg(J) vector and the normal to plane I. γ is the angle between the Cg(I)→Cg(J) vector and the normal to plane J.

Cg(I)	Cg(J)	d_Cg–Cg	α	β	γ
N25	N25ⁱ	3.7374 (10)	0.02 (9)	9.2	9.2
N31	N37ⁱⁱ	3.7358 (9)	20.79 (8)	21.4	13.1
N43	N43ⁱⁱⁱ	3.8576 (9)	0.00 (7)	23.8	23.8
Symmetry codes: (i) −x, 2 − y, 1 − z; (ii) x, y, z; (iii) 1 − x, 2 − y, 1 − z.

Figure 5
Hydrogen-bonding pattern of solvate water molecules, forming infinite chains along the [001] direction. All other atoms apart from those of the water molecules are omitted for clarity.

Figure 6
π–π stacking pattern of the solvent 4,4′-bipyridine molecules in the [100] pores. All other atoms (except water molecules hydrogen-bonded to N atoms of these bipyridines) are omitted for clarity. Pyridyl centroids are displayed as green spheres.

4. Database survey

A survey was performed in the Cambridge Structural Database (CSD Version 5.36; Groom et al., 2016). Beside the structures corresponding to the bare or hydrated [Cu(SiF₆)(C₁₀H₈N₂)₂]_n coordination polymer framework [CSD refcodes: GORWUF (Noro et al., 2000), AFEKAX (Noro et al., 2002), HAPKOA (Burd et al., 2012)], several structures related to the title compound have been described. In particular, Noro et al. showed that the hydrated form of the title compound {[Cu(SiF₆)(4,4′-bpy)₂]·8H₂O}_n undergoes a structural conversion when immersed in water, leading to an interpenetrated network where SiF₆²⁻ anions are shifted out of the coordination sphere of copper ions and are replaced by water molecules [CSD refcodes: AFEHOI (Noro et al., 2002); JEZRUB (Gable et al., 1990 )]. When copper is replaced by zinc, an isostructural compound is obtained [CSD refcodes: WONZIJ (Lin et al., 2009 ); ZESFUY (Subramanian & Zaworotko, 1995 )].

5. Synthesis and crystallization

An aqueous solution (5 cm³) of hydrated copper(II) tetrafluoridoborate (47.43 mg, 0.2 mmol) was added to a refluxing acetonitrile solution (5 cm³) of 4,4′-bipyridine (62.48 mg, 0.4 mmol). After filtration, Et₂O vapor was diffused into the mother liquor for seven days, and then the solvent was allowed to evaporate very slowly. A mixture of blue and violet crystals was obtained; whereas the diffraction spots of the blue crystals could not be properly indexed, the violet crystals were of very good quality and led to the structure reported on herein.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All hydrogen atoms of water molecules were freely refined in an isotropic approximation. Aromatic hydrogen atoms were refined with riding coordinates and U_iso(H) = 1.2U_iso(C).

Table 4
Experimental details

Crystal data
Chemical formula	[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀H₈N₂·5H₂O
M_r	920.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	16.3875 (2), 16.6136 (2), 14.7959 (2)
β (°)	90.654 (1)
V (Å³)	4028.00 (9)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.78
Crystal size (mm)	0.25 × 0.16 × 0.14

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova (Cu) X-ray Source
Absorption correction	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ ) based on expressions derived by Clark & Reid (1995 )]
T_min, T_max	0.708, 0.824
No. of measured, independent and observed [I > 2σ(I)] reflections	68271, 8435, 7846
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.110, 1.06
No. of reflections	8435
No. of parameters	593
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.50
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1510381

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016016686/vn2118sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016016686/vn2118Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[bis(µ₂-4,4'-bipyridine)(µ₂-hexafluoridosilicato)copper(II)] 4,4'-bipyridine disolvate pentahydrate] top

Crystal data top

[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀H₈N₂·5H₂O	F(000) = 1900
M_r = 920.44	D_x = 1.518 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 16.3875 (2) Å	Cell parameters from 32121 reflections
b = 16.6136 (2) Å	θ = 3.7–76.5°
c = 14.7959 (2) Å	µ = 1.78 mm⁻¹
β = 90.654 (1)°	T = 110 K
V = 4028.00 (9) Å³	Prism, violet
Z = 4	0.25 × 0.16 × 0.14 mm

Data collection top

Rigaku Oxford Diffraction SuperNova (Cu) X-ray Source diffractometer	7846 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.029
ω scans	θ_max = 76.2°, θ_min = 3.8°
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015)]; analytical numeric absorption correction using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)	h = −20→20
T_min = 0.708, T_max = 0.824	k = 0→20
68271 measured reflections	l = 0→18
8435 independent reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0562P)² + 2.6502P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
8435 reflections	Δρ_max = 0.47 e Å⁻³
593 parameters	Δρ_min = −0.50 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	0.0000	0.5000	0.5000	0.00740 (9)
Cu2	0.5000	0.5000	0.5000	0.00808 (9)
Si1	0.24851 (2)	0.50181 (2)	0.49951 (2)	0.01085 (11)
F1	0.14392 (6)	0.50149 (4)	0.50157 (6)	0.01423 (19)
F2	0.35288 (6)	0.49872 (4)	0.49705 (6)	0.01514 (19)
F5	0.25214 (6)	0.49217 (7)	0.61255 (7)	0.0327 (3)
F6	0.25001 (5)	0.60099 (6)	0.50857 (8)	0.0313 (3)
F3	0.24470 (6)	0.51068 (7)	0.38628 (7)	0.0305 (2)
F4	0.24575 (5)	0.40086 (6)	0.48849 (9)	0.0356 (3)
N1	−0.00035 (7)	0.41543 (7)	0.59766 (8)	0.0104 (2)
O52	0.24669 (7)	0.22533 (8)	0.69796 (10)	0.0304 (3)
N7	−0.00003 (7)	0.09067 (7)	0.90635 (7)	0.0104 (2)
N19	0.50157 (7)	0.08206 (7)	0.10342 (7)	0.0103 (2)
N13	0.50009 (7)	0.40834 (7)	0.41061 (7)	0.0102 (2)
O53	0.29213 (8)	0.07136 (8)	0.73649 (9)	0.0319 (3)
O50	0.27901 (8)	0.11159 (8)	0.42810 (9)	0.0326 (3)
O51	0.29696 (9)	0.24956 (9)	0.52512 (10)	0.0374 (3)
N43	0.55301 (8)	0.94138 (8)	0.35053 (9)	0.0224 (3)
O49	0.22422 (9)	0.11500 (9)	0.25239 (9)	0.0375 (3)
N37	0.23466 (8)	0.82015 (8)	0.64527 (10)	0.0244 (3)
N31	0.26526 (8)	0.82439 (10)	0.32164 (10)	0.0281 (3)
C16	0.50172 (8)	0.27683 (8)	0.29304 (9)	0.0117 (3)
C17	0.56598 (8)	0.33166 (8)	0.29579 (9)	0.0136 (3)
H17	0.6114	0.3250	0.2572	0.016*
C22	0.50242 (8)	0.20746 (8)	0.23027 (9)	0.0113 (3)
C4	−0.00106 (8)	0.28967 (8)	0.72282 (9)	0.0131 (3)
C20	0.43162 (8)	0.11255 (8)	0.13529 (9)	0.0141 (3)
H20	0.3814	0.0907	0.1139	0.017*
C10	−0.00090 (8)	0.22170 (8)	0.78738 (9)	0.0132 (3)
C15	0.43615 (8)	0.29027 (8)	0.35038 (9)	0.0146 (3)
H15	0.3911	0.2543	0.3504	0.018*
C18	0.56320 (8)	0.39594 (8)	0.35523 (9)	0.0125 (3)
H18	0.6076	0.4327	0.3569	0.015*
C9	0.07202 (8)	0.18464 (9)	0.81404 (10)	0.0164 (3)
H9	0.1227	0.2038	0.7920	0.020*
C3	−0.06460 (8)	0.34570 (8)	0.71891 (9)	0.0144 (3)
H3	−0.1089	0.3418	0.7595	0.017*
C21	0.42956 (8)	0.17432 (9)	0.19781 (9)	0.0145 (3)
H21	0.3787	0.1941	0.2186	0.017*
C14	0.43721 (8)	0.35642 (8)	0.40738 (9)	0.0147 (3)
H14	0.3919	0.3654	0.4455	0.018*
C8	0.06999 (8)	0.11997 (9)	0.87270 (10)	0.0155 (3)
H8	0.1200	0.0952	0.8900	0.019*
C5	0.06262 (8)	0.29879 (9)	0.66202 (10)	0.0162 (3)
H5	0.1066	0.2616	0.6620	0.019*
C24	0.57206 (8)	0.11186 (9)	0.13636 (10)	0.0156 (3)
H24	0.6220	0.0897	0.1158	0.019*
C23	0.57484 (8)	0.17385 (9)	0.19922 (10)	0.0160 (3)
H23	0.6259	0.1933	0.2210	0.019*
C11	−0.07321 (8)	0.19167 (9)	0.82304 (9)	0.0147 (3)
H11	−0.1240	0.2156	0.8072	0.018*
C12	−0.07035 (8)	0.12663 (9)	0.88184 (9)	0.0142 (3)
H12	−0.1200	0.1068	0.9057	0.017*
C2	−0.06252 (8)	0.40681 (8)	0.65549 (9)	0.0130 (3)
H2	−0.1065	0.4440	0.6527	0.016*
C45	0.42153 (9)	0.96535 (9)	0.41679 (11)	0.0208 (3)
H45	0.3752	0.9994	0.4215	0.025*
C6	0.06131 (8)	0.36237 (9)	0.60178 (10)	0.0152 (3)
H6	0.1058	0.3687	0.5618	0.018*
C46	0.42614 (9)	0.89392 (9)	0.46622 (10)	0.0173 (3)
C44	0.48547 (10)	0.98589 (10)	0.36069 (11)	0.0226 (3)
H44	0.4811	1.0346	0.3273	0.027*
C47	0.49637 (9)	0.84765 (9)	0.45646 (10)	0.0201 (3)
H47	0.5025	0.7986	0.4889	0.024*
C38	0.28158 (9)	0.76657 (9)	0.60272 (10)	0.0208 (3)
H38	0.2714	0.7110	0.6125	0.025*
N25	−0.12407 (9)	0.91210 (10)	0.49597 (11)	0.0340 (4)
C39	0.34424 (9)	0.78762 (9)	0.54526 (10)	0.0195 (3)
H39	0.3764	0.7470	0.5179	0.023*
C40	0.36000 (9)	0.86869 (9)	0.52772 (10)	0.0180 (3)
C36	0.22422 (10)	0.77389 (11)	0.37480 (11)	0.0253 (3)
H36	0.2459	0.7215	0.3846	0.030*
C48	0.55719 (9)	0.87357 (10)	0.39917 (11)	0.0222 (3)
H48	0.6047	0.8413	0.3941	0.027*
C34	0.11765 (9)	0.86961 (10)	0.40037 (10)	0.0224 (3)
C35	0.15162 (9)	0.79402 (10)	0.41632 (11)	0.0231 (3)
H35	0.1254	0.7568	0.4551	0.028*
C33	0.16047 (10)	0.92295 (10)	0.34582 (11)	0.0266 (3)
H33	0.1399	0.9754	0.3338	0.032*
C28	0.03559 (10)	0.88875 (10)	0.43575 (11)	0.0232 (3)
C41	0.31092 (10)	0.92455 (10)	0.57120 (12)	0.0254 (3)
H41	0.3184	0.9805	0.5613	0.030*
C27	0.01285 (10)	0.86650 (11)	0.52287 (12)	0.0286 (4)
H27	0.0513	0.8423	0.5630	0.034*
C32	0.23375 (10)	0.89772 (11)	0.30952 (12)	0.0286 (4)
H32	0.2634	0.9349	0.2738	0.034*
C42	0.25108 (10)	0.89764 (10)	0.62910 (13)	0.0299 (4)
H42	0.2195	0.9370	0.6595	0.036*
C26	−0.06647 (11)	0.88027 (12)	0.54980 (13)	0.0335 (4)
H26	−0.0808	0.8663	0.6098	0.040*
C29	−0.02335 (11)	0.92411 (11)	0.38086 (12)	0.0302 (4)
H29	−0.0100	0.9422	0.3219	0.036*
C30	−0.10216 (12)	0.93284 (12)	0.41284 (14)	0.0367 (4)
H30	−0.1425	0.9547	0.3734	0.044*
H53B	0.2849 (14)	0.0514 (14)	0.7835 (17)	0.034 (6)*
H52B	0.2595 (15)	0.1754 (16)	0.7175 (17)	0.046 (7)*
H53A	0.3396 (18)	0.0590 (18)	0.720 (2)	0.066 (9)*
H52A	0.2588 (15)	0.2311 (15)	0.6395 (18)	0.046 (7)*
H50A	0.2641 (16)	0.1230 (17)	0.360 (2)	0.060 (8)*
H49B	0.2334 (18)	0.0814 (19)	0.201 (2)	0.069 (9)*
H50B	0.2281 (19)	0.0997 (19)	0.457 (2)	0.072 (9)*
H49A	0.234 (2)	0.174 (2)	0.241 (2)	0.100 (12)*
H51B	0.2650 (13)	0.2899 (15)	0.5027 (14)	0.034 (6)*
H51A	0.281 (2)	0.207 (2)	0.480 (2)	0.093 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01176 (16)	0.00446 (15)	0.00599 (15)	−0.00002 (9)	0.00097 (11)	0.00010 (8)
Cu2	0.01341 (16)	0.00456 (15)	0.00628 (15)	0.00000 (9)	0.00100 (11)	−0.00001 (8)
Si1	0.0105 (2)	0.0103 (2)	0.0118 (2)	0.00012 (11)	0.00098 (16)	−0.00039 (12)
F1	0.0130 (4)	0.0140 (5)	0.0157 (4)	−0.0002 (3)	0.0016 (3)	−0.0021 (3)
F2	0.0138 (4)	0.0154 (5)	0.0162 (5)	0.0010 (3)	0.0015 (3)	0.0020 (3)
F5	0.0194 (5)	0.0653 (8)	0.0135 (5)	−0.0001 (4)	0.0007 (4)	0.0059 (4)
F6	0.0196 (5)	0.0126 (5)	0.0616 (7)	−0.0008 (3)	0.0034 (5)	−0.0057 (4)
F3	0.0187 (5)	0.0589 (7)	0.0139 (5)	0.0055 (4)	0.0012 (4)	−0.0002 (4)
F4	0.0198 (5)	0.0123 (5)	0.0746 (8)	0.0007 (3)	0.0011 (5)	−0.0033 (4)
N1	0.0130 (5)	0.0087 (5)	0.0096 (5)	−0.0006 (4)	0.0001 (4)	0.0019 (4)
O52	0.0243 (6)	0.0258 (6)	0.0412 (8)	0.0045 (5)	0.0085 (5)	0.0034 (5)
N7	0.0137 (5)	0.0086 (5)	0.0088 (5)	−0.0003 (4)	0.0007 (4)	0.0019 (4)
N19	0.0145 (5)	0.0079 (5)	0.0085 (5)	0.0004 (4)	0.0004 (4)	−0.0010 (4)
N13	0.0139 (5)	0.0072 (5)	0.0094 (5)	0.0003 (4)	0.0005 (4)	−0.0011 (4)
O53	0.0346 (7)	0.0311 (7)	0.0302 (7)	0.0059 (5)	0.0124 (5)	0.0096 (5)
O50	0.0271 (6)	0.0342 (7)	0.0366 (7)	0.0047 (5)	0.0013 (5)	−0.0021 (5)
O51	0.0474 (8)	0.0258 (7)	0.0389 (7)	0.0018 (6)	−0.0021 (6)	0.0054 (6)
N43	0.0228 (6)	0.0233 (7)	0.0212 (6)	−0.0028 (5)	0.0009 (5)	−0.0016 (5)
O49	0.0472 (8)	0.0342 (7)	0.0310 (7)	0.0016 (6)	0.0001 (6)	0.0007 (6)
N37	0.0198 (6)	0.0231 (7)	0.0305 (7)	−0.0016 (5)	0.0044 (5)	−0.0003 (6)
N31	0.0206 (6)	0.0401 (8)	0.0238 (7)	−0.0031 (6)	0.0021 (5)	−0.0034 (6)
C16	0.0136 (6)	0.0099 (6)	0.0118 (6)	0.0007 (5)	−0.0003 (5)	−0.0022 (5)
C17	0.0134 (6)	0.0136 (6)	0.0138 (6)	−0.0008 (5)	0.0031 (5)	−0.0031 (5)
C22	0.0142 (6)	0.0089 (6)	0.0109 (6)	−0.0007 (5)	0.0007 (5)	−0.0015 (5)
C4	0.0139 (6)	0.0118 (6)	0.0137 (6)	−0.0001 (5)	0.0003 (5)	0.0042 (5)
C20	0.0133 (6)	0.0127 (6)	0.0162 (7)	−0.0014 (5)	0.0012 (5)	−0.0040 (5)
C10	0.0148 (6)	0.0116 (6)	0.0132 (6)	0.0004 (5)	0.0016 (5)	0.0047 (5)
C15	0.0143 (6)	0.0126 (6)	0.0171 (7)	−0.0030 (5)	0.0032 (5)	−0.0043 (5)
C18	0.0140 (6)	0.0113 (6)	0.0122 (6)	−0.0010 (5)	0.0006 (5)	−0.0018 (5)
C9	0.0121 (6)	0.0179 (7)	0.0193 (7)	−0.0003 (5)	0.0022 (5)	0.0080 (6)
C3	0.0141 (6)	0.0155 (7)	0.0136 (6)	0.0015 (5)	0.0032 (5)	0.0042 (5)
C21	0.0126 (6)	0.0145 (7)	0.0164 (7)	0.0000 (5)	0.0022 (5)	−0.0045 (5)
C14	0.0159 (6)	0.0126 (6)	0.0157 (6)	−0.0011 (5)	0.0037 (5)	−0.0035 (5)
C8	0.0139 (6)	0.0148 (7)	0.0179 (7)	0.0016 (5)	0.0015 (5)	0.0058 (5)
C5	0.0131 (6)	0.0151 (7)	0.0205 (7)	0.0028 (5)	0.0032 (5)	0.0071 (5)
C24	0.0136 (6)	0.0154 (7)	0.0177 (7)	0.0016 (5)	0.0009 (5)	−0.0061 (5)
C23	0.0125 (6)	0.0175 (7)	0.0179 (7)	−0.0002 (5)	−0.0012 (5)	−0.0067 (5)
C11	0.0119 (6)	0.0153 (7)	0.0168 (6)	0.0016 (5)	0.0009 (5)	0.0057 (5)
C12	0.0132 (6)	0.0148 (7)	0.0147 (6)	−0.0005 (5)	0.0008 (5)	0.0044 (5)
C2	0.0145 (6)	0.0128 (6)	0.0118 (6)	0.0018 (5)	0.0005 (5)	0.0018 (5)
C45	0.0192 (7)	0.0177 (7)	0.0255 (8)	0.0006 (6)	−0.0016 (6)	−0.0001 (6)
C6	0.0139 (6)	0.0145 (7)	0.0174 (7)	0.0014 (5)	0.0032 (5)	0.0058 (5)
C46	0.0176 (7)	0.0174 (7)	0.0169 (7)	−0.0015 (5)	−0.0028 (5)	−0.0021 (5)
C44	0.0252 (8)	0.0187 (7)	0.0237 (8)	−0.0015 (6)	−0.0007 (6)	0.0022 (6)
C47	0.0205 (7)	0.0192 (7)	0.0205 (7)	0.0017 (6)	−0.0016 (6)	0.0003 (6)
C38	0.0222 (7)	0.0182 (7)	0.0219 (7)	−0.0019 (6)	−0.0013 (6)	0.0005 (6)
N25	0.0270 (7)	0.0306 (8)	0.0446 (9)	0.0051 (6)	0.0069 (7)	−0.0021 (7)
C39	0.0228 (7)	0.0171 (7)	0.0186 (7)	0.0014 (6)	−0.0001 (6)	−0.0008 (6)
C40	0.0158 (6)	0.0190 (7)	0.0193 (7)	−0.0011 (5)	−0.0024 (5)	0.0000 (6)
C36	0.0198 (7)	0.0319 (9)	0.0241 (8)	0.0008 (6)	−0.0012 (6)	−0.0023 (7)
C48	0.0194 (7)	0.0242 (8)	0.0230 (8)	0.0018 (6)	0.0002 (6)	−0.0020 (6)
C34	0.0214 (7)	0.0263 (8)	0.0194 (7)	−0.0025 (6)	0.0009 (6)	−0.0037 (6)
C35	0.0203 (7)	0.0283 (8)	0.0205 (7)	−0.0026 (6)	−0.0004 (6)	0.0006 (6)
C33	0.0294 (8)	0.0249 (8)	0.0255 (8)	−0.0039 (6)	0.0021 (6)	−0.0007 (6)
C28	0.0239 (8)	0.0210 (8)	0.0247 (8)	−0.0023 (6)	0.0024 (6)	−0.0037 (6)
C41	0.0216 (7)	0.0160 (7)	0.0387 (9)	−0.0005 (6)	0.0060 (7)	−0.0003 (6)
C27	0.0259 (8)	0.0352 (9)	0.0246 (8)	0.0020 (7)	0.0019 (6)	0.0002 (7)
C32	0.0260 (8)	0.0347 (9)	0.0253 (8)	−0.0092 (7)	0.0043 (6)	−0.0018 (7)
C42	0.0239 (8)	0.0204 (8)	0.0455 (10)	0.0011 (6)	0.0122 (7)	−0.0028 (7)
C26	0.0317 (9)	0.0346 (10)	0.0343 (10)	0.0012 (7)	0.0113 (7)	0.0000 (8)
C29	0.0334 (9)	0.0264 (9)	0.0308 (9)	0.0047 (7)	0.0041 (7)	0.0029 (7)
C30	0.0318 (9)	0.0341 (10)	0.0442 (11)	0.0112 (8)	0.0010 (8)	0.0038 (8)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	2.0156 (11)	C10—C9	1.3971 (19)
Cu1—N1	2.0156 (11)	C15—C14	1.3852 (19)
Cu1—N7ⁱⁱ	2.0467 (11)	C15—H15	0.9500
Cu1—N7ⁱⁱⁱ	2.0467 (11)	C18—H18	0.9500
Cu1—F1ⁱ	2.3585 (9)	C9—C8	1.3818 (19)
Cu1—F1	2.3585 (9)	C9—H9	0.9500
Cu2—N13^iv	2.0170 (11)	C3—C2	1.3832 (19)
Cu2—N13	2.0170 (11)	C3—H3	0.9500
Cu2—N19^v	2.0494 (11)	C21—H21	0.9500
Cu2—N19^vi	2.0494 (11)	C14—H14	0.9500
Cu2—F2	2.4109 (9)	C8—H8	0.9500
Cu2—F2^iv	2.4109 (9)	C5—C6	1.3821 (19)
Si1—F6	1.6534 (11)	C5—H5	0.9500
Si1—F5	1.6806 (10)	C24—C23	1.3882 (19)
Si1—F3	1.6823 (10)	C24—H24	0.9500
Si1—F4	1.6855 (11)	C23—H23	0.9500
Si1—F2	1.7120 (10)	C11—C12	1.3877 (19)
Si1—F1	1.7145 (10)	C11—H11	0.9500
N1—C6	1.3418 (18)	C12—H12	0.9500
N1—C2	1.3455 (17)	C2—H2	0.9500
O52—H52B	0.90 (3)	C45—C44	1.387 (2)
O52—H52A	0.90 (3)	C45—C46	1.396 (2)
N7—C12	1.3442 (18)	C45—H45	0.9500
N7—C8	1.3470 (18)	C6—H6	0.9500
N7—Cu1^vii	2.0467 (11)	C46—C47	1.393 (2)
N19—C24	1.3432 (18)	C46—C40	1.484 (2)
N19—C20	1.3436 (18)	C44—H44	0.9500
N19—Cu2^viii	2.0494 (11)	C47—C48	1.384 (2)
N13—C18	1.3426 (17)	C47—H47	0.9500
N13—C14	1.3443 (18)	C38—C39	1.385 (2)
O53—H53B	0.78 (2)	C38—H38	0.9500
O53—H53A	0.85 (3)	N25—C30	1.331 (3)
O50—H50A	1.05 (3)	N25—C26	1.337 (3)
O50—H50B	0.96 (3)	C39—C40	1.396 (2)
O51—H51B	0.91 (3)	C39—H39	0.9500
O51—H51A	1.00 (4)	C40—C41	1.391 (2)
N43—C48	1.338 (2)	C36—C35	1.386 (2)
N43—C44	1.341 (2)	C36—H36	0.9500
O49—H49B	0.96 (3)	C48—H48	0.9500
O49—H49A	1.00 (4)	C34—C35	1.393 (2)
N37—C42	1.337 (2)	C34—C33	1.394 (2)
N37—C38	1.338 (2)	C34—C28	1.483 (2)
N31—C32	1.334 (2)	C35—H35	0.9500
N31—C36	1.337 (2)	C33—C32	1.386 (2)
C16—C17	1.3927 (19)	C33—H33	0.9500
C16—C15	1.3947 (18)	C28—C29	1.386 (2)
C16—C22	1.4803 (19)	C28—C27	1.396 (2)
C17—C18	1.3845 (19)	C41—C42	1.384 (2)
C17—H17	0.9500	C41—H41	0.9500
C22—C23	1.3942 (19)	C27—C26	1.383 (2)
C22—C21	1.3950 (19)	C27—H27	0.9500
C4—C5	1.3938 (19)	C32—H32	0.9500
C4—C3	1.3974 (19)	C42—H42	0.9500
C4—C10	1.4791 (19)	C26—H26	0.9500
C20—C21	1.3823 (19)	C29—C30	1.388 (3)
C20—H20	0.9500	C29—H29	0.9500
C10—C11	1.3948 (19)	C30—H30	0.9500

N1ⁱ—Cu1—N1	180.00 (6)	C2—C3—C4	119.53 (12)
N1ⁱ—Cu1—N7ⁱⁱ	91.58 (5)	C2—C3—H3	120.2
N1—Cu1—N7ⁱⁱ	88.42 (5)	C4—C3—H3	120.2
N1ⁱ—Cu1—N7ⁱⁱⁱ	88.42 (5)	C20—C21—C22	119.74 (12)
N1—Cu1—N7ⁱⁱⁱ	91.58 (5)	C20—C21—H21	120.1
N7ⁱⁱ—Cu1—N7ⁱⁱⁱ	180.0	C22—C21—H21	120.1
N1ⁱ—Cu1—F1ⁱ	90.65 (4)	N13—C14—C15	122.35 (12)
N1—Cu1—F1ⁱ	89.35 (4)	N13—C14—H14	118.8
N7ⁱⁱ—Cu1—F1ⁱ	89.60 (4)	C15—C14—H14	118.8
N7ⁱⁱⁱ—Cu1—F1ⁱ	90.40 (4)	N7—C8—C9	122.68 (13)
N1ⁱ—Cu1—F1	89.35 (4)	N7—C8—H8	118.7
N1—Cu1—F1	90.65 (4)	C9—C8—H8	118.7
N7ⁱⁱ—Cu1—F1	90.40 (4)	C6—C5—C4	119.54 (13)
N7ⁱⁱⁱ—Cu1—F1	89.60 (4)	C6—C5—H5	120.2
F1ⁱ—Cu1—F1	180.0	C4—C5—H5	120.2
N13^iv—Cu2—N13	180.0	N19—C24—C23	122.55 (12)
N13^iv—Cu2—N19^v	90.73 (5)	N19—C24—H24	118.7
N13—Cu2—N19^v	89.27 (5)	C23—C24—H24	118.7
N13^iv—Cu2—N19^vi	89.27 (5)	C24—C23—C22	119.76 (12)
N13—Cu2—N19^vi	90.73 (5)	C24—C23—H23	120.1
N19^v—Cu2—N19^vi	180.0	C22—C23—H23	120.1
N13^iv—Cu2—F2	90.59 (4)	C12—C11—C10	119.54 (12)
N13—Cu2—F2	89.41 (4)	C12—C11—H11	120.2
N19^v—Cu2—F2	90.67 (4)	C10—C11—H11	120.2
N19^vi—Cu2—F2	89.33 (4)	N7—C12—C11	122.54 (12)
N13^iv—Cu2—F2^iv	89.41 (4)	N7—C12—H12	118.7
N13—Cu2—F2^iv	90.59 (4)	C11—C12—H12	118.7
N19^v—Cu2—F2^iv	89.33 (4)	N1—C2—C3	122.29 (12)
N19^vi—Cu2—F2^iv	90.67 (4)	N1—C2—H2	118.9
F2—Cu2—F2^iv	180.0	C3—C2—H2	118.9
F6—Si1—F5	90.80 (6)	C44—C45—C46	119.09 (14)
F6—Si1—F3	89.64 (6)	C44—C45—H45	120.5
F5—Si1—F3	179.55 (6)	C46—C45—H45	120.5
F6—Si1—F4	178.87 (6)	N1—C6—C5	122.51 (12)
F5—Si1—F4	90.12 (6)	N1—C6—H6	118.7
F3—Si1—F4	89.44 (6)	C5—C6—H6	118.7
F6—Si1—F2	91.01 (4)	C47—C46—C45	117.06 (14)
F5—Si1—F2	89.67 (5)	C47—C46—C40	121.19 (14)
F3—Si1—F2	90.41 (5)	C45—C46—C40	121.74 (13)
F4—Si1—F2	89.64 (4)	N43—C44—C45	124.17 (15)
F6—Si1—F1	90.89 (4)	N43—C44—H44	117.9
F5—Si1—F1	90.35 (5)	C45—C44—H44	117.9
F3—Si1—F1	89.56 (5)	C48—C47—C46	119.55 (14)
F4—Si1—F1	88.45 (4)	C48—C47—H47	120.2
F2—Si1—F1	178.09 (4)	C46—C47—H47	120.2
Si1—F1—Cu1	178.36 (5)	N37—C38—C39	123.69 (14)
Si1—F2—Cu2	176.83 (5)	N37—C38—H38	118.2
C6—N1—C2	118.46 (12)	C39—C38—H38	118.2
C6—N1—Cu1	118.82 (9)	C30—N25—C26	117.18 (15)
C2—N1—Cu1	122.58 (9)	C38—C39—C40	119.83 (14)
H52B—O52—H52A	111 (2)	C38—C39—H39	120.1
C12—N7—C8	118.09 (12)	C40—C39—H39	120.1
C12—N7—Cu1^vii	120.22 (9)	C41—C40—C39	116.65 (14)
C8—N7—Cu1^vii	121.50 (9)	C41—C40—C46	121.72 (14)
C24—N19—C20	117.86 (12)	C39—C40—C46	121.64 (13)
C24—N19—Cu2^viii	121.30 (9)	N31—C36—C35	123.33 (16)
C20—N19—Cu2^viii	120.62 (9)	N31—C36—H36	118.3
C18—N13—C14	118.38 (12)	C35—C36—H36	118.3
C18—N13—Cu2	121.49 (9)	N43—C48—C47	123.95 (14)
C14—N13—Cu2	120.10 (9)	N43—C48—H48	118.0
H53B—O53—H53A	108 (3)	C47—C48—H48	118.0
H50A—O50—H50B	105 (2)	C35—C34—C33	117.94 (15)
H51B—O51—H51A	98 (2)	C35—C34—C28	119.72 (14)
C48—N43—C44	116.18 (14)	C33—C34—C28	122.19 (15)
H49B—O49—H49A	114 (3)	C36—C35—C34	119.07 (15)
C42—N37—C38	115.99 (14)	C36—C35—H35	120.5
C32—N31—C36	117.09 (14)	C34—C35—H35	120.5
C17—C16—C15	117.72 (12)	C32—C33—C34	118.45 (16)
C17—C16—C22	121.09 (12)	C32—C33—H33	120.8
C15—C16—C22	121.19 (12)	C34—C33—H33	120.8
C18—C17—C16	119.51 (12)	C29—C28—C27	117.51 (15)
C18—C17—H17	120.2	C29—C28—C34	120.85 (15)
C16—C17—H17	120.2	C27—C28—C34	121.46 (15)
C23—C22—C21	117.19 (12)	C42—C41—C40	119.25 (15)
C23—C22—C16	122.08 (12)	C42—C41—H41	120.4
C21—C22—C16	120.70 (12)	C40—C41—H41	120.4
C5—C4—C3	117.65 (12)	C26—C27—C28	118.95 (17)
C5—C4—C10	120.26 (13)	C26—C27—H27	120.5
C3—C4—C10	122.08 (12)	C28—C27—H27	120.5
N19—C20—C21	122.84 (13)	N31—C32—C33	124.04 (16)
N19—C20—H20	118.6	N31—C32—H32	118.0
C21—C20—H20	118.6	C33—C32—H32	118.0
C11—C10—C9	117.59 (12)	N37—C42—C41	124.56 (15)
C11—C10—C4	121.48 (13)	N37—C42—H42	117.7
C9—C10—C4	120.93 (12)	C41—C42—H42	117.7
C14—C15—C16	119.54 (13)	N25—C26—C27	123.59 (17)
C14—C15—H15	120.2	N25—C26—H26	118.2
C16—C15—H15	120.2	C27—C26—H26	118.2
N13—C18—C17	122.50 (12)	C28—C29—C30	119.30 (17)
N13—C18—H18	118.8	C28—C29—H29	120.3
C17—C18—H18	118.8	C30—C29—H29	120.3
C8—C9—C10	119.56 (13)	N25—C30—C29	123.38 (18)
C8—C9—H9	120.2	N25—C30—H30	118.3
C10—C9—H9	120.2	C29—C30—H30	118.3

C15—C16—C17—C18	0.9 (2)	C4—C3—C2—N1	−1.1 (2)
C22—C16—C17—C18	179.87 (12)	C2—N1—C6—C5	1.0 (2)
C17—C16—C22—C23	26.6 (2)	Cu1—N1—C6—C5	−174.86 (11)
C15—C16—C22—C23	−154.49 (14)	C4—C5—C6—N1	−1.6 (2)
C17—C16—C22—C21	−151.72 (14)	C44—C45—C46—C47	0.7 (2)
C15—C16—C22—C21	27.22 (19)	C44—C45—C46—C40	179.73 (14)
C24—N19—C20—C21	2.0 (2)	C48—N43—C44—C45	−0.5 (2)
Cu2^viii—N19—C20—C21	−172.69 (11)	C46—C45—C44—N43	−0.3 (2)
C5—C4—C10—C11	−154.60 (14)	C45—C46—C47—C48	−0.3 (2)
C3—C4—C10—C11	24.2 (2)	C40—C46—C47—C48	−179.31 (14)
C5—C4—C10—C9	24.7 (2)	C42—N37—C38—C39	0.3 (2)
C3—C4—C10—C9	−156.55 (14)	N37—C38—C39—C40	−1.4 (2)
C17—C16—C15—C14	−0.2 (2)	C38—C39—C40—C41	0.7 (2)
C22—C16—C15—C14	−179.17 (13)	C38—C39—C40—C46	−179.63 (13)
C14—N13—C18—C17	−0.5 (2)	C47—C46—C40—C41	149.49 (16)
Cu2—N13—C18—C17	177.47 (10)	C45—C46—C40—C41	−29.5 (2)
C16—C17—C18—N13	−0.6 (2)	C47—C46—C40—C39	−30.1 (2)
C11—C10—C9—C8	0.9 (2)	C45—C46—C40—C39	150.90 (15)
C4—C10—C9—C8	−178.38 (14)	C32—N31—C36—C35	0.5 (2)
C5—C4—C3—C2	0.5 (2)	C44—N43—C48—C47	1.0 (2)
C10—C4—C3—C2	−178.27 (13)	C46—C47—C48—N43	−0.6 (2)
N19—C20—C21—C22	0.0 (2)	N31—C36—C35—C34	2.0 (2)
C23—C22—C21—C20	−2.0 (2)	C33—C34—C35—C36	−2.6 (2)
C16—C22—C21—C20	176.33 (13)	C28—C34—C35—C36	173.10 (15)
C18—N13—C14—C15	1.2 (2)	C35—C34—C33—C32	0.8 (2)
Cu2—N13—C14—C15	−176.76 (11)	C28—C34—C33—C32	−174.74 (15)
C16—C15—C14—N13	−0.9 (2)	C35—C34—C28—C29	−132.33 (17)
C12—N7—C8—C9	−0.4 (2)	C33—C34—C28—C29	43.2 (2)
Cu1^vii—N7—C8—C9	−175.57 (11)	C35—C34—C28—C27	42.8 (2)
C10—C9—C8—N7	−0.4 (2)	C33—C34—C28—C27	−141.73 (17)
C3—C4—C5—C6	0.8 (2)	C39—C40—C41—C42	0.8 (2)
C10—C4—C5—C6	179.62 (13)	C46—C40—C41—C42	−178.85 (15)
C20—N19—C24—C23	−2.0 (2)	C29—C28—C27—C26	0.3 (3)
Cu2^viii—N19—C24—C23	172.69 (11)	C34—C28—C27—C26	−174.98 (16)
N19—C24—C23—C22	−0.1 (2)	C36—N31—C32—C33	−2.4 (3)
C21—C22—C23—C24	2.1 (2)	C34—C33—C32—N31	1.8 (3)
C16—C22—C23—C24	−176.27 (13)	C38—N37—C42—C41	1.3 (3)
C9—C10—C11—C12	−0.8 (2)	C40—C41—C42—N37	−1.9 (3)
C4—C10—C11—C12	178.56 (13)	C30—N25—C26—C27	−1.5 (3)
C8—N7—C12—C11	0.6 (2)	C28—C27—C26—N25	1.8 (3)
Cu1^vii—N7—C12—C11	175.83 (11)	C27—C28—C29—C30	−2.6 (3)
C10—C11—C12—N7	0.0 (2)	C34—C28—C29—C30	172.72 (17)
C6—N1—C2—C3	0.4 (2)	C26—N25—C30—C29	−1.0 (3)
Cu1—N1—C2—C3	176.11 (10)	C28—C29—C30—N25	3.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N31^viii	0.95	2.34	3.2849 (19)	170
C20—H20···F2ⁱⁱ	0.95	2.32	3.0341 (16)	131
C20—H20···F5ⁱⁱ	0.95	2.53	3.4305 (17)	159
C18—H18···F2^iv	0.95	2.52	3.1085 (16)	120
C9—H9···O52	0.95	2.50	3.4223 (18)	163
C3—H3···N37^vii	0.95	2.54	3.4803 (19)	173
C21—H21···O52ⁱⁱ	0.95	2.56	3.4294 (18)	152
C14—H14···F2	0.95	2.43	3.0497 (16)	123
C14—H14···F4	0.95	2.55	3.4519 (17)	158
C8—H8···F1^v	0.95	2.33	3.0205 (16)	129
C8—H8···F4^v	0.95	2.51	3.3524 (18)	148
C5—H5···O52	0.95	2.43	3.2916 (18)	151
C24—H24···F2^viii	0.95	2.29	2.9997 (16)	131
C24—H24···F3^viii	0.95	2.55	3.4609 (17)	161
C11—H11···N37^vii	0.95	2.61	3.4358 (19)	145
C12—H12···F1^vii	0.95	2.26	2.9662 (16)	131
C12—H12···F6^vii	0.95	2.49	3.4040 (16)	161
C2—H2···F1ⁱ	0.95	2.52	3.0708 (16)	117
C2—H2···F3ⁱ	0.95	2.45	3.3364 (17)	156
C45—H45···O50^ix	0.95	2.44	3.376 (2)	167
C6—H6···F1	0.95	2.46	3.0691 (16)	122
C6—H6···F4	0.95	2.60	3.5313 (17)	166
C38—H38···F6	0.95	2.41	3.1240 (19)	132
C48—H48···O51^iv	0.95	2.50	3.330 (2)	146
O53—H53B···F3^v	0.78 (2)	1.96 (3)	2.7228 (17)	166 (2)
O52—H52B···O53	0.90 (3)	1.83 (3)	2.7227 (18)	170 (2)
O53—H53A···N43^iv	0.85 (3)	2.05 (3)	2.8666 (19)	161 (3)
O52—H52A···O51	0.90 (3)	1.84 (3)	2.726 (2)	172 (2)
O50—H50A···O49	1.05 (3)	1.72 (3)	2.741 (2)	163 (2)
O49—H49B···F5ⁱⁱ	0.96 (3)	1.82 (3)	2.7716 (18)	173 (3)
O50—H50B···N25ⁱ	0.96 (3)	1.86 (3)	2.816 (2)	173 (3)
O49—H49A···O52ⁱⁱ	1.00 (4)	1.81 (4)	2.798 (2)	169 (3)
O51—H51B···F4	0.91 (3)	1.88 (3)	2.7029 (18)	149 (2)
O51—H51A···O50	1.00 (4)	1.76 (4)	2.719 (2)	158 (3)

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

Geometrical parameters (Å, °) for the π–π stacking of the 4,4'-bipyridine molecules within the pores top

Cg(I) is the centroid of the atoms defining plane I: Cg(N25) = N25/C26–C30; Cg(N31) = N31/C32–C36; Cg(N43) = N43/C44-7-C48 and Cg(N37) = N37/C38–C42. d_Cg_–_Cg is the distance between Cg(I) and Cg(J). α is the dihedral angle between planes I and J. β is the angle between the Cg(I)→Cg(J) vector and the normal to plane I. γ is the angle between the Cg(I)→Cg(J) vector and the normal to plane J.

Cg(I)	Cg(J)	d_Cg_–_Cg	α	β	γ
N25	N25ⁱ	3.7374 (10)	0.02 (9)	9.2	9.2
N31	N37ⁱⁱ	3.7358 (9)	20.79 (8)	21.4	13.1
N43	N43ⁱⁱⁱ	3.8576 (9)	0.00 (7)	23.8	23.8

Symmetry codes: (i) -x, 2 - y, 1 - z; (ii) x, y, z; (iii) 1 - x, 2 - y, 1 - z.

Acknowledgements

The Service Commun de Diffraction des Rayons X – Lorraine University is thanked for providing access to crystallographic facilities.

References

Blake, A. J., Hill, S. J., Hubberstey, P. & Li, W.-S. (1997). J. Chem. Soc. Dalton Trans. pp. 913–914. CSD CrossRef Google Scholar
Burd, S. D., Ma, S., Perman, J. A., Sikora, B. J., Snurr, R. Q., Thallapally, P. K., Tian, J., Wojtas, L. & Zaworotko, M. J. (2012). J. Am. Chem. Soc. 134, 3663–3666. Web of Science CSD CrossRef CAS PubMed Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fan, S., Sun, F., Xie, J., Guo, J., Zhang, L., Wang, C., Pan, Q. & Zhu, G. (2013). J. Mater. Chem. A, 1, 11438–11442. CrossRef CAS Google Scholar
Gable, R. W., Hoskins, B. F. & Robson, R. (1990). J. Chem. Soc. Chem. Commun. pp. 1677–1678. CrossRef Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lin, M.-J., Jouaiti, A., Kyritsakas, N. & Hosseini, M. W. (2009). CrystEngComm, 11, 189–191. CSD CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Noro, S., Kitagawa, S., Kondo, M. & Seki, K. (2000). Angew. Chem. Int. Ed. 39, 2081–2084. CrossRef Google Scholar
Noro, S., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. & Yamashita, M. (2002). J. Am. Chem. Soc. 124, 2568–2583. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Subramanian, S. & Zaworotko, M. J. (1995). Angew. Chem. Int. Ed. Engl. 34, 2127–2129. CSD CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, Q., Yang, J., Zhao, Q., Dong, J. & Li, J. (2012). J. Coord. Chem. 65, 1645–1654. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.