Tetra­kis(pyridine-κN)bis­(tetrafluorido­borato-κF)copper(II)

De Silva, N.; Pannu, A.P.S.; Plieger, P.G.

doi:10.1107/S1600536813018643

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m450-m451

doi:10.1107/S1600536813018643

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Tetrakis(pyridine-κN)bis(tetrafluoridoborato-κF)copper(II)

Nirosha De Silva,^a Ajay Pal Singh Pannu ^a and Paul G. Plieger ^a ^*

^aInstitute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, New Zealand
^*Correspondence e-mail: P.G.Plieger@massey.ac.nz

(Received 2 July 2013; accepted 5 July 2013; online 13 July 2013)

In the title complex, [Cu(BF₄)₂(C₅H₅N)₂], the Cu^II ion is in an octahedral coordination environment and is surrounded by four pyridine and two tetrafluoridoborate molecules. The four pyridine molecules are coordinated to the copper ion through their N atoms in the equatorial plane and display a right-handed screw arrangement around the Cu^II ion. The remaining two trans positions in the octahedron are occupied by the BF₄⁻ anions, each coordinating weakly through an F atom. The crystal packing shows a two-dimensional sheet structure parallel to the ab plane that is formed by C—H⋯F hydrogen-bonding interactions.

Related literature

For related [Cu(C₅H₅N)₄Y₂] complexes (where Y = ClO₄⁻, NO₃⁻, BF₄⁻, PF₆⁻, SO₃CF₃⁻) see: Ibers (1953 ); Brown et al. (1966 ); Alleyne & Thompson (1974 ); Pradilla Sorzano et al. (1979 ); Barker & Stobart (1980 ); Haynes et al. (1988 ); Agnus et al. (1994 ); Beurskens et al. (1995 ); Li & Zhang (2004 ); Bowmaker et al. (2011 ). For Cu^II complexes containing an N₄F₂ donor set, see: Su & Li (1994 ); Heier et al. (1998 ); Conner et al. (2006 ); Noro et al. (2009 , 2011 ).

Experimental

Crystal data

[Cu(BF₄)₂(C₅H₅N)₄]
M_r = 553.56
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.162 (3) Å
b = 13.831 (5) Å
c = 16.350 (4) Å
V = 2298.0 (12) Å³
Z = 4
Cu Kα radiation
μ = 2.10 mm⁻¹
T = 295 K
0.20 × 0.14 × 0.14 mm

Data collection

Rigaku Spider X-ray diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2005 ) T_min = 0.769, T_max = 1
17937 measured reflections
4378 independent reflections
3186 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.117
S = 1.01
4378 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.68 e Å⁻³
Absolute structure: Flack (1983 ), 1868 Friedel pairs
Flack parameter: 0.22 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯F5ⁱ	0.93	2.63	3.016 (6)	105
C7—H7⋯F8ⁱ	0.93	2.51	3.380 (6)	155
C13—H13⋯F6ⁱⁱ	0.93	2.5	3.135 (6)	126
C17—H17⋯F5ⁱⁱⁱ	0.93	2.51	3.169 (6)	128
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: CrystalClear-SM Expert (Rigaku, 2005); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813018643/sj5342sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018643/sj5342Isup2.hkl

checkCIF report

Comment top

X-ray data on complexes of the type [Cu(C₅H₅N)₄Y₂] (Y = ClO₄^-, NO₃^-, BF₄^-, PF₆^-, NCS^-, I₃^-, SO₃CF₃^-, CF₃CO₂^-) started appearing from the 1950's onwards (Ibers, 1953; Brown et al., 1966; Alleyne et al., 1974; Pradilla et al., 1979; Barker et al., 1980; Haynes et al., 1988; Agnus et al., 1994; Beurskens et al., 1995; Li et al., 2004; Bowmaker et al., 2011). Among these complexes, preliminary structural investigations on [Cu(C₅H₅N)₂(BF₄)₂] were carried out by Ibers (Ibers, 1953) but were limited to the unit cell and space group determination. At that time because of the size and complexity of the unit cell no further work was completed. Based on Ibers' analysis, Agnus and co-workers in their paper on the structural determination of the related complex [Cu(C₅H₅N)₄(ClO₄)₂], predicted that the tetrafluoridoborate analogue would also crystalize as a structural enantiomer. A CCDC search reveals that although there have been many reports on Cu^II complexes with the [Cu(C₅H₅N)₄Y₂] structural motif there are no single-crystal X-ray reports with BF₄ as the counter ion (Y = BF₄). Therefore, in the present work we report the single-crystal X-ray analysis of this complex, [Cu(C₅H₅N)₂(BF₄)₂].

The molecular structure of present complex is shown in Fig. 1 along with the atom labelling scheme. In this complex, the four pyridine ligand molecules are coordinating through their nitrogen atoms forming a square plane around the Cu^II center while the remaining two trans positions in the distorted octahedron are occupied by the BF₄ molecules, each coordinating through an F atom. The Cu—N distance varies from 2.009 (4) Å to 2.037 (4) Å while the two long Cu—F trans distances of 2.406 (4) Å and 2.476 (3) Å are consistent with other hexacoordinate Cu^II complexes containing an N₄F₂ donor set (2.394 (3) Å, Su et al., 1994; 2.452 (3) Å, Heier et al., 1998; 2.376 (2) Å, Conner et al., 2006; 2.501 (3) – 2.503 (3) Å, Noro et al., 2011; 2.528 (3) – 2.587 (2) Å, Noro et al., 2009). The dihedral angle values of 47.6 (3)° (N1—Cu1—N4—C25), 58.4 (3)° (N2—Cu1—N1—C6), 40.7 (2)° (N3—Cu1—N2—C1) and 58.3 (3)° (N4—Cu1—N3—C20) indicate a similar orientation for each pyridine ring with respect to the equatorial plane (plane containing the Cu^II and the four coordinated nitrogen atoms). Fig. 2. gives a pictorial view of this similarity in orientation along with confirming the right handed screw arrangement of all the four coordinated pyridine rings. This as predicted by Agnus and co-workers is very similar to the isomorphous perchlorate complex [Cu(C₅H₅N)₄(ClO₄)₂] (Agnus et al., 1994) which also crystalizes in orthorhombic crystal system with P2₁2₁2₁ space group and similar unit-cell parameters. The crystal packing investigations in present complex show a two-dimensional sheet structure parallel to the ab plane is formed by C—H···F hydrogen bonding interactions (Fig. 3, Table 1).

Related literature top

For related [Cu(C₅H₅N)₄Y₂] complexes (where Y = ClO₄^-, NO₃^-, BF₄^-, PF₆^-, SO₃CF₃^-) see: Ibers (1953); Brown et al. (1966); Alleyne et al. (1974); Pradilla et al. (1979); Barker & Stobart (1980); Haynes et al. (1988); Agnus et al. (1994); Beurskens et al. (1995); Li & Zhang (2004); Bowmaker et al. (2011). For Cu^II complexes containing an N₄F₂ donor set, see: Su & Li (1994); Heier et al. (1998); Conner et al. (2006); Noro et al. (2009, 2011).

Experimental top

Crystals of [Cu(C₅H₅N)₄(BF₄)₂] were obtained by the slow evaporation of a mixed solvent solution (MeOH: H₂O: pyridine, 15: 10: 5 ml respectively) containing copper(II) tetrafluoridoborate hexahydrate (0.345 g, 1.0 mmol). Blue crystals of [Cu(C₅H₅N)₂(BF₄)₂] were obtained after 2–3 weeks from the filtrate.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2005); cell refinement: CrystalClear-SM Expert (Rigaku, 2005); data reduction: CrystalClear-SM Expert (Rigaku, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP diagram showing the molecular structure of the title complex. The ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Showing the similarity in orientation and right handed screw arrangement of all the four coordinated pyridine rings with respect to the central metal ion.
	Fig. 3. A two-dimensional sheet structure parallel to ab plane is formed by C—H···F hydrogen bonding interactions. The hydrogen atoms other than those involved in H-bonding have been omitted for clarity. Hydrogen bonds are shown in dashed lines.

Tetrakis(pyridine-κN)bis(tetrafluoridoborato-κF)copper(II) top

Crystal data top

[Cu(BF₄)₂(C₅H₅N)₄]	F(000) = 1116
M_r = 553.56	D_x = 1.6 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2453 reflections
a = 10.162 (3) Å	θ = 7–71.4°
b = 13.831 (5) Å	µ = 2.10 mm⁻¹
c = 16.350 (4) Å	T = 295 K
V = 2298.0 (12) Å³	Block, blue
Z = 4	0.2 × 0.14 × 0.14 mm

Data collection top

Rigaku Spider X-ray diffractometer	4378 independent reflections
Radiation source: Rotating Anode	3186 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 10 pixels mm^-1	θ_max = 71.8°, θ_min = 7.0°
profile data from ω–scans	h = −10→12
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2005)	k = −16→16
T_min = 0.769, T_max = 1	l = −19→20
17937 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.030P)² + 2.2291P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
4378 reflections	Δρ_max = 0.39 e Å⁻³
317 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1868 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.22 (5)

Crystal data top

[Cu(BF₄)₂(C₅H₅N)₄]	V = 2298.0 (12) Å³
M_r = 553.56	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 10.162 (3) Å	µ = 2.10 mm⁻¹
b = 13.831 (5) Å	T = 295 K
c = 16.350 (4) Å	0.2 × 0.14 × 0.14 mm

Data collection top

Rigaku Spider X-ray diffractometer	4378 independent reflections
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2005)	3186 reflections with I > 2σ(I)
T_min = 0.769, T_max = 1	R_int = 0.065
17937 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.117	Δρ_max = 0.39 e Å⁻³
S = 1.01	Δρ_min = −0.68 e Å⁻³
4378 reflections	Absolute structure: Flack (1983), 1868 Friedel pairs
317 parameters	Absolute structure parameter: 0.22 (5)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.8793 (5)	0.0901 (4)	0.1770 (3)	0.0447 (12)
H1	0.9558	0.1139	0.2008	0.054*
C2	0.8868 (5)	0.0101 (3)	0.1268 (3)	0.0484 (13)
H2	0.9676	−0.0192	0.1168	0.058*
C3	0.7746 (5)	−0.0259 (3)	0.0918 (3)	0.0473 (12)
H3	0.7787	−0.0789	0.0568	0.057*
C4	0.6545 (5)	0.0176 (4)	0.1092 (3)	0.0474 (13)
H4	0.5764	−0.0068	0.088	0.057*
C5	0.6548 (5)	0.0982 (4)	0.1591 (3)	0.0424 (12)
H5	0.575	0.1285	0.17	0.051*
C6	0.6032 (5)	0.1434 (3)	0.3647 (3)	0.0449 (12)
H6	0.6802	0.1072	0.368	0.054*
C7	0.4944 (5)	0.1140 (4)	0.4088 (3)	0.0454 (12)
H7	0.4982	0.0594	0.4418	0.054*
C8	0.3803 (5)	0.1671 (4)	0.4029 (3)	0.0465 (12)
H8	0.3057	0.1489	0.4322	0.056*
C9	0.3779 (4)	0.2478 (3)	0.3530 (3)	0.0428 (11)
H9	0.3012	0.2838	0.3473	0.051*
C10	0.4888 (4)	0.2738 (3)	0.3124 (3)	0.0422 (11)
H10	0.4871	0.3291	0.28	0.051*
C20	0.9163 (5)	0.3097 (4)	0.1054 (3)	0.0471 (13)
H20	0.8419	0.2878	0.078	0.057*
C19	1.0217 (5)	0.3422 (4)	0.0604 (3)	0.0523 (14)
H19	1.0172	0.3436	0.0036	0.063*
C18	1.1332 (5)	0.3726 (4)	0.0996 (3)	0.0500 (13)
H18	1.2053	0.3945	0.0698	0.06*
C17	1.1373 (5)	0.3703 (4)	0.1849 (3)	0.0500 (13)
H17	1.2121	0.3897	0.2132	0.06*
C16	1.0275 (5)	0.3384 (3)	0.2257 (3)	0.0456 (12)
H16	1.0294	0.3375	0.2826	0.055*
C15	0.7589 (4)	0.4783 (3)	0.2670 (3)	0.0424 (10)
H15	0.7678	0.4753	0.2104	0.051*
C14	0.7524 (5)	0.5676 (3)	0.3032 (3)	0.0470 (11)
H14	0.7554	0.6236	0.2718	0.056*
C13	0.7415 (5)	0.5726 (3)	0.3870 (3)	0.0503 (12)
H13	0.7395	0.6324	0.413	0.06*
C12	0.7335 (5)	0.4887 (3)	0.4318 (3)	0.0487 (12)
H12	0.7245	0.4908	0.4884	0.058*
C11	0.7390 (5)	0.4010 (3)	0.3908 (3)	0.0431 (11)
H11	0.7329	0.3442	0.421	0.052*
B1	1.0010 (6)	0.1685 (5)	0.4073 (4)	0.0490 (15)
B2	0.4990 (6)	0.3467 (4)	0.1079 (4)	0.0454 (14)
N2	0.6013 (4)	0.2225 (3)	0.3173 (2)	0.0385 (9)
N1	0.7637 (4)	0.1349 (3)	0.1924 (2)	0.0381 (8)
N4	0.9169 (4)	0.3084 (3)	0.1878 (2)	0.0397 (9)
N3	0.7529 (4)	0.3950 (2)	0.30907 (19)	0.0341 (8)
F1	0.8975 (3)	0.1997 (3)	0.3593 (2)	0.0807 (11)
F2	0.9527 (5)	0.1251 (3)	0.4732 (2)	0.1131 (15)
F3	1.0755 (3)	0.1081 (3)	0.3611 (3)	0.1038 (14)
F4	1.0738 (3)	0.2493 (3)	0.4275 (2)	0.0841 (11)
F5	0.4395 (3)	0.41614 (19)	0.15695 (18)	0.0565 (8)
F6	0.4263 (3)	0.2628 (2)	0.1097 (2)	0.0658 (9)
F7	0.6239 (3)	0.3276 (2)	0.13865 (18)	0.0545 (7)
F8	0.5108 (4)	0.3811 (2)	0.02866 (18)	0.0716 (10)
Cu1	0.75983 (6)	0.26389 (4)	0.25232 (4)	0.03806 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.037 (3)	0.040 (3)	0.056 (3)	0.001 (2)	0.005 (2)	0.009 (2)
C2	0.043 (3)	0.041 (3)	0.062 (3)	0.006 (2)	0.010 (3)	0.009 (3)
C3	0.055 (3)	0.040 (3)	0.047 (3)	−0.001 (3)	0.004 (2)	−0.002 (2)
C4	0.049 (3)	0.042 (3)	0.052 (3)	−0.003 (3)	−0.003 (2)	−0.004 (2)
C5	0.034 (3)	0.042 (3)	0.051 (3)	0.001 (2)	−0.002 (2)	0.002 (2)
C6	0.041 (3)	0.039 (3)	0.054 (3)	0.002 (2)	0.000 (2)	−0.001 (2)
C7	0.049 (3)	0.040 (3)	0.048 (3)	−0.005 (3)	0.003 (2)	0.003 (2)
C8	0.043 (3)	0.052 (3)	0.045 (3)	−0.006 (3)	0.008 (2)	−0.006 (2)
C9	0.034 (2)	0.047 (3)	0.048 (2)	0.005 (2)	0.004 (2)	−0.002 (2)
C10	0.040 (3)	0.039 (3)	0.047 (2)	0.003 (2)	−0.003 (2)	0.003 (2)
C20	0.033 (3)	0.052 (3)	0.057 (3)	−0.006 (2)	−0.003 (2)	−0.002 (3)
C19	0.042 (3)	0.066 (4)	0.048 (3)	−0.006 (3)	0.002 (2)	0.007 (3)
C18	0.038 (3)	0.064 (4)	0.048 (3)	−0.003 (3)	0.007 (2)	0.007 (3)
C17	0.034 (3)	0.063 (3)	0.053 (3)	−0.008 (3)	0.001 (2)	0.003 (3)
C16	0.037 (3)	0.050 (3)	0.050 (3)	−0.005 (2)	−0.001 (2)	0.001 (2)
C15	0.035 (3)	0.042 (2)	0.051 (3)	0.000 (2)	0.003 (2)	0.004 (2)
C14	0.045 (3)	0.041 (3)	0.054 (3)	0.005 (3)	0.001 (3)	0.009 (2)
C13	0.044 (3)	0.039 (3)	0.068 (3)	0.005 (3)	0.000 (3)	−0.002 (2)
C12	0.047 (3)	0.051 (3)	0.049 (3)	0.004 (3)	−0.001 (3)	−0.007 (2)
C11	0.038 (3)	0.043 (2)	0.048 (2)	0.001 (3)	0.000 (2)	0.009 (2)
B1	0.037 (4)	0.056 (4)	0.055 (3)	0.003 (3)	0.006 (3)	0.000 (3)
B2	0.035 (3)	0.044 (3)	0.057 (3)	−0.001 (3)	0.000 (3)	0.005 (3)
N2	0.035 (2)	0.036 (2)	0.0443 (19)	−0.0009 (18)	0.0007 (17)	−0.0012 (17)
N1	0.030 (2)	0.038 (2)	0.0459 (19)	0.003 (2)	−0.0002 (18)	0.0019 (16)
N4	0.037 (2)	0.041 (2)	0.041 (2)	−0.0015 (19)	0.0015 (18)	−0.0003 (18)
N3	0.034 (2)	0.0341 (18)	0.0344 (16)	−0.0019 (19)	0.0024 (18)	0.0004 (14)
F1	0.055 (2)	0.092 (3)	0.095 (2)	0.0015 (19)	−0.0267 (19)	0.030 (2)
F2	0.164 (4)	0.104 (3)	0.071 (2)	−0.012 (3)	0.017 (3)	0.035 (2)
F3	0.054 (2)	0.107 (3)	0.149 (4)	0.014 (2)	0.011 (2)	−0.063 (3)
F4	0.060 (2)	0.094 (3)	0.098 (2)	−0.024 (2)	0.0140 (18)	−0.044 (2)
F5	0.0586 (19)	0.0407 (16)	0.0703 (19)	0.0070 (14)	0.0111 (16)	0.0029 (15)
F6	0.0495 (18)	0.0472 (18)	0.101 (2)	−0.0135 (15)	0.0000 (16)	−0.0033 (18)
F7	0.0362 (16)	0.0633 (19)	0.0641 (18)	0.0026 (14)	−0.0068 (14)	0.0026 (15)
F8	0.103 (3)	0.064 (2)	0.0479 (16)	0.007 (2)	−0.0089 (18)	0.0095 (15)
Cu1	0.0327 (3)	0.0364 (3)	0.0450 (3)	−0.0019 (3)	0.0014 (3)	0.0001 (3)

Geometric parameters (Å, º) top

C1—N1	1.352 (6)	C17—C16	1.373 (6)
C1—C2	1.380 (7)	C17—H17	0.93
C1—H1	0.93	C16—N4	1.349 (5)
C2—C3	1.370 (7)	C16—H16	0.93
C2—H2	0.93	C15—N3	1.344 (5)
C3—C4	1.391 (7)	C15—C14	1.371 (6)
C3—H3	0.93	C15—H15	0.93
C4—C5	1.381 (7)	C14—C13	1.376 (6)
C4—H4	0.93	C14—H14	0.93
C5—N1	1.333 (6)	C13—C12	1.375 (6)
C5—H5	0.93	C13—H13	0.93
C6—N2	1.341 (6)	C12—C11	1.387 (6)
C6—C7	1.381 (6)	C12—H12	0.93
C6—H6	0.93	C11—N3	1.346 (5)
C7—C8	1.376 (7)	C11—H11	0.93
C7—H7	0.93	B1—F2	1.328 (7)
C8—C9	1.383 (7)	B1—F3	1.357 (7)
C8—H8	0.93	B1—F4	1.381 (7)
C9—C10	1.356 (6)	B1—F1	1.382 (6)
C9—H9	0.93	B2—F6	1.375 (6)
C10—N2	1.348 (5)	B2—F5	1.390 (6)
C10—H10	0.93	B2—F7	1.390 (6)
C20—N4	1.347 (6)	B2—F8	1.386 (6)
C20—C19	1.375 (7)	N2—Cu1	2.013 (4)
C20—H20	0.93	N1—Cu1	2.036 (4)
C19—C18	1.368 (7)	N4—Cu1	2.010 (4)
C19—H19	0.93	N3—Cu1	2.038 (3)
C18—C17	1.396 (6)	F1—Cu1	2.409 (3)
C18—H18	0.93

N1—C1—C2	121.7 (5)	C13—C14—C15	118.7 (4)
N1—C1—H1	119.1	C13—C14—H14	120.7
C2—C1—H1	119.1	C15—C14—H14	120.7
C3—C2—C1	119.6 (5)	C14—C13—C12	119.5 (4)
C3—C2—H2	120.2	C14—C13—H13	120.2
C1—C2—H2	120.2	C12—C13—H13	120.2
C2—C3—C4	119.2 (4)	C13—C12—C11	118.5 (4)
C2—C3—H3	120.4	C13—C12—H12	120.7
C4—C3—H3	120.4	C11—C12—H12	120.7
C5—C4—C3	118.0 (5)	N3—C11—C12	122.6 (4)
C5—C4—H4	121	N3—C11—H11	118.7
C3—C4—H4	121	C12—C11—H11	118.7
N1—C5—C4	123.4 (5)	F2—B1—F3	112.3 (6)
N1—C5—H5	118.3	F2—B1—F4	111.7 (5)
C4—C5—H5	118.3	F3—B1—F4	109.5 (5)
N2—C6—C7	122.0 (5)	F2—B1—F1	108.7 (5)
N2—C6—H6	119	F3—B1—F1	107.5 (5)
C7—C6—H6	119	F4—B1—F1	107.0 (5)
C8—C7—C6	118.8 (5)	F6—B2—F5	109.7 (4)
C8—C7—H7	120.6	F6—B2—F7	108.8 (4)
C6—C7—H7	120.6	F5—B2—F7	108.7 (4)
C9—C8—C7	119.1 (5)	F6—B2—F8	110.9 (5)
C9—C8—H8	120.5	F5—B2—F8	109.8 (4)
C7—C8—H8	120.5	F7—B2—F8	108.9 (5)
C10—C9—C8	119.3 (4)	C6—N2—C10	118.4 (4)
C10—C9—H9	120.4	C6—N2—Cu1	121.7 (3)
C8—C9—H9	120.4	C10—N2—Cu1	119.9 (3)
N2—C10—C9	122.4 (4)	C5—N1—C1	118.1 (4)
N2—C10—H10	118.8	C5—N1—Cu1	120.9 (3)
C9—C10—H10	118.8	C1—N1—Cu1	120.5 (3)
N4—C20—C19	122.4 (5)	C20—N4—C16	117.3 (4)
N4—C20—H20	118.8	C20—N4—Cu1	121.7 (3)
C19—C20—H20	118.8	C16—N4—Cu1	121.0 (3)
C18—C19—C20	119.6 (5)	C15—N3—C11	117.3 (4)
C18—C19—H19	120.2	C15—N3—Cu1	121.9 (3)
C20—C19—H19	120.2	C11—N3—Cu1	120.7 (3)
C19—C18—C17	119.1 (5)	B1—F1—Cu1	165.8 (3)
C19—C18—H18	120.5	N4—Cu1—N2	178.68 (15)
C17—C18—H18	120.5	N4—Cu1—N3	89.65 (15)
C16—C17—C18	117.9 (5)	N2—Cu1—N3	89.15 (14)
C16—C17—H17	121	N4—Cu1—N1	90.04 (15)
C18—C17—H17	121	N2—Cu1—N1	91.15 (15)
N4—C16—C17	123.6 (4)	N3—Cu1—N1	178.11 (14)
N4—C16—H16	118.2	N4—Cu1—F1	91.87 (14)
C17—C16—H16	118.2	N2—Cu1—F1	88.69 (14)
N3—C15—C14	123.3 (4)	N3—Cu1—F1	91.01 (13)
N3—C15—H15	118.3	N1—Cu1—F1	90.87 (14)
C14—C15—H15	118.3

N1—C1—C2—C3	−0.4 (7)	F2—B1—F1—Cu1	−173.6 (12)
C1—C2—C3—C4	−1.6 (7)	F3—B1—F1—Cu1	−51.8 (17)
C2—C3—C4—C5	2.4 (7)	F4—B1—F1—Cu1	65.6 (16)
C3—C4—C5—N1	−1.4 (7)	C20—N4—Cu1—N3	−121.7 (4)
N2—C6—C7—C8	0.8 (7)	C16—N4—Cu1—N3	58.2 (4)
C6—C7—C8—C9	0.2 (7)	C20—N4—Cu1—N1	56.5 (4)
C7—C8—C9—C10	−1.4 (7)	C16—N4—Cu1—N1	−123.6 (4)
C8—C9—C10—N2	1.6 (7)	C20—N4—Cu1—F1	147.3 (4)
N4—C20—C19—C18	1.6 (8)	C16—N4—Cu1—F1	−32.8 (4)
C20—C19—C18—C17	−0.3 (8)	C6—N2—Cu1—N3	−123.6 (4)
C19—C18—C17—C16	−0.8 (8)	C10—N2—Cu1—N3	57.7 (3)
C18—C17—C16—N4	0.7 (8)	C6—N2—Cu1—N1	58.3 (4)
N3—C15—C14—C13	1.1 (8)	C10—N2—Cu1—N1	−120.4 (3)
C15—C14—C13—C12	−1.9 (9)	C6—N2—Cu1—F1	−32.6 (4)
C14—C13—C12—C11	1.1 (8)	C10—N2—Cu1—F1	148.7 (3)
C13—C12—C11—N3	0.5 (8)	C15—N3—Cu1—N4	48.4 (4)
C7—C6—N2—C10	−0.6 (7)	C11—N3—Cu1—N4	−133.2 (4)
C7—C6—N2—Cu1	−179.3 (4)	C15—N3—Cu1—N2	−131.1 (4)
C9—C10—N2—C6	−0.6 (7)	C11—N3—Cu1—N2	47.4 (4)
C9—C10—N2—Cu1	178.1 (3)	C15—N3—Cu1—F1	140.2 (4)
C4—C5—N1—C1	−0.6 (7)	C11—N3—Cu1—F1	−41.3 (4)
C4—C5—N1—Cu1	171.6 (4)	C5—N1—Cu1—N4	−130.8 (4)
C2—C1—N1—C5	1.5 (7)	C1—N1—Cu1—N4	41.2 (4)
C2—C1—N1—Cu1	−170.7 (3)	C5—N1—Cu1—N2	48.6 (4)
C19—C20—N4—C16	−1.6 (8)	C1—N1—Cu1—N2	−139.4 (3)
C19—C20—N4—Cu1	178.3 (4)	C5—N1—Cu1—F1	137.3 (3)
C17—C16—N4—C20	0.4 (7)	C1—N1—Cu1—F1	−50.7 (3)
C17—C16—N4—Cu1	−179.5 (4)	B1—F1—Cu1—N4	−6.8 (15)
C14—C15—N3—C11	0.5 (7)	B1—F1—Cu1—N2	174.4 (15)
C14—C15—N3—Cu1	179.0 (4)	B1—F1—Cu1—N3	−96.5 (15)
C12—C11—N3—C15	−1.3 (8)	B1—F1—Cu1—N1	83.2 (15)
C12—C11—N3—Cu1	−179.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F5ⁱ	0.93	2.63	3.016 (6)	105
C7—H7···F8ⁱ	0.93	2.51	3.380 (6)	155
C13—H13···F6ⁱⁱ	0.93	2.5	3.135 (6)	126
C17—H17···F5ⁱⁱⁱ	0.93	2.51	3.169 (6)	128

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

Experimental details

Crystal data
Chemical formula	[Cu(BF₄)₂(C₅H₅N)₄]
M_r	553.56
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	10.162 (3), 13.831 (5), 16.350 (4)
V (Å³)	2298.0 (12)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.10
Crystal size (mm)	0.2 × 0.14 × 0.14

Data collection
Diffractometer	Rigaku Spider X-ray diffractometer
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 2005)
T_min, T_max	0.769, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	17937, 4378, 3186
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.117, 1.01
No. of reflections	4378
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.68
Absolute structure	Flack (1983), 1868 Friedel pairs
Absolute structure parameter	0.22 (5)

Computer programs: CrystalClear-SM Expert (Rigaku, 2005), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F5ⁱ	0.93	2.63	3.016 (6)	105.4
C7—H7···F8ⁱ	0.93	2.51	3.380 (6)	155.1
C13—H13···F6ⁱⁱ	0.93	2.5	3.135 (6)	126
C17—H17···F5ⁱⁱⁱ	0.93	2.51	3.169 (6)	127.7

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

Acknowledgements

APSP would like to acknowledge Massey University for the Post-Doctoral fellowship. PGP would like to acknowledge financial assistance from the Massey University Research Fund.

References

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