Tetra-kis(pyridine-κN)bis-(tetrafluorido-borato-κF)copper(II).

In the title complex, [Cu(BF4)2(C5H5N)2], the Cu(II) ion is in an octa-hedral coordination environment and is surrounded by four pyridine and two tetra-fluoridoborate mol-ecules. The four pyridine mol-ecules 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 octa-hedron 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 inter-actions.

Related literature

For related [Cu(C5H5N)4 Y 2] 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 CuII 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 = 553.56

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.117

S = 1.01

4378 reflections

317 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.68 e Å−3

Absolute structure: Flack (1983 ▶), 1868 Friedel pairs

Flack parameter: 0.22 (5)

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 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813018643/sj5342sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(BF4)2(C5H5N)4]	F(000) = 1116
Mr = 553.56	Dx = 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

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

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(Fo2) + (0.030P)2 + 2.2291P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
4378 reflections	Δρmax = 0.39 e Å−3
317 parameters	Δρmin = −0.68 e Å−3
0 restraints	Absolute structure: Flack (1983), 1868 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.22 (5)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) ; (iii) .