trans-Bis(hexafluoroantimonato)(phthalocyaninato)copper(II)

The title compound, trans-bis­(hexa­fluoro­antimonato-F)(phthalocyaninato-κ⁴N^29,30,31,32)copper(II), [Cu(SbF₆)₂(C₃₂­H₁₆N₈)] or Cu(pc)(SbF₆)₂ (pc is phthalocyaninate), comprises a six-coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF₆⁻ groups. The compound is presumed to consist of a Cu^II center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO₄)₂.

S1. Comment

Whereas galvanostatic oxidations of phthalocyanine (pc) and metallophthalocyanines normally lead to solid-state structures comprising stacks of partially oxidized macrocycles with counterions occupying the adjacent channels (Godfrey et al., 1990; Yakushi et al., 1987), the recently discovered compound trans-bis(perrhenato)(phthalocyaninato)copper(II), Cu(pc)(ReO₄)₂, (II) (Gardberg, Doan et al., 2001), prepared by galvanostatic oxidation, is a molecular compound in which the six-coordinate Cu center is bonded to four N atoms of the pc ring and to O atoms of two trans ReO₄ groups. EPR (electron paramagnetic resonance) measurements indicate that this is a Cu^II compound with a doubly ring-oxidized pc ring. A modification of the synthesis of (II) yielded a few very small crystals of the title compound, Cu(pc)(SbF₆)₂, (I). \sch

From the present single-crystal X-ray diffraction study, compound (I) is found to be analogous with (II), in that it is a molecular complex containing a six-coordinate Cu center (Fig. 1). The Cu atom is at an inversion center and hence lies in the least-squares plane of the pc molecule. The mean deviation from this plane is 0.0196 Å, and the maximum deviation is 0.046 (10) Å for atom C5. The Cu—F bond of (I) makes an angle of 4.7(2.5)° query with the normal to this plane. The two Cu—N distances, 1.955 (9) and 1.957 (9) Å, are normal. The largest residual peak, the electron density of which is about half that of a typical F peak, is located 1.21 Å from atom F1 and 1.79 Å from atom Cu1. A search of the April 2000 release of the Cambridge Structural Database (Allen & Kennard, 1993) for structures containing a Cu atom bonded to four equatorial N atoms (with the N—Cu—N' angle constrained to lie between 80 and 100° and the N—Cu—N'' angle constrained to lie between 170 and 190°) and to at least one axial F atom (F—Cu—N angle not constrained) revealed 17 structures. The range of Cu—F bond distances in these structures is 2.22–2.73 Å; the Cu—F distance in (I) is 2.626 (7) Å.

In the structure of (I), the Cu(pc) macrocycles are parallel to one another, with the peripheral benzene rings partially overlapping at a distance of 3.4 Å. This is to be contrasted with the structure of (II), in which the Cu(pc) rings are perpendicular to one another, creating a herringbone-type packing arrangement. Compound (I) is the second example of an oxidized copper phthalocyanine with a structure which is molecular and which does not comprise stacks of partially oxidized macrocycles. Whether (I) and (II) are isolated examples or whether they are the forerunners of many others remains to be determined.

Related literature

For related literature, see: Allen & Kennard (1993); Gardberg et al. (2001); Godfrey et al. (1990); Thompson et al. (1993); Yakushi et al. (1987).

S2. Experimental

Single crystals of the title compound grew at the anode of an electrolytic cell that consisted of two compartments separated by a glass frit. The Cu(pc) starting material was synthesized by metallation of very pure H₂(pc) (Thompson et al., 1993) with CuCl₂.xH₂O (99.9999%, dehydrated), followed by repeated sublimation. The cell was protected from light, kept purged with dry N₂ and maintained at 403 (5) K. Each half-cell contained a 1-chloronaphthalene solution in [N(n—Bu)₄][SbF₆] (20 ml, 0.0125 M); the solution in the anode compartment was saturated with Cu(pc). A 3.00 µA current was passed through the cell via Pt electrodes for one month, during which time the initially blue solution turned green. A few small crystals of (I) grew on the anode, amid several long needles of [Cu(pc)]₃[SbF₆]₂·C₁₀H₇Cl (Gardberg, Brazis et al., 2001). Semi-quantitative energy dispersive spectroscopy indicated that the small crystals contain Cu and Sb, but no Cl. They are air- and light-stable, but there was not enough material for CHN analysis.

S3. Refinement

Please provide brief details of H-atom refinement.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT+ (Bruker, 1999); data reduction: SAINT+; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL.

Figures

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-labeling scheme. H atoms are displayed as small spheres of arbitrary radii.

trans-bis(hexafluoroantimonato-F)(phthalocyaninato- κ⁴N²⁹,N³⁰,N³¹,N³²)copper(II)

Crystal data

[Cu(C32H16N8)(SbF6)2]	Z = 1
Mr = 1047.57	F(000) = 503
Triclinic, P1	Dx = 2.142 Mg m^−3
a = 8.596 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.150 (5) Å	Cell parameters from 1358 reflections
c = 10.724 (5) Å	θ = 2.3–21.7°
α = 92.528 (9)°	µ = 2.41 mm^−1
β = 101.917 (9)°	T = 153 K
γ = 99.127 (9)°	Prism, purple
V = 812.3 (7) Å^3	0.10 × 0.06 × 0.04 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer	2880 independent reflections
Radiation source: standard focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
0.3° ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: numerical face-indexed correction [XPREP and SADABS, both in SMART (Bruker, 1999)]	h = −10→10
Tmin = 0.815, Tmax = 0.920	k = −10→10
7294 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.34	w = 1/[σ^2(Fo^2) + (0.04Fo^2)^2]
2880 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 2.49 e Å^−3
0 restraints	Δρmin = −1.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0	0	0	0.0226 (5)
N1	0.1724 (11)	0.1331 (9)	−0.0521 (9)	0.018 (2)
N2	0.0169 (10)	0.2321 (9)	−0.2309 (9)	0.018 (2)
N3	−0.1589 (11)	0.0569 (9)	−0.1397 (8)	0.018 (2)
N4	−0.4034 (11)	−0.0913 (10)	−0.1077 (8)	0.019 (2)
C1	0.3336 (14)	0.1543 (12)	0.0075 (10)	0.020 (3)
C2	0.4244 (13)	0.2648 (11)	−0.0573 (11)	0.017 (3)
C3	0.5870 (15)	0.3236 (13)	−0.0321 (12)	0.030 (3)
H3A	0.6617	0.2933	0.0360	0.036*
C4	0.6359 (14)	0.4310 (13)	−0.1128 (11)	0.025 (3)
H4A	0.7464	0.4751	−0.1002	0.030*
C5	0.5216 (15)	0.4727 (13)	−0.2117 (12)	0.029 (3)
H5A	0.5571	0.5473	−0.2634	0.035*
C6	0.3629 (15)	0.4121 (13)	−0.2375 (11)	0.026 (3)
H6A	0.2890	0.4398	−0.3076	0.031*
C7	0.3131 (13)	0.3091 (12)	−0.1583 (10)	0.018 (3)
C8	0.1605 (14)	0.2231 (12)	−0.1492 (11)	0.021 (3)
C9	−0.1295 (14)	0.1556 (12)	−0.2287 (11)	0.022 (3)
C10	−0.2770 (13)	0.1706 (12)	−0.3168 (11)	0.020 (3)
C11	−0.3108 (14)	0.2523 (13)	−0.4219 (10)	0.023 (3)
H11A	−0.2283	0.3163	−0.4494	0.028*
C12	−0.4706 (15)	0.2361 (13)	−0.4845 (13)	0.031 (3)
H12A	−0.4977	0.2895	−0.5576	0.038*
C13	−0.5936 (15)	0.1448 (12)	−0.4448 (11)	0.025 (3)
H13A	−0.7022	0.1403	−0.4891	0.030*
C14	−0.5601 (14)	0.0599 (12)	−0.3413 (11)	0.023 (3)
H14A	−0.6431	−0.0040	−0.3143	0.027*
C15	−0.3981 (13)	0.0735 (11)	−0.2789 (10)	0.015 (3)
C16	−0.3212 (13)	0.0062 (12)	−0.1686 (10)	0.019 (3)
Sb1	0.00304 (10)	−0.27865 (10)	−0.30961 (9)	0.0210 (3)
F1	0.0559 (8)	−0.2242 (8)	−0.1357 (6)	0.0354 (19)
F2	0.0331 (8)	−0.0794 (7)	−0.3376 (7)	0.0371 (19)
F3	0.2171 (7)	−0.2836 (7)	−0.3087 (6)	0.0322 (18)
F4	−0.0267 (9)	−0.4800 (8)	−0.2789 (7)	0.040 (2)
F5	−0.2123 (8)	−0.2741 (8)	−0.3050 (7)	0.0389 (19)
F6	−0.0537 (9)	−0.3229 (8)	−0.4868 (7)	0.048 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0216 (12)	0.0240 (12)	0.0185 (12)	−0.0013 (9)	−0.0012 (9)	0.0048 (9)
N1	0.023 (5)	0.013 (5)	0.019 (5)	0.006 (4)	0.004 (4)	0.000 (4)
N2	0.010 (5)	0.018 (5)	0.023 (6)	0.001 (4)	−0.001 (4)	−0.004 (4)
N3	0.030 (6)	0.011 (5)	0.009 (5)	−0.002 (4)	0.003 (4)	0.002 (4)
N4	0.026 (6)	0.017 (5)	0.013 (5)	0.005 (4)	0.003 (4)	0.000 (4)
C1	0.026 (7)	0.016 (6)	0.015 (6)	0.001 (5)	−0.001 (5)	−0.005 (5)
C2	0.021 (6)	0.006 (6)	0.027 (7)	0.005 (5)	0.011 (5)	0.006 (5)
C3	0.032 (8)	0.029 (8)	0.026 (8)	0.001 (6)	0.007 (6)	−0.001 (6)
C4	0.021 (7)	0.029 (7)	0.026 (7)	0.000 (6)	0.011 (6)	0.001 (6)
C5	0.037 (8)	0.021 (7)	0.032 (8)	0.001 (6)	0.016 (7)	0.006 (6)
C6	0.027 (7)	0.031 (8)	0.021 (7)	0.003 (6)	0.006 (6)	0.007 (6)
C7	0.023 (7)	0.017 (6)	0.016 (6)	0.008 (5)	0.007 (5)	0.000 (5)
C8	0.019 (6)	0.021 (7)	0.026 (7)	0.001 (5)	0.008 (5)	0.010 (5)
C9	0.021 (7)	0.019 (7)	0.024 (7)	0.006 (5)	0.003 (5)	−0.004 (5)
C10	0.019 (6)	0.017 (6)	0.026 (7)	0.006 (5)	0.004 (5)	0.004 (5)
C11	0.024 (7)	0.028 (7)	0.017 (7)	−0.006 (6)	0.007 (6)	0.010 (6)
C12	0.031 (8)	0.026 (8)	0.041 (9)	0.010 (6)	0.010 (7)	0.019 (6)
C13	0.027 (7)	0.021 (7)	0.024 (7)	0.004 (6)	−0.002 (6)	0.000 (6)
C14	0.027 (7)	0.022 (7)	0.019 (7)	0.004 (6)	0.006 (6)	0.002 (5)
C15	0.022 (6)	0.008 (6)	0.015 (6)	0.005 (5)	0.000 (5)	−0.001 (5)
C16	0.022 (7)	0.013 (6)	0.019 (7)	−0.003 (5)	0.006 (5)	−0.003 (5)
Sb1	0.0202 (4)	0.0190 (5)	0.0223 (5)	0.0022 (3)	0.0017 (3)	0.0034 (3)
F1	0.031 (4)	0.047 (5)	0.022 (4)	0.002 (4)	−0.001 (3)	−0.014 (4)
F2	0.039 (5)	0.016 (4)	0.058 (5)	0.011 (3)	0.011 (4)	0.008 (4)
F3	0.019 (4)	0.043 (5)	0.034 (4)	0.000 (3)	0.007 (3)	0.007 (4)
F4	0.049 (5)	0.033 (5)	0.039 (5)	0.005 (4)	0.011 (4)	0.012 (4)
F5	0.019 (4)	0.051 (5)	0.047 (5)	0.005 (4)	0.006 (4)	0.014 (4)
F6	0.048 (5)	0.050 (5)	0.047 (5)	0.023 (4)	0.003 (4)	0.000 (4)

Geometric parameters (Å, º)

Cu1—N1	1.955 (9)	C5—C6	1.355 (16)
Cu1—N3	1.957 (9)	C6—C7	1.374 (15)
Cu1—F1	2.626 (7)	C7—C8	1.443 (15)
N1—C8	1.353 (14)	C9—C10	1.446 (15)
N1—C1	1.379 (14)	C10—C11	1.386 (15)
N2—C9	1.345 (14)	C10—C15	1.398 (15)
N2—C8	1.375 (14)	C11—C12	1.381 (16)
N3—C16	1.364 (14)	C12—C13	1.390 (16)
N3—C9	1.376 (14)	C13—C14	1.390 (15)
N4—C1^i	1.321 (14)	C14—C15	1.399 (15)
N4—C16	1.327 (13)	C15—C16	1.444 (15)
C1—N4^i	1.321 (14)	Sb1—F3	1.846 (6)
C1—C2	1.466 (15)	Sb1—F2	1.847 (7)
C2—C3	1.381 (15)	Sb1—F1	1.852 (7)
C2—C7	1.409 (15)	Sb1—F5	1.869 (7)
C3—C4	1.410 (16)	Sb1—F6	1.870 (8)
C4—C5	1.401 (17)	Sb1—F4	1.873 (7)
N1^i—Cu1—N1	180.0	N2—C9—N3	124.3 (11)
N1^i—Cu1—N3	89.7 (4)	N2—C9—C10	124.3 (11)
N1—Cu1—N3	90.3 (4)	N3—C9—C10	111.4 (10)
N3^i—Cu1—N3	180.0	C11—C10—C15	121.5 (10)
N1^i—Cu1—F1	89.4 (3)	C11—C10—C9	133.5 (11)
N1—Cu1—F1	90.6 (3)	C15—C10—C9	104.9 (10)
N3^i—Cu1—F1	85.6 (3)	C12—C11—C10	116.6 (10)
N3—Cu1—F1	94.4 (3)	C11—C12—C13	122.6 (12)
C8—N1—C1	106.4 (9)	C14—C13—C12	121.1 (12)
C8—N1—Cu1	128.4 (8)	C13—C14—C15	116.6 (11)
C1—N1—Cu1	125.2 (8)	C10—C15—C14	121.5 (10)
C9—N2—C8	126.8 (10)	C10—C15—C16	107.0 (10)
C16—N3—C9	106.2 (9)	C14—C15—C16	131.5 (10)
C16—N3—Cu1	126.8 (7)	N4—C16—N3	127.1 (11)
C9—N3—Cu1	127.0 (8)	N4—C16—C15	122.4 (10)
C1^i—N4—C16	122.6 (10)	N3—C16—C15	110.5 (9)
N4^i—C1—N1	128.5 (10)	F3—Sb1—F2	90.5 (3)
N4^i—C1—C2	122.4 (10)	F3—Sb1—F1	90.3 (3)
N1—C1—C2	109.1 (10)	F2—Sb1—F1	88.3 (3)
C3—C2—C7	122.1 (10)	F3—Sb1—F5	178.2 (3)
C3—C2—C1	130.6 (11)	F2—Sb1—F5	90.0 (3)
C7—C2—C1	107.3 (10)	F1—Sb1—F5	88.0 (3)
C2—C3—C4	116.4 (12)	F3—Sb1—F6	91.1 (3)
C5—C4—C3	119.9 (11)	F2—Sb1—F6	88.7 (3)
C6—C5—C4	123.3 (12)	F1—Sb1—F6	176.7 (4)
C5—C6—C7	117.3 (12)	F5—Sb1—F6	90.7 (3)
C6—C7—C2	121.0 (10)	F3—Sb1—F4	89.5 (3)
C6—C7—C8	135.3 (11)	F2—Sb1—F4	179.2 (3)
C2—C7—C8	103.7 (10)	F1—Sb1—F4	90.9 (3)
N1—C8—N2	123.3 (10)	F5—Sb1—F4	89.9 (3)
N1—C8—C7	113.4 (10)	F6—Sb1—F4	92.1 (3)
N2—C8—C7	123.3 (10)	Sb1—F1—Cu1	132.0 (4)

Symmetry code: (i) −x, −y, −z.