Bis{[phthalocyaninato(2-)]arsenic(III)} tetradecaiodotetraarsenic(III)

Crystals of the novel title arsenic(III) phthalocyanine complex, [As(C₃₂H₁₆N₈)]₂[As₄I₁₄] or [(AsPc)⁺]₂·[As₄I₁₄]^2-, where Pc is phthalocyaninate(2-), have been obtained by the reaction of pure powdered As with phthalo­nitrile under a stream of iodine vapour at 493 K. The crystals are built up of separate but interacting [AsPc]⁺ cations and [As₄I₁₂]^2- anions. The As atom of the [AsPc]⁺ unit is bonded to the four iso­indole N atoms of the Pc macrocycle and lies 0.743 (2) Å out of the plane defined by these four N atoms. The anionic part of the complex consists of AsI₃ and [AsI₄]^- units joined together into an [As₄I₁₄]^2- anion. The arrangement of the oppositely charged moieties, [AsPc]⁺ and [As₄I₁₄]^2-, in the crystal is determined mainly by ionic attraction and by donor-acceptor interactions between the [AsPc]⁺ and [As₄I₁₄]^2- ions.

S1. Comment

This study is continuation of our investigation of the synthesis and characterization of iodine-doped metallophthalocyanines. Earlier, we reported that, besides the well characterized I-doped metallophthalocyanines and diphthalocyanines, in which the I-doped atoms form chains of disordered symmetrical triiodide ions (Janczak et al., 1998, 2000; Janczak, Kubiak & Jezierski, 1999; Janczak & Kubiak, 1999a; Janczak & Idemori, 2001a), and metallophthalocyanines in which the I atoms are directly joined to the central metal ion, yielding mono- or diiodometallophthalocyanine complexes (Janczak & Kubiak, 1999b,c; Janczak & Idemori, 2001b), the I atoms can form a neutral I₂ molecule, which acts as a bridge for the dimerization of monoiodometallophthalocyanines (Janczak, Kubiak & Hahn, 1999) or for developing a polymeric supramolecular diiodometallophthalocyanine structure (Janczak, Razik & Kubiak, 1999; Janczak & Idemori, 2002a). More recently, we reported that, depending on the condition of the synthesis, the I atoms could form ordered but unsymmetrical triiodide ions (Janczak & Kubiak, 1999 d; Kubiak et al., 1999; Janczak & Idemori, 2002b). The title As^III phthalocyanine-As^III iodine complex, (I), is unique and, to our knowledge, with the two isostructural complexes of [(SbPc)₄(Sb₄I₁₆)] (Janczak & Idemori, 2002c) and [(BiPc)₄(Bi₄I₁₆)] (Kubiak & Ejsmont, 1999), it is only the third structurally characterized phthalocyaninate compound which contains the same metal in both ionic parts of the complex, i.e. in the [AsPc]⁺ moiety as well as in the [As₄I₁₄]²⁻ moiety. \sch

The crystal of (I) is built up of separate but interacting units of [AsPc]⁺ and [As₄I₁₄]²⁻ (Fig. 1). The phthalocyaninato(2-) macrocyclic ring of the AsPc moiety has a saucer-shaped form, as a result of the interaction of the central As^III ion with the oppositely charged [As₄I₁₄]²⁻ counterion. The greatest deviations from the plane defined by the four isoindole N atoms of the phthalocyaninato(2-) macrocycle are observed for the C atoms of the phenyl rings: 0.039 (3)–0.219 (3) Å for C2—C7, 0.124 (3)–0.377 (3) Å for C10—C15, 0.061 (3)–9.228 (3) Å for C18—C23 and 0.103 (3)–0.377 (3) Å for C26—C31. The positively charged As^III atom, which is coordinated by the four isoindole N atoms, is significantly displaced from the N₄-isoindole plane [0.743 (3) Å] towards atom I3 of the [As₄I₁₄]²⁻ counter-ion.

The displacement of the As^III atom from the N₄-isoindole plane is comparable with that observed in [phthalocyaninato(2-)]arsenic(III) triiodide [0.757 (2) Å; Janczak & Idemori, 2002b]. In Sb^III phthalocyanine iodine (Kubiak & Razik, 1998), Sb^III phthalocyanine triiodide (Kubiak et al., 1999) and the Sb^III phthalocyanine-Sb^III iodine complex (Janczak & Idemori, 2002c), the displacement of the central Sb atom from the N₄-isoindole plane is about 0.22 Å greater than that observed for the As atom in As^III phthalocyaninato(2-) complexes. This is quite reasonable, because of the difference between the ionic radii of As^III and Sb^III (Shannon, 1976), as well as because of the ionic attraction between the positively charged central As^III atom of the [AsPc] unit with the oppositely charged atom I3 of the [As₄I₁₄]²⁻ counter-ion.

A similar interaction between the positively charged central atom and I exists in the Sb phthalocyaninate structures. The influence of the As···I interaction is clearly manifested in the As—N coordination, leading to the molecular symmetry of the As—N₄ core being close to C_s and not to C_4v, consistent with the fully optimized ab initio molecular geometry calculations performed for the isolated and non-interacting [AsPc]⁺ cation (Janczak, 2002), which corresponds to the conformation in solution. The displacement of the As atom from the N₄-plane is significantly greater [0.975 (3) Å] in the unique example of a partially oxidized iodine-doped As^III phthalocyaninate-metal-free phthalocyanine complex (Janczak, Kubiak & Jezierski, 1999), due to the location of As between the two phthalocyaninate rings.

The anionic part of (I), [As₄I₁₄]²⁻, consists of two AsI₆ deformed octahedra joined together by two bridging I atoms and two AsI₅ deformed square pyramids, that are linked to the AsI₆ octahedra to form the centrosymmetric [As₄I₁₄]²⁻ counterion. The As—I bond lengths fall into groups, namely shorter As—I bonds, which show that the [As₄I₁₄]²⁻ counterion consists of two pairs of AsI₃ and AsI₄ units, and longer As—I bonds, with the I bridging atoms. The distortion of the two joined AsI₆ octahedra and the two AsI₅ square polyhedra in the [As₄I₁₄]²⁻ anion is likely to be due to the lone electron pair on the As^III atom. This is in agreement with the steric effect of a lone electron pair predicted by the valence-shell electron-pair repulsion model (VSEPR; Gillespie, 1963, 1992).

Looking in more detail at the differences between the As—I bond lengths, as well as the coordination geometry around atoms As2 and As3, it is clear that they have different coordination. The square-pyramidal coordination of atom As2 joins three I atoms with relatively short As—I bonds, and with two I atoms it forms significantly longer As—I bonds. Atom As3 joins four I atoms with short As—I bonds and two I atoms with longer As—I bonds. The longer As—I bonds involve the I atoms that are linked to two As atoms, while the shorter bonds involve mainly terminal I atoms. A similar pattern of short and long M—I bonds is observed in the [Bi₄I₁₆]⁴⁻ and [Sb₄I₁₆]⁻ counterions of the two isostructural Bi and Sb phthalocyaninate complexes (Kubiak & Ejsmont, 1999; Janczak & Idemori, 2002c). Alternatively, the [As₄I₁₄]²⁻ anion can be regarded as composed of two pairs of symmetrically equivalent AsI₃ and AsI₄⁻ units. However, the mutual orientation and arrangement of both AsI₃ and AsI₄⁻ units related by an inversion centre in the crystal leads to the formation of an [As₄I₁₄]²⁻ moiety.

The ionic attraction between the [AsPc]⁺ and [As₄I₁₄]²⁻ ions seems to be significant (Fig. 2). The basic packing unit includes two [AsPc]⁺ macrocycles associated by an inversion center and an [As₄I₁₄]²⁻ ion. The central atom As1 of the AsPc moiety interacts with atom I3, since the As···I contact of 3.801 (3) Å is shorter than the sum of the van der Waals radii of As and I atoms (Pauling, 1960). In the crystal (Fig. 2), pairs of [AsPc]⁺ macrocycles related by inversion are separated by 12.580 (5) Å (N₄-isoindole-N₄-isoindole distance). The centrosymmetric [(AsPc)(As₄I₁₄)(AsPc)] aggregates in the crystal form π–π interactions between adjacent pairs of Pc macrocycles. The stacks are inclined by 23.00 (3), 52.65 (3) and 43.83 (3)° to the a, b and c axes, respectively. The interplanar distance within the stack is 3.203 (5) Å. Strong π–π interactions are a common feature in the structures of phthalocyanine and its metal complexes (Nevin et al., 1987; Terekhov et al., 1996; Isago et al., 1997, 1998).

The electrical conductivity of (I), measured on a single-crystal along the stack, exhibits non-metallic character (dσ/dT > 0). At room temperature, the conductivity 4.5–5 × 10⁻⁶ Ω⁻¹ cm⁻¹.

Although the crystal of (I) is built up from oppositely charged [AsPc]⁺ and [As₄I₁₄]²⁻ moieties, the compound does not possess the characteristic properties of ionic crystals. The solubility of this compound in polar solvents, such as water, methanol or ethanol, is insignificant, and it is only slightly soluble in pyridine, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, chloronaphthalene and other aromatic solvents. A search of the Cambridge Structural Database (Version?; Allen 2002) for structures containing both [MPc]⁺ and [M₄I₁₄]²⁻ units showed no similar examples of phthalocyaninate complexes, so this As-phthalocyaninate complex is the first of this type to be structurally characterized.

S2. Experimental

Crystals of (I) were obtained by the direct reaction of pure powdered arsenic with phthalonitrile (Kubiak & Janczak, 1993) under a stream of iodine vapour at 493 K.

S3. Refinement

H atoms were treated as riding with a C—H distance of 0.93 Å.

Computing details

Data collection: KM-4 CCD Software (Kuma Diffraction, 1999); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (a) the [AsPc]^+ unit and (b) the [Ab4I14]^2− counterion of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii [symmetry code: (i) −x, 1 − y, 1 − z].
	Fig. 2. The molecular packing in the unit cell of (I), showing the As···I interactions (dashed lines).

Bis{[phthalocyaninato(2-)]arsenic(III)} tetradecaiodotetraarsenic(III)

Crystal data

[As(C32H16N8)]2[As4I14]	Z = 1
Mr = 3251.18	F(000) = 1468
Triclinic, P1	Dx = 2.713 Mg m^−3 Dm = 2.71 Mg m^−3 Dm measured by flotation in what
Hall symbol: -P 1	Melting point: decomposition K
a = 12.081 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.600 (2) Å	Cell parameters from 6210 reflections
c = 13.950 (3) Å	θ = 3.3–26.7°
α = 82.32 (3)°	µ = 7.97 mm^−1
β = 71.63 (3)°	T = 293 K
γ = 83.05 (3)°	Paralellepiped, black-violet
V = 1990.2 (7) Å^3	0.44 × 0.15 × 0.14 mm

Data collection

Kuma KM-4 with two-dimensional CCD area-detector diffractometer	8037 independent reflections
Radiation source: fine-focus sealed tube	6210 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θmax = 26.7°, θmin = 3.3°
ω scans	h = −12→15
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990)	k = −15→15
Tmin = 0.127, Tmax = 0.402	l = −17→17
15578 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0294P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.003
8037 reflections	Δρmax = 0.60 e Å^−3
452 parameters	Δρmin = −0.65 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00059 (6)

Special details

Experimental. The measurement was performed on a KUMA KM-4 diffractometer equipped with a two-dimensional CCD area-detector. The ω scan technique was used, with Δω = 0.75° for one image. The 960 images for six different runs covered about 95% of the Ewald sphere. The lattice parameters were calculated using 258 reflections obtained from 50 images for 10 runs with different orientations in reciprocal space, and after data collection were refined on all reflections.

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
I1	−0.14007 (2)	0.66906 (2)	0.34360 (2)	0.05007 (8)
I2	−0.04973 (2)	0.61635 (2)	0.599871 (18)	0.04586 (7)
I3	0.20274 (2)	0.63400 (2)	0.177721 (19)	0.04840 (8)
I4	0.09710 (3)	0.84230 (2)	0.38551 (3)	0.06963 (10)
I5	0.31390 (3)	0.54212 (3)	0.45388 (3)	0.07663 (11)
I6	0.51900 (3)	0.77568 (3)	0.39807 (3)	0.06907 (10)
I7	0.59899 (3)	0.54383 (3)	0.22108 (3)	0.08061 (11)
As1	0.23402 (3)	0.91727 (3)	0.04461 (3)	0.03357 (9)
As2	0.42009 (4)	0.67076 (4)	0.30478 (4)	0.05515 (12)
As3	0.05523 (3)	0.63816 (3)	0.38813 (3)	0.03906 (10)
N1	0.3455 (2)	0.9230 (2)	−0.1030 (2)	0.0356 (7)
N2	0.4668 (2)	1.0653 (2)	−0.1056 (2)	0.0385 (7)
N3	0.2841 (2)	1.0705 (2)	0.0352 (2)	0.0334 (6)
N4	0.1360 (2)	1.1358 (2)	0.1837 (2)	0.0364 (7)
N5	0.0756 (2)	0.9880 (2)	0.1217 (2)	0.0316 (6)
N6	−0.0573 (2)	0.8608 (2)	0.1126 (2)	0.0356 (7)
N7	0.1357 (2)	0.8430 (2)	−0.0159 (2)	0.0361 (7)
N8	0.2869 (3)	0.7711 (2)	−0.1592 (2)	0.0399 (7)
C1	0.3615 (3)	0.8418 (3)	−0.1664 (3)	0.0381 (8)
C2	0.4720 (3)	0.8466 (3)	−0.2437 (3)	0.0439 (9)
C3	0.5279 (3)	0.7848 (3)	−0.3231 (3)	0.0466 (9)
H3	0.4928	0.7275	−0.3335	0.056*
C4	0.6374 (3)	0.8101 (4)	−0.3868 (3)	0.0536 (11)
H4	0.6767	0.7689	−0.4399	0.064*
C5	0.6895 (4)	0.8990 (4)	−0.3709 (3)	0.0581 (12)
H5	0.7633	0.9142	−0.4138	0.070*
C6	0.6347 (3)	0.9635 (3)	−0.2942 (3)	0.0487 (10)
H6	0.6688	1.0223	−0.2854	0.058*
C7	0.5233 (3)	0.9354 (3)	−0.2293 (3)	0.0404 (9)
C8	0.4439 (3)	0.9808 (3)	−0.1414 (3)	0.0381 (9)
C9	0.3900 (3)	1.1075 (3)	−0.0250 (3)	0.0362 (8)
C10	0.4119 (3)	1.1986 (3)	0.0136 (3)	0.0341 (8)
C11	0.5047 (3)	1.2655 (3)	−0.0189 (3)	0.0434 (9)
H11	0.5679	1.2537	−0.0763	0.052*
C12	0.4985 (3)	1.3491 (3)	0.0373 (3)	0.0506 (11)
H12	0.5600	1.3931	0.0179	0.061*
C13	0.4025 (3)	1.3707 (3)	0.1233 (3)	0.0491 (10)
H13	0.4016	1.4277	0.1596	0.059*
C14	0.3091 (3)	1.3062 (3)	0.1534 (3)	0.0434 (9)
H14	0.2434	1.3208	0.2080	0.052*
C15	0.3175 (3)	1.2195 (3)	0.0991 (3)	0.0390 (9)
C16	0.2377 (3)	1.1394 (3)	0.1099 (3)	0.0393 (8)
C17	0.0603 (3)	1.0669 (3)	0.1869 (3)	0.0352 (8)
C18	−0.0561 (3)	1.0702 (3)	0.2584 (3)	0.0362 (8)
C19	−0.1103 (3)	1.1331 (3)	0.3358 (3)	0.0442 (9)
H19	−0.0722	1.1864	0.3496	0.053*
C20	−0.2235 (3)	1.1142 (4)	0.3924 (3)	0.0552 (11)
H20	−0.2624	1.1547	0.4462	0.066*
C21	−0.2810 (3)	1.0346 (3)	0.3699 (3)	0.0479 (10)
H21	−0.3575	1.0241	0.4094	0.058*
C22	−0.2286 (3)	0.9716 (3)	0.2920 (3)	0.0409 (9)
H22	−0.2676	0.9192	0.2779	0.049*
C23	−0.1124 (3)	0.9907 (3)	0.2343 (3)	0.0384 (9)
C24	−0.0304 (3)	0.9388 (3)	0.1505 (3)	0.0383 (9)
C25	0.0204 (3)	0.8157 (3)	0.0360 (3)	0.0374 (8)
C26	−0.0047 (3)	0.7296 (3)	−0.0087 (3)	0.0369 (8)
C27	−0.1041 (3)	0.6734 (3)	0.0133 (3)	0.0464 (9)
H27	−0.1702	0.6889	0.0672	0.056*
C28	−0.1019 (4)	0.5949 (3)	−0.0466 (3)	0.0499 (10)
H28	−0.1670	0.5560	−0.0318	0.060*
C29	−0.0037 (4)	0.5715 (3)	−0.1297 (3)	0.0507 (10)
H29	−0.0054	0.5188	−0.1700	0.061*
C30	0.0959 (4)	0.6267 (3)	−0.1521 (3)	0.0488 (10)
H30	0.1610	0.6116	−0.2070	0.059*
C31	0.0962 (3)	0.7032 (3)	−0.0920 (3)	0.0410 (9)
C32	0.1819 (3)	0.7738 (3)	−0.0914 (3)	0.0386 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.03352 (13)	0.06031 (17)	0.05398 (16)	−0.00404 (12)	−0.01486 (12)	0.00649 (13)
I2	0.05039 (15)	0.04536 (15)	0.03614 (13)	−0.00687 (12)	−0.00399 (11)	−0.00420 (10)
I3	0.03833 (14)	0.06077 (17)	0.03991 (14)	−0.01447 (12)	−0.00229 (11)	0.00216 (12)
I4	0.1052 (3)	0.04647 (17)	0.0705 (2)	−0.03018 (17)	−0.04276 (19)	0.00902 (14)
I5	0.04972 (17)	0.0941 (3)	0.0809 (2)	−0.03012 (18)	−0.01815 (16)	0.02663 (19)
I6	0.04821 (17)	0.0753 (2)	0.0884 (2)	−0.01425 (16)	−0.02117 (16)	−0.01537 (18)
I7	0.0622 (2)	0.0930 (3)	0.0830 (2)	−0.00308 (19)	−0.01381 (18)	−0.0196 (2)
As1	0.02712 (17)	0.0376 (2)	0.03404 (19)	−0.00241 (15)	−0.00896 (15)	0.00195 (15)
As2	0.0404 (2)	0.0689 (3)	0.0568 (3)	−0.0147 (2)	−0.0181 (2)	0.0087 (2)
As3	0.03171 (19)	0.0435 (2)	0.0405 (2)	−0.01045 (17)	−0.00990 (16)	0.00509 (16)
N1	0.0297 (15)	0.0420 (17)	0.0325 (15)	−0.0052 (13)	−0.0088 (13)	0.0052 (13)
N2	0.0328 (15)	0.0398 (17)	0.0365 (16)	−0.0066 (13)	−0.0013 (13)	−0.0005 (13)
N3	0.0204 (13)	0.0383 (16)	0.0361 (16)	−0.0030 (12)	−0.0041 (12)	0.0042 (13)
N4	0.0283 (15)	0.0425 (17)	0.0368 (16)	−0.0044 (13)	−0.0080 (13)	−0.0013 (13)
N5	0.0243 (13)	0.0359 (15)	0.0337 (15)	−0.0066 (12)	−0.0092 (12)	0.0044 (12)
N6	0.0288 (15)	0.0393 (17)	0.0352 (16)	−0.0139 (13)	−0.0028 (13)	0.0019 (13)
N7	0.0300 (15)	0.0324 (16)	0.0459 (18)	−0.0033 (13)	−0.0136 (13)	0.0022 (13)
N8	0.0343 (16)	0.0442 (18)	0.0397 (17)	−0.0032 (14)	−0.0122 (14)	0.0034 (14)
C1	0.0333 (18)	0.040 (2)	0.038 (2)	0.0032 (16)	−0.0090 (16)	−0.0059 (16)
C2	0.036 (2)	0.050 (2)	0.045 (2)	0.0011 (18)	−0.0157 (17)	−0.0017 (18)
C3	0.041 (2)	0.051 (2)	0.044 (2)	0.0026 (18)	−0.0055 (18)	−0.0164 (19)
C4	0.040 (2)	0.072 (3)	0.043 (2)	0.010 (2)	−0.0056 (18)	−0.017 (2)
C5	0.036 (2)	0.086 (3)	0.042 (2)	0.000 (2)	0.0002 (19)	−0.005 (2)
C6	0.033 (2)	0.056 (3)	0.049 (2)	−0.0040 (19)	−0.0037 (18)	0.0008 (19)
C7	0.0308 (18)	0.044 (2)	0.042 (2)	0.0040 (16)	−0.0084 (16)	0.0001 (17)
C8	0.0285 (17)	0.040 (2)	0.040 (2)	−0.0025 (16)	−0.0084 (16)	0.0133 (16)
C9	0.0292 (17)	0.0373 (19)	0.040 (2)	−0.0043 (15)	−0.0097 (15)	0.0042 (15)
C10	0.0247 (16)	0.0355 (19)	0.0370 (19)	−0.0012 (15)	−0.0062 (15)	0.0048 (15)
C11	0.0317 (19)	0.050 (2)	0.043 (2)	−0.0038 (17)	−0.0053 (17)	0.0012 (18)
C12	0.036 (2)	0.041 (2)	0.070 (3)	−0.0116 (18)	−0.013 (2)	0.012 (2)
C13	0.043 (2)	0.039 (2)	0.065 (3)	−0.0008 (18)	−0.017 (2)	−0.0062 (19)
C14	0.0328 (19)	0.043 (2)	0.054 (2)	−0.0022 (17)	−0.0109 (17)	−0.0086 (18)
C15	0.0246 (17)	0.038 (2)	0.052 (2)	−0.0021 (15)	−0.0097 (16)	0.0015 (17)
C16	0.0291 (18)	0.045 (2)	0.044 (2)	−0.0076 (16)	−0.0128 (16)	0.0014 (17)
C17	0.0262 (17)	0.040 (2)	0.0379 (19)	−0.0023 (15)	−0.0090 (15)	−0.0011 (16)
C18	0.0249 (16)	0.0382 (19)	0.039 (2)	−0.0044 (15)	−0.0030 (15)	0.0033 (15)
C19	0.0318 (19)	0.049 (2)	0.050 (2)	0.0002 (17)	−0.0096 (17)	−0.0057 (18)
C20	0.038 (2)	0.073 (3)	0.050 (2)	−0.002 (2)	−0.0056 (19)	−0.010 (2)
C21	0.0265 (18)	0.068 (3)	0.040 (2)	−0.0026 (19)	0.0006 (16)	0.0004 (19)
C22	0.0277 (17)	0.045 (2)	0.045 (2)	−0.0044 (16)	−0.0083 (16)	0.0071 (17)
C23	0.0214 (16)	0.046 (2)	0.042 (2)	−0.0069 (15)	−0.0072 (15)	0.0148 (16)
C24	0.0207 (16)	0.046 (2)	0.045 (2)	−0.0090 (15)	−0.0089 (15)	0.0094 (17)
C25	0.0320 (18)	0.038 (2)	0.042 (2)	−0.0017 (16)	−0.0134 (16)	0.0005 (16)
C26	0.0365 (19)	0.0295 (18)	0.051 (2)	−0.0085 (16)	−0.0231 (17)	0.0043 (16)
C27	0.042 (2)	0.049 (2)	0.048 (2)	−0.0061 (19)	−0.0143 (18)	0.0001 (19)
C28	0.047 (2)	0.045 (2)	0.063 (3)	−0.0097 (19)	−0.025 (2)	0.001 (2)
C29	0.063 (3)	0.042 (2)	0.056 (3)	−0.011 (2)	−0.029 (2)	−0.0019 (19)
C30	0.052 (2)	0.056 (3)	0.045 (2)	−0.004 (2)	−0.024 (2)	−0.0051 (19)
C31	0.041 (2)	0.042 (2)	0.041 (2)	−0.0071 (17)	−0.0138 (17)	−0.0024 (17)
C32	0.0367 (19)	0.0358 (19)	0.044 (2)	−0.0036 (16)	−0.0145 (17)	0.0008 (16)

Geometric parameters (Å, º)

I1—As3	2.5963 (7)	C5—H5	0.9300
I2—As3	2.8133 (10)	C6—C7	1.420 (5)
I3—As3	2.9182 (11)	C6—H6	0.9300
I4—As3	2.6742 (8)	C7—C8	1.436 (5)
I5—As2	2.5533 (12)	C9—C10	1.416 (5)
I6—As2	2.5868 (9)	C10—C15	1.394 (5)
I7—As2	2.5816 (12)	C10—C11	1.407 (5)
As1—N7	2.028 (3)	C11—C12	1.377 (6)
As1—N5	2.039 (3)	C11—H11	0.9300
As1—N3	2.068 (3)	C12—C13	1.411 (6)
As1—N1	2.073 (3)	C12—H12	0.9300
As1—I3	3.8004 (13)	C13—C14	1.394 (5)
As2—I3	3.7011 (10)	C13—H13	0.9300
As2—I4	4.1238 (15)	C14—C15	1.387 (5)
As3—I5	3.5590 (10)	C14—H14	0.9300
As3—I2^i	3.1964 (9)	C15—C16	1.440 (5)
N1—C8	1.390 (4)	C17—C18	1.446 (4)
N1—C1	1.397 (5)	C18—C19	1.371 (5)
N2—C8	1.327 (5)	C18—C23	1.407 (5)
N2—C9	1.338 (5)	C19—C20	1.377 (5)
N3—C16	1.382 (5)	C19—H19	0.9300
N3—C9	1.387 (4)	C20—C21	1.407 (6)
N4—C17	1.322 (4)	C20—H20	0.9300
N4—C16	1.333 (4)	C21—C22	1.374 (5)
N5—C17	1.393 (5)	C21—H21	0.9300
N5—C24	1.409 (4)	C22—C23	1.412 (5)
N6—C24	1.295 (5)	C22—H22	0.9300
N6—C25	1.322 (4)	C23—C24	1.446 (5)
N7—C32	1.392 (5)	C25—C26	1.427 (5)
N7—C25	1.413 (4)	C26—C27	1.398 (5)
N8—C1	1.316 (5)	C26—C31	1.434 (5)
N8—C32	1.321 (5)	C27—C28	1.370 (6)
C1—C2	1.429 (5)	C27—H27	0.9300
C2—C3	1.386 (5)	C28—C29	1.407 (6)
C2—C7	1.409 (5)	C28—H28	0.9300
C3—C4	1.387 (5)	C29—C30	1.392 (6)
C3—H3	0.9300	C29—H29	0.9300
C4—C5	1.423 (6)	C30—C31	1.360 (5)
C4—H4	0.9300	C30—H30	0.9300
C5—C6	1.378 (6)	C31—C32	1.447 (5)
N7—As1—N5	83.18 (12)	N2—C9—N3	128.1 (3)
N7—As1—N3	137.15 (11)	N2—C9—C10	122.1 (3)
N5—As1—N3	82.03 (11)	N3—C9—C10	109.8 (3)
N7—As1—N1	82.21 (12)	C15—C10—C11	119.8 (3)
N5—As1—N1	137.90 (11)	C15—C10—C9	107.7 (3)
N3—As1—N1	82.43 (12)	C11—C10—C9	132.5 (3)
N1—As1—I3	113.51 (9)	C12—C11—C10	117.6 (3)
N3—As1—I3	149.95 (8)	C12—C11—H11	121.2
N5—As1—I3	99.02 (8)	C10—C11—H11	121.2
N7—As1—I3	72.21 (8)	C11—C12—C13	122.6 (4)
I5—As2—I7	99.50 (4)	C11—C12—H12	118.7
I5—As2—I6	99.29 (3)	C13—C12—H12	118.7
I7—As2—I6	98.39 (3)	C14—C13—C12	119.7 (4)
I1—As3—I4	99.68 (3)	C14—C13—H13	120.2
I1—As3—I2	95.52 (3)	C12—C13—H13	120.2
I4—As3—I2	92.79 (4)	C15—C14—C13	117.6 (4)
I1—As3—I3	94.68 (3)	C15—C14—H14	121.2
I4—As3—I3	90.53 (4)	C13—C14—H14	121.2
I2—As3—I3	168.59 (2)	C14—C15—C10	122.6 (3)
I1—As3—I5	168.89 (2)	C14—C15—C16	131.4 (3)
I1—As3—I2^i	90.83 (3)	C10—C15—C16	105.9 (3)
I3—As2—I6	155.07 (2)	N4—C16—N3	127.6 (3)
I3—As2—I7	103.73 (3)	N4—C16—C15	122.5 (4)
I3—As2—I5	88.36 (3)	N3—C16—C15	109.9 (3)
I3—As2—I4	60.80 (3)	N4—C17—N5	127.0 (3)
I4—As2—I6	96.74 (3)	N4—C17—C18	122.0 (3)
I4—As2—I7	164.53 (2)	N5—C17—C18	110.8 (3)
I4—As2—I5	81.16 (3)	C19—C18—C23	122.7 (3)
I2—As3—I2^i	86.47 (3)	C19—C18—C17	131.8 (3)
As1—I3—As3	110.72 (3)	C23—C18—C17	105.5 (3)
As2—I3—As3	78.83 (2)	C18—C19—C20	117.3 (4)
As2—I4—As3	73.87 (3)	C18—C19—H19	121.3
As2—I5—As3	86.36 (3)	C20—C19—H19	121.3
C8—N1—C1	106.4 (3)	C19—C20—C21	120.9 (4)
C8—N1—As1	125.7 (2)	C19—C20—H20	119.6
C1—N1—As1	123.9 (2)	C21—C20—H20	119.6
C8—N2—C9	121.1 (3)	C22—C21—C20	122.6 (3)
C16—N3—C9	106.6 (3)	C22—C21—H21	118.7
C16—N3—As1	124.2 (2)	C20—C21—H21	118.7
C9—N3—As1	125.9 (2)	C21—C22—C23	116.5 (4)
C17—N4—C16	121.0 (3)	C21—C22—H22	121.8
C17—N5—C24	106.8 (3)	C23—C22—H22	121.8
C17—N5—As1	124.4 (2)	C18—C23—C22	120.0 (4)
C24—N5—As1	124.3 (2)	C18—C23—C24	108.3 (3)
C24—N6—C25	120.3 (3)	C22—C23—C24	131.6 (4)
C32—N7—C25	106.6 (3)	N6—C24—N5	129.2 (3)
C32—N7—As1	124.0 (2)	N6—C24—C23	122.3 (3)
C25—N7—As1	124.4 (2)	N5—C24—C23	108.5 (3)
C1—N8—C32	121.9 (3)	N6—C25—N7	128.1 (3)
N8—C1—N1	126.3 (3)	N6—C25—C26	122.6 (3)
N8—C1—C2	123.5 (3)	N7—C25—C26	109.3 (3)
N1—C1—C2	110.2 (3)	C27—C26—C25	132.4 (4)
C3—C2—C7	120.9 (3)	C27—C26—C31	119.4 (3)
C3—C2—C1	132.5 (4)	C25—C26—C31	108.1 (3)
C7—C2—C1	106.7 (3)	C28—C27—C26	118.4 (4)
C4—C3—C2	118.8 (4)	C28—C27—H27	120.8
C4—C3—H3	120.6	C26—C27—H27	120.8
C2—C3—H3	120.6	C27—C28—C29	121.7 (4)
C3—C4—C5	120.0 (4)	C27—C28—H28	119.1
C3—C4—H4	120.0	C29—C28—H28	119.1
C5—C4—H4	120.0	C30—C29—C28	120.3 (4)
C6—C5—C4	122.5 (4)	C30—C29—H29	119.8
C6—C5—H5	118.7	C28—C29—H29	119.8
C4—C5—H5	118.7	C31—C30—C29	118.7 (4)
C5—C6—C7	116.5 (4)	C31—C30—H30	120.6
C5—C6—H6	121.7	C29—C30—H30	120.6
C7—C6—H6	121.7	C30—C31—C26	121.3 (3)
C2—C7—C6	121.3 (4)	C30—C31—C32	133.8 (4)
C2—C7—C8	106.7 (3)	C26—C31—C32	104.8 (3)
C6—C7—C8	132.0 (4)	N8—C32—N7	127.8 (3)
N2—C8—N1	127.6 (3)	N8—C32—C31	121.1 (3)
N2—C8—C7	122.4 (3)	N7—C32—C31	111.0 (3)
N1—C8—C7	110.0 (3)

Symmetry code: (i) −x, −y+1, −z+1.