[Phthalocyaninato(2–)]­arsenic(III) triiodide

A new arsenic(III) phthalocyanine complex with the formula [As(C₃₂H₁₆N₈)]I₃, or AsPcI₃ (Pc = C₃₂H₁₆N₈), has been obtained by the reaction of pure powdered arsenic with phthalo­nitrile under a stream of iodine vapor. The four-coordinate As atom is bonded to the four iso­indole N atoms of the phthalocyaninate(2−) macro-ring and lies significantly out of the plane defined by the four iso­indole N atoms [0.757 (2) Å]. The I atoms form linear asymmetric triiodide I₃⁻ ions. In the crystal, the I₃⁻ ions related by an inversion center form (I—I—I...I—I—I)²⁻ ions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.041
• Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           29.00
         From the CIF: _reflns_number_total               7507
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         7907
         Completeness (_total/calc)             94.94%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The crystal of the title compound, (I), is built up from separate but interacting units of (AsPc)⁺ and I₃^- (Fig. 1). The arsenic phthalocyaninate unit is not planar, since in the crystal it interacts with the oppositely charged I₃^- ion. This interaction leads to the deviation of the arsenic cation from the phtahlocyaninate(2-) macro-ring towards the I₃^- ion. The deviation of the arsenic cation from the weighted least-squares plane through the four isoindole N atoms is 0.757 (2) Å. For comparison, the deviation of the Sb³⁺ cation from the N₄-isoindole plane in isostructural SbPcI₃ is 0.966 (2) Å (Kubiak et al., 1999). The difference between the displacements of the central metal cations (As³⁺ and Sb³⁺) correlates well with the difference between their ionic radii (Shannon, 1976).

The interaction of the arsenic cation with the I₃^- ion leads to the deformation of the phthalocyaninate macro-ring into a saucer-shaped form. The influence of the As···I interactions is manifested in the As—N_isoindole coordination. The four As—N_isoindole bonds are more asymmetrical and a little longer (0.03–0.06 Å) than the Sb—N_isoindole bonds in SbPcI₃ (Kubiak et al., 1999). Thus, the molecular symmetry of the As—N core is close to C_s symmetry and not to C_4v, which is possible for saucer shaped M^IIPc complexes (Friedel et al., 1970; Ukei, 1973; Iyechika et al., 1982). The largest deviation from the N₄-isoindole plane is observed for the outermost C atoms of the phenyl rings C18–C23 and C27–C31, as a result of the repulsive interaction of the delocalized π-electron system with the negatively charged I₃^- ion, which in the crystal is located close to the half of Pc unit containing these two phenyl rings, not direct over As atom of the AsPc unit.

Because two of the three I atoms of the I₃^- ion in the crystal of AsPcI₃ interact with the oppositely charged central arsenic cation of the (AsPc)⁺ unit, the I₃^- ion is asymmetric. One of the terminal I atoms (I3) of the I₃^- ion interacts stronger than the central iodine (I1). This interaction correlates well with the charge on the I atoms (-0.419 on both terminal I atoms and -0.163 on the central I atom) calculated by Landrum et al. (1997). The bond As···I3 (terminal) distance is ~0.1 Å shorter than the distance of As···I1 (I1 central) bond. The interaction (repulsive force) between two triiodide ions related by an inversion center (with a I2···I2 distance of 3.72 Å) and the As···I interactions (attractive force) present in the crystal are responsible for the difference of the bond lengths within the I₃^- ions and are important for stacking interactions between the ring systems. The basic packing unit includes two (AsPc)⁺ macrocycles and two interacting I₃^- ions, but each of those two macrocycles are closely associated with another macrocycle across an inversion center. The molecules related by a screw axis and glide plane are approximately perpendicular to each other (Fig. 2). A search of the Cambridge Structural Database (Allen & Kennard, 1993) for structures containing both (I—I—I···I—I—I)^2- and MN₄ groups showed only one example with the (I—I—I···I—I—I)^2-, but not comment was made on the I₃···I₃ interaction (Kubiak et al., 1999). The I—I bond lengths in the AsPcI₃ complex are just slightly (0.02 Å) more similar than those observed in the SbPcI₃ complex [2.861 (2) and 2.999 (2) Å; Kubiak et al., 1999]. A similar asymmetric triiodide I₃ ions is present in the crystal of oxomolybdenum(V) phthalocyanine triiodide, but the I—I distances are significantly larger [2.9737 (7) and 3.1934 (7) Å] than in the present As complex (Janczak & Kubiak, 1999).

S2. Experimental

Crystals of AsPcI₃ were obtained by direct reaction of pure powdered arsenic with phthalonitrile (Kubiak & Janczak, 1993) under a stream of iodine vapours at about 493 K. At this temperature, the liquid phthalonitrile undergoes catalytic tetramerization with simultaneous transfer of two electrons from the As metal to the formation of the Pc ring, the third electron from As is transferred to the I atoms forming a I₃^- ion.

Computing details

Data collection: Kuma KM-4 CCD Software (Kuma, 2000); cell refinement: Kuma KM-4 CCD Software; data reduction: Kuma 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. The molecular structure of (I) showing 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radii.
	Fig. 2. The molecular packing in the unit cell showing the As···I and I3^-···I3^- interactions (dashed lines).

(I)

Crystal data

[As(C32H16N8)]I3	F(000) = 1824
Mr = 968.15	Dx = 2.162 Mg m^−3 Dm = 2.16 Mg m^−3 Dm measured by flotation
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.652 (2) Å	Cell parameters from 2585 reflections
b = 17.558 (4) Å	θ = 5–26°
c = 19.668 (4) Å	µ = 4.30 mm^−1
β = 95.42 (3)°	T = 295 K
V = 2974.4 (11) Å^3	Parallelepiped, violet
Z = 4	0.30 × 0.12 × 0.10 mm

Data collection

Kuma KM-4 with two-dimensional area CCD detector diffractometer	7507 independent reflections
Radiation source: fine-focus sealed tube	4287 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.0°, θmin = 3.6°
ω scans	h = −8→11
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990)	k = −23→23
Tmin = 0.359, Tmax = 0.673	l = −26→26
26611 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.042	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0071P)^2] where P = (Fo^2 + 2Fc^2)/3
7507 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

Experimental. The measurement has been performed on a Kuma KM-4 diffractometer equipped with a CCD detector using ω–scans, Δω=0.75° per image. The 960 images from six different runs covered about 95% of the Ewald sphere. The lattice parameters were refined from 2585 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	0.27718 (3)	0.194102 (15)	0.124827 (15)	0.04829 (8)
I2	0.39422 (4)	0.069774 (17)	0.049510 (15)	0.06243 (10)
I3	0.15385 (3)	0.321420 (17)	0.204488 (17)	0.06437 (10)
As	0.34861 (4)	0.39137 (2)	0.057285 (19)	0.03048 (10)
N1	0.3323 (3)	0.41963 (16)	−0.04593 (14)	0.0297 (7)
N2	0.1577 (3)	0.52872 (16)	−0.04701 (16)	0.0320 (7)
N3	0.2866 (3)	0.50464 (15)	0.06586 (15)	0.0290 (7)
N4	0.3579 (3)	0.52371 (17)	0.18678 (15)	0.0357 (8)
N5	0.4953 (3)	0.41574 (15)	0.14081 (14)	0.0317 (7)
N6	0.6761 (3)	0.30996 (17)	0.14123 (16)	0.0331 (7)
N7	0.5365 (3)	0.33020 (15)	0.03016 (15)	0.0301 (7)
N8	0.4571 (3)	0.30854 (16)	−0.09043 (16)	0.0350 (7)
C1	0.3653 (4)	0.3690 (2)	−0.09685 (19)	0.0303 (9)
C2	0.2819 (4)	0.3912 (2)	−0.16076 (18)	0.0283 (8)
C3	0.2766 (4)	0.3594 (2)	−0.2262 (2)	0.0424 (10)
H3	0.3401	0.3189	−0.2359	0.051*
C4	0.1718 (5)	0.3915 (2)	−0.2757 (2)	0.0472 (11)
H4	0.1609	0.3700	−0.3191	0.057*
C5	0.0814 (4)	0.4555 (2)	−0.2623 (2)	0.0415 (10)
H5	0.0136	0.4758	−0.2971	0.050*
C6	0.0920 (4)	0.4887 (2)	−0.19780 (19)	0.0364 (10)
H6	0.0347	0.5317	−0.1885	0.044*
C7	0.1925 (4)	0.4542 (2)	−0.14857 (18)	0.0301 (9)
C8	0.2243 (4)	0.4717 (2)	−0.07675 (18)	0.0284 (9)
C9	0.1895 (4)	0.54435 (19)	0.0185 (2)	0.0287 (9)
C10	0.1259 (4)	0.6088 (2)	0.05120 (19)	0.0302 (9)
C11	0.0211 (4)	0.6649 (2)	0.0246 (2)	0.0383 (10)
H11	−0.0169	0.6660	−0.0212	0.046*
C12	−0.0225 (4)	0.7188 (2)	0.0710 (2)	0.0421 (10)
H12	−0.0934	0.7564	0.0561	0.051*
C13	0.0380 (4)	0.7177 (2)	0.1397 (2)	0.0461 (11)
H13	0.0061	0.7549	0.1690	0.055*
C14	0.1450 (4)	0.6627 (2)	0.1658 (2)	0.0413 (10)
H14	0.1869	0.6627	0.2111	0.050*
C15	0.1841 (4)	0.6077 (2)	0.11868 (19)	0.0309 (9)
C16	0.2850 (4)	0.5416 (2)	0.1280 (2)	0.0319 (9)
C17	0.4560 (4)	0.4661 (2)	0.19321 (19)	0.0332 (9)
C18	0.5479 (4)	0.4478 (2)	0.2556 (2)	0.0386 (10)
C19	0.5543 (4)	0.4809 (2)	0.3198 (2)	0.0399 (10)
H19	0.4905	0.5216	0.3287	0.048*
C20	0.6577 (5)	0.4513 (3)	0.3695 (2)	0.0537 (12)
H20	0.6634	0.4721	0.4131	0.064*
C21	0.7572 (5)	0.3894 (2)	0.3564 (2)	0.0497 (11)
H21	0.8265	0.3705	0.3914	0.060*
C22	0.7515 (4)	0.3571 (2)	0.2916 (2)	0.0414 (10)
H22	0.8168	0.3171	0.2821	0.050*
C23	0.6450 (4)	0.3866 (2)	0.24202 (19)	0.0332 (9)
C24	0.6095 (4)	0.3665 (2)	0.1707 (2)	0.0322 (9)
C25	0.6425 (4)	0.29380 (19)	0.0768 (2)	0.0307 (9)
C26	0.7142 (4)	0.2322 (2)	0.0419 (2)	0.0326 (9)
C27	0.8331 (4)	0.1811 (2)	0.0654 (2)	0.0437 (10)
H27	0.8795	0.1825	0.1100	0.052*
C28	0.8771 (5)	0.1285 (2)	0.0179 (2)	0.0497 (11)
H28	0.9563	0.0942	0.0311	0.060*
C29	0.8059 (5)	0.1255 (2)	−0.0487 (2)	0.0456 (11)
H29	0.8361	0.0882	−0.0782	0.055*
C30	0.6911 (4)	0.1769 (2)	−0.0718 (2)	0.0435 (10)
H30	0.6455	0.1755	−0.1165	0.052*
C31	0.6463 (4)	0.2311 (2)	−0.02489 (19)	0.0331 (9)
C32	0.5381 (4)	0.2923 (2)	−0.0318 (2)	0.0325 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.04042 (16)	0.05433 (17)	0.04863 (19)	−0.00532 (14)	−0.00356 (13)	0.01367 (15)
I2	0.0800 (2)	0.0646 (2)	0.04028 (19)	−0.00647 (17)	−0.00643 (16)	−0.00551 (15)
I3	0.0611 (2)	0.05784 (19)	0.0772 (2)	0.01099 (16)	0.02269 (17)	0.00935 (18)
As	0.0266 (2)	0.0342 (2)	0.0304 (2)	−0.00322 (18)	0.00190 (17)	0.00100 (19)
N1	0.0254 (17)	0.0391 (18)	0.0238 (18)	−0.0037 (15)	−0.0016 (14)	−0.0023 (15)
N2	0.0301 (18)	0.0346 (18)	0.031 (2)	−0.0017 (15)	0.0023 (15)	−0.0018 (16)
N3	0.0300 (18)	0.0335 (17)	0.0233 (18)	−0.0002 (14)	0.0018 (15)	0.0019 (15)
N4	0.0345 (19)	0.0387 (19)	0.033 (2)	−0.0003 (16)	−0.0019 (16)	−0.0008 (15)
N5	0.0304 (17)	0.0377 (18)	0.0270 (18)	−0.0025 (15)	0.0025 (14)	0.0012 (15)
N6	0.0285 (18)	0.0351 (18)	0.036 (2)	0.0008 (15)	0.0042 (15)	0.0045 (16)
N7	0.0251 (17)	0.0369 (18)	0.0280 (19)	0.0042 (14)	0.0004 (14)	0.0020 (15)
N8	0.0326 (18)	0.0366 (18)	0.036 (2)	0.0001 (16)	0.0034 (15)	0.0043 (16)
C1	0.023 (2)	0.035 (2)	0.033 (2)	−0.0038 (18)	0.0031 (18)	−0.0059 (19)
C2	0.027 (2)	0.031 (2)	0.027 (2)	−0.0059 (18)	0.0037 (18)	0.0043 (18)
C3	0.052 (3)	0.039 (2)	0.036 (3)	0.000 (2)	0.006 (2)	−0.001 (2)
C4	0.062 (3)	0.057 (3)	0.023 (2)	−0.009 (2)	0.003 (2)	−0.004 (2)
C5	0.038 (2)	0.049 (3)	0.035 (3)	−0.004 (2)	−0.006 (2)	0.007 (2)
C6	0.043 (2)	0.038 (2)	0.027 (2)	−0.0016 (19)	−0.002 (2)	−0.0008 (19)
C7	0.030 (2)	0.039 (2)	0.023 (2)	−0.0037 (18)	0.0044 (18)	−0.0023 (18)
C8	0.027 (2)	0.033 (2)	0.025 (2)	−0.0048 (18)	0.0043 (18)	0.0039 (18)
C9	0.021 (2)	0.027 (2)	0.038 (3)	−0.0053 (17)	0.0034 (19)	0.0015 (19)
C10	0.025 (2)	0.030 (2)	0.036 (2)	−0.0027 (18)	0.0059 (18)	0.0053 (19)
C11	0.037 (2)	0.035 (2)	0.042 (3)	−0.0098 (19)	0.000 (2)	0.003 (2)
C12	0.028 (2)	0.034 (2)	0.065 (3)	0.0027 (18)	0.008 (2)	0.004 (2)
C13	0.048 (3)	0.039 (3)	0.053 (3)	−0.003 (2)	0.013 (2)	−0.010 (2)
C14	0.043 (3)	0.037 (2)	0.045 (3)	−0.005 (2)	0.007 (2)	0.001 (2)
C15	0.031 (2)	0.031 (2)	0.030 (2)	−0.0095 (18)	0.0042 (18)	−0.0013 (19)
C16	0.028 (2)	0.041 (2)	0.027 (2)	0.0020 (19)	−0.0004 (18)	0.004 (2)
C17	0.030 (2)	0.043 (2)	0.027 (2)	−0.007 (2)	0.0027 (19)	0.0025 (19)
C18	0.037 (2)	0.040 (2)	0.039 (3)	−0.007 (2)	0.004 (2)	0.008 (2)
C19	0.045 (3)	0.048 (2)	0.026 (2)	0.001 (2)	−0.001 (2)	0.001 (2)
C20	0.051 (3)	0.068 (3)	0.042 (3)	−0.008 (2)	−0.002 (2)	−0.010 (2)
C21	0.050 (3)	0.060 (3)	0.038 (3)	−0.003 (2)	−0.007 (2)	0.006 (2)
C22	0.029 (2)	0.046 (2)	0.047 (3)	0.0035 (19)	−0.006 (2)	0.000 (2)
C23	0.032 (2)	0.034 (2)	0.033 (2)	−0.0070 (19)	0.0004 (19)	0.0002 (19)
C24	0.029 (2)	0.029 (2)	0.038 (3)	0.0015 (18)	−0.0043 (19)	0.0084 (19)
C25	0.026 (2)	0.032 (2)	0.035 (3)	−0.0064 (17)	0.0047 (19)	0.0002 (19)
C26	0.024 (2)	0.032 (2)	0.042 (3)	−0.0031 (18)	0.0054 (19)	0.006 (2)
C27	0.033 (2)	0.046 (3)	0.053 (3)	−0.004 (2)	0.007 (2)	0.011 (2)
C28	0.044 (3)	0.036 (2)	0.071 (4)	0.010 (2)	0.013 (3)	0.004 (2)
C29	0.046 (3)	0.041 (3)	0.051 (3)	0.002 (2)	0.015 (2)	−0.004 (2)
C30	0.034 (2)	0.044 (2)	0.053 (3)	0.000 (2)	0.007 (2)	−0.004 (2)
C31	0.027 (2)	0.033 (2)	0.040 (3)	−0.0062 (19)	0.0061 (19)	0.001 (2)
C32	0.027 (2)	0.038 (2)	0.033 (2)	0.0041 (18)	0.0083 (19)	−0.0019 (19)

Geometric parameters (Å, º)

I1—I2	2.8755 (7)	C9—C10	1.438 (5)
I1—I3	2.9844 (7)	C10—C15	1.375 (4)
As—N5	2.025 (3)	C10—C11	1.406 (5)
As—N7	2.060 (3)	C11—C12	1.391 (5)
As—N3	2.071 (3)	C11—H11	0.9300
As—N1	2.082 (3)	C12—C13	1.402 (5)
As—I1	3.7813 (9)	C12—H12	0.9300
As—I3	3.6948 (9)	C13—C14	1.401 (5)
N1—C1	1.389 (4)	C13—H13	0.9300
N1—C8	1.403 (4)	C14—C15	1.403 (5)
N2—C8	1.319 (4)	C14—H14	0.9300
N2—C9	1.320 (4)	C15—C16	1.454 (5)
N3—C9	1.383 (4)	C17—C18	1.434 (5)
N3—C16	1.386 (4)	C18—C19	1.387 (5)
N4—C16	1.301 (4)	C18—C23	1.404 (5)
N4—C17	1.320 (4)	C19—C20	1.363 (5)
N5—C24	1.400 (4)	C19—H19	0.9300
N5—C17	1.423 (4)	C20—C21	1.425 (5)
N6—C25	1.304 (4)	C20—H20	0.9300
N6—C24	1.311 (4)	C21—C22	1.392 (5)
N7—C32	1.389 (4)	C21—H21	0.9300
N7—C25	1.390 (4)	C22—C23	1.378 (5)
N8—C32	1.323 (4)	C22—H22	0.9300
N8—C1	1.325 (4)	C23—C24	1.450 (5)
C1—C2	1.443 (5)	C25—C26	1.451 (5)
C2—C7	1.384 (5)	C26—C31	1.387 (4)
C2—C3	1.399 (5)	C26—C27	1.409 (5)
C3—C4	1.386 (5)	C27—C28	1.391 (5)
C3—H3	0.9300	C27—H27	0.9300
C4—C5	1.408 (5)	C28—C29	1.395 (5)
C4—H4	0.9300	C28—H28	0.9300
C5—C6	1.392 (5)	C29—C30	1.387 (5)
C5—H5	0.9300	C29—H29	0.9300
C6—C7	1.379 (5)	C30—C31	1.406 (5)
C6—H6	0.9300	C30—H30	0.9300
C7—C8	1.446 (4)	C31—C32	1.422 (5)
I2—I1—I3	179.12 (2)	C14—C13—H13	118.8
N5—As—N7	82.6 (1)	C12—C13—H13	118.8
N5—As—N3	83.0 (1)	C13—C14—C15	115.1 (4)
N7—As—N3	137.6 (1)	C13—C14—H14	122.4
N5—As—N1	136.1 (1)	C15—C14—H14	122.4
N7—As—N1	81.6 (1)	C10—C15—C14	122.6 (4)
N3—As—N1	81.7 (1)	C10—C15—C16	107.2 (3)
C1—N1—C8	106.2 (3)	C14—C15—C16	130.2 (4)
C1—N1—As	123.4 (2)	N4—C16—N3	128.8 (3)
C8—N1—As	123.9 (2)	N4—C16—C15	122.7 (3)
C8—N2—C9	122.1 (3)	N3—C16—C15	108.5 (3)
C9—N3—C16	107.6 (3)	N4—C17—N5	127.0 (3)
C9—N3—As	125.1 (2)	N4—C17—C18	123.6 (4)
C16—N3—As	123.1 (2)	N5—C17—C18	109.2 (3)
C16—N4—C17	121.6 (3)	C19—C18—C23	121.4 (4)
C24—N5—C17	106.6 (3)	C19—C18—C17	131.0 (4)
C24—N5—As	125.0 (2)	C23—C18—C17	107.6 (3)
C17—N5—As	123.0 (2)	C20—C19—C18	117.4 (4)
C25—N6—C24	121.9 (3)	C20—C19—H19	121.3
C32—N7—C25	107.3 (3)	C18—C19—H19	121.3
C32—N7—As	123.4 (2)	C19—C20—C21	121.9 (4)
C25—N7—As	123.8 (2)	C19—C20—H20	119.1
C32—N8—C1	121.3 (3)	C21—C20—H20	119.1
N8—C1—N1	127.3 (3)	C22—C21—C20	120.4 (4)
N8—C1—C2	123.1 (3)	C22—C21—H21	119.8
N1—C1—C2	109.6 (3)	C20—C21—H21	119.8
C7—C2—C3	120.5 (3)	C23—C22—C21	117.2 (4)
C7—C2—C1	107.9 (3)	C23—C22—H22	121.4
C3—C2—C1	131.6 (4)	C21—C22—H22	121.4
C4—C3—C2	116.5 (4)	C22—C23—C18	121.7 (4)
C4—C3—H3	121.7	C22—C23—C24	131.2 (4)
C2—C3—H3	121.7	C18—C23—C24	107.1 (3)
C3—C4—C5	122.1 (4)	N6—C24—N5	127.1 (3)
C3—C4—H4	119.0	N6—C24—C23	123.4 (3)
C5—C4—H4	119.0	N5—C24—C23	109.4 (3)
C6—C5—C4	121.0 (3)	N6—C25—N7	127.9 (3)
C6—C5—H5	119.5	N6—C25—C26	123.8 (3)
C4—C5—H5	119.5	N7—C25—C26	108.4 (3)
C7—C6—C5	116.0 (3)	C31—C26—C27	122.2 (4)
C7—C6—H6	122.0	C31—C26—C25	107.2 (3)
C5—C6—H6	122.0	C27—C26—C25	130.6 (4)
C6—C7—C2	123.7 (3)	C28—C27—C26	116.1 (4)
C6—C7—C8	129.9 (4)	C28—C27—H27	121.9
C2—C7—C8	106.3 (3)	C26—C27—H27	121.9
N2—C8—N1	127.1 (3)	C27—C28—C29	122.0 (4)
N2—C8—C7	122.9 (3)	C27—C28—H28	119.0
N1—C8—C7	110.0 (3)	C29—C28—H28	119.0
N2—C9—N3	127.6 (3)	C30—C29—C28	121.5 (4)
N2—C9—C10	123.2 (3)	C30—C29—H29	119.3
N3—C9—C10	109.2 (3)	C28—C29—H29	119.3
C15—C10—C11	122.3 (4)	C29—C30—C31	117.3 (4)
C15—C10—C9	107.4 (3)	C29—C30—H30	121.3
C11—C10—C9	130.2 (4)	C31—C30—H30	121.3
C12—C11—C10	116.0 (4)	C26—C31—C30	120.8 (4)
C12—C11—H11	122.0	C26—C31—C32	107.2 (3)
C10—C11—H11	122.0	C30—C31—C32	132.0 (4)
C11—C12—C13	121.6 (4)	N8—C32—N7	127.8 (3)
C11—C12—H12	119.2	N8—C32—C31	122.4 (3)
C13—C12—H12	119.2	N7—C32—C31	109.8 (3)
C14—C13—C12	122.4 (4)