Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801021365/na6120sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801021365/na6120Isup2.hkl |
CCDC reference: 180524
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
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.
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.
[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) Å3 | Parallelepiped, violet |
Z = 4 | 0.30 × 0.12 × 0.10 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.042 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0071P)2] where P = (Fo2 + 2Fc2)/3 |
7507 reflections | (Δ/σ)max = 0.001 |
397 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
[As(C32H16N8)]I3 | V = 2974.4 (11) Å3 |
Mr = 968.15 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.652 (2) Å | µ = 4.30 mm−1 |
b = 17.558 (4) Å | T = 295 K |
c = 19.668 (4) Å | 0.30 × 0.12 × 0.10 mm |
β = 95.42 (3)° |
Kuma KM-4 with two-dimensional area CCD detector diffractometer | 7507 independent reflections |
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) | 4287 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 0.673 | Rint = 0.039 |
26611 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.042 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.48 e Å−3 |
7507 reflections | Δρmin = −0.46 e Å−3 |
397 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | [As(C32H16N8)]I3 |
Mr | 968.15 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 8.652 (2), 17.558 (4), 19.668 (4) |
β (°) | 95.42 (3) |
V (Å3) | 2974.4 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.30 |
Crystal size (mm) | 0.30 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Kuma KM-4 with two-dimensional area CCD detector diffractometer |
Absorption correction | Analytical face-indexed (SHELXTL; Sheldrick, 1990) |
Tmin, Tmax | 0.359, 0.673 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26611, 7507, 4287 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.042, 0.99 |
No. of reflections | 7507 |
No. of parameters | 397 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.46 |
Computer programs: Kuma KM-4 CCD Software (Kuma, 2000), Kuma KM-4 CCD Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990), SHELXL97.
I1—I2 | 2.8755 (7) | As—N3 | 2.071 (3) |
I1—I3 | 2.9844 (7) | As—N1 | 2.082 (3) |
As—N5 | 2.025 (3) | As—I1 | 3.7813 (9) |
As—N7 | 2.060 (3) | As—I3 | 3.6948 (9) |
I2—I1—I3 | 179.12 (2) | N5—As—N1 | 136.1 (1) |
N5—As—N7 | 82.6 (1) | N7—As—N1 | 81.6 (1) |
N5—As—N3 | 83.0 (1) | N3—As—N1 | 81.7 (1) |
N7—As—N3 | 137.6 (1) |
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—Nisoindole coordination. The four As—Nisoindole bonds are more asymmetrical and a little longer (0.03–0.06 Å) than the Sb—Nisoindole bonds in SbPcI3 (Kubiak et al., 1999). Thus, the molecular symmetry of the As—N core is close to Cs symmetry and not to C4v, which is possible for saucer shaped MIIPc 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).