Jul 1, 2016 - Discussion. TPP and pyrene are building a network of TPP layers with mole- cules of pyrene in between (Fig. 1). This group of clathrates was.
Ζ. Kristallogr. NCS 215 (2000) 263-264
263
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of pyrene—5,10,15,20-tetraphenyl-21//,23//-porphyrin (1/1),
C60H40N4
J. Blömker 1 and W. Frey11 I II
Universität Stuttgart, Physikalisches Institut, Pfaffenwaldring 57, D-70569 Stuttgart, Germany Universität Stuttgart, Institut für Organische Chemie, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
Received October 12, 1999, CCDC-No. 1267/309
Abstract C60H40N4, triclinic, P\ (No. 2), α = 9.727(3) Ä, b = 10.854(3) A, c = 11.620(3) Ä, α = 106.30(2)°, β = 104.11(2)°, γ = 104.43(2)°, 3 V= 1073.5 Ä , Z = 1, Rgt(F) = 0.061, wRgl(F2) = 0.142, Τ = 293 Κ. Source of material Crystals were usually obtained from a solution of tetraphenylporhin (TPP) and pyrene in mesitylene with a stoichiometry 1 : 1 by slow evaporation of the solvent analogue to [1], The crystals were washed with petroleum ether.
Fig. 1. TPP layers with molecules of pyrene in between.
Discussion TPP and pyrene are building a network of TPP layers with molecules of pyrene in between (Fig. 1). This group of clathrates was already mentioned by Byrn et. al. [2]. In this network the plane of the pyrene molecule is not parallel to the plane of the porphin because the pyrene is located above one phenyl group of the TPP (Fig. 2). The angle between the planes of C1C5C6C11 (the porphyrin plane) and the phenyl group CI 1 to C16 is 89.9°. The same angle exists for the phenyl group C11A to C16A due to the inversion symmetry of the molecule. The angle between the other two phenyl groups (CI7 to C20 and C17A to C20A) and the porphin-plane is 67.1°. In comparison to pure TPP in triclinic conformation [3] (the angles between the phenyl groups and the porphyrin plane are 61.0° and 63.1°), the location of the pyrene above one phenyl group causes a rotation of +6.10 (for the groups C17 to C20) and of +26.8° (for the groups C l l to C16), respectively.
Table 1. Data collection and handling. Crystal: Wavelength:
μ: Diffractometer, scan mode: 20max: N(hkl)measured, N(hkl)unjque: Criterion for /obs, N(hkl)gc. N(param,(refined: Programs:
Fig. 2. Plot of the molecules.
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black-violett block, size 0.25 χ 0.40 χ 0.75 mm Mo Ka radiation (0.71073 Ä) 0.74 cm" 1 Nicolet P3, Wyckoff 52° 4476, 3905
/obs > 2 af/obsj, 3221 290 SHELXS-86 [4], SHELXL-93 [5]
264
Pyrene—5,10,15,20-tetraphenyl-2li/,23W-porphyrin (1/1)
Table 2. Atomic coordinates and displacement parameters (in Ä 2 ).
Table 2. Continued.
Atom
Site
Atom
Site
H(l) H(2) H(3) H(7) H(8) H(12) H(13) H(14) H(15) H(16)
2i 2i 2i
H(18) H(19) H(20) H(21) H(22) H(2P) H(3P) H(4P) H(7P) H(8P)
2i 2/ 2i
2i 2i
2i 2i
2i 2i 2i
0.0659(2) 0.1535(2) 0.3942(2) -0.4174(2) -0.5516(2) -0.1855(3) -0.2674(4) -0.2886(3) -0.2191(3) -0.1363(3)
0.4982(2) 0.3561(2) 0.4938(2) 0.1805(2) 0.2137(2) 0.4085(3) 0.2900(3) 0.0657(3) -0.0415(2) 0.0756(2)
0.6042(2) 0.8832(2) 0.8817(2) 0.5838(2) 0.3947(2) 0.8938(3) 1.0159(3) 0.9679(2) 0.8025(2) 0.6801(2)
0.049 0.057 0.057 0.059 0.060 0.078 0.089 0.071 0.072 0.066
-0.6020(3) -0.8530(3) -0.9405(3) -0.7761(3) -0.5246(3) 0.4110(5) 0.3470(7) 0.1033(7) 0.3354(5) 0.1604(5)
2i
2i 2i 2i 2i 2i 2i
0.4566(2) 0.3859(3) 0.2297(3) 0.1492(3) 0.2201(2) 1.1335(5) 0.9509(6) 0.7955(5) 1.2620(4) 1.2865(3)
0.3623(2) 0.2396(3) 0.0347(3) -0.0509(2) 0.0699(2) 0.7294(4) 0.7938(4) 0.7084(4) 0.5919(4) 0.4407(4)
0.062 0.072 0.072 0.070 0.060 0.128 0.141 0.131 0.116 0.117
Table 3. Atomic coordinates and displacement parameters (in Ä 2 ). Atom
Site
N(l) C(l) N(2) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(ll) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(1P) C(2P) C(3P) C(4P) C(5P) C(6P) C(7P) C(8P)
2i 2i 2i 2i
2i 2i 2i 2i 2i
2i 2i
2i
2i 2i 2i 2i 2i
2i 2i 2i 2i 2i 2i
2i
2i 2i 2i 2i 2i 2i
2i 2i
Acknowledgment. crystal samples.
X
0.1133(2) 0.0486(2) -0.2009(2) 0.1661(2) 0.2989(2) 0.2660(2) -0.1059(2) -0.2185(2) -0.3754(2) -0.4490(2) -0.3400(2) -0.3732(2) -0.1538(2) -0.1925(3) -0.2420(4) -0.2534(3) -0.2132(3) -0.1635(3) -0.5354(2) -0.6361(3) -0.7870(3) -0.8390(3) -0.7410(3) -0.5901(3) 0.2050(4) 0.3130(5) 0.2744(7) 0.1275(7) 0.0168(5) 0.0556(3) 0.2382(5) 0.1340(5)
ii
y
ζ
U
0.4812(2) 0.4025(2) 0.3868(2) 0.4012(2) 0.4774(2) 0.5281(2) 0.3292(2) 0.3206(2) 0.2366(2) 0.2546(2) 0.3492(2) 0.3911(2) 0.2539(2) 0.3175(3) 0.2461(3) 0.1132(3) 0.0491(2) 0.1197(2) 0.3460(2) 0.3947(2) 0.3519(3) 0.2594(3) 0.2110(3) 0.2537(2) 1.0888(4) 1.0714(5) 0.9621(6) 0.8681(5) 0.8819(4) 0.9922(3) 1.1984(4) 1.2134(3)
0.6674(2) 0.7266(2) 0.5027(2) 0.8273(2) 0.8266(2) 0.7258(2) 0.6907(2) 0.5855(2) 0.5448(2) 0.4409(2) 0.4137(2) 0.3095(2) 0.7730(2) 0.8741(3) 0.9474(3) 0.9197(2) 0.8207(2) 0.7474(2) 0.2295(2) 0.2791(2) 0.2057(3) 0.0832(3) 0.0325(2) 0.1051(2) 0.6015(4) 0.6939(4) 0.7326(4) 0.6809(4) 0.5884(4) 0.5474(3) 0.5574(4) 0.4672(4)
0.0380(9) 0.043(1) 0.0397(9) 0.048(1) 0.041(1) 0.039(1) 0.042(1) 0.040(1) 0.041(1) 0.037(1) 0.038(1) 0.037(1) 0.037(1) 0.093(2) 0.103(2) 0.060(2) 0.077(2) 0.077(2) 0.039(1) 0.049(1) 0.046(1) 0.038(1) 0.058(2) 0.048(1) 0.094(2) 0.104(3) 0.146(4) 0.164(4) 0.122(3) 0.090(2) 0.108(3) 0.138(4)
We thank W. Tuffentsammer for the preparation of the
References 1. Byra, M.P.; Curtis,C.J.;Goldberg,I.; Hsiou,Y.;Khan, S.I.;Sawin,P. Α.; Tendick, S. K.; Strouse, C. E.: Porphyrin Sponges: Structural Systematics of the Host Lattice. J. Am. Chem. Soc. 113 (1991) 6549-6557.
1/22
i/33
U12
U13
t/23
0.046(1) 0.040(1) 0.045(1) 0.051(1) 0.054(1) 0.042(1) 0.039(1) 0.043(1) 0.055(1) 0.055(1) 0.042(1) 0.040(1) 0.044(1) 0.054(1) 0.077(2) 0.063(2) 0.040(1) 0.045(1) 0.042(1) 0.053(1) 0.069(2) 0.067(2) 0.053(1) 0.054(1) 0.080(2) 0.126(4) 0.142(4) 0.104(3) 0.077(2) 0.063(2) 0.073(2) 0.061(2)
0.0410(9) 0.042(1) 0.0395(9) 0.047(1) 0.045(1) 0.040(1) 0.042(1) 0.044(1) 0.054(1) 0.053(1) 0.042(1) 0.040(1) 0.041(1) 0.078(2) 0.084(2) 0.060(2) 0.056(1) 0.047(1) 0.044(1) 0.051(1) 0.074(2) 0.070(2) 0.047(1) 0.046(1) 0.090(2) 0.099(3) 0.099(3) 0.110(3) 0.091(2) 0.084(2) 0.114(3) 0.120(3)
0.0085(7) 0.0105(9) 0.0092(7) 0.010(1) 0.0087(9) 0.0070(9) 0.0094(9) 0.0087(9) 0.004(1) 0.002(1) 0.0063(9) 0.0055(8) 0.0071(9) 0.031(1) 0.042(2) 0.006(1) 0.003(1) 0.016(1) 0.0057(9) 0.015(1) 0.022(1) 0.004(1) 0.002(1) 0.009(1) 0.031(2) 0.048(3) 0.081(4) 0.075(3) 0.050(2) 0.031(2) 0.018(2) 0.028(2)
0.0132(7) 0.0171(9) 0.0131(8) 0.015(1) 0.0087(9) 0.0105(9) 0.0178(9) 0.0184(9) 0.018(1) 0.014(1) 0.0133(9) 0.0113(9) 0.0143(9) 0.056(2) 0.069(2) 0.027(1) 0.019(1) 0.028(1) 0.0114(9) 0.015(1) 0.021(1) 0.002(1) 0.002(1) 0.015(1) 0.061(2) 0.058(3) 0.067(3) 0.089(3) 0.073(2) 0.062(2) 0.077(3) 0.095(3)
0.0255(8) 0.0214(9) 0.0233(8) 0.031(1) 0.027(1) 0.0190(9) 0.0208(9) 0.0218(9) 0.032(1) 0.027(1) 0.0204(9) 0.0179(9) 0.0233(9) 0.039(1) 0.048(2) 0.039(1) 0.025(1) 0.021(1) 0.0250(9) 0.022(1) 0.038(1) 0.041(1) 0.024(1) 0.024(1) 0.019(2) 0.027(3) 0.043(3) 0.050(3) 0.036(2) 0.022(2) 0.021(2) 0.035(2)
Byrn, M. P.; Curtis, C. J.; Khan, S. I.; Sawin, P. Α.; Tsurumi, R.; Strouse, C. E.: Tetraarylporphyrin Sponges. Composition, Structural Systematics, and Applications of a Large Class of Programmable Lattice Clathrates. J. Am. Chem. Soc. 112 (1990) 1865-1874. Silvers, S.J.; Tulinsky, Α.: The Triclinic Crystal Form of α,β,γ,δ-Tetraphenylporphine. J. Am. Chem. Soc. 86 (1964) 927-928. Sheldrick, G. M.: Phase Annealing in SHELX-90: Direct Methods for Larger Structures. Acta Crystallogr. A46 (1990) 476. Sheldrick, G. M.: SHELXL-93. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1993.
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