5,15-Bis(3,5-di-tert-butyl­phen­yl)-3,7,13,17-tetra­methyl-2,8,12,18-tetra­propyl­porphyrin

The title mol­ecule, C₆₄H₈₆N₄, possesses a crystallographically imposed centre of symmetry with a recta­ngular distortion of the porphyrin core. In the crystal structure, mol­ecules form laddered assemblies via partial π stacking of porphyrins. The assemblies are further formed into layers separated by tert-butyl groups.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.087
• wR factor = 0.182
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.98 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.71 Ratio

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.854     0.999
            Tmin(prime) and Tmax expected:      0.973     0.997
            RR(prime) =      0.877
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C25
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C29
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C14
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C15

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

5,15-Bis(3,5-di-tert-butylphenyl)-3,7,13,17- tetramethyl-2,8,12,18-tetrapropylporphyrin

Crystal data

C64H86N4	F(000) = 996
Mr = 911.37	Dx = 1.103 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.9467 (6) Å	Cell parameters from 3022 reflections
b = 16.3352 (5) Å	θ = 2.7–25.1°
c = 8.0916 (1) Å	µ = 0.06 mm^−1
β = 97.486 (1)°	T = 200 K
V = 2745.09 (12) Å^3	Needle, red
Z = 2	0.44 × 0.07 × 0.04 mm

Data collection

Siemens SMART CCD diffractometer	4786 independent reflections
Radiation source: fine-focus sealed tube	2464 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 25.1°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.854, Tmax = 0.999	k = 0→19
12519 measured reflections	l = 0→9

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)] = 0.088	H-atom parameters constrained
wR(F^2) = 0.182	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 3.8177P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
4786 reflections	Δρmax = 0.22 e Å^−3
316 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0049 (7)

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	Occ. (<1)
N1	0.06947 (15)	−0.03097 (19)	0.6977 (4)	0.0302 (8)
H1A	0.0448	−0.0127	0.6090	0.036*	0.50
N2	0.08198 (14)	0.03535 (18)	0.3948 (4)	0.0280 (8)
H2	0.0518	0.0153	0.4492	0.034*	0.50
C1	−0.01381 (18)	−0.0837 (2)	0.8579 (5)	0.0305 (10)
H1	−0.0177	−0.1080	0.9627	0.037*
C2	0.04974 (18)	−0.0672 (2)	0.8334 (5)	0.0272 (9)
C3	0.10445 (18)	−0.0883 (2)	0.9544 (5)	0.0295 (10)
C4	0.15792 (18)	−0.0651 (2)	0.8881 (5)	0.0307 (10)
C5	0.13538 (18)	−0.0284 (2)	0.7260 (5)	0.0273 (9)
C6	0.17286 (18)	0.0035 (2)	0.6078 (5)	0.0288 (10)
C7	0.14715 (18)	0.0353 (2)	0.4507 (5)	0.0283 (9)
C8	0.17945 (18)	0.0739 (2)	0.3249 (5)	0.0313 (10)
C9	0.13353 (18)	0.0964 (2)	0.1976 (5)	0.0297 (10)
C10	0.07199 (18)	0.0716 (2)	0.2405 (5)	0.0288 (9)
C11	0.0997 (2)	−0.1301 (3)	1.1179 (5)	0.0366 (11)
H11A	0.0630	−0.1067	1.1677	0.044*
H11B	0.1394	−0.1190	1.1952	0.044*
C12	0.0905 (2)	−0.2233 (3)	1.1000 (5)	0.0424 (12)
H12A	0.0784	−0.2455	1.2053	0.051*
H12B	0.0546	−0.2344	1.0107	0.051*
C13	0.1505 (2)	−0.2678 (3)	1.0590 (6)	0.0547 (14)
H13A	0.1627	−0.2465	0.9543	0.082*
H13B	0.1414	−0.3265	1.0472	0.082*
H13C	0.1859	−0.2591	1.1490	0.082*
C14	0.22604 (18)	−0.0761 (3)	0.9730 (5)	0.0420 (11)
H14A	0.2252	−0.1032	1.0807	0.063*
H14B	0.2467	−0.0224	0.9906	0.063*
H14C	0.2503	−0.1097	0.9026	0.063*
C15	0.25006 (19)	0.0927 (3)	0.3287 (5)	0.0452 (12)
H15A	0.2572	0.1194	0.2242	0.068*
H15B	0.2748	0.0417	0.3418	0.068*
H15C	0.2640	0.1292	0.4226	0.068*
C16	0.1446 (2)	0.1419 (3)	0.0420 (5)	0.0375 (11)
H16A	0.1075	0.1323	−0.0449	0.045*
H16B	0.1835	0.1195	0.0006	0.045*
C17	0.1533 (2)	0.2342 (3)	0.0686 (5)	0.0459 (12)
H17A	0.1881	0.2437	0.1618	0.055*
H17B	0.1669	0.2587	−0.0330	0.055*
C18	0.0925 (2)	0.2772 (3)	0.1073 (6)	0.0515 (13)
H18A	0.0594	0.2741	0.0099	0.077*
H18B	0.1022	0.3347	0.1344	0.077*
H18C	0.0766	0.2504	0.2025	0.077*
C19	0.24448 (18)	0.0007 (2)	0.6444 (5)	0.0304 (10)
C24	0.27792 (19)	−0.0633 (3)	0.5799 (5)	0.0355 (10)
H22A	0.2545	−0.1048	0.5158	0.043*
C23	0.3447 (2)	−0.0675 (3)	0.6075 (5)	0.0408 (11)
C22	0.3772 (2)	−0.0054 (3)	0.7026 (5)	0.0435 (12)
H24A	0.4229	−0.0072	0.7230	0.052*
C21	0.34523 (19)	0.0594 (3)	0.7688 (5)	0.0371 (11)
C20	0.27867 (19)	0.0615 (3)	0.7372 (5)	0.0344 (10)
H26A	0.2560	0.1055	0.7798	0.041*
C29	0.3803 (2)	−0.1345 (3)	0.5232 (6)	0.0521 (13)
C25	0.3833 (2)	0.1247 (3)	0.8760 (6)	0.0497 (13)
C31	0.3425 (3)	−0.2149 (3)	0.5105 (7)	0.0796 (19)
H31A	0.3676	−0.2573	0.4624	0.119*
H31B	0.3015	−0.2071	0.4391	0.119*
H31C	0.3343	−0.2320	0.6219	0.119*
C30	0.3869 (3)	−0.1056 (3)	0.3452 (7)	0.0724 (17)
H30A	0.4123	−0.0551	0.3502	0.109*
H30B	0.3440	−0.0954	0.2846	0.109*
H30C	0.4085	−0.1481	0.2875	0.109*
C26	0.3436 (3)	0.2024 (3)	0.8905 (7)	0.0830 (19)
H26B	0.3701	0.2434	0.9558	0.125*
H26C	0.3060	0.1894	0.9460	0.125*
H26D	0.3293	0.2241	0.7789	0.125*
C28	0.4002 (3)	0.0901 (4)	1.0516 (6)	0.086 (2)
H28A	0.4287	0.0428	1.0481	0.129*
H28B	0.3607	0.0732	1.0949	0.129*
H28C	0.4221	0.1323	1.1244	0.129*
C32	0.4468 (3)	−0.1506 (4)	0.6164 (8)	0.106 (2)
H32A	0.4738	−0.1019	0.6108	0.160*
H32B	0.4664	−0.1971	0.5654	0.160*
H32C	0.4431	−0.1632	0.7332	0.160*
C27	0.4442 (3)	0.1481 (4)	0.8062 (8)	0.101 (2)
H27A	0.4749	0.1026	0.8214	0.151*
H27B	0.4632	0.1965	0.8647	0.151*
H27C	0.4340	0.1603	0.6871	0.151*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.032 (2)	0.028 (2)	0.0305 (19)	−0.0013 (15)	0.0045 (16)	0.0036 (16)
N2	0.0258 (19)	0.0276 (19)	0.0307 (19)	−0.0022 (15)	0.0045 (15)	−0.0009 (15)
C1	0.036 (3)	0.029 (2)	0.027 (2)	−0.0008 (19)	0.0060 (19)	−0.0008 (18)
C2	0.033 (2)	0.019 (2)	0.029 (2)	0.0016 (18)	0.0052 (19)	0.0009 (18)
C3	0.033 (2)	0.024 (2)	0.031 (2)	0.0000 (18)	0.004 (2)	−0.0018 (19)
C4	0.031 (2)	0.029 (2)	0.031 (2)	0.0007 (19)	−0.0002 (19)	−0.0005 (19)
C5	0.027 (2)	0.024 (2)	0.030 (2)	−0.0012 (18)	0.0005 (18)	−0.0044 (18)
C6	0.029 (2)	0.024 (2)	0.033 (2)	0.0004 (18)	0.0043 (19)	−0.0025 (19)
C7	0.027 (2)	0.024 (2)	0.034 (2)	−0.0006 (18)	0.0053 (19)	0.0014 (19)
C8	0.030 (2)	0.030 (2)	0.035 (2)	−0.0044 (19)	0.011 (2)	0.000 (2)
C9	0.032 (2)	0.031 (2)	0.028 (2)	−0.0016 (18)	0.009 (2)	−0.0016 (19)
C10	0.034 (2)	0.026 (2)	0.028 (2)	0.0017 (19)	0.0084 (19)	0.0026 (19)
C11	0.039 (3)	0.041 (3)	0.029 (2)	0.003 (2)	0.001 (2)	0.007 (2)
C12	0.049 (3)	0.043 (3)	0.036 (3)	0.003 (2)	0.006 (2)	0.012 (2)
C13	0.071 (4)	0.044 (3)	0.049 (3)	0.010 (3)	0.007 (3)	0.004 (2)
C14	0.037 (3)	0.049 (3)	0.039 (3)	−0.002 (2)	0.000 (2)	0.009 (2)
C15	0.041 (3)	0.047 (3)	0.051 (3)	−0.001 (2)	0.019 (2)	0.013 (2)
C16	0.038 (3)	0.041 (3)	0.036 (3)	0.000 (2)	0.014 (2)	0.003 (2)
C17	0.050 (3)	0.047 (3)	0.041 (3)	−0.014 (2)	0.005 (2)	0.012 (2)
C18	0.068 (4)	0.037 (3)	0.049 (3)	−0.005 (2)	0.006 (3)	0.009 (2)
C19	0.030 (2)	0.030 (2)	0.031 (2)	−0.0017 (19)	0.0048 (19)	0.0069 (19)
C24	0.035 (3)	0.031 (3)	0.039 (2)	0.001 (2)	0.002 (2)	−0.003 (2)
C23	0.033 (3)	0.048 (3)	0.042 (3)	0.008 (2)	0.008 (2)	0.009 (2)
C22	0.027 (2)	0.055 (3)	0.048 (3)	0.001 (2)	0.002 (2)	0.006 (2)
C21	0.033 (3)	0.044 (3)	0.034 (2)	−0.004 (2)	0.005 (2)	0.002 (2)
C20	0.033 (3)	0.034 (3)	0.037 (2)	−0.005 (2)	0.010 (2)	−0.003 (2)
C29	0.040 (3)	0.050 (3)	0.066 (3)	0.015 (2)	0.008 (3)	−0.003 (3)
C25	0.035 (3)	0.060 (4)	0.053 (3)	−0.012 (2)	0.001 (2)	−0.005 (3)
C31	0.099 (5)	0.048 (4)	0.102 (5)	0.015 (3)	0.048 (4)	−0.006 (3)
C30	0.081 (4)	0.066 (4)	0.079 (4)	0.016 (3)	0.044 (3)	−0.006 (3)
C26	0.077 (4)	0.066 (4)	0.101 (5)	−0.014 (3)	−0.007 (4)	−0.036 (4)
C28	0.087 (5)	0.108 (5)	0.055 (4)	−0.021 (4)	−0.023 (3)	−0.006 (3)
C32	0.070 (4)	0.114 (6)	0.127 (6)	0.055 (4)	−0.019 (4)	−0.033 (5)
C27	0.068 (4)	0.100 (5)	0.140 (6)	−0.050 (4)	0.037 (4)	−0.035 (5)

Geometric parameters (Å, º)

N1—C2	1.359 (4)	C17—C18	1.522 (6)
N1—C5	1.370 (4)	C17—H17A	0.9900
N1—H1A	0.8800	C17—H17B	0.9900
N2—C10	1.373 (5)	C18—H18A	0.9800
N2—C7	1.381 (4)	C18—H18B	0.9800
N2—H2	0.8800	C18—H18C	0.9800
C1—C10^i	1.380 (5)	C19—C20	1.388 (5)
C1—C2	1.397 (5)	C19—C24	1.397 (5)
C1—H1	0.9500	C24—C23	1.390 (5)
C2—C3	1.448 (5)	C24—H22A	0.9500
C3—C4	1.357 (5)	C23—C22	1.395 (6)
C3—C11	1.504 (5)	C23—C29	1.533 (6)
C4—C5	1.463 (5)	C22—C21	1.396 (6)
C4—C14	1.512 (5)	C22—H24A	0.9500
C5—C6	1.414 (5)	C21—C20	1.385 (5)
C6—C7	1.414 (5)	C21—C25	1.532 (6)
C6—C19	1.492 (5)	C20—H26A	0.9500
C7—C8	1.439 (5)	C29—C32	1.518 (6)
C8—C9	1.365 (5)	C29—C31	1.531 (7)
C8—C15	1.507 (5)	C29—C30	1.538 (6)
C9—C10	1.436 (5)	C25—C27	1.510 (6)
C9—C16	1.506 (5)	C25—C28	1.527 (6)
C10—C1^i	1.380 (5)	C25—C26	1.530 (7)
C11—C12	1.538 (5)	C31—H31A	0.9800
C11—H11A	0.9900	C31—H31B	0.9800
C11—H11B	0.9900	C31—H31C	0.9800
C12—C13	1.525 (6)	C30—H30A	0.9800
C12—H12A	0.9900	C30—H30B	0.9800
C12—H12B	0.9900	C30—H30C	0.9800
C13—H13A	0.9800	C26—H26B	0.9800
C13—H13B	0.9800	C26—H26C	0.9800
C13—H13C	0.9800	C26—H26D	0.9800
C14—H14A	0.9800	C28—H28A	0.9800
C14—H14B	0.9800	C28—H28B	0.9800
C14—H14C	0.9800	C28—H28C	0.9800
C15—H15A	0.9800	C32—H32A	0.9800
C15—H15B	0.9800	C32—H32B	0.9800
C15—H15C	0.9800	C32—H32C	0.9800
C16—C17	1.530 (6)	C27—H27A	0.9800
C16—H16A	0.9900	C27—H27B	0.9800
C16—H16B	0.9900	C27—H27C	0.9800
C2—N1—C5	106.5 (3)	C18—C17—H17B	108.9
C2—N1—H1A	126.7	C16—C17—H17B	108.9
C5—N1—H1A	126.7	H17A—C17—H17B	107.7
C10—N2—C7	109.0 (3)	C17—C18—H18A	109.5
C10—N2—H2	125.5	C17—C18—H18B	109.5
C7—N2—H2	125.5	H18A—C18—H18B	109.5
C10^i—C1—C2	132.6 (4)	C17—C18—H18C	109.5
C10^i—C1—H1	113.7	H18A—C18—H18C	109.5
C2—C1—H1	113.7	H18B—C18—H18C	109.5
N1—C2—C1	126.4 (4)	C20—C19—C24	119.3 (4)
N1—C2—C3	110.7 (3)	C20—C19—C6	121.3 (4)
C1—C2—C3	122.9 (3)	C24—C19—C6	119.3 (4)
C4—C3—C2	106.7 (3)	C23—C24—C19	121.3 (4)
C4—C3—C11	128.8 (4)	C23—C24—H22A	119.3
C2—C3—C11	124.5 (3)	C19—C24—H22A	119.3
C3—C4—C5	106.4 (3)	C24—C23—C22	117.5 (4)
C3—C4—C14	124.5 (4)	C24—C23—C29	120.1 (4)
C5—C4—C14	129.1 (3)	C22—C23—C29	122.3 (4)
N1—C5—C6	122.3 (3)	C21—C22—C23	122.6 (4)
N1—C5—C4	109.7 (3)	C21—C22—H24A	118.7
C6—C5—C4	127.9 (3)	C23—C22—H24A	118.7
C7—C6—C5	124.3 (3)	C20—C21—C22	118.0 (4)
C7—C6—C19	116.5 (3)	C20—C21—C25	121.7 (4)
C5—C6—C19	119.1 (3)	C22—C21—C25	120.3 (4)
N2—C7—C6	122.6 (3)	C21—C20—C19	121.2 (4)
N2—C7—C8	107.7 (3)	C21—C20—H26A	119.4
C6—C7—C8	129.6 (4)	C19—C20—H26A	119.4
C9—C8—C7	107.5 (3)	C32—C29—C31	108.5 (5)
C9—C8—C15	123.7 (4)	C32—C29—C23	111.8 (4)
C7—C8—C15	128.7 (4)	C31—C29—C23	111.4 (4)
C8—C9—C10	108.0 (3)	C32—C29—C30	109.3 (4)
C8—C9—C16	126.4 (4)	C31—C29—C30	108.0 (4)
C10—C9—C16	125.6 (4)	C23—C29—C30	107.8 (4)
N2—C10—C1^i	127.2 (3)	C27—C25—C28	109.7 (4)
N2—C10—C9	107.8 (3)	C27—C25—C26	108.2 (5)
C1^i—C10—C9	125.0 (3)	C28—C25—C26	107.3 (4)
C3—C11—C12	112.8 (3)	C27—C25—C21	111.6 (4)
C3—C11—H11A	109.0	C28—C25—C21	108.1 (4)
C12—C11—H11A	109.0	C26—C25—C21	111.9 (4)
C3—C11—H11B	109.0	C29—C31—H31A	109.5
C12—C11—H11B	109.0	C29—C31—H31B	109.5
H11A—C11—H11B	107.8	H31A—C31—H31B	109.5
C13—C12—C11	113.3 (4)	C29—C31—H31C	109.5
C13—C12—H12A	108.9	H31A—C31—H31C	109.5
C11—C12—H12A	108.9	H31B—C31—H31C	109.5
C13—C12—H12B	108.9	C29—C30—H30A	109.5
C11—C12—H12B	108.9	C29—C30—H30B	109.5
H12A—C12—H12B	107.7	H30A—C30—H30B	109.5
C12—C13—H13A	109.5	C29—C30—H30C	109.5
C12—C13—H13B	109.5	H30A—C30—H30C	109.5
H13A—C13—H13B	109.5	H30B—C30—H30C	109.5
C12—C13—H13C	109.5	C25—C26—H26B	109.5
H13A—C13—H13C	109.5	C25—C26—H26C	109.5
H13B—C13—H13C	109.5	H26B—C26—H26C	109.5
C4—C14—H14A	109.5	C25—C26—H26D	109.5
C4—C14—H14B	109.5	H26B—C26—H26D	109.5
H14A—C14—H14B	109.5	H26C—C26—H26D	109.5
C4—C14—H14C	109.5	C25—C28—H28A	109.5
H14A—C14—H14C	109.5	C25—C28—H28B	109.5
H14B—C14—H14C	109.5	H28A—C28—H28B	109.5
C8—C15—H15A	109.5	C25—C28—H28C	109.5
C8—C15—H15B	109.5	H28A—C28—H28C	109.5
H15A—C15—H15B	109.5	H28B—C28—H28C	109.5
C8—C15—H15C	109.5	C29—C32—H32A	109.5
H15A—C15—H15C	109.5	C29—C32—H32B	109.5
H15B—C15—H15C	109.5	H32A—C32—H32B	109.5
C9—C16—C17	113.4 (3)	C29—C32—H32C	109.5
C9—C16—H16A	108.9	H32A—C32—H32C	109.5
C17—C16—H16A	108.9	H32B—C32—H32C	109.5
C9—C16—H16B	108.9	C25—C27—H27A	109.5
C17—C16—H16B	108.9	C25—C27—H27B	109.5
H16A—C16—H16B	107.7	H27A—C27—H27B	109.5
C18—C17—C16	113.4 (4)	C25—C27—H27C	109.5
C18—C17—H17A	108.9	H27A—C27—H27C	109.5
C16—C17—H17A	108.9	H27B—C27—H27C	109.5

Symmetry code: (i) −x, −y, −z+1.