(1RS,4SR,8SR,11RS,15SR,18RS,22RS,25SR)-1,4:8,11:15,18:22,25-Tetraethano-29H,31H-tetrabenzo­[b,g,l,q]­porphine chloro­form disolvate

In the title compound, C₄₄H₃₈N₄·2CHCl₃, the porphine (CP) is a soluble precursor of metal-free porphyrin which exhibits an excellent field-effect transistor characteristic. The CP skeleton is entirely flat and characterized by crystallographic C_i symmetry. In the present geometrical isomer, the C-C single-bond linkages of the four peripheries are arranged in an above-above-below-below manner with respect to the CP skeleton.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.125
• wR factor = 0.311
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.183
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.18
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         36 Perc.

Alert level C
RFACG01_ALERT_3_C  The value of the R factor is > 0.10
            R factor given   0.125
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.311
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.81
PLAT082_ALERT_2_C High R1 Value ..................................       0.12
PLAT084_ALERT_2_C High R2 Value ..................................       0.31
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C23
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.18 Ratio

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

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

---

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2004); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure.

(I)

Crystal data

C44H38N4·2CHCl3	F(000) = 892.00
Mr = 861.52	Dx = 1.427 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 9212 reflections
a = 10.282 (2) Å	θ = 4.5–68.0°
b = 17.433 (3) Å	µ = 4.22 mm^−1
c = 11.664 (2) Å	T = 93 K
β = 106.51 (1)°	Block, dark red
V = 2004.5 (6) Å^3	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	1286 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.183
48 frames, δ ω = 15° scans	θmax = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
Tmin = 0.400, Tmax = 0.430	k = −20→20
18024 measured reflections	l = −13→14
3592 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.125	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.311	(Δ/σ)max < 0.001
S = 1.32	Δρmax = 0.92 e Å^−3
3592 reflections	Δρmin = −0.67 e Å^−3
254 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.4440 (2)	−0.0242 (1)	0.1270 (2)	0.0961 (9)
Cl2	0.2157 (2)	−0.1016 (1)	0.1748 (2)	0.0933 (9)
Cl3	0.3934 (2)	−0.0097 (1)	0.3548 (2)	0.0707 (7)
N1	−0.0576 (5)	0.0457 (3)	0.1475 (4)	0.039 (1)
N2	0.1182 (5)	0.0941 (3)	0.0037 (4)	0.035 (1)
C1	0.0740 (6)	0.1650 (3)	0.1707 (5)	0.032 (1)
C2	0.1376 (6)	0.1558 (3)	0.0801 (5)	0.034 (1)
C3	0.2349 (6)	0.2085 (3)	0.0554 (5)	0.038 (2)
C4	0.2768 (6)	0.1780 (3)	−0.0364 (5)	0.033 (1)
C5	0.2019 (7)	0.1073 (3)	−0.0686 (5)	0.036 (1)
C6	0.3068 (6)	0.2806 (3)	0.1063 (5)	0.040 (2)
C7	0.4618 (6)	0.2576 (4)	0.1540 (5)	0.042 (2)
C8	0.5097 (6)	0.2208 (4)	0.0546 (5)	0.041 (2)
C9	0.3902 (6)	0.2208 (3)	−0.0641 (5)	0.040 (2)
C10	0.3048 (6)	0.3340 (3)	0.0036 (5)	0.041 (2)
C11	0.3466 (6)	0.3028 (3)	−0.0847 (5)	0.037 (2)
C12	−0.0113 (6)	0.1145 (3)	0.2027 (5)	0.038 (2)
C13	−0.0715 (6)	0.1197 (3)	0.3002 (5)	0.036 (1)
C14	−0.1480 (6)	0.0568 (3)	0.3003 (5)	0.035 (1)
C15	−0.1428 (6)	0.0088 (3)	0.2018 (5)	0.035 (1)
C16	−0.0729 (6)	0.1782 (3)	0.3954 (5)	0.038 (2)
C17	−0.2249 (7)	0.1988 (3)	0.3731 (6)	0.049 (2)
C18	−0.3096 (6)	0.1278 (3)	0.3755 (5)	0.042 (2)
C19	−0.2210 (6)	0.0548 (3)	0.3952 (5)	0.041 (2)
C20	−0.0365 (7)	0.1324 (4)	0.5148 (5)	0.044 (2)
C21	−0.1123 (6)	0.0687 (4)	0.5142 (5)	0.045 (2)
C22	−0.2089 (6)	−0.0599 (3)	0.1641 (5)	0.039 (2)
C23	0.3160 (7)	−0.0196 (4)	0.1996 (6)	0.056 (2)
H1	−0.0335	0.0261	0.0803	0.047*
H2	0.0921	0.2115	0.2148	0.038*
H3	0.2723	0.3034	0.1657	0.048*
H4	0.4154	0.1993	−0.1295	0.048*
H5	0.5143	0.3022	0.1819	0.050*
H6	0.4732	0.2221	0.2180	0.050*
H7	0.5376	0.1695	0.0759	0.049*
H8	0.5838	0.2492	0.0430	0.049*
H9	0.2760	0.3859	0.0018	0.049*
H10	0.3484	0.3303	−0.1545	0.045*
H11	−0.2712	0.0089	0.3945	0.050*
H12	−0.0161	0.2213	0.3962	0.046*
H13	−0.3782	0.1236	0.3015	0.050*
H14	−0.3505	0.1324	0.4387	0.050*
H15	−0.2337	0.2333	0.4336	0.059*
H16	−0.2571	0.2228	0.2971	0.059*
H17	−0.0993	0.0357	0.5813	0.054*
H18	0.0338	0.1479	0.5830	0.053*
H19	−0.2657	−0.0770	0.2081	0.046*
H20	0.2604	0.0239	0.1715	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.086 (2)	0.156 (2)	0.056 (1)	0.036 (2)	0.035 (1)	0.022 (1)
Cl2	0.084 (2)	0.073 (2)	0.099 (2)	−0.009 (1)	−0.013 (1)	−0.018 (1)
Cl3	0.082 (2)	0.082 (1)	0.051 (1)	−0.015 (1)	0.023 (1)	−0.0153 (9)
N1	0.046 (3)	0.038 (3)	0.034 (3)	−0.002 (3)	0.015 (2)	−0.002 (2)
N2	0.038 (3)	0.036 (3)	0.030 (3)	−0.001 (2)	0.008 (2)	0.001 (2)
C1	0.038 (4)	0.031 (3)	0.026 (3)	−0.006 (3)	0.009 (3)	−0.004 (2)
C2	0.036 (4)	0.034 (3)	0.031 (3)	−0.001 (3)	0.008 (3)	0.003 (3)
C3	0.050 (4)	0.034 (3)	0.031 (3)	0.001 (3)	0.012 (3)	0.002 (3)
C4	0.042 (4)	0.031 (3)	0.024 (3)	0.002 (3)	0.008 (3)	0.000 (2)
C5	0.046 (4)	0.035 (3)	0.027 (3)	0.007 (3)	0.011 (3)	0.001 (3)
C6	0.050 (5)	0.043 (4)	0.035 (3)	−0.003 (3)	0.025 (3)	−0.002 (3)
C7	0.043 (5)	0.056 (4)	0.030 (3)	−0.002 (3)	0.015 (3)	0.002 (3)
C8	0.038 (4)	0.049 (4)	0.039 (4)	−0.002 (3)	0.015 (3)	0.001 (3)
C9	0.041 (4)	0.049 (4)	0.033 (3)	−0.008 (3)	0.016 (3)	−0.005 (3)
C10	0.051 (4)	0.031 (3)	0.042 (4)	−0.005 (3)	0.014 (3)	0.010 (3)
C11	0.040 (4)	0.035 (3)	0.038 (3)	−0.005 (3)	0.010 (3)	−0.000 (3)
C12	0.051 (4)	0.034 (3)	0.027 (3)	0.004 (3)	0.009 (3)	−0.003 (3)
C13	0.032 (4)	0.044 (4)	0.035 (3)	0.002 (3)	0.011 (3)	−0.003 (3)
C14	0.044 (4)	0.033 (3)	0.027 (3)	0.001 (3)	0.010 (3)	−0.002 (3)
C15	0.043 (4)	0.035 (3)	0.031 (3)	0.003 (3)	0.019 (3)	0.005 (3)
C16	0.048 (4)	0.038 (4)	0.035 (3)	0.001 (3)	0.020 (3)	−0.003 (3)
C17	0.066 (5)	0.042 (4)	0.044 (4)	0.004 (3)	0.023 (3)	−0.008 (3)
C18	0.045 (4)	0.045 (4)	0.034 (3)	0.003 (3)	0.011 (3)	0.000 (3)
C19	0.057 (5)	0.040 (4)	0.033 (3)	−0.017 (3)	0.023 (3)	−0.003 (3)
C20	0.045 (4)	0.058 (4)	0.030 (3)	−0.007 (3)	0.010 (3)	−0.009 (3)
C21	0.050 (4)	0.053 (4)	0.029 (3)	0.001 (4)	0.008 (3)	0.005 (3)
C22	0.040 (4)	0.043 (4)	0.035 (3)	−0.002 (3)	0.014 (3)	0.001 (3)
C23	0.069 (5)	0.059 (5)	0.040 (4)	0.018 (4)	0.017 (4)	0.015 (3)

Geometric parameters (Å, º)

Cl1—C23	1.758 (8)	C13—C16	1.511 (8)
Cl2—C23	1.738 (7)	C14—C13	1.350 (8)
Cl3—C23	1.767 (6)	C14—C15	1.434 (8)
N1—C12	1.381 (7)	C14—C19	1.505 (9)
N1—C15	1.377 (8)	C15—C22	1.385 (8)
N1—H1	0.9500	C16—C13	1.511 (8)
N2—C2	1.375 (7)	C16—C17	1.551 (9)
N2—C5	1.385 (9)	C16—C20	1.555 (8)
C1—C2	1.401 (9)	C16—H12	0.9500
C1—C12	1.367 (9)	C17—C18	1.519 (9)
C1—H2	0.9500	C17—H15	0.9500
C2—C3	1.446 (9)	C17—H16	0.9500
C3—C4	1.370 (9)	C18—C19	1.543 (8)
C3—C6	1.493 (8)	C18—H13	0.9500
C4—C5	1.446 (8)	C18—H14	0.9500
C4—C9	1.495 (9)	C19—C21	1.534 (7)
C5—C22^i	1.404 (8)	C19—H11	0.9500
C6—C7	1.583 (8)	C20—C21	1.356 (9)
C6—C10	1.513 (8)	C20—H18	0.9500
C6—H3	0.9500	C21—H17	0.9500
C7—C8	1.525 (9)	C22—C5^i	1.404 (8)
C7—H5	0.9500	C22—H19	0.9300
C7—H6	0.9500	C23—H20	0.9500
C8—C9	1.568 (7)	H4—C9	0.9500
C8—H7	0.9500	H6—C7	0.9500
C8—H8	0.9500	H7—C8	0.9500
C9—C11	1.496 (8)	H9—C10	0.9500
C9—H4	0.9500	H10—C11	0.9500
C10—C6	1.513 (8)	H11—C19	0.9500
C10—C11	1.339 (9)	H12—C16	0.9500
C10—H9	0.9500	H13—C18	0.9500
C11—C10	1.339 (9)	H14—C18	0.9500
C11—H10	0.9500	H15—C17	0.9500
C12—C13	1.443 (9)	H16—C17	0.9500
C13—C12	1.443 (9)	H18—C20	0.9500
C13—C14	1.350 (8)	H20—C23	0.9500
Cl1—C23—H20	109.1680	H7—C8—C9	109.5271
Cl2—C23—H20	109.1675	H8—C8—C9	109.5272
Cl3—C23—H20	109.1675	H8—C8—H7	109.4607
N1—C12—C1	126.5 (6)	C9—C11—C10	114.3 (6)
N1—C12—C13	104.7 (5)	H4—C9—C11	112.6158
C15—N1—C12	111.8 (5)	C9—C11—H10	122.8553
H1—N1—C12	124.1125	H9—C10—C11	122.4574
N1—C15—C14	105.6 (5)	C10—C11—H10	122.8555
N1—C15—C22	125.2 (6)	C12—C13—C14	109.3 (5)
H1—N1—C15	124.1134	C12—C13—C16	135.8 (6)
N2—C2—C1	124.4 (5)	C13—C14—C15	108.6 (6)
N2—C2—C3	110.4 (5)	C16—C13—C14	114.9 (6)
C5—N2—C2	105.3 (5)	C13—C14—C19	115.6 (5)
N2—C5—C4	111.1 (5)	C13—C16—C17	104.6 (4)
N2—C5—C22^i	124.5 (5)	C13—C16—C20	105.1 (5)
C12—C1—C2	127.4 (5)	C13—C16—H12	113.9563
C1—C2—C3	125.2 (5)	C14—C15—C22	129.2 (6)
H2—C1—C2	116.3225	C19—C14—C15	135.7 (5)
C1—C12—C13	128.8 (5)	C14—C19—C21	105.9 (5)
H2—C1—C12	116.3218	C14—C19—C18	105.5 (5)
C2—C3—C4	107.3 (5)	C14—C19—H11	113.3321
C2—C3—C6	138.4 (6)	C15—C22—H19	115.5218
C3—C4—C5	105.8 (6)	C15—C22—C5^i	128.9 (6)
C6—C3—C4	114.1 (6)	C20—C16—C17	104.1 (5)
C3—C4—C9	114.4 (5)	H12—C16—C17	113.9566
C3—C6—C7	105.1 (5)	C16—C17—H16	109.0174
C3—C6—C10	108.0 (4)	C16—C17—C18	111.3 (5)
C3—C6—H3	113.3666	C16—C17—H15	109.0170
C4—C5—C22^i	124.4 (6)	C16—C20—C21	115.1 (5)
C9—C4—C5	139.5 (6)	H12—C16—C20	113.9565
C4—C9—C11	107.2 (5)	C16—C20—H18	122.4532
C4—C9—C8	105.8 (5)	C17—C18—C19	111.0 (5)
C4—C9—H4	112.6163	H16—C17—C18	109.0171
C5—C22^i—H19^i	115.5284	C17—C18—H13	109.0910
C5—C22^i—C15^i	128.9 (6)	H15—C17—C18	109.0168
C10—C6—C7	102.8 (5)	C17—C18—H14	109.0908
H3—C6—C7	113.3665	H16—C17—H15	109.4604
C6—C7—H6	109.2220	C18—C19—C21	104.6 (5)
C6—C7—C8	110.5 (4)	C18—C19—H11	113.3326
C6—C7—H5	109.2222	H13—C18—C19	109.0905
C6—C10—C11	115.1 (5)	H14—C18—C19	109.0911
H3—C6—C10	113.3670	H14—C18—H13	109.4601
C6—C10—H9	122.4567	C19—C21—C20	113.9 (5)
C7—C8—C9	109.3 (5)	H11—C19—C21	113.3321
H6—C7—C8	109.2223	C19—C21—H17	123.0720
C7—C8—H7	109.5267	H18—C20—C21	122.4533
H5—C7—C8	109.2222	C20—C21—H17	123.0726
C7—C8—H8	109.5265	H19—C22—C5^i	115.5284
H6—C7—H5	109.4599	C22—C5^i—N2^i	124.5 (5)
C8—C9—C11	105.4 (4)	C22—C5^i—C4^i	124.4 (6)
C8—C9—H4	112.6162

Symmetry code: (i) −x, −y, −z.