29H,31H-Tetrabenzo­[b,g,l,q]­porphin

The title compound, C₃₆H₂₂N₄, has recently been found to exhibit an excellent field effect transistor characteristic. The mol­ecule is not entirely flat in its crystal structure (i.e. not D_2h) but is slightly deformed, as characterized by crystallographic C_i symmetry. The mol­ecules are stacked along the b axis in a herring-bone fashion.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.033
• wR factor = 0.066
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level A
GOODF01_ALERT_2_A  The least squares goodness of fit parameter lies
            outside the range 0.40 <> 6.00
            Goodness of fit given =      0.334
PLAT026_ALERT_3_A Ratio Observed / Unique Reflections too Low ....         21 Perc.
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.92

Alert level B
PLAT086_ALERT_2_B Unsatisfactory S Value (Too Low or Not Given) ..       0.33

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           68.23
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               2013
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2178
           Completeness (_total/calc)             92.42%
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.111
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.92
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   3 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 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
   7 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SHELX86 (Sheldrick, 1985); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C36H22N4	F(000) = 532.0
Mr = 510.60	Dx = 1.417 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2yn	Cell parameters from 4837 reflections
a = 12.405 (1) Å	θ = 3.6–68.2°
b = 6.5910 (7) Å	µ = 0.66 mm^−1
c = 14.927 (1) Å	T = 93 K
β = 101.445 (8)°	Needle, blue
V = 1196.2 (2) Å^3	0.30 × 0.05 × 0.05 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer	419 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.111
48 frames, δ–ω = 15° scans	θmax = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.817, Tmax = 0.968	k = −6→6
10724 measured reflections	l = −17→17
2013 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2)]
wR(F^2) = 0.066	(Δ/σ)max = 0.001
S = 0.33	Δρmax = 0.07 e Å^−3
2013 reflections	Δρmin = −0.11 e Å^−3
184 parameters

Special details

Refinement. Refinement using reflections with F² > -10.0 σ(F²). 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
N1	0.6290 (2)	0.0806 (5)	0.9397 (2)	0.0199 (9)
N2	0.4101 (2)	0.2622 (5)	0.9471 (2)	0.0192 (10)
C1	0.7290 (3)	−0.0173 (6)	0.9462 (2)	0.022 (1)
C2	0.8027 (3)	0.1017 (6)	0.9020 (2)	0.019 (1)
C3	0.9115 (3)	0.0771 (6)	0.8910 (2)	0.023 (1)
C4	0.9582 (3)	0.2272 (6)	0.8465 (2)	0.024 (1)
C5	0.8989 (3)	0.4002 (7)	0.8125 (2)	0.027 (1)
C6	0.7910 (3)	0.4297 (6)	0.8233 (2)	0.022 (1)
C7	0.7451 (3)	0.2757 (6)	0.8675 (2)	0.019 (1)
C8	0.6363 (3)	0.2572 (6)	0.8939 (2)	0.023 (1)
C9	0.5564 (3)	0.4061 (6)	0.8748 (2)	0.023 (1)
C10	0.4530 (3)	0.4080 (6)	0.8990 (2)	0.020 (1)
C11	0.3708 (3)	0.5677 (6)	0.8775 (2)	0.019 (1)
C12	0.3709 (3)	0.7531 (6)	0.8347 (2)	0.027 (1)
C13	0.2756 (3)	0.8694 (6)	0.8199 (2)	0.029 (1)
C14	0.1814 (3)	0.8010 (6)	0.8512 (2)	0.026 (1)
C15	0.1831 (3)	0.6200 (6)	0.8987 (2)	0.025 (1)
C16	0.2776 (3)	0.5022 (6)	0.9123 (2)	0.022 (1)
C17	0.3046 (3)	0.3125 (6)	0.9587 (2)	0.022 (1)
C18	0.2426 (3)	0.1973 (6)	1.0076 (2)	0.021 (1)
H1	0.438 (3)	0.148 (5)	0.962 (2)	0.0283*
H2	0.9526	−0.0404	0.9138	0.0274*
H3	1.0318	0.2128	0.8386	0.0292*
H4	0.9329	0.5002	0.7813	0.0334*
H5	0.7506	0.5487	0.8019	0.0265*
H6	0.5738	0.5204	0.8415	0.0273*
H7	0.4351	0.8002	0.8159	0.0328*
H8	0.2739	0.9964	0.7890	0.0351*
H9	0.1161	0.8800	0.8391	0.0308*
H10	0.1206	0.5782	0.9217	0.0299*
H11	0.1714	0.2469	1.0100	0.0253*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.024 (2)	0.015 (2)	0.021 (2)	0.000 (2)	0.006 (1)	0.001 (2)
N2	0.021 (2)	0.014 (2)	0.023 (2)	0.009 (2)	0.006 (1)	0.003 (2)
C1	0.027 (2)	0.021 (3)	0.016 (2)	−0.001 (2)	−0.004 (2)	−0.003 (2)
C2	0.024 (2)	0.017 (3)	0.017 (2)	0.007 (2)	0.005 (2)	0.000 (2)
C3	0.025 (2)	0.017 (3)	0.029 (2)	0.009 (2)	0.011 (2)	0.000 (2)
C4	0.018 (2)	0.034 (3)	0.023 (2)	−0.003 (2)	0.009 (2)	−0.001 (2)
C5	0.021 (2)	0.034 (3)	0.028 (2)	0.001 (2)	0.009 (2)	0.009 (2)
C6	0.025 (2)	0.019 (3)	0.022 (2)	0.002 (2)	0.001 (2)	0.002 (2)
C7	0.019 (2)	0.022 (3)	0.016 (2)	−0.001 (2)	0.004 (2)	−0.004 (2)
C8	0.030 (2)	0.021 (3)	0.017 (2)	0.000 (2)	0.004 (2)	−0.001 (2)
C9	0.028 (2)	0.019 (3)	0.023 (2)	−0.009 (2)	0.006 (2)	−0.001 (2)
C10	0.027 (2)	0.012 (3)	0.022 (2)	−0.005 (2)	0.005 (2)	−0.001 (2)
C11	0.021 (2)	0.017 (3)	0.020 (2)	0.002 (2)	0.006 (2)	−0.008 (2)
C12	0.034 (2)	0.030 (3)	0.018 (2)	−0.007 (3)	0.009 (2)	−0.002 (2)
C13	0.038 (2)	0.025 (3)	0.024 (2)	−0.002 (2)	0.002 (2)	−0.003 (2)
C14	0.027 (2)	0.031 (3)	0.020 (2)	0.005 (2)	0.002 (2)	0.001 (2)
C15	0.023 (2)	0.028 (3)	0.023 (2)	0.001 (2)	0.006 (2)	−0.006 (2)
C16	0.032 (2)	0.018 (3)	0.013 (2)	−0.001 (2)	0.001 (2)	0.000 (2)
C17	0.021 (2)	0.025 (3)	0.017 (2)	−0.001 (2)	0.002 (2)	−0.004 (2)
C18	0.019 (2)	0.019 (3)	0.023 (2)	0.006 (2)	0.003 (2)	−0.004 (2)

Geometric parameters (Å, º)

N1—C1	1.384 (4)	C8—C9	1.384 (5)
N1—C8	1.362 (4)	C9—C10	1.400 (4)
N2—C10	1.369 (4)	C9—H6	0.951
N2—C17	1.394 (4)	C10—C11	1.457 (5)
N2—H1	0.84 (3)	C11—C12	1.379 (5)
C1—C2	1.458 (5)	C11—C16	1.424 (5)
C1—C18^i	1.382 (5)	C12—C13	1.390 (5)
C2—C3	1.401 (5)	C12—H7	0.948
C2—C7	1.394 (5)	C13—C14	1.415 (5)
C3—C4	1.382 (5)	C13—H8	0.953
C3—H2	0.952	C14—C15	1.386 (5)
C4—C5	1.397 (5)	C14—H9	0.950
C4—H3	0.948	C15—C16	1.388 (5)
C5—C6	1.393 (5)	C15—H10	0.949
C5—H4	0.952	C16—C17	1.436 (4)
C6—C7	1.393 (5)	C17—C18	1.386 (4)
C6—H5	0.951	C18—H11	0.950
C7—C8	1.483 (4)
N1···C12^ii	3.541 (4)	C8···C16^ii	3.287 (5)
N1···C13^ii	3.564 (4)	C8···C15^ii	3.537 (5)
N1···C16^ii	3.574 (5)	C8···C17^ii	3.576 (5)
N1···C11^ii	3.581 (4)	C9···C17^ii	3.300 (5)
N1···C15^ii	3.594 (4)	C9···C16^ii	3.480 (5)
N2···C10^ii	3.368 (5)	C10···C10^ii	3.246 (7)
N2···C9^ii	3.403 (5)	C11···C13^v	3.400 (5)
N2···C13^iii	3.440 (5)	C11···H1^ii	3.56 (3)
N2···C11^ii	3.561 (4)	C12···H1^vi	3.23 (3)
C1···C14^ii	3.329 (5)	C12···H1^ii	3.52 (3)
C1···C15^ii	3.522 (5)	C13···H1^vi	3.20 (3)
C2···C15^ii	3.469 (5)	C13···C16^vii	3.507 (5)
C2···C6^iv	3.520 (5)	C13···C17^vi	3.557 (5)
C7···C15^ii	3.494 (5)	C14···C18^vi	3.485 (5)
C1—N1—C8	106.6 (3)	C8—C9—H6	116.2
C10—N2—C17	111.7 (3)	C10—C9—H6	116.3
C10—N2—H1	126 (2)	N2—C10—C9	126.9 (4)
C17—N2—H1	121 (2)	N2—C10—C11	107.1 (3)
N1—C1—C2	110.5 (3)	C9—C10—C11	126.0 (4)
N1—C1—C18^i	124.8 (4)	C10—C11—C12	132.6 (4)
C2—C1—C18^i	124.6 (4)	C10—C11—C16	106.5 (3)
C1—C2—C3	134.1 (4)	C12—C11—C16	120.9 (4)
C1—C2—C7	106.7 (3)	C11—C12—C13	118.9 (3)
C3—C2—C7	119.1 (4)	C11—C12—H7	120.4
C2—C3—C4	118.7 (4)	C13—C12—H7	120.7
C2—C3—H2	120.8	C12—C13—C14	120.2 (4)
C4—C3—H2	120.5	C12—C13—H8	119.9
C3—C4—C5	121.2 (3)	C14—C13—H8	119.9
C3—C4—H3	119.6	C13—C14—C15	121.0 (4)
C5—C4—H3	119.1	C13—C14—H9	119.5
C4—C5—C6	121.4 (4)	C15—C14—H9	119.6
C4—C5—H4	119.4	C14—C15—C16	118.8 (4)
C6—C5—H4	119.3	C14—C15—H10	120.4
C5—C6—C7	116.5 (4)	C16—C15—H10	120.8
C5—C6—H5	122.0	C11—C16—C15	120.0 (4)
C7—C6—H5	121.5	C11—C16—C17	108.2 (3)
C2—C7—C6	123.1 (3)	C15—C16—C17	131.8 (4)
C2—C7—C8	105.1 (3)	N2—C17—C16	106.3 (3)
C6—C7—C8	131.7 (4)	N2—C17—C18	124.6 (4)
N1—C8—C7	111.0 (4)	C16—C17—C18	129.1 (4)
N1—C8—C9	126.4 (3)	C1^i—C18—C17	128.3 (3)
C7—C8—C9	122.6 (4)	C1^i—C18—H11	115.0
C8—C9—C10	127.5 (4)	C17—C18—H11	116.6

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y+1, −z+2; (iii) x, y−1, z; (iv) −x+3/2, y−1/2, −z+3/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) x, y+1, z; (vii) −x+1/2, y+1/2, −z+3/2.