The [4 + 4] thermocyclization of 9-anthraldehyde: synthesis, crystal structure, experimental and theoretical UV spectra, natural bonding orbital analysis and prediction of third-order nonlinear optical properties

Zarei, S.A.; Akhtari, K.; Piltan, M.; Kamel, S.M.; Mague, J.T.

doi:10.1107/S2053229618003534

The [4 + 4] thermocyclization of 9-anthraldehyde: synthesis, crystal structure, experimental and theoretical UV spectra, natural bonding orbital analysis and prediction of third-order nonlinear optical properties

S. A. Zarei, K. Akhtari, M. Piltan, S. M. Kamel and J. T. Mague

The dimer of 9-anthraldehyde, namely heptacyclo[8.6.6.6^2,9.0^3,8.0^11,16.0^17,22.0^23,28]octacosa-3,5,7,11,13,15,17(22),18,20,23(28),24,26-dodecaene-1,9-carbaldehyde, C₃₀H₂₀O₂, has been synthesized by refluxing an ethanol solution in the presence of M(ClO₄)₂ and 1,3-diaminopropan-2-ol (M = Co²⁺ or Cu²⁺). Its structure has been determined by single-crystal X-ray diffraction, showing it to be a new polymorph, referred to as polymorph II, in the monoclinic space group P2₁/n. It is compared with the previously reported triclinic modification [Ehrenberg (1968). Acta Cryst. B24, 1123–1125], which is referred to as polymorph I. The asymmetric unit of polymorph II contains two half molecules located on crystallographic centres, while the asymmetric unit of polymorph I includes one half molecule, also located on a crystallographic centre. Time-dependent density functional theory (TD-DFT) at the RB3LYP level using the 6-31G(d,p) basis set was applied. The predicted electronic absorption spectrum is in good agreement with the experimental one. The analysis of the calculated electronic absorption spectrum of polymorph II was carried out in order to assign the observed electronic transitions and to determine their character. A natural bonding orbital (NBO) analysis was executed at the same level to evaluate charge-transfer, intramolecular hydrogen-bonding interactions and hyperconjugative interactions. The third-order nonlinear optical (NLO) properties of the compound were appraised by the ZINDO/sum-over-states method in both static and dynamic states. The orientationally averaged (isotropic) value of γ for the compound is greater than the corresponding value of 4-nitroaniline (pNA).

Keywords: polymorph; TD-DFT; ZINDO/SOS; NBO; 9-anthraldehyde dimer; thermocyclization; third-order nonlinear optical property; UV analysis; crystal structure.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618003534/yp3151sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618003534/yp3151Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618003534/yp3151sup3.pdf Molecular orbital diagrams and details of the hyperconjugative interactions

CCDC reference: 1577449

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Heptacyclo[8.6.6.6^2,9.0^3,8.0^11,16.0^17,22.0^23,28]octacosa-3,5,7,11,13,15,17(22),18,20,23(28),24,26-dodecaene-1,9-carbaldehyde top

Crystal data top

C₃₀H₂₀O₂	F(000) = 864
M_r = 412.46	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 12.9627 (3) Å	Cell parameters from 9953 reflections
b = 9.6666 (2) Å	θ = 3.9–72.4°
c = 16.6887 (4) Å	µ = 0.66 mm⁻¹
β = 105.2170 (11)°	T = 100 K
V = 2017.86 (8) Å³	Plate, colourless
Z = 4	0.16 × 0.15 × 0.03 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3965 independent reflections
Radiation source: INCOATEC IµS micro-focus source	3312 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.051
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.5°, θ_min = 3.9°
ω scans	h = −16→16
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −11→11
T_min = 0.90, T_max = 0.98	l = −10→20
43545 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.071	H-atom parameters constrained
wR(F²) = 0.197	w = 1/[σ²(F_o²) + (0.1517P)² + 0.1114P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3965 reflections	Δρ_max = 0.46 e Å⁻³
290 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (6)

Special details top

Experimental. Analysis of 1283 reflections having I/σI > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008a) showed the crystal to belong to the monoclinic system and to consist of two components related by a 5.3° rotation about the reciprocal axis (-0.13, -0.28, 1). The raw data were processed using the multi-component version of SAINT under control of the two-component orientation filegenerated by CELL_NOW.

X-ray intensity data were collected using ω scans on a Bruker D8 Venture diffractometer equipped with a CMOS PHOTON100 detector and monochromated Cu Kα radiation. Cell refinement and data reduction were carried out using SAINT (Bruker, 2013). The structure was solved by direct methods (SHELXT (Sheldrick, 2015a) and then refined by full-matrix least squares procedures on F² using the SHELXL (Sheldrick, 2015b).

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. H-atoms were placed in calculated positions (C—H = 0.95 - 1.0 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached carbon atoms. Trial refinements with both the 1-component reflection file extracted from the full data set with TWINABS and the full 2-component data file showed the former to be more satisfactory.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.57456 (13)	0.84984 (15)	0.91465 (11)	0.0223 (4)
C1	0.49219 (15)	0.66196 (19)	0.97261 (12)	0.0109 (4)
C2	0.47261 (15)	0.6688 (2)	1.05888 (12)	0.0116 (4)
C3	0.49877 (16)	0.7834 (2)	1.11115 (13)	0.0159 (5)
H3	0.5302	0.8626	1.0934	0.019*
C4	0.47899 (16)	0.7818 (2)	1.18907 (13)	0.0178 (5)
H4	0.4965	0.8602	1.2244	0.021*
C5	0.43348 (16)	0.6655 (2)	1.21536 (13)	0.0159 (5)
H5	0.4196	0.6648	1.2685	0.019*
C6	0.40830 (15)	0.5499 (2)	1.16354 (13)	0.0147 (4)
H6	0.3775	0.4704	1.1816	0.018*
C7	0.42830 (15)	0.5511 (2)	1.08587 (12)	0.0113 (4)
C8	0.40415 (15)	0.4284 (2)	1.02735 (12)	0.0114 (4)
H8	0.3527	0.3672	1.0460	0.014*
C9	0.34848 (15)	0.4821 (2)	0.94195 (12)	0.0112 (4)
C10	0.25857 (16)	0.4195 (2)	0.89086 (14)	0.0156 (4)
H10	0.2295	0.3392	0.9095	0.019*
C11	0.21087 (16)	0.4734 (2)	0.81277 (13)	0.0173 (5)
H11	0.1492	0.4301	0.7784	0.021*
C12	0.25278 (16)	0.5897 (2)	0.78478 (13)	0.0175 (5)
H12	0.2201	0.6262	0.7313	0.021*
C13	0.34300 (16)	0.6532 (2)	0.83518 (13)	0.0148 (5)
H13	0.3718	0.7331	0.8159	0.018*
C14	0.39157 (15)	0.6002 (2)	0.91402 (12)	0.0111 (4)
C15	0.50360 (17)	0.8092 (2)	0.94262 (13)	0.0161 (4)
H15	0.4500	0.8741	0.9464	0.019*
O2	−0.26265 (12)	0.00705 (18)	0.07182 (10)	0.0248 (4)
C16	−0.08065 (15)	0.0233 (2)	0.05773 (12)	0.0104 (4)
C17	−0.00127 (15)	−0.08280 (19)	0.10765 (12)	0.0099 (4)
C18	−0.02704 (16)	−0.1773 (2)	0.16270 (12)	0.0122 (4)
H18	−0.0975	−0.1798	0.1694	0.015*
C19	0.05067 (16)	−0.2682 (2)	0.20798 (13)	0.0149 (4)
H19	0.0329	−0.3315	0.2458	0.018*
C20	0.15311 (16)	−0.2664 (2)	0.19798 (13)	0.0165 (5)
H20	0.2057	−0.3278	0.2292	0.020*
C21	0.17918 (16)	−0.1742 (2)	0.14188 (13)	0.0147 (4)
H21	0.2493	−0.1739	0.1344	0.018*
C22	0.10261 (15)	−0.0827 (2)	0.09692 (12)	0.0109 (4)
C23	0.12751 (15)	0.0216 (2)	0.03727 (12)	0.0110 (4)
H23	0.2069	0.0299	0.0487	0.013*
C24	0.08358 (16)	0.15856 (19)	0.05681 (12)	0.0115 (4)
C25	0.14479 (16)	0.2784 (2)	0.06891 (12)	0.0153 (4)
H25	0.2166	0.2752	0.0652	0.018*
C26	0.10173 (18)	0.4030 (2)	0.08643 (14)	0.0190 (5)
H26	0.1444	0.4843	0.0959	0.023*
C27	−0.00398 (18)	0.4079 (2)	0.09005 (14)	0.0179 (5)
H27	−0.0346	0.4936	0.0996	0.022*
C28	−0.06557 (16)	0.2875 (2)	0.07979 (12)	0.0136 (4)
H28	−0.1376	0.2912	0.0831	0.016*
C29	−0.02131 (16)	0.16185 (19)	0.06471 (12)	0.0111 (4)
C30	−0.17041 (16)	0.0381 (2)	0.10118 (13)	0.0135 (4)
H30	−0.1519	0.0749	0.1559	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0243 (9)	0.0199 (8)	0.0249 (9)	−0.0061 (6)	0.0106 (7)	0.0048 (6)
C1	0.0095 (9)	0.0137 (10)	0.0098 (10)	−0.0020 (7)	0.0031 (7)	0.0025 (7)
C2	0.0079 (9)	0.0167 (10)	0.0100 (10)	−0.0002 (7)	0.0019 (7)	0.0012 (7)
C3	0.0134 (10)	0.0175 (10)	0.0166 (11)	−0.0028 (8)	0.0038 (8)	−0.0015 (8)
C4	0.0142 (10)	0.0245 (11)	0.0141 (11)	0.0005 (8)	0.0029 (8)	−0.0047 (8)
C5	0.0121 (10)	0.0264 (11)	0.0091 (10)	0.0047 (8)	0.0026 (7)	0.0011 (8)
C6	0.0091 (9)	0.0230 (10)	0.0127 (10)	0.0026 (8)	0.0040 (7)	0.0059 (8)
C7	0.0069 (9)	0.0169 (10)	0.0103 (10)	−0.0002 (7)	0.0024 (7)	0.0022 (7)
C8	0.0083 (9)	0.0162 (10)	0.0098 (10)	−0.0025 (7)	0.0027 (7)	0.0022 (7)
C9	0.0096 (9)	0.0160 (9)	0.0086 (10)	−0.0014 (7)	0.0035 (7)	0.0002 (7)
C10	0.0123 (10)	0.0181 (10)	0.0159 (11)	−0.0015 (8)	0.0029 (8)	−0.0026 (8)
C11	0.0115 (10)	0.0258 (11)	0.0137 (11)	0.0004 (8)	0.0016 (8)	−0.0071 (8)
C12	0.0116 (10)	0.0291 (12)	0.0108 (10)	0.0039 (8)	0.0013 (8)	−0.0003 (8)
C13	0.0141 (10)	0.0196 (10)	0.0119 (11)	0.0016 (7)	0.0056 (8)	0.0040 (7)
C14	0.0087 (9)	0.0151 (10)	0.0101 (10)	−0.0005 (7)	0.0034 (7)	0.0001 (7)
C15	0.0180 (10)	0.0153 (10)	0.0149 (11)	−0.0029 (8)	0.0043 (8)	0.0023 (8)
O2	0.0109 (8)	0.0408 (10)	0.0247 (10)	−0.0038 (7)	0.0082 (6)	−0.0044 (7)
C16	0.0097 (9)	0.0140 (9)	0.0087 (10)	−0.0010 (7)	0.0044 (7)	−0.0026 (7)
C17	0.0097 (9)	0.0130 (9)	0.0073 (9)	−0.0024 (7)	0.0027 (7)	−0.0027 (7)
C18	0.0130 (9)	0.0141 (9)	0.0100 (10)	−0.0044 (7)	0.0039 (7)	−0.0029 (7)
C19	0.0212 (11)	0.0138 (9)	0.0105 (10)	−0.0022 (8)	0.0055 (8)	0.0000 (7)
C20	0.0184 (11)	0.0176 (10)	0.0121 (11)	0.0032 (8)	0.0018 (8)	−0.0003 (8)
C21	0.0115 (10)	0.0202 (10)	0.0127 (10)	0.0013 (8)	0.0038 (8)	−0.0004 (8)
C22	0.0096 (9)	0.0152 (10)	0.0080 (10)	−0.0013 (7)	0.0025 (7)	−0.0029 (7)
C23	0.0088 (9)	0.0174 (10)	0.0070 (10)	−0.0022 (7)	0.0027 (7)	−0.0020 (7)
C24	0.0125 (10)	0.0153 (10)	0.0070 (9)	−0.0028 (7)	0.0031 (7)	−0.0016 (7)
C25	0.0174 (10)	0.0199 (10)	0.0101 (10)	−0.0067 (8)	0.0061 (8)	−0.0022 (8)
C26	0.0265 (12)	0.0141 (10)	0.0186 (12)	−0.0069 (8)	0.0100 (9)	−0.0029 (8)
C27	0.0278 (12)	0.0132 (10)	0.0147 (11)	0.0004 (8)	0.0089 (9)	−0.0023 (8)
C28	0.0153 (10)	0.0167 (10)	0.0098 (10)	0.0001 (8)	0.0053 (7)	0.0000 (7)
C29	0.0120 (10)	0.0151 (10)	0.0068 (9)	−0.0013 (7)	0.0035 (7)	−0.0009 (7)
C30	0.0136 (10)	0.0152 (9)	0.0137 (10)	0.0006 (7)	0.0072 (8)	0.0010 (7)

Geometric parameters (Å, º) top

O1—C15	1.201 (3)	O2—C30	1.205 (3)
C1—C2	1.528 (3)	C16—C30	1.531 (3)
C1—C15	1.529 (3)	C16—C29	1.533 (3)
C1—C14	1.531 (3)	C16—C17	1.535 (3)
C1—C8ⁱ	1.603 (3)	C16—C23ⁱⁱ	1.602 (3)
C2—C3	1.395 (3)	C17—C18	1.397 (3)
C2—C7	1.402 (3)	C17—C22	1.404 (3)
C3—C4	1.390 (3)	C18—C19	1.399 (3)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.393 (3)	C19—C20	1.381 (3)
C4—H4	0.9500	C19—H19	0.9500
C5—C6	1.399 (3)	C20—C21	1.397 (3)
C5—H5	0.9500	C20—H20	0.9500
C6—C7	1.387 (3)	C21—C22	1.393 (3)
C6—H6	0.9500	C21—H21	0.9500
C7—C8	1.516 (3)	C22—C23	1.510 (3)
C8—C9	1.510 (3)	C23—C24	1.510 (3)
C8—C1ⁱ	1.602 (3)	C23—C16ⁱⁱ	1.602 (3)
C8—H8	1.0000	C23—H23	1.0000
C9—C10	1.389 (3)	C24—C25	1.388 (3)
C9—C14	1.404 (3)	C24—C29	1.400 (3)
C10—C11	1.389 (3)	C25—C26	1.391 (3)
C10—H10	0.9500	C25—H25	0.9500
C11—C12	1.382 (3)	C26—C27	1.388 (3)
C11—H11	0.9500	C26—H26	0.9500
C12—C13	1.391 (3)	C27—C28	1.397 (3)
C12—H12	0.9500	C27—H27	0.9500
C13—C14	1.398 (3)	C28—C29	1.394 (3)
C13—H13	0.9500	C28—H28	0.9500
C15—H15	0.9500	C30—H30	0.9500

C2—C1—C15	108.81 (16)	C30—C16—C29	108.11 (15)
C2—C1—C14	107.12 (15)	C30—C16—C17	106.86 (15)
C15—C1—C14	107.06 (16)	C29—C16—C17	106.92 (15)
C2—C1—C8ⁱ	111.71 (15)	C30—C16—C23ⁱⁱ	110.87 (16)
C15—C1—C8ⁱ	110.76 (15)	C29—C16—C23ⁱⁱ	111.35 (16)
C14—C1—C8ⁱ	111.20 (15)	C17—C16—C23ⁱⁱ	112.48 (15)
C3—C2—C7	119.77 (18)	C18—C17—C22	119.18 (18)
C3—C2—C1	123.39 (17)	C18—C17—C16	123.51 (17)
C7—C2—C1	116.81 (17)	C22—C17—C16	117.31 (16)
C4—C3—C2	120.15 (19)	C17—C18—C19	120.21 (18)
C4—C3—H3	119.9	C17—C18—H18	119.9
C2—C3—H3	119.9	C19—C18—H18	119.9
C3—C4—C5	120.04 (19)	C20—C19—C18	120.37 (19)
C3—C4—H4	120.0	C20—C19—H19	119.8
C5—C4—H4	120.0	C18—C19—H19	119.8
C4—C5—C6	119.99 (19)	C19—C20—C21	119.88 (19)
C4—C5—H5	120.0	C19—C20—H20	120.1
C6—C5—H5	120.0	C21—C20—H20	120.1
C7—C6—C5	120.04 (19)	C22—C21—C20	120.18 (18)
C7—C6—H6	120.0	C22—C21—H21	119.9
C5—C6—H6	120.0	C20—C21—H21	119.9
C6—C7—C2	119.99 (19)	C21—C22—C17	120.15 (18)
C6—C7—C8	122.55 (18)	C21—C22—C23	122.25 (17)
C2—C7—C8	117.46 (17)	C17—C22—C23	117.58 (17)
C9—C8—C7	107.81 (16)	C22—C23—C24	106.54 (15)
C9—C8—C1ⁱ	112.37 (16)	C22—C23—C16ⁱⁱ	112.37 (15)
C7—C8—C1ⁱ	113.25 (15)	C24—C23—C16ⁱⁱ	112.62 (15)
C9—C8—H8	107.7	C22—C23—H23	108.4
C7—C8—H8	107.7	C24—C23—H23	108.4
C1ⁱ—C8—H8	107.7	C16ⁱⁱ—C23—H23	108.4
C10—C9—C14	119.56 (18)	C25—C24—C29	119.95 (18)
C10—C9—C8	123.06 (18)	C25—C24—C23	121.96 (18)
C14—C9—C8	117.37 (17)	C29—C24—C23	118.08 (16)
C11—C10—C9	120.52 (19)	C24—C25—C26	120.52 (19)
C11—C10—H10	119.7	C24—C25—H25	119.7
C9—C10—H10	119.7	C26—C25—H25	119.7
C12—C11—C10	120.30 (19)	C27—C26—C25	119.59 (19)
C12—C11—H11	119.9	C27—C26—H26	120.2
C10—C11—H11	119.9	C25—C26—H26	120.2
C11—C12—C13	119.8 (2)	C26—C27—C28	120.35 (19)
C11—C12—H12	120.1	C26—C27—H27	119.8
C13—C12—H12	120.1	C28—C27—H27	119.8
C12—C13—C14	120.46 (19)	C29—C28—C27	119.96 (19)
C12—C13—H13	119.8	C29—C28—H28	120.0
C14—C13—H13	119.8	C27—C28—H28	120.0
C13—C14—C9	119.36 (18)	C28—C29—C24	119.51 (17)
C13—C14—C1	123.78 (18)	C28—C29—C16	123.54 (18)
C9—C14—C1	116.85 (17)	C24—C29—C16	116.94 (16)
O1—C15—C1	125.5 (2)	O2—C30—C16	125.5 (2)
O1—C15—H15	117.2	O2—C30—H30	117.3
C1—C15—H15	117.2	C16—C30—H30	117.3

C15—C1—C2—C3	−20.5 (3)	C30—C16—C17—C18	19.2 (2)
C14—C1—C2—C3	−135.92 (19)	C29—C16—C17—C18	134.81 (19)
C8ⁱ—C1—C2—C3	102.1 (2)	C23ⁱⁱ—C16—C17—C18	−102.7 (2)
C15—C1—C2—C7	161.04 (17)	C30—C16—C17—C22	−160.36 (17)
C14—C1—C2—C7	45.6 (2)	C29—C16—C17—C22	−44.8 (2)
C8ⁱ—C1—C2—C7	−76.4 (2)	C23ⁱⁱ—C16—C17—C22	77.8 (2)
C7—C2—C3—C4	−1.3 (3)	C22—C17—C18—C19	1.5 (3)
C1—C2—C3—C4	−179.72 (18)	C16—C17—C18—C19	−178.04 (17)
C2—C3—C4—C5	0.4 (3)	C17—C18—C19—C20	−0.7 (3)
C3—C4—C5—C6	0.4 (3)	C18—C19—C20—C21	−0.5 (3)
C4—C5—C6—C7	−0.2 (3)	C19—C20—C21—C22	0.9 (3)
C5—C6—C7—C2	−0.7 (3)	C20—C21—C22—C17	−0.1 (3)
C5—C6—C7—C8	179.19 (17)	C20—C21—C22—C23	178.34 (18)
C3—C2—C7—C6	1.5 (3)	C18—C17—C22—C21	−1.1 (3)
C1—C2—C7—C6	−179.99 (17)	C16—C17—C22—C21	178.48 (17)
C3—C2—C7—C8	−178.45 (18)	C18—C17—C22—C23	−179.64 (17)
C1—C2—C7—C8	0.1 (3)	C16—C17—C22—C23	0.0 (3)
C6—C7—C8—C9	134.24 (19)	C21—C22—C23—C24	−132.17 (19)
C2—C7—C8—C9	−45.8 (2)	C17—C22—C23—C24	46.3 (2)
C6—C7—C8—C1ⁱ	−100.8 (2)	C21—C22—C23—C16ⁱⁱ	104.0 (2)
C2—C7—C8—C1ⁱ	79.1 (2)	C17—C22—C23—C16ⁱⁱ	−77.5 (2)
C7—C8—C9—C10	−135.34 (19)	C22—C23—C24—C25	130.0 (2)
C1ⁱ—C8—C9—C10	99.2 (2)	C16ⁱⁱ—C23—C24—C25	−106.3 (2)
C7—C8—C9—C14	45.2 (2)	C22—C23—C24—C29	−48.4 (2)
C1ⁱ—C8—C9—C14	−80.3 (2)	C16ⁱⁱ—C23—C24—C29	75.3 (2)
C14—C9—C10—C11	−0.4 (3)	C29—C24—C25—C26	−1.9 (3)
C8—C9—C10—C11	−179.85 (18)	C23—C24—C25—C26	179.69 (19)
C9—C10—C11—C12	0.4 (3)	C24—C25—C26—C27	−1.4 (3)
C10—C11—C12—C13	−0.2 (3)	C25—C26—C27—C28	2.8 (3)
C11—C12—C13—C14	0.0 (3)	C26—C27—C28—C29	−0.9 (3)
C12—C13—C14—C9	0.0 (3)	C27—C28—C29—C24	−2.4 (3)
C12—C13—C14—C1	178.72 (18)	C27—C28—C29—C16	176.29 (19)
C10—C9—C14—C13	0.2 (3)	C25—C24—C29—C28	3.8 (3)
C8—C9—C14—C13	179.67 (18)	C23—C24—C29—C28	−177.73 (18)
C10—C9—C14—C1	−178.60 (17)	C25—C24—C29—C16	−174.97 (18)
C8—C9—C14—C1	0.9 (3)	C23—C24—C29—C16	3.5 (3)
C2—C1—C14—C13	135.05 (19)	C30—C16—C29—C28	−21.2 (3)
C15—C1—C14—C13	18.5 (3)	C17—C16—C29—C28	−135.89 (19)
C8ⁱ—C1—C14—C13	−102.6 (2)	C23ⁱⁱ—C16—C29—C28	100.9 (2)
C2—C1—C14—C9	−46.2 (2)	C30—C16—C29—C24	157.61 (17)
C15—C1—C14—C9	−162.81 (17)	C17—C16—C29—C24	42.9 (2)
C8ⁱ—C1—C14—C9	76.1 (2)	C23ⁱⁱ—C16—C29—C24	−80.4 (2)
C2—C1—C15—O1	130.3 (2)	C29—C16—C30—O2	129.5 (2)
C14—C1—C15—O1	−114.3 (2)	C17—C16—C30—O2	−115.7 (2)
C8ⁱ—C1—C15—O1	7.1 (3)	C23ⁱⁱ—C16—C30—O2	7.2 (3)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y, −z.

Selected geometric parameters (°, Å) in polymorph I and polymorph II top

Polymorph I		Polymorph II
		Molecule 1		Molecule 2
C9—C12	1.49	C1—C2	1.528 (3)	C16—17	1.535 (3)
C12—C11	1.41	C2—C7	1.402 (3)	C17—C22	1.404 (3)
C12—C8	1.42	C2—C3	1.395 (3)	C17—C18	1.397 (3)
C7—C6	1.36	C4—C5	1.393 (3)	C19—C20	1.381 (3)
C9—C10	1.61	C1—C8	1.602 (3)	C16—C23	1.602 (3)

C15—C9—C10A	108.2	C15—C1—C8	110.76 (15)	C30—C16—C23	110.87 (16)
C13—C9—C12	109.0	C14—C1—C2	107.12 (15)	C29—C16—C17	106.92 (15)
C9—C12—C11	117.7	C1—C2—C7	116.81 (17)	C16—C17—C22	117.31 (16)
C12—C11—C5	118.3	C2—C7—C6	119.99 (19)	C17—C22—C21	120.15 (18)

Calculated wavelengths (λ_max), oscillator strengths (f > 0.01) and main orbital transition contributions (>=20%) of absorption spectrum of the compound using TD-DFT, as well as their character and related experimental values top

Wavelength, λ (nm)		f	Assignment (major contributions)	Character
Experimental	Theoretical
300	282.853	0.0053	HOMO→LUMO+1 (0.99)	π–π*
255	249.654	0.0104	HOMO-1→LUMO+4 (0.66)	π–π*
	248.763	0.0063	HOMO→LUMO+4 (0.25)	π–π*
			HOMO→LUMO+6 (0.31)
	246.291	0.0168	HOMO-1→LUMO (0.28)	π–π*
			HOMO→LUMO+5 (0.26)
			HOMO→LUMO+6 (0.20)
	236.691	0.0086	HOMO-5→LUMO (0.45)	π–π*
			HOMO-4→LUMO (0.40)

The second hyperpolarizabilities (<γ>) computed by ZINDO/SOS top

Photon energy (eV)	0.0000	1.7464	1.7815
Compound	Molecule	pNA	Molecule	pNA	Molecule	pNA
<γ> (a.u.)	215981.00	39692.90	246197.00	96184.20	247566.00	100827.00
α (a.u.)	128.26	-	-	-	-	-

Experimental details top

Crystal data
	Polymorph (II) (present study)	Polymorph (I) (Ehrenberg, 1968)
Chemical formula	?C₃₀H₂₀O₂?	?C₃₀H₂₀O₂?
M_r	?412.46?	412.46
Crystal system, space group	?Monoclinic?, ?P2₁/n?	Triclinic , Pī
Temperature (K)	100	295
a, b, c (Å)	?12.9627 (3)?, ?9.6666 (2)?, ?16.6887 (4)?	?9.62?, ?7.86?, ?8.80?
α, β, γ (°)	90, ?105.2170 (11)?, 90	?59.67?, ?90?, ?65.93?
V (Å³)	?2017.86 (8)?	506.74
Z	?4?	1
Radiation type	?Cu Kα?	-
µ (mm^-1)	?0.66?	-
Crystal size (mm)	?0.16? × ?0.15? × ?0.03?	-

Data collection
Diffractometer	?Bruker D8 VENTURE PHOTON 100 CMOS?	-
Absorption correction	Multi-scan TWINABS (Sheldrick, 2009)?	none
T_min, T_max	?0.90?, ?0.98?	-
No. of measured, independent and observed [?I > 2σ(I)?] reflections	?43545?, ?3965?, ?3312?	-
R_int	?0.051?	-
(sin θ/λ)_max (Å^-1)	0.618	-

Refinement
R[F² > 2σ(F²)], wR(F²), S	?0.071?, ?0.197?, ?1.06?	0.088, -, -
No. of reflections	?3965?	640
No. of parameters	?290?	64
H-atom treatment	?H-atom parameters constrained?	?H-atom parameters constrained?
Δρ_max, Δρ_min (e Å^-3)	?0.46?, ?-0.42?	-

Computer programs in the present study: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a), SHELXL2013 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), TWINABS (Sheldrick, 2008a).

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page