The dimer of 9-anthraldehyde, namely heptacyclo[8.6.6.62,9.03,8.011,16.017,22.023,28]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).
Supporting information
CCDC reference: 1577449
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 |
Mr = 412.46 | Dx = 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 | Rint = 0.051 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.5°, θmin = 3.9° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | k = −11→11 |
Tmin = 0.90, Tmax = 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(Fo2) + (0.1517P)2 + 0.1114P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3965 reflections | Δρmax = 0.46 e Å−3 |
290 parameters | Δρmin = −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 | Uiso*/Ueq | |
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 topPolymorph 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 (λmax), 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 topWavelength, 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 topPhoton 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 topCrystal data | | |
| Polymorph (II) (present study) | Polymorph (I) (Ehrenberg, 1968) |
Chemical formula | ?C30H20O2? | ?C30H20O2? |
Mr | ?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 |
Tmin, Tmax | ?0.90?, ?0.98? | - |
No. of measured, independent and
observed [?I > 2σ(I)?] reflections | ?43545?, ?3965?, ?3312? | - |
Rint | ?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? |
Δρmax, Δρmin (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). |