Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109043339/fn3034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109043339/fn3034Isup2.hkl |
CCDC reference: 763602
Lead(II) iodide (24 mg, 0.05 mmol), potassium iodide (17 mg, 0.1 mmol) and the parent spirooxazine, 1,3,3-trimethyl-6'-(piperidin-1-yl)spiro[indoline-2,3'-3'H-naphtho[2,1-b][1,4]oxazine] (21 mg, 0.05 mmol), were heated in a Teflon-lined stainless steel autoclave with ethanol (10 ml) at 393 K. Chunky pale-yellow crystals of (I) were obtained by slow evaporation of the reaction solution.
Compound (I) dissolves in ethanol (EtOH), dimethylbenzene (C8H10), dichloromethane (CH2Cl2) and chloroform (CHCl3), and appears colourless, yellow, pale green and colourless, respectively. After irradiation with UV light, these solutions change to aqua green, light blue, green and pale bluish–green, respectively. A pale-green solution is observed when (I) is dissolved in chloroform-d (CDCl3) which turns purple when exposed to sunlight. However, no colour change was observed under UV light.
H atoms were added at calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H. [Please check added text]
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C29H33N3O2 | Z = 4 |
Mr = 455.58 | F(000) = 976 |
Triclinic, P1 | Dx = 1.204 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 10.001 (2) Å | Cell parameters from 12969 reflections |
b = 12.345 (3) Å | θ = 3.1–27.5° |
c = 20.513 (4) Å | µ = 0.08 mm−1 |
α = 88.49 (3)° | T = 296 K |
β = 87.32 (3)° | Block, yellow |
γ = 83.62 (3)° | 0.43 × 0.37 × 0.28 mm |
V = 2513.6 (9) Å3 |
Rigaku R-AXIS RAPID diffractometer | 11325 independent reflections |
Radiation source: fine-focus sealed tube | 5097 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −16→15 |
Tmin = 0.968, Tmax = 0.979 | l = −26→26 |
24807 measured reflections |
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)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.189 | w = 1/[σ2(Fo2) + (0.0846P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
11325 reflections | Δρmax = 0.21 e Å−3 |
621 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0083 (12) |
C29H33N3O2 | γ = 83.62 (3)° |
Mr = 455.58 | V = 2513.6 (9) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.001 (2) Å | Mo Kα radiation |
b = 12.345 (3) Å | µ = 0.08 mm−1 |
c = 20.513 (4) Å | T = 296 K |
α = 88.49 (3)° | 0.43 × 0.37 × 0.28 mm |
β = 87.32 (3)° |
Rigaku R-AXIS RAPID diffractometer | 11325 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5097 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.979 | Rint = 0.033 |
24807 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.189 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.21 e Å−3 |
11325 reflections | Δρmin = −0.28 e Å−3 |
621 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.46493 (18) | 0.26659 (17) | 0.51199 (8) | 0.0832 (6) | |
O2 | −0.12153 (15) | 0.22614 (12) | 0.45679 (6) | 0.0552 (4) | |
O3 | 0.96570 (16) | 0.09168 (15) | 0.12882 (8) | 0.0733 (5) | |
O4 | 0.61987 (14) | 0.19400 (11) | 0.11737 (6) | 0.0500 (4) | |
N1 | −0.2393 (2) | 0.13182 (15) | 0.53471 (9) | 0.0619 (5) | |
N2 | −0.35855 (19) | 0.35948 (17) | 0.43074 (9) | 0.0622 (5) | |
N3 | 0.13034 (18) | 0.40203 (15) | 0.28729 (8) | 0.0522 (5) | |
N4 | 0.73884 (19) | 0.12827 (15) | 0.20726 (8) | 0.0540 (5) | |
N5 | 0.85784 (19) | 0.16636 (16) | 0.03974 (9) | 0.0587 (5) | |
N6 | 0.36956 (18) | 0.36184 (14) | −0.06043 (8) | 0.0518 (4) | |
C1 | −0.1434 (3) | 0.1080 (2) | 0.58175 (11) | 0.0651 (7) | |
C2 | −0.0940 (4) | 0.0083 (2) | 0.60732 (15) | 0.0976 (10) | |
H2 | −0.1240 | −0.0554 | 0.5932 | 0.117* | |
C3 | −0.0005 (5) | 0.0042 (4) | 0.65356 (19) | 0.1321 (16) | |
H3 | 0.0327 | −0.0628 | 0.6715 | 0.158* | |
C4 | 0.0454 (5) | 0.0968 (4) | 0.67407 (17) | 0.1356 (16) | |
H4 | 0.1096 | 0.0920 | 0.7057 | 0.163* | |
C5 | −0.0027 (4) | 0.1996 (3) | 0.64827 (14) | 0.1045 (11) | |
H5 | 0.0292 | 0.2628 | 0.6619 | 0.125* | |
C6 | −0.0990 (3) | 0.2033 (2) | 0.60205 (11) | 0.0658 (7) | |
C7 | −0.1743 (2) | 0.29945 (18) | 0.56764 (10) | 0.0562 (6) | |
C8 | −0.2258 (2) | 0.23843 (18) | 0.50900 (9) | 0.0504 (5) | |
C9 | −0.3529 (2) | 0.2938 (2) | 0.47950 (11) | 0.0598 (6) | |
C10 | −0.2353 (2) | 0.37487 (18) | 0.39774 (10) | 0.0520 (5) | |
C11 | −0.2287 (2) | 0.45873 (17) | 0.34926 (9) | 0.0498 (5) | |
C12 | −0.3420 (3) | 0.5347 (2) | 0.33662 (11) | 0.0642 (6) | |
H12 | −0.4240 | 0.5269 | 0.3585 | 0.077* | |
C13 | −0.3330 (3) | 0.6187 (2) | 0.29307 (12) | 0.0718 (7) | |
H13 | −0.4084 | 0.6678 | 0.2855 | 0.086* | |
C14 | −0.2103 (3) | 0.6316 (2) | 0.25946 (11) | 0.0687 (7) | |
H14 | −0.2042 | 0.6902 | 0.2304 | 0.082* | |
C15 | −0.0999 (3) | 0.55872 (19) | 0.26914 (10) | 0.0601 (6) | |
H15 | −0.0194 | 0.5676 | 0.2461 | 0.072* | |
C16 | −0.1057 (2) | 0.46982 (17) | 0.31366 (9) | 0.0485 (5) | |
C17 | 0.0098 (2) | 0.39240 (17) | 0.32549 (9) | 0.0477 (5) | |
C18 | 0.0000 (2) | 0.31395 (17) | 0.37342 (9) | 0.0496 (5) | |
H18 | 0.0746 | 0.2646 | 0.3819 | 0.060* | |
C19 | −0.1206 (2) | 0.30703 (17) | 0.40980 (9) | 0.0483 (5) | |
C20 | 0.1244 (3) | 0.3605 (2) | 0.22117 (10) | 0.0652 (7) | |
H20A | 0.0406 | 0.3904 | 0.2024 | 0.078* | |
H20B | 0.1264 | 0.2818 | 0.2233 | 0.078* | |
C21 | 0.2418 (3) | 0.3915 (3) | 0.17813 (12) | 0.0838 (8) | |
H21A | 0.2350 | 0.4702 | 0.1725 | 0.101* | |
H21B | 0.2387 | 0.3602 | 0.1354 | 0.101* | |
C22 | 0.3750 (3) | 0.3509 (3) | 0.20808 (13) | 0.0849 (8) | |
H22A | 0.3883 | 0.2719 | 0.2076 | 0.102* | |
H22B | 0.4485 | 0.3784 | 0.1824 | 0.102* | |
C23 | 0.3755 (3) | 0.3888 (2) | 0.27728 (12) | 0.0738 (7) | |
H23A | 0.3747 | 0.4674 | 0.2771 | 0.089* | |
H23B | 0.4573 | 0.3569 | 0.2971 | 0.089* | |
C24 | 0.2547 (2) | 0.3567 (2) | 0.31708 (11) | 0.0639 (6) | |
H24A | 0.2584 | 0.2778 | 0.3197 | 0.077* | |
H24B | 0.2562 | 0.3833 | 0.3611 | 0.077* | |
C25 | −0.2742 (3) | 0.0474 (2) | 0.49213 (14) | 0.0940 (10) | |
H25A | −0.1947 | 0.0167 | 0.4682 | 0.141* | |
H25B | −0.3393 | 0.0787 | 0.4621 | 0.141* | |
H25C | −0.3114 | −0.0088 | 0.5180 | 0.141* | |
C26 | −0.0890 (3) | 0.3903 (2) | 0.54633 (13) | 0.0764 (7) | |
H26A | −0.0573 | 0.4219 | 0.5842 | 0.115* | |
H26B | −0.1426 | 0.4453 | 0.5221 | 0.115* | |
H26C | −0.0135 | 0.3608 | 0.5193 | 0.115* | |
C27 | −0.2918 (3) | 0.3474 (2) | 0.61226 (12) | 0.0768 (8) | |
H27A | −0.3464 | 0.2909 | 0.6260 | 0.115* | |
H27B | −0.3454 | 0.4036 | 0.5889 | 0.115* | |
H27C | −0.2575 | 0.3777 | 0.6499 | 0.115* | |
C28 | −0.7002 (3) | 0.2667 (3) | 0.52684 (19) | 0.1236 (13) | |
H28A | −0.6898 | 0.1894 | 0.5202 | 0.185* | |
H28B | −0.7863 | 0.2976 | 0.5123 | 0.185* | |
H28C | −0.6945 | 0.2805 | 0.5724 | 0.185* | |
C29 | −0.5926 (3) | 0.3166 (3) | 0.48935 (16) | 0.1131 (12) | |
H29A | −0.5985 | 0.3043 | 0.4431 | 0.136* | |
H29B | −0.6015 | 0.3946 | 0.4961 | 0.136* | |
C30 | 0.6423 (2) | 0.07325 (19) | 0.24151 (10) | 0.0583 (6) | |
C31 | 0.5927 (3) | 0.0879 (3) | 0.30506 (12) | 0.0854 (9) | |
H31 | 0.6224 | 0.1403 | 0.3310 | 0.103* | |
C32 | 0.4980 (4) | 0.0225 (3) | 0.32870 (17) | 0.1165 (12) | |
H32 | 0.4632 | 0.0310 | 0.3713 | 0.140* | |
C33 | 0.4534 (4) | −0.0551 (3) | 0.29081 (19) | 0.1205 (13) | |
H33 | 0.3894 | −0.0984 | 0.3080 | 0.145* | |
C34 | 0.5039 (3) | −0.0694 (2) | 0.22627 (15) | 0.0920 (9) | |
H34 | 0.4736 | −0.1214 | 0.2003 | 0.110* | |
C35 | 0.5987 (2) | −0.00513 (19) | 0.20246 (11) | 0.0596 (6) | |
C36 | 0.6755 (2) | −0.00388 (17) | 0.13711 (10) | 0.0529 (5) | |
C37 | 0.7264 (2) | 0.11151 (17) | 0.13898 (10) | 0.0489 (5) | |
C38 | 0.8527 (2) | 0.12677 (18) | 0.09753 (11) | 0.0544 (5) | |
C39 | 0.7340 (2) | 0.20795 (17) | 0.01361 (10) | 0.0491 (5) | |
C40 | 0.7298 (2) | 0.24092 (17) | −0.05351 (10) | 0.0498 (5) | |
C41 | 0.8436 (3) | 0.2246 (2) | −0.09657 (11) | 0.0656 (6) | |
H41 | 0.9254 | 0.1946 | −0.0806 | 0.079* | |
C42 | 0.8360 (3) | 0.2520 (2) | −0.16136 (13) | 0.0778 (8) | |
H42 | 0.9123 | 0.2404 | −0.1891 | 0.093* | |
C43 | 0.7154 (3) | 0.2969 (2) | −0.18592 (12) | 0.0755 (8) | |
H43 | 0.7111 | 0.3145 | −0.2302 | 0.091* | |
C44 | 0.6022 (3) | 0.31594 (19) | −0.14589 (10) | 0.0636 (6) | |
H44 | 0.5220 | 0.3465 | −0.1632 | 0.076* | |
C45 | 0.6062 (2) | 0.28950 (17) | −0.07812 (9) | 0.0493 (5) | |
C46 | 0.4900 (2) | 0.30835 (16) | −0.03475 (10) | 0.0476 (5) | |
C47 | 0.4976 (2) | 0.27300 (16) | 0.02907 (9) | 0.0466 (5) | |
H47 | 0.4217 | 0.2826 | 0.0572 | 0.056* | |
C48 | 0.6189 (2) | 0.22256 (16) | 0.05197 (9) | 0.0448 (5) | |
C49 | 0.3752 (3) | 0.48055 (18) | −0.06930 (12) | 0.0652 (7) | |
H49A | 0.4601 | 0.4937 | −0.0912 | 0.078* | |
H49B | 0.3702 | 0.5144 | −0.0270 | 0.078* | |
C50 | 0.2604 (3) | 0.5308 (2) | −0.10905 (13) | 0.0789 (8) | |
H50A | 0.2693 | 0.5012 | −0.1526 | 0.095* | |
H50B | 0.2635 | 0.6089 | −0.1130 | 0.095* | |
C51 | 0.1272 (3) | 0.5077 (2) | −0.07715 (15) | 0.0893 (9) | |
H51A | 0.0548 | 0.5345 | −0.1053 | 0.107* | |
H51B | 0.1127 | 0.5456 | −0.0362 | 0.107* | |
C52 | 0.1251 (3) | 0.3860 (2) | −0.06459 (13) | 0.0747 (7) | |
H52A | 0.0424 | 0.3729 | −0.0406 | 0.090* | |
H52B | 0.1277 | 0.3491 | −0.1059 | 0.090* | |
C53 | 0.2450 (2) | 0.3408 (2) | −0.02582 (11) | 0.0627 (6) | |
H53A | 0.2393 | 0.3745 | 0.0165 | 0.075* | |
H53B | 0.2437 | 0.2629 | −0.0189 | 0.075* | |
C54 | 0.7740 (3) | 0.2317 (2) | 0.23008 (12) | 0.0726 (7) | |
H54A | 0.6956 | 0.2843 | 0.2309 | 0.109* | |
H54B | 0.8425 | 0.2574 | 0.2011 | 0.109* | |
H54C | 0.8071 | 0.2218 | 0.2732 | 0.109* | |
C55 | 0.5897 (3) | −0.0187 (2) | 0.07882 (11) | 0.0699 (7) | |
H55A | 0.5600 | −0.0901 | 0.0812 | 0.105* | |
H55B | 0.6425 | −0.0108 | 0.0390 | 0.105* | |
H55C | 0.5129 | 0.0354 | 0.0796 | 0.105* | |
C56 | 0.7943 (3) | −0.09406 (19) | 0.13666 (13) | 0.0754 (7) | |
H56A | 0.8484 | −0.0860 | 0.1733 | 0.113* | |
H56B | 0.8480 | −0.0885 | 0.0969 | 0.113* | |
H56C | 0.7607 | −0.1640 | 0.1394 | 0.113* | |
C57 | 1.2024 (3) | 0.0625 (3) | 0.13793 (18) | 0.1083 (11) | |
H57A | 1.1890 | 0.1022 | 0.1777 | 0.162* | |
H57B | 1.2880 | 0.0745 | 0.1175 | 0.162* | |
H57C | 1.2007 | −0.0139 | 0.1475 | 0.162* | |
C58 | 1.0931 (3) | 0.1008 (3) | 0.09305 (16) | 0.0970 (10) | |
H58A | 1.0997 | 0.1758 | 0.0793 | 0.116* | |
H58B | 1.1001 | 0.0561 | 0.0546 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0484 (11) | 0.1201 (16) | 0.0791 (11) | −0.0088 (10) | 0.0012 (9) | 0.0250 (11) |
O2 | 0.0576 (10) | 0.0588 (9) | 0.0464 (8) | 0.0013 (8) | 0.0048 (7) | 0.0073 (7) |
O3 | 0.0453 (10) | 0.0896 (13) | 0.0830 (11) | 0.0006 (9) | −0.0082 (8) | 0.0097 (10) |
O4 | 0.0508 (9) | 0.0523 (8) | 0.0441 (7) | 0.0064 (7) | −0.0029 (6) | 0.0043 (6) |
N1 | 0.0703 (14) | 0.0544 (11) | 0.0613 (11) | −0.0111 (10) | −0.0006 (10) | 0.0066 (9) |
N2 | 0.0478 (12) | 0.0833 (14) | 0.0529 (10) | 0.0007 (10) | −0.0004 (9) | 0.0117 (10) |
N3 | 0.0486 (11) | 0.0623 (11) | 0.0452 (9) | −0.0046 (9) | 0.0009 (8) | −0.0038 (8) |
N4 | 0.0563 (12) | 0.0595 (11) | 0.0468 (9) | −0.0061 (9) | −0.0114 (8) | 0.0003 (9) |
N5 | 0.0490 (12) | 0.0640 (12) | 0.0613 (11) | −0.0015 (9) | −0.0010 (9) | 0.0069 (10) |
N6 | 0.0539 (12) | 0.0493 (10) | 0.0525 (10) | −0.0055 (9) | −0.0098 (9) | 0.0049 (8) |
C1 | 0.0772 (18) | 0.0611 (15) | 0.0522 (13) | 0.0066 (13) | 0.0084 (12) | 0.0095 (11) |
C2 | 0.128 (3) | 0.0710 (19) | 0.0847 (19) | 0.0202 (19) | 0.001 (2) | 0.0238 (16) |
C3 | 0.178 (4) | 0.109 (3) | 0.093 (3) | 0.058 (3) | −0.016 (3) | 0.021 (2) |
C4 | 0.155 (4) | 0.152 (4) | 0.086 (2) | 0.065 (3) | −0.054 (2) | 0.002 (3) |
C5 | 0.119 (3) | 0.115 (3) | 0.0737 (17) | 0.034 (2) | −0.0394 (19) | −0.0195 (18) |
C6 | 0.0739 (18) | 0.0695 (16) | 0.0490 (12) | 0.0163 (13) | −0.0060 (12) | −0.0004 (12) |
C7 | 0.0601 (15) | 0.0575 (14) | 0.0488 (12) | 0.0036 (12) | −0.0018 (11) | −0.0028 (10) |
C8 | 0.0478 (14) | 0.0578 (13) | 0.0441 (11) | −0.0030 (11) | 0.0036 (10) | 0.0062 (10) |
C9 | 0.0445 (14) | 0.0795 (17) | 0.0546 (13) | −0.0070 (12) | 0.0028 (11) | 0.0042 (12) |
C10 | 0.0462 (14) | 0.0633 (14) | 0.0447 (11) | 0.0013 (11) | −0.0007 (10) | 0.0010 (10) |
C11 | 0.0505 (14) | 0.0567 (13) | 0.0408 (10) | 0.0017 (11) | −0.0060 (10) | −0.0006 (10) |
C12 | 0.0584 (16) | 0.0734 (16) | 0.0576 (13) | 0.0081 (13) | −0.0064 (11) | 0.0027 (12) |
C13 | 0.0737 (19) | 0.0733 (17) | 0.0637 (14) | 0.0153 (14) | −0.0126 (14) | 0.0062 (13) |
C14 | 0.084 (2) | 0.0581 (15) | 0.0604 (14) | 0.0037 (14) | −0.0082 (14) | 0.0137 (12) |
C15 | 0.0708 (17) | 0.0609 (14) | 0.0485 (12) | −0.0068 (13) | −0.0038 (11) | 0.0034 (11) |
C16 | 0.0529 (14) | 0.0522 (12) | 0.0399 (10) | −0.0013 (11) | −0.0043 (10) | −0.0037 (9) |
C17 | 0.0469 (13) | 0.0546 (13) | 0.0413 (10) | −0.0039 (10) | 0.0016 (9) | −0.0055 (10) |
C18 | 0.0468 (13) | 0.0545 (13) | 0.0450 (11) | 0.0041 (10) | 0.0018 (9) | −0.0014 (10) |
C19 | 0.0517 (14) | 0.0532 (12) | 0.0387 (10) | −0.0014 (11) | 0.0003 (9) | 0.0005 (9) |
C20 | 0.0675 (17) | 0.0813 (17) | 0.0466 (12) | −0.0083 (14) | 0.0033 (11) | −0.0091 (12) |
C21 | 0.081 (2) | 0.114 (2) | 0.0558 (14) | −0.0159 (18) | 0.0189 (14) | −0.0075 (15) |
C22 | 0.069 (2) | 0.103 (2) | 0.0810 (18) | −0.0086 (17) | 0.0224 (15) | −0.0100 (16) |
C23 | 0.0519 (16) | 0.0862 (18) | 0.0823 (17) | −0.0064 (14) | 0.0049 (13) | −0.0041 (14) |
C24 | 0.0512 (15) | 0.0788 (17) | 0.0608 (13) | −0.0039 (13) | 0.0004 (11) | −0.0010 (12) |
C25 | 0.114 (3) | 0.0750 (19) | 0.098 (2) | −0.0331 (18) | −0.0037 (18) | −0.0063 (16) |
C26 | 0.081 (2) | 0.0745 (17) | 0.0765 (16) | −0.0165 (15) | −0.0079 (14) | −0.0076 (14) |
C27 | 0.085 (2) | 0.0783 (17) | 0.0607 (14) | 0.0141 (15) | 0.0108 (13) | −0.0053 (13) |
C28 | 0.059 (2) | 0.150 (3) | 0.163 (3) | −0.024 (2) | 0.012 (2) | −0.014 (3) |
C29 | 0.0481 (19) | 0.176 (4) | 0.111 (2) | −0.005 (2) | −0.0067 (17) | 0.037 (2) |
C30 | 0.0600 (15) | 0.0642 (15) | 0.0486 (12) | 0.0005 (12) | −0.0034 (11) | 0.0101 (11) |
C31 | 0.099 (2) | 0.098 (2) | 0.0564 (15) | −0.0031 (19) | 0.0030 (15) | 0.0060 (15) |
C32 | 0.139 (3) | 0.131 (3) | 0.077 (2) | −0.021 (3) | 0.032 (2) | 0.013 (2) |
C33 | 0.122 (3) | 0.126 (3) | 0.113 (3) | −0.039 (3) | 0.044 (2) | 0.028 (2) |
C34 | 0.095 (2) | 0.082 (2) | 0.100 (2) | −0.0272 (18) | 0.0146 (18) | 0.0104 (17) |
C35 | 0.0602 (16) | 0.0566 (14) | 0.0616 (13) | −0.0085 (12) | 0.0026 (11) | 0.0091 (11) |
C36 | 0.0550 (14) | 0.0477 (12) | 0.0554 (12) | −0.0025 (11) | −0.0051 (10) | 0.0001 (10) |
C37 | 0.0416 (13) | 0.0512 (12) | 0.0522 (12) | 0.0034 (10) | −0.0056 (10) | 0.0001 (10) |
C38 | 0.0424 (14) | 0.0561 (13) | 0.0637 (14) | −0.0007 (11) | −0.0072 (11) | 0.0038 (11) |
C39 | 0.0461 (13) | 0.0501 (12) | 0.0506 (11) | −0.0048 (10) | −0.0002 (10) | 0.0022 (10) |
C40 | 0.0530 (14) | 0.0476 (12) | 0.0492 (11) | −0.0104 (10) | 0.0045 (10) | −0.0004 (10) |
C41 | 0.0614 (16) | 0.0699 (16) | 0.0648 (14) | −0.0094 (13) | 0.0108 (12) | 0.0007 (12) |
C42 | 0.081 (2) | 0.0866 (19) | 0.0640 (16) | −0.0141 (16) | 0.0204 (14) | 0.0014 (14) |
C43 | 0.094 (2) | 0.0827 (18) | 0.0500 (13) | −0.0187 (17) | 0.0100 (14) | 0.0040 (13) |
C44 | 0.0768 (18) | 0.0636 (15) | 0.0516 (13) | −0.0132 (13) | −0.0055 (12) | 0.0039 (11) |
C45 | 0.0579 (15) | 0.0480 (12) | 0.0440 (11) | −0.0143 (11) | −0.0024 (10) | 0.0008 (9) |
C46 | 0.0525 (14) | 0.0419 (11) | 0.0497 (11) | −0.0075 (10) | −0.0101 (10) | −0.0019 (9) |
C47 | 0.0456 (13) | 0.0473 (12) | 0.0465 (11) | −0.0021 (10) | −0.0025 (9) | −0.0018 (9) |
C48 | 0.0495 (13) | 0.0433 (11) | 0.0411 (10) | −0.0033 (10) | −0.0010 (9) | 0.0013 (9) |
C49 | 0.0817 (19) | 0.0480 (13) | 0.0668 (14) | −0.0044 (12) | −0.0223 (13) | 0.0023 (11) |
C50 | 0.101 (2) | 0.0534 (15) | 0.0818 (17) | 0.0051 (15) | −0.0364 (17) | 0.0022 (13) |
C51 | 0.086 (2) | 0.089 (2) | 0.0883 (19) | 0.0254 (17) | −0.0342 (17) | −0.0114 (16) |
C52 | 0.0598 (17) | 0.091 (2) | 0.0715 (15) | 0.0065 (14) | −0.0145 (13) | −0.0079 (14) |
C53 | 0.0560 (16) | 0.0730 (16) | 0.0581 (13) | −0.0018 (13) | −0.0032 (11) | −0.0007 (12) |
C54 | 0.084 (2) | 0.0733 (17) | 0.0638 (14) | −0.0155 (14) | −0.0198 (13) | −0.0072 (13) |
C55 | 0.0764 (18) | 0.0634 (15) | 0.0728 (15) | −0.0155 (13) | −0.0122 (13) | −0.0067 (13) |
C56 | 0.079 (2) | 0.0543 (14) | 0.0881 (17) | 0.0134 (13) | −0.0059 (15) | −0.0032 (13) |
C57 | 0.0529 (19) | 0.111 (3) | 0.160 (3) | 0.0051 (17) | −0.0222 (19) | −0.015 (2) |
C58 | 0.0433 (17) | 0.130 (3) | 0.115 (2) | −0.0036 (17) | 0.0046 (16) | 0.010 (2) |
O1—C9 | 1.347 (3) | C26—H26A | 0.9600 |
O1—C29 | 1.446 (3) | C26—H26B | 0.9600 |
O2—C19 | 1.370 (2) | C26—H26C | 0.9600 |
O2—C8 | 1.458 (2) | C27—H27A | 0.9600 |
O3—C38 | 1.349 (3) | C27—H27B | 0.9600 |
O3—C58 | 1.454 (3) | C27—H27C | 0.9600 |
O4—C48 | 1.378 (2) | C28—C29 | 1.474 (4) |
O4—C37 | 1.466 (2) | C28—H28A | 0.9600 |
N1—C1 | 1.395 (3) | C28—H28B | 0.9600 |
N1—C8 | 1.423 (3) | C28—H28C | 0.9600 |
N1—C25 | 1.459 (3) | C29—H29A | 0.9700 |
N2—C9 | 1.270 (3) | C29—H29B | 0.9700 |
N2—C10 | 1.408 (3) | C30—C31 | 1.382 (3) |
N3—C17 | 1.421 (3) | C30—C35 | 1.391 (3) |
N3—C24 | 1.460 (3) | C31—C32 | 1.375 (4) |
N3—C20 | 1.468 (3) | C31—H31 | 0.9300 |
N4—C30 | 1.394 (3) | C32—C33 | 1.374 (5) |
N4—C37 | 1.434 (2) | C32—H32 | 0.9300 |
N4—C54 | 1.457 (3) | C33—C34 | 1.403 (4) |
N5—C38 | 1.271 (3) | C33—H33 | 0.9300 |
N5—C39 | 1.411 (3) | C34—C35 | 1.368 (3) |
N6—C46 | 1.424 (3) | C34—H34 | 0.9300 |
N6—C53 | 1.450 (3) | C35—C36 | 1.514 (3) |
N6—C49 | 1.479 (3) | C36—C55 | 1.530 (3) |
C1—C2 | 1.375 (4) | C36—C56 | 1.535 (3) |
C1—C6 | 1.384 (3) | C36—C37 | 1.568 (3) |
C2—C3 | 1.358 (5) | C37—C38 | 1.516 (3) |
C2—H2 | 0.9300 | C39—C48 | 1.361 (3) |
C3—C4 | 1.362 (5) | C39—C40 | 1.426 (3) |
C3—H3 | 0.9300 | C40—C41 | 1.408 (3) |
C4—C5 | 1.405 (5) | C40—C45 | 1.421 (3) |
C4—H4 | 0.9300 | C41—C42 | 1.366 (3) |
C5—C6 | 1.379 (4) | C41—H41 | 0.9300 |
C5—H5 | 0.9300 | C42—C43 | 1.382 (4) |
C6—C7 | 1.510 (3) | C42—H42 | 0.9300 |
C7—C26 | 1.525 (3) | C43—C44 | 1.369 (4) |
C7—C27 | 1.531 (3) | C43—H43 | 0.9300 |
C7—C8 | 1.573 (3) | C44—C45 | 1.421 (3) |
C8—C9 | 1.518 (3) | C44—H44 | 0.9300 |
C10—C19 | 1.371 (3) | C45—C46 | 1.432 (3) |
C10—C11 | 1.421 (3) | C46—C47 | 1.372 (3) |
C11—C12 | 1.417 (3) | C47—C48 | 1.397 (3) |
C11—C16 | 1.418 (3) | C47—H47 | 0.9300 |
C12—C13 | 1.358 (3) | C49—C50 | 1.507 (3) |
C12—H12 | 0.9300 | C49—H49A | 0.9700 |
C13—C14 | 1.401 (4) | C49—H49B | 0.9700 |
C13—H13 | 0.9300 | C50—C51 | 1.509 (4) |
C14—C15 | 1.364 (3) | C50—H50A | 0.9700 |
C14—H14 | 0.9300 | C50—H50B | 0.9700 |
C15—C16 | 1.413 (3) | C51—C52 | 1.520 (4) |
C15—H15 | 0.9300 | C51—H51A | 0.9700 |
C16—C17 | 1.441 (3) | C51—H51B | 0.9700 |
C17—C18 | 1.370 (3) | C52—C53 | 1.516 (3) |
C18—C19 | 1.398 (3) | C52—H52A | 0.9700 |
C18—H18 | 0.9300 | C52—H52B | 0.9700 |
C20—C21 | 1.513 (3) | C53—H53A | 0.9700 |
C20—H20A | 0.9700 | C53—H53B | 0.9700 |
C20—H20B | 0.9700 | C54—H54A | 0.9600 |
C21—C22 | 1.521 (4) | C54—H54B | 0.9600 |
C21—H21A | 0.9700 | C54—H54C | 0.9600 |
C21—H21B | 0.9700 | C55—H55A | 0.9600 |
C22—C23 | 1.507 (3) | C55—H55B | 0.9600 |
C22—H22A | 0.9700 | C55—H55C | 0.9600 |
C22—H22B | 0.9700 | C56—H56A | 0.9600 |
C23—C24 | 1.510 (3) | C56—H56B | 0.9600 |
C23—H23A | 0.9700 | C56—H56C | 0.9600 |
C23—H23B | 0.9700 | C57—C58 | 1.491 (4) |
C24—H24A | 0.9700 | C57—H57A | 0.9600 |
C24—H24B | 0.9700 | C57—H57B | 0.9600 |
C25—H25A | 0.9600 | C57—H57C | 0.9600 |
C25—H25B | 0.9600 | C58—H58A | 0.9700 |
C25—H25C | 0.9600 | C58—H58B | 0.9700 |
C9—O1—C29 | 117.0 (2) | C29—C28—H28C | 109.5 |
C19—O2—C8 | 117.89 (16) | H28A—C28—H28C | 109.5 |
C38—O3—C58 | 116.7 (2) | H28B—C28—H28C | 109.5 |
C48—O4—C37 | 118.00 (15) | O1—C29—C28 | 107.7 (3) |
C1—N1—C8 | 107.94 (18) | O1—C29—H29A | 110.2 |
C1—N1—C25 | 120.9 (2) | C28—C29—H29A | 110.2 |
C8—N1—C25 | 120.01 (19) | O1—C29—H29B | 110.2 |
C9—N2—C10 | 116.4 (2) | C28—C29—H29B | 110.2 |
C17—N3—C24 | 115.64 (17) | H29A—C29—H29B | 108.5 |
C17—N3—C20 | 112.34 (16) | C31—C30—C35 | 121.4 (2) |
C24—N3—C20 | 110.51 (18) | C31—C30—N4 | 128.3 (2) |
C30—N4—C37 | 107.82 (16) | C35—C30—N4 | 110.22 (18) |
C30—N4—C54 | 120.69 (19) | C32—C31—C30 | 117.9 (3) |
C37—N4—C54 | 120.64 (18) | C32—C31—H31 | 121.1 |
C38—N5—C39 | 116.60 (19) | C30—C31—H31 | 121.1 |
C46—N6—C53 | 116.00 (17) | C33—C32—C31 | 121.5 (3) |
C46—N6—C49 | 112.02 (16) | C33—C32—H32 | 119.2 |
C53—N6—C49 | 110.25 (19) | C31—C32—H32 | 119.2 |
C2—C1—C6 | 121.1 (3) | C32—C33—C34 | 120.3 (3) |
C2—C1—N1 | 129.0 (3) | C32—C33—H33 | 119.8 |
C6—C1—N1 | 109.9 (2) | C34—C33—H33 | 119.8 |
C3—C2—C1 | 119.0 (3) | C35—C34—C33 | 118.5 (3) |
C3—C2—H2 | 120.5 | C35—C34—H34 | 120.8 |
C1—C2—H2 | 120.5 | C33—C34—H34 | 120.8 |
C2—C3—C4 | 121.0 (3) | C34—C35—C30 | 120.3 (2) |
C2—C3—H3 | 119.5 | C34—C35—C36 | 131.0 (2) |
C4—C3—H3 | 119.5 | C30—C35—C36 | 108.67 (19) |
C3—C4—C5 | 121.1 (3) | C35—C36—C55 | 114.0 (2) |
C3—C4—H4 | 119.5 | C35—C36—C56 | 109.58 (19) |
C5—C4—H4 | 119.5 | C55—C36—C56 | 108.69 (18) |
C6—C5—C4 | 117.6 (3) | C35—C36—C37 | 99.76 (16) |
C6—C5—H5 | 121.2 | C55—C36—C37 | 113.74 (18) |
C4—C5—H5 | 121.2 | C56—C36—C37 | 110.82 (19) |
C5—C6—C1 | 120.2 (3) | N4—C37—O4 | 106.32 (16) |
C5—C6—C7 | 130.5 (3) | N4—C37—C38 | 113.99 (17) |
C1—C6—C7 | 109.3 (2) | O4—C37—C38 | 107.41 (17) |
C6—C7—C26 | 114.9 (2) | N4—C37—C36 | 103.63 (17) |
C6—C7—C27 | 109.22 (19) | O4—C37—C36 | 109.08 (16) |
C26—C7—C27 | 108.7 (2) | C38—C37—C36 | 115.97 (17) |
C6—C7—C8 | 99.07 (17) | N5—C38—O3 | 121.5 (2) |
C26—C7—C8 | 113.56 (18) | N5—C38—C37 | 126.5 (2) |
C27—C7—C8 | 111.1 (2) | O3—C38—C37 | 112.06 (19) |
N1—C8—O2 | 106.47 (17) | C48—C39—N5 | 121.26 (18) |
N1—C8—C9 | 113.74 (19) | C48—C39—C40 | 118.9 (2) |
O2—C8—C9 | 107.43 (16) | N5—C39—C40 | 119.71 (19) |
N1—C8—C7 | 103.95 (16) | C41—C40—C45 | 118.8 (2) |
O2—C8—C7 | 109.84 (17) | C41—C40—C39 | 122.0 (2) |
C9—C8—C7 | 115.08 (18) | C45—C40—C39 | 119.13 (19) |
N2—C9—O1 | 121.7 (2) | C42—C41—C40 | 121.2 (3) |
N2—C9—C8 | 126.4 (2) | C42—C41—H41 | 119.4 |
O1—C9—C8 | 111.9 (2) | C40—C41—H41 | 119.4 |
C19—C10—N2 | 120.9 (2) | C41—C42—C43 | 120.3 (2) |
C19—C10—C11 | 118.7 (2) | C41—C42—H42 | 119.8 |
N2—C10—C11 | 120.4 (2) | C43—C42—H42 | 119.8 |
C12—C11—C16 | 118.5 (2) | C44—C43—C42 | 120.8 (2) |
C12—C11—C10 | 121.4 (2) | C44—C43—H43 | 119.6 |
C16—C11—C10 | 120.0 (2) | C42—C43—H43 | 119.6 |
C13—C12—C11 | 121.2 (2) | C43—C44—C45 | 120.7 (2) |
C13—C12—H12 | 119.4 | C43—C44—H44 | 119.7 |
C11—C12—H12 | 119.4 | C45—C44—H44 | 119.7 |
C12—C13—C14 | 120.2 (2) | C44—C45—C40 | 118.2 (2) |
C12—C13—H13 | 119.9 | C44—C45—C46 | 122.2 (2) |
C14—C13—H13 | 119.9 | C40—C45—C46 | 119.56 (18) |
C15—C14—C13 | 120.3 (2) | C47—C46—N6 | 122.62 (19) |
C15—C14—H14 | 119.9 | C47—C46—C45 | 119.33 (19) |
C13—C14—H14 | 119.9 | N6—C46—C45 | 118.04 (18) |
C14—C15—C16 | 121.1 (2) | C46—C47—C48 | 120.24 (19) |
C14—C15—H15 | 119.5 | C46—C47—H47 | 119.9 |
C16—C15—H15 | 119.5 | C48—C47—H47 | 119.9 |
C15—C16—C11 | 118.6 (2) | C39—C48—O4 | 120.56 (18) |
C15—C16—C17 | 122.2 (2) | C39—C48—C47 | 122.66 (19) |
C11—C16—C17 | 119.10 (19) | O4—C48—C47 | 116.64 (18) |
C18—C17—N3 | 122.8 (2) | N6—C49—C50 | 110.58 (19) |
C18—C17—C16 | 119.01 (19) | N6—C49—H49A | 109.5 |
N3—C17—C16 | 118.23 (19) | C50—C49—H49A | 109.5 |
C17—C18—C19 | 121.0 (2) | N6—C49—H49B | 109.5 |
C17—C18—H18 | 119.5 | C50—C49—H49B | 109.5 |
C19—C18—H18 | 119.5 | H49A—C49—H49B | 108.1 |
O2—C19—C10 | 120.78 (19) | C49—C50—C51 | 110.5 (2) |
O2—C19—C18 | 117.15 (19) | C49—C50—H50A | 109.6 |
C10—C19—C18 | 122.0 (2) | C51—C50—H50A | 109.6 |
N3—C20—C21 | 110.79 (19) | C49—C50—H50B | 109.6 |
N3—C20—H20A | 109.5 | C51—C50—H50B | 109.6 |
C21—C20—H20A | 109.5 | H50A—C50—H50B | 108.1 |
N3—C20—H20B | 109.5 | C50—C51—C52 | 110.5 (2) |
C21—C20—H20B | 109.5 | C50—C51—H51A | 109.6 |
H20A—C20—H20B | 108.1 | C52—C51—H51A | 109.6 |
C20—C21—C22 | 110.8 (2) | C50—C51—H51B | 109.6 |
C20—C21—H21A | 109.5 | C52—C51—H51B | 109.6 |
C22—C21—H21A | 109.5 | H51A—C51—H51B | 108.1 |
C20—C21—H21B | 109.5 | C53—C52—C51 | 110.3 (2) |
C22—C21—H21B | 109.5 | C53—C52—H52A | 109.6 |
H21A—C21—H21B | 108.1 | C51—C52—H52A | 109.6 |
C23—C22—C21 | 110.2 (2) | C53—C52—H52B | 109.6 |
C23—C22—H22A | 109.6 | C51—C52—H52B | 109.6 |
C21—C22—H22A | 109.6 | H52A—C52—H52B | 108.1 |
C23—C22—H22B | 109.6 | N6—C53—C52 | 110.36 (19) |
C21—C22—H22B | 109.6 | N6—C53—H53A | 109.6 |
H22A—C22—H22B | 108.1 | C52—C53—H53A | 109.6 |
C22—C23—C24 | 111.1 (2) | N6—C53—H53B | 109.6 |
C22—C23—H23A | 109.4 | C52—C53—H53B | 109.6 |
C24—C23—H23A | 109.4 | H53A—C53—H53B | 108.1 |
C22—C23—H23B | 109.4 | N4—C54—H54A | 109.5 |
C24—C23—H23B | 109.4 | N4—C54—H54B | 109.5 |
H23A—C23—H23B | 108.0 | H54A—C54—H54B | 109.5 |
N3—C24—C23 | 110.4 (2) | N4—C54—H54C | 109.5 |
N3—C24—H24A | 109.6 | H54A—C54—H54C | 109.5 |
C23—C24—H24A | 109.6 | H54B—C54—H54C | 109.5 |
N3—C24—H24B | 109.6 | C36—C55—H55A | 109.5 |
C23—C24—H24B | 109.6 | C36—C55—H55B | 109.5 |
H24A—C24—H24B | 108.1 | H55A—C55—H55B | 109.5 |
N1—C25—H25A | 109.5 | C36—C55—H55C | 109.5 |
N1—C25—H25B | 109.5 | H55A—C55—H55C | 109.5 |
H25A—C25—H25B | 109.5 | H55B—C55—H55C | 109.5 |
N1—C25—H25C | 109.5 | C36—C56—H56A | 109.5 |
H25A—C25—H25C | 109.5 | C36—C56—H56B | 109.5 |
H25B—C25—H25C | 109.5 | H56A—C56—H56B | 109.5 |
C7—C26—H26A | 109.5 | C36—C56—H56C | 109.5 |
C7—C26—H26B | 109.5 | H56A—C56—H56C | 109.5 |
H26A—C26—H26B | 109.5 | H56B—C56—H56C | 109.5 |
C7—C26—H26C | 109.5 | C58—C57—H57A | 109.5 |
H26A—C26—H26C | 109.5 | C58—C57—H57B | 109.5 |
H26B—C26—H26C | 109.5 | H57A—C57—H57B | 109.5 |
C7—C27—H27A | 109.5 | C58—C57—H57C | 109.5 |
C7—C27—H27B | 109.5 | H57A—C57—H57C | 109.5 |
H27A—C27—H27B | 109.5 | H57B—C57—H57C | 109.5 |
C7—C27—H27C | 109.5 | O3—C58—C57 | 107.2 (3) |
H27A—C27—H27C | 109.5 | O3—C58—H58A | 110.3 |
H27B—C27—H27C | 109.5 | C57—C58—H58A | 110.3 |
C29—C28—H28A | 109.5 | O3—C58—H58B | 110.3 |
C29—C28—H28B | 109.5 | C57—C58—H58B | 110.3 |
H28A—C28—H28B | 109.5 | H58A—C58—H58B | 108.5 |
C8—N1—C1—C2 | −161.3 (3) | C37—N4—C30—C31 | −161.7 (2) |
C25—N1—C1—C2 | −17.6 (4) | C54—N4—C30—C31 | −17.3 (4) |
C8—N1—C1—C6 | 18.7 (3) | C37—N4—C30—C35 | 19.2 (3) |
C25—N1—C1—C6 | 162.4 (2) | C54—N4—C30—C35 | 163.6 (2) |
C6—C1—C2—C3 | 0.4 (5) | C35—C30—C31—C32 | −0.2 (4) |
N1—C1—C2—C3 | −179.5 (3) | N4—C30—C31—C32 | −179.3 (3) |
C1—C2—C3—C4 | −0.8 (6) | C30—C31—C32—C33 | 0.0 (6) |
C2—C3—C4—C5 | 0.2 (7) | C31—C32—C33—C34 | −0.2 (6) |
C3—C4—C5—C6 | 0.7 (6) | C32—C33—C34—C35 | 0.5 (6) |
C4—C5—C6—C1 | −1.1 (5) | C33—C34—C35—C30 | −0.7 (5) |
C4—C5—C6—C7 | 177.0 (3) | C33—C34—C35—C36 | 177.2 (3) |
C2—C1—C6—C5 | 0.6 (4) | C31—C30—C35—C34 | 0.6 (4) |
N1—C1—C6—C5 | −179.5 (2) | N4—C30—C35—C34 | 179.8 (2) |
C2—C1—C6—C7 | −177.9 (2) | C31—C30—C35—C36 | −177.8 (2) |
N1—C1—C6—C7 | 2.0 (3) | N4—C30—C35—C36 | 1.5 (3) |
C5—C6—C7—C26 | 41.2 (4) | C34—C35—C36—C55 | 41.3 (4) |
C1—C6—C7—C26 | −140.6 (2) | C30—C35—C36—C55 | −140.6 (2) |
C5—C6—C7—C27 | −81.2 (4) | C34—C35—C36—C56 | −80.8 (3) |
C1—C6—C7—C27 | 97.0 (2) | C30—C35—C36—C56 | 97.3 (2) |
C5—C6—C7—C8 | 162.5 (3) | C34—C35—C36—C37 | 162.9 (3) |
C1—C6—C7—C8 | −19.2 (2) | C30—C35—C36—C37 | −19.0 (2) |
C1—N1—C8—O2 | 85.60 (19) | C30—N4—C37—O4 | 84.3 (2) |
C25—N1—C8—O2 | −58.5 (3) | C54—N4—C37—O4 | −60.1 (2) |
C1—N1—C8—C9 | −156.29 (18) | C30—N4—C37—C38 | −157.53 (19) |
C25—N1—C8—C9 | 59.6 (3) | C54—N4—C37—C38 | 58.0 (3) |
C1—N1—C8—C7 | −30.4 (2) | C30—N4—C37—C36 | −30.6 (2) |
C25—N1—C8—C7 | −174.5 (2) | C54—N4—C37—C36 | −175.0 (2) |
C19—O2—C8—N1 | 157.65 (16) | C48—O4—C37—N4 | 157.23 (16) |
C19—O2—C8—C9 | 35.4 (2) | C48—O4—C37—C38 | 34.8 (2) |
C19—O2—C8—C7 | −90.4 (2) | C48—O4—C37—C36 | −91.6 (2) |
C6—C7—C8—N1 | 29.3 (2) | C35—C36—C37—N4 | 29.3 (2) |
C26—C7—C8—N1 | 151.6 (2) | C55—C36—C37—N4 | 151.12 (19) |
C27—C7—C8—N1 | −85.5 (2) | C56—C36—C37—N4 | −86.1 (2) |
C6—C7—C8—O2 | −84.3 (2) | C35—C36—C37—O4 | −83.59 (19) |
C26—C7—C8—O2 | 38.0 (2) | C55—C36—C37—O4 | 38.2 (2) |
C27—C7—C8—O2 | 160.95 (18) | C56—C36—C37—O4 | 160.99 (17) |
C6—C7—C8—C9 | 154.36 (19) | C35—C36—C37—C38 | 155.04 (18) |
C26—C7—C8—C9 | −83.3 (2) | C55—C36—C37—C38 | −83.2 (2) |
C27—C7—C8—C9 | 39.6 (2) | C56—C36—C37—C38 | 39.6 (2) |
C10—N2—C9—O1 | −175.2 (2) | C39—N5—C38—O3 | −175.41 (19) |
C10—N2—C9—C8 | 5.7 (3) | C39—N5—C38—C37 | 5.3 (3) |
C29—O1—C9—N2 | −0.7 (4) | C58—O3—C38—N5 | −0.4 (3) |
C29—O1—C9—C8 | 178.5 (2) | C58—O3—C38—C37 | 179.0 (2) |
N1—C8—C9—N2 | −146.3 (2) | N4—C37—C38—N5 | −144.9 (2) |
O2—C8—C9—N2 | −28.7 (3) | O4—C37—C38—N5 | −27.4 (3) |
C7—C8—C9—N2 | 93.9 (3) | C36—C37—C38—N5 | 94.8 (3) |
N1—C8—C9—O1 | 34.5 (3) | N4—C37—C38—O3 | 35.7 (3) |
O2—C8—C9—O1 | 152.09 (18) | O4—C37—C38—O3 | 153.25 (17) |
C7—C8—C9—O1 | −85.3 (2) | C36—C37—C38—O3 | −84.5 (2) |
C9—N2—C10—C19 | 12.3 (3) | C38—N5—C39—C48 | 11.3 (3) |
C9—N2—C10—C11 | −170.2 (2) | C38—N5—C39—C40 | −172.09 (19) |
C19—C10—C11—C12 | −176.99 (19) | C48—C39—C40—C41 | −177.59 (19) |
N2—C10—C11—C12 | 5.5 (3) | N5—C39—C40—C41 | 5.7 (3) |
C19—C10—C11—C16 | 1.1 (3) | C48—C39—C40—C45 | 1.0 (3) |
N2—C10—C11—C16 | −176.46 (17) | N5—C39—C40—C45 | −175.77 (18) |
C16—C11—C12—C13 | −2.2 (3) | C45—C40—C41—C42 | −1.7 (3) |
C10—C11—C12—C13 | 175.9 (2) | C39—C40—C41—C42 | 176.8 (2) |
C11—C12—C13—C14 | 0.2 (3) | C40—C41—C42—C43 | 0.2 (4) |
C12—C13—C14—C15 | 1.4 (4) | C41—C42—C43—C44 | 0.8 (4) |
C13—C14—C15—C16 | −0.9 (3) | C42—C43—C44—C45 | −0.2 (4) |
C14—C15—C16—C11 | −1.1 (3) | C43—C44—C45—C40 | −1.3 (3) |
C14—C15—C16—C17 | −179.15 (19) | C43—C44—C45—C46 | 179.9 (2) |
C12—C11—C16—C15 | 2.6 (3) | C41—C40—C45—C44 | 2.2 (3) |
C10—C11—C16—C15 | −175.50 (18) | C39—C40—C45—C44 | −176.41 (18) |
C12—C11—C16—C17 | −179.29 (17) | C41—C40—C45—C46 | −178.97 (18) |
C10—C11—C16—C17 | 2.6 (3) | C39—C40—C45—C46 | 2.4 (3) |
C24—N3—C17—C18 | −24.0 (3) | C53—N6—C46—C47 | −23.2 (3) |
C20—N3—C17—C18 | 104.1 (2) | C49—N6—C46—C47 | 104.6 (2) |
C24—N3—C17—C16 | 154.97 (18) | C53—N6—C46—C45 | 155.63 (17) |
C20—N3—C17—C16 | −76.9 (2) | C49—N6—C46—C45 | −76.6 (2) |
C15—C16—C17—C18 | 174.30 (18) | C44—C45—C46—C47 | 174.77 (19) |
C11—C16—C17—C18 | −3.7 (3) | C40—C45—C46—C47 | −4.0 (3) |
C15—C16—C17—N3 | −4.7 (3) | C44—C45—C46—N6 | −4.1 (3) |
C11—C16—C17—N3 | 177.25 (16) | C40—C45—C46—N6 | 177.08 (17) |
N3—C17—C18—C19 | −179.81 (16) | N6—C46—C47—C48 | −178.95 (17) |
C16—C17—C18—C19 | 1.2 (3) | C45—C46—C47—C48 | 2.2 (3) |
C8—O2—C19—C10 | −23.0 (3) | N5—C39—C48—O4 | −1.8 (3) |
C8—O2—C19—C18 | 159.57 (17) | C40—C39—C48—O4 | −178.51 (17) |
N2—C10—C19—O2 | −3.5 (3) | N5—C39—C48—C47 | 173.78 (18) |
C11—C10—C19—O2 | 178.95 (17) | C40—C39—C48—C47 | −2.9 (3) |
N2—C10—C19—C18 | 173.80 (17) | C37—O4—C48—C39 | −23.7 (2) |
C11—C10—C19—C18 | −3.7 (3) | C37—O4—C48—C47 | 160.42 (16) |
C17—C18—C19—O2 | −179.98 (17) | C46—C47—C48—C39 | 1.3 (3) |
C17—C18—C19—C10 | 2.6 (3) | C46—C47—C48—O4 | 177.08 (17) |
C17—N3—C20—C21 | 169.1 (2) | C46—N6—C49—C50 | 168.2 (2) |
C24—N3—C20—C21 | −60.1 (3) | C53—N6—C49—C50 | −61.0 (2) |
N3—C20—C21—C22 | 56.2 (3) | N6—C49—C50—C51 | 57.0 (3) |
C20—C21—C22—C23 | −53.0 (3) | C49—C50—C51—C52 | −53.9 (3) |
C21—C22—C23—C24 | 53.8 (3) | C50—C51—C52—C53 | 54.1 (3) |
C17—N3—C24—C23 | −170.32 (17) | C46—N6—C53—C52 | −170.09 (18) |
C20—N3—C24—C23 | 60.7 (2) | C49—N6—C53—C52 | 61.3 (2) |
C22—C23—C24—N3 | −57.9 (3) | C51—C52—C53—N6 | −58.0 (3) |
C9—O1—C29—C28 | 174.0 (2) | C38—O3—C58—C57 | 177.4 (2) |
Experimental details
Crystal data | |
Chemical formula | C29H33N3O2 |
Mr | 455.58 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.001 (2), 12.345 (3), 20.513 (4) |
α, β, γ (°) | 88.49 (3), 87.32 (3), 83.62 (3) |
V (Å3) | 2513.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.43 × 0.37 × 0.28 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.968, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24807, 11325, 5097 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.189, 1.11 |
No. of reflections | 11325 |
No. of parameters | 621 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.28 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Organic photochromic compounds play an important role in various organic–inorganic hybrid photochromic systems. They are employed to implement the photochromic function. In such organic compounds interesting reversible chemical and physical conversions have also been observed, based on photoinduced ring opening and closing, cycloaddition, or electron- and energy-transfer processes (Raymo & Tomasulo, 2005; Shimizu et al., 2006; Aldoshin, 2008).
Spirooxazines are one of the well known families of organic photochromic molecules with fast photocoloring rates and high light-fatigue resistance. Over the past several decades, numerous types of spirooxazine derivatives have been characterized. It is certain that C—O bond cleavage in spirooxazines induced by UV irradiation or heating is the main reason for their photochromism, and the C═N bond in the oxazinic ring improves its durability (Clegg et al., 1991; Osano et al., 1991; Reboul et al., 1995; Pèpe et al., 1995; Malatesta et al., 1995; Sun et al., 1997; Liang et al., 1998; Chamontin et al., 1998; Guo et al., 2005), but there are still some details of the structure–property relationships needing further explanation. For example, it was assumed that the more planar the oxazinic ring, the less photochromatic the molecule (Reboul et al., 1995). However, investigation of the molecular geometry of spirooxazines by Chamontin et al. (1998) showed that there is no obvious correlation. Additional research on the influence of substituent groups in 2'-substituted spirooxazines is also baffling (Clegg et al., 1991; Liang et al., 1998; Uznanski et al., 2001).
In the title compound, (I), there are two equivalent spirooxazine molecules in the asymmetric unit (Fig. 1). The least-squares planes through the aromatic rings show that the two benzene rings [maximum deviations of 0.0024 (1) and 0.0062 (2) Å for which rings?, respectively] and two phenanthroline rings [maximum deviations of 0.0250 (2) and 0.0312 (2) Å for which rings?, respectively] both exhibit expected planar geometries, and the dihedral angles between the two types of plane are 108.1 (2) and 109.3 (2)°. Atoms C7 and N1 (or C36 and N4) attached to the benzene rings lie very close to the ring planes in the two molecules, with deviations of 0.062 (4) and 0.002 (4) Å [or 0.057 (4) and 0.011 (4) Å], respectively. Similarly, atoms N2 and O2 (or N5 and O4) are also approximately coplanar with the phenanthroline ring planes, with deviations of 0.072 (3) and 0.126 (2) Å [or 0.090 (3) and 0.050 (2) Å], respectively. The non-aromatic five- and six-membered rings around Cspiro are twisted and their conformations may be characterized as half-chair according to the method given by Cremer & Pople (1975). Furthermore, there are two substitutent groups in the molecule; the piperidine ring at the 6'-C site is in a chair conformation and the ethoxy group at the 2'-C site is approximately coplanar with C═N.
The oxazine rings (the key zone of the photochromism) suggest bond delocalization involving the C, N and O atoms, including the adjacent aromatic ring (Sun et al., 1997; Liang et al., 1998.). This is confirmed by the bond lengths involving the C, N and O atoms. For instance, the C1—N1 bond length is 1.395 (3) Å, which is between the values of 1.48 Å for a C—N single bond and 1.28 Å for a C═N double bond (Allen et al., 1987), indicating partial delocalization of the π-electron density over the indole ring. Similarly, the C19—O2 bond length is 1.370 (2) Å, which is between the values of 1.43 Å for a C—O single bond and 1.23 Å for a C═O double bond (Allen et al., 1987). The C10—N2 bond length is 1.408 (3) Å, indicating that atoms O2, N2 in the oxazine ring are conjugated with the π-electron system of the naphthalene ring. All of these delocalizations are beneficial to the stabilization of the open-ring form of the spirooxazine.
The distances of the Cspiro—O and Cspiro—N bonds are two key points in the structure of (I). The former cleaves upon photoexcitation to give an open form of the spirooxazine, and the latter has an influence on the stability of the open form. Here, the Cspiro—O bond lengths are 1.458 (2) and 1.466 (3) Å, respectively, for atoms C8 and C37, and the Cspiro—N bond lengths are 1.423 (3) and 1.434 (3) Å, respectively, for atoms C8 and C37. These bond lengths show no significant differences compared with other photochromic spirooxazines (Clegg et al., 1991; Osano et al., 1991; Reboul et al., 1995; Pèpe et al., 1995; Malatesta et al., 1995; Sun et al., 1997; Liang et al., 1998; Chamontin et al., 1998; Guo et al., 2005).
A characteristic of (I) is that there is an ethoxy group at the 2'-position. A similar ethoxy-substituted compound, 2'-ethoxy-1,3,3-trimethyl-5-nitrospiro[indoline-2,3'-naphtho[2,1- b][1,4]oxazine], was synthesized by Uznanski et al. (2001), but it displays no photochromic properties. Interestingly, this ethoxy substituent at the 2'-position (atoms C2 and C38) leads to an obvious change in (I) compared with the parent spirooxazine, (II). The parent shows no colour change under UV light or sunlight, but the substituted compound displays various photochromic conversions in different solvents under UV exposure.
The different photochromic properties found in compound (I) require further study of its structure–property relationships. Research on the mechanism of the ethoxy reaction at the 2'-position of spirooxazine is also in progress.