Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111004951/ln3147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111004951/ln3147Isup2.hkl |
CCDC reference: 819306
For related literature, see: Allen (2002); Bernstein et al. (1995); Bunsel & Keum (1983); Das et al. (2007); Kolev et al. (1992); Kumar et al. (2007); Langer & Becker (1992, 1993); Magomedova & Bel'skii (1986); Marder et al. (1994); Pan et al. (1996); Ramesh et al. (2010); Siaka et al. (1998); Spek (2009); Teshome et al. (2010); Yang et al. (2007).
To a cooled solution of 2-anthracen-9-yl-indan-1,3-dione (1.6 g) in distilled water (40 ml) was added KOH (1 g), and the mixture was stirred for 30 min. A solution of 4-aminopyridinium chloride (0.7 g) in distilled water (10 ml) was then added dropwise, whereupon a red solid formed almost immediately. After 10 min, the solid product was collected by filtration, washed with several small portions of distilled water and air-dried to give a red powder. The crude product was purified by recrystallization from ethanol. Crystals of (I) were obtained by dissolving the compound in chloroform–acetone–toluene (4:5:1 v/v) and allowing the solution to evaporate slowly, whereupon dark-red crystals formed [m.p. 491–493 K (decomposition)].
Spectroscopic analysis: 1H NMR (DMSO-d6, 500 MHz, δ, p.p.m.): 8.33 (s, 1H), 8.02–7.95 (m, 3H), 7.88 (d, J = 5.0 Hz, 2H), 7.50 (s, 2H), 7.40 (t, 2H), 7.30 (m, 3H), 7.22 (s, 2H), 6.60 (d, J = 5.0 Hz, 2H), 2.04 (s, 2H); 13C NMR (DMSO-d6, 125 MHz, δ, p.p.m.): 188.4, 182.5, 158.4, 141.4, 140.8, 134.6, 133.8, 133.1, 131.4, 130.8, 129.3, 128.9, 127.9, 126.8, 124.7, 123.6, 123.5, 117.1, 108.5, 103.7. Mass spectroscopy, negative mode: found m/z 321.0915; C23H13O2 requires m/z 321.0916, Δ = 0.3 p.p.m. Positive mode, found m/z 95.0618; C5H7N2 requires m/z 95.0609, Δ = 9.5 p.p.m.
Ten reflections affected by the beam stop were omitted from the final refinement. Aromatic ring H atoms were constrained to an ideal geometry, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C). All N-bound H atoms were placed in positions determined from a difference Fourier map and refined freely, with Uiso(H) = 1.2Ueq(N). Water H atoms were located in a difference Fourier map and then refined freely, with Uiso(H) = 1.5Ueq(O).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005) and SADABS (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
2C5H7N2+·2C23H13O2−·H2O | Z = 2 |
Mr = 850.94 | F(000) = 892 |
Triclinic, P1 | Dx = 1.318 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1990 (3) Å | Cell parameters from 9869 reflections |
b = 13.9977 (6) Å | θ = 2.3–30.4° |
c = 17.9153 (7) Å | µ = 0.09 mm−1 |
α = 100.962 (2)° | T = 116 K |
β = 97.628 (2)° | Block, red |
γ = 105.265 (2)° | 0.70 × 0.31 × 0.18 mm |
V = 2143.78 (14) Å3 |
Bruker APEXII CCD diffractometer | 7568 independent reflections |
Graphite monochromator | 6771 reflections with I > 2σ(I) |
Detector resolution: 8.333 pixels mm-1 | Rint = 0.036 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (Blessing, 1995) | h = −10→10 |
Tmin = 0.637, Tmax = 0.746 | k = −16→16 |
41534 measured reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.032P)2 + 1.1299P] where P = (Fo2 + 2Fc2)/3 |
7568 reflections | (Δ/σ)max < 0.001 |
610 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
2C5H7N2+·2C23H13O2−·H2O | γ = 105.265 (2)° |
Mr = 850.94 | V = 2143.78 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.1990 (3) Å | Mo Kα radiation |
b = 13.9977 (6) Å | µ = 0.09 mm−1 |
c = 17.9153 (7) Å | T = 116 K |
α = 100.962 (2)° | 0.70 × 0.31 × 0.18 mm |
β = 97.628 (2)° |
Bruker APEXII CCD diffractometer | 7568 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6771 reflections with I > 2σ(I) |
Tmin = 0.637, Tmax = 0.746 | Rint = 0.036 |
41534 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.21 e Å−3 |
7568 reflections | Δρmin = −0.22 e Å−3 |
610 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.86467 (13) | 0.17884 (9) | 0.43690 (6) | 0.0230 (3) | |
O2 | 0.90595 (13) | 0.40933 (9) | 0.67461 (6) | 0.0210 (3) | |
C1 | 0.90919 (17) | 0.25205 (12) | 0.49499 (9) | 0.0163 (3) | |
C2 | 0.84918 (17) | 0.26511 (12) | 0.56506 (9) | 0.0165 (3) | |
C3 | 0.92742 (17) | 0.36418 (12) | 0.61096 (9) | 0.0159 (3) | |
C4 | 1.05001 (17) | 0.41386 (12) | 0.57041 (9) | 0.0162 (3) | |
C5 | 1.15955 (18) | 0.50755 (12) | 0.59197 (10) | 0.0194 (3) | |
H5 | 1.1672 | 0.5538 | 0.6396 | 0.023* | |
C6 | 1.25988 (18) | 0.53273 (12) | 0.54117 (10) | 0.0203 (4) | |
H6 | 1.3360 | 0.5972 | 0.5545 | 0.024* | |
C7 | 1.24922 (18) | 0.46518 (13) | 0.47231 (10) | 0.0206 (4) | |
H7 | 1.3185 | 0.4835 | 0.4389 | 0.025* | |
C8 | 1.13748 (18) | 0.36993 (12) | 0.45097 (9) | 0.0186 (3) | |
H8 | 1.1299 | 0.3232 | 0.4036 | 0.022* | |
C9 | 1.03891 (17) | 0.34607 (12) | 0.50072 (9) | 0.0158 (3) | |
C10 | 0.72140 (17) | 0.18681 (12) | 0.58140 (9) | 0.0157 (3) | |
C11 | 0.58225 (17) | 0.20747 (12) | 0.59306 (9) | 0.0165 (3) | |
C12 | 0.55839 (19) | 0.30393 (13) | 0.59045 (10) | 0.0204 (4) | |
H12 | 0.6397 | 0.3569 | 0.5827 | 0.024* | |
C13 | 0.42200 (19) | 0.32161 (13) | 0.59880 (10) | 0.0243 (4) | |
H13 | 0.4096 | 0.3865 | 0.5971 | 0.029* | |
C14 | 0.29859 (19) | 0.24372 (14) | 0.60993 (10) | 0.0244 (4) | |
H14 | 0.2035 | 0.2564 | 0.6152 | 0.029* | |
C15 | 0.31569 (18) | 0.15164 (13) | 0.61311 (10) | 0.0223 (4) | |
H15 | 0.2322 | 0.1004 | 0.6211 | 0.027* | |
C16 | 0.45660 (18) | 0.12929 (12) | 0.60478 (9) | 0.0181 (3) | |
C17 | 0.47146 (18) | 0.03300 (12) | 0.60415 (9) | 0.0198 (3) | |
H17 | 0.3872 | −0.0188 | 0.6108 | 0.024* | |
C18 | 0.60729 (18) | 0.01093 (12) | 0.59402 (9) | 0.0181 (3) | |
C19 | 0.62289 (19) | −0.08794 (12) | 0.59445 (10) | 0.0221 (4) | |
H19 | 0.5383 | −0.1397 | 0.6009 | 0.027* | |
C20 | 0.7557 (2) | −0.10939 (13) | 0.58587 (10) | 0.0247 (4) | |
H20 | 0.7641 | −0.1754 | 0.5869 | 0.030* | |
C21 | 0.8823 (2) | −0.03319 (13) | 0.57540 (10) | 0.0222 (4) | |
H21 | 0.9755 | −0.0485 | 0.5696 | 0.027* | |
C22 | 0.87214 (18) | 0.06147 (13) | 0.57359 (9) | 0.0189 (3) | |
H22 | 0.9585 | 0.1110 | 0.5661 | 0.023* | |
C23 | 0.73496 (17) | 0.08857 (12) | 0.58264 (9) | 0.0156 (3) | |
O1' | 0.42132 (13) | 0.20381 (9) | 0.01015 (7) | 0.0245 (3) | |
O2' | 0.04183 (13) | 0.34312 (10) | 0.09840 (7) | 0.0287 (3) | |
C1' | 0.34140 (18) | 0.24437 (12) | 0.05129 (9) | 0.0178 (3) | |
C2' | 0.20833 (18) | 0.27011 (12) | 0.02745 (9) | 0.0183 (3) | |
C3' | 0.15690 (18) | 0.31186 (13) | 0.09448 (10) | 0.0207 (4) | |
C4' | 0.26892 (18) | 0.31249 (13) | 0.16478 (9) | 0.0201 (4) | |
C5' | 0.2737 (2) | 0.34343 (15) | 0.24305 (10) | 0.0305 (4) | |
H5' | 0.1984 | 0.3716 | 0.2616 | 0.037* | |
C6' | 0.3936 (2) | 0.33191 (15) | 0.29439 (10) | 0.0301 (4) | |
H6' | 0.3994 | 0.3528 | 0.3486 | 0.036* | |
C7' | 0.50317 (19) | 0.29089 (14) | 0.26773 (10) | 0.0250 (4) | |
H7' | 0.5830 | 0.2836 | 0.3037 | 0.030* | |
C8' | 0.49766 (19) | 0.25991 (13) | 0.18811 (10) | 0.0220 (4) | |
H8' | 0.5730 | 0.2319 | 0.1692 | 0.026* | |
C9' | 0.37980 (17) | 0.27128 (12) | 0.13811 (9) | 0.0176 (3) | |
C10' | 0.14152 (18) | 0.25457 (12) | −0.05583 (9) | 0.0184 (3) | |
C11' | 0.02273 (19) | 0.16579 (13) | −0.09512 (9) | 0.0207 (4) | |
C12' | −0.0475 (2) | 0.09019 (14) | −0.05684 (10) | 0.0274 (4) | |
H12' | −0.0156 | 0.1004 | −0.0025 | 0.033* | |
C13' | −0.1591 (2) | 0.00397 (15) | −0.09666 (11) | 0.0369 (5) | |
H13' | −0.2032 | −0.0454 | −0.0699 | 0.044* | |
C14' | −0.2108 (2) | −0.01330 (16) | −0.17746 (12) | 0.0431 (5) | |
H14' | −0.2894 | −0.0737 | −0.2045 | 0.052* | |
C15' | −0.1482 (2) | 0.05620 (15) | −0.21624 (11) | 0.0365 (5) | |
H15' | −0.1839 | 0.0439 | −0.2704 | 0.044* | |
C16' | −0.0298 (2) | 0.14744 (13) | −0.17748 (10) | 0.0245 (4) | |
C17' | 0.0395 (2) | 0.21682 (13) | −0.21767 (10) | 0.0240 (4) | |
H17' | 0.0066 | 0.2033 | −0.2722 | 0.029* | |
C18' | 0.15583 (19) | 0.30550 (13) | −0.18000 (10) | 0.0205 (4) | |
C19' | 0.2229 (2) | 0.37928 (14) | −0.22081 (10) | 0.0246 (4) | |
H19' | 0.1937 | 0.3649 | −0.2756 | 0.030* | |
C20' | 0.3271 (2) | 0.46902 (14) | −0.18280 (11) | 0.0295 (4) | |
H20' | 0.3713 | 0.5166 | −0.2109 | 0.035* | |
C21' | 0.3704 (2) | 0.49196 (14) | −0.10113 (11) | 0.0310 (4) | |
H21' | 0.4404 | 0.5563 | −0.0746 | 0.037* | |
C22' | 0.31302 (19) | 0.42310 (13) | −0.06011 (11) | 0.0254 (4) | |
H22' | 0.3455 | 0.4397 | −0.0054 | 0.030* | |
C23' | 0.20500 (18) | 0.32634 (13) | −0.09751 (10) | 0.0195 (3) | |
O5W | 0.92879 (15) | 0.39664 (10) | 0.23334 (8) | 0.0275 (3) | |
H5W1 | 0.974 (2) | 0.3872 (17) | 0.1918 (14) | 0.041* | |
H5W2 | 0.980 (3) | 0.4554 (18) | 0.2632 (13) | 0.041* | |
C24 | 0.73817 (19) | 0.32855 (13) | 0.93506 (10) | 0.0232 (4) | |
C25 | 0.87778 (19) | 0.38332 (13) | 0.91918 (10) | 0.0243 (4) | |
H25 | 0.9676 | 0.4082 | 0.9586 | 0.029* | |
C26 | 0.8840 (2) | 0.40052 (14) | 0.84769 (11) | 0.0262 (4) | |
H26 | 0.9793 | 0.4364 | 0.8373 | 0.031* | |
N27 | 0.75841 (18) | 0.36803 (12) | 0.79094 (9) | 0.0288 (4) | |
H27 | 0.773 (2) | 0.3759 (15) | 0.7438 (13) | 0.035* | |
C28 | 0.6201 (2) | 0.32122 (16) | 0.80525 (11) | 0.0337 (4) | |
H28 | 0.5314 | 0.3013 | 0.7654 | 0.040* | |
C29 | 0.6067 (2) | 0.30236 (15) | 0.87608 (11) | 0.0308 (4) | |
H29 | 0.5084 | 0.2714 | 0.8860 | 0.037* | |
N30 | 0.73216 (19) | 0.30329 (13) | 1.00307 (9) | 0.0299 (4) | |
H30A | 0.821 (2) | 0.3192 (16) | 1.0385 (13) | 0.036* | |
H30B | 0.641 (2) | 0.2692 (16) | 1.0137 (12) | 0.036* | |
C24' | 0.82090 (19) | 0.12900 (13) | 0.23086 (10) | 0.0232 (4) | |
C25' | 0.7987 (2) | 0.13074 (14) | 0.15164 (10) | 0.0287 (4) | |
H25' | 0.8261 | 0.1937 | 0.1368 | 0.034* | |
C26' | 0.7380 (2) | 0.04225 (15) | 0.09695 (11) | 0.0324 (4) | |
H26' | 0.7218 | 0.0442 | 0.0439 | 0.039* | |
N27' | 0.70022 (19) | −0.04846 (13) | 0.11595 (10) | 0.0330 (4) | |
H27' | 0.661 (2) | −0.1065 (17) | 0.0772 (13) | 0.040* | |
C28' | 0.7259 (2) | −0.05313 (15) | 0.19079 (12) | 0.0351 (5) | |
H28' | 0.7026 | −0.1177 | 0.2034 | 0.042* | |
C29' | 0.7842 (2) | 0.03232 (14) | 0.24836 (11) | 0.0303 (4) | |
H29' | 0.8005 | 0.0273 | 0.3008 | 0.036* | |
N30' | 0.87372 (19) | 0.21402 (12) | 0.28657 (9) | 0.0294 (4) | |
H31' | 0.896 (2) | 0.2761 (17) | 0.2731 (12) | 0.035* | |
H32' | 0.880 (2) | 0.2079 (16) | 0.3372 (13) | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0296 (6) | 0.0190 (6) | 0.0165 (6) | 0.0024 (5) | 0.0055 (5) | 0.0014 (5) |
O2 | 0.0237 (6) | 0.0209 (6) | 0.0152 (6) | 0.0025 (5) | 0.0070 (5) | 0.0004 (5) |
C1 | 0.0183 (8) | 0.0153 (8) | 0.0155 (8) | 0.0061 (6) | 0.0020 (6) | 0.0036 (7) |
C2 | 0.0164 (8) | 0.0167 (8) | 0.0167 (8) | 0.0048 (6) | 0.0026 (6) | 0.0054 (6) |
C3 | 0.0156 (8) | 0.0186 (8) | 0.0143 (8) | 0.0057 (6) | 0.0017 (6) | 0.0057 (7) |
C4 | 0.0159 (8) | 0.0176 (8) | 0.0170 (8) | 0.0065 (6) | 0.0033 (6) | 0.0068 (7) |
C5 | 0.0196 (8) | 0.0174 (8) | 0.0194 (9) | 0.0041 (7) | 0.0041 (7) | 0.0016 (7) |
C6 | 0.0179 (8) | 0.0168 (8) | 0.0253 (9) | 0.0017 (6) | 0.0047 (7) | 0.0074 (7) |
C7 | 0.0197 (8) | 0.0222 (9) | 0.0251 (9) | 0.0076 (7) | 0.0108 (7) | 0.0114 (7) |
C8 | 0.0227 (8) | 0.0190 (8) | 0.0172 (8) | 0.0093 (7) | 0.0071 (7) | 0.0052 (7) |
C9 | 0.0156 (7) | 0.0170 (8) | 0.0158 (8) | 0.0057 (6) | 0.0023 (6) | 0.0056 (6) |
C10 | 0.0172 (8) | 0.0170 (8) | 0.0105 (8) | 0.0022 (6) | 0.0016 (6) | 0.0021 (6) |
C11 | 0.0183 (8) | 0.0183 (8) | 0.0105 (8) | 0.0035 (6) | 0.0010 (6) | 0.0019 (6) |
C12 | 0.0210 (8) | 0.0192 (9) | 0.0202 (9) | 0.0044 (7) | 0.0030 (7) | 0.0054 (7) |
C13 | 0.0280 (9) | 0.0215 (9) | 0.0250 (9) | 0.0111 (7) | 0.0032 (7) | 0.0051 (7) |
C14 | 0.0189 (8) | 0.0313 (10) | 0.0245 (9) | 0.0113 (7) | 0.0046 (7) | 0.0042 (8) |
C15 | 0.0169 (8) | 0.0281 (10) | 0.0196 (9) | 0.0025 (7) | 0.0037 (7) | 0.0053 (7) |
C16 | 0.0179 (8) | 0.0215 (9) | 0.0137 (8) | 0.0036 (7) | 0.0023 (6) | 0.0052 (7) |
C17 | 0.0188 (8) | 0.0193 (9) | 0.0183 (8) | −0.0007 (7) | 0.0041 (6) | 0.0056 (7) |
C18 | 0.0212 (8) | 0.0169 (8) | 0.0132 (8) | 0.0026 (7) | 0.0013 (6) | 0.0023 (6) |
C19 | 0.0267 (9) | 0.0160 (8) | 0.0198 (9) | 0.0008 (7) | 0.0025 (7) | 0.0040 (7) |
C20 | 0.0355 (10) | 0.0173 (9) | 0.0219 (9) | 0.0108 (7) | 0.0031 (7) | 0.0036 (7) |
C21 | 0.0269 (9) | 0.0243 (9) | 0.0176 (9) | 0.0127 (7) | 0.0045 (7) | 0.0031 (7) |
C22 | 0.0196 (8) | 0.0214 (9) | 0.0148 (8) | 0.0050 (7) | 0.0040 (6) | 0.0035 (7) |
C23 | 0.0187 (8) | 0.0166 (8) | 0.0093 (8) | 0.0033 (6) | 0.0007 (6) | 0.0017 (6) |
O1' | 0.0224 (6) | 0.0305 (7) | 0.0186 (6) | 0.0077 (5) | 0.0063 (5) | −0.0005 (5) |
O2' | 0.0264 (7) | 0.0434 (8) | 0.0180 (6) | 0.0180 (6) | 0.0023 (5) | 0.0022 (6) |
C1' | 0.0192 (8) | 0.0130 (8) | 0.0167 (8) | −0.0020 (6) | 0.0042 (6) | 0.0017 (6) |
C2' | 0.0184 (8) | 0.0185 (8) | 0.0155 (8) | 0.0016 (6) | 0.0029 (6) | 0.0035 (7) |
C3' | 0.0202 (8) | 0.0216 (9) | 0.0177 (9) | 0.0034 (7) | 0.0026 (7) | 0.0033 (7) |
C4' | 0.0194 (8) | 0.0224 (9) | 0.0159 (8) | 0.0036 (7) | 0.0025 (6) | 0.0028 (7) |
C5' | 0.0270 (9) | 0.0465 (12) | 0.0186 (9) | 0.0153 (9) | 0.0045 (7) | 0.0028 (8) |
C6' | 0.0286 (9) | 0.0451 (12) | 0.0129 (9) | 0.0096 (8) | 0.0018 (7) | 0.0016 (8) |
C7' | 0.0219 (9) | 0.0290 (10) | 0.0200 (9) | 0.0046 (7) | −0.0031 (7) | 0.0049 (7) |
C8' | 0.0200 (8) | 0.0212 (9) | 0.0232 (9) | 0.0043 (7) | 0.0035 (7) | 0.0044 (7) |
C9' | 0.0165 (8) | 0.0146 (8) | 0.0172 (8) | −0.0018 (6) | 0.0029 (6) | 0.0021 (6) |
C10' | 0.0192 (8) | 0.0212 (9) | 0.0145 (8) | 0.0069 (7) | 0.0032 (6) | 0.0022 (7) |
C11' | 0.0230 (8) | 0.0219 (9) | 0.0162 (9) | 0.0057 (7) | 0.0042 (7) | 0.0030 (7) |
C12' | 0.0333 (10) | 0.0273 (10) | 0.0167 (9) | 0.0022 (8) | 0.0039 (7) | 0.0041 (7) |
C13' | 0.0476 (12) | 0.0255 (10) | 0.0271 (11) | −0.0074 (9) | 0.0061 (9) | 0.0076 (8) |
C14' | 0.0490 (13) | 0.0324 (11) | 0.0260 (11) | −0.0151 (9) | −0.0035 (9) | 0.0006 (9) |
C15' | 0.0449 (12) | 0.0333 (11) | 0.0173 (10) | −0.0048 (9) | −0.0025 (8) | 0.0021 (8) |
C16' | 0.0273 (9) | 0.0247 (9) | 0.0171 (9) | 0.0032 (7) | 0.0016 (7) | 0.0029 (7) |
C17' | 0.0297 (9) | 0.0262 (9) | 0.0127 (8) | 0.0057 (7) | 0.0010 (7) | 0.0021 (7) |
C18' | 0.0224 (8) | 0.0224 (9) | 0.0189 (9) | 0.0096 (7) | 0.0055 (7) | 0.0052 (7) |
C19' | 0.0287 (9) | 0.0301 (10) | 0.0188 (9) | 0.0113 (8) | 0.0071 (7) | 0.0091 (8) |
C20' | 0.0289 (10) | 0.0282 (10) | 0.0338 (11) | 0.0053 (8) | 0.0093 (8) | 0.0154 (8) |
C21' | 0.0281 (10) | 0.0244 (10) | 0.0342 (11) | −0.0011 (8) | 0.0018 (8) | 0.0073 (8) |
C22' | 0.0228 (9) | 0.0254 (10) | 0.0231 (9) | 0.0027 (7) | −0.0001 (7) | 0.0034 (7) |
C23' | 0.0176 (8) | 0.0221 (9) | 0.0196 (9) | 0.0074 (7) | 0.0039 (6) | 0.0044 (7) |
O5W | 0.0327 (7) | 0.0208 (7) | 0.0273 (7) | 0.0049 (6) | 0.0114 (6) | 0.0016 (6) |
C24 | 0.0246 (9) | 0.0270 (9) | 0.0203 (9) | 0.0109 (7) | 0.0074 (7) | 0.0047 (7) |
C25 | 0.0209 (8) | 0.0247 (9) | 0.0273 (10) | 0.0073 (7) | 0.0060 (7) | 0.0047 (8) |
C26 | 0.0250 (9) | 0.0251 (10) | 0.0335 (11) | 0.0102 (7) | 0.0133 (8) | 0.0095 (8) |
N27 | 0.0351 (9) | 0.0347 (9) | 0.0207 (8) | 0.0109 (7) | 0.0130 (7) | 0.0101 (7) |
C28 | 0.0295 (10) | 0.0440 (12) | 0.0244 (10) | 0.0062 (9) | 0.0032 (8) | 0.0086 (9) |
C29 | 0.0228 (9) | 0.0434 (12) | 0.0244 (10) | 0.0041 (8) | 0.0072 (7) | 0.0098 (9) |
N30 | 0.0234 (8) | 0.0455 (10) | 0.0207 (8) | 0.0071 (7) | 0.0040 (7) | 0.0121 (7) |
C24' | 0.0245 (9) | 0.0236 (9) | 0.0213 (9) | 0.0066 (7) | 0.0069 (7) | 0.0042 (7) |
C25' | 0.0357 (10) | 0.0282 (10) | 0.0216 (10) | 0.0071 (8) | 0.0076 (8) | 0.0066 (8) |
C26' | 0.0356 (10) | 0.0397 (12) | 0.0205 (10) | 0.0097 (9) | 0.0087 (8) | 0.0033 (8) |
N27' | 0.0368 (9) | 0.0291 (9) | 0.0269 (9) | 0.0083 (7) | 0.0054 (7) | −0.0057 (7) |
C28' | 0.0451 (12) | 0.0245 (10) | 0.0336 (11) | 0.0087 (9) | 0.0064 (9) | 0.0051 (8) |
C29' | 0.0406 (11) | 0.0285 (10) | 0.0213 (10) | 0.0099 (8) | 0.0044 (8) | 0.0060 (8) |
N30' | 0.0438 (10) | 0.0225 (8) | 0.0184 (8) | 0.0044 (7) | 0.0067 (7) | 0.0035 (7) |
O1—C1 | 1.2494 (19) | C8'—C9' | 1.375 (2) |
O2—C3 | 1.2610 (19) | C8'—H8' | 0.9500 |
C1—C2 | 1.437 (2) | C10'—C11' | 1.408 (2) |
C1—C9 | 1.502 (2) | C10'—C23' | 1.414 (2) |
C2—C3 | 1.414 (2) | C11'—C12' | 1.429 (2) |
C2—C10 | 1.485 (2) | C11'—C16' | 1.441 (2) |
C3—C4 | 1.510 (2) | C12'—C13' | 1.358 (3) |
C4—C5 | 1.376 (2) | C12'—H12' | 0.9500 |
C4—C9 | 1.391 (2) | C13'—C14' | 1.415 (3) |
C5—C6 | 1.406 (2) | C13'—H13' | 0.9500 |
C5—H5 | 0.9500 | C14'—C15' | 1.352 (3) |
C6—C7 | 1.379 (2) | C14'—H14' | 0.9500 |
C6—H6 | 0.9500 | C15'—C16' | 1.424 (2) |
C7—C8 | 1.400 (2) | C15'—H15' | 0.9500 |
C7—H7 | 0.9500 | C16'—C17' | 1.389 (2) |
C8—C9 | 1.377 (2) | C17'—C18' | 1.390 (2) |
C8—H8 | 0.9500 | C17'—H17' | 0.9500 |
C10—C23 | 1.417 (2) | C18'—C19' | 1.433 (2) |
C10—C11 | 1.417 (2) | C18'—C23' | 1.436 (2) |
C11—C12 | 1.432 (2) | C19'—C20' | 1.352 (3) |
C11—C16 | 1.436 (2) | C19'—H19' | 0.9500 |
C12—C13 | 1.363 (2) | C20'—C21' | 1.415 (3) |
C12—H12 | 0.9500 | C20'—H20' | 0.9500 |
C13—C14 | 1.417 (2) | C21'—C22' | 1.361 (3) |
C13—H13 | 0.9500 | C21'—H21' | 0.9500 |
C14—C15 | 1.350 (2) | C22'—C23' | 1.428 (2) |
C14—H14 | 0.9500 | C22'—H22' | 0.9500 |
C15—C16 | 1.431 (2) | O5W—H5W1 | 0.90 (2) |
C15—H15 | 0.9500 | O5W—H5W2 | 0.86 (2) |
C16—C17 | 1.388 (2) | C24—N30 | 1.336 (2) |
C17—C18 | 1.390 (2) | C24—C25 | 1.407 (2) |
C17—H17 | 0.9500 | C24—C29 | 1.412 (2) |
C18—C19 | 1.430 (2) | C25—C26 | 1.353 (3) |
C18—C23 | 1.441 (2) | C25—H25 | 0.9500 |
C19—C20 | 1.354 (2) | C26—N27 | 1.345 (2) |
C19—H19 | 0.9500 | C26—H26 | 0.9500 |
C20—C21 | 1.417 (2) | N27—C28 | 1.351 (2) |
C20—H20 | 0.9500 | N27—H27 | 0.89 (2) |
C21—C22 | 1.359 (2) | C28—C29 | 1.359 (3) |
C21—H21 | 0.9500 | C28—H28 | 0.9500 |
C22—C23 | 1.430 (2) | C29—H29 | 0.9500 |
C22—H22 | 0.9500 | N30—H30A | 0.91 (2) |
O1'—C1' | 1.2691 (19) | N30—H30B | 0.91 (2) |
O2'—C3' | 1.252 (2) | C24'—N30' | 1.328 (2) |
C1'—C2' | 1.401 (2) | C24'—C29' | 1.412 (3) |
C1'—C9' | 1.499 (2) | C24'—C25' | 1.413 (2) |
C2'—C3' | 1.427 (2) | C25'—C26' | 1.355 (3) |
C2'—C10' | 1.488 (2) | C25'—H25' | 0.9500 |
C3'—C4' | 1.515 (2) | C26'—N27' | 1.346 (3) |
C4'—C5' | 1.378 (2) | C26'—H26' | 0.9500 |
C4'—C9' | 1.391 (2) | N27'—C28' | 1.347 (3) |
C5'—C6' | 1.403 (3) | N27'—H27' | 0.91 (2) |
C5'—H5' | 0.9500 | C28'—C29' | 1.352 (3) |
C6'—C7' | 1.379 (3) | C28'—H28' | 0.9500 |
C6'—H6' | 0.9500 | C29'—H29' | 0.9500 |
C7'—C8' | 1.400 (2) | N30'—H31' | 0.92 (2) |
C7'—H7' | 0.9500 | N30'—H32' | 0.92 (2) |
O1—C1—C2 | 128.78 (15) | C9'—C8'—H8' | 121.1 |
O1—C1—C9 | 123.27 (14) | C7'—C8'—H8' | 121.1 |
C2—C1—C9 | 107.93 (13) | C8'—C9'—C4' | 121.82 (15) |
C3—C2—C1 | 108.24 (13) | C8'—C9'—C1' | 130.58 (15) |
C3—C2—C10 | 128.04 (14) | C4'—C9'—C1' | 107.60 (14) |
C1—C2—C10 | 123.66 (14) | C11'—C10'—C23' | 119.38 (15) |
O2—C3—C2 | 129.61 (15) | C11'—C10'—C2' | 120.81 (15) |
O2—C3—C4 | 122.26 (14) | C23'—C10'—C2' | 119.67 (14) |
C2—C3—C4 | 108.12 (13) | C10'—C11'—C12' | 122.54 (15) |
C5—C4—C9 | 121.13 (15) | C10'—C11'—C16' | 119.90 (15) |
C5—C4—C3 | 131.02 (15) | C12'—C11'—C16' | 117.54 (15) |
C9—C4—C3 | 107.85 (13) | C13'—C12'—C11' | 121.22 (17) |
C4—C5—C6 | 117.85 (15) | C13'—C12'—H12' | 119.4 |
C4—C5—H5 | 121.1 | C11'—C12'—H12' | 119.4 |
C6—C5—H5 | 121.1 | C12'—C13'—C14' | 120.94 (18) |
C7—C6—C5 | 120.92 (15) | C12'—C13'—H13' | 119.5 |
C7—C6—H6 | 119.5 | C14'—C13'—H13' | 119.5 |
C5—C6—H6 | 119.5 | C15'—C14'—C13' | 120.04 (17) |
C6—C7—C8 | 120.78 (15) | C15'—C14'—H14' | 120.0 |
C6—C7—H7 | 119.6 | C13'—C14'—H14' | 120.0 |
C8—C7—H7 | 119.6 | C14'—C15'—C16' | 121.35 (18) |
C9—C8—C7 | 118.00 (15) | C14'—C15'—H15' | 119.3 |
C9—C8—H8 | 121.0 | C16'—C15'—H15' | 119.3 |
C7—C8—H8 | 121.0 | C17'—C16'—C15' | 121.49 (16) |
C8—C9—C4 | 121.32 (15) | C17'—C16'—C11' | 119.55 (15) |
C8—C9—C1 | 130.98 (15) | C15'—C16'—C11' | 118.91 (16) |
C4—C9—C1 | 107.70 (13) | C16'—C17'—C18' | 121.55 (16) |
C23—C10—C11 | 118.94 (14) | C16'—C17'—H17' | 119.2 |
C23—C10—C2 | 120.17 (14) | C18'—C17'—H17' | 119.2 |
C11—C10—C2 | 120.84 (14) | C17'—C18'—C19' | 121.65 (16) |
C10—C11—C12 | 122.17 (14) | C17'—C18'—C23' | 119.30 (15) |
C10—C11—C16 | 120.26 (14) | C19'—C18'—C23' | 118.98 (15) |
C12—C11—C16 | 117.53 (14) | C20'—C19'—C18' | 121.23 (17) |
C13—C12—C11 | 121.62 (16) | C20'—C19'—H19' | 119.4 |
C13—C12—H12 | 119.2 | C18'—C19'—H19' | 119.4 |
C11—C12—H12 | 119.2 | C19'—C20'—C21' | 119.95 (17) |
C12—C13—C14 | 120.34 (16) | C19'—C20'—H20' | 120.0 |
C12—C13—H13 | 119.8 | C21'—C20'—H20' | 120.0 |
C14—C13—H13 | 119.8 | C22'—C21'—C20' | 120.89 (17) |
C15—C14—C13 | 120.24 (15) | C22'—C21'—H21' | 119.6 |
C15—C14—H14 | 119.9 | C20'—C21'—H21' | 119.6 |
C13—C14—H14 | 119.9 | C21'—C22'—C23' | 121.42 (17) |
C14—C15—C16 | 121.58 (16) | C21'—C22'—H22' | 119.3 |
C14—C15—H15 | 119.2 | C23'—C22'—H22' | 119.3 |
C16—C15—H15 | 119.2 | C10'—C23'—C22' | 122.33 (15) |
C17—C16—C15 | 121.49 (15) | C10'—C23'—C18' | 120.19 (15) |
C17—C16—C11 | 119.76 (14) | C22'—C23'—C18' | 117.41 (15) |
C15—C16—C11 | 118.68 (15) | H5W1—O5W—H5W2 | 108 (2) |
C16—C17—C18 | 121.28 (15) | N30—C24—C25 | 120.88 (16) |
C16—C17—H17 | 119.4 | N30—C24—C29 | 122.28 (16) |
C18—C17—H17 | 119.4 | C25—C24—C29 | 116.84 (16) |
C17—C18—C19 | 121.13 (15) | C26—C25—C24 | 119.91 (16) |
C17—C18—C23 | 119.76 (15) | C26—C25—H25 | 120.0 |
C19—C18—C23 | 119.11 (14) | C24—C25—H25 | 120.0 |
C20—C19—C18 | 121.38 (16) | N27—C26—C25 | 121.60 (16) |
C20—C19—H19 | 119.3 | N27—C26—H26 | 119.2 |
C18—C19—H19 | 119.3 | C25—C26—H26 | 119.2 |
C19—C20—C21 | 119.86 (16) | C26—N27—C28 | 120.34 (16) |
C19—C20—H20 | 120.1 | C26—N27—H27 | 116.9 (13) |
C21—C20—H20 | 120.1 | C28—N27—H27 | 122.7 (13) |
C22—C21—C20 | 120.81 (15) | N27—C28—C29 | 120.62 (18) |
C22—C21—H21 | 119.6 | N27—C28—H28 | 119.7 |
C20—C21—H21 | 119.6 | C29—C28—H28 | 119.7 |
C21—C22—C23 | 121.77 (15) | C28—C29—C24 | 120.33 (17) |
C21—C22—H22 | 119.1 | C28—C29—H29 | 119.8 |
C23—C22—H22 | 119.1 | C24—C29—H29 | 119.8 |
C10—C23—C22 | 122.97 (14) | C24—N30—H30A | 119.2 (13) |
C10—C23—C18 | 119.98 (14) | C24—N30—H30B | 120.7 (13) |
C22—C23—C18 | 117.05 (14) | H30A—N30—H30B | 120.1 (19) |
O1'—C1'—C2' | 128.88 (15) | N30'—C24'—C29' | 121.25 (17) |
O1'—C1'—C9' | 122.32 (14) | N30'—C24'—C25' | 121.88 (17) |
C2'—C1'—C9' | 108.79 (14) | C29'—C24'—C25' | 116.87 (16) |
C1'—C2'—C3' | 108.77 (14) | C26'—C25'—C24' | 119.77 (18) |
C1'—C2'—C10' | 122.07 (14) | C26'—C25'—H25' | 120.1 |
C3'—C2'—C10' | 129.16 (14) | C24'—C25'—H25' | 120.1 |
O2'—C3'—C2' | 128.94 (15) | N27'—C26'—C25' | 121.65 (18) |
O2'—C3'—C4' | 123.68 (15) | N27'—C26'—H26' | 119.2 |
C2'—C3'—C4' | 107.37 (14) | C25'—C26'—H26' | 119.2 |
C5'—C4'—C9' | 120.67 (15) | C26'—N27'—C28' | 120.10 (17) |
C5'—C4'—C3' | 131.86 (15) | C26'—N27'—H27' | 118.9 (14) |
C9'—C4'—C3' | 107.46 (14) | C28'—N27'—H27' | 120.9 (14) |
C4'—C5'—C6' | 117.80 (16) | N27'—C28'—C29' | 121.29 (18) |
C4'—C5'—H5' | 121.1 | N27'—C28'—H28' | 119.4 |
C6'—C5'—H5' | 121.1 | C29'—C28'—H28' | 119.4 |
C7'—C6'—C5' | 121.35 (16) | C28'—C29'—C24' | 120.23 (18) |
C7'—C6'—H6' | 119.3 | C28'—C29'—H29' | 119.9 |
C5'—C6'—H6' | 119.3 | C24'—C29'—H29' | 119.9 |
C6'—C7'—C8' | 120.48 (16) | C24'—N30'—H31' | 119.0 (13) |
C6'—C7'—H7' | 119.8 | C24'—N30'—H32' | 117.7 (13) |
C8'—C7'—H7' | 119.8 | H31'—N30'—H32' | 123.1 (18) |
C9'—C8'—C7' | 117.88 (16) | ||
O1—C1—C2—C3 | −174.50 (15) | O2'—C3'—C4'—C5' | 0.4 (3) |
C9—C1—C2—C3 | 3.94 (17) | C2'—C3'—C4'—C5' | −179.40 (19) |
O1—C1—C2—C10 | 2.8 (3) | O2'—C3'—C4'—C9' | 179.25 (16) |
C9—C1—C2—C10 | −178.73 (14) | C2'—C3'—C4'—C9' | −0.55 (18) |
C1—C2—C3—O2 | 175.76 (16) | C9'—C4'—C5'—C6' | 0.0 (3) |
C10—C2—C3—O2 | −1.4 (3) | C3'—C4'—C5'—C6' | 178.71 (18) |
C1—C2—C3—C4 | −3.81 (17) | C4'—C5'—C6'—C7' | −0.1 (3) |
C10—C2—C3—C4 | 179.01 (14) | C5'—C6'—C7'—C8' | 0.3 (3) |
O2—C3—C4—C5 | 2.9 (3) | C6'—C7'—C8'—C9' | −0.3 (3) |
C2—C3—C4—C5 | −177.46 (16) | C7'—C8'—C9'—C4' | 0.3 (2) |
O2—C3—C4—C9 | −177.38 (14) | C7'—C8'—C9'—C1' | −178.94 (16) |
C2—C3—C4—C9 | 2.23 (17) | C5'—C4'—C9'—C8' | −0.1 (3) |
C9—C4—C5—C6 | 0.1 (2) | C3'—C4'—C9'—C8' | −179.09 (15) |
C3—C4—C5—C6 | 179.79 (15) | C5'—C4'—C9'—C1' | 179.27 (16) |
C4—C5—C6—C7 | −0.5 (2) | C3'—C4'—C9'—C1' | 0.27 (17) |
C5—C6—C7—C8 | 0.4 (2) | O1'—C1'—C9'—C8' | 0.2 (3) |
C6—C7—C8—C9 | 0.1 (2) | C2'—C1'—C9'—C8' | 179.38 (16) |
C7—C8—C9—C4 | −0.4 (2) | O1'—C1'—C9'—C4' | −179.10 (15) |
C7—C8—C9—C1 | −179.93 (15) | C2'—C1'—C9'—C4' | 0.11 (18) |
C5—C4—C9—C8 | 0.3 (2) | C1'—C2'—C10'—C11' | 95.13 (19) |
C3—C4—C9—C8 | −179.39 (14) | C3'—C2'—C10'—C11' | −85.7 (2) |
C5—C4—C9—C1 | 179.93 (14) | C1'—C2'—C10'—C23' | −80.5 (2) |
C3—C4—C9—C1 | 0.20 (16) | C3'—C2'—C10'—C23' | 98.7 (2) |
O1—C1—C9—C8 | −4.5 (3) | C23'—C10'—C11'—C12' | −179.66 (16) |
C2—C1—C9—C8 | 177.01 (16) | C2'—C10'—C11'—C12' | 4.7 (2) |
O1—C1—C9—C4 | 176.01 (14) | C23'—C10'—C11'—C16' | 1.8 (2) |
C2—C1—C9—C4 | −2.53 (17) | C2'—C10'—C11'—C16' | −173.79 (15) |
C3—C2—C10—C23 | −124.32 (17) | C10'—C11'—C12'—C13' | −178.22 (18) |
C1—C2—C10—C23 | 58.9 (2) | C16'—C11'—C12'—C13' | 0.3 (3) |
C3—C2—C10—C11 | 58.1 (2) | C11'—C12'—C13'—C14' | −0.7 (3) |
C1—C2—C10—C11 | −118.71 (17) | C12'—C13'—C14'—C15' | 0.4 (4) |
C23—C10—C11—C12 | −178.22 (14) | C13'—C14'—C15'—C16' | 0.2 (4) |
C2—C10—C11—C12 | −0.6 (2) | C14'—C15'—C16'—C17' | 177.1 (2) |
C23—C10—C11—C16 | −0.9 (2) | C14'—C15'—C16'—C11' | −0.5 (3) |
C2—C10—C11—C16 | 176.73 (14) | C10'—C11'—C16'—C17' | 1.2 (3) |
C10—C11—C12—C13 | 177.44 (16) | C12'—C11'—C16'—C17' | −177.38 (16) |
C16—C11—C12—C13 | 0.1 (2) | C10'—C11'—C16'—C15' | 178.87 (17) |
C11—C12—C13—C14 | −0.4 (3) | C12'—C11'—C16'—C15' | 0.3 (3) |
C12—C13—C14—C15 | 0.7 (3) | C15'—C16'—C17'—C18' | −179.51 (18) |
C13—C14—C15—C16 | −0.6 (3) | C11'—C16'—C17'—C18' | −1.9 (3) |
C14—C15—C16—C17 | −176.69 (16) | C16'—C17'—C18'—C19' | −177.28 (16) |
C14—C15—C16—C11 | 0.2 (2) | C16'—C17'—C18'—C23' | −0.4 (3) |
C10—C11—C16—C17 | −0.4 (2) | C17'—C18'—C19'—C20' | 174.59 (17) |
C12—C11—C16—C17 | 177.01 (15) | C23'—C18'—C19'—C20' | −2.3 (2) |
C10—C11—C16—C15 | −177.41 (14) | C18'—C19'—C20'—C21' | −0.8 (3) |
C12—C11—C16—C15 | 0.0 (2) | C19'—C20'—C21'—C22' | 2.6 (3) |
C15—C16—C17—C18 | 178.30 (15) | C20'—C21'—C22'—C23' | −1.4 (3) |
C11—C16—C17—C18 | 1.4 (2) | C11'—C10'—C23'—C22' | 172.70 (15) |
C16—C17—C18—C19 | 179.14 (15) | C2'—C10'—C23'—C22' | −11.7 (2) |
C16—C17—C18—C23 | −1.0 (2) | C11'—C10'—C23'—C18' | −4.2 (2) |
C17—C18—C19—C20 | −178.91 (16) | C2'—C10'—C23'—C18' | 171.49 (14) |
C23—C18—C19—C20 | 1.2 (2) | C21'—C22'—C23'—C10' | −178.62 (17) |
C18—C19—C20—C21 | −0.7 (3) | C21'—C22'—C23'—C18' | −1.7 (2) |
C19—C20—C21—C22 | −0.2 (3) | C17'—C18'—C23'—C10' | 3.5 (2) |
C20—C21—C22—C23 | 0.5 (2) | C19'—C18'—C23'—C10' | −179.55 (15) |
C11—C10—C23—C22 | −178.23 (14) | C17'—C18'—C23'—C22' | −173.52 (15) |
C2—C10—C23—C22 | 4.1 (2) | C19'—C18'—C23'—C22' | 3.4 (2) |
C11—C10—C23—C18 | 1.3 (2) | N30—C24—C25—C26 | 174.32 (17) |
C2—C10—C23—C18 | −176.36 (14) | C29—C24—C25—C26 | −5.8 (3) |
C21—C22—C23—C10 | 179.66 (15) | C24—C25—C26—N27 | 1.2 (3) |
C21—C22—C23—C18 | 0.1 (2) | C25—C26—N27—C28 | 3.2 (3) |
C17—C18—C23—C10 | −0.3 (2) | C26—N27—C28—C29 | −2.8 (3) |
C19—C18—C23—C10 | 179.50 (15) | N27—C28—C29—C24 | −2.1 (3) |
C17—C18—C23—C22 | 179.19 (14) | N30—C24—C29—C28 | −173.90 (19) |
C19—C18—C23—C22 | −1.0 (2) | C25—C24—C29—C28 | 6.2 (3) |
O1'—C1'—C2'—C3' | 178.68 (16) | N30'—C24'—C25'—C26' | −177.03 (18) |
C9'—C1'—C2'—C3' | −0.46 (18) | C29'—C24'—C25'—C26' | 2.9 (3) |
O1'—C1'—C2'—C10' | −2.0 (3) | C24'—C25'—C26'—N27' | −1.1 (3) |
C9'—C1'—C2'—C10' | 178.87 (14) | C25'—C26'—N27'—C28' | −1.7 (3) |
C1'—C2'—C3'—O2' | −179.17 (17) | C26'—N27'—C28'—C29' | 2.5 (3) |
C10'—C2'—C3'—O2' | 1.6 (3) | N27'—C28'—C29'—C24' | −0.6 (3) |
C1'—C2'—C3'—C4' | 0.62 (18) | N30'—C24'—C29'—C28' | 177.86 (18) |
C10'—C2'—C3'—C4' | −178.66 (15) | C25'—C24'—C29'—C28' | −2.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5W—H5W1···O2′i | 0.90 (2) | 1.91 (2) | 2.8064 (19) | 169 (2) |
O5W—H5W2···O2ii | 0.86 (2) | 1.94 (2) | 2.8043 (18) | 177 (2) |
N27—H27···O2 | 0.90 (2) | 1.89 (2) | 2.705 (2) | 150.4 (18) |
N27′—H27′···O1′iii | 0.92 (2) | 1.79 (2) | 2.695 (2) | 169 (2) |
N30—H30A···O2′iv | 0.91 (2) | 2.08 (2) | 2.975 (2) | 167.5 (19) |
N30—H30B···O1′v | 0.91 (2) | 1.97 (2) | 2.863 (2) | 164.3 (19) |
N30′—H31′···O5W | 0.92 (2) | 1.92 (2) | 2.842 (2) | 173 (2) |
N30′—H32′···O1 | 0.92 (2) | 1.92 (2) | 2.8364 (19) | 171 (2) |
C5—H5···O5Wii | 0.95 | 2.59 | 3.451 (2) | 151 |
C5′—H5′···O5Wvi | 0.95 | 2.59 | 3.435 (2) | 148 |
C15′—H15′···Cg1vii | 0.95 | 2.51 | 3.452 (2) | 170 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) x+1, y, z+1; (v) x, y, z+1; (vi) x−1, y, z; (vii) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | 2C5H7N2+·2C23H13O2−·H2O |
Mr | 850.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 116 |
a, b, c (Å) | 9.1990 (3), 13.9977 (6), 17.9153 (7) |
α, β, γ (°) | 100.962 (2), 97.628 (2), 105.265 (2) |
V (Å3) | 2143.78 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.70 × 0.31 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.637, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41534, 7568, 6771 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.097, 1.12 |
No. of reflections | 7568 |
No. of parameters | 610 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005) and SADABS (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O5W—H5W1···O2'i | 0.90 (2) | 1.91 (2) | 2.8064 (19) | 169 (2) |
O5W—H5W2···O2ii | 0.86 (2) | 1.94 (2) | 2.8043 (18) | 177 (2) |
N27—H27···O2 | 0.90 (2) | 1.89 (2) | 2.705 (2) | 150.4 (18) |
N27'—H27'···O1'iii | 0.92 (2) | 1.79 (2) | 2.695 (2) | 169 (2) |
N30—H30A···O2'iv | 0.91 (2) | 2.08 (2) | 2.975 (2) | 167.5 (19) |
N30—H30B···O1'v | 0.91 (2) | 1.97 (2) | 2.863 (2) | 164.3 (19) |
N30'—H31'···O5W | 0.92 (2) | 1.92 (2) | 2.842 (2) | 173 (2) |
N30'—H32'···O1 | 0.92 (2) | 1.92 (2) | 2.8364 (19) | 171 (2) |
C5—H5···O5Wii | 0.95 | 2.59 | 3.451 (2) | 151 |
C5'—H5'···O5Wvi | 0.95 | 2.59 | 3.435 (2) | 148 |
C15'—H15'···Cg1vii | 0.95 | 2.51 | 3.452 (2) | 170 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) x+1, y, z+1; (v) x, y, z+1; (vi) x−1, y, z; (vii) x−1, y, z−1. |
Compound | Anion 1 | Anion 2 | DUCWUT1 | DUCWUT2 | JOTGII |
O1—C1 | 1.2494 (19) | 1.2691 (19) | 1.238 (5) | 1.229 (5) | 1.220 (3) |
O2—C3 | 1.2610 (19) | 1.252 (2) | 1.242 (5) | 1.246 (6) | 1.212 (4) |
C1—C2 | 1.437 (2) | 1.401 (2) | 1.429 (7) | 1.437 (6) | 1.523 (4) |
C2—C3 | 1.414 (2) | 1.427 (2) | 1.426 (6) | 1.425 (6) | 1.530 (3) |
C3—C4 | 1.510 (2) | 1.515 (2) | 1.493 (7) | 1.504 (6) | 1.479 (4) |
C4—C9 | 1.391 (2) | 1.391 (2) | 1.380 (7) | 1.378 (6) | 1.389 (4) |
C1—C9 | 1.502 (2) | 1.499 (2) | 1.507 (6) | 1.513 (6) | 1.480 (3) |
C4—C5 | 1.376 (2) | 1.378 (2) | 1.383 (7) | 1.380 (6) | 1.396 (3) |
C2—C10 | 1.485 (2) | 1.488 (2) | 1.438 (6) | 1.438 (6) | 1.514 (3) |
C10—C11 | 1.417 (2) | 1.408 (2) | 1.410 (6) | 1.406 (6) | 1.383 (3) |
C10—C23 | 1.417 (2) | 1.414 (2) | 1.391 (5) | 1.388 (6) | 1.382 (4) |
C1—C2—C10 | 123.66 (14) | 122.07 (14) | 125.7 (4) | 125.4 (4) | 117.8 (2) |
C3—C2—C10 | 128.04 (14) | 129.16 (14) | 125.8 (4) | 125.4 (4) | 113.3 (2) |
C1—C2—C10—C11 | -118.71 (17) | 95.13 (19) | 3.0 (7) | -6.9 (7) | -140.5 (2) |
Superscripts for DUCWUT refer to the two independent molecules in the structure. The atom labels used are those for anion 1 of (I). |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Organic ionic salts have long been considered as promising materials for use in nonlinear optics (NLO) (Marder et al., 1994). This is because such compounds can exhibit large first-order hyperpolarizabilities (β), can be easily tuned (for example, by changing the counterion), and have high melting points and crystal hardnesses (Yang et al., 2007). By way of example, the crystalline organic salt 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST) is a very promising NLO material and has been shown to have a very large NLO susceptibility, with r11 values of 53 pm V-1 at 1310 nm and 92 pm V-1 at 720 nm (Pan et al., 1996). In our previous work, we have successfully synthesized a series of ionic chromophores in order to observe the impact on the second-order NLO response of changing the donor group, the polarity of the solvent or the counterion (i.e. tosylate, 2-naphthalene sulfonate and iodide) (Teshome et al., 2010). As part of our ongoing work to develop novel NLO materials, we were interested in preparing a compound containing an electron-rich indanedione acceptor, a dihydroanthracene-azo interconnection and a 1,4-dihydropyridinylidene donor unit [viz. compound (3) in the first scheme].
Our initial attempt to prepare this target molecule by adding 2-anthracen-9-yl-indan-1,3-dione to the diazonium salt of 4-aminopyridine (first scheme) was unsuccessful, as we only recovered the original diketone unchanged. One possible reason for this is the lack of stability of the diazonium salt of 4-aminopyridine, (2), which has been reported to be very unstable (Bunsel & Keum, 1983), so it may have decomposed before reacting with the anthracenyl component. Consequently, we decided to prepare the diazonium salt in situ by dissolving the amine and diketone together at 273–278 K and adding sodium nitrite and hydrochloric acid. This resulted in the rapid appearance of an orange precipitate which, following isolation and characterization, was found to be the title compound, (I), and not the desired diazo intermediate. As a matter of procedure we then resynthesized (I) using the method described in the Experimental section, which involves coupling the sodium salt of 2-anthracen-9-yl-indan-1,3-dione with 4-aminopyridinium chloride.
Only one structure, 1-n-butyl-3-(indan-1,3-dionyl-2)pyridinium [Cambridge Structural Database (CSD, Version 5.32 with November 2010 updates; Allen, 2002) refcode DUCWUT; Magomedova & Bel'skii, 1986], has been reported in which deprotonation of the indan-1,3-dione ring has occurred, but in that case the coordinated pyridinium ring is formally charged, giving overall molecular neutrality. There are 25 structures in the CSD containing the neutral -1H-indene-1,3(2H)-dione entity, for example JOTGII (Kolev et al., 1992), but (I) represents the first report of a unique 3-oxo-3H-inden-1-olate anion coupled with the (more commonly observed) 4-aminopyridinium cation.
A view of the asymmetric unit contents and atom-labelling scheme of (I) is shown in Fig. 1. Along with a single water molecule, there are two independent cations and anions, with the labels of the second matching the first with an appended apostrophe (e.g. C2 and C2'). There are minor differences in bond lengths and angles between the two anions, with examples given in Table 1. The non-hydrogen bond lengths have an r.m.s. fit of 0.0055 Å for the two anions, compared with an r.m.s. fit of 0.0044 Å for the two cations (PLATON; Spek, 2009). As shown in Table 1, the anions have quite different geometries from a typical -1H-indene-1,3(2H)-dione molecule (JOTGII), particularly with respect to the bond lengths of the five-membered ring, but they are somewhat similar to those found in the two independent molecules in the DUCWUT structure. Specifically, the C1—C2 and C2—C3 distances average to shorter distances of 1.420 (14) Å in (I) and 1.429 (5) Å in DUCWUT, compared with 1.526 (4) Å in JOTGII [an average of 1.538 (11) Å was found for these bonds in four similar molecules, SEZKAK (Kumar et al., 2007), CEZCAM (Das et al., 2007) and HOHWIK (Siaka et al., 1998; two symmetry-independent molecules)]. Likewise, the C3—C4 and C1—C9 bonds average to longer values of 1.507 (7) Å in (I) and 1.504 (8) Å in DUCWUT, compared with 1.479 (1) Å for JOTGII. Of all the remaining bond lengths in the anions, including the six-membered ring, only two are significantly different: the average of the C5—C6 and C7–C8 bonds in (I), at 1.404 (3) Å, is slightly longer than its counterparts of 1.391 (13) Å in DUCWUT and 1.377 (6) Å in JOTGII [an average value of 1.375 (8) Å was found in the set of similar structures noted above]. The C6—C7 distances are shorter, at 1.379 (2) and 1.363 (11) Å in (I) and DUCWUT, respectively, compared with 1.395 (4) Å in JOTGII. The geometry of the anthracenyl part of the anion is identical with that reported for 3-(9-anthryl)-1-methoxy-1H-2,3-dihydrobenz(de)anthracene (PAMRIE; Langer & Becker, 1992) and 2-(9-anthryl)-2-propanol (VAFNEV01; Langer & Becker, 1993), except for the connection link (C2—C10) bonds which are single-bond lengths in these compounds. The likely source of these variations in geometry is discussed below.
The individual five- and six-membered rings vary from being statistically planar [e.g. atoms C11–C16, mean out-of-plane distance of the constituent atoms = 0.003 (2) Å; atoms C4'–C9', mean out-of-plane distance = 0.001 (2) Å] to approximately planar [e.g. atoms C1–C4/C9 = 0.026 (2) Å]. Both the 3-oxo-3H-inden-1-olate and anthracyl rings are essentially planar, with average mean out-of-plane distances for both independent anions of 0.013 (2) and 0.038 (2) Å, respectively. The most significant difference between the two anions involves the relative orientations of these anthracenyl and indan-1,3,-dione rings: the interplanar angles are 59.07 (5) and 83.92 (5)° for the anions containing atoms O1 and O1', respectively. Even more significant is the fact that, in the only really comparative structure (DUWCUT), the interplanar angles are much closer to, but not exactly, zero, at 6.1 (2) and 10.4 (2)° for the two independent molecules. Examination of the intermolecular packing (Fig. 2) confirms that these ring orientations allow close hydrogen-bonding contacts between anion and cation acceptors and donors, and a C—H···π interaction. It seems likely that the anion charge here is localized on the 3-oxo-3H-inden-1-olate rings, rather than partially delocalized through both rings as seen in DUCWUT; indeed, this would enhance the acceptor status of the O atoms. This is consistent with the fact that the link bond C2—C10 is significantly shorter in DUCWUT by 0.048 (7) Å, and with the bond-length differences noted above with shorter average C1—C2 and C2—C3 distances.
Over 88 compounds containing the 4-aminopyridinium cation are found in the CSD and those reported here show identical dimensions. For example, the average C24—N30(amino) distance here is 1.332 (2) Å, compared with 1.328 (2) Å in 4-aminopyridinium picrate (KUVLAP; Ramesh et al., 2010).
Overall, the crystal packing of (I) is dominated by strong (classical) hydrogen bonds (Table 2 and Fig. 2), building a three-dimensional matrix based on D(2) primary graph-set motifs (Bernstein et al., 1995) using all amine and water H atoms. These motifs combine to generate three discrete D12(3) secondary motifs which involve bifurcated interactions at the acceptor atoms (e.g. O2, entries 1 and 5 in Table 2) and sets of D22(n) motifs, where n = 4, 5, 7, 8 or 9. Thus, the ketone O atoms act as acceptors for both amine and pyridinium donors of the 4-aminopyridinium cation. The single water molecule acts as a hydrogen-bond donor to the two independent anions, and as an acceptor to the amino H atom of one 4-aminopyridinium cation. The alignment of the anthracyl groups permits a significant C—H···π interaction (last entry in Table 2) between two symmetry-independent anions. There are also very weak C—H···O interactions with water atom O5W, which are included in Table 2 for completeness, and other fortuitous weak C—H···π interactions, but no significant π–π interactions.
This packing is in striking contrast with that of the related compound DUCWUT, where lattice binding is provided by C—H···O interactions only, with no C—H···π-type or other interactions involving the pyridinium ring atoms. It is noteworthy that, although the D(2) motif interactions are observed in DUWUT, there are also several intramolecular C—H···O interactions displaying the S(6) motif that are only possible because of the near coplanarity of the adjacent indan-1,3-dionyl and pyridinium rings (dihedral angle ~0°; Table 1, last entry).
The formation of this unexpected product, (I), is considered to be due to the negative charge on the 2-anthracenyl indanedione anion residing predominately across the 1–3 diketone system. Therefore, it is not able to impart the requisite negative charge on to the anthracene unit to make it sufficiently reactive toward the diazonium salt derived from 4-aminopyridine. Consequently, formation of the title salt occurs in preference and the equilibrium of the reaction is presumably driven by precipitation. Alternative synthetic routes are under investigation.