Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112033781/em3051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112033781/em3051Isup2.hkl |
CCDC reference: 908136
For related literature, see: Aakeröy et al. (2010); Allen (2002); Beatty et al. (2002); Bernstein et al. (1995); Boufas et al. (2006, 2007); Jeffrey (1997); Lemmerer & Billing (2006); Zon et al. (2011).
All chemicals were obtained commercially, with the exception of 5-(dihydroxyphosphoryl)pyridine-3-carboxylic acid, which was synthesized according to the method of Zon et al. (2011). For the preparation of the title compound, 5-(dihydroxyphosphoryl)pyridine-3-carboxylic acid (20 mg, 0.1 mmol) in distilled water (1.7 ml) and 1,5-diaminonaphthalene (8 mg, 0.05 mmol) in ethanol (0.5 ml) were dissolved with stirring and heating. These solutions were then mixed and the resulting mixture was allowed to evaporate slowly at room temperature. After one week, colourless parallelepiped-shaped crystals of (I) were grown.
H atoms attached to aromatic rings were loctated in their geometric positions, with Uiso(H) = 1.2Ueq(C). The H atoms of the NH2 and NH3 groups were located from Δρ maps and their positions (except for H52C, which was restrained with N52—H52C = 0.88 Å) were refined, with Uiso(H) = 1.5Ueq(N). The positions of the H atoms of the phosphonate groups (except for H13O, H33O and H43O which were restrained with O—H = 0.83 Å) were refined, with Uiso(H) = 1.5Ueq(O).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
3C10H12N22+·2C10H11N2+·8C6H5NO5P− | F(000) = 2504 |
Mr = 2415.70 | Dx = 1.476 Mg m−3 Dm = 1.47 Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1252 reflections |
a = 14.306 (3) Å | θ = 2.4–29.5° |
b = 26.675 (5) Å | µ = 0.23 mm−1 |
c = 14.436 (3) Å | T = 295 K |
β = 99.26 (3)° | Parallelepiped, colourless |
V = 5437.2 (19) Å3 | 0.42 × 0.20 × 0.12 mm |
Z = 2 |
Kuma KM-4 diffractometer with a CCD area detector | 13812 independent reflections |
Radiation source: fine-focus sealed tube | 6933 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 29.5°, θmin = 2.4° |
ω scans | h = −19→19 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | k = −36→36 |
Tmin = 0.917, Tmax = 0.975 | l = −18→19 |
71634 measured reflections |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0235P)2] where P = (Fo2 + 2Fc2)/3 |
13812 reflections | (Δ/σ)max = 0.001 |
805 parameters | Δρmax = 0.37 e Å−3 |
4 restraints | Δρmin = −0.30 e Å−3 |
3C10H12N22+·2C10H11N2+·8C6H5NO5P− | V = 5437.2 (19) Å3 |
Mr = 2415.70 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.306 (3) Å | µ = 0.23 mm−1 |
b = 26.675 (5) Å | T = 295 K |
c = 14.436 (3) Å | 0.42 × 0.20 × 0.12 mm |
β = 99.26 (3)° |
Kuma KM-4 diffractometer with a CCD area detector | 13812 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 6933 reflections with I > 2σ(I) |
Tmin = 0.917, Tmax = 0.975 | Rint = 0.086 |
71634 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 4 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.37 e Å−3 |
13812 reflections | Δρmin = −0.30 e Å−3 |
805 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 | ||
P11 | 0.19150 (4) | 0.58733 (2) | 0.14201 (4) | 0.02849 (15) | |
O11 | 0.25434 (10) | 0.56097 (5) | 0.08437 (10) | 0.0380 (4) | |
O12 | 0.20782 (10) | 0.57738 (5) | 0.24693 (9) | 0.0396 (4) | |
O13 | 0.08658 (11) | 0.57563 (6) | 0.10571 (9) | 0.0419 (4) | |
H13O | 0.0718 (17) | 0.5741 (9) | 0.0475 (4) | 0.063* | |
N11 | 0.21789 (16) | 0.73630 (8) | 0.19352 (14) | 0.0529 (6) | |
C16 | 0.22057 (18) | 0.75480 (9) | 0.10678 (17) | 0.0523 (7) | |
H16 | 0.2256 | 0.7893 | 0.1002 | 0.063* | |
C15 | 0.21621 (18) | 0.72536 (9) | 0.02714 (16) | 0.0422 (6) | |
C14 | 0.20866 (15) | 0.67387 (8) | 0.03705 (15) | 0.0353 (6) | |
H14 | 0.2060 | 0.6529 | −0.0148 | 0.042* | |
C13 | 0.20514 (15) | 0.65383 (8) | 0.12557 (15) | 0.0302 (6) | |
C12 | 0.20997 (16) | 0.68638 (9) | 0.20127 (16) | 0.0427 (7) | |
H12 | 0.2076 | 0.6729 | 0.2603 | 0.051* | |
C17 | 0.2173 (2) | 0.75001 (11) | −0.06629 (18) | 0.0544 (8) | |
O14 | 0.21404 (17) | 0.79450 (7) | −0.07731 (12) | 0.0873 (7) | |
O15 | 0.22231 (15) | 0.71763 (7) | −0.13559 (12) | 0.0660 (6) | |
H15O | 0.225 (2) | 0.7338 (10) | −0.193 (2) | 0.099* | |
P21 | 0.43085 (4) | 0.58811 (2) | 0.40406 (4) | 0.02989 (15) | |
O21 | 0.47073 (10) | 0.56361 (5) | 0.32552 (10) | 0.0386 (4) | |
O22 | 0.47204 (10) | 0.57087 (5) | 0.50130 (9) | 0.0385 (4) | |
O23 | 0.32322 (11) | 0.58073 (6) | 0.39547 (10) | 0.0452 (5) | |
H23O | 0.2893 (18) | 0.5820 (9) | 0.3400 (17) | 0.068* | |
N21 | 0.46976 (16) | 0.73533 (8) | 0.46834 (16) | 0.0604 (7) | |
C26 | 0.4735 (2) | 0.75465 (10) | 0.3829 (2) | 0.0606 (8) | |
H26 | 0.4806 | 0.7892 | 0.3788 | 0.073* | |
C25 | 0.46784 (18) | 0.72762 (10) | 0.30147 (18) | 0.0492 (7) | |
C24 | 0.45678 (16) | 0.67622 (9) | 0.30817 (17) | 0.0432 (6) | |
H24 | 0.4537 | 0.6563 | 0.2549 | 0.052* | |
C23 | 0.45031 (15) | 0.65421 (8) | 0.39496 (16) | 0.0358 (6) | |
C22 | 0.45722 (18) | 0.68485 (10) | 0.47309 (18) | 0.0506 (7) | |
H22 | 0.4532 | 0.6704 | 0.5310 | 0.061* | |
C27 | 0.4717 (2) | 0.75319 (12) | 0.2077 (2) | 0.0610 (8) | |
O24 | 0.47127 (17) | 0.79693 (8) | 0.19879 (13) | 0.0905 (7) | |
O25 | 0.47405 (15) | 0.72029 (7) | 0.13682 (13) | 0.0733 (6) | |
H25O | 0.470 (2) | 0.7428 (11) | 0.081 (2) | 0.110* | |
P31 | 0.67845 (4) | 0.58464 (2) | 0.67169 (4) | 0.02840 (15) | |
O32 | 0.71628 (10) | 0.56461 (5) | 0.76867 (9) | 0.0370 (4) | |
O31 | 0.71179 (10) | 0.56102 (5) | 0.58823 (9) | 0.0343 (4) | |
O33 | 0.56945 (10) | 0.58109 (6) | 0.66351 (10) | 0.0420 (4) | |
H33O | 0.5400 (15) | 0.5804 (9) | 0.6085 (7) | 0.063* | |
N31 | 0.72101 (15) | 0.73034 (7) | 0.74841 (13) | 0.0467 (6) | |
C36 | 0.72485 (18) | 0.75225 (9) | 0.66482 (17) | 0.0470 (7) | |
H36 | 0.7309 | 0.7869 | 0.6633 | 0.056* | |
C35 | 0.72033 (17) | 0.72625 (8) | 0.58091 (15) | 0.0383 (6) | |
C34 | 0.70993 (15) | 0.67475 (8) | 0.58365 (15) | 0.0353 (6) | |
H34 | 0.7074 | 0.6560 | 0.5289 | 0.042* | |
C33 | 0.70325 (15) | 0.65076 (8) | 0.66831 (15) | 0.0300 (5) | |
C32 | 0.70960 (16) | 0.68057 (9) | 0.74877 (16) | 0.0399 (6) | |
H32 | 0.7057 | 0.6650 | 0.8056 | 0.048* | |
C37 | 0.72391 (19) | 0.75401 (10) | 0.49070 (17) | 0.0485 (7) | |
O34 | 0.72481 (16) | 0.79847 (7) | 0.48516 (12) | 0.0811 (7) | |
O35 | 0.72251 (15) | 0.72380 (6) | 0.41730 (12) | 0.0656 (6) | |
H35O | 0.724 (2) | 0.7418 (10) | 0.367 (2) | 0.098* | |
P41 | 0.95719 (4) | 0.58552 (2) | 0.85731 (4) | 0.02967 (15) | |
O41 | 1.03512 (11) | 0.56885 (6) | 0.93215 (10) | 0.0467 (4) | |
O42 | 0.95404 (10) | 0.56276 (5) | 0.76187 (9) | 0.0351 (4) | |
O43 | 0.86068 (11) | 0.57732 (6) | 0.89379 (9) | 0.0390 (4) | |
H43O | 0.8154 (11) | 0.5767 (9) | 0.8493 (11) | 0.058* | |
N41 | 0.96989 (15) | 0.73456 (8) | 0.91432 (14) | 0.0517 (6) | |
C46 | 0.97216 (18) | 0.75403 (9) | 0.82857 (17) | 0.0503 (7) | |
H46 | 0.9751 | 0.7887 | 0.8235 | 0.060* | |
C45 | 0.97046 (17) | 0.72645 (9) | 0.74836 (16) | 0.0411 (6) | |
C44 | 0.96652 (15) | 0.67458 (9) | 0.75615 (15) | 0.0369 (6) | |
H44 | 0.9655 | 0.6545 | 0.7033 | 0.044* | |
C43 | 0.96418 (15) | 0.65265 (8) | 0.84339 (15) | 0.0319 (6) | |
C42 | 0.96613 (17) | 0.68434 (9) | 0.92045 (17) | 0.0444 (7) | |
H42 | 0.9648 | 0.6700 | 0.9790 | 0.053* | |
C47 | 0.97065 (19) | 0.75233 (11) | 0.65457 (17) | 0.0494 (7) | |
O45 | 0.97263 (14) | 0.72025 (7) | 0.58328 (12) | 0.0625 (6) | |
H45O | 0.9681 (19) | 0.7388 (10) | 0.5252 (19) | 0.094* | |
O44 | 0.96863 (15) | 0.79647 (7) | 0.64641 (12) | 0.0729 (6) | |
N51 | 0.40999 (14) | 0.50679 (8) | 0.17459 (14) | 0.0340 (5) | |
H51A | 0.3697 (15) | 0.4812 (8) | 0.1893 (14) | 0.051* | |
H51B | 0.3725 (16) | 0.5236 (8) | 0.1348 (15) | 0.051* | |
H51C | 0.4217 (15) | 0.5282 (8) | 0.2274 (15) | 0.051* | |
C50 | 0.55862 (16) | 0.52203 (9) | 0.11196 (14) | 0.0318 (6) | |
C51 | 0.49587 (16) | 0.48772 (9) | 0.14457 (14) | 0.0345 (6) | |
C52 | 0.51630 (18) | 0.43825 (9) | 0.15455 (16) | 0.0456 (7) | |
H52 | 0.4735 | 0.4166 | 0.1759 | 0.055* | |
C53 | 0.60085 (18) | 0.41977 (10) | 0.13306 (17) | 0.0530 (7) | |
H53 | 0.6145 | 0.3858 | 0.1401 | 0.064* | |
C54 | 0.66363 (17) | 0.45091 (9) | 0.10190 (15) | 0.0431 (6) | |
H54 | 0.7205 | 0.4381 | 0.0886 | 0.052* | |
C55 | 0.70562 (16) | 0.53676 (9) | 0.05472 (15) | 0.0354 (6) | |
C56 | 0.68597 (18) | 0.58615 (10) | 0.04459 (16) | 0.0473 (7) | |
H56 | 0.7285 | 0.6075 | 0.0220 | 0.057* | |
C57 | 0.60205 (19) | 0.60504 (9) | 0.06791 (18) | 0.0513 (7) | |
H57 | 0.5886 | 0.6391 | 0.0609 | 0.062* | |
C58 | 0.53972 (17) | 0.57398 (9) | 0.10089 (15) | 0.0437 (6) | |
H58 | 0.4839 | 0.5870 | 0.1164 | 0.052* | |
N52 | 0.79499 (15) | 0.51784 (9) | 0.03113 (14) | 0.0406 (5) | |
H52A | 0.8221 (16) | 0.5392 (9) | −0.0081 (15) | 0.061* | |
H52B | 0.7894 (17) | 0.4867 (9) | 0.0034 (16) | 0.061* | |
H52C | 0.8414 (12) | 0.5129 (9) | 0.0779 (11) | 0.061* | |
C59 | 0.64392 (16) | 0.50278 (8) | 0.08915 (14) | 0.0315 (5) | |
N61 | 0.62132 (15) | 0.50993 (8) | 0.43251 (15) | 0.0361 (5) | |
H61A | 0.5919 (16) | 0.4836 (9) | 0.4558 (16) | 0.054* | |
H61B | 0.5766 (16) | 0.5251 (8) | 0.3959 (16) | 0.054* | |
H61C | 0.6435 (16) | 0.5285 (8) | 0.4873 (16) | 0.054* | |
N62 | 0.93560 (16) | 0.53489 (9) | 0.19443 (15) | 0.0515 (6) | |
H62A | 0.9674 (18) | 0.5643 (9) | 0.1768 (17) | 0.077* | |
H62B | 0.9616 (18) | 0.5011 (9) | 0.2064 (17) | 0.077* | |
C60 | 0.74690 (15) | 0.53140 (9) | 0.34380 (14) | 0.0332 (6) | |
C61 | 0.69710 (16) | 0.49387 (9) | 0.38467 (15) | 0.0347 (6) | |
C62 | 0.71815 (17) | 0.44480 (9) | 0.38152 (17) | 0.0477 (7) | |
H62 | 0.6834 | 0.4214 | 0.4095 | 0.057* | |
C63 | 0.79192 (18) | 0.42920 (10) | 0.33640 (18) | 0.0549 (7) | |
H63 | 0.8074 | 0.3954 | 0.3352 | 0.066* | |
C64 | 0.84114 (17) | 0.46318 (10) | 0.29433 (17) | 0.0468 (7) | |
H64 | 0.8895 | 0.4522 | 0.2633 | 0.056* | |
C65 | 0.87102 (17) | 0.55138 (10) | 0.25132 (16) | 0.0415 (6) | |
C66 | 0.85018 (19) | 0.60099 (10) | 0.25674 (17) | 0.0534 (7) | |
H66 | 0.8836 | 0.6245 | 0.2275 | 0.064* | |
C67 | 0.7791 (2) | 0.61686 (10) | 0.30587 (18) | 0.0587 (8) | |
H67 | 0.7669 | 0.6509 | 0.3105 | 0.070* | |
C68 | 0.72690 (17) | 0.58286 (9) | 0.34747 (16) | 0.0463 (6) | |
H68 | 0.6783 | 0.5939 | 0.3781 | 0.056* | |
C69 | 0.82118 (16) | 0.51489 (9) | 0.29615 (15) | 0.0354 (6) | |
N71 | 0.85970 (14) | 0.49642 (7) | 0.64266 (13) | 0.0288 (5) | |
H71A | 0.8416 (15) | 0.4712 (8) | 0.6790 (14) | 0.043* | |
H71B | 0.8079 (15) | 0.5120 (8) | 0.6087 (14) | 0.043* | |
H71C | 0.8916 (15) | 0.5169 (8) | 0.6878 (15) | 0.043* | |
C70 | 0.96786 (14) | 0.51004 (8) | 0.52792 (13) | 0.0258 (5) | |
C71 | 0.92107 (14) | 0.47602 (8) | 0.58019 (14) | 0.0271 (5) | |
C72 | 0.93412 (16) | 0.42599 (8) | 0.57639 (15) | 0.0374 (6) | |
H72 | 0.9015 | 0.4046 | 0.6107 | 0.045* | |
C77 | 1.00322 (17) | 0.59357 (9) | 0.47923 (15) | 0.0432 (6) | |
H77 | 0.9946 | 0.6281 | 0.4820 | 0.052* | |
C78 | 0.95456 (16) | 0.56246 (9) | 0.52948 (14) | 0.0362 (6) | |
H78 | 0.9121 | 0.5760 | 0.5652 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P11 | 0.0314 (4) | 0.0329 (4) | 0.0213 (3) | −0.0031 (3) | 0.0044 (3) | 0.0028 (3) |
O11 | 0.0411 (10) | 0.0357 (9) | 0.0393 (9) | 0.0033 (8) | 0.0129 (8) | −0.0018 (7) |
O12 | 0.0452 (10) | 0.0472 (10) | 0.0243 (8) | −0.0112 (8) | −0.0004 (7) | 0.0083 (7) |
O13 | 0.0324 (10) | 0.0667 (12) | 0.0256 (9) | −0.0143 (8) | 0.0019 (8) | 0.0001 (9) |
N11 | 0.0901 (18) | 0.0364 (14) | 0.0336 (13) | −0.0017 (12) | 0.0138 (12) | −0.0032 (10) |
C16 | 0.084 (2) | 0.0297 (15) | 0.0432 (17) | −0.0017 (14) | 0.0098 (15) | 0.0009 (13) |
C15 | 0.0603 (18) | 0.0360 (16) | 0.0303 (15) | −0.0029 (13) | 0.0077 (13) | 0.0037 (12) |
C14 | 0.0471 (16) | 0.0344 (15) | 0.0251 (13) | −0.0019 (12) | 0.0080 (12) | −0.0015 (11) |
C13 | 0.0327 (14) | 0.0326 (14) | 0.0253 (13) | 0.0007 (11) | 0.0050 (11) | 0.0000 (11) |
C12 | 0.0604 (18) | 0.0414 (16) | 0.0278 (14) | 0.0015 (14) | 0.0120 (13) | 0.0010 (12) |
C17 | 0.089 (2) | 0.0386 (18) | 0.0360 (17) | −0.0046 (16) | 0.0130 (15) | 0.0041 (15) |
O14 | 0.177 (2) | 0.0388 (12) | 0.0483 (12) | −0.0090 (14) | 0.0264 (13) | 0.0102 (10) |
O15 | 0.1230 (18) | 0.0448 (12) | 0.0331 (11) | −0.0035 (11) | 0.0215 (12) | 0.0084 (9) |
P21 | 0.0312 (4) | 0.0325 (4) | 0.0252 (3) | −0.0028 (3) | 0.0023 (3) | 0.0013 (3) |
O21 | 0.0438 (10) | 0.0380 (10) | 0.0342 (9) | −0.0001 (8) | 0.0068 (8) | −0.0051 (7) |
O22 | 0.0386 (10) | 0.0450 (10) | 0.0294 (9) | −0.0036 (8) | −0.0018 (8) | 0.0063 (7) |
O23 | 0.0330 (10) | 0.0691 (12) | 0.0322 (9) | −0.0098 (9) | 0.0006 (8) | 0.0055 (9) |
N21 | 0.0884 (19) | 0.0420 (15) | 0.0511 (15) | −0.0001 (13) | 0.0118 (13) | −0.0138 (12) |
C26 | 0.085 (2) | 0.0409 (18) | 0.055 (2) | −0.0034 (16) | 0.0113 (17) | 0.0076 (16) |
C25 | 0.0590 (19) | 0.0395 (17) | 0.0474 (18) | −0.0003 (14) | 0.0032 (15) | 0.0012 (14) |
C24 | 0.0527 (17) | 0.0363 (16) | 0.0401 (16) | −0.0030 (13) | 0.0062 (13) | 0.0032 (12) |
C23 | 0.0375 (15) | 0.0335 (15) | 0.0355 (15) | 0.0020 (11) | 0.0029 (12) | −0.0041 (12) |
C22 | 0.0625 (19) | 0.0419 (17) | 0.0467 (17) | 0.0020 (15) | 0.0067 (14) | −0.0034 (14) |
C27 | 0.087 (2) | 0.046 (2) | 0.051 (2) | −0.0028 (18) | 0.0152 (17) | 0.0062 (17) |
O24 | 0.159 (2) | 0.0514 (14) | 0.0626 (14) | −0.0065 (14) | 0.0234 (14) | 0.0184 (11) |
O25 | 0.1219 (19) | 0.0603 (14) | 0.0405 (12) | 0.0028 (12) | 0.0213 (12) | 0.0095 (10) |
P31 | 0.0307 (4) | 0.0287 (3) | 0.0259 (3) | −0.0021 (3) | 0.0046 (3) | 0.0003 (3) |
O32 | 0.0367 (10) | 0.0403 (10) | 0.0321 (9) | −0.0066 (8) | 0.0001 (8) | 0.0092 (7) |
O31 | 0.0366 (10) | 0.0341 (9) | 0.0333 (9) | 0.0000 (7) | 0.0089 (7) | −0.0040 (7) |
O33 | 0.0291 (10) | 0.0661 (12) | 0.0306 (9) | −0.0078 (9) | 0.0041 (8) | −0.0025 (9) |
N31 | 0.0779 (16) | 0.0332 (13) | 0.0303 (12) | −0.0044 (11) | 0.0124 (11) | −0.0060 (10) |
C36 | 0.074 (2) | 0.0234 (14) | 0.0442 (17) | 0.0000 (13) | 0.0129 (14) | −0.0011 (12) |
C35 | 0.0586 (18) | 0.0278 (14) | 0.0293 (14) | 0.0014 (12) | 0.0094 (12) | 0.0005 (11) |
C34 | 0.0464 (16) | 0.0310 (14) | 0.0287 (14) | 0.0007 (12) | 0.0071 (12) | −0.0053 (11) |
C33 | 0.0355 (14) | 0.0293 (13) | 0.0244 (12) | 0.0015 (11) | 0.0023 (11) | 0.0005 (11) |
C32 | 0.0555 (17) | 0.0351 (15) | 0.0294 (14) | −0.0021 (13) | 0.0081 (12) | −0.0002 (12) |
C37 | 0.078 (2) | 0.0306 (15) | 0.0392 (16) | 0.0029 (15) | 0.0172 (14) | −0.0013 (13) |
O34 | 0.165 (2) | 0.0303 (11) | 0.0535 (12) | 0.0048 (12) | 0.0350 (13) | 0.0056 (9) |
O35 | 0.1378 (19) | 0.0342 (11) | 0.0290 (11) | 0.0061 (11) | 0.0266 (12) | 0.0054 (8) |
P41 | 0.0333 (4) | 0.0335 (4) | 0.0215 (3) | −0.0038 (3) | 0.0022 (3) | −0.0006 (3) |
O41 | 0.0464 (11) | 0.0551 (11) | 0.0338 (9) | 0.0034 (8) | −0.0080 (8) | 0.0012 (8) |
O42 | 0.0378 (9) | 0.0399 (9) | 0.0275 (8) | −0.0027 (8) | 0.0052 (7) | −0.0071 (7) |
O43 | 0.0385 (10) | 0.0534 (11) | 0.0256 (9) | −0.0111 (9) | 0.0067 (7) | 0.0009 (8) |
N41 | 0.0770 (17) | 0.0401 (14) | 0.0392 (14) | −0.0047 (12) | 0.0127 (12) | −0.0110 (11) |
C46 | 0.076 (2) | 0.0375 (16) | 0.0387 (16) | −0.0012 (14) | 0.0126 (14) | 0.0061 (13) |
C45 | 0.0510 (17) | 0.0414 (16) | 0.0323 (15) | −0.0034 (13) | 0.0109 (13) | 0.0014 (12) |
C44 | 0.0445 (16) | 0.0380 (15) | 0.0290 (14) | −0.0041 (12) | 0.0086 (12) | −0.0027 (12) |
C43 | 0.0321 (14) | 0.0363 (14) | 0.0276 (13) | −0.0050 (11) | 0.0056 (11) | −0.0068 (11) |
C42 | 0.0572 (18) | 0.0400 (16) | 0.0369 (15) | −0.0051 (13) | 0.0103 (13) | −0.0015 (13) |
C47 | 0.069 (2) | 0.0433 (18) | 0.0372 (17) | −0.0036 (15) | 0.0117 (14) | 0.0025 (15) |
O45 | 0.1134 (17) | 0.0478 (12) | 0.0298 (11) | 0.0007 (11) | 0.0221 (11) | 0.0051 (9) |
O44 | 0.1316 (19) | 0.0413 (12) | 0.0500 (12) | 0.0010 (12) | 0.0276 (12) | 0.0114 (10) |
N51 | 0.0313 (13) | 0.0419 (14) | 0.0308 (12) | −0.0049 (10) | 0.0110 (10) | −0.0043 (10) |
C50 | 0.0369 (15) | 0.0364 (14) | 0.0227 (13) | −0.0051 (11) | 0.0070 (11) | −0.0034 (10) |
C51 | 0.0386 (15) | 0.0412 (15) | 0.0263 (13) | −0.0065 (12) | 0.0129 (11) | −0.0047 (11) |
C52 | 0.0564 (18) | 0.0374 (15) | 0.0492 (16) | −0.0084 (13) | 0.0268 (14) | −0.0011 (13) |
C53 | 0.068 (2) | 0.0368 (16) | 0.0625 (18) | 0.0021 (15) | 0.0362 (15) | 0.0051 (14) |
C54 | 0.0474 (17) | 0.0435 (16) | 0.0416 (15) | 0.0054 (13) | 0.0170 (13) | 0.0024 (12) |
C55 | 0.0339 (15) | 0.0435 (16) | 0.0299 (13) | −0.0031 (12) | 0.0081 (11) | −0.0027 (12) |
C56 | 0.0502 (17) | 0.0441 (16) | 0.0510 (16) | −0.0101 (14) | 0.0183 (13) | −0.0026 (14) |
C57 | 0.0611 (19) | 0.0291 (14) | 0.0676 (19) | −0.0012 (14) | 0.0224 (16) | 0.0045 (13) |
C58 | 0.0500 (17) | 0.0407 (16) | 0.0435 (15) | 0.0017 (13) | 0.0165 (13) | −0.0016 (12) |
N52 | 0.0375 (14) | 0.0479 (14) | 0.0396 (14) | −0.0078 (12) | 0.0157 (10) | −0.0026 (11) |
C59 | 0.0344 (14) | 0.0369 (14) | 0.0247 (12) | −0.0035 (11) | 0.0092 (11) | −0.0019 (10) |
N61 | 0.0345 (14) | 0.0407 (14) | 0.0337 (13) | 0.0012 (10) | 0.0073 (10) | 0.0014 (10) |
N62 | 0.0458 (15) | 0.0639 (17) | 0.0494 (14) | −0.0017 (12) | 0.0215 (11) | 0.0060 (13) |
C60 | 0.0323 (14) | 0.0395 (15) | 0.0268 (13) | 0.0004 (12) | 0.0018 (11) | −0.0029 (11) |
C61 | 0.0321 (15) | 0.0407 (15) | 0.0334 (14) | 0.0052 (12) | 0.0118 (11) | 0.0007 (12) |
C62 | 0.0502 (17) | 0.0431 (17) | 0.0560 (17) | 0.0004 (13) | 0.0269 (14) | 0.0013 (13) |
C63 | 0.0602 (19) | 0.0417 (17) | 0.0693 (19) | 0.0088 (14) | 0.0299 (16) | 0.0003 (14) |
C64 | 0.0393 (16) | 0.0518 (18) | 0.0521 (17) | 0.0095 (14) | 0.0155 (13) | −0.0059 (14) |
C65 | 0.0377 (15) | 0.0533 (18) | 0.0338 (15) | −0.0038 (13) | 0.0067 (12) | −0.0006 (13) |
C66 | 0.064 (2) | 0.0525 (19) | 0.0472 (17) | −0.0107 (15) | 0.0191 (15) | 0.0048 (14) |
C67 | 0.079 (2) | 0.0383 (16) | 0.0615 (19) | −0.0005 (16) | 0.0211 (17) | 0.0003 (14) |
C68 | 0.0550 (17) | 0.0435 (16) | 0.0431 (15) | 0.0019 (14) | 0.0166 (13) | 0.0002 (13) |
C69 | 0.0322 (14) | 0.0450 (16) | 0.0288 (13) | −0.0010 (12) | 0.0043 (11) | −0.0032 (11) |
N71 | 0.0307 (12) | 0.0336 (12) | 0.0227 (11) | −0.0028 (9) | 0.0065 (9) | −0.0005 (9) |
C70 | 0.0288 (13) | 0.0289 (13) | 0.0190 (12) | 0.0008 (10) | 0.0015 (9) | −0.0006 (10) |
C71 | 0.0290 (13) | 0.0328 (14) | 0.0200 (12) | −0.0005 (11) | 0.0053 (10) | −0.0027 (10) |
C72 | 0.0484 (16) | 0.0342 (15) | 0.0334 (14) | −0.0048 (12) | 0.0182 (12) | 0.0020 (11) |
C77 | 0.0626 (18) | 0.0290 (14) | 0.0421 (15) | 0.0017 (13) | 0.0203 (14) | −0.0002 (12) |
C78 | 0.0435 (15) | 0.0391 (15) | 0.0282 (13) | 0.0084 (12) | 0.0126 (11) | −0.0009 (11) |
P11—O11 | 1.4953 (15) | C42—H42 | 0.9300 |
P11—O12 | 1.5184 (14) | C47—O44 | 1.183 (3) |
P11—O13 | 1.5401 (16) | C47—O45 | 1.342 (3) |
P11—C13 | 1.804 (2) | O45—H45O | 0.97 (3) |
O13—H13O | 0.834 (5) | N51—C51 | 1.459 (3) |
N11—C12 | 1.342 (3) | N51—H51A | 0.94 (2) |
N11—C16 | 1.352 (3) | N51—H51B | 0.85 (2) |
C16—C15 | 1.386 (3) | N51—H51C | 0.95 (2) |
C16—H16 | 0.9300 | C50—C59 | 1.411 (3) |
C15—C14 | 1.387 (3) | C50—C51 | 1.415 (3) |
C15—C17 | 1.503 (3) | C50—C58 | 1.416 (3) |
C14—C13 | 1.394 (3) | C51—C52 | 1.354 (3) |
C14—H14 | 0.9300 | C52—C53 | 1.387 (3) |
C13—C12 | 1.389 (3) | C52—H52 | 0.9300 |
C12—H12 | 0.9300 | C53—C54 | 1.353 (3) |
C17—O14 | 1.197 (3) | C53—H53 | 0.9300 |
C17—O15 | 1.332 (3) | C54—C59 | 1.418 (3) |
O15—H15O | 0.94 (3) | C54—H54 | 0.9300 |
P21—O21 | 1.4988 (15) | C55—C56 | 1.350 (3) |
P21—O22 | 1.5044 (14) | C55—C59 | 1.410 (3) |
P21—O23 | 1.5373 (16) | C55—N52 | 1.465 (3) |
P21—C23 | 1.793 (2) | C56—C57 | 1.392 (3) |
O23—H23O | 0.87 (2) | C56—H56 | 0.9300 |
N21—C26 | 1.346 (3) | C57—C58 | 1.358 (3) |
N21—C22 | 1.362 (3) | C57—H57 | 0.9300 |
C26—C25 | 1.370 (3) | C58—H58 | 0.9300 |
C26—H26 | 0.9300 | N52—H52A | 0.93 (2) |
C25—C24 | 1.385 (3) | N52—H52B | 0.92 (2) |
C25—C27 | 1.525 (4) | N52—H52C | 0.877 (5) |
C24—C23 | 1.400 (3) | N61—C61 | 1.441 (3) |
C24—H24 | 0.9300 | N61—H61A | 0.91 (2) |
C23—C22 | 1.384 (3) | N61—H61B | 0.86 (2) |
C22—H22 | 0.9300 | N61—H61C | 0.94 (2) |
C27—O24 | 1.174 (3) | N62—C65 | 1.402 (3) |
C27—O25 | 1.352 (3) | N62—H62A | 0.96 (2) |
O25—H25O | 1.00 (3) | N62—H62B | 0.98 (2) |
P31—O31 | 1.5037 (14) | C60—C68 | 1.405 (3) |
P31—O32 | 1.5147 (14) | C60—C61 | 1.412 (3) |
P31—O33 | 1.5476 (16) | C60—C69 | 1.425 (3) |
P31—C33 | 1.801 (2) | C61—C62 | 1.346 (3) |
O33—H33O | 0.837 (5) | C62—C63 | 1.390 (3) |
N31—C32 | 1.338 (3) | C62—H62 | 0.9300 |
N31—C36 | 1.350 (3) | C63—C64 | 1.351 (3) |
C36—C35 | 1.388 (3) | C63—H63 | 0.9300 |
C36—H36 | 0.9300 | C64—C69 | 1.410 (3) |
C35—C34 | 1.383 (3) | C64—H64 | 0.9300 |
C35—C37 | 1.506 (3) | C65—C66 | 1.362 (3) |
C34—C33 | 1.396 (3) | C65—C69 | 1.422 (3) |
C34—H34 | 0.9300 | C66—C67 | 1.396 (3) |
C33—C32 | 1.399 (3) | C66—H66 | 0.9300 |
C32—H32 | 0.9300 | C67—C68 | 1.373 (3) |
C37—O34 | 1.189 (3) | C67—H67 | 0.9300 |
C37—O35 | 1.329 (3) | C68—H68 | 0.9300 |
O35—H35O | 0.88 (3) | N71—C71 | 1.461 (3) |
P41—O41 | 1.4900 (15) | N71—H71A | 0.92 (2) |
P41—O42 | 1.4996 (14) | N71—H71B | 0.92 (2) |
P41—O43 | 1.5700 (16) | N71—H71C | 0.91 (2) |
P41—C43 | 1.807 (2) | C70—C78 | 1.412 (3) |
O43—H43O | 0.836 (5) | C70—C71 | 1.415 (3) |
N41—C42 | 1.344 (3) | C70—C70i | 1.422 (4) |
N41—C46 | 1.348 (3) | C71—C72 | 1.350 (3) |
C46—C45 | 1.369 (3) | C72—C77i | 1.397 (3) |
C46—H46 | 0.9300 | C72—H72 | 0.9300 |
C45—C44 | 1.390 (3) | C77—C78 | 1.365 (3) |
C45—C47 | 1.520 (3) | C77—C72i | 1.397 (3) |
C44—C43 | 1.394 (3) | C77—H77 | 0.9300 |
C44—H44 | 0.9300 | C78—H78 | 0.9300 |
C43—C42 | 1.394 (3) | ||
O11—P11—O12 | 117.59 (9) | O44—C47—C45 | 122.5 (2) |
O11—P11—O13 | 110.84 (9) | O45—C47—C45 | 113.4 (2) |
O12—P11—O13 | 106.79 (9) | C47—O45—H45O | 109.4 (17) |
O11—P11—C13 | 107.57 (9) | C51—N51—H51A | 113.0 (14) |
O12—P11—C13 | 107.49 (9) | C51—N51—H51B | 117.0 (16) |
O13—P11—C13 | 105.94 (9) | H51A—N51—H51B | 101 (2) |
P11—O13—H13O | 115.3 (17) | C51—N51—H51C | 113.7 (13) |
C12—N11—C16 | 117.0 (2) | H51A—N51—H51C | 107.0 (18) |
N11—C16—C15 | 123.9 (2) | H51B—N51—H51C | 104 (2) |
N11—C16—H16 | 118.1 | C59—C50—C51 | 117.5 (2) |
C15—C16—H16 | 118.1 | C59—C50—C58 | 119.1 (2) |
C16—C15—C14 | 118.0 (2) | C51—C50—C58 | 123.4 (2) |
C16—C15—C17 | 119.4 (2) | C52—C51—C50 | 121.9 (2) |
C14—C15—C17 | 122.6 (2) | C52—C51—N51 | 119.1 (2) |
C15—C14—C13 | 119.3 (2) | C50—C51—N51 | 118.9 (2) |
C15—C14—H14 | 120.3 | C51—C52—C53 | 120.2 (2) |
C13—C14—H14 | 120.3 | C51—C52—H52 | 119.9 |
C12—C13—C14 | 118.5 (2) | C53—C52—H52 | 119.9 |
C12—C13—P11 | 120.27 (17) | C54—C53—C52 | 120.4 (2) |
C14—C13—P11 | 121.22 (17) | C54—C53—H53 | 119.8 |
N11—C12—C13 | 123.3 (2) | C52—C53—H53 | 119.8 |
N11—C12—H12 | 118.4 | C53—C54—C59 | 120.9 (2) |
C13—C12—H12 | 118.4 | C53—C54—H54 | 119.6 |
O14—C17—O15 | 123.3 (2) | C59—C54—H54 | 119.6 |
O14—C17—C15 | 123.2 (2) | C56—C55—C59 | 122.3 (2) |
O15—C17—C15 | 113.6 (2) | C56—C55—N52 | 119.0 (2) |
C17—O15—H15O | 112.3 (17) | C59—C55—N52 | 118.7 (2) |
O21—P21—O22 | 115.65 (9) | C55—C56—C57 | 120.0 (2) |
O21—P21—O23 | 112.42 (9) | C55—C56—H56 | 120.0 |
O22—P21—O23 | 105.84 (9) | C57—C56—H56 | 120.0 |
O21—P21—C23 | 106.91 (10) | C58—C57—C56 | 120.3 (2) |
O22—P21—C23 | 109.08 (10) | C58—C57—H57 | 119.9 |
O23—P21—C23 | 106.58 (10) | C56—C57—H57 | 119.9 |
P21—O23—H23O | 118.3 (17) | C57—C58—C50 | 120.8 (2) |
C26—N21—C22 | 116.7 (2) | C57—C58—H58 | 119.6 |
N21—C26—C25 | 125.4 (3) | C50—C58—H58 | 119.6 |
N21—C26—H26 | 117.3 | C55—N52—H52A | 113.2 (15) |
C25—C26—H26 | 117.3 | C55—N52—H52B | 113.2 (15) |
C26—C25—C24 | 116.9 (3) | H52A—N52—H52B | 108 (2) |
C26—C25—C27 | 121.4 (3) | C55—N52—H52C | 116.9 (16) |
C24—C25—C27 | 121.7 (2) | H52A—N52—H52C | 103 (2) |
C25—C24—C23 | 120.1 (2) | H52B—N52—H52C | 102 (2) |
C25—C24—H24 | 119.9 | C55—C59—C50 | 117.5 (2) |
C23—C24—H24 | 119.9 | C55—C59—C54 | 123.4 (2) |
C22—C23—C24 | 118.4 (2) | C50—C59—C54 | 119.1 (2) |
C22—C23—P21 | 120.85 (19) | C61—N61—H61A | 112.0 (15) |
C24—C23—P21 | 120.75 (18) | C61—N61—H61B | 112.8 (16) |
N21—C22—C23 | 122.4 (2) | H61A—N61—H61B | 104 (2) |
N21—C22—H22 | 118.8 | C61—N61—H61C | 112.4 (14) |
C23—C22—H22 | 118.8 | H61A—N61—H61C | 102.0 (19) |
O24—C27—O25 | 124.2 (3) | H61B—N61—H61C | 113 (2) |
O24—C27—C25 | 122.8 (3) | C65—N62—H62A | 106.5 (16) |
O25—C27—C25 | 113.0 (2) | C65—N62—H62B | 117.0 (15) |
C27—O25—H25O | 102.4 (17) | H62A—N62—H62B | 128 (2) |
O31—P31—O32 | 118.72 (9) | C68—C60—C61 | 123.9 (2) |
O31—P31—O33 | 111.03 (9) | C68—C60—C69 | 119.5 (2) |
O32—P31—O33 | 104.76 (9) | C61—C60—C69 | 116.6 (2) |
O31—P31—C33 | 107.41 (9) | C62—C61—C60 | 123.0 (2) |
O32—P31—C33 | 109.13 (9) | C62—C61—N61 | 119.7 (2) |
O33—P31—C33 | 104.96 (10) | C60—C61—N61 | 117.3 (2) |
P31—O33—H33O | 114.9 (17) | C61—C62—C63 | 119.9 (2) |
C32—N31—C36 | 117.1 (2) | C61—C62—H62 | 120.1 |
N31—C36—C35 | 124.1 (2) | C63—C62—H62 | 120.1 |
N31—C36—H36 | 117.9 | C64—C63—C62 | 120.0 (2) |
C35—C36—H36 | 117.9 | C64—C63—H63 | 120.0 |
C34—C35—C36 | 117.5 (2) | C62—C63—H63 | 120.0 |
C34—C35—C37 | 122.1 (2) | C63—C64—C69 | 121.8 (2) |
C36—C35—C37 | 120.4 (2) | C63—C64—H64 | 119.1 |
C35—C34—C33 | 120.2 (2) | C69—C64—H64 | 119.1 |
C35—C34—H34 | 119.9 | C66—C65—N62 | 120.6 (2) |
C33—C34—H34 | 119.9 | C66—C65—C69 | 120.6 (2) |
C34—C33—C32 | 117.5 (2) | N62—C65—C69 | 118.5 (2) |
C34—C33—P31 | 120.93 (17) | C65—C66—C67 | 120.5 (2) |
C32—C33—P31 | 121.40 (17) | C65—C66—H66 | 119.7 |
N31—C32—C33 | 123.6 (2) | C67—C66—H66 | 119.7 |
N31—C32—H32 | 118.2 | C68—C67—C66 | 120.9 (3) |
C33—C32—H32 | 118.2 | C68—C67—H67 | 119.5 |
O34—C37—O35 | 123.4 (2) | C66—C67—H67 | 119.5 |
O34—C37—C35 | 123.4 (2) | C67—C68—C60 | 120.0 (2) |
O35—C37—C35 | 113.1 (2) | C67—C68—H68 | 120.0 |
C37—O35—H35O | 109.4 (19) | C60—C68—H68 | 120.0 |
O41—P41—O42 | 116.98 (9) | C64—C69—C65 | 122.9 (2) |
O41—P41—O43 | 108.12 (9) | C64—C69—C60 | 118.7 (2) |
O42—P41—O43 | 110.71 (9) | C65—C69—C60 | 118.4 (2) |
O41—P41—C43 | 109.15 (10) | C71—N71—H71A | 109.5 (13) |
O42—P41—C43 | 107.04 (9) | C71—N71—H71B | 110.6 (13) |
O43—P41—C43 | 104.06 (10) | H71A—N71—H71B | 111.0 (19) |
P41—O43—H43O | 111.1 (17) | C71—N71—H71C | 112.5 (13) |
C42—N41—C46 | 116.9 (2) | H71A—N71—H71C | 100.7 (18) |
N41—C46—C45 | 124.8 (2) | H71B—N71—H71C | 112.2 (19) |
N41—C46—H46 | 117.6 | C78—C70—C71 | 123.36 (19) |
C45—C46—H46 | 117.6 | C78—C70—C70i | 118.9 (2) |
C46—C45—C44 | 117.5 (2) | C71—C70—C70i | 117.7 (2) |
C46—C45—C47 | 120.5 (2) | C72—C71—C70 | 122.1 (2) |
C44—C45—C47 | 122.0 (2) | C72—C71—N71 | 119.6 (2) |
C45—C44—C43 | 119.9 (2) | C70—C71—N71 | 118.22 (19) |
C45—C44—H44 | 120.1 | C71—C72—C77i | 119.9 (2) |
C43—C44—H44 | 120.1 | C71—C72—H72 | 120.1 |
C44—C43—C42 | 117.8 (2) | C77i—C72—H72 | 120.1 |
C44—C43—P41 | 121.76 (17) | C78—C77—C72i | 120.5 (2) |
C42—C43—P41 | 120.45 (18) | C78—C77—H77 | 119.7 |
N41—C42—C43 | 123.2 (2) | C72i—C77—H77 | 119.7 |
N41—C42—H42 | 118.4 | C77—C78—C70 | 120.8 (2) |
C43—C42—H42 | 118.4 | C77—C78—H78 | 119.6 |
O44—C47—O45 | 124.2 (2) | C70—C78—H78 | 119.6 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N51—H51A···O32ii | 0.94 (2) | 1.90 (2) | 2.835 (2) | 172 (2) |
N51—H51B···O11 | 0.85 (2) | 2.00 (2) | 2.795 (3) | 156 (2) |
N51—H51C···O21 | 0.95 (2) | 1.75 (2) | 2.681 (2) | 167 (2) |
N52—H52A···O43iii | 0.93 (2) | 1.90 (2) | 2.816 (3) | 169 (2) |
N52—H52B···O11iv | 0.92 (2) | 1.83 (2) | 2.705 (3) | 157 (2) |
N52—H52C···N62 | 0.88 (1) | 2.06 (1) | 2.878 (3) | 154 (2) |
N71—H71A···O12ii | 0.92 (2) | 1.89 (2) | 2.801 (2) | 174.1 (19) |
N71—H71B···O31 | 0.92 (2) | 1.89 (2) | 2.744 (2) | 154.3 (19) |
N71—H71C···O42 | 0.91 (2) | 1.77 (2) | 2.677 (2) | 171.7 (19) |
N61—H61A···O22ii | 0.91 (2) | 1.87 (2) | 2.784 (3) | 177 (2) |
N61—H61B···O21 | 0.86 (2) | 1.97 (2) | 2.830 (3) | 173 (2) |
N61—H61C···O31 | 0.94 (2) | 1.84 (2) | 2.766 (3) | 168 (2) |
N62—H62A···O13v | 0.96 (2) | 2.15 (3) | 2.894 (3) | 133 (2) |
N62—H62B···O42i | 0.98 (2) | 2.10 (3) | 3.059 (3) | 167 (2) |
O13—H13O···O41vi | 0.83 (1) | 1.67 (1) | 2.502 (2) | 176 (3) |
O15—H15O···N11vii | 0.94 (3) | 1.81 (3) | 2.748 (3) | 174 (3) |
O23—H23O···O12 | 0.87 (2) | 1.64 (2) | 2.489 (2) | 167 (3) |
O25—H25O···N21vii | 1.00 (3) | 1.72 (3) | 2.697 (3) | 162 (3) |
O33—H33O···O22 | 0.84 (1) | 1.71 (1) | 2.540 (2) | 171 (3) |
O35—H35O···N31vii | 0.88 (3) | 1.86 (3) | 2.725 (2) | 170 (3) |
O43—H43O···O32 | 0.84 (1) | 1.71 (1) | 2.539 (2) | 168 (2) |
O45—H45O···N41vii | 0.97 (3) | 1.76 (3) | 2.715 (2) | 172 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1; (iv) −x+1, −y+1, −z; (v) x+1, y, z; (vi) x−1, y, z−1; (vii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | 3C10H12N22+·2C10H11N2+·8C6H5NO5P− |
Mr | 2415.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 14.306 (3), 26.675 (5), 14.436 (3) |
β (°) | 99.26 (3) |
V (Å3) | 5437.2 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.42 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer with a CCD area detector |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.917, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 71634, 13812, 6933 |
Rint | 0.086 |
(sin θ/λ)max (Å−1) | 0.692 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.085, 1.00 |
No. of reflections | 13812 |
No. of parameters | 805 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.30 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N51—H51A···O32i | 0.94 (2) | 1.90 (2) | 2.835 (2) | 172 (2) |
N51—H51B···O11 | 0.85 (2) | 2.00 (2) | 2.795 (3) | 156 (2) |
N51—H51C···O21 | 0.95 (2) | 1.75 (2) | 2.681 (2) | 167 (2) |
N52—H52A···O43ii | 0.93 (2) | 1.90 (2) | 2.816 (3) | 169 (2) |
N52—H52B···O11iii | 0.92 (2) | 1.83 (2) | 2.705 (3) | 157 (2) |
N52—H52C···N62 | 0.877 (5) | 2.064 (12) | 2.878 (3) | 154 (2) |
N71—H71A···O12i | 0.92 (2) | 1.89 (2) | 2.801 (2) | 174.1 (19) |
N71—H71B···O31 | 0.92 (2) | 1.89 (2) | 2.744 (2) | 154.3 (19) |
N71—H71C···O42 | 0.91 (2) | 1.77 (2) | 2.677 (2) | 171.7 (19) |
N61—H61A···O22i | 0.91 (2) | 1.87 (2) | 2.784 (3) | 177 (2) |
N61—H61B···O21 | 0.86 (2) | 1.97 (2) | 2.830 (3) | 173 (2) |
N61—H61C···O31 | 0.94 (2) | 1.84 (2) | 2.766 (3) | 168 (2) |
N62—H62A···O13iv | 0.96 (2) | 2.15 (3) | 2.894 (3) | 133 (2) |
N62—H62B···O42v | 0.98 (2) | 2.10 (3) | 3.059 (3) | 167 (2) |
O13—H13O···O41vi | 0.834 (5) | 1.669 (6) | 2.502 (2) | 176 (3) |
O15—H15O···N11vii | 0.94 (3) | 1.81 (3) | 2.748 (3) | 174 (3) |
O23—H23O···O12 | 0.87 (2) | 1.64 (2) | 2.489 (2) | 167 (3) |
O25—H25O···N21vii | 1.00 (3) | 1.72 (3) | 2.697 (3) | 162 (3) |
O33—H33O···O22 | 0.837 (5) | 1.709 (7) | 2.540 (2) | 171 (3) |
O35—H35O···N31vii | 0.88 (3) | 1.86 (3) | 2.725 (2) | 170 (3) |
O43—H43O···O32 | 0.836 (5) | 1.714 (7) | 2.539 (2) | 168 (2) |
O45—H45O···N41vii | 0.97 (3) | 1.76 (3) | 2.715 (2) | 172 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) −x+2, −y+1, −z+1; (vi) x−1, y, z−1; (vii) x, −y+3/2, z−1/2. |
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The growth of crystal engineering has been accompanied by significant interest in the nature of intermolecular interactions and their use in trying to control solid-state structures (Aakeröy et al., 2010). Hydrogen bonds and π–π stacking interactions have been the most widely used organizing forces in crystal engineering. Hydrogen bonds are especially important because of their properties, such as directionality, selectivity and strength (Jeffrey, 1997). Naphthalene-1,5-diamine can serve as an excellent hydrogen-bond donor, whether in its intact or protonated forms. In addition, it can also participate in π–π stacking interactions. As far as the protonated forms are concerned, a search of the Cambridge Structural Database (CSD, Version 5.33, November 2011; Allen, 2002) retrieved three crystal structures of salts containing the diprotonated naphthalene-1,5-diaminium cation (Lemmerer & Billing, 2006; Boufas et al., 2006, 2007), but there are no structures involving the monoprotonated 5-aminonaphthalen-1-aminium cation. 5-(Dihydroxyphosphoryl)pyridine-3-carboxylic acid and its anions can act as both hydrogen-bond donors and acceptors. It is worth noting that, in contrast with the flat carboxyl group, the nonplanar phosphonic group allows the formation of hydrogen bonds in three dimensions. To the best of our knowledge, no molecular complexes based on the 5-(dihydroxyphosphoryl)pyridine-3-carboxylic acid monoanion have been prepared. We report here the crystal structure of the title compound, (I), which demonstrates an interesting supramolecular architecture established via hydrogen bonds and π–π stacking interactions.
The molecular structure of (I) consists of three naphthalene-1,5-diaminium cations, two 5-aminonaphthalen-1-aminium cations and eight hydrogen (5-carboxypyridin-3-yl)phosphonate anions. One of the diprotonated diammonium [diaminium?] cations is centrosymmetric, with an inversion centre imposed at the mid-point of the C≐C bond of the naphthalene ring. Therefore, the asymmetric unit contains only one and a half diprotonated and one monoprotonated 1,5-diaminonaphthalene entities, as well as four anions (Fig. 1).
The hydrogen (5-carboxypyridin-3-yl)phosphonate anions are connected into one-dimensional C11(4) chains (Bernstein et al., 1995) along the [101] direction via four strong phosphonate–phosphonate hydrogen-bonding interactions, viz. O13—H13O···O41vi, O23—H23O···O12, O33—H33O···O22 and O43—H43O···O32 [symmetry code: (vi) x - 1, y, z - 1]. Glide-related chains are linked together by four different hydrogen bonds to form a two-dimensional hydrogen-bonded network parallel to the (010) plane (Fig. 2). The interchain hydrogen bonds, viz. O15—H15O···N11vii, O25—H25O···N21vii, O35—H35O···N31vii and O45—H45O···N41vii [symmetry code: (vii) x, -y + 3/2, z - 1/2], are donated from the carboxyl groups of one chain towards the pyridine N atoms of an adjacent chain. The anionic network undulates, with large R44(28) ring motifs encircled by two (P)O—H···O(P) and two (C)O—H···Npy hydrogen bonds. The monolayer is further supported by C═O···π(pyridine ring) interactions [C17—O14···Cg2vii = 3.669 (3) Å, C27—O24···Cg3vii = 3.592 (3) Å and C47—O44···Cg1viii = 3.597 (2) Å, where Cg1 is the centroid of the N11/C12–C16 ring, Cg2 is the centroid of the N21/C22–C26 ring and Cg3 is the centroid of the N31/C32–C36 ring; symmetry code: (viii) x + 1, -y + 3/2, z + 1/2].
The cations fill the space between the anionic layers. The naphthalene rings of the 5-aminonaphthalen-1-aminium and naphthalene-1,5-diaminium cations are planar, with a maximum deviation from the mean plane of 0.026 (3) Å. An N52—H52C···N62 hydrogen bond, formed between the ammonium [aminium?] group of the naphthalene-1,5-diaminium cation located on a general position (entity 5) and the amino group of the 5-aminonaphthalen-1-aminium cation (entity 6), joins these two entities into a dimeric unit (Fig. 3). The dimeric units are also supported by face-to-face (FF) π–π interactions between their aromatic systems [Cg4···Cg6 = 3.8065 (15) Å and Cg5···Cg7 = 3.7616 (16) Å, where Cg4 is the centroid of the C50–C54/C59 ring, Cg5 is the centroid of the C50/C59/C55–C58 ring, Cg6 is the centroid of the C60–C64/C69 ring and Cg7 is the centroid of the C60/C69/C65–C68 ring]. The diprotonated diammonium [diaminium?] cation (entity 7), which is located on a special position (at the inversion centre), serves to connect two inversion-related dimeric units via FF π–π interactions [Cg6···Cg8 = 3.7667 (15) Å and Cg7···Cg9 = 3.7395 (15) Å, where Cg8 is the centroid of the C70/C71/C72/C77v/C78v/C70v ring and Cg9 is the centroid of the C70/C78/C77/C72v/C71v/C70v ring [symmetry code: (v) -x + 2, -y + 1, -z + 1] to form five-membered cationic sequences. Inversion-related sequences are extended along the [101] direction by FF [Cg4···Cg5iii = 3.8109 (15) Å and Cg5···Cg4iii = 3.8109 (15) Å] and off-set face-to face (OFF) π–π interactions [Cg4···Cg4iii = 4.2019 (16) Å, slippage distance = 2.281 Å, and Cg5···Cg5iii = 4.8274 (17) Å, slippage distance = 3.273 Å; symmetry code: (iii) -x + 1, -y + 1, ??? Please complete] (Fig. 3).
The organic cations serve both to balance the charge of the anionic network and to connect adjacent inversion-related monolayers via multiple hydrogen-bonding interactions. N—H···O hydrogen bonds, donated from the ammonium [aminium?] and amino groups towards the phosphonate sites, lead to the formation of a three-dimensional network (Table 1 and Fig. 4). Atoms O11, O21, O31 and O42 each accept two hydrogen bonds, while atoms O12, O13, O22, O32 and O43 are involved in just one hydrogen bond.
5-(Dihydroxyphosphoryl)pyridine-3-carboxylic acid can be considered an analogue of pyridine-3,5-dicarboxylic acid, in which one of the carboxyl groups has been replaced by a phosphonic group. Therefore, the present structure can be compared with two similar complexes formed between 3-carboxy-pyridine-5-carboxylate anions and decane-1,10- or dodecane-1,12-diammonium [diaminium?] cations and which contain water molecules (Beatty et al., 2002). The compounds also demonstrate layered structures, but their connectivity patterns, both within and between the monolayers, are quite different from those considered above. In (I), the acid monoanions are organized into chains via phosphonate–phosphonate hydrogen-bonding interactions, and the (C)O—H···Npy hydrogen bonds crosslink the chains to form a monolayer without the aid of the diammonium [diaminium?] cations. The cations serve to connect neighbouring layers via N—H···Ophosphonate hydrogen-bonding interactions. As far as the dinicotinate-containing salts are concerned, the acid monoanions are also connected into zigzag chains but they use carboxylic–carboxylate hydrogen bonds. The diammonium cations [diaminium?], providing interchain N—H···Npy or N—H···Ocarboxylate hydrogen bonds, appear to be essential for layer formation. Furthermore, water molecules are also necessary for linkages between adjacent layers via O—H···Ocarboxyl and N—H···Owater hydrogen bonds.