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The title compounds, dimethylammonium 2-{4-[1-(4-carboxymethoxyphenyl)-1-methylethyl]phenoxy}acetate, C
2H
8N
+·C
19H
19O
6-, (I), and 2,2'-[isopropylidenebis(
p-phenyleneoxy)]diacetic acid-4,4'-bipyridine (1/1), C
19H
20O
6·C
10H
8N
2, (II), are 1:1 adducts of 2,2'-[isopropylidenebis(
p-phenyleneoxy)]diacetic acid (H
2L) with dimethylammonium or 4,4'-bipyridine. The component ions in (I) are linked by N-H
O, O-H
O and C-H
O hydrogen bonds into continuous two-dimensional layers parallel to the (001) plane. Adjacent layers are stacked
via C-H
O hydrogen bonds into a three-dimensional network with an -
ABAB- alternation of the two-dimensional layers. In (II), two H
2L molecules, one bipy molecule and two half bipy molecules are linked by O-H
N hydrogen bonds into one-dimensional chains and rectanglar-shaped rings. They are assembled
via -
stacking interactions and C-H
O hydrogen bonds into an intriguing zero-dimensional plus one-dimensional poly(pseudo)rotaxane motif.
Supporting information
CCDC references: 760130; 760131
H2L was synthesized by the literature method (Inouye et al.,
1995). Compound (I) was obtained by heating a mixture of La(NO3)3.6H2O
(0.130 g, 0.3 mmol), H2L (0.206 g, 0.6 mmol) and dimethylformamide
(DMF; 3 ml) in a sealed 5 ml reactor at 433 K for 48 h, followed by gradual
cooling to room temperature. Colourless block-like crystals of (I) were
collected by filtration and air-dried. Compound (II) was obtained when a
mixture of Pb(NO3)3 (0.109 g, 0.33 mmol), bipy (0.019 g, 0.12 mmol) and
H2L (0.042 mg, 0.12 mmol) in H2O (8 ml) was sealed in a 25 ml
Teflon-lined stainless steel reactor and heated at 443 K for 72 h. A crop of
colourless single crystals of compound (II) was obtained after cooling the
solution to room temperature. The platelet-shaped crystals were collected and
washed with distilled water.
All H atoms were placed in idealized positions, with O—H = 0.82, N—H = 0.90
and C—H = 0.93–0.97 Å, and refined as riding atoms, with Uiso(H)
= 1.2Ueq(C,N) or 1.5Ueq(O). For structure (II), the R
factor is slightly higher than normally expected due to the fact that the
crystal diffracted weakly, and only 50% of the data can be considered to be
observed [I > 2σ(I)].
For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2009).
(I) dimethylammonium 2-{4-[1-(4-carboxymethoxyphenyl)-1-methylethyl]phenoxy}acetate
top
Crystal data top
C2H8N+·C19H19O6− | F(000) = 832 |
Mr = 389.44 | Dx = 1.238 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1412 reflections |
a = 6.9028 (14) Å | θ = 2.9–21.1° |
b = 27.756 (6) Å | µ = 0.09 mm−1 |
c = 12.624 (4) Å | T = 295 K |
β = 120.21 (2)° | Block, colourless |
V = 2090.2 (9) Å3 | 0.20 × 0.18 × 0.17 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3693 independent reflections |
Radiation source: fine-focus sealed tube | 2126 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→7 |
Tmin = 0.982, Tmax = 0.985 | k = −32→24 |
10877 measured reflections | l = −13→15 |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0596P)2 + 0.0341P] where P = (Fo2 + 2Fc2)/3 |
3693 reflections | (Δ/σ)max < 0.001 |
257 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C2H8N+·C19H19O6− | V = 2090.2 (9) Å3 |
Mr = 389.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9028 (14) Å | µ = 0.09 mm−1 |
b = 27.756 (6) Å | T = 295 K |
c = 12.624 (4) Å | 0.20 × 0.18 × 0.17 mm |
β = 120.21 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3693 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2126 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.985 | Rint = 0.043 |
10877 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.12 e Å−3 |
3693 reflections | Δρmin = −0.17 e Å−3 |
257 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.2193 (3) | 0.95382 (7) | 0.42290 (16) | 0.0730 (6) | |
O2 | 0.4092 (2) | 0.96870 (6) | 0.32783 (15) | 0.0559 (5) | |
O3 | 0.7206 (2) | 0.90150 (6) | 0.45967 (14) | 0.0555 (5) | |
O4 | 0.7744 (3) | 0.53223 (7) | 0.43833 (16) | 0.0725 (5) | |
O5 | 0.8680 (3) | 0.53345 (6) | 0.29336 (15) | 0.0601 (5) | |
H5 | 0.7748 | 0.5118 | 0.2629 | 0.090* | |
O6 | 1.1384 (3) | 0.60835 (6) | 0.39396 (16) | 0.0669 (5) | |
N1 | 0.7816 (3) | 0.98577 (8) | 0.30070 (18) | 0.0651 (6) | |
H1A | 0.6973 | 0.9735 | 0.3301 | 0.078* | |
H1B | 0.9231 | 0.9754 | 0.3495 | 0.078* | |
C1 | 0.3801 (4) | 0.94797 (9) | 0.4074 (2) | 0.0470 (6) | |
C2 | 0.5586 (4) | 0.91318 (9) | 0.4934 (2) | 0.0538 (7) | |
H2A | 0.6349 | 0.9270 | 0.5751 | 0.065* | |
H2B | 0.4865 | 0.8837 | 0.4970 | 0.065* | |
C3 | 0.6648 (4) | 0.86726 (8) | 0.3704 (2) | 0.0460 (6) | |
C4 | 0.8409 (4) | 0.84983 (9) | 0.3592 (2) | 0.0570 (7) | |
H4 | 0.9855 | 0.8611 | 0.4108 | 0.068* | |
C5 | 0.8028 (4) | 0.81587 (9) | 0.2722 (2) | 0.0564 (7) | |
H5A | 0.9238 | 0.8042 | 0.2668 | 0.068* | |
C6 | 0.5898 (4) | 0.79809 (8) | 0.1916 (2) | 0.0471 (6) | |
C7 | 0.4184 (4) | 0.81615 (9) | 0.2051 (2) | 0.0546 (7) | |
H7 | 0.2736 | 0.8050 | 0.1532 | 0.066* | |
C8 | 0.4521 (4) | 0.85036 (9) | 0.2931 (2) | 0.0538 (6) | |
H8 | 0.3318 | 0.8617 | 0.2997 | 0.065* | |
C9 | 0.5619 (4) | 0.75964 (9) | 0.0977 (2) | 0.0532 (6) | |
C10 | 0.3186 (4) | 0.74245 (10) | 0.0195 (2) | 0.0723 (8) | |
H10A | 0.3105 | 0.7179 | −0.0361 | 0.109* | |
H10B | 0.2252 | 0.7691 | −0.0262 | 0.109* | |
H10C | 0.2678 | 0.7296 | 0.0719 | 0.109* | |
C11 | 0.6308 (5) | 0.78168 (10) | 0.0099 (2) | 0.0790 (9) | |
H11A | 0.7844 | 0.7919 | 0.0556 | 0.119* | |
H11B | 0.5370 | 0.8089 | −0.0311 | 0.119* | |
H11C | 0.6139 | 0.7580 | −0.0497 | 0.119* | |
C12 | 0.7102 (4) | 0.71674 (8) | 0.1689 (2) | 0.0472 (6) | |
C13 | 0.8967 (4) | 0.70208 (9) | 0.1646 (2) | 0.0572 (7) | |
H13 | 0.9317 | 0.7172 | 0.1106 | 0.069* | |
C14 | 1.0327 (4) | 0.66550 (9) | 0.2385 (3) | 0.0610 (7) | |
H14 | 1.1575 | 0.6563 | 0.2336 | 0.073* | |
C15 | 0.9863 (4) | 0.64252 (8) | 0.3191 (2) | 0.0513 (6) | |
C16 | 0.7964 (4) | 0.65502 (9) | 0.3220 (2) | 0.0556 (7) | |
H16 | 0.7580 | 0.6387 | 0.3732 | 0.067* | |
C17 | 0.6637 (4) | 0.69186 (9) | 0.2484 (2) | 0.0537 (6) | |
H17 | 0.5371 | 0.7004 | 0.2522 | 0.064* | |
C18 | 0.8879 (4) | 0.54642 (9) | 0.3980 (2) | 0.0527 (6) | |
C19 | 1.0778 (4) | 0.58096 (9) | 0.4678 (2) | 0.0681 (8) | |
H19A | 1.0367 | 0.6029 | 0.5129 | 0.082* | |
H19B | 1.2079 | 0.5629 | 0.5271 | 0.082* | |
C20 | 0.6992 (5) | 0.96651 (12) | 0.1766 (2) | 0.0796 (9) | |
H20A | 0.5526 | 0.9792 | 0.1220 | 0.119* | |
H20B | 0.6916 | 0.9320 | 0.1784 | 0.119* | |
H20C | 0.7997 | 0.9757 | 0.1484 | 0.119* | |
C21 | 0.7791 (5) | 1.03860 (11) | 0.3086 (3) | 0.0759 (8) | |
H21A | 0.8740 | 1.0522 | 0.2810 | 0.114* | |
H21B | 0.8330 | 1.0480 | 0.3921 | 0.114* | |
H21C | 0.6287 | 1.0501 | 0.2579 | 0.114* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0584 (11) | 0.1045 (16) | 0.0696 (12) | 0.0165 (10) | 0.0422 (10) | 0.0207 (10) |
O2 | 0.0565 (10) | 0.0563 (11) | 0.0653 (11) | 0.0106 (8) | 0.0382 (9) | 0.0155 (9) |
O3 | 0.0485 (9) | 0.0525 (11) | 0.0574 (10) | 0.0056 (8) | 0.0207 (8) | −0.0056 (8) |
O4 | 0.0794 (13) | 0.0832 (14) | 0.0656 (12) | 0.0006 (11) | 0.0443 (11) | 0.0043 (10) |
O5 | 0.0638 (11) | 0.0568 (11) | 0.0639 (11) | −0.0150 (8) | 0.0354 (9) | −0.0116 (9) |
O6 | 0.0527 (10) | 0.0501 (11) | 0.0814 (12) | −0.0010 (9) | 0.0214 (9) | −0.0001 (10) |
N1 | 0.0483 (12) | 0.0894 (19) | 0.0642 (14) | 0.0051 (11) | 0.0333 (11) | 0.0152 (12) |
C1 | 0.0475 (14) | 0.0518 (15) | 0.0431 (14) | −0.0015 (12) | 0.0238 (12) | −0.0026 (11) |
C2 | 0.0626 (16) | 0.0556 (16) | 0.0465 (14) | 0.0043 (13) | 0.0299 (12) | 0.0006 (12) |
C3 | 0.0504 (14) | 0.0365 (13) | 0.0444 (13) | 0.0041 (11) | 0.0189 (11) | 0.0025 (11) |
C4 | 0.0406 (13) | 0.0543 (16) | 0.0639 (16) | 0.0031 (12) | 0.0172 (12) | −0.0059 (13) |
C5 | 0.0502 (14) | 0.0559 (17) | 0.0634 (16) | 0.0054 (12) | 0.0288 (13) | −0.0061 (13) |
C6 | 0.0515 (14) | 0.0416 (14) | 0.0446 (13) | 0.0022 (11) | 0.0215 (11) | 0.0059 (11) |
C7 | 0.0452 (14) | 0.0534 (16) | 0.0554 (15) | −0.0010 (12) | 0.0180 (12) | −0.0009 (12) |
C8 | 0.0465 (14) | 0.0515 (16) | 0.0617 (15) | 0.0041 (12) | 0.0261 (12) | −0.0016 (13) |
C9 | 0.0651 (16) | 0.0508 (15) | 0.0432 (13) | 0.0008 (13) | 0.0270 (12) | 0.0018 (11) |
C10 | 0.0719 (18) | 0.0678 (19) | 0.0539 (16) | 0.0019 (14) | 0.0143 (14) | −0.0093 (14) |
C11 | 0.110 (2) | 0.076 (2) | 0.0603 (17) | 0.0085 (18) | 0.0497 (16) | 0.0161 (15) |
C12 | 0.0591 (15) | 0.0428 (14) | 0.0444 (13) | −0.0046 (12) | 0.0296 (12) | −0.0081 (11) |
C13 | 0.0699 (17) | 0.0524 (16) | 0.0669 (17) | −0.0082 (14) | 0.0476 (14) | −0.0057 (13) |
C14 | 0.0555 (15) | 0.0548 (17) | 0.0831 (19) | −0.0043 (13) | 0.0426 (14) | −0.0102 (15) |
C15 | 0.0517 (14) | 0.0388 (14) | 0.0566 (15) | −0.0032 (12) | 0.0222 (12) | −0.0103 (12) |
C16 | 0.0733 (17) | 0.0485 (16) | 0.0557 (15) | 0.0047 (14) | 0.0405 (13) | 0.0044 (12) |
C17 | 0.0604 (15) | 0.0519 (16) | 0.0608 (16) | 0.0079 (13) | 0.0395 (13) | 0.0034 (13) |
C18 | 0.0574 (16) | 0.0472 (16) | 0.0464 (15) | 0.0121 (12) | 0.0209 (13) | 0.0062 (12) |
C19 | 0.0659 (17) | 0.0530 (17) | 0.0583 (16) | 0.0043 (14) | 0.0111 (14) | 0.0039 (14) |
C20 | 0.0732 (19) | 0.098 (2) | 0.0666 (18) | −0.0084 (17) | 0.0344 (15) | −0.0073 (17) |
C21 | 0.0695 (18) | 0.084 (2) | 0.085 (2) | −0.0080 (16) | 0.0471 (16) | −0.0062 (16) |
Geometric parameters (Å, º) top
O1—C1 | 1.231 (3) | C9—C10 | 1.534 (3) |
O2—C1 | 1.258 (3) | C9—C11 | 1.536 (4) |
O3—C3 | 1.373 (3) | C10—H10A | 0.9600 |
O3—C2 | 1.420 (3) | C10—H10B | 0.9600 |
O4—C18 | 1.196 (3) | C10—H10C | 0.9600 |
O5—C18 | 1.308 (3) | C11—H11A | 0.9600 |
O5—H5 | 0.8206 | C11—H11B | 0.9600 |
O6—C15 | 1.377 (3) | C11—H11C | 0.9600 |
O6—C19 | 1.419 (3) | C12—C13 | 1.377 (3) |
N1—C21 | 1.470 (3) | C12—C17 | 1.382 (3) |
N1—C20 | 1.472 (3) | C13—C14 | 1.379 (3) |
N1—H1A | 0.8997 | C13—H13 | 0.9300 |
N1—H1B | 0.9003 | C14—C15 | 1.368 (3) |
C1—C2 | 1.511 (3) | C14—H14 | 0.9300 |
C2—H2A | 0.9700 | C15—C16 | 1.374 (3) |
C2—H2B | 0.9700 | C16—C17 | 1.375 (3) |
C3—C8 | 1.373 (3) | C16—H16 | 0.9300 |
C3—C4 | 1.380 (3) | C17—H17 | 0.9300 |
C4—C5 | 1.369 (3) | C18—C19 | 1.501 (3) |
C4—H4 | 0.9300 | C19—H19A | 0.9700 |
C5—C6 | 1.391 (3) | C19—H19B | 0.9700 |
C5—H5A | 0.9300 | C20—H20A | 0.9600 |
C6—C7 | 1.372 (3) | C20—H20B | 0.9600 |
C6—C9 | 1.534 (3) | C20—H20C | 0.9600 |
C7—C8 | 1.389 (3) | C21—H21A | 0.9600 |
C7—H7 | 0.9300 | C21—H21B | 0.9600 |
C8—H8 | 0.9300 | C21—H21C | 0.9600 |
C9—C12 | 1.533 (3) | | |
| | | |
C3—O3—C2 | 117.80 (18) | H10B—C10—H10C | 109.5 |
C18—O5—H5 | 109.5 | C9—C11—H11A | 109.5 |
C15—O6—C19 | 116.4 (2) | C9—C11—H11B | 109.5 |
C21—N1—C20 | 115.0 (2) | H11A—C11—H11B | 109.5 |
C21—N1—H1A | 108.5 | C9—C11—H11C | 109.5 |
C20—N1—H1A | 108.5 | H11A—C11—H11C | 109.5 |
C21—N1—H1B | 108.5 | H11B—C11—H11C | 109.5 |
C20—N1—H1B | 108.5 | C13—C12—C17 | 116.4 (2) |
H1A—N1—H1B | 107.5 | C13—C12—C9 | 124.6 (2) |
O1—C1—O2 | 125.8 (2) | C17—C12—C9 | 119.0 (2) |
O1—C1—C2 | 116.4 (2) | C12—C13—C14 | 121.5 (2) |
O2—C1—C2 | 117.8 (2) | C12—C13—H13 | 119.3 |
O3—C2—C1 | 114.2 (2) | C14—C13—H13 | 119.3 |
O3—C2—H2A | 108.7 | C15—C14—C13 | 120.8 (2) |
C1—C2—H2A | 108.7 | C15—C14—H14 | 119.6 |
O3—C2—H2B | 108.7 | C13—C14—H14 | 119.6 |
C1—C2—H2B | 108.7 | C14—C15—C16 | 119.0 (2) |
H2A—C2—H2B | 107.6 | C14—C15—O6 | 116.6 (2) |
C8—C3—O3 | 125.3 (2) | C16—C15—O6 | 124.3 (2) |
C8—C3—C4 | 119.3 (2) | C15—C16—C17 | 119.3 (2) |
O3—C3—C4 | 115.4 (2) | C15—C16—H16 | 120.3 |
C5—C4—C3 | 120.0 (2) | C17—C16—H16 | 120.3 |
C5—C4—H4 | 120.0 | C16—C17—C12 | 122.9 (2) |
C3—C4—H4 | 120.0 | C16—C17—H17 | 118.6 |
C4—C5—C6 | 122.5 (2) | C12—C17—H17 | 118.6 |
C4—C5—H5A | 118.8 | O4—C18—O5 | 125.5 (2) |
C6—C5—H5A | 118.8 | O4—C18—C19 | 121.8 (3) |
C7—C6—C5 | 116.1 (2) | O5—C18—C19 | 112.7 (3) |
C7—C6—C9 | 124.7 (2) | O6—C19—C18 | 114.6 (2) |
C5—C6—C9 | 119.2 (2) | O6—C19—H19A | 108.6 |
C6—C7—C8 | 122.8 (2) | C18—C19—H19A | 108.6 |
C6—C7—H7 | 118.6 | O6—C19—H19B | 108.6 |
C8—C7—H7 | 118.6 | C18—C19—H19B | 108.6 |
C3—C8—C7 | 119.4 (2) | H19A—C19—H19B | 107.6 |
C3—C8—H8 | 120.3 | N1—C20—H20A | 109.5 |
C7—C8—H8 | 120.3 | N1—C20—H20B | 109.5 |
C12—C9—C6 | 107.44 (17) | H20A—C20—H20B | 109.5 |
C12—C9—C10 | 109.1 (2) | N1—C20—H20C | 109.5 |
C6—C9—C10 | 112.6 (2) | H20A—C20—H20C | 109.5 |
C12—C9—C11 | 112.0 (2) | H20B—C20—H20C | 109.5 |
C6—C9—C11 | 108.5 (2) | N1—C21—H21A | 109.5 |
C10—C9—C11 | 107.2 (2) | N1—C21—H21B | 109.5 |
C9—C10—H10A | 109.5 | H21A—C21—H21B | 109.5 |
C9—C10—H10B | 109.5 | N1—C21—H21C | 109.5 |
H10A—C10—H10B | 109.5 | H21A—C21—H21C | 109.5 |
C9—C10—H10C | 109.5 | H21B—C21—H21C | 109.5 |
H10A—C10—H10C | 109.5 | | |
| | | |
C3—O3—C2—C1 | −80.7 (2) | C6—C9—C12—C13 | −113.2 (3) |
O1—C1—C2—O3 | 170.0 (2) | C10—C9—C12—C13 | 124.4 (2) |
O2—C1—C2—O3 | −10.8 (3) | C11—C9—C12—C13 | 5.8 (3) |
C2—O3—C3—C8 | 14.1 (3) | C6—C9—C12—C17 | 63.4 (3) |
C2—O3—C3—C4 | −166.7 (2) | C10—C9—C12—C17 | −59.0 (3) |
C8—C3—C4—C5 | −0.3 (4) | C11—C9—C12—C17 | −177.5 (2) |
O3—C3—C4—C5 | −179.5 (2) | C17—C12—C13—C14 | −1.9 (3) |
C3—C4—C5—C6 | 0.8 (4) | C9—C12—C13—C14 | 174.8 (2) |
C4—C5—C6—C7 | −0.8 (4) | C12—C13—C14—C15 | −0.1 (4) |
C4—C5—C6—C9 | −179.3 (2) | C13—C14—C15—C16 | 2.7 (4) |
C5—C6—C7—C8 | 0.3 (4) | C13—C14—C15—O6 | −176.4 (2) |
C9—C6—C7—C8 | 178.8 (2) | C19—O6—C15—C14 | −173.4 (2) |
O3—C3—C8—C7 | 178.9 (2) | C19—O6—C15—C16 | 7.6 (3) |
C4—C3—C8—C7 | −0.2 (4) | C14—C15—C16—C17 | −3.2 (3) |
C6—C7—C8—C3 | 0.2 (4) | O6—C15—C16—C17 | 175.8 (2) |
C7—C6—C9—C12 | −120.9 (2) | C15—C16—C17—C12 | 1.2 (4) |
C5—C6—C9—C12 | 57.5 (3) | C13—C12—C17—C16 | 1.4 (3) |
C7—C6—C9—C10 | −0.8 (3) | C9—C12—C17—C16 | −175.6 (2) |
C5—C6—C9—C10 | 177.7 (2) | C15—O6—C19—C18 | 69.4 (3) |
C7—C6—C9—C11 | 117.7 (3) | O4—C18—C19—O6 | −156.7 (2) |
C5—C6—C9—C11 | −63.8 (3) | O5—C18—C19—O6 | 25.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O2i | 0.82 | 1.70 | 2.507 (2) | 167 |
N1—H1B···O1ii | 0.90 | 1.87 | 2.758 (3) | 169 |
N1—H1A···O3 | 0.90 | 2.54 | 3.245 (3) | 136 |
N1—H1A···O2 | 0.90 | 1.98 | 2.800 (3) | 151 |
C20—H20A···O4iii | 0.96 | 2.47 | 3.368 (4) | 155 |
C20—H20C···O4iv | 0.96 | 2.58 | 3.300 (4) | 132 |
C20—H20C···O5v | 0.96 | 2.58 | 3.374 (3) | 140 |
C21—H21A···O5v | 0.96 | 2.45 | 3.282 (3) | 145 |
C21—H21B···O1vi | 0.96 | 2.54 | 3.390 (4) | 148 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) −x+2, y+1/2, −z+1/2; (vi) −x+1, −y+2, −z+1. |
(II) 2,2'-[isopropylidenebis(
p-phenyleneoxy)]diacetic acid–4,4'-bipyridine
(1/1)
top
Crystal data top
C19H20O6·C10H8N2 | Z = 4 |
Mr = 500.53 | F(000) = 1056 |
Triclinic, P1 | Dx = 1.305 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8698 (15) Å | Cell parameters from 1666 reflections |
b = 14.673 (2) Å | θ = 2.7–20.7° |
c = 20.087 (3) Å | µ = 0.09 mm−1 |
α = 96.749 (2)° | T = 295 K |
β = 94.180 (3)° | Block, colourless |
γ = 99.751 (4)° | 0.22 × 0.18 × 0.16 mm |
V = 2547.1 (7) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 8949 independent reflections |
Radiation source: fine-focus sealed tube | 4313 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→10 |
Tmin = 0.980, Tmax = 0.985 | k = −17→15 |
13525 measured reflections | l = −21→23 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.070 | H-atom parameters constrained |
wR(F2) = 0.235 | w = 1/[σ2(Fo2) + (0.1089P)2 + 0.0613P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
8949 reflections | Δρmax = 0.74 e Å−3 |
670 parameters | Δρmin = −0.41 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: 0.0033 (10) |
Crystal data top
C19H20O6·C10H8N2 | γ = 99.751 (4)° |
Mr = 500.53 | V = 2547.1 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.8698 (15) Å | Mo Kα radiation |
b = 14.673 (2) Å | µ = 0.09 mm−1 |
c = 20.087 (3) Å | T = 295 K |
α = 96.749 (2)° | 0.22 × 0.18 × 0.16 mm |
β = 94.180 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 8949 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4313 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.985 | Rint = 0.045 |
13525 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.070 | 0 restraints |
wR(F2) = 0.235 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.74 e Å−3 |
8949 reflections | Δρmin = −0.41 e Å−3 |
670 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.1165 (4) | 0.0986 (2) | −0.21956 (14) | 0.0670 (9) | |
O2 | −0.3273 (4) | 0.0581 (2) | −0.32715 (17) | 0.0835 (11) | |
O3 | −0.5169 (4) | 0.0527 (3) | −0.25995 (16) | 0.0883 (11) | |
H3 | −0.5717 | 0.0347 | −0.2953 | 0.132* | |
O4 | 0.2862 (4) | 0.48368 (18) | 0.17580 (13) | 0.0582 (8) | |
O5 | 0.4833 (4) | 0.4676 (2) | 0.27727 (14) | 0.0721 (9) | |
H5 | 0.5463 | 0.4754 | 0.3103 | 0.108* | |
O6 | 0.3237 (4) | 0.4930 (2) | 0.35426 (15) | 0.0791 (10) | |
O7 | 0.6834 (4) | 0.7702 (2) | 0.60863 (14) | 0.0720 (9) | |
O8 | 0.3011 (4) | 0.7886 (3) | 0.56925 (16) | 0.0998 (13) | |
H8 | 0.2461 | 0.7820 | 0.5337 | 0.150* | |
O9 | 0.4771 (4) | 0.7688 (3) | 0.50218 (15) | 0.0938 (10) | |
O10 | 1.1784 (3) | 0.43722 (18) | 0.89018 (14) | 0.0562 (8) | |
O11 | 0.7802 (4) | 0.3336 (2) | 0.87660 (15) | 0.0654 (9) | |
H11 | 0.7140 | 0.3186 | 0.8447 | 0.098* | |
O12 | 0.9382 (3) | 0.3539 (2) | 0.79488 (15) | 0.0636 (8) | |
N1 | 0.4475 (4) | 0.6900 (2) | 0.22014 (18) | 0.0527 (9) | |
N2 | 1.0848 (5) | 0.7662 (3) | 0.46775 (19) | 0.0667 (11) | |
N3 | 0.6984 (5) | 0.4780 (3) | 0.3716 (2) | 0.0710 (11) | |
N4 | 0.2859 (5) | 0.0173 (3) | 0.6350 (2) | 0.0732 (12) | |
C1 | −0.0066 (5) | 0.1165 (3) | −0.1650 (2) | 0.0496 (11) | |
C2 | 0.1409 (5) | 0.1227 (3) | −0.1798 (2) | 0.0587 (12) | |
H2 | 0.1623 | 0.1154 | −0.2246 | 0.070* | |
C3 | 0.2607 (5) | 0.1399 (3) | −0.1289 (2) | 0.0573 (12) | |
H3A | 0.3614 | 0.1449 | −0.1400 | 0.069* | |
C4 | 0.2320 (5) | 0.1497 (3) | −0.06123 (19) | 0.0456 (10) | |
C5 | 0.0817 (5) | 0.1425 (3) | −0.0483 (2) | 0.0545 (11) | |
H5A | 0.0594 | 0.1495 | −0.0037 | 0.065* | |
C6 | −0.0400 (5) | 0.1252 (3) | −0.0988 (2) | 0.0543 (11) | |
H6 | −0.1411 | 0.1198 | −0.0881 | 0.065* | |
C7 | −0.2718 (5) | 0.0875 (3) | −0.2066 (2) | 0.0626 (13) | |
H7A | −0.2917 | 0.1446 | −0.1821 | 0.075* | |
H7B | −0.2947 | 0.0378 | −0.1790 | 0.075* | |
C8 | −0.3727 (6) | 0.0642 (3) | −0.2722 (3) | 0.0595 (13) | |
C9 | 0.3594 (5) | 0.1647 (3) | −0.0033 (2) | 0.0530 (11) | |
C10 | 0.3446 (6) | 0.0735 (3) | 0.0282 (2) | 0.0693 (14) | |
H10A | 0.2452 | 0.0600 | 0.0445 | 0.104* | |
H10B | 0.4228 | 0.0800 | 0.0650 | 0.104* | |
H10C | 0.3567 | 0.0233 | −0.0051 | 0.104* | |
C11 | 0.5223 (5) | 0.1848 (4) | −0.0274 (2) | 0.0774 (15) | |
H11A | 0.5387 | 0.1319 | −0.0570 | 0.116* | |
H11B | 0.5976 | 0.1966 | 0.0109 | 0.116* | |
H11C | 0.5314 | 0.2385 | −0.0509 | 0.116* | |
C12 | 0.3425 (4) | 0.2483 (3) | 0.04726 (19) | 0.0465 (10) | |
C13 | 0.3478 (5) | 0.3363 (3) | 0.0269 (2) | 0.0530 (11) | |
H13 | 0.3619 | 0.3433 | −0.0177 | 0.064* | |
C14 | 0.3329 (5) | 0.4127 (3) | 0.07031 (19) | 0.0522 (11) | |
H14 | 0.3393 | 0.4707 | 0.0553 | 0.063* | |
C15 | 0.3082 (4) | 0.4034 (3) | 0.13671 (19) | 0.0452 (10) | |
C16 | 0.3050 (5) | 0.3185 (3) | 0.1590 (2) | 0.0494 (10) | |
H16 | 0.2930 | 0.3124 | 0.2040 | 0.059* | |
C17 | 0.3198 (4) | 0.2408 (3) | 0.1139 (2) | 0.0478 (10) | |
H17 | 0.3143 | 0.1830 | 0.1291 | 0.057* | |
C18 | 0.2302 (5) | 0.4766 (3) | 0.2397 (2) | 0.0552 (11) | |
H18A | 0.1576 | 0.4185 | 0.2369 | 0.066* | |
H18B | 0.1748 | 0.5272 | 0.2503 | 0.066* | |
C19 | 0.3515 (5) | 0.4795 (3) | 0.2961 (2) | 0.0504 (11) | |
C20 | 0.7944 (5) | 0.7806 (3) | 0.6629 (2) | 0.0513 (11) | |
C21 | 0.8936 (5) | 0.7179 (3) | 0.6592 (2) | 0.0558 (11) | |
H21 | 0.8800 | 0.6697 | 0.6237 | 0.067* | |
C22 | 1.0136 (5) | 0.7272 (3) | 0.7090 (2) | 0.0550 (11) | |
H22 | 1.0822 | 0.6858 | 0.7052 | 0.066* | |
C23 | 1.0357 (5) | 0.7961 (3) | 0.76432 (19) | 0.0449 (10) | |
C24 | 0.9327 (5) | 0.8565 (3) | 0.7664 (2) | 0.0550 (11) | |
H24 | 0.9438 | 0.9037 | 0.8026 | 0.066* | |
C25 | 0.8125 (5) | 0.8495 (3) | 0.7163 (2) | 0.0603 (12) | |
H25 | 0.7449 | 0.8915 | 0.7192 | 0.072* | |
C26 | 0.5463 (6) | 0.7999 (4) | 0.6199 (2) | 0.0808 (16) | |
H26A | 0.5669 | 0.8660 | 0.6366 | 0.097* | |
H26B | 0.4974 | 0.7668 | 0.6539 | 0.097* | |
C27 | 0.4401 (7) | 0.7831 (5) | 0.5566 (3) | 0.0938 (10) | |
C28 | 1.1733 (5) | 0.8028 (3) | 0.8175 (2) | 0.0555 (11) | |
C29 | 1.1589 (7) | 0.8714 (3) | 0.8801 (2) | 0.0853 (18) | |
H29A | 1.0606 | 0.8540 | 0.8966 | 0.128* | |
H29B | 1.1683 | 0.9335 | 0.8681 | 0.128* | |
H29C | 1.2389 | 0.8696 | 0.9145 | 0.128* | |
C30 | 1.3190 (6) | 0.8405 (4) | 0.7854 (3) | 0.098 (2) | |
H30A | 1.4076 | 0.8426 | 0.8164 | 0.146* | |
H30B | 1.3144 | 0.9022 | 0.7749 | 0.146* | |
H30C | 1.3261 | 0.8004 | 0.7448 | 0.146* | |
C31 | 1.1775 (4) | 0.7066 (3) | 0.83881 (19) | 0.0440 (10) | |
C32 | 1.0711 (5) | 0.6680 (3) | 0.8788 (2) | 0.0511 (11) | |
H32 | 1.0003 | 0.7032 | 0.8949 | 0.061* | |
C33 | 1.0654 (5) | 0.5787 (3) | 0.8961 (2) | 0.0514 (11) | |
H33 | 0.9893 | 0.5543 | 0.9219 | 0.062* | |
C34 | 1.1719 (5) | 0.5263 (3) | 0.87506 (19) | 0.0436 (10) | |
C35 | 1.2821 (5) | 0.5634 (3) | 0.8365 (2) | 0.0530 (11) | |
H35 | 1.3551 | 0.5289 | 0.8221 | 0.064* | |
C36 | 1.2850 (5) | 0.6522 (3) | 0.8190 (2) | 0.0535 (11) | |
H36 | 1.3613 | 0.6763 | 0.7932 | 0.064* | |
C37 | 1.0442 (5) | 0.3861 (3) | 0.9106 (2) | 0.0578 (12) | |
H37A | 1.0084 | 0.4238 | 0.9470 | 0.069* | |
H37B | 1.0692 | 0.3309 | 0.9278 | 0.069* | |
C38 | 0.9154 (5) | 0.3564 (3) | 0.8541 (2) | 0.0511 (11) | |
C39 | 0.5847 (5) | 0.6722 (3) | 0.2055 (2) | 0.0518 (11) | |
H39 | 0.5960 | 0.6506 | 0.1610 | 0.062* | |
C40 | 0.7106 (5) | 0.6837 (3) | 0.2519 (2) | 0.0511 (11) | |
H40 | 0.8038 | 0.6705 | 0.2388 | 0.061* | |
C41 | 0.6964 (5) | 0.7153 (3) | 0.3188 (2) | 0.0470 (10) | |
C42 | 0.5519 (5) | 0.7301 (3) | 0.3347 (2) | 0.0574 (12) | |
H42 | 0.5355 | 0.7487 | 0.3791 | 0.069* | |
C43 | 0.4334 (5) | 0.7171 (3) | 0.2845 (2) | 0.0585 (12) | |
H43 | 0.3379 | 0.7279 | 0.2963 | 0.070* | |
C44 | 0.8315 (5) | 0.7337 (3) | 0.37042 (19) | 0.0468 (10) | |
C45 | 0.9795 (5) | 0.7559 (3) | 0.3534 (2) | 0.0687 (14) | |
H45 | 0.9976 | 0.7602 | 0.3088 | 0.082* | |
C46 | 1.1021 (6) | 0.7720 (4) | 0.4032 (2) | 0.0761 (15) | |
H46 | 1.2010 | 0.7875 | 0.3906 | 0.091* | |
C47 | 0.9420 (6) | 0.7478 (3) | 0.4831 (2) | 0.0687 (13) | |
H47 | 0.9266 | 0.7469 | 0.5284 | 0.082* | |
C48 | 0.8133 (5) | 0.7298 (3) | 0.4374 (2) | 0.0618 (12) | |
H48 | 0.7158 | 0.7153 | 0.4517 | 0.074* | |
C49 | 0.8451 (6) | 0.4955 (3) | 0.3585 (2) | 0.0679 (13) | |
H49 | 0.8672 | 0.5022 | 0.3146 | 0.082* | |
C50 | 0.9643 (5) | 0.5038 (3) | 0.4074 (2) | 0.0607 (12) | |
H50 | 1.0650 | 0.5154 | 0.3962 | 0.073* | |
C51 | 0.9366 (5) | 0.4951 (3) | 0.4727 (2) | 0.0581 (12) | |
C52 | 0.7853 (6) | 0.4784 (4) | 0.4862 (3) | 0.0919 (18) | |
H52 | 0.7606 | 0.4725 | 0.5299 | 0.110* | |
C53 | 0.6698 (6) | 0.4703 (4) | 0.4343 (3) | 0.0946 (18) | |
H53 | 0.5680 | 0.4590 | 0.4442 | 0.114* | |
C54 | 0.1414 (7) | −0.0080 (4) | 0.6425 (3) | 0.0881 (18) | |
H54 | 0.1147 | −0.0220 | 0.6845 | 0.106* | |
C55 | 0.0244 (6) | −0.0156 (4) | 0.5913 (2) | 0.0831 (16) | |
H55 | −0.0776 | −0.0332 | 0.5994 | 0.100* | |
C56 | 0.0610 (5) | 0.0034 (3) | 0.5281 (2) | 0.0574 (12) | |
C57 | 0.2143 (6) | 0.0290 (4) | 0.5213 (3) | 0.0886 (17) | |
H57 | 0.2460 | 0.0422 | 0.4798 | 0.106* | |
C58 | 0.3228 (6) | 0.0354 (4) | 0.5757 (3) | 0.0878 (17) | |
H58 | 0.4261 | 0.0532 | 0.5696 | 0.105* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.063 (2) | 0.081 (2) | 0.0501 (19) | 0.0081 (17) | −0.0143 (17) | 0.0025 (15) |
O2 | 0.082 (3) | 0.110 (3) | 0.056 (2) | 0.022 (2) | −0.017 (2) | 0.0066 (19) |
O3 | 0.070 (3) | 0.116 (3) | 0.066 (2) | −0.016 (2) | −0.022 (2) | 0.023 (2) |
O4 | 0.082 (2) | 0.0487 (16) | 0.0411 (16) | 0.0096 (15) | −0.0065 (16) | 0.0038 (13) |
O5 | 0.050 (2) | 0.118 (3) | 0.0454 (18) | 0.0229 (19) | −0.0070 (16) | −0.0040 (18) |
O6 | 0.074 (2) | 0.120 (3) | 0.0402 (18) | 0.014 (2) | 0.0047 (17) | 0.0012 (17) |
O7 | 0.063 (2) | 0.108 (3) | 0.0466 (18) | 0.0314 (19) | −0.0089 (17) | 0.0011 (16) |
O8 | 0.064 (3) | 0.177 (4) | 0.056 (2) | 0.039 (2) | −0.0118 (19) | −0.011 (2) |
O9 | 0.060 (2) | 0.174 (3) | 0.0478 (17) | 0.0291 (19) | −0.0004 (17) | 0.009 (2) |
O10 | 0.0464 (18) | 0.0528 (17) | 0.0708 (19) | 0.0115 (14) | −0.0048 (15) | 0.0164 (14) |
O11 | 0.045 (2) | 0.078 (2) | 0.072 (2) | 0.0043 (16) | −0.0025 (17) | 0.0221 (17) |
O12 | 0.058 (2) | 0.085 (2) | 0.0507 (19) | 0.0289 (16) | −0.0018 (16) | 0.0010 (16) |
N1 | 0.043 (2) | 0.050 (2) | 0.063 (2) | 0.0077 (16) | −0.0051 (19) | 0.0045 (17) |
N2 | 0.056 (3) | 0.092 (3) | 0.050 (2) | 0.020 (2) | −0.003 (2) | −0.002 (2) |
N3 | 0.060 (3) | 0.094 (3) | 0.056 (3) | 0.020 (2) | −0.011 (2) | −0.001 (2) |
N4 | 0.069 (3) | 0.076 (3) | 0.066 (3) | −0.005 (2) | −0.016 (2) | 0.015 (2) |
C1 | 0.052 (3) | 0.052 (2) | 0.042 (2) | 0.008 (2) | −0.011 (2) | 0.0026 (19) |
C2 | 0.062 (3) | 0.071 (3) | 0.041 (3) | 0.009 (2) | 0.001 (2) | 0.003 (2) |
C3 | 0.055 (3) | 0.062 (3) | 0.056 (3) | 0.011 (2) | 0.006 (2) | 0.007 (2) |
C4 | 0.047 (3) | 0.046 (2) | 0.044 (2) | 0.0116 (19) | 0.001 (2) | 0.0055 (18) |
C5 | 0.053 (3) | 0.069 (3) | 0.041 (2) | 0.013 (2) | 0.000 (2) | 0.004 (2) |
C6 | 0.045 (3) | 0.069 (3) | 0.048 (3) | 0.012 (2) | −0.001 (2) | 0.006 (2) |
C7 | 0.062 (3) | 0.060 (3) | 0.059 (3) | 0.003 (2) | −0.015 (3) | 0.008 (2) |
C8 | 0.065 (4) | 0.052 (3) | 0.058 (3) | 0.006 (2) | −0.020 (3) | 0.014 (2) |
C9 | 0.047 (3) | 0.062 (3) | 0.050 (3) | 0.016 (2) | −0.005 (2) | 0.003 (2) |
C10 | 0.089 (4) | 0.061 (3) | 0.059 (3) | 0.032 (3) | −0.017 (3) | 0.004 (2) |
C11 | 0.055 (3) | 0.103 (4) | 0.075 (3) | 0.028 (3) | −0.002 (3) | −0.001 (3) |
C12 | 0.038 (2) | 0.052 (2) | 0.048 (2) | 0.0068 (18) | −0.007 (2) | 0.0068 (19) |
C13 | 0.059 (3) | 0.062 (3) | 0.039 (2) | 0.011 (2) | −0.001 (2) | 0.013 (2) |
C14 | 0.066 (3) | 0.046 (2) | 0.044 (2) | 0.009 (2) | −0.005 (2) | 0.0127 (19) |
C15 | 0.043 (3) | 0.043 (2) | 0.046 (2) | 0.0048 (18) | −0.007 (2) | 0.0047 (19) |
C16 | 0.052 (3) | 0.052 (3) | 0.042 (2) | 0.006 (2) | −0.006 (2) | 0.0090 (19) |
C17 | 0.043 (3) | 0.048 (2) | 0.052 (3) | 0.0042 (19) | −0.004 (2) | 0.014 (2) |
C18 | 0.055 (3) | 0.058 (3) | 0.051 (3) | 0.014 (2) | −0.004 (2) | 0.003 (2) |
C19 | 0.051 (3) | 0.054 (3) | 0.045 (3) | 0.008 (2) | −0.003 (2) | 0.0062 (19) |
C20 | 0.051 (3) | 0.065 (3) | 0.038 (2) | 0.013 (2) | −0.006 (2) | 0.008 (2) |
C21 | 0.072 (3) | 0.062 (3) | 0.035 (2) | 0.021 (2) | 0.001 (2) | 0.0058 (19) |
C22 | 0.061 (3) | 0.060 (3) | 0.049 (3) | 0.025 (2) | 0.000 (2) | 0.012 (2) |
C23 | 0.042 (3) | 0.042 (2) | 0.049 (2) | 0.0025 (18) | −0.004 (2) | 0.0137 (19) |
C24 | 0.063 (3) | 0.052 (2) | 0.046 (3) | 0.012 (2) | −0.011 (2) | 0.0008 (19) |
C25 | 0.063 (3) | 0.065 (3) | 0.056 (3) | 0.028 (2) | −0.004 (2) | 0.007 (2) |
C26 | 0.053 (3) | 0.130 (5) | 0.056 (3) | 0.027 (3) | −0.009 (3) | −0.007 (3) |
C27 | 0.060 (2) | 0.174 (3) | 0.0478 (17) | 0.0291 (19) | −0.0004 (17) | 0.009 (2) |
C28 | 0.043 (3) | 0.054 (3) | 0.065 (3) | 0.001 (2) | −0.012 (2) | 0.014 (2) |
C29 | 0.118 (5) | 0.052 (3) | 0.076 (3) | 0.018 (3) | −0.048 (3) | −0.003 (2) |
C30 | 0.055 (3) | 0.088 (4) | 0.151 (5) | −0.008 (3) | −0.011 (4) | 0.066 (4) |
C31 | 0.035 (2) | 0.048 (2) | 0.047 (2) | 0.0086 (19) | −0.006 (2) | 0.0057 (18) |
C32 | 0.041 (3) | 0.057 (3) | 0.058 (3) | 0.019 (2) | 0.004 (2) | 0.006 (2) |
C33 | 0.041 (3) | 0.064 (3) | 0.053 (3) | 0.011 (2) | 0.009 (2) | 0.015 (2) |
C34 | 0.037 (2) | 0.051 (2) | 0.043 (2) | 0.0114 (19) | −0.007 (2) | 0.0079 (18) |
C35 | 0.039 (3) | 0.063 (3) | 0.060 (3) | 0.016 (2) | 0.006 (2) | 0.008 (2) |
C36 | 0.044 (3) | 0.061 (3) | 0.055 (3) | 0.003 (2) | 0.010 (2) | 0.016 (2) |
C37 | 0.055 (3) | 0.055 (3) | 0.062 (3) | 0.003 (2) | −0.007 (2) | 0.019 (2) |
C38 | 0.052 (3) | 0.041 (2) | 0.062 (3) | 0.019 (2) | −0.010 (3) | 0.007 (2) |
C39 | 0.049 (3) | 0.053 (2) | 0.051 (3) | 0.009 (2) | −0.001 (2) | 0.0028 (19) |
C40 | 0.042 (3) | 0.059 (3) | 0.051 (3) | 0.010 (2) | 0.003 (2) | −0.001 (2) |
C41 | 0.035 (3) | 0.050 (2) | 0.054 (3) | 0.0081 (18) | 0.000 (2) | 0.0036 (19) |
C42 | 0.045 (3) | 0.066 (3) | 0.058 (3) | 0.008 (2) | 0.003 (2) | −0.002 (2) |
C43 | 0.039 (3) | 0.065 (3) | 0.072 (3) | 0.014 (2) | 0.002 (2) | 0.003 (2) |
C44 | 0.042 (3) | 0.055 (2) | 0.042 (2) | 0.0092 (19) | 0.001 (2) | 0.0005 (18) |
C45 | 0.049 (3) | 0.107 (4) | 0.044 (3) | 0.005 (3) | 0.004 (2) | 0.001 (2) |
C46 | 0.044 (3) | 0.118 (4) | 0.058 (3) | 0.006 (3) | −0.001 (3) | −0.004 (3) |
C47 | 0.065 (4) | 0.098 (4) | 0.047 (3) | 0.024 (3) | 0.008 (3) | 0.011 (2) |
C48 | 0.052 (3) | 0.087 (3) | 0.049 (3) | 0.021 (2) | 0.006 (2) | 0.007 (2) |
C49 | 0.067 (4) | 0.086 (3) | 0.051 (3) | 0.026 (3) | −0.004 (3) | −0.004 (2) |
C50 | 0.050 (3) | 0.078 (3) | 0.051 (3) | 0.019 (2) | −0.006 (2) | −0.007 (2) |
C51 | 0.053 (3) | 0.069 (3) | 0.050 (3) | 0.017 (2) | −0.012 (2) | 0.000 (2) |
C52 | 0.052 (4) | 0.158 (6) | 0.061 (3) | 0.007 (3) | −0.008 (3) | 0.019 (3) |
C53 | 0.053 (4) | 0.152 (6) | 0.075 (4) | 0.009 (3) | −0.010 (3) | 0.020 (4) |
C54 | 0.082 (4) | 0.116 (4) | 0.055 (3) | −0.016 (3) | −0.015 (3) | 0.022 (3) |
C55 | 0.066 (4) | 0.119 (4) | 0.054 (3) | −0.012 (3) | −0.011 (3) | 0.020 (3) |
C56 | 0.058 (3) | 0.061 (3) | 0.046 (3) | −0.002 (2) | −0.010 (2) | 0.008 (2) |
C57 | 0.064 (4) | 0.131 (5) | 0.065 (3) | −0.006 (3) | −0.007 (3) | 0.033 (3) |
C58 | 0.051 (4) | 0.122 (5) | 0.085 (4) | −0.004 (3) | −0.009 (3) | 0.027 (3) |
Geometric parameters (Å, º) top
O1—C1 | 1.382 (4) | C22—C23 | 1.390 (5) |
O1—C7 | 1.406 (5) | C22—H22 | 0.9300 |
O2—C8 | 1.201 (5) | C23—C24 | 1.376 (6) |
O3—C8 | 1.306 (6) | C23—C28 | 1.544 (6) |
O3—H3 | 0.8200 | C24—C25 | 1.395 (6) |
O4—C15 | 1.388 (4) | C24—H24 | 0.9300 |
O4—C18 | 1.418 (5) | C25—H25 | 0.9300 |
O5—C19 | 1.289 (5) | C26—C27 | 1.495 (7) |
O5—H5 | 0.8200 | C26—H26A | 0.9700 |
O6—C19 | 1.211 (5) | C26—H26B | 0.9700 |
O7—C26 | 1.384 (5) | C28—C31 | 1.528 (5) |
O7—C20 | 1.391 (5) | C28—C30 | 1.535 (6) |
O8—C27 | 1.291 (6) | C28—C29 | 1.544 (6) |
O8—H8 | 0.8200 | C29—H29A | 0.9600 |
O9—C27 | 1.169 (5) | C29—H29B | 0.9600 |
O10—C34 | 1.386 (4) | C29—H29C | 0.9600 |
O10—C37 | 1.410 (5) | C30—H30A | 0.9600 |
O11—C38 | 1.316 (5) | C30—H30B | 0.9600 |
O11—H11 | 0.8200 | C30—H30C | 0.9600 |
O12—C38 | 1.218 (5) | C31—C32 | 1.376 (5) |
N1—C43 | 1.329 (5) | C31—C36 | 1.394 (5) |
N1—C39 | 1.333 (5) | C32—C33 | 1.388 (5) |
N2—C47 | 1.317 (6) | C32—H32 | 0.9300 |
N2—C46 | 1.327 (6) | C33—C34 | 1.375 (5) |
N3—C53 | 1.318 (6) | C33—H33 | 0.9300 |
N3—C49 | 1.334 (6) | C34—C35 | 1.371 (5) |
N4—C54 | 1.297 (6) | C35—C36 | 1.384 (5) |
N4—C58 | 1.303 (6) | C35—H35 | 0.9300 |
C1—C2 | 1.353 (6) | C36—H36 | 0.9300 |
C1—C6 | 1.380 (5) | C37—C38 | 1.519 (6) |
C2—C3 | 1.389 (6) | C37—H37A | 0.9700 |
C2—H2 | 0.9300 | C37—H37B | 0.9700 |
C3—C4 | 1.396 (5) | C39—C40 | 1.376 (5) |
C3—H3A | 0.9300 | C39—H39 | 0.9300 |
C4—C5 | 1.366 (5) | C40—C41 | 1.391 (5) |
C4—C9 | 1.530 (5) | C40—H40 | 0.9300 |
C5—C6 | 1.394 (5) | C41—C42 | 1.389 (5) |
C5—H5A | 0.9300 | C41—C44 | 1.493 (5) |
C6—H6 | 0.9300 | C42—C43 | 1.375 (6) |
C7—C8 | 1.509 (6) | C42—H42 | 0.9300 |
C7—H7A | 0.9700 | C43—H43 | 0.9300 |
C7—H7B | 0.9700 | C44—C48 | 1.374 (5) |
C9—C12 | 1.534 (5) | C44—C45 | 1.375 (6) |
C9—C10 | 1.537 (6) | C45—C46 | 1.392 (6) |
C9—C11 | 1.548 (6) | C45—H45 | 0.9300 |
C10—H10A | 0.9600 | C46—H46 | 0.9300 |
C10—H10B | 0.9600 | C47—C48 | 1.380 (6) |
C10—H10C | 0.9600 | C47—H47 | 0.9300 |
C11—H11A | 0.9600 | C48—H48 | 0.9300 |
C11—H11B | 0.9600 | C49—C50 | 1.369 (6) |
C11—H11C | 0.9600 | C49—H49 | 0.9300 |
C12—C17 | 1.382 (5) | C50—C51 | 1.369 (6) |
C12—C13 | 1.393 (5) | C50—H50 | 0.9300 |
C13—C14 | 1.368 (5) | C51—C52 | 1.375 (6) |
C13—H13 | 0.9300 | C51—C51i | 1.488 (8) |
C14—C15 | 1.386 (5) | C52—C53 | 1.387 (7) |
C14—H14 | 0.9300 | C52—H52 | 0.9300 |
C15—C16 | 1.369 (5) | C53—H53 | 0.9300 |
C16—C17 | 1.400 (5) | C54—C55 | 1.388 (7) |
C16—H16 | 0.9300 | C54—H54 | 0.9300 |
C17—H17 | 0.9300 | C55—C56 | 1.381 (6) |
C18—C19 | 1.496 (6) | C55—H55 | 0.9300 |
C18—H18A | 0.9700 | C56—C57 | 1.370 (7) |
C18—H18B | 0.9700 | C56—C56ii | 1.487 (8) |
C20—C25 | 1.365 (6) | C57—C58 | 1.386 (7) |
C20—C21 | 1.376 (6) | C57—H57 | 0.9300 |
C21—C22 | 1.384 (6) | C58—H58 | 0.9300 |
C21—H21 | 0.9300 | | |
| | | |
C1—O1—C7 | 117.8 (3) | O9—C27—O8 | 123.6 (5) |
C8—O3—H3 | 109.5 | O9—C27—C26 | 125.0 (5) |
C15—O4—C18 | 119.0 (3) | O8—C27—C26 | 111.3 (4) |
C19—O5—H5 | 109.5 | C31—C28—C30 | 112.0 (4) |
C26—O7—C20 | 118.1 (3) | C31—C28—C29 | 109.0 (3) |
C27—O8—H8 | 109.5 | C30—C28—C29 | 108.6 (4) |
C34—O10—C37 | 117.3 (3) | C31—C28—C23 | 109.5 (3) |
C38—O11—H11 | 109.5 | C30—C28—C23 | 107.2 (4) |
C43—N1—C39 | 116.4 (4) | C29—C28—C23 | 110.6 (4) |
C47—N2—C46 | 115.8 (4) | C28—C29—H29A | 109.5 |
C53—N3—C49 | 117.8 (4) | C28—C29—H29B | 109.5 |
C54—N4—C58 | 117.9 (5) | H29A—C29—H29B | 109.5 |
C2—C1—C6 | 120.2 (4) | C28—C29—H29C | 109.5 |
C2—C1—O1 | 115.8 (4) | H29A—C29—H29C | 109.5 |
C6—C1—O1 | 124.0 (4) | H29B—C29—H29C | 109.5 |
C1—C2—C3 | 120.7 (4) | C28—C30—H30A | 109.5 |
C1—C2—H2 | 119.7 | C28—C30—H30B | 109.5 |
C3—C2—H2 | 119.7 | H30A—C30—H30B | 109.5 |
C2—C3—C4 | 121.0 (4) | C28—C30—H30C | 109.5 |
C2—C3—H3A | 119.5 | H30A—C30—H30C | 109.5 |
C4—C3—H3A | 119.5 | H30B—C30—H30C | 109.5 |
C5—C4—C3 | 116.6 (4) | C32—C31—C36 | 115.9 (4) |
C5—C4—C9 | 120.5 (4) | C32—C31—C28 | 120.7 (4) |
C3—C4—C9 | 122.9 (4) | C36—C31—C28 | 123.4 (4) |
C4—C5—C6 | 123.2 (4) | C31—C32—C33 | 122.5 (4) |
C4—C5—H5A | 118.4 | C31—C32—H32 | 118.7 |
C6—C5—H5A | 118.4 | C33—C32—H32 | 118.7 |
C1—C6—C5 | 118.3 (4) | C34—C33—C32 | 120.1 (4) |
C1—C6—H6 | 120.8 | C34—C33—H33 | 120.0 |
C5—C6—H6 | 120.8 | C32—C33—H33 | 120.0 |
O1—C7—C8 | 109.6 (4) | C35—C34—C33 | 118.9 (4) |
O1—C7—H7A | 109.8 | C35—C34—O10 | 116.2 (4) |
C8—C7—H7A | 109.8 | C33—C34—O10 | 124.9 (4) |
O1—C7—H7B | 109.8 | C34—C35—C36 | 120.3 (4) |
C8—C7—H7B | 109.8 | C34—C35—H35 | 119.9 |
H7A—C7—H7B | 108.2 | C36—C35—H35 | 119.9 |
O2—C8—O3 | 125.4 (4) | C35—C36—C31 | 122.2 (4) |
O2—C8—C7 | 125.2 (5) | C35—C36—H36 | 118.9 |
O3—C8—C7 | 109.4 (4) | C31—C36—H36 | 118.9 |
C4—C9—C12 | 109.6 (3) | O10—C37—C38 | 113.2 (3) |
C4—C9—C10 | 106.8 (3) | O10—C37—H37A | 108.9 |
C12—C9—C10 | 112.5 (3) | C38—C37—H37A | 108.9 |
C4—C9—C11 | 112.7 (3) | O10—C37—H37B | 108.9 |
C12—C9—C11 | 107.5 (3) | C38—C37—H37B | 108.9 |
C10—C9—C11 | 107.8 (4) | H37A—C37—H37B | 107.7 |
C9—C10—H10A | 109.5 | O12—C38—O11 | 125.0 (4) |
C9—C10—H10B | 109.5 | O12—C38—C37 | 122.5 (4) |
H10A—C10—H10B | 109.5 | O11—C38—C37 | 112.5 (4) |
C9—C10—H10C | 109.5 | N1—C39—C40 | 124.2 (4) |
H10A—C10—H10C | 109.5 | N1—C39—H39 | 117.9 |
H10B—C10—H10C | 109.5 | C40—C39—H39 | 117.9 |
C9—C11—H11A | 109.5 | C39—C40—C41 | 119.0 (4) |
C9—C11—H11B | 109.5 | C39—C40—H40 | 120.5 |
H11A—C11—H11B | 109.5 | C41—C40—H40 | 120.5 |
C9—C11—H11C | 109.5 | C42—C41—C40 | 116.9 (4) |
H11A—C11—H11C | 109.5 | C42—C41—C44 | 122.0 (4) |
H11B—C11—H11C | 109.5 | C40—C41—C44 | 121.1 (4) |
C17—C12—C13 | 117.0 (4) | C43—C42—C41 | 119.6 (4) |
C17—C12—C9 | 122.6 (4) | C43—C42—H42 | 120.2 |
C13—C12—C9 | 120.4 (4) | C41—C42—H42 | 120.2 |
C14—C13—C12 | 122.3 (4) | N1—C43—C42 | 123.8 (4) |
C14—C13—H13 | 118.8 | N1—C43—H43 | 118.1 |
C12—C13—H13 | 118.8 | C42—C43—H43 | 118.1 |
C13—C14—C15 | 119.8 (4) | C48—C44—C45 | 116.9 (4) |
C13—C14—H14 | 120.1 | C48—C44—C41 | 121.3 (4) |
C15—C14—H14 | 120.1 | C45—C44—C41 | 121.8 (4) |
C16—C15—C14 | 119.6 (4) | C44—C45—C46 | 119.8 (4) |
C16—C15—O4 | 124.9 (4) | C44—C45—H45 | 120.1 |
C14—C15—O4 | 115.5 (3) | C46—C45—H45 | 120.1 |
C15—C16—C17 | 119.8 (4) | N2—C46—C45 | 123.3 (5) |
C15—C16—H16 | 120.1 | N2—C46—H46 | 118.4 |
C17—C16—H16 | 120.1 | C45—C46—H46 | 118.4 |
C12—C17—C16 | 121.4 (4) | N2—C47—C48 | 125.1 (4) |
C12—C17—H17 | 119.3 | N2—C47—H47 | 117.4 |
C16—C17—H17 | 119.3 | C48—C47—H47 | 117.4 |
O4—C18—C19 | 114.7 (4) | C44—C48—C47 | 119.0 (4) |
O4—C18—H18A | 108.6 | C44—C48—H48 | 120.5 |
C19—C18—H18A | 108.6 | C47—C48—H48 | 120.5 |
O4—C18—H18B | 108.6 | N3—C49—C50 | 122.4 (4) |
C19—C18—H18B | 108.6 | N3—C49—H49 | 118.8 |
H18A—C18—H18B | 107.6 | C50—C49—H49 | 118.8 |
O6—C19—O5 | 124.6 (4) | C51—C50—C49 | 120.6 (5) |
O6—C19—C18 | 120.8 (4) | C51—C50—H50 | 119.7 |
O5—C19—C18 | 114.6 (4) | C49—C50—H50 | 119.7 |
C25—C20—C21 | 119.9 (4) | C50—C51—C52 | 116.9 (4) |
C25—C20—O7 | 124.3 (4) | C50—C51—C51i | 122.0 (6) |
C21—C20—O7 | 115.7 (4) | C52—C51—C51i | 121.1 (5) |
C20—C21—C22 | 119.4 (4) | C51—C52—C53 | 119.7 (5) |
C20—C21—H21 | 120.3 | C51—C52—H52 | 120.1 |
C22—C21—H21 | 120.3 | C53—C52—H52 | 120.1 |
C21—C22—C23 | 122.5 (4) | N3—C53—C52 | 122.6 (5) |
C21—C22—H22 | 118.8 | N3—C53—H53 | 118.7 |
C23—C22—H22 | 118.8 | C52—C53—H53 | 118.7 |
C24—C23—C22 | 116.2 (4) | N4—C54—C55 | 123.7 (5) |
C24—C23—C28 | 124.2 (4) | N4—C54—H54 | 118.1 |
C22—C23—C28 | 119.6 (4) | C55—C54—H54 | 118.1 |
C23—C24—C25 | 122.3 (4) | C56—C55—C54 | 119.3 (5) |
C23—C24—H24 | 118.8 | C56—C55—H55 | 120.3 |
C25—C24—H24 | 118.8 | C54—C55—H55 | 120.3 |
C20—C25—C24 | 119.7 (4) | C57—C56—C55 | 115.8 (4) |
C20—C25—H25 | 120.2 | C57—C56—C56ii | 123.2 (5) |
C24—C25—H25 | 120.2 | C55—C56—C56ii | 121.0 (6) |
O7—C26—C27 | 111.1 (4) | C56—C57—C58 | 120.6 (5) |
O7—C26—H26A | 109.4 | C56—C57—H57 | 119.7 |
C27—C26—H26A | 109.4 | C58—C57—H57 | 119.7 |
O7—C26—H26B | 109.4 | N4—C58—C57 | 122.6 (5) |
C27—C26—H26B | 109.4 | N4—C58—H58 | 118.7 |
H26A—C26—H26B | 108.0 | C57—C58—H58 | 118.7 |
| | | |
C7—O1—C1—C2 | 177.3 (4) | C22—C23—C28—C30 | 72.0 (5) |
C7—O1—C1—C6 | −0.9 (6) | C24—C23—C28—C29 | 12.4 (6) |
C6—C1—C2—C3 | −1.3 (6) | C22—C23—C28—C29 | −169.7 (4) |
O1—C1—C2—C3 | −179.6 (3) | C30—C28—C31—C32 | 168.6 (4) |
C1—C2—C3—C4 | 1.0 (6) | C29—C28—C31—C32 | 48.5 (5) |
C2—C3—C4—C5 | −0.7 (6) | C23—C28—C31—C32 | −72.6 (5) |
C2—C3—C4—C9 | 177.4 (4) | C30—C28—C31—C36 | −12.3 (6) |
C3—C4—C5—C6 | 0.7 (6) | C29—C28—C31—C36 | −132.5 (4) |
C9—C4—C5—C6 | −177.4 (4) | C23—C28—C31—C36 | 106.5 (4) |
C2—C1—C6—C5 | 1.4 (6) | C36—C31—C32—C33 | −3.0 (6) |
O1—C1—C6—C5 | 179.5 (4) | C28—C31—C32—C33 | 176.1 (4) |
C4—C5—C6—C1 | −1.1 (6) | C31—C32—C33—C34 | 2.3 (6) |
C1—O1—C7—C8 | −177.3 (3) | C32—C33—C34—C35 | −0.6 (6) |
O1—C7—C8—O2 | −1.5 (6) | C32—C33—C34—O10 | 179.0 (4) |
O1—C7—C8—O3 | 179.2 (4) | C37—O10—C34—C35 | −160.6 (3) |
C5—C4—C9—C12 | −52.2 (5) | C37—O10—C34—C33 | 19.8 (5) |
C3—C4—C9—C12 | 129.7 (4) | C33—C34—C35—C36 | −0.2 (6) |
C5—C4—C9—C10 | 69.9 (5) | O10—C34—C35—C36 | −179.8 (4) |
C3—C4—C9—C10 | −108.2 (4) | C34—C35—C36—C31 | −0.6 (6) |
C5—C4—C9—C11 | −172.0 (4) | C32—C31—C36—C35 | 2.1 (6) |
C3—C4—C9—C11 | 10.0 (5) | C28—C31—C36—C35 | −177.0 (4) |
C4—C9—C12—C17 | 120.0 (4) | C34—O10—C37—C38 | 69.6 (4) |
C10—C9—C12—C17 | 1.3 (6) | O10—C37—C38—O12 | 19.1 (6) |
C11—C9—C12—C17 | −117.2 (4) | O10—C37—C38—O11 | −161.5 (3) |
C4—C9—C12—C13 | −59.3 (5) | C43—N1—C39—C40 | −2.6 (6) |
C10—C9—C12—C13 | −177.9 (4) | N1—C39—C40—C41 | 0.4 (6) |
C11—C9—C12—C13 | 63.6 (5) | C39—C40—C41—C42 | 2.3 (6) |
C17—C12—C13—C14 | 0.6 (6) | C39—C40—C41—C44 | −176.8 (3) |
C9—C12—C13—C14 | 179.9 (4) | C40—C41—C42—C43 | −2.7 (6) |
C12—C13—C14—C15 | −1.5 (6) | C44—C41—C42—C43 | 176.3 (4) |
C13—C14—C15—C16 | 2.6 (6) | C39—N1—C43—C42 | 2.2 (6) |
C13—C14—C15—O4 | −176.6 (4) | C41—C42—C43—N1 | 0.5 (6) |
C18—O4—C15—C16 | −11.6 (6) | C42—C41—C44—C48 | 26.2 (6) |
C18—O4—C15—C14 | 167.5 (4) | C40—C41—C44—C48 | −154.8 (4) |
C14—C15—C16—C17 | −2.8 (6) | C42—C41—C44—C45 | −153.3 (4) |
O4—C15—C16—C17 | 176.2 (4) | C40—C41—C44—C45 | 25.8 (6) |
C13—C12—C17—C16 | −0.8 (6) | C48—C44—C45—C46 | 0.9 (7) |
C9—C12—C17—C16 | 179.9 (4) | C41—C44—C45—C46 | −179.7 (4) |
C15—C16—C17—C12 | 2.0 (6) | C47—N2—C46—C45 | −2.7 (7) |
C15—O4—C18—C19 | 86.2 (4) | C44—C45—C46—N2 | 0.6 (8) |
O4—C18—C19—O6 | 164.9 (4) | C46—N2—C47—C48 | 3.5 (7) |
O4—C18—C19—O5 | −14.5 (5) | C45—C44—C48—C47 | −0.2 (6) |
C26—O7—C20—C25 | −29.7 (6) | C41—C44—C48—C47 | −179.7 (4) |
C26—O7—C20—C21 | 152.7 (5) | N2—C47—C48—C44 | −2.1 (7) |
C25—C20—C21—C22 | −1.9 (6) | C53—N3—C49—C50 | 1.1 (7) |
O7—C20—C21—C22 | 175.8 (4) | N3—C49—C50—C51 | −0.5 (7) |
C20—C21—C22—C23 | 2.3 (6) | C49—C50—C51—C52 | −0.4 (7) |
C21—C22—C23—C24 | −1.4 (6) | C49—C50—C51—C51i | −179.1 (5) |
C21—C22—C23—C28 | −179.4 (4) | C50—C51—C52—C53 | 0.6 (8) |
C22—C23—C24—C25 | 0.2 (6) | C51i—C51—C52—C53 | 179.4 (6) |
C28—C23—C24—C25 | 178.1 (4) | C49—N3—C53—C52 | −0.8 (8) |
C21—C20—C25—C24 | 0.8 (7) | C51—C52—C53—N3 | −0.1 (9) |
O7—C20—C25—C24 | −176.7 (4) | C58—N4—C54—C55 | −1.0 (9) |
C23—C24—C25—C20 | 0.0 (7) | N4—C54—C55—C56 | 0.9 (9) |
C20—O7—C26—C27 | −179.6 (4) | C54—C55—C56—C57 | −0.1 (8) |
O7—C26—C27—O9 | −17.6 (9) | C54—C55—C56—C56ii | −179.7 (5) |
O7—C26—C27—O8 | 164.1 (5) | C55—C56—C57—C58 | −0.4 (8) |
C24—C23—C28—C31 | 132.5 (4) | C56ii—C56—C57—C58 | 179.2 (5) |
C22—C23—C28—C31 | −49.7 (5) | C54—N4—C58—C57 | 0.4 (8) |
C24—C23—C28—C30 | −105.8 (5) | C56—C57—C58—N4 | 0.3 (9) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N4iii | 0.82 | 1.78 | 2.584 (5) | 166 |
O5—H5···N3 | 0.82 | 1.75 | 2.561 (5) | 169 |
O8—H8···N2iv | 0.82 | 1.84 | 2.647 (5) | 166 |
O11—H11···N1v | 0.82 | 1.84 | 2.647 (4) | 167 |
C18—H18B···O12v | 0.97 | 2.39 | 3.227 (5) | 144 |
C35—H35···O5i | 0.93 | 2.54 | 3.245 (5) | 133 |
C40—H40···O12i | 0.93 | 2.50 | 3.432 (5) | 176 |
C42—H42···O9 | 0.93 | 2.56 | 3.476 (5) | 170 |
C50—H50···O6vi | 0.93 | 2.56 | 3.458 (6) | 162 |
C52—H52···O6v | 0.93 | 2.52 | 3.414 (6) | 162 |
C16—H16···Cg1v | 0.93 | 2.90 | 3.669 (5) | 141 |
C32—H32···Cg2v | 0.93 | 2.89 | 3.625 (5) | 137 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) x−1, y, z−1; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C2H8N+·C19H19O6− | C19H20O6·C10H8N2 |
Mr | 389.44 | 500.53 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 6.9028 (14), 27.756 (6), 12.624 (4) | 8.8698 (15), 14.673 (2), 20.087 (3) |
α, β, γ (°) | 90, 120.21 (2), 90 | 96.749 (2), 94.180 (3), 99.751 (4) |
V (Å3) | 2090.2 (9) | 2547.1 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 | 0.22 × 0.18 × 0.16 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.982, 0.985 | 0.980, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10877, 3693, 2126 | 13525, 8949, 4313 |
Rint | 0.043 | 0.045 |
(sin θ/λ)max (Å−1) | 0.596 | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.134, 1.03 | 0.070, 0.235, 1.02 |
No. of reflections | 3693 | 8949 |
No. of parameters | 257 | 670 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.17 | 0.74, −0.41 |
Selected geometric parameters (Å, º) for (I) topO1—C1 | 1.231 (3) | O4—C18 | 1.196 (3) |
O2—C1 | 1.258 (3) | O5—C18 | 1.308 (3) |
| | | |
C3—O3—C2—C1 | −80.7 (2) | C19—O6—C15—C14 | −173.4 (2) |
O1—C1—C2—O3 | 170.0 (2) | C15—O6—C19—C18 | 69.4 (3) |
C2—O3—C3—C4 | −166.7 (2) | O5—C18—C19—O6 | 25.0 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O2i | 0.82 | 1.70 | 2.507 (2) | 167 |
N1—H1B···O1ii | 0.90 | 1.87 | 2.758 (3) | 169 |
N1—H1A···O3 | 0.90 | 2.54 | 3.245 (3) | 136 |
N1—H1A···O2 | 0.90 | 1.98 | 2.800 (3) | 151 |
C20—H20A···O4iii | 0.96 | 2.47 | 3.368 (4) | 155 |
C20—H20C···O4iv | 0.96 | 2.58 | 3.300 (4) | 132 |
C20—H20C···O5v | 0.96 | 2.58 | 3.374 (3) | 140 |
C21—H21A···O5v | 0.96 | 2.45 | 3.282 (3) | 145 |
C21—H21B···O1vi | 0.96 | 2.54 | 3.390 (4) | 148 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) −x+2, y+1/2, −z+1/2; (vi) −x+1, −y+2, −z+1. |
Selected geometric parameters (Å, º) for (II) topO2—C8 | 1.201 (5) | O8—C27 | 1.291 (6) |
O3—C8 | 1.306 (6) | O9—C27 | 1.169 (5) |
O5—C19 | 1.289 (5) | O11—C38 | 1.316 (5) |
O6—C19 | 1.211 (5) | O12—C38 | 1.218 (5) |
| | | |
C7—O1—C1—C2 | 177.3 (4) | C26—O7—C20—C21 | 152.7 (5) |
C1—O1—C7—C8 | −177.3 (3) | C20—O7—C26—C27 | −179.6 (4) |
O1—C7—C8—O3 | 179.2 (4) | O7—C26—C27—O8 | 164.1 (5) |
C18—O4—C15—C14 | 167.5 (4) | C37—O10—C34—C35 | −160.6 (3) |
C15—O4—C18—C19 | 86.2 (4) | C34—O10—C37—C38 | 69.6 (4) |
O4—C18—C19—O5 | −14.5 (5) | O10—C37—C38—O11 | −161.5 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N4i | 0.82 | 1.78 | 2.584 (5) | 166 |
O5—H5···N3 | 0.82 | 1.75 | 2.561 (5) | 169 |
O8—H8···N2ii | 0.82 | 1.84 | 2.647 (5) | 166 |
O11—H11···N1iii | 0.82 | 1.84 | 2.647 (4) | 167 |
C18—H18B···O12iii | 0.97 | 2.39 | 3.227 (5) | 144 |
C35—H35···O5iv | 0.93 | 2.54 | 3.245 (5) | 133 |
C40—H40···O12iv | 0.93 | 2.50 | 3.432 (5) | 176 |
C42—H42···O9 | 0.93 | 2.56 | 3.476 (5) | 170 |
C50—H50···O6v | 0.93 | 2.56 | 3.458 (6) | 162 |
C52—H52···O6iii | 0.93 | 2.52 | 3.414 (6) | 162 |
C16—H16···Cg1iii | 0.93 | 2.90 | 3.669 (5) | 141 |
C32—H32···Cg2iii | 0.93 | 2.89 | 3.625 (5) | 137 |
Symmetry codes: (i) x−1, y, z−1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) x+1, y, z. |
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Over the past decade, the rational design and synthesis of metal–organic frameworks have received extensive attention in the fields of supramolecular chemistry and crystal engineering (Rosi et al., 2003; Dalgarno et al., 2008). These materials exhibit interesting properties such as catalysis, biological activity, electrical conductivity, magnetism and photochemical activity. In the past five years there has been a growing interest in metal–organic frameworks involving semi-rigid V-shaped dicarboxylate ligands (Tanaka et al., 2008; Zang et al., 2006; Mahata et al., 2008; Furukawa et al., 2008). 4,4'-[Isopropylidenebis(p-phenyleneoxy)]diacetic acid (H2L) is a typical example of a semi-rigid V-shaped dicarboxylate ligand. To the best of our knowledge there has been no report to date concerning its coordination compounds. Recently, we have focused on preparing metal–organic frameworks containing this organic ligand and metal ions. During this process, two interesting adducts of H2L with dimethylammonium and 4,4'-bipyridine, compounds (I) and (II), respectively, were obtained, and we report here their synthesis and crystal structures.
Although we failed to formulate coordination polymers at this stage, the present characterization of the crystalline products provids useful information. Thus, when H2L was reacted with a lanthanum nitrate salt (see Experimental) in the presence of N,N-dimethylformamide (DMF) under hydrothermal conditions, no metal ions were incorporated into the structure. Instead, the 1:1 salt, (I), formed between the monodeprotonated H2L and a dimethylammonium cation (a product resulting from hydrolysis of DMF). The H atom of one carboxyl group is transferred to the dimethylamine N atom, while the other remains as the acid. The carboxyl and carboxylate groups are almost perpendicular to the benzene ring, with dihedral angles of 80.9 (1) and 86.2 (2)° (Table 1 and Fig. 1), respectively. The arrangement in the carboxylic acid is the less common syn–anti conformation (Kennard et al., 1982; Lynch et al., 2003). The benzene rings of the bent H2L molecule subtend a dihedral angle of 86.5 (1)°.
The supramolecular structure of (I) can be simply analyzed in terms of three substructures. Firstly, the HL- anions result in discrete one-dimensional chains via an O5—H5···O2A hydrogen bond [symmetry code: (A) 1 - x, -1/2 + y, 1/2 - z] running parallel to the [010] direction. Secondly, adjacent [010] chains are linked together by dimethylammonium cations through strong N—H···O hydrogen bonds in concert with C—H···O hydrogen bonds (Table 2), forming two-dimensional layers built from R46(46) hydrogen-bond motifs (Bernstein et al., 1995) which are parallel to the (001) plane (Fig. 2). Finally, neighbouring two-dimensional layers are assembled into a three-dimensional network by means of C—H···O hydrogen bonds with –ABAB– alternation (Fig. 3 and Table 2).
The reaction of H2L with PbII ions in the presence of 4,4'-bipyridyl (bipy) yielded compound (II). As shown in Fig. 4, the asymmetric unit of (II) consists of two H2L molecules and one bipy molecule, together with two half-bipy molecules, these last both possessing inversion centres. The C—O bond distances support the existence of unionized acid molecules, indicating cocrystal formation (Table 3). H2L and bipy crystallize to form two different independent networks: a four-member rectangular-shaped ring (Fig. 5a) and a one-dimensional wavelike chain (Fig. 5b). In both networks, the H2L and bipy molecules are linked together by strong O—H···N hydrogen bonds (Table 4). In the rectangular-shaped ring, the planes of the pyridyl rings of the bipy molecule are twisted by 25.9 (6)° with respect to each other. One of the phenoxyacetic acid groups, that containing atom O11, adopts an antiperiplanar conformation, with a dihedral angle of 44.3 (2)° between the carboxyl group and the benzene ring. The other phenoxyacetic acid group, containing atom O8, adopts a synplanar conformation, with a dihedral angle of 82.2 (1)°. The dihedral angle between the two benzene rings is 88.2 (2)°. In the chain network the bipy molecules, which lie on centres of symmetry, both have planar central portions. The conformation of the H2L molecule shows some differences from the H2L molecule in the rectangular ring. One phenoxyacetic acid group (containing atom O3) has an antiperiplanar conformation and the acetic acid arm is almost in the same plane as the benzene ring. The other phenoxyacetic acid group adopts an uncommon syn–anti conformation, like that in (I), and here the dihedral angle between the two benzene rings is 85.9 (2)°.
Interestingly, the rectangular rings and wave-like chains are assembled by π–π stacking interactions and C18—H18B···O12 hydrogen bonds into an intriguing zero-dimensional plus one-dimensional poly(pseudo) rotaxane motif. The π–π interactions occur between the bipy rings, with a ring centroid distance of 3.874 (3) Å, an interplanar spacing of 3.541 (2) Å and an offset angle of 4.20 (1)°. The poly(pseudo) rotaxane motifs are linked into a three-dimensional network by a combination of C—H···O and C—H···π hydrogen bonds (Table 4 and Fig. 6).
In conclusion, the two 1:1 organic compounds formed by H2L with dimethylammonium and bipy are the first examples of H2L adducts to be descibed. The phenoxyacetic acid groups in these two adducts show interesting conformations, and an intriguing zero-dimensional plus one-dimensional poly(pseudo) rotaxane structure is found in compound (II).