Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005499/wn6012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005499/wn6012Isup2.hkl |
CCDC reference: 165646
The title compound was prepared according to the literature method of Ding et al. (1986). Single crystals suitable for X-ray determination were obtained by slow evaporation of an MeCN solution over a period of several days.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Siemens, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL-Plus.
C20H24N2O6 | F(000) = 412 |
Mr = 388.41 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.467 (1) Å | Cell parameters from 19 reflections |
b = 16.002 (2) Å | θ = 4.3–14.9° |
c = 8.256 (1) Å | µ = 0.10 mm−1 |
β = 98.96 (1)° | T = 296 K |
V = 974.4 (2) Å3 | Block, white |
Z = 2 | 0.48 × 0.46 × 0.42 mm |
Siemens P4 diffractometer | Rint = 0.014 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.6° |
Graphite monochromator | h = 0→9 |
ω scans | k = 0→20 |
2458 measured reflections | l = −10→10 |
2129 independent reflections | 3 standard reflections every 97 reflections |
1354 reflections with I > 2σ(I) | intensity decay: 6.0% |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.001 |
2129 reflections | Δρmax = 0.16 e Å−3 |
129 parameters | Δρmin = −0.11 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.086 (6) |
C20H24N2O6 | V = 974.4 (2) Å3 |
Mr = 388.41 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.467 (1) Å | µ = 0.10 mm−1 |
b = 16.002 (2) Å | T = 296 K |
c = 8.256 (1) Å | 0.48 × 0.46 × 0.42 mm |
β = 98.96 (1)° |
Siemens P4 diffractometer | Rint = 0.014 |
2458 measured reflections | 3 standard reflections every 97 reflections |
2129 independent reflections | intensity decay: 6.0% |
1354 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.16 e Å−3 |
2129 reflections | Δρmin = −0.11 e Å−3 |
129 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.13396 (13) | 0.30022 (6) | 0.08524 (12) | 0.0546 (3) | |
O2 | −0.17231 (15) | 0.55137 (7) | 0.21894 (14) | 0.0732 (4) | |
O3 | 0.27821 (14) | 0.49699 (6) | 0.38105 (12) | 0.0607 (3) | |
N | 0.00240 (15) | 0.43887 (7) | 0.18061 (14) | 0.0507 (3) | |
H0 | 0.1108 | 0.4199 | 0.2068 | 0.061* | |
C1 | −0.04592 (18) | 0.31235 (8) | 0.02712 (15) | 0.0453 (3) | |
C2 | −0.1546 (2) | 0.25761 (9) | −0.07294 (17) | 0.0523 (4) | |
H2 | −0.1064 | 0.2082 | −0.1070 | 0.063* | |
C3 | −0.3355 (2) | 0.27640 (10) | −0.12254 (19) | 0.0619 (4) | |
H3 | −0.4088 | 0.2394 | −0.1899 | 0.074* | |
C4 | −0.4077 (2) | 0.34894 (10) | −0.07346 (19) | 0.0633 (4) | |
H4 | −0.5298 | 0.3608 | −0.1072 | 0.076* | |
C5 | −0.2997 (2) | 0.40476 (9) | 0.02634 (18) | 0.0558 (4) | |
H5 | −0.3491 | 0.4542 | 0.0589 | 0.067* | |
C6 | −0.11839 (18) | 0.38704 (8) | 0.07752 (15) | 0.0453 (3) | |
C7 | −0.0290 (2) | 0.51418 (9) | 0.24366 (17) | 0.0494 (4) | |
C8 | 0.1303 (2) | 0.55213 (9) | 0.35304 (17) | 0.0529 (4) | |
H8A | 0.1669 | 0.6028 | 0.3027 | 0.063* | |
H8B | 0.0943 | 0.5672 | 0.4571 | 0.063* | |
C9 | 0.4285 (2) | 0.53219 (9) | 0.4850 (2) | 0.0639 (5) | |
H9A | 0.3928 | 0.5496 | 0.5878 | 0.077* | |
H9B | 0.4730 | 0.5807 | 0.4331 | 0.077* | |
C10 | 0.2185 (2) | 0.22778 (9) | 0.0340 (2) | 0.0637 (4) | |
H10A | 0.1649 | 0.1790 | 0.0742 | 0.076* | |
H10B | 0.3456 | 0.2291 | 0.0768 | 0.076* | |
H10C | 0.2024 | 0.2261 | −0.0836 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0483 (6) | 0.0518 (6) | 0.0575 (6) | 0.0042 (5) | −0.0109 (5) | −0.0041 (5) |
O2 | 0.0574 (7) | 0.0690 (7) | 0.0888 (9) | 0.0115 (6) | −0.0023 (6) | −0.0179 (6) |
O3 | 0.0594 (7) | 0.0492 (6) | 0.0639 (7) | −0.0021 (5) | −0.0202 (5) | −0.0067 (5) |
N | 0.0454 (7) | 0.0490 (7) | 0.0521 (7) | 0.0017 (5) | −0.0098 (5) | −0.0043 (5) |
C1 | 0.0446 (8) | 0.0482 (8) | 0.0394 (7) | −0.0042 (6) | −0.0051 (6) | 0.0078 (6) |
C2 | 0.0574 (10) | 0.0479 (8) | 0.0470 (8) | −0.0047 (7) | −0.0061 (7) | 0.0020 (6) |
C3 | 0.0575 (10) | 0.0612 (10) | 0.0594 (9) | −0.0158 (8) | −0.0142 (8) | 0.0017 (8) |
C4 | 0.0450 (9) | 0.0687 (11) | 0.0702 (10) | −0.0068 (8) | −0.0099 (8) | 0.0064 (8) |
C5 | 0.0479 (9) | 0.0565 (9) | 0.0594 (9) | 0.0012 (7) | −0.0027 (7) | 0.0002 (7) |
C6 | 0.0440 (8) | 0.0478 (8) | 0.0408 (7) | −0.0032 (6) | −0.0030 (6) | 0.0039 (6) |
C7 | 0.0526 (9) | 0.0492 (8) | 0.0450 (8) | 0.0002 (7) | 0.0034 (7) | 0.0034 (6) |
C8 | 0.0606 (9) | 0.0468 (8) | 0.0479 (8) | −0.0022 (7) | −0.0023 (7) | −0.0001 (6) |
C9 | 0.0640 (11) | 0.0546 (9) | 0.0643 (9) | −0.0094 (7) | −0.0178 (8) | −0.0048 (7) |
C10 | 0.0549 (10) | 0.0603 (10) | 0.0737 (11) | 0.0032 (8) | 0.0033 (8) | −0.0025 (8) |
O1—C1 | 1.3680 (16) | C1—C6 | 1.4016 (19) |
O1—C10 | 1.4155 (17) | C2—C3 | 1.382 (2) |
O2—C7 | 1.2138 (17) | C3—C4 | 1.368 (2) |
O3—C8 | 1.4044 (17) | C4—C5 | 1.386 (2) |
O3—C9 | 1.4189 (17) | C5—C6 | 1.3832 (19) |
N—C7 | 1.3477 (18) | C7—C8 | 1.5047 (19) |
N—C6 | 1.4095 (16) | C9—C9i | 1.476 (3) |
C1—C2 | 1.3782 (18) | ||
C1—O1—C10 | 118.08 (11) | C6—C5—C4 | 120.06 (15) |
C8—O3—C9 | 112.20 (11) | C5—C6—C1 | 119.26 (12) |
C7—N—C6 | 128.76 (12) | C5—C6—N | 124.59 (13) |
O1—C1—C2 | 125.05 (13) | C1—C6—N | 116.15 (12) |
O1—C1—C6 | 114.85 (11) | O2—C7—N | 125.12 (14) |
C2—C1—C6 | 120.09 (13) | O2—C7—C8 | 119.79 (13) |
C1—C2—C3 | 119.76 (14) | N—C7—C8 | 115.09 (13) |
C4—C3—C2 | 120.60 (14) | O3—C8—C7 | 111.91 (12) |
C3—C4—C5 | 120.22 (15) | O3—C9—C9i | 107.92 (15) |
C10—O1—C1—C2 | 2.82 (19) | O1—C1—C6—N | −0.20 (16) |
C10—O1—C1—C6 | −177.44 (12) | C2—C1—C6—N | 179.56 (12) |
O1—C1—C2—C3 | 179.33 (12) | C7—N—C6—C5 | −2.5 (2) |
C6—C1—C2—C3 | −0.4 (2) | C7—N—C6—C1 | 178.32 (13) |
C1—C2—C3—C4 | 0.1 (2) | C6—N—C7—O2 | −0.9 (2) |
C2—C3—C4—C5 | 0.3 (2) | C6—N—C7—C8 | 178.76 (12) |
C3—C4—C5—C6 | −0.4 (2) | C9—O3—C8—C7 | −179.62 (12) |
C4—C5—C6—C1 | 0.1 (2) | O2—C7—C8—O3 | 173.90 (13) |
C4—C5—C6—N | −179.10 (12) | N—C7—C8—O3 | −5.79 (18) |
O1—C1—C6—C5 | −179.47 (12) | C8—O3—C9—C9i | 176.47 (15) |
C2—C1—C6—C5 | 0.29 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C20H24N2O6 |
Mr | 388.41 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.467 (1), 16.002 (2), 8.256 (1) |
β (°) | 98.96 (1) |
V (Å3) | 974.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.48 × 0.46 × 0.42 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2458, 2129, 1354 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 0.94 |
No. of reflections | 2129 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.11 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL-Plus (Siemens, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL-Plus.
Glycol-O,O'-diacetamide compounds are excellent extractors and have been widely studied in the extraction of rare earths and some actinide ions (Ding et al., 1986). For example, N,N,N',N'-tetraphenyl-3,6-dioxaoctanediamide (TDD) has a large separation factor, and both the separation factor and distribution ratio of lighter lanthanide ions for TDD are larger than those for dicyclohexyl-18-crown-6 (Gao & Ni, 1983), if picrate is used as the accompanying ion. Further research into these compounds can help us design better extractors, exploring the relationship between structure and properties, and acquiring better property data (Yang et al., 1984).
As part of a systematic investigation of a new extractor of rare earths, the present paper reports the crystal structure of N,N'-bis(2-methoxyphenyl)-3,6-dioxaoctanediamide, (I), which can act as a tetradentate ligand. In the molecule, two carbonyl O atoms and two ether O atoms can coordinate to a metal ion. There is a centre of symmetry and a zigzag skeleton, indicating that the ligand has good flexibility. In this structure, the average C—O(ether) distance is 1.4017 Å, longer than the C—O(carbonyl) distance of 1.2138 Å. The two benzene rings are almost parallel to each other and perpendicular to the ether chain. When coordinating to a metal ion, this kind of ligand can form half-ring coordination structures (Fan et al., 1999; S.-X. Liu et al., 1997; W.-S. Liu et al., 1997). The size of the cavity will change with different terminal groups, so that the extractive properties will be different for different metal ions. A study of the selectivity of this ligand to s- and f-block metal ions is in progress.