Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012391/ja1006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012391/ja1006Isup2.hkl |
CCDC reference: 140927
[Cd(S-thpc12)](ClO4)2·H2O:- A solution of cadmium perchlorate hexahydrate (356 mg, 0.84 mmol) in dry ethanol (4 cm3) was added over several minutes to a refluxing solution of S-thpc12 (229 mg, 0.56 mmol) in dry ethanol (10 cm3). The solution was heated under reflux for 1 h, then allowed to cool slowly overnight. Very large white needles formed that were filtered off and washed with cold ethanol (2 cm3). Yield 328 mg, 81%. 13C NMR (DMSO-d6) δ 62.01 (4 C), 59.42 (4 C), 49.99 (4 C), 48.03 (4 C), 20.96 (4 C). Analysis calculated for C20H46CdCl2N4O13: C 32.73, H 6.32, N 7.63%. Found C 32.88, H 5.98, N 7.64%. Conductivity 153 Ω−1 cm2 mol−1 (0.001 M, DMF) (1:2).
The title compound was prepared by adding sodium p-nitrophenolate (46 mg, 0.28 mmol) to a solution of [Cd(S-thpc12)](ClO4)2·H2O (205 mg, 0.28 mmol) in dry acetonitrile (15 cm3). The yellow solution was then heated under reflux for 2 h, cooled and the solvent removed in vacuo. The yellow solid residue that remained was dissolved in boiling ethanol (10 cm3) and allowed to cool slowly. Fine pale yellow needles formed that were collected by filtration and dried under vacuum. Yield: 131 mg, 60%. 13C NMR (DMSO-d6) δ 177.16 (1 C), 131.77 (1 C), 127.19 (2 C), 118.94 (2 C), 61.79 (4 C), 59.77 (4 C), 50.06 (4 C), 48.09 (4 C), 20.98 (4 C). Analysis calculated for C26H50CdClN5O12: C 40.42, H 6.52, N 9.07%. Found C 40.67, H 6.40, N 9.10%. Crystals suitable for X-ray analysis were grown by diffusion of ether into a solution of the complex in acetonitrile.
Attempts to collect the data at 150 K failed because the crystal appeared to undergo a phase change. At 200 K there was a high degree of streaking in parts of reciprocal space leading to large background imbalances for some reflections. 363 measured reflections where the background ratios were greater than 2:1 were removed from the data set. All reflections (6622) with F2 > 0.0 were used in the refinement. Bondlength restraints for the bonds of the macrocycle and the phenyl C—C bonds were used in the refinement. The chirality followed from the synthesis. The absolute configuration was checked by refining a Flack parameter in early refinement cycles. No additional rotational symmetry was found by BUNYIP (Hester & Hall, 1995).
Data reduction: DIFDAT, SORTRF and ADDREF in Xtal (Hall et al., 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYLSQ in Xtal; molecular graphics: Xtal; software used to prepare material for publication: BONDLA and CIFIO in Xtal.
[Cd(C20H44N4O4)](C6H4NO3)(ClO4)·H2O | F(000) = 3216 |
Mr = 772.57 | Dx = 1.498 Mg m−3 |
Orthorhombic, P212121 | Mo_ Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 13.9929 (11) Å | θ = 15.2–19.4° |
b = 19.6661 (11) Å | µ = 0.78 mm−1 |
c = 24.890 (3) Å | T = 200 K |
V = 6849.3 (11) Å3 | Tabular, pale yellow |
Z = 8 | 0.40 × 0.24 × 0.20 mm |
CAD4/PC diffractometer | 5325 reflections with I > 2σ(I) |
Radiation source: xray tube | Rint = 0.025 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
ω/2θ scans | h = −16→17 |
Absorption correction: gaussian (ABSORB; Hall et al., 1995) | k = 0→24 |
Tmin = 0.831, Tmax = 0.864 | l = 0→30 |
13751 measured reflections | 3 standard reflections every 120 min |
7229 independent reflections | intensity decay: 2% |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: geometrical |
wR(F2) = 0.070 | H-atom parameters not refined |
S = 1.47 | Weighting scheme based on measured s.u.'s |
6622 reflections | (Δ/σ)max = 0.003 |
811 parameters | Δρmax = 0.58 e Å−3 |
36 restraints | Δρmin = −0.82 e Å−3 |
[Cd(C20H44N4O4)](C6H4NO3)(ClO4)·H2O | V = 6849.3 (11) Å3 |
Mr = 772.57 | Z = 8 |
Orthorhombic, P212121 | Mo_ Kα radiation, λ = 0.71073 Å |
a = 13.9929 (11) Å | µ = 0.78 mm−1 |
b = 19.6661 (11) Å | T = 200 K |
c = 24.890 (3) Å | 0.40 × 0.24 × 0.20 mm |
CAD4/PC diffractometer | 5325 reflections with I > 2σ(I) |
Absorption correction: gaussian (ABSORB; Hall et al., 1995) | Rint = 0.025 |
Tmin = 0.831, Tmax = 0.864 | 3 standard reflections every 120 min |
13751 measured reflections | intensity decay: 2% |
7229 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 36 restraints |
wR(F2) = 0.070 | H-atom parameters not refined |
S = 1.47 | Δρmax = 0.58 e Å−3 |
6622 reflections | Δρmin = −0.82 e Å−3 |
811 parameters |
x | y | z | Uiso*/Ueq | ||
Cd1a | 0.95302 (4) | 0.17800 (3) | 0.11266 (2) | 0.0247 (3) | |
C11a | 1.0232 (7) | 0.3112 (5) | 0.0384 (4) | 0.039 (5) | |
C12a | 0.9143 (6) | 0.3072 (5) | 0.0344 (3) | 0.035 (5) | |
C13a | 0.8731 (7) | 0.3784 (5) | 0.0240 (4) | 0.048 (6) | |
C1a | 1.0885 (6) | 0.2039 (4) | 0.0075 (3) | 0.044 (5) | |
C21a | 0.9459 (8) | 0.0834 (4) | 0.0003 (3) | 0.039 (5) | |
C22a | 0.8427 (6) | 0.0835 (4) | 0.0189 (4) | 0.032 (5) | |
C23a | 0.7773 (8) | 0.0654 (5) | −0.0276 (4) | 0.058 (7) | |
C2a | 1.1025 (5) | 0.1296 (4) | 0.0213 (3) | 0.039 (5) | |
C31a | 0.9472 (7) | 0.0353 (4) | 0.1860 (3) | 0.035 (4) | |
C32a | 0.8556 (7) | 0.0723 (5) | 0.1969 (3) | 0.038 (5) | |
C33a | 0.7777 (7) | 0.0243 (6) | 0.2153 (4) | 0.049 (6) | |
C3a | 1.0387 (5) | 0.0336 (3) | 0.0726 (3) | 0.034 (4) | |
C41a | 1.0188 (7) | 0.2620 (4) | 0.2215 (4) | 0.039 (5) | |
C42a | 0.9232 (6) | 0.2930 (4) | 0.2063 (3) | 0.035 (5) | |
C43a | 0.8754 (8) | 0.3271 (6) | 0.2535 (4) | 0.057 (6) | |
C4a | 1.0860 (5) | 0.0441 (4) | 0.1272 (3) | 0.031 (4) | |
C5a | 1.0744 (5) | 0.1120 (4) | 0.2110 (3) | 0.041 (5) | |
C6a | 1.1312 (5) | 0.1747 (3) | 0.1953 (3) | 0.038 (4) | |
C7a | 1.1246 (5) | 0.2809 (4) | 0.1453 (3) | 0.040 (5) | |
C8a | 1.1520 (5) | 0.2582 (4) | 0.0895 (3) | 0.042 (5) | |
N1a | 1.0658 (5) | 0.2450 (4) | 0.0561 (3) | 0.033 (4) | |
N2a | 1.0147 (5) | 0.0985 (4) | 0.0448 (3) | 0.032 (4) | |
N3a | 1.0210 (5) | 0.0816 (4) | 0.1643 (3) | 0.034 (5) | |
N4a | 1.0675 (5) | 0.2295 (3) | 0.1753 (3) | 0.030 (4) | |
O12a | 0.8839 (3) | 0.2808 (2) | 0.0844 (2) | 0.034 (3) | |
O22a | 0.8256 (3) | 0.1505 (3) | 0.0383 (2) | 0.043 (3) | |
O32a | 0.8292 (3) | 0.1014 (3) | 0.1456 (2) | 0.037 (3) | |
O42a | 0.8638 (4) | 0.2357 (2) | 0.1886 (2) | 0.035 (3) | |
Cd1b | 0.54836 (5) | 0.32404 (3) | 0.38430 (2) | 0.0259 (3) | |
C11b | 0.4846 (7) | 0.2184 (5) | 0.2849 (4) | 0.037 (5) | |
C12b | 0.5917 (6) | 0.2312 (4) | 0.2795 (3) | 0.035 (5) | |
C13b | 0.6405 (8) | 0.1722 (5) | 0.2516 (4) | 0.053 (6) | |
C1b | 0.4114 (5) | 0.3304 (4) | 0.2785 (2) | 0.036 (4) | |
C21b | 0.5496 (7) | 0.4509 (4) | 0.2976 (4) | 0.043 (5) | |
C22b | 0.6524 (7) | 0.4484 (4) | 0.3165 (4) | 0.041 (5) | |
C23b | 0.7180 (7) | 0.4816 (5) | 0.2756 (5) | 0.050 (6) | |
C2b | 0.3951 (5) | 0.3972 (4) | 0.3068 (3) | 0.039 (5) | |
C31b | 0.5473 (8) | 0.4367 (5) | 0.4859 (3) | 0.042 (5) | |
C32b | 0.6415 (7) | 0.3988 (5) | 0.4890 (4) | 0.042 (5) | |
C33b | 0.7166 (7) | 0.4400 (6) | 0.5188 (4) | 0.052 (6) | |
C3b | 0.4545 (5) | 0.4732 (4) | 0.3766 (3) | 0.043 (5) | |
C41b | 0.4900 (7) | 0.2043 (5) | 0.4702 (4) | 0.046 (6) | |
C42b | 0.5809 (6) | 0.1813 (5) | 0.4461 (3) | 0.039 (4) | |
C43b | 0.6312 (9) | 0.1273 (6) | 0.4793 (5) | 0.063 (8) | |
C4b | 0.4100 (5) | 0.4440 (4) | 0.4267 (3) | 0.047 (5) | |
C5b | 0.4229 (6) | 0.3513 (4) | 0.4931 (3) | 0.051 (6) | |
C6b | 0.3692 (5) | 0.2952 (4) | 0.4650 (3) | 0.050 (5) | |
C7b | 0.3810 (5) | 0.2104 (4) | 0.3950 (3) | 0.045 (5) | |
C8b | 0.3537 (5) | 0.2494 (4) | 0.3449 (3) | 0.038 (5) | |
N1b | 0.4381 (5) | 0.2753 (3) | 0.3160 (3) | 0.034 (4) | |
N2b | 0.4814 (5) | 0.4205 (4) | 0.3359 (3) | 0.028 (4) | |
N3b | 0.4756 (5) | 0.3969 (4) | 0.4556 (3) | 0.035 (4) | |
N4b | 0.4367 (5) | 0.2508 (4) | 0.4343 (3) | 0.036 (4) | |
O12b | 0.6242 (4) | 0.2387 (3) | 0.3331 (2) | 0.040 (3) | |
O22b | 0.6717 (3) | 0.3780 (3) | 0.3225 (2) | 0.042 (3) | |
O32b | 0.6686 (3) | 0.3887 (3) | 0.4342 (2) | 0.036 (3) | |
O42b | 0.6403 (3) | 0.2413 (3) | 0.4435 (2) | 0.037 (3) | |
N1c | 1.0383 (14) | 0.0027 (7) | 0.3480 (5) | 0.093 (10) | |
C1c | 0.8509 (6) | 0.1697 (4) | 0.3686 (4) | 0.036 (5) | |
C2c | 0.9506 (5) | 0.1793 (4) | 0.3652 (3) | 0.037 (5) | |
C3c | 1.0129 (7) | 0.1250 (5) | 0.3580 (4) | 0.050 (7) | |
C4c | 0.9741 (8) | 0.0610 (6) | 0.3548 (4) | 0.054 (7) | |
C5c | 0.8763 (8) | 0.0486 (5) | 0.3561 (4) | 0.059 (7) | |
C6c | 0.8171 (7) | 0.1031 (4) | 0.3642 (5) | 0.059 (7) | |
O1c | 1.0048 (9) | −0.0544 (6) | 0.3463 (5) | 0.130 (10) | |
O2c | 1.1233 (9) | 0.0135 (6) | 0.3444 (5) | 0.117 (10) | |
O3c | 0.7935 (4) | 0.2206 (3) | 0.3764 (3) | 0.043 (4) | |
N1d | 0.4546 (12) | 0.4982 (6) | 0.1474 (4) | 0.070 (8) | |
C1d | 0.6527 (5) | 0.3365 (4) | 0.1324 (3) | 0.034 (5) | |
C2d | 0.5541 (6) | 0.3233 (4) | 0.1383 (3) | 0.037 (5) | |
C3d | 0.4892 (6) | 0.3765 (4) | 0.1432 (3) | 0.035 (6) | |
C4d | 0.5215 (8) | 0.4429 (5) | 0.1423 (4) | 0.043 (6) | |
C5d | 0.6180 (7) | 0.4573 (5) | 0.1359 (4) | 0.056 (7) | |
C6d | 0.6829 (7) | 0.4046 (4) | 0.1328 (4) | 0.041 (6) | |
O1d | 0.4833 (9) | 0.5564 (6) | 0.1432 (4) | 0.117 (9) | |
O2d | 0.3694 (9) | 0.4835 (6) | 0.1586 (5) | 0.111 (9) | |
O3d | 0.7124 (4) | 0.2866 (3) | 0.1274 (3) | 0.043 (4) | |
Cl1e | 1.1205 (2) | 0.35364 (14) | 0.36630 (14) | 0.0559 (17) | |
O1e | 1.0271 (4) | 0.3782 (4) | 0.3755 (4) | 0.114 (6) | |
O2e | 1.1308 (6) | 0.2878 (4) | 0.3909 (4) | 0.093 (6) | |
O3e | 1.1850 (5) | 0.4003 (4) | 0.3902 (3) | 0.057 (4) | |
O4e | 1.1413 (7) | 0.3506 (5) | 0.3103 (3) | 0.123 (8) | |
Cl1f | 0.39051 (18) | 0.14944 (15) | 0.13008 (12) | 0.0477 (15) | |
O1f | 0.4708 (5) | 0.1443 (4) | 0.0940 (3) | 0.092 (5) | |
O2f | 0.3141 (4) | 0.1103 (4) | 0.1085 (3) | 0.055 (4) | |
O3f | 0.3633 (5) | 0.2165 (4) | 0.1377 (5) | 0.126 (7) | |
O4f | 0.4193 (6) | 0.1221 (4) | 0.1804 (3) | 0.102 (6) | |
O5e | 0.8348 (4) | 0.3481 (3) | 0.3951 (3) | 0.048 (4) | |
O5f | 0.6691 (4) | 0.1599 (3) | 0.1045 (3) | 0.046 (4) | |
H1a | 0.81763 | 0.26789 | 0.08554 | 0.08000* | |
H2a | 0.76585 | 0.15492 | 0.05870 | 0.08000* | |
H3a | 0.77386 | 0.12939 | 0.14660 | 0.08000* | |
H4a | 0.80939 | 0.24828 | 0.16768 | 0.08000* | |
H1b | 0.68680 | 0.22275 | 0.33958 | 0.08000* | |
H2b | 0.73656 | 0.36771 | 0.33147 | 0.08000* | |
H3b | 0.72938 | 0.36772 | 0.42937 | 0.08000* | |
H4b | 0.69421 | 0.23713 | 0.42047 | 0.08000* | |
H11a | 1.03710 | 0.20778 | −0.01747 | 0.07000* | |
H12a | 1.14528 | 0.22071 | −0.00847 | 0.07000* | |
H21a | 1.11849 | 0.10543 | −0.01050 | 0.07000* | |
H22a | 1.15287 | 0.12577 | 0.04653 | 0.07000* | |
H31a | 0.98134 | 0.00843 | 0.07755 | 0.07000* | |
H32a | 1.08104 | 0.00846 | 0.05029 | 0.07000* | |
H41a | 1.10090 | 0.00103 | 0.14230 | 0.07000* | |
H42a | 1.14295 | 0.06963 | 0.12259 | 0.07000* | |
H51a | 1.03000 | 0.12404 | 0.23803 | 0.07000* | |
H52a | 1.11759 | 0.07878 | 0.22460 | 0.07000* | |
H61a | 1.16475 | 0.19082 | 0.22604 | 0.07000* | |
H62a | 1.17559 | 0.16294 | 0.16805 | 0.07000* | |
H71a | 1.08800 | 0.32145 | 0.14264 | 0.07000* | |
H72a | 1.18145 | 0.28977 | 0.16494 | 0.07000* | |
H81a | 1.18854 | 0.29348 | 0.07289 | 0.07000* | |
H82a | 1.18908 | 0.21829 | 0.09169 | 0.07000* | |
H111a | 1.03992 | 0.34532 | 0.06353 | 0.07000* | |
H112a | 1.04841 | 0.32261 | 0.00405 | 0.07000* | |
H211a | 0.95311 | 0.11676 | −0.02691 | 0.07000* | |
H212a | 0.96013 | 0.03974 | −0.01406 | 0.07000* | |
H311a | 0.93529 | 0.00019 | 0.16056 | 0.07000* | |
H312a | 0.96985 | 0.01567 | 0.21851 | 0.07000* | |
H411a | 1.00896 | 0.22879 | 0.24865 | 0.07000* | |
H412a | 1.05898 | 0.29711 | 0.23525 | 0.07000* | |
H121a | 0.89321 | 0.27958 | 0.00543 | 0.07000* | |
H221a | 0.83018 | 0.05101 | 0.04627 | 0.07000* | |
H321a | 0.86407 | 0.10524 | 0.22454 | 0.07000* | |
H421a | 0.93177 | 0.32621 | 0.17916 | 0.07000* | |
H131a | 0.89050 | 0.40766 | 0.05262 | 0.07000* | |
H132a | 0.89848 | 0.39559 | −0.00880 | 0.07000* | |
H133a | 0.80563 | 0.37593 | 0.02140 | 0.07000* | |
H231a | 0.78576 | 0.09787 | −0.05581 | 0.07000* | |
H232a | 0.79395 | 0.02147 | −0.04095 | 0.07000* | |
H233a | 0.71316 | 0.06553 | −0.01625 | 0.07000* | |
H331a | 0.76684 | −0.00853 | 0.18872 | 0.07000* | |
H332a | 0.79839 | 0.00267 | 0.24781 | 0.07000* | |
H333a | 0.72006 | 0.04817 | 0.22279 | 0.07000* | |
H431a | 0.86636 | 0.29519 | 0.28128 | 0.07000* | |
H432a | 0.91679 | 0.36276 | 0.26611 | 0.07000* | |
H433a | 0.81607 | 0.34680 | 0.24392 | 0.07000* | |
H11b | 0.46122 | 0.33630 | 0.25294 | 0.07000* | |
H12b | 0.35421 | 0.31791 | 0.26030 | 0.07000* | |
H21b | 0.37763 | 0.43056 | 0.28114 | 0.07000* | |
H22b | 0.34431 | 0.39156 | 0.33198 | 0.07000* | |
H31b | 0.51031 | 0.49760 | 0.38645 | 0.07000* | |
H32b | 0.40982 | 0.50343 | 0.36053 | 0.07000* | |
H41b | 0.39395 | 0.48060 | 0.45019 | 0.07000* | |
H42b | 0.35381 | 0.42010 | 0.41717 | 0.07000* | |
H51b | 0.46752 | 0.33134 | 0.51725 | 0.07000* | |
H52b | 0.37836 | 0.37788 | 0.51291 | 0.07000* | |
H61b | 0.33657 | 0.26852 | 0.49092 | 0.07000* | |
H62b | 0.32455 | 0.31466 | 0.44082 | 0.07000* | |
H71b | 0.41803 | 0.17216 | 0.38459 | 0.07000* | |
H72b | 0.32397 | 0.19532 | 0.41205 | 0.07000* | |
H81b | 0.31882 | 0.22009 | 0.32170 | 0.07000* | |
H82b | 0.31446 | 0.28680 | 0.35487 | 0.07000* | |
H111b | 0.47461 | 0.17688 | 0.30329 | 0.07000* | |
H112b | 0.45691 | 0.21609 | 0.25013 | 0.07000* | |
H211b | 0.54531 | 0.42670 | 0.26477 | 0.07000* | |
H212b | 0.53249 | 0.49689 | 0.29229 | 0.07000* | |
H311b | 0.55669 | 0.47901 | 0.46821 | 0.07000* | |
H312b | 0.52396 | 0.44454 | 0.52116 | 0.07000* | |
H411b | 0.50338 | 0.22709 | 0.50300 | 0.07000* | |
H412b | 0.45126 | 0.16543 | 0.47746 | 0.07000* | |
H121b | 0.60579 | 0.26989 | 0.25807 | 0.07000* | |
H221b | 0.66277 | 0.47279 | 0.34886 | 0.07000* | |
H321b | 0.63479 | 0.35761 | 0.50824 | 0.07000* | |
H421b | 0.56864 | 0.16124 | 0.41205 | 0.07000* | |
H131b | 0.63037 | 0.13238 | 0.27209 | 0.07000* | |
H132b | 0.61340 | 0.16707 | 0.21693 | 0.07000* | |
H133b | 0.70702 | 0.18039 | 0.24827 | 0.07000* | |
H231b | 0.71283 | 0.45876 | 0.24247 | 0.07000* | |
H232b | 0.69926 | 0.52807 | 0.27123 | 0.07000* | |
H233b | 0.78258 | 0.48061 | 0.28752 | 0.07000* | |
H331b | 0.72667 | 0.48179 | 0.50024 | 0.07000* | |
H332b | 0.69509 | 0.44889 | 0.55404 | 0.07000* | |
H333b | 0.77611 | 0.41637 | 0.52054 | 0.07000* | |
H431b | 0.64450 | 0.14549 | 0.51378 | 0.07000* | |
H432b | 0.59026 | 0.08912 | 0.48262 | 0.07000* | |
H433b | 0.68985 | 0.11262 | 0.46362 | 0.07000* | |
H2c | 0.97556 | 0.22406 | 0.36790 | 0.08000* | |
H3c | 1.08020 | 0.13227 | 0.35539 | 0.08000* | |
H5c | 0.85176 | 0.00399 | 0.35248 | 0.08000* | |
H6c | 0.75018 | 0.09534 | 0.36576 | 0.08000* | |
H2d | 0.53197 | 0.27767 | 0.13910 | 0.08000* | |
H3d | 0.42312 | 0.36724 | 0.14708 | 0.08000* | |
H5d | 0.63959 | 0.50340 | 0.13453 | 0.08000* | |
H6d | 0.74880 | 0.41462 | 0.13012 | 0.08000* | |
H51e | 0.82830 | 0.31400 | 0.37941 | 0.08000* | |
H52e | 0.88089 | 0.37200 | 0.38460 | 0.08000* | |
H51f | 0.67160 | 0.20089 | 0.11250 | 0.08000* | |
H52f | 0.62100 | 0.14000 | 0.10600 | 0.08000* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1a | 0.0188 (3) | 0.0284 (4) | 0.0268 (3) | 0.0008 (3) | 0.0012 (3) | 0.0003 (3) |
C11a | 0.029 (4) | 0.044 (5) | 0.045 (5) | −0.005 (4) | −0.001 (4) | 0.014 (4) |
C12a | 0.031 (4) | 0.039 (5) | 0.034 (4) | −0.001 (4) | −0.004 (4) | −0.000 (4) |
C13a | 0.042 (6) | 0.047 (6) | 0.056 (6) | 0.015 (5) | −0.009 (5) | 0.013 (5) |
C1a | 0.033 (4) | 0.049 (5) | 0.048 (5) | −0.001 (4) | 0.020 (4) | 0.003 (4) |
C21a | 0.042 (5) | 0.041 (5) | 0.035 (4) | 0.013 (4) | −0.002 (4) | 0.000 (4) |
C22a | 0.019 (4) | 0.036 (5) | 0.042 (5) | 0.008 (4) | −0.001 (4) | −0.006 (4) |
C23a | 0.067 (8) | 0.047 (6) | 0.060 (6) | 0.009 (5) | −0.030 (6) | −0.004 (5) |
C2a | 0.033 (5) | 0.047 (5) | 0.035 (5) | −0.001 (4) | 0.014 (4) | 0.003 (4) |
C31a | 0.036 (4) | 0.036 (4) | 0.033 (4) | −0.001 (4) | 0.005 (4) | 0.006 (3) |
C32a | 0.031 (5) | 0.046 (5) | 0.037 (5) | −0.007 (4) | 0.007 (4) | −0.004 (4) |
C33a | 0.043 (6) | 0.054 (6) | 0.050 (6) | −0.007 (5) | 0.017 (5) | −0.008 (5) |
C3a | 0.034 (4) | 0.034 (4) | 0.035 (4) | 0.005 (4) | 0.001 (4) | −0.003 (3) |
C41a | 0.042 (5) | 0.036 (5) | 0.038 (5) | −0.001 (4) | −0.009 (4) | −0.006 (4) |
C42a | 0.036 (5) | 0.034 (4) | 0.036 (5) | −0.004 (4) | −0.001 (4) | −0.010 (4) |
C43a | 0.050 (6) | 0.062 (7) | 0.060 (6) | 0.013 (6) | 0.009 (5) | −0.020 (6) |
C4a | 0.024 (4) | 0.034 (4) | 0.036 (4) | 0.005 (3) | −0.001 (3) | 0.008 (3) |
C5a | 0.029 (5) | 0.054 (6) | 0.041 (5) | 0.004 (4) | −0.005 (4) | 0.004 (4) |
C6a | 0.026 (4) | 0.039 (4) | 0.048 (4) | 0.010 (4) | −0.011 (3) | 0.001 (4) |
C7a | 0.029 (4) | 0.036 (5) | 0.055 (6) | −0.005 (4) | −0.007 (4) | −0.006 (4) |
C8a | 0.027 (4) | 0.049 (5) | 0.051 (5) | −0.001 (4) | 0.006 (4) | 0.004 (4) |
N1a | 0.024 (4) | 0.038 (4) | 0.037 (4) | 0.001 (4) | 0.010 (3) | 0.005 (3) |
N2a | 0.028 (4) | 0.044 (5) | 0.024 (4) | −0.002 (4) | 0.003 (3) | 0.004 (4) |
N3a | 0.020 (4) | 0.034 (5) | 0.049 (5) | 0.002 (4) | 0.001 (4) | 0.002 (4) |
N4a | 0.021 (4) | 0.035 (4) | 0.033 (4) | −0.002 (3) | −0.007 (3) | −0.003 (3) |
O12a | 0.027 (3) | 0.035 (3) | 0.040 (3) | 0.000 (2) | −0.001 (2) | 0.010 (2) |
O22a | 0.032 (3) | 0.042 (3) | 0.056 (4) | 0.001 (2) | 0.006 (3) | −0.010 (3) |
O32a | 0.019 (3) | 0.042 (3) | 0.048 (3) | −0.001 (2) | −0.002 (2) | 0.004 (3) |
O42a | 0.031 (3) | 0.033 (3) | 0.041 (3) | 0.003 (2) | −0.002 (3) | −0.001 (2) |
Cd1b | 0.0200 (3) | 0.0305 (4) | 0.0271 (3) | 0.0015 (3) | 0.0015 (3) | −0.0035 (3) |
C11b | 0.033 (5) | 0.039 (5) | 0.039 (5) | 0.003 (4) | 0.003 (4) | −0.007 (4) |
C12b | 0.038 (5) | 0.035 (5) | 0.032 (4) | 0.005 (4) | 0.007 (4) | −0.001 (4) |
C13b | 0.058 (6) | 0.053 (6) | 0.048 (5) | 0.005 (6) | 0.015 (5) | −0.011 (5) |
C1b | 0.038 (4) | 0.043 (5) | 0.027 (4) | −0.000 (4) | 0.000 (3) | 0.001 (4) |
C21b | 0.036 (5) | 0.040 (5) | 0.054 (5) | −0.000 (5) | −0.004 (5) | −0.002 (4) |
C22b | 0.036 (5) | 0.038 (5) | 0.048 (5) | −0.004 (4) | −0.005 (4) | 0.003 (4) |
C23b | 0.040 (6) | 0.046 (6) | 0.065 (7) | −0.019 (5) | 0.008 (5) | −0.003 (5) |
C2b | 0.028 (5) | 0.038 (5) | 0.051 (5) | 0.003 (4) | −0.011 (4) | −0.002 (4) |
C31b | 0.030 (5) | 0.061 (6) | 0.035 (4) | 0.008 (5) | 0.000 (4) | −0.026 (4) |
C32b | 0.034 (5) | 0.060 (6) | 0.033 (5) | −0.008 (5) | 0.002 (4) | −0.010 (4) |
C33b | 0.031 (5) | 0.071 (7) | 0.055 (6) | 0.007 (5) | −0.005 (5) | −0.013 (5) |
C3b | 0.029 (4) | 0.043 (4) | 0.056 (5) | 0.009 (4) | −0.005 (4) | −0.006 (4) |
C41b | 0.045 (6) | 0.061 (7) | 0.031 (5) | −0.008 (5) | 0.005 (4) | 0.012 (4) |
C42b | 0.033 (4) | 0.035 (4) | 0.049 (5) | −0.007 (4) | −0.006 (4) | 0.005 (5) |
C43b | 0.063 (8) | 0.060 (7) | 0.064 (8) | −0.013 (7) | 0.003 (7) | 0.017 (6) |
C4b | 0.036 (5) | 0.050 (5) | 0.053 (5) | 0.008 (4) | −0.000 (4) | −0.026 (4) |
C5b | 0.042 (5) | 0.071 (7) | 0.038 (5) | 0.005 (5) | 0.010 (4) | −0.016 (5) |
C6b | 0.030 (4) | 0.076 (6) | 0.043 (5) | −0.003 (4) | 0.017 (4) | −0.002 (4) |
C7b | 0.036 (5) | 0.058 (5) | 0.042 (5) | −0.020 (4) | 0.004 (4) | 0.010 (4) |
C8b | 0.023 (4) | 0.046 (5) | 0.044 (5) | −0.008 (4) | −0.008 (3) | −0.003 (4) |
N1b | 0.033 (4) | 0.032 (4) | 0.038 (4) | 0.004 (4) | −0.000 (3) | −0.003 (3) |
N2b | 0.026 (4) | 0.034 (5) | 0.024 (4) | −0.000 (4) | 0.004 (4) | −0.008 (3) |
N3b | 0.024 (4) | 0.042 (5) | 0.037 (4) | 0.004 (4) | 0.003 (3) | −0.011 (4) |
N4b | 0.027 (4) | 0.050 (4) | 0.032 (4) | 0.006 (4) | 0.003 (3) | −0.007 (3) |
O12b | 0.028 (3) | 0.049 (4) | 0.041 (3) | 0.009 (3) | −0.001 (3) | −0.005 (3) |
O22b | 0.025 (3) | 0.043 (3) | 0.056 (4) | 0.002 (3) | 0.004 (3) | −0.005 (3) |
O32b | 0.025 (3) | 0.044 (3) | 0.039 (3) | 0.004 (2) | 0.005 (2) | −0.011 (3) |
O42b | 0.027 (3) | 0.043 (3) | 0.041 (3) | −0.001 (3) | 0.004 (2) | 0.003 (3) |
N1c | 0.134 (12) | 0.080 (10) | 0.065 (7) | 0.059 (11) | −0.019 (9) | −0.006 (7) |
C1c | 0.038 (5) | 0.030 (5) | 0.040 (5) | −0.001 (5) | −0.005 (4) | 0.003 (5) |
C2c | 0.022 (5) | 0.048 (6) | 0.042 (5) | −0.001 (5) | 0.009 (4) | 0.009 (5) |
C3c | 0.048 (8) | 0.073 (9) | 0.029 (6) | 0.020 (7) | 0.005 (5) | 0.012 (6) |
C4c | 0.064 (8) | 0.058 (8) | 0.041 (6) | 0.042 (7) | −0.009 (6) | 0.005 (6) |
C5c | 0.098 (10) | 0.035 (6) | 0.045 (6) | −0.013 (7) | −0.014 (6) | 0.003 (5) |
C6c | 0.047 (7) | 0.043 (6) | 0.086 (9) | −0.012 (5) | −0.015 (6) | 0.002 (6) |
O1c | 0.192 (15) | 0.045 (6) | 0.153 (10) | 0.047 (7) | −0.002 (8) | −0.021 (6) |
O2c | 0.103 (9) | 0.127 (10) | 0.121 (10) | 0.084 (8) | −0.003 (8) | −0.002 (7) |
O3c | 0.024 (3) | 0.037 (3) | 0.068 (4) | −0.001 (3) | 0.008 (3) | −0.011 (4) |
N1d | 0.102 (9) | 0.054 (8) | 0.055 (6) | 0.045 (8) | −0.016 (7) | −0.006 (5) |
C1d | 0.022 (5) | 0.044 (6) | 0.036 (5) | 0.000 (4) | 0.001 (4) | −0.007 (5) |
C2d | 0.036 (5) | 0.036 (5) | 0.040 (5) | 0.013 (5) | −0.009 (5) | −0.002 (5) |
C3d | 0.030 (6) | 0.046 (7) | 0.027 (5) | 0.013 (5) | 0.001 (4) | −0.000 (4) |
C4d | 0.072 (8) | 0.035 (6) | 0.023 (5) | 0.012 (6) | 0.003 (5) | −0.005 (4) |
C5d | 0.091 (10) | 0.036 (6) | 0.040 (6) | 0.001 (6) | −0.002 (6) | 0.004 (5) |
C6d | 0.044 (6) | 0.036 (5) | 0.041 (5) | −0.010 (5) | 0.010 (5) | −0.010 (4) |
O1d | 0.165 (12) | 0.061 (7) | 0.126 (8) | 0.060 (7) | −0.010 (7) | 0.009 (6) |
O2d | 0.083 (8) | 0.117 (9) | 0.132 (10) | 0.064 (7) | −0.008 (8) | −0.019 (7) |
O3d | 0.029 (4) | 0.045 (4) | 0.055 (4) | 0.004 (3) | −0.005 (3) | −0.002 (3) |
Cl1e | 0.0293 (14) | 0.0484 (16) | 0.090 (2) | −0.0029 (12) | −0.0114 (14) | −0.0022 (15) |
O1e | 0.021 (3) | 0.071 (4) | 0.251 (12) | 0.000 (3) | 0.017 (6) | 0.029 (6) |
O2e | 0.057 (5) | 0.051 (4) | 0.170 (8) | −0.002 (4) | −0.010 (5) | 0.009 (5) |
O3e | 0.045 (4) | 0.073 (4) | 0.053 (4) | −0.029 (4) | 0.009 (4) | −0.002 (4) |
O4e | 0.145 (8) | 0.153 (9) | 0.070 (5) | −0.033 (7) | −0.041 (6) | −0.032 (5) |
Cl1f | 0.0283 (13) | 0.0532 (16) | 0.0616 (17) | −0.0069 (11) | −0.0007 (11) | −0.0029 (13) |
O1f | 0.031 (3) | 0.169 (8) | 0.077 (5) | −0.035 (5) | 0.001 (3) | −0.013 (5) |
O2f | 0.024 (3) | 0.070 (4) | 0.072 (5) | −0.012 (3) | −0.007 (4) | −0.013 (4) |
O3f | 0.038 (4) | 0.047 (5) | 0.293 (13) | −0.005 (4) | −0.019 (6) | −0.015 (6) |
O4f | 0.128 (8) | 0.107 (6) | 0.072 (5) | −0.026 (6) | −0.035 (5) | 0.012 (5) |
O5e | 0.024 (4) | 0.045 (4) | 0.075 (5) | −0.002 (3) | 0.015 (3) | −0.009 (4) |
O5f | 0.022 (3) | 0.049 (4) | 0.066 (4) | −0.000 (3) | −0.002 (3) | −0.014 (4) |
Cd1a—N1a | 2.492 (7) | C12b—C13b | 1.515 (13) |
Cd1a—N2a | 2.458 (7) | C13b—H131b | 0.945 |
Cd1a—N3a | 2.480 (7) | C13b—H133b | 0.948 |
Cd1a—N4a | 2.454 (7) | C13b—H132b | 0.949 |
Cd1a—O12a | 2.349 (5) | C1b—H11b | 0.951 (7) |
Cd1a—O22a | 2.626 (5) | C1b—H12b | 0.952 (7) |
Cd1a—O32a | 2.438 (5) | C1b—N1b | 1.478 (9) |
Cd1a—O42a | 2.534 (5) | C1b—C2b | 1.508 (10) |
O12a—O3d | 2.630 (8) | C21b—H212b | 0.946 |
O22a—O5f | 2.746 (8) | C21b—H211b | 0.946 |
O32a—O5f | 2.720 (8) | C21b—N2b | 1.476 (12) |
O42a—O3d | 2.797 (8) | C21b—C22b | 1.514 (14) |
O5f—O3d | 2.627 (9) | C22b—H221b | 0.949 |
O5f—O1f | 2.803 (9) | C22b—O22b | 1.418 (10) |
Cd1b—N1b | 2.488 (7) | C22b—C23b | 1.519 (14) |
Cd1b—N2b | 2.435 (7) | C23b—H231b | 0.942 |
Cd1b—N3b | 2.498 (7) | C23b—H233b | 0.951 |
Cd1b—N4b | 2.463 (7) | C23b—H232b | 0.957 |
Cd1b—O12b | 2.359 (5) | C2b—H21b | 0.947 |
Cd1b—O22b | 2.544 (5) | C2b—H22b | 0.955 |
Cd1b—O32b | 2.448 (5) | C2b—N2b | 1.481 (10) |
Cd1b—O42b | 2.543 (5) | C31b—H311b | 0.950 |
O12b—O3c | 2.627 (8) | C31b—H312b | 0.950 |
O22b—O5e | 2.970 (8) | C31b—N3b | 1.479 (12) |
O32b—O5e | 2.645 (8) | C31b—C32b | 1.516 (14) |
O42b—O3c | 2.749 (8) | C32b—H321b | 0.946 |
O5e—O3c | 2.615 (8) | C32b—O32b | 1.428 (10) |
O5e—O1e | 2.798 (9) | C32b—C33b | 1.521 (14) |
C11a—H111a | 0.947 | C33b—H332b | 0.944 |
C11a—H112a | 0.950 | C33b—H331b | 0.952 |
C11a—N1a | 1.499 (12) | C33b—H333b | 0.956 |
C11a—C12a | 1.529 (12) | C3b—H31b | 0.948 (7) |
C12a—H121a | 0.950 | C3b—H32b | 0.951 (7) |
C12a—O12a | 1.413 (9) | C3b—N2b | 1.497 (10) |
C12a—C13a | 1.536 (13) | C3b—C4b | 1.507 (10) |
C13a—H133a | 0.948 | C41b—H411b | 0.949 |
C13a—H131a | 0.949 | C41b—H412b | 0.955 |
C13a—H132a | 0.952 | C41b—C42b | 1.477 (13) |
C1a—H12a | 0.948 | C41b—N4b | 1.479 (12) |
C1a—H11a | 0.954 | C42b—H421b | 0.949 |
C1a—N1a | 1.489 (10) | C42b—O42b | 1.446 (10) |
C1a—C2a | 1.515 (10) | C42b—C43b | 1.519 (15) |
C21a—H211a | 0.948 | C43b—H431b | 0.947 (12) |
C21a—H212a | 0.950 | C43b—H432b | 0.948 (12) |
C21a—N2a | 1.499 (12) | C43b—H433b | 0.954 (12) |
C21a—C22a | 1.516 (14) | C4b—H42b | 0.946 (7) |
C22a—H221a | 0.950 | C4b—H41b | 0.954 (7) |
C22a—O22a | 1.425 (10) | C4b—N3b | 1.491 (10) |
C22a—C23a | 1.517 (14) | C5b—H51b | 0.951 |
C23a—H233a | 0.941 | C5b—H52b | 0.951 |
C23a—H232a | 0.955 | C5b—N3b | 1.489 (11) |
C23a—H231a | 0.957 | C5b—C6b | 1.507 (11) |
C2a—H22a | 0.947 | C6b—H62b | 0.948 (7) |
C2a—H21a | 0.950 | C6b—H61b | 0.948 |
C2a—N2a | 1.491 (10) | C6b—N4b | 1.497 (10) |
C31a—H312a | 0.951 | C7b—H71b | 0.949 |
C31a—H311a | 0.952 | C7b—H72b | 0.951 (7) |
C31a—N3a | 1.478 (11) | C7b—N4b | 1.482 (10) |
C31a—C32a | 1.499 (13) | C7b—C8b | 1.515 (10) |
C32a—H321a | 0.952 | C8b—H81b | 0.950 (7) |
C32a—O32a | 1.447 (10) | C8b—H82b | 0.952 (7) |
C32a—C33a | 1.513 (14) | C8b—N1b | 1.474 (10) |
C33a—H331a | 0.937 | O12b—H1b | 0.945 (5) |
C33a—H333a | 0.952 | O22b—H2b | 0.956 (5) |
C33a—H332a | 0.959 | O32b—H3b | 0.952 (5) |
C3a—H31a | 0.951 | O42b—H4b | 0.951 (5) |
C3a—H32a | 0.951 | N1c—O2c | 1.21 (2) |
C3a—N2a | 1.488 (10) | N1c—O1c | 1.22 (2) |
C3a—C4a | 1.525 (9) | N1c—C4c | 1.47 (2) |
C41a—H411a | 0.949 | C1c—O3c | 1.297 (10) |
C41a—H412a | 0.954 | C1c—C6c | 1.397 (12) |
C41a—N4a | 1.483 (11) | C1c—C2c | 1.410 (11) |
C41a—C42a | 1.517 (12) | C2c—H2c | 0.950 |
C42a—H421a | 0.947 | C2c—C3c | 1.389 (13) |
C42a—O42a | 1.468 (9) | C3c—H3c | 0.955 |
C42a—C43a | 1.508 (13) | C3c—C4c | 1.373 (15) |
C43a—H431a | 0.942 | C4c—C5c | 1.392 (16) |
C43a—H433a | 0.947 | C5c—H5c | 0.947 |
C43a—H432a | 0.961 | C5c—C6c | 1.369 (14) |
C4a—H42a | 0.948 | C6c—H6c | 0.950 |
C4a—H41a | 0.951 | N1d—O1d | 1.219 (17) |
C4a—N3a | 1.491 (10) | N1d—O2d | 1.26 (2) |
C5a—H51a | 0.945 | N1d—C4d | 1.439 (17) |
C5a—H52a | 0.952 | C1d—O3d | 1.293 (10) |
C5a—N3a | 1.506 (10) | C1d—C6d | 1.405 (11) |
C5a—C6a | 1.518 (10) | C1d—C2d | 1.412 (11) |
C6a—H62a | 0.948 | C2d—H2d | 0.950 |
C6a—H61a | 0.952 | C2d—C3d | 1.390 (11) |
C6a—N4a | 1.485 (9) | C3d—H3d | 0.947 |
C7a—H72a | 0.950 | C3d—C4d | 1.383 (12) |
C7a—H71a | 0.951 | C4d—C5d | 1.389 (15) |
C7a—N4a | 1.488 (10) | C5d—H5d | 0.956 |
C7a—C8a | 1.508 (10) | C5d—C6d | 1.380 (13) |
C8a—H82a | 0.942 | C6d—H6d | 0.945 |
C8a—H81a | 0.956 | Cl1e—O1e | 1.413 (7) |
C8a—N1a | 1.488 (10) | Cl1e—O3e | 1.417 (7) |
O12a—H1a | 0.961 | Cl1e—O4e | 1.425 (9) |
O22a—H2a | 0.982 | Cl1e—O2e | 1.440 (8) |
O32a—H3a | 0.951 | Cl1f—O3f | 1.385 (8) |
O42a—H4a | 0.956 | Cl1f—O4f | 1.421 (8) |
C11b—H111b | 0.948 | Cl1f—O2f | 1.423 (7) |
C11b—H112b | 0.948 | Cl1f—O1f | 1.442 (7) |
C11b—N1b | 1.508 (11) | O5e—H51e | 0.781 |
C11b—C12b | 1.526 (13) | O5e—H52e | 0.840 |
C12b—H121b | 0.950 | O5f—H52f | 0.780 |
C12b—O12b | 1.417 (9) | O5f—H51f | 0.831 |
O12a—Cd1a—O32a | 109.87 (16) | H111b—C11b—H112b | 109.8 (9) |
O12a—Cd1a—N4a | 95.99 (19) | H111b—C11b—N1b | 109.1 |
O12a—Cd1a—N2a | 119.1 (2) | H111b—C11b—C12b | 109.2 |
O12a—Cd1a—N3a | 166.2 (2) | H112b—C11b—N1b | 109.2 |
O12a—Cd1a—N1a | 68.7 (2) | H112b—C11b—C12b | 109.3 |
O12a—Cd1a—O42a | 68.62 (16) | N1b—C11b—C12b | 110.2 (7) |
O12a—Cd1a—O22a | 71.68 (16) | H121b—C12b—O12b | 112.3 (7) |
O32a—Cd1a—N4a | 120.4 (2) | H121b—C12b—C13b | 105.2 (7) |
O32a—Cd1a—N2a | 95.0 (2) | H121b—C12b—C11b | 112.6 |
O32a—Cd1a—N3a | 68.0 (2) | O12b—C12b—C13b | 111.5 (7) |
O32a—Cd1a—N1a | 165.2 (2) | O12b—C12b—C11b | 104.5 (6) |
O32a—Cd1a—O42a | 71.10 (16) | C13b—C12b—C11b | 110.9 (7) |
O32a—Cd1a—O22a | 68.15 (16) | H131b—C13b—H133b | 109.6 |
N4a—Cd1a—N2a | 118.0 (2) | H131b—C13b—H132b | 110.0 |
N4a—Cd1a—N3a | 74.7 (2) | H131b—C13b—C12b | 108.7 (9) |
N4a—Cd1a—N1a | 74.2 (2) | H133b—C13b—H132b | 109.3 |
N4a—Cd1a—O42a | 70.3 (2) | H133b—C13b—C12b | 110.7 (9) |
N4a—Cd1a—O22a | 167.36 (19) | H132b—C13b—C12b | 108.6 (9) |
N2a—Cd1a—N3a | 74.6 (2) | H11b—C1b—H12b | 109.3 (6) |
N2a—Cd1a—N1a | 74.1 (2) | H11b—C1b—N1b | 109.0 (6) |
N2a—Cd1a—O42a | 166.1 (2) | H11b—C1b—C2b | 108.5 (6) |
N2a—Cd1a—O22a | 67.9 (2) | H12b—C1b—N1b | 108.9 (6) |
N3a—Cd1a—N1a | 117.0 (2) | H12b—C1b—C2b | 108.7 (6) |
N3a—Cd1a—O42a | 98.3 (2) | N1b—C1b—C2b | 112.5 (6) |
N3a—Cd1a—O22a | 117.9 (2) | H212b—C21b—H211b | 110.2 (9) |
N1a—Cd1a—O42a | 119.8 (2) | H212b—C21b—N2b | 108.2 |
N1a—Cd1a—O22a | 98.07 (19) | H212b—C21b—C22b | 108.4 |
O42a—Cd1a—O22a | 106.49 (16) | H211b—C21b—N2b | 108.3 |
H111a—C11a—H112a | 109.7 | H211b—C21b—C22b | 108.2 (9) |
H111a—C11a—N1a | 108.8 | N2b—C21b—C22b | 113.6 (7) |
H111a—C11a—C12a | 109.0 | H221b—C22b—O22b | 112.1 |
H112a—C11a—N1a | 108.8 | H221b—C22b—C21b | 113.2 |
H112a—C11a—C12a | 108.9 | H221b—C22b—C23b | 104.9 |
N1a—C11a—C12a | 111.7 (7) | O22b—C22b—C21b | 104.2 (7) |
H121a—C12a—O12a | 111.4 | O22b—C22b—C23b | 112.1 (7) |
H121a—C12a—C11a | 112.9 | C21b—C22b—C23b | 110.6 (8) |
H121a—C12a—C13a | 106.0 (7) | H231b—C23b—H233b | 109.6 |
O12a—C12a—C11a | 105.3 (6) | H231b—C23b—H232b | 109.6 |
O12a—C12a—C13a | 111.8 (7) | H231b—C23b—C22b | 109.5 (9) |
C11a—C12a—C13a | 109.7 (7) | H233b—C23b—H232b | 108.4 |
H133a—C13a—H131a | 109.7 | H233b—C23b—C22b | 110.9 |
H133a—C13a—H132a | 109.4 | H232b—C23b—C22b | 108.8 (9) |
H133a—C13a—C12a | 109.8 | H21b—C2b—H22b | 109.3 (7) |
H131a—C13a—H132a | 109.4 | H21b—C2b—N2b | 109.1 (7) |
H131a—C13a—C12a | 109.3 | H21b—C2b—C1b | 109.1 (7) |
H132a—C13a—C12a | 109.3 | H22b—C2b—N2b | 108.8 (7) |
H12a—C1a—H11a | 109.3 (7) | H22b—C2b—C1b | 108.5 (6) |
H12a—C1a—N1a | 109.3 (6) | N2b—C2b—C1b | 112.0 (6) |
H12a—C1a—C2a | 108.9 (7) | H311b—C31b—H312b | 109.5 (9) |
H11a—C1a—N1a | 109.0 (7) | H311b—C31b—N3b | 108.8 |
H11a—C1a—C2a | 108.8 (7) | H311b—C31b—C32b | 109.5 (9) |
N1a—C1a—C2a | 111.5 (6) | H312b—C31b—N3b | 108.9 (9) |
H211a—C21a—H212a | 109.6 | H312b—C31b—C32b | 109.4 |
H211a—C21a—N2a | 108.8 | N3b—C31b—C32b | 110.8 (7) |
H211a—C21a—C22a | 108.6 | H321b—C32b—O32b | 113.0 |
H212a—C21a—N2a | 108.8 | H321b—C32b—C31b | 111.2 (9) |
H212a—C21a—C22a | 108.4 | H321b—C32b—C33b | 106.1 |
N2a—C21a—C22a | 112.6 (7) | O32b—C32b—C31b | 104.6 (7) |
H221a—C22a—O22a | 110.4 | O32b—C32b—C33b | 110.9 (7) |
H221a—C22a—C21a | 113.3 | C31b—C32b—C33b | 111.3 (8) |
H221a—C22a—C23a | 106.1 | H332b—C33b—H331b | 109.8 |
O22a—C22a—C21a | 105.4 (6) | H332b—C33b—H333b | 109.0 |
O22a—C22a—C23a | 111.9 (7) | H332b—C33b—C32b | 109.4 (9) |
C21a—C22a—C23a | 109.9 (8) | H331b—C33b—H333b | 108.2 |
H233a—C23a—H232a | 109.9 | H331b—C33b—C32b | 109.0 (9) |
H233a—C23a—H231a | 109.6 | H333b—C33b—C32b | 111.4 |
H233a—C23a—C22a | 110.3 | H31b—C3b—H32b | 109.5 (7) |
H232a—C23a—H231a | 108.5 | H31b—C3b—N2b | 108.6 (7) |
H232a—C23a—C22a | 109.3 | H31b—C3b—C4b | 108.7 (6) |
H231a—C23a—C22a | 109.2 | H32b—C3b—N2b | 108.2 (6) |
H22a—C2a—H21a | 109.7 | H32b—C3b—C4b | 108.3 (7) |
H22a—C2a—N2a | 108.7 (7) | N2b—C3b—C4b | 113.6 (6) |
H22a—C2a—C1a | 108.8 (7) | H411b—C41b—H412b | 109.1 (9) |
H21a—C2a—N2a | 108.5 (7) | H411b—C41b—C42b | 109.0 (9) |
H21a—C2a—C1a | 108.9 (7) | H411b—C41b—N4b | 109.1 (9) |
N2a—C2a—C1a | 112.3 (6) | H412b—C41b—C42b | 108.6 (9) |
H312a—C31a—H311a | 109.2 | H412b—C41b—N4b | 108.8 |
H312a—C31a—N3a | 109.2 | C42b—C41b—N4b | 112.2 (7) |
H312a—C31a—C32a | 109.1 (7) | H421b—C42b—O42b | 113.7 (7) |
H311a—C31a—N3a | 109.0 (7) | H421b—C42b—C41b | 109.6 |
H311a—C31a—C32a | 108.8 | H421b—C42b—C43b | 106.2 |
N3a—C31a—C32a | 111.4 (7) | O42b—C42b—C41b | 105.2 (7) |
H321a—C32a—O32a | 113.6 | O42b—C42b—C43b | 109.2 (7) |
H321a—C32a—C31a | 110.8 | C41b—C42b—C43b | 113.1 (8) |
H321a—C32a—C33a | 107.2 | H431b—C43b—H432b | 109.9 (12) |
O32a—C32a—C31a | 104.5 (6) | H431b—C43b—H433b | 108.4 (12) |
O32a—C32a—C33a | 109.3 (7) | H431b—C43b—C42b | 108.7 |
C31a—C32a—C33a | 111.6 (8) | H432b—C43b—H433b | 108.4 |
H331a—C33a—H333a | 109.9 | H432b—C43b—C42b | 108.7 |
H331a—C33a—H332a | 109.9 | H433b—C43b—C42b | 112.7 |
H331a—C33a—C32a | 109.5 | H42b—C4b—H41b | 109.5 (7) |
H333a—C33a—H332a | 108.0 | H42b—C4b—N3b | 108.8 (7) |
H333a—C33a—C32a | 111.2 | H42b—C4b—C3b | 109.1 (7) |
H332a—C33a—C32a | 108.4 | H41b—C4b—N3b | 108.5 (6) |
H31a—C3a—H32a | 109.3 | H41b—C4b—C3b | 108.5 (7) |
H31a—C3a—N2a | 108.5 | N3b—C4b—C3b | 112.4 (6) |
H31a—C3a—C4a | 108.7 | H51b—C5b—H52b | 109.3 |
H32a—C3a—N2a | 108.4 | H51b—C5b—N3b | 108.7 (7) |
H32a—C3a—C4a | 108.6 | H51b—C5b—C6b | 108.6 |
N2a—C3a—C4a | 113.3 (6) | H52b—C5b—N3b | 108.6 |
H411a—C41a—H412a | 109.2 | H52b—C5b—C6b | 108.4 (7) |
H411a—C41a—N4a | 108.8 | N3b—C5b—C6b | 113.3 (6) |
H411a—C41a—C42a | 109.1 | H62b—C6b—H61b | 109.8 (7) |
H412a—C41a—N4a | 108.5 | H62b—C6b—N4b | 109.1 (7) |
H412a—C41a—C42a | 108.5 | H62b—C6b—C5b | 109.2 (7) |
N4a—C41a—C42a | 112.7 (7) | H61b—C6b—N4b | 109.1 (7) |
H421a—C42a—O42a | 112.7 | H61b—C6b—C5b | 109.2 (7) |
H421a—C42a—C43a | 107.8 | N4b—C6b—C5b | 110.4 (6) |
H421a—C42a—C41a | 110.1 | H71b—C7b—H72b | 109.5 |
O42a—C42a—C43a | 108.9 (7) | H71b—C7b—N4b | 108.5 (7) |
O42a—C42a—C41a | 105.4 (6) | H71b—C7b—C8b | 108.3 (6) |
C43a—C42a—C41a | 112.0 (7) | H72b—C7b—N4b | 108.3 (6) |
H431a—C43a—H433a | 109.8 | H72b—C7b—C8b | 108.3 (6) |
H431a—C43a—H432a | 109.2 | N4b—C7b—C8b | 113.9 (6) |
H431a—C43a—C42a | 109.6 | H81b—C8b—H82b | 109.3 (7) |
H433a—C43a—H432a | 108.2 | H81b—C8b—N1b | 109.0 (6) |
H433a—C43a—C42a | 112.0 | H81b—C8b—C7b | 108.8 (7) |
H432a—C43a—C42a | 108.1 | H82b—C8b—N1b | 108.9 (7) |
H42a—C4a—H41a | 109.5 | H82b—C8b—C7b | 108.7 (6) |
H42a—C4a—N3a | 109.0 | N1b—C8b—C7b | 112.1 (6) |
H42a—C4a—C3a | 109.3 | C8b—N1b—C1b | 111.0 (6) |
H41a—C4a—N3a | 109.2 | C8b—N1b—C11b | 109.8 (6) |
H41a—C4a—C3a | 109.1 | C8b—N1b—Cd1b | 107.3 (4) |
N3a—C4a—C3a | 110.7 (6) | C1b—N1b—C11b | 109.2 (6) |
H51a—C5a—H52a | 109.7 | C1b—N1b—Cd1b | 107.8 (4) |
H51a—C5a—N3a | 108.9 | C11b—N1b—Cd1b | 111.7 (5) |
H51a—C5a—C6a | 108.9 | C21b—N2b—C2b | 109.6 (6) |
H52a—C5a—N3a | 108.4 | C21b—N2b—C3b | 108.7 (6) |
H52a—C5a—C6a | 108.4 | C21b—N2b—Cd1b | 112.7 (5) |
N3a—C5a—C6a | 112.5 (6) | C2b—N2b—C3b | 109.9 (6) |
H62a—C6a—H61a | 109.5 | C2b—N2b—Cd1b | 108.3 (5) |
H62a—C6a—N4a | 109.3 | C3b—N2b—Cd1b | 107.6 (4) |
H62a—C6a—C5a | 109.3 | C31b—N3b—C5b | 109.6 (6) |
H61a—C6a—N4a | 108.8 | C31b—N3b—C4b | 109.5 (6) |
H61a—C6a—C5a | 108.8 | C31b—N3b—Cd1b | 112.9 (5) |
N4a—C6a—C5a | 111.2 (5) | C5b—N3b—C4b | 111.9 (6) |
H72a—C7a—H71a | 109.4 | C5b—N3b—Cd1b | 107.6 (5) |
H72a—C7a—N4a | 108.4 | C4b—N3b—Cd1b | 105.4 (4) |
H72a—C7a—C8a | 108.4 | C41b—N4b—C7b | 109.5 (7) |
H71a—C7a—N4a | 108.4 | C41b—N4b—C6b | 111.8 (6) |
H71a—C7a—C8a | 108.8 | C41b—N4b—Cd1b | 110.3 (5) |
N4a—C7a—C8a | 113.4 (6) | C7b—N4b—C6b | 108.5 (6) |
H82a—C8a—H81a | 109.6 | C7b—N4b—Cd1b | 108.3 (4) |
H82a—C8a—N1a | 109.5 | C6b—N4b—Cd1b | 108.5 (5) |
H82a—C8a—C7a | 109.4 | H1b—O12b—C12b | 115.0 (6) |
H81a—C8a—N1a | 108.6 | H1b—O12b—Cd1b | 124.2 (4) |
H81a—C8a—C7a | 108.6 | C12b—O12b—Cd1b | 116.0 (4) |
N1a—C8a—C7a | 111.1 (6) | H2b—O22b—C22b | 114.3 (6) |
C8a—N1a—C1a | 112.0 (6) | H2b—O22b—Cd1b | 114.5 (4) |
C8a—N1a—C11a | 109.6 (6) | C22b—O22b—Cd1b | 109.9 (5) |
C8a—N1a—Cd1a | 106.9 (4) | H3b—O32b—C32b | 114.8 (6) |
C1a—N1a—C11a | 108.5 (6) | H3b—O32b—Cd1b | 109.0 (4) |
C1a—N1a—Cd1a | 107.9 (5) | C32b—O32b—Cd1b | 111.9 (5) |
C11a—N1a—Cd1a | 112.0 (5) | H4b—O42b—C42b | 114.4 (5) |
C3a—N2a—C2a | 110.4 (6) | H4b—O42b—Cd1b | 96.2 (3) |
C3a—N2a—C21a | 108.6 (6) | C42b—O42b—Cd1b | 104.9 (4) |
C3a—N2a—Cd1a | 107.8 (4) | O2c—N1c—O1c | 122.5 (16) |
C2a—N2a—C21a | 108.7 (6) | O2c—N1c—C4c | 118.2 (13) |
C2a—N2a—Cd1a | 107.3 (5) | O1c—N1c—C4c | 119.3 (17) |
C21a—N2a—Cd1a | 114.1 (5) | O3c—C1c—C6c | 121.7 (8) |
C31a—N3a—C4a | 110.4 (6) | O3c—C1c—C2c | 121.2 (7) |
C31a—N3a—C5a | 108.0 (6) | C6c—C1c—C2c | 117.0 (8) |
C31a—N3a—Cd1a | 113.1 (5) | H2c—C2c—C3c | 119.3 (8) |
C4a—N3a—C5a | 111.9 (6) | H2c—C2c—C1c | 118.9 (8) |
C4a—N3a—Cd1a | 106.9 (4) | C3c—C2c—C1c | 121.8 (8) |
C5a—N3a—Cd1a | 106.6 (5) | H3c—C3c—C4c | 121.5 (10) |
C41a—N4a—C6a | 109.2 (6) | H3c—C3c—C2c | 120.9 (10) |
C41a—N4a—C7a | 110.1 (6) | C4c—C3c—C2c | 117.6 (9) |
C41a—N4a—Cd1a | 111.7 (5) | C3c—C4c—C5c | 123.2 (10) |
C6a—N4a—C7a | 109.8 (6) | C3c—C4c—N1c | 118.8 (11) |
C6a—N4a—Cd1a | 107.8 (4) | C5c—C4c—N1c | 118.0 (11) |
C7a—N4a—Cd1a | 108.2 (4) | H5c—C5c—C6c | 121.4 (11) |
H1a—O12a—C12a | 114.5 (5) | H5c—C5c—C4c | 121.1 (11) |
H1a—O12a—Cd1a | 99.3 (3) | C6c—C5c—C4c | 117.5 (10) |
C12a—O12a—Cd1a | 117.1 (4) | H6c—C6c—C5c | 118.4 (9) |
H2a—O22a—C22a | 113.5 (5) | H6c—C6c—C1c | 118.8 (9) |
H2a—O22a—Cd1a | 101.3 (3) | C5c—C6c—C1c | 122.8 (9) |
C22a—O22a—Cd1a | 108.3 (4) | O1d—N1d—O2d | 123.1 (14) |
H3a—O32a—C32a | 114.5 (6) | O1d—N1d—C4d | 119.2 (14) |
H3a—O32a—Cd1a | 103.3 (4) | O2d—N1d—C4d | 117.5 (11) |
C32a—O32a—Cd1a | 111.1 (4) | O3d—C1d—C6d | 122.0 (7) |
H4a—O42a—C42a | 114.7 (5) | O3d—C1d—C2d | 120.2 (7) |
H4a—O42a—Cd1a | 95.8 (3) | C6d—C1d—C2d | 117.8 (8) |
C42a—O42a—Cd1a | 106.8 (4) | H2d—C2d—C3d | 119.8 (8) |
O12b—Cd1b—N2b | 117.4 (2) | H2d—C2d—C1d | 119.5 (8) |
O12b—Cd1b—O32b | 109.54 (17) | C3d—C2d—C1d | 120.7 (8) |
O12b—Cd1b—N4b | 98.2 (2) | H3d—C3d—C4d | 120.1 (8) |
O12b—Cd1b—N1b | 68.6 (2) | H3d—C3d—C2d | 120.2 (8) |
O12b—Cd1b—N3b | 167.2 (2) | C4d—C3d—C2d | 119.7 (8) |
O12b—Cd1b—O42b | 68.29 (17) | C3d—C4d—C5d | 120.8 (9) |
O12b—Cd1b—O22b | 70.43 (17) | C3d—C4d—N1d | 120.0 (10) |
N2b—Cd1b—O32b | 96.4 (2) | C5d—C4d—N1d | 119.2 (10) |
N2b—Cd1b—N4b | 117.5 (2) | H5d—C5d—C6d | 120.1 (10) |
N2b—Cd1b—N1b | 73.9 (2) | H5d—C5d—C4d | 120.3 (10) |
N2b—Cd1b—N3b | 75.4 (2) | C6d—C5d—C4d | 119.6 (9) |
N2b—Cd1b—O42b | 168.3 (2) | H6d—C6d—C5d | 119.3 (8) |
N2b—Cd1b—O22b | 68.7 (2) | H6d—C6d—C1d | 119.4 (8) |
O32b—Cd1b—N4b | 118.9 (2) | C5d—C6d—C1d | 121.3 (9) |
O32b—Cd1b—N1b | 166.72 (19) | O1e—Cl1e—O3e | 107.4 (5) |
O32b—Cd1b—N3b | 67.8 (2) | O1e—Cl1e—O4e | 111.1 (6) |
O32b—Cd1b—O42b | 71.97 (16) | O1e—Cl1e—O2e | 109.4 (5) |
O32b—Cd1b—O22b | 67.91 (17) | O3e—Cl1e—O4e | 107.9 (5) |
N4b—Cd1b—N1b | 74.2 (2) | O3e—Cl1e—O2e | 110.0 (5) |
N4b—Cd1b—N3b | 73.6 (2) | O4e—Cl1e—O2e | 111.0 (6) |
N4b—Cd1b—O42b | 69.7 (2) | O3f—Cl1f—O4f | 108.5 (6) |
N4b—Cd1b—O22b | 168.5 (2) | O3f—Cl1f—O2f | 111.1 (5) |
N1b—Cd1b—N3b | 117.0 (2) | O3f—Cl1f—O1f | 111.5 (6) |
N1b—Cd1b—O42b | 117.58 (19) | O4f—Cl1f—O2f | 109.9 (5) |
N1b—Cd1b—O22b | 99.7 (2) | O4f—Cl1f—O1f | 107.5 (5) |
N3b—Cd1b—O42b | 99.3 (2) | O2f—Cl1f—O1f | 108.2 (4) |
N3b—Cd1b—O22b | 117.9 (2) | H51e—O5e—H52e | 114.5 (8) |
O42b—Cd1b—O22b | 105.88 (16) | H52f—O5f—H51f | 120.8 (7) |
Experimental details
Crystal data | |
Chemical formula | [Cd(C20H44N4O4)](C6H4NO3)(ClO4)·H2O |
Mr | 772.57 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 13.9929 (11), 19.6661 (11), 24.890 (3) |
V (Å3) | 6849.3 (11) |
Z | 8 |
Radiation type | Mo_ Kα, λ = 0.71073 Å |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.40 × 0.24 × 0.20 |
Data collection | |
Diffractometer | CAD-4-PC diffractometer |
Absorption correction | Gaussian (ABSORB; Hall et al., 1995) |
Tmin, Tmax | 0.831, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13751, 7229, 5325 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.070, 1.47 |
No. of reflections | 6622 |
No. of parameters | 811 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.58, −0.82 |
Computer programs: DIFDAT, SORTRF and ADDREF in Xtal (Hall et al., 1995), SIR92 (Altomare et al., 1994), CRYLSQ in Xtal, BONDLA and CIFIO in Xtal.
Cd1a—N1a | 2.492 (7) | Cd1b—N1b | 2.488 (7) |
Cd1a—N2a | 2.458 (7) | Cd1b—N2b | 2.435 (7) |
Cd1a—N3a | 2.480 (7) | Cd1b—N3b | 2.498 (7) |
Cd1a—N4a | 2.454 (7) | Cd1b—N4b | 2.463 (7) |
Cd1a—O12a | 2.349 (5) | Cd1b—O12b | 2.359 (5) |
Cd1a—O22a | 2.626 (5) | Cd1b—O22b | 2.544 (5) |
Cd1a—O32a | 2.438 (5) | Cd1b—O32b | 2.448 (5) |
Cd1a—O42a | 2.534 (5) | Cd1b—O42b | 2.543 (5) |
O12a—O3d | 2.630 (8) | O12b—O3c | 2.627 (8) |
O22a—O5f | 2.746 (8) | O22b—O5e | 2.970 (8) |
O32a—O5f | 2.720 (8) | O32b—O5e | 2.645 (8) |
O42a—O3d | 2.797 (8) | O42b—O3c | 2.749 (8) |
O5f—O3d | 2.627 (9) | O5e—O3c | 2.615 (8) |
O5f—O1f | 2.803 (9) | O5e—O1e | 2.798 (9) |
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The ability of optically active pendant hydroxyl donor macrocyclic ligands based on cyclen (cyclen is 1,4,7,10-tetraazacyclododecane) to coordinate in a diastereoselective manner has been noted previously (Dhillon et al., 1997, 1998). The structures of such complexes generally approximate to that of a square antiprism (Buøen et al., 1982; Chin et al., 1994; Hancock et al., 1988; Luckay et al., 1997) and as such have an inherent helicity which may be described as Λ or Δ according to whether the four hydroxyl donors are displaced anticlockwise or clockwise, with respect to the nitrogen atom to which each is attached, when the molecule is viewed from the plane of the hydroxyl groups towards the plane of the four nitrogen atoms along the C4 axis (Dhillon et al., 1995). Recent research has been directed towards attaching aromatic groups to each of the pendant arms in such a way that they will juxtapose to form a cavity suitable for the inclusion of smaller guest molecules (Smith et al., 1999). In the present work the attached group is the smaller methyl group and it was of interest to determine whether association with potential guest molecules for the larger complexes would occur in the absence of aromatic attachments.
There are two formula units of Δ[Cd(S-thpc12)] p-nitrophenolate perchlorate hydrate, (I), in the asymmetric unit which, apart from their orientation in the crystal, are very nearly identical, so they will be discussed as one (Fig. 1). There is a high degree of pseudosymmetry in the structure with average weak intensity data indicating approximate glide planes and a space group that tends towards Pcab. This space group is precluded because of the presence of enantiomerically pure chiral cations. Fig. 2 shows the relationship between the crystallographically independent species and illustrates one of the approximate glide planes.
The structures of the two cations (A and B) show the expected, approximately square antiprismatic, geometry with Cd—O (hydroxyl) bond lengths in the range 2.349 (5)–2.626 (5) Å and Cd—N bond lengths in the range 2.435 (7)–2.492 (7) Å. The twist angles for the cations are ca +12.5° giving both complexes the Δ helicity. This is similar to the configuration for [K(S-thpc12)]+ predicted by molecular orbital calculations (Dhillon et al., 1997). The p-nitrophenolate is associated with two adjacent pendant hydroxyl donors via hydrogen bonds (Fig. 1 & Table 1). The CdII-phenolate O distances are 4.005 (6) and 3.993 (6) Å for A & B, respectively, eliminating the possibility of significant ionic interaction between these two charged centres. The displacement ellipsoids of the nitro groups indicate that there is considerable positional freedom for the p-nitrophenolate anions (Fig. 1). There are no base-stacking interactions between the p-nitrophenolates. The other pair of adjacent hydroxyl groups is hydrogen bonded to the water molecule (Fig. 1 & Table 1). The water molecule also acts as the donor in hydrogen bonds to the phenolate O and to perchlorate.
The results of the crystal structure of (I) described here, show that p-nitrophenolate and water can both associate with the complex in the solid state. The electrical conductivity of the complex in DMF solution (92 Ω−1 cm2 mol−1), however, is above the range normally shown by 1:1 electrolytes in this solvent (65–90 and 130–170 Ω−1cm2mol−1) for 1:1 and 1:2 electrolytes, respectively (Geary, 1971), showing that the p-nitrophenolate, at least, is partially dissociated in DMF, and probably more so in solvents of higher dielectric constant.