Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801021316/cf6134sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801021316/cf6134Isup2.hkl |
CCDC reference: 180523
Key indicators
- Single-crystal X-ray study
- T = 168 K
- Mean (C-C) = 0.010 Å
- H-atom completeness 99%
- Disorder in solvent or counterion
- R factor = 0.037
- wR factor = 0.061
- Data-to-parameter ratio = 8.4
checkCIF results
No syntax errors found
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Alert Level B:
PLAT_111 Alert B ADDSYM detects (pseudo) centre of symmetry ... 95 Perc Fit PLAT_113 Alert B ADDSYM suggests Pseudo/New Spacegroup ........ P21/m PLAT_213 Alert B Atom C1G has ADP max/min Ratio ........... 4.60 oblate
Alert Level C:
PLAT_162 Alert C Missing or Zero su (esd) on y-coordinate for . CD PLAT_214 Alert C Atom O8 (Anion/Solvent) ADP max/min Ratio 4.50 prolate PLAT_302 Alert C Anion/Solvent Disorder ....................... 8.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C27 H50 Cd1 Cl1 N4 O11.5 Atom count from the _atom_site data: C27 H49 Cd1 Cl1 N4 O11.5 CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C27 H50 Cd1 Cl1 N4 O11.5 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 54.00 54.00 0.00 H 100.00 98.00 2.00 Cd 2.00 2.00 0.00 Cl 2.00 2.00 0.00 N 8.00 8.00 0.00 O 23.00 23.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? REFLT_03 From the CIF: _diffrn_reflns_theta_max 26.41 From the CIF: _reflns_number_total 3539 Count of symmetry unique reflns 3565 Completeness (_total/calc) 99.27% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
1 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
3 Alert Level C = Please check
The title compound was prepared by adding sodium salicylate (sodium o-hydroxybenzoate) (53 mg, 0.33 mmol) to a solution of [Cd(S-thpc12)](ClO4)2·H2O (233 mg, 0.33 mmol) (Davies et al., 2000) in dry methanol (15 ml). The sodium salt dissolved and after 5 min the solution became turbid. After heating under reflux for 2 h, the then clear solution was cooled overnight. Large colourless rod-like crystals of the pure product formed and were collected by filtration. Yield: 171 mg, 67%. 13C NMR (DMSO-d6): δ 172.72 (C═O), 161.73, 132.48, 130.53, 119.33, 117.21, 116.10, 61.55, 59.67, 50.32, 47.98, 20.97. Analysis calculated for C27H50CdClN4O11.5: C 42.53, H 6.61, N 7.35%; found: C 42.29, H 6.42, N 7.21%.
The occupancy of the water molecule O atom, O9, refined to 0.522 (12). As this was not significantly different from 0.5 and this fitted the analytical data, the occupancy of O9 was fixed at 0.5 in the final cycles. H atoms of the water molecule were not found. All other H atoms were observed in a difference map. Hydroxyl H-atom positions were obtained from the difference map and others were placed in calculated positions. Checking software shows that the structure has an approximate mirror plane. The existence of a true mirror plane is precluded by the presence of enantiomerically pure chiral cations and the successful refinement of a Flack parameter; Friedel-related reflections were treated as independent.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 2000) and Xtal3.7 ADDREF SORTRF (Hall et al., 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: Xtal3.7 CRYLSQ; molecular graphics: Xtal3.7; software used to prepare material for publication: Xtal3.7 BONDLA CIFIO.
[Cd(C20H44N4O4)(C7H5O3)]ClO4·0.5H2O | Z = 2 |
Mr = 762.57 | Dx = 1.531 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2y1 | Cell parameters from 6178 reflections |
a = 9.608 (2) Å | θ = 2.8–26.4° |
b = 12.423 (3) Å | µ = 0.80 mm−1 |
c = 14.549 (4) Å | T = 168 K |
β = 107.47 (1)° | Plate, colourless |
V = 1656.5 (7) Å3 | 0.35 × 0.28 × 0.07 mm |
Bruker P4 diffractometer | 3421 reflections with F2 > 0 |
ω scans | Rint = 0.032 |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1997) | θmax = 26.4° |
Tmin = 0.769, Tmax = 0.945 | h = −11→11 |
6081 measured reflections | k = −15→13 |
3539 independent reflections | l = −18→18 |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.01Fo2)2]1/2 |
wR(F2) = 0.061 | (Δ/σ)max = 0.001 |
S = 1.42 | Δρmax = 0.80 e Å−3 |
3421 reflections | Δρmin = −0.90 e Å−3 |
406 parameters | Absolute structure: Flack (1983), 2542 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (3) |
Secondary atom site location: structure-invariant direct methods |
[Cd(C20H44N4O4)(C7H5O3)]ClO4·0.5H2O | V = 1656.5 (7) Å3 |
Mr = 762.57 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.608 (2) Å | µ = 0.80 mm−1 |
b = 12.423 (3) Å | T = 168 K |
c = 14.549 (4) Å | 0.35 × 0.28 × 0.07 mm |
β = 107.47 (1)° |
Bruker P4 diffractometer | 3539 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1997) | 3421 reflections with F2 > 0 |
Tmin = 0.769, Tmax = 0.945 | Rint = 0.032 |
6081 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters not refined |
wR(F2) = 0.061 | Δρmax = 0.80 e Å−3 |
S = 1.42 | Δρmin = −0.90 e Å−3 |
3421 reflections | Absolute structure: Flack (1983), 2542 Friedel pairs |
406 parameters | Absolute structure parameter: 0.04 (3) |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cd | 0.31271 (3) | 0.17934 | 0.75191 (2) | 0.02168 (18) | |
O1 | 0.3844 (4) | 0.3023 (4) | 0.8905 (3) | 0.033 (3) | |
O2 | 0.5567 (4) | 0.2704 (4) | 0.7581 (3) | 0.033 (3) | |
O3 | 0.5098 (4) | 0.0488 (4) | 0.7903 (3) | 0.030 (2) | |
O4 | 0.3302 (5) | 0.0894 (4) | 0.9086 (3) | 0.031 (3) | |
N1 | 0.1041 (8) | 0.2955 (7) | 0.7510 (6) | 0.025 (4) | |
N2 | 0.2853 (7) | 0.3092 (7) | 0.6188 (5) | 0.024 (4) | |
N3 | 0.2957 (8) | 0.0693 (7) | 0.6101 (6) | 0.031 (4) | |
N4 | 0.1078 (8) | 0.0523 (7) | 0.7406 (5) | 0.027 (4) | |
C1 | 0.0563 (7) | 0.3525 (7) | 0.6581 (5) | 0.030 (4) | |
C11 | 0.1483 (9) | 0.3726 (8) | 0.8334 (7) | 0.032 (5) | |
C21 | 0.4251 (10) | 0.3624 (9) | 0.6209 (8) | 0.031 (5) | |
C31 | 0.4127 (11) | −0.0148 (10) | 0.6300 (8) | 0.037 (5) | |
C41 | 0.1112 (9) | −0.0010 (9) | 0.8332 (7) | 0.031 (5) | |
C2 | 0.1810 (7) | 0.3971 (7) | 0.6261 (5) | 0.033 (4) | |
C12 | 0.2565 (8) | 0.3241 (8) | 0.9217 (6) | 0.036 (5) | |
C22 | 0.5265 (8) | 0.3773 (7) | 0.7215 (6) | 0.031 (4) | |
C32 | 0.5505 (8) | 0.0233 (7) | 0.7038 (6) | 0.030 (4) | |
C42 | 0.2650 (8) | −0.0135 (7) | 0.9014 (5) | 0.026 (4) | |
C3 | 0.2266 (6) | 0.2484 (6) | 0.5293 (4) | 0.033 (4) | |
C13 | 0.2952 (11) | 0.4016 (11) | 1.0038 (8) | 0.056 (6) | |
C23 | 0.6604 (11) | 0.4408 (10) | 0.7189 (9) | 0.044 (6) | |
C33 | 0.6645 (10) | −0.0645 (10) | 0.7266 (9) | 0.039 (6) | |
C43 | 0.2600 (10) | −0.0509 (9) | 1.0019 (7) | 0.038 (5) | |
C4 | 0.3060 (6) | 0.1413 (5) | 0.5313 (4) | 0.032 (4) | |
C5 | 0.1522 (7) | 0.0143 (7) | 0.5818 (5) | 0.034 (4) | |
C6 | 0.1141 (8) | −0.0324 (7) | 0.6681 (5) | 0.031 (4) | |
C7 | −0.0239 (6) | 0.1193 (6) | 0.7064 (5) | 0.029 (3) | |
C8 | −0.0134 (6) | 0.2223 (6) | 0.7628 (4) | 0.032 (4) | |
O1g | 0.9831 (3) | 0.1797 (10) | 0.9882 (2) | 0.052 (2) | |
O2g | 0.7098 (3) | 0.1742 (9) | 0.9302 (2) | 0.036 (2) | |
O3g | 0.5798 (3) | 0.1831 (9) | 1.0336 (2) | 0.043 (2) | |
C1g | 0.8397 (4) | 0.1780 (11) | 1.0977 (3) | 0.027 (2) | |
C2g | 0.9752 (5) | 0.1766 (13) | 1.0799 (3) | 0.031 (3) | |
C3g | 1.1035 (5) | 0.1814 (13) | 1.1553 (4) | 0.040 (3) | |
C4g | 1.0986 (5) | 0.1825 (13) | 1.2485 (3) | 0.041 (3) | |
C5g | 0.9657 (5) | 0.1811 (12) | 1.2678 (3) | 0.041 (3) | |
C6g | 0.8379 (5) | 0.1789 (13) | 1.1937 (3) | 0.035 (3) | |
C7g | 0.6999 (5) | 0.1767 (13) | 1.0156 (3) | 0.031 (3) | |
Cl | 0.69442 (13) | 0.1843 (4) | 0.46382 (10) | 0.0416 (8) | |
O5 | 0.6783 (11) | 0.2703 (8) | 0.5190 (8) | 0.132 (8) | |
O6 | 0.8326 (5) | 0.1930 (13) | 0.4543 (4) | 0.124 (5) | |
O7 | 0.6912 (8) | 0.0872 (7) | 0.5192 (5) | 0.070 (4) | |
O8 | 0.5926 (8) | 0.1802 (14) | 0.3788 (5) | 0.206 (7) | |
O9 | 0.4565 (10) | 0.154 (2) | 1.1829 (7) | 0.104 (12) | .50000 |
H1a | −0.00436 | 0.41234 | 0.66403 | 0.03900* | |
H1b | 0.00161 | 0.30539 | 0.61031 | 0.03900* | |
H11a | 0.06369 | 0.39431 | 0.84957 | 0.04300* | |
H11b | 0.19104 | 0.43496 | 0.81374 | 0.04300* | |
H21a | 0.40462 | 0.43226 | 0.59123 | 0.03700* | |
H21b | 0.47386 | 0.32049 | 0.58601 | 0.03700* | |
H31a | 0.43280 | −0.02938 | 0.57172 | 0.04600* | |
H31b | 0.37782 | −0.07629 | 0.65338 | 0.04600* | |
H41a | 0.06850 | −0.06929 | 0.81910 | 0.03700* | |
H41b | 0.05670 | 0.04197 | 0.86461 | 0.03700* | |
H2a | 0.14266 | 0.43075 | 0.56522 | 0.04100* | |
H2b | 0.23225 | 0.44932 | 0.67204 | 0.04100* | |
H12 | 0.21937 | 0.26320 | 0.94345 | 0.04100* | |
H22 | 0.48660 | 0.42045 | 0.76229 | 0.03800* | |
H32 | 0.59158 | 0.08471 | 0.68122 | 0.03600* | |
H42 | 0.31883 | −0.06633 | 0.87916 | 0.03600* | |
H3a | 0.23651 | 0.29113 | 0.47685 | 0.04100* | |
H3b | 0.12637 | 0.23502 | 0.52030 | 0.04100* | |
H13a | 0.36335 | 0.37095 | 1.05870 | 0.08600* | |
H13b | 0.20929 | 0.42193 | 1.02067 | 0.08600* | |
H13c | 0.33665 | 0.46660 | 0.98694 | 0.08600* | |
H23a | 0.72298 | 0.44973 | 0.78147 | 0.06100* | |
H23b | 0.63101 | 0.50857 | 0.68914 | 0.06100* | |
H23c | 0.70859 | 0.40110 | 0.68082 | 0.06100* | |
H33a | 0.75170 | −0.03965 | 0.77401 | 0.05900* | |
H33b | 0.68789 | −0.08482 | 0.67044 | 0.05900* | |
H33c | 0.62883 | −0.12550 | 0.75243 | 0.05900* | |
H43a | 0.35569 | −0.05772 | 1.04331 | 0.05900* | |
H43b | 0.20924 | −0.11636 | 0.99552 | 0.05900* | |
H43c | 0.20915 | 0.00309 | 1.02661 | 0.05900* | |
H4a | 0.26458 | 0.10670 | 0.47129 | 0.04200* | |
H4b | 0.40613 | 0.15677 | 0.53925 | 0.04200* | |
H5a | 0.15428 | −0.04153 | 0.53833 | 0.04300* | |
H5b | 0.07884 | 0.06580 | 0.55006 | 0.04300* | |
H6a | 0.02216 | −0.06564 | 0.64629 | 0.04100* | |
H6b | 0.18687 | −0.08245 | 0.69888 | 0.04100* | |
H7a | −0.10532 | 0.07996 | 0.71128 | 0.03800* | |
H7b | −0.03756 | 0.13756 | 0.64028 | 0.03800* | |
H8a | −0.10430 | 0.25990 | 0.74140 | 0.03800* | |
H8b | 0.00737 | 0.20602 | 0.82915 | 0.03800* | |
H3g | 1.19482 | 0.18538 | 1.14259 | 0.05200* | |
H4g | 1.18674 | 0.18533 | 1.30013 | 0.05000* | |
H5g | 0.96322 | 0.18329 | 1.33284 | 0.05000* | |
H6g | 0.74704 | 0.17672 | 1.20740 | 0.04300* | |
H1o | 0.45536 | 0.26991 | 0.93948 | 0.04900* | |
H2o | 0.59870 | 0.27299 | 0.82436 | 0.05100* | |
H4o | 0.43370 | 0.09755 | 0.95140 | 0.04500* | |
H3o | 0.60054 | 0.07419 | 0.83749 | 0.04400* | |
H1g | 0.88475 | 0.18100 | 0.95453 | 0.07600* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.02139 (14) | 0.0245 (3) | 0.01937 (17) | −0.0002 (5) | 0.00642 (11) | 0.0006 (5) |
O1 | 0.026 (2) | 0.038 (4) | 0.033 (3) | 0.001 (2) | 0.006 (2) | 0.003 (2) |
O2 | 0.040 (3) | 0.027 (4) | 0.026 (3) | 0.002 (2) | 0.000 (2) | 0.001 (3) |
O3 | 0.030 (2) | 0.037 (4) | 0.022 (2) | 0.005 (2) | 0.0057 (18) | 0.004 (3) |
O4 | 0.028 (2) | 0.034 (4) | 0.029 (3) | −0.008 (2) | 0.006 (2) | −0.001 (3) |
N1 | 0.030 (4) | 0.022 (5) | 0.026 (4) | 0.004 (3) | 0.012 (3) | 0.004 (4) |
N2 | 0.022 (3) | 0.028 (5) | 0.020 (4) | −0.001 (3) | 0.003 (3) | 0.003 (4) |
N3 | 0.033 (4) | 0.036 (6) | 0.026 (4) | −0.004 (3) | 0.012 (3) | −0.004 (4) |
N4 | 0.025 (4) | 0.032 (6) | 0.021 (4) | −0.003 (3) | 0.002 (3) | 0.001 (4) |
C1 | 0.029 (3) | 0.030 (6) | 0.033 (4) | 0.005 (3) | 0.011 (3) | 0.005 (4) |
C11 | 0.037 (5) | 0.021 (6) | 0.039 (5) | 0.007 (4) | 0.015 (4) | 0.000 (4) |
C21 | 0.028 (4) | 0.027 (7) | 0.040 (6) | −0.004 (4) | 0.015 (4) | 0.004 (5) |
C31 | 0.035 (5) | 0.043 (8) | 0.031 (6) | −0.006 (5) | 0.005 (4) | −0.016 (5) |
C41 | 0.028 (4) | 0.033 (6) | 0.032 (5) | −0.000 (4) | 0.010 (3) | 0.003 (4) |
C2 | 0.029 (3) | 0.033 (6) | 0.038 (5) | 0.010 (3) | 0.013 (3) | 0.015 (4) |
C12 | 0.034 (4) | 0.044 (7) | 0.031 (5) | 0.005 (4) | 0.012 (3) | 0.003 (5) |
C22 | 0.029 (3) | 0.025 (6) | 0.039 (5) | −0.002 (3) | 0.011 (3) | 0.000 (4) |
C32 | 0.036 (4) | 0.028 (6) | 0.032 (4) | 0.004 (4) | 0.018 (3) | 0.000 (5) |
C42 | 0.036 (4) | 0.018 (6) | 0.022 (4) | 0.000 (3) | 0.006 (3) | 0.000 (4) |
C3 | 0.030 (3) | 0.042 (5) | 0.028 (4) | 0.002 (3) | 0.012 (3) | 0.004 (4) |
C13 | 0.073 (6) | 0.043 (8) | 0.053 (7) | 0.004 (5) | 0.020 (5) | −0.025 (6) |
C23 | 0.039 (5) | 0.051 (9) | 0.036 (6) | −0.008 (5) | 0.005 (4) | 0.003 (6) |
C33 | 0.032 (5) | 0.034 (7) | 0.057 (7) | 0.002 (4) | 0.021 (5) | 0.001 (6) |
C43 | 0.049 (5) | 0.033 (7) | 0.030 (5) | 0.001 (4) | 0.006 (4) | 0.010 (4) |
C4 | 0.038 (3) | 0.038 (7) | 0.020 (3) | 0.000 (3) | 0.010 (3) | 0.003 (3) |
C5 | 0.038 (4) | 0.032 (6) | 0.034 (4) | −0.009 (3) | 0.013 (3) | −0.010 (4) |
C6 | 0.037 (4) | 0.025 (6) | 0.030 (4) | −0.004 (3) | 0.006 (3) | −0.008 (4) |
C7 | 0.022 (3) | 0.036 (5) | 0.030 (4) | −0.008 (3) | 0.007 (3) | 0.002 (4) |
C8 | 0.022 (3) | 0.046 (6) | 0.029 (4) | 0.002 (3) | 0.010 (3) | 0.006 (4) |
O1g | 0.0411 (18) | 0.092 (4) | 0.0268 (19) | 0.015 (6) | 0.0150 (15) | 0.013 (6) |
O2g | 0.0419 (17) | 0.040 (3) | 0.0211 (18) | 0.013 (4) | 0.0018 (14) | −0.006 (5) |
O3g | 0.0319 (16) | 0.057 (3) | 0.040 (2) | 0.008 (5) | 0.0088 (15) | 0.003 (6) |
C1g | 0.035 (2) | 0.022 (4) | 0.022 (3) | −0.005 (6) | 0.0050 (19) | −0.020 (7) |
C2g | 0.036 (2) | 0.037 (4) | 0.019 (2) | 0.008 (7) | 0.007 (2) | −0.006 (8) |
C3g | 0.034 (2) | 0.043 (4) | 0.042 (3) | 0.003 (8) | 0.010 (2) | 0.006 (10) |
C4g | 0.043 (3) | 0.046 (4) | 0.026 (3) | 0.000 (8) | −0.002 (2) | −0.018 (8) |
C5g | 0.061 (3) | 0.040 (4) | 0.019 (3) | −0.010 (8) | 0.008 (2) | −0.018 (8) |
C6g | 0.046 (3) | 0.035 (4) | 0.028 (3) | 0.004 (8) | 0.019 (2) | 0.012 (9) |
C7g | 0.038 (2) | 0.025 (4) | 0.028 (3) | 0.002 (7) | 0.006 (2) | −0.005 (8) |
Cl | 0.0404 (6) | 0.0455 (12) | 0.0421 (8) | 0.002 (2) | 0.0171 (6) | 0.002 (2) |
O5 | 0.195 (9) | 0.064 (8) | 0.203 (10) | 0.046 (7) | 0.158 (8) | 0.003 (7) |
O6 | 0.083 (3) | 0.218 (10) | 0.090 (4) | −0.071 (7) | 0.055 (3) | −0.003 (8) |
O7 | 0.085 (4) | 0.041 (6) | 0.054 (4) | −0.009 (4) | −0.023 (3) | 0.019 (4) |
O8 | 0.167 (6) | 0.254 (11) | 0.105 (5) | −0.139 (10) | −0.098 (5) | 0.112 (9) |
O9 | 0.055 (5) | 0.20 (3) | 0.063 (6) | −0.044 (11) | 0.024 (5) | −0.029 (12) |
Cd—O1 | 2.457 (5) | C32—H32 | 0.961 |
Cd—O2 | 2.580 (5) | C42—C43 | 1.548 (14) |
Cd—O3 | 2.428 (4) | C42—H42 | 0.951 |
Cd—O4 | 2.499 (5) | C3—C4 | 1.530 (10) |
Cd—N1 | 2.467 (8) | C3—H3a | 0.958 |
Cd—N2 | 2.473 (8) | C3—H3b | 0.947 |
Cd—N3 | 2.440 (9) | C13—H13a | 0.947 |
Cd—N4 | 2.490 (8) | C13—H13b | 0.963 |
O1—C12 | 1.458 (10) | C13—H13c | 0.965 |
O1—H1o | 0.918 | C23—H23a | 0.935 |
O2—C22 | 1.428 (10) | C23—H23b | 0.950 |
O2—H2o | 0.927 | C23—H23c | 0.958 |
O3—C32 | 1.459 (10) | C33—H33a | 0.962 |
O3—H3o | 0.986 | C33—H33b | 0.945 |
O4—C42 | 1.413 (10) | C33—H33c | 0.954 |
O4—H4o | 1.007 | C43—H43a | 0.940 |
N1—C1 | 1.472 (11) | C43—H43b | 0.939 |
N1—C11 | 1.492 (13) | C43—H43c | 0.961 |
N1—C8 | 1.499 (11) | C4—H4a | 0.946 |
N2—C21 | 1.489 (13) | C4—H4b | 0.954 |
N2—C2 | 1.508 (11) | C5—C6 | 1.525 (12) |
N2—C3 | 1.463 (10) | C5—H5a | 0.942 |
N3—C31 | 1.498 (14) | C5—H5b | 0.961 |
N3—C4 | 1.481 (11) | C6—H6a | 0.940 |
N3—C5 | 1.482 (10) | C6—H6b | 0.942 |
N4—C41 | 1.493 (13) | C7—C8 | 1.507 (10) |
N4—C6 | 1.503 (12) | C7—H7a | 0.943 |
N4—C7 | 1.471 (10) | C7—H7b | 0.958 |
C1—C2 | 1.514 (11) | C8—H8a | 0.956 |
C1—H1a | 0.965 | C8—H8b | 0.948 |
C1—H1b | 0.940 | O1g—C2g | 1.359 (6) |
C11—C12 | 1.514 (12) | O1g—H1g | 0.925 |
C11—H11a | 0.951 | O2g—C7g | 1.274 (6) |
C11—H11b | 0.959 | O3g—C7g | 1.260 (6) |
C21—C22 | 1.507 (12) | C1g—C2g | 1.402 (7) |
C21—H21a | 0.962 | C1g—C6g | 1.402 (7) |
C21—H21b | 0.944 | C1g—C7g | 1.506 (5) |
C31—C32 | 1.509 (12) | C2g—C3g | 1.384 (5) |
C31—H31a | 0.941 | C3g—C4g | 1.371 (7) |
C31—H31b | 0.938 | C3g—H3g | 0.951 |
C41—C42 | 1.521 (10) | C4g—C5g | 1.387 (8) |
C41—H41a | 0.938 | C4g—H4g | 0.949 |
C41—H41b | 0.955 | C5g—C6g | 1.370 (6) |
C2—H2a | 0.948 | C5g—H5g | 0.953 |
C2—H2b | 0.955 | C6g—H6g | 0.953 |
C12—C13 | 1.493 (15) | Cl—O5 | 1.373 (12) |
C12—H12 | 0.931 | Cl—O6 | 1.380 (6) |
C22—C23 | 1.519 (14) | Cl—O7 | 1.456 (9) |
C22—H22 | 0.960 | Cl—O8 | 1.328 (6) |
C32—C33 | 1.511 (14) | ||
O1—Cd—O2 | 70.76 (16) | O2—C22—C21 | 104.4 (7) |
O1—Cd—O3 | 102.68 (14) | O2—C22—C23 | 114.4 (7) |
O1—Cd—O4 | 66.66 (16) | O2—C22—H22 | 111.3 |
O1—Cd—N1 | 70.6 (2) | C21—C22—C23 | 110.1 (8) |
O1—Cd—N2 | 100.1 (2) | C21—C22—H22 | 114.1 |
O1—Cd—N3 | 166.8 (2) | C23—C22—H22 | 103.0 |
O1—Cd—N4 | 118.0 (2) | O3—C32—C31 | 106.1 (7) |
O2—Cd—O3 | 69.33 (16) | O3—C32—C33 | 109.4 (7) |
O2—Cd—O4 | 110.64 (14) | O3—C32—H32 | 111.5 |
O2—Cd—N1 | 118.1 (2) | C31—C32—C33 | 110.6 (8) |
O2—Cd—N2 | 67.88 (18) | C31—C32—H32 | 111.6 |
O2—Cd—N3 | 96.0 (2) | C33—C32—H32 | 107.7 |
O2—Cd—N4 | 166.5 (2) | O4—C42—C41 | 106.2 (6) |
O3—Cd—O4 | 69.98 (16) | O4—C42—C43 | 109.9 (6) |
O3—Cd—N1 | 165.6 (2) | O4—C42—H42 | 112.0 |
O3—Cd—N2 | 120.5 (2) | C41—C42—C43 | 110.4 (7) |
O3—Cd—N3 | 70.7 (2) | C41—C42—H42 | 111.6 |
O3—Cd—N4 | 98.0 (2) | C43—C42—H42 | 106.8 |
O4—Cd—N1 | 95.6 (2) | N2—C3—C4 | 112.0 (5) |
O4—Cd—N2 | 165.5 (2) | N2—C3—H3a | 108.6 |
O4—Cd—N3 | 119.4 (2) | N2—C3—H3b | 108.6 |
O4—Cd—N4 | 67.2 (2) | C4—C3—H3a | 109.1 |
N1—Cd—N2 | 73.7 (3) | C4—C3—H3b | 109.3 |
N1—Cd—N3 | 118.4 (2) | H3a—C3—H3b | 109.1 |
N1—Cd—N4 | 75.3 (3) | C12—C13—H13a | 111.0 |
N2—Cd—N3 | 74.9 (3) | C12—C13—H13b | 110.3 |
N2—Cd—N4 | 117.7 (2) | C12—C13—H13c | 111.0 |
N3—Cd—N4 | 74.8 (3) | H13a—C13—H13b | 108.7 |
Cd—O1—C12 | 108.4 (4) | H13a—C13—H13c | 108.5 |
Cd—O1—H1o | 108.9 | H13b—C13—H13c | 107.2 |
C12—O1—H1o | 109.8 | C22—C23—H23a | 109.8 |
Cd—O2—C22 | 108.3 (4) | C22—C23—H23b | 109.5 |
Cd—O2—H2o | 99.2 | C22—C23—H23c | 107.9 |
C22—O2—H2o | 109.4 | H23a—C23—H23b | 110.7 |
Cd—O3—C32 | 109.8 (4) | H23a—C23—H23c | 110.1 |
Cd—O3—H3o | 114.3 | H23b—C23—H23c | 108.8 |
C32—O3—H3o | 105.1 | C32—C33—H33a | 110.1 |
Cd—O4—C42 | 115.5 (4) | C32—C33—H33b | 110.4 |
Cd—O4—H4o | 107.6 | C32—C33—H33c | 109.8 |
C42—O4—H4o | 118.0 | H33a—C33—H33b | 108.8 |
Cd—N1—C1 | 108.4 (5) | H33a—C33—H33c | 108.1 |
Cd—N1—C11 | 109.6 (5) | H33b—C33—H33c | 109.6 |
Cd—N1—C8 | 106.4 (5) | C42—C43—H43a | 109.3 |
C1—N1—C11 | 111.3 (8) | C42—C43—H43b | 109.3 |
C1—N1—C8 | 111.0 (5) | C42—C43—H43c | 107.9 |
C11—N1—C8 | 109.9 (7) | H43a—C43—H43b | 111.3 |
Cd—N2—C21 | 113.0 (5) | H43a—C43—H43c | 109.4 |
Cd—N2—C2 | 109.5 (5) | H43b—C43—H43c | 109.5 |
Cd—N2—C3 | 106.4 (5) | N3—C4—C3 | 113.0 (6) |
C21—N2—C2 | 106.9 (7) | N3—C4—H4a | 109.4 |
C21—N2—C3 | 110.6 (7) | N3—C4—H4b | 109.1 |
C2—N2—C3 | 110.4 (5) | C3—C4—H4a | 108.0 |
Cd—N3—C31 | 111.8 (5) | C3—C4—H4b | 107.8 |
Cd—N3—C4 | 108.2 (5) | H4a—C4—H4b | 109.5 |
Cd—N3—C5 | 108.3 (6) | N3—C5—C6 | 112.3 (6) |
C31—N3—C4 | 110.5 (8) | N3—C5—H5a | 108.7 |
C31—N3—C5 | 108.3 (8) | N3—C5—H5b | 108.3 |
C4—N3—C5 | 109.6 (6) | C6—C5—H5a | 109.3 |
Cd—N4—C41 | 114.8 (5) | C6—C5—H5b | 109.0 |
Cd—N4—C6 | 107.0 (5) | H5a—C5—H5b | 109.2 |
Cd—N4—C7 | 104.3 (5) | N4—C6—C5 | 112.4 (7) |
C41—N4—C6 | 109.1 (7) | N4—C6—H6a | 108.2 |
C41—N4—C7 | 109.8 (7) | N4—C6—H6b | 108.0 |
C6—N4—C7 | 111.8 (6) | C5—C6—H6a | 108.8 |
N1—C1—C2 | 113.7 (5) | C5—C6—H6b | 108.3 |
N1—C1—H1a | 108.6 | H6a—C6—H6b | 111.1 |
N1—C1—H1b | 109.3 | N4—C7—C8 | 112.7 (5) |
C2—C1—H1a | 107.5 | N4—C7—H7a | 109.3 |
C2—C1—H1b | 108.6 | N4—C7—H7b | 108.5 |
H1a—C1—H1b | 109.1 | C8—C7—H7a | 108.7 |
N1—C11—C12 | 112.5 (8) | C8—C7—H7b | 108.1 |
N1—C11—H11a | 108.8 | H7a—C7—H7b | 109.4 |
N1—C11—H11b | 108.9 | N1—C8—C7 | 112.5 (6) |
C12—C11—H11a | 108.8 | N1—C8—H8a | 108.2 |
C12—C11—H11b | 109.2 | N1—C8—H8b | 108.1 |
H11a—C11—H11b | 108.6 | C7—C8—H8a | 109.4 |
N2—C21—C22 | 113.0 (9) | C7—C8—H8b | 109.4 |
N2—C21—H21a | 109.3 | H8a—C8—H8b | 109.2 |
N2—C21—H21b | 109.5 | C2g—O1g—H1g | 99.8 |
C22—C21—H21a | 108.1 | C2g—C1g—C6g | 118.3 (4) |
C22—C21—H21b | 108.0 | C2g—C1g—C7g | 120.7 (4) |
H21a—C21—H21b | 108.9 | C6g—C1g—C7g | 121.0 (4) |
N3—C31—C32 | 111.4 (9) | O1g—C2g—C1g | 120.7 (3) |
N3—C31—H31a | 107.8 | O1g—C2g—C3g | 118.5 (4) |
N3—C31—H31b | 108.0 | C1g—C2g—C3g | 120.6 (4) |
C32—C31—H31a | 109.1 | C2g—C3g—C4g | 119.8 (5) |
C32—C31—H31b | 109.3 | C2g—C3g—H3g | 120.1 |
H31a—C31—H31b | 111.3 | C4g—C3g—H3g | 120.0 |
N4—C41—C42 | 112.8 (8) | C3g—C4g—C5g | 120.5 (4) |
N4—C41—H41a | 108.3 | C3g—C4g—H4g | 119.7 |
N4—C41—H41b | 108.5 | C5g—C4g—H4g | 119.8 |
C42—C41—H41a | 109.0 | C4g—C5g—C6g | 120.1 (5) |
C42—C41—H41b | 108.0 | C4g—C5g—H5g | 119.9 |
H41a—C41—H41b | 110.1 | C6g—C5g—H5g | 119.9 |
N2—C2—C1 | 111.1 (7) | C1g—C6g—C5g | 120.6 (5) |
N2—C2—H2a | 109.5 | C1g—C6g—H6g | 119.6 |
N2—C2—H2b | 109.1 | C5g—C6g—H6g | 119.8 |
C1—C2—H2a | 109.1 | O2g—C7g—O3g | 123.0 (4) |
C1—C2—H2b | 108.8 | O2g—C7g—C1g | 117.6 (4) |
H2a—C2—H2b | 109.2 | O3g—C7g—C1g | 119.3 (4) |
O1—C12—C11 | 103.8 (7) | O5—Cl—O6 | 106.2 (8) |
O1—C12—C13 | 109.8 (7) | O5—Cl—O7 | 107.3 (6) |
O1—C12—H12 | 113.6 | O5—Cl—O8 | 113.2 (8) |
C11—C12—C13 | 111.4 (8) | O6—Cl—O7 | 107.5 (7) |
C11—C12—H12 | 112.1 | O6—Cl—O8 | 111.8 (4) |
C13—C12—H12 | 106.3 | O7—Cl—O8 | 110.6 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1o···O3g | 0.92 | 1.87 | 2.776 (8) | 170 |
O2—H2o···O2g | 0.93 | 2.01 | 2.766 (7) | 138 |
O3—H3o···O2g | 0.99 | 1.90 | 2.814 (7) | 153 |
O4—H4o···O3g | 1.01 | 1.88 | 2.791 (7) | 150 |
O1g—H1g···O2g | 0.93 | 1.61 | 2.507 (4) | 161 |
O9···O3g | 2.792 (12) | |||
O9···O8i | 2.774 (12) |
Symmetry code: (i) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C20H44N4O4)(C7H5O3)]ClO4·0.5H2O |
Mr | 762.57 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 168 |
a, b, c (Å) | 9.608 (2), 12.423 (3), 14.549 (4) |
β (°) | 107.47 (1) |
V (Å3) | 1656.5 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.35 × 0.28 × 0.07 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.769, 0.945 |
No. of measured, independent and observed (F2 > 0) reflections | 6081, 3539, 3421 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.061, 1.42 |
No. of reflections | 3421 |
No. of parameters | 406 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.80, −0.90 |
Absolute structure | Flack (1983), 2542 Friedel pairs |
Absolute structure parameter | 0.04 (3) |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 2000) and Xtal3.7 ADDREF SORTRF (Hall et al., 2000), SIR97 (Altomare et al., 1994), Xtal3.7 CRYLSQ, Xtal3.7 BONDLA CIFIO.
Cd—O1 | 2.457 (5) | Cd—N1 | 2.467 (8) |
Cd—O2 | 2.580 (5) | Cd—N2 | 2.473 (8) |
Cd—O3 | 2.428 (4) | Cd—N3 | 2.440 (9) |
Cd—O4 | 2.499 (5) | Cd—N4 | 2.490 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1o···O3g | 0.92 | 1.87 | 2.776 (8) | 170.2 |
O2—H2o···O2g | 0.93 | 2.01 | 2.766 (7) | 137.9 |
O3—H3o···O2g | 0.99 | 1.90 | 2.814 (7) | 152.6 |
O4—H4o···O3g | 1.01 | 1.88 | 2.791 (7) | 149.5 |
O1g—H1g···O2g | 0.93 | 1.61 | 2.507 (4) | 161.3 |
O9···O3g | . | . | 2.792 (12) | . |
O9···O8i | . | . | 2.774 (12) | . |
Symmetry code: (i) x, y, z+1. |
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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., 1995) and as such have an inherent helicity which may be described as Λ or Δ depending on whether the four hydroxyl donors are displaced anticlockwise or clockwise, with respect to the N atom to which each is attached, when the molecule is viewed from the plane of the hydroxyl groups towards the plane of the four N atoms along the pseudo-C4 axis (Dhillon et al., 1995). Recent research has been directed towards attaching aromatic groups to each of the pendant arms in such away that they will juxtapose to form a cavity suitable for the inclusion of smaller guest molecules (Smith et al., 1999, 2002). 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.
The structure of Δ-[Cd(S-thpc12)(salicylate)]ClO4·0.5H2O, (I) {S-thpc12 is 1,4,7,10-tetrakis[(S)-2-hydroxypropyl]-1,4,7,10-tetraazacyclododecane} (Fig. 1) shows the expected approximately square antiprismatic geometry with Cd–ligand atom bond lengths given in Table 1. The plane of the four O atoms is rotated clockwise by ca 15.0°, with respect to the plane of the four N atoms, giving the complex the Δ helicity. The salicylate anion associates with the complex through hydrogen bonding between pendant arm hydroxyl groups and the carboxylate group; each carboxylate O atom of the salicylate acts as the receptor, and a pair of cis-related hydroxyl groups of the complex act as donors, with detailed geometry given in Table 2 and shown in Fig. 1. The hydroxyl group of the salicylate is internally hydrogen bonded to the adjacent carboxylate O atom and does not interact with the complex. Neither the perchlorate anion nor the water molecule play a direct role in the host–guest interaction. The CdII–carboxylate O distances are 3.918 (3) and 4.131 (3) Å, precluding the possibility of significant ionic interaction between these charged centres. There is a marked similarity in the configuration of hydrogen bonds from the Cd(S-thpc12)2+ species to the guest in (I) and that found in the corresponding 4-nitrophenolate adduct (Davies et al., 2000), although in the latter, the second cis pair of hydroxyl groups is hydrogen bonded to a perchlorate O atom.
The crystal structure of (I) shows that salicylate associates with the complex in the solid state. The electrical conductivity for the receptor complex in DMF solution (86 Ω-1 cm2 mol-1), however, is at the high end of the range normally shown by 1:1 electrolytes in this solvent (65–90 and 130–170 Ω-1 cm2 mol-1) for 1:1 and 1:2 electrolytes, respectively (Geary, 1971), suggesting that the salicylate may be partially dissociated in DMF, and probably more so in solvents of higher dielectric constant.