Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016315/gs1067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016315/gs1067Isup2.hkl |
CCDC reference: 143270
Please give some indication of the method of preparation of the compound (reference?).
H atoms were located from a difference map, the phenolic H atom was refined isotropically, H atoms of the ligand were kept fixed at calculated positions (C—H = 0.95 Å) with Uiso = 1.2Ueq of the atom to which each is attached. H atoms of the water molecule were not included in the calculations.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Cascarano et al., 1996), KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Reference? 1962), KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996), KRYSTAL; software used to prepare material for publication: KRYSTAL.
C36H44N6O4+·2Cl−·2ClO4−·0.132H2O | F(000) = 1773.3 |
Mr = 848.97 | Dx = 1.425 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5631 reflections |
a = 20.376 (1) Å | θ = 1.9–29.8° |
b = 13.0504 (8) Å | µ = 0.36 mm−1 |
c = 15.8870 (9) Å | T = 120 K |
β = 110.491 (1)° | Prism, colourless |
V = 3957.4 (4) Å3 | 0.40 × 0.24 × 0.10 mm |
Z = 4 |
Siemens SMART CCD diffractometer | 10979 independent reflections |
Radiation source: x-ray tube | 6374 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.055 |
ω rotation scans with narrow frames | θmax = 29.8°, θmin = 1.9° |
Absorption correction: integration (XPREP; Siemens, 1995) | h = −26→25 |
Tmin = 0.885, Tmax = 0.975 | k = −17→18 |
39525 measured reflections | l = −22→21 |
Refinement on F | 0 constraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.033 | 1/{[σcs(F2) + 1.03F2]1/2 - F|}2 1/{[σcs(F2) + 1.03F2]1/2 - F|}2 |
wR(F2) = 0.037 | (Δ/σ)max = 0.002 |
S = 1.08 | Δρmax = 0.40 (5) e Å−3 |
6374 reflections | Δρmin = −0.46 (5) e Å−3 |
506 parameters | Extinction correction: Becker & Coppens (1974) type 1 Lorentzian isotropic |
0 restraints | Extinction coefficient: 150 (17) |
C36H44N6O4+·2Cl−·2ClO4−·0.132H2O | V = 3957.4 (4) Å3 |
Mr = 848.97 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.376 (1) Å | µ = 0.36 mm−1 |
b = 13.0504 (8) Å | T = 120 K |
c = 15.8870 (9) Å | 0.40 × 0.24 × 0.10 mm |
β = 110.491 (1)° |
Siemens SMART CCD diffractometer | 10979 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1995) | 6374 reflections with I > 3σ(I) |
Tmin = 0.885, Tmax = 0.975 | Rint = 0.055 |
39525 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.40 (5) e Å−3 |
6374 reflections | Δρmin = −0.46 (5) e Å−3 |
506 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.53355 (3) | −0.15020 (4) | 0.27732 (3) | 0.0222 (3) | |
Cl2 | −0.03101 (3) | −0.21425 (4) | 0.36138 (3) | 0.0202 (3) | |
Cl3 | 0.22969 (3) | −0.36994 (4) | 0.49059 (3) | 0.0220 (3) | |
Cl4 | 0.28673 (3) | −0.27507 (4) | 0.25560 (3) | 0.0247 (3) | |
O1 | 0.2192 (1) | −0.1475 (1) | 0.3543 (1) | 0.019 (1) | |
O2 | 0.6034 (1) | −0.1307 (1) | 0.2773 (1) | 0.032 (1) | |
O3 | 0.5266 (1) | −0.1068 (1) | 0.3567 (1) | 0.043 (1) | |
O4 | 0.5213 (1) | −0.2590 (1) | 0.2742 (1) | 0.032 (1) | |
O5 | 0.4839 (1) | −0.1028 (1) | 0.1993 (1) | 0.032 (1) | |
O6 | −0.0123 (1) | −0.1193 (1) | 0.4098 (1) | 0.031 (1) | |
O7 | 0.0221 (1) | −0.2899 (1) | 0.4014 (1) | 0.043 (1) | |
O8 | −0.0965 (1) | −0.2496 (1) | 0.3661 (1) | 0.034 (1) | |
O9 | −0.0385 (1) | −0.1980 (1) | 0.2693 (1) | 0.039 (1) | |
N1 | 0.1265 (1) | −0.0691 (1) | 0.1783 (1) | 0.018 (1) | |
N2 | 0.3569 (1) | −0.1432 (1) | 0.5299 (1) | 0.017 (1) | |
N11 | 0.1118 (1) | −0.2636 (1) | 0.2242 (1) | 0.024 (1) | |
N21 | 0.2743 (1) | −0.0511 (1) | 0.1946 (1) | 0.020 (1) | |
N31 | 0.3723 (1) | −0.3489 (1) | 0.4705 (1) | 0.022 (1) | |
N41 | 0.2234 (1) | −0.1400 (1) | 0.5437 (1) | 0.019 (1) | |
C12 | 0.1126 (1) | −0.3566 (2) | 0.2617 (1) | 0.028 (1) | |
C13 | 0.0579 (1) | −0.4224 (2) | 0.2237 (1) | 0.028 (1) | |
C14 | 0.0031 (1) | −0.3907 (2) | 0.1484 (1) | 0.027 (1) | |
C15 | 0.0035 (1) | −0.2946 (2) | 0.1127 (1) | 0.025 (1) | |
C16 | 0.0594 (1) | −0.2301 (2) | 0.1521 (1) | 0.022 (1) | |
C17 | 0.0665 (1) | −0.1249 (2) | 0.1173 (1) | 0.025 (1) | |
C22 | 0.3442 (1) | −0.0413 (2) | 0.2273 (1) | 0.024 (1) | |
C23 | 0.3737 (1) | 0.0544 (2) | 0.2428 (1) | 0.027 (1) | |
C24 | 0.3304 (1) | 0.1389 (2) | 0.2259 (1) | 0.027 (1) | |
C25 | 0.2583 (1) | 0.1262 (1) | 0.1917 (1) | 0.023 (1) | |
C26 | 0.2297 (1) | 0.0292 (1) | 0.1750 (1) | 0.020 (1) | |
C27 | 0.1529 (1) | 0.0078 (1) | 0.1308 (1) | 0.022 (1) | |
C32 | 0.3706 (1) | −0.4286 (2) | 0.4171 (1) | 0.028 (1) | |
C33 | 0.4259 (1) | −0.4490 (2) | 0.3898 (1) | 0.031 (1) | |
C34 | 0.4824 (1) | −0.3829 (2) | 0.4164 (1) | 0.033 (1) | |
C35 | 0.4822 (1) | −0.2995 (2) | 0.4703 (1) | 0.029 (1) | |
C36 | 0.4266 (1) | −0.2830 (1) | 0.4987 (1) | 0.021 (1) | |
C37 | 0.4229 (1) | −0.2004 (2) | 0.5625 (1) | 0.023 (1) | |
C42 | 0.1540 (1) | −0.1306 (2) | 0.5246 (1) | 0.021 (1) | |
C43 | 0.1280 (1) | −0.0434 (2) | 0.5494 (1) | 0.023 (1) | |
C44 | 0.1741 (1) | 0.0331 (2) | 0.5943 (1) | 0.026 (1) | |
C45 | 0.2450 (1) | 0.0211 (2) | 0.6119 (1) | 0.023 (1) | |
C46 | 0.2698 (1) | −0.0674 (1) | 0.5856 (1) | 0.018 (1) | |
C47 | 0.3458 (1) | −0.0889 (1) | 0.6046 (1) | 0.020 (1) | |
C51 | 0.2305 (1) | −0.0440 (1) | 0.3669 (1) | 0.015 (1) | |
C52 | 0.2948 (1) | −0.0040 (1) | 0.4207 (1) | 0.016 (1) | |
C53 | 0.2996 (1) | 0.1016 (1) | 0.4371 (1) | 0.017 (1) | |
C54 | 0.2425 (1) | 0.1677 (1) | 0.4014 (1) | 0.016 (1) | |
C55 | 0.1803 (1) | 0.1242 (1) | 0.3433 (1) | 0.016 (1) | |
C56 | 0.1737 (1) | 0.0204 (1) | 0.3242 (1) | 0.016 (1) | |
C57 | 0.3587 (1) | −0.0711 (1) | 0.4586 (1) | 0.019 (1) | |
C58 | 0.1093 (1) | −0.0230 (1) | 0.2536 (1) | 0.019 (1) | |
C59 | 0.2457 (1) | 0.2829 (1) | 0.4214 (1) | 0.019 (1) | |
C60 | 0.2368 (1) | 0.3437 (2) | 0.3350 (1) | 0.027 (1) | |
C61 | 0.3150 (1) | 0.3140 (2) | 0.4932 (1) | 0.027 (1) | |
C62 | 0.1854 (1) | 0.3121 (2) | 0.4540 (1) | 0.029 (1) | |
O10 | 0.9244 (7) | 0.0260 (10) | 0.0858 (8) | 0.043 (5)* | 0.132 (5) |
HO1 | 0.249 (1) | −0.178 (2) | 0.341 (2) | 0.043 (8)* | |
HN11 | 0.1506 | −0.2193 | 0.2506 | 0.029* | |
HN21 | 0.2551 | −0.1182 | 0.1846 | 0.025* | |
HN31 | 0.3335 | −0.3381 | 0.4895 | 0.026* | |
HN41 | 0.2405 | −0.2014 | 0.5266 | 0.022* | |
H12 | 0.1507 | −0.3761 | 0.3138 | 0.033* | |
H13 | 0.0576 | −0.4885 | 0.2486 | 0.034* | |
H14 | −0.0352 | −0.4356 | 0.1210 | 0.033* | |
H15 | −0.0345 | −0.2729 | 0.0613 | 0.029* | |
H17a | 0.0722 | −0.1316 | 0.0607 | 0.030* | |
H17b | 0.0250 | −0.0871 | 0.1102 | 0.030* | |
H22 | 0.3732 | −0.1005 | 0.2397 | 0.028* | |
H23 | 0.4232 | 0.0624 | 0.2648 | 0.032* | |
H24 | 0.3499 | 0.2057 | 0.2378 | 0.033* | |
H25 | 0.2285 | 0.1845 | 0.1796 | 0.027* | |
H27a | 0.1279 | 0.0699 | 0.1284 | 0.026* | |
H27b | 0.1447 | −0.0161 | 0.0715 | 0.026* | |
H32 | 0.3304 | −0.4716 | 0.3978 | 0.033* | |
H33 | 0.4255 | −0.5071 | 0.3536 | 0.037* | |
H34 | 0.5213 | −0.3946 | 0.3978 | 0.039* | |
H35 | 0.5207 | −0.2533 | 0.4877 | 0.034* | |
H37a | 0.4275 | −0.2310 | 0.6185 | 0.028* | |
H37b | 0.4605 | −0.1540 | 0.5704 | 0.028* | |
H42 | 0.1232 | −0.1841 | 0.4941 | 0.025* | |
H43 | 0.0790 | −0.0355 | 0.5359 | 0.028* | |
H44 | 0.1571 | 0.0935 | 0.6130 | 0.031* | |
H45 | 0.2768 | 0.0737 | 0.6420 | 0.028* | |
H47a | 0.3705 | −0.0258 | 0.6142 | 0.025* | |
H47b | 0.3632 | −0.1298 | 0.6572 | 0.025* | |
H53 | 0.3433 | 0.1295 | 0.4739 | 0.020* | |
H55 | 0.1411 | 0.1675 | 0.3160 | 0.019* | |
H57a | 0.3636 | −0.1102 | 0.4107 | 0.022* | |
H57b | 0.3983 | −0.0279 | 0.4830 | 0.022* | |
H58a | 0.0897 | −0.0742 | 0.2802 | 0.023* | |
H58b | 0.0761 | 0.0304 | 0.2308 | 0.023* | |
H60a | 0.2388 | 0.4151 | 0.3474 | 0.032* | |
H60b | 0.1927 | 0.3276 | 0.2907 | 0.032* | |
H60c | 0.2732 | 0.3259 | 0.3134 | 0.032* | |
H61a | 0.3170 | 0.3854 | 0.5056 | 0.032* | |
H61b | 0.3522 | 0.2967 | 0.4729 | 0.032* | |
H61c | 0.3203 | 0.2775 | 0.5469 | 0.032* | |
H62a | 0.1875 | 0.3835 | 0.4664 | 0.034* | |
H62b | 0.1898 | 0.2749 | 0.5071 | 0.034* | |
H62c | 0.1419 | 0.2961 | 0.4087 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0193 (3) | 0.0198 (2) | 0.0263 (3) | −0.0036 (2) | 0.0063 (2) | −0.0038 (2) |
Cl2 | 0.0178 (3) | 0.0205 (2) | 0.0205 (2) | −0.0006 (2) | 0.0044 (2) | −0.0034 (2) |
Cl3 | 0.0240 (3) | 0.0208 (2) | 0.0213 (2) | −0.0048 (2) | 0.0079 (2) | 0.0004 (2) |
Cl4 | 0.0310 (3) | 0.0204 (3) | 0.0229 (3) | 0.0062 (2) | 0.0097 (2) | −0.0013 (2) |
O1 | 0.022 (1) | 0.014 (1) | 0.023 (1) | 0.001 (1) | 0.008 (1) | −0.002 (1) |
O2 | 0.018 (1) | 0.027 (1) | 0.049 (1) | −0.003 (1) | 0.009 (1) | −0.006 (1) |
O3 | 0.055 (1) | 0.046 (1) | 0.036 (1) | −0.015 (1) | 0.025 (1) | −0.017 (1) |
O4 | 0.035 (1) | 0.020 (1) | 0.039 (1) | −0.007 (1) | 0.009 (1) | 0.000 (1) |
O5 | 0.025 (1) | 0.029 (1) | 0.037 (1) | 0.005 (1) | 0.006 (1) | 0.005 (1) |
O6 | 0.035 (1) | 0.022 (1) | 0.032 (1) | −0.008 (1) | 0.006 (1) | −0.009 (1) |
O7 | 0.036 (1) | 0.036 (1) | 0.048 (1) | 0.017 (1) | 0.002 (1) | 0.001 (1) |
O8 | 0.028 (1) | 0.029 (1) | 0.049 (1) | −0.009 (1) | 0.018 (1) | −0.005 (1) |
O9 | 0.046 (1) | 0.051 (1) | 0.024 (1) | −0.003 (1) | 0.017 (1) | −0.003 (1) |
N1 | 0.019 (1) | 0.017 (1) | 0.017 (1) | −0.001 (1) | 0.004 (1) | −0.003 (1) |
N2 | 0.014 (1) | 0.017 (1) | 0.017 (1) | 0.002 (1) | 0.003 (1) | 0.002 (1) |
N11 | 0.019 (1) | 0.021 (1) | 0.027 (1) | −0.005 (1) | 0.003 (1) | −0.005 (1) |
N21 | 0.021 (1) | 0.020 (1) | 0.021 (1) | 0.001 (1) | 0.008 (1) | −0.002 (1) |
N31 | 0.022 (1) | 0.021 (1) | 0.022 (1) | 0.002 (1) | 0.008 (1) | 0.002 (1) |
N41 | 0.020 (1) | 0.019 (1) | 0.017 (1) | −0.002 (1) | 0.007 (1) | 0.000 (1) |
C12 | 0.030 (1) | 0.024 (1) | 0.028 (1) | −0.001 (1) | 0.007 (1) | 0.000 (1) |
C13 | 0.034 (1) | 0.025 (1) | 0.031 (1) | −0.007 (1) | 0.016 (1) | −0.005 (1) |
C14 | 0.024 (1) | 0.031 (1) | 0.032 (1) | −0.008 (1) | 0.016 (1) | −0.013 (1) |
C15 | 0.019 (1) | 0.030 (1) | 0.025 (1) | −0.001 (1) | 0.008 (1) | −0.010 (1) |
C16 | 0.019 (1) | 0.025 (1) | 0.022 (1) | 0.001 (1) | 0.007 (1) | −0.007 (1) |
C17 | 0.022 (1) | 0.024 (1) | 0.022 (1) | 0.000 (1) | 0.000 (1) | −0.006 (1) |
C22 | 0.021 (1) | 0.028 (1) | 0.024 (1) | 0.003 (1) | 0.011 (1) | −0.001 (1) |
C23 | 0.024 (1) | 0.031 (1) | 0.028 (1) | −0.003 (1) | 0.013 (1) | −0.001 (1) |
C24 | 0.031 (1) | 0.025 (1) | 0.030 (1) | −0.006 (1) | 0.016 (1) | −0.001 (1) |
C25 | 0.029 (1) | 0.021 (1) | 0.022 (1) | 0.003 (1) | 0.014 (1) | 0.004 (1) |
C26 | 0.023 (1) | 0.024 (1) | 0.015 (1) | 0.004 (1) | 0.010 (1) | 0.002 (1) |
C27 | 0.023 (1) | 0.022 (1) | 0.019 (1) | 0.003 (1) | 0.006 (1) | 0.001 (1) |
C32 | 0.035 (1) | 0.018 (1) | 0.027 (1) | −0.002 (1) | 0.007 (1) | 0.001 (1) |
C33 | 0.041 (1) | 0.024 (1) | 0.029 (1) | 0.011 (1) | 0.013 (1) | 0.002 (1) |
C34 | 0.033 (1) | 0.033 (1) | 0.038 (1) | 0.016 (1) | 0.020 (1) | 0.013 (1) |
C35 | 0.023 (1) | 0.026 (1) | 0.037 (1) | 0.004 (1) | 0.011 (1) | 0.007 (1) |
C36 | 0.019 (1) | 0.017 (1) | 0.023 (1) | 0.003 (1) | 0.003 (1) | 0.007 (1) |
C37 | 0.018 (1) | 0.021 (1) | 0.026 (1) | 0.001 (1) | 0.001 (1) | 0.001 (1) |
C42 | 0.018 (1) | 0.026 (1) | 0.019 (1) | −0.006 (1) | 0.006 (1) | 0.000 (1) |
C43 | 0.019 (1) | 0.031 (1) | 0.021 (1) | −0.001 (1) | 0.008 (1) | −0.001 (1) |
C44 | 0.025 (1) | 0.026 (1) | 0.028 (1) | 0.000 (1) | 0.013 (1) | −0.006 (1) |
C45 | 0.024 (1) | 0.023 (1) | 0.024 (1) | −0.005 (1) | 0.009 (1) | −0.006 (1) |
C46 | 0.019 (1) | 0.020 (1) | 0.014 (1) | −0.004 (1) | 0.006 (1) | 0.001 (1) |
C47 | 0.019 (1) | 0.023 (1) | 0.018 (1) | −0.003 (1) | 0.004 (1) | 0.000 (1) |
C51 | 0.018 (1) | 0.015 (1) | 0.015 (1) | −0.001 (1) | 0.008 (1) | 0.000 (1) |
C52 | 0.016 (1) | 0.019 (1) | 0.015 (1) | 0.002 (1) | 0.006 (1) | 0.003 (1) |
C53 | 0.016 (1) | 0.019 (1) | 0.017 (1) | −0.003 (1) | 0.006 (1) | 0.000 (1) |
C54 | 0.018 (1) | 0.017 (1) | 0.017 (1) | 0.000 (1) | 0.009 (1) | 0.000 (1) |
C55 | 0.016 (1) | 0.016 (1) | 0.016 (1) | 0.002 (1) | 0.007 (1) | 0.000 (1) |
C56 | 0.015 (1) | 0.018 (1) | 0.015 (1) | −0.001 (1) | 0.006 (1) | −0.001 (1) |
C57 | 0.017 (1) | 0.019 (1) | 0.020 (1) | 0.000 (1) | 0.007 (1) | 0.001 (1) |
C58 | 0.017 (1) | 0.018 (1) | 0.021 (1) | 0.000 (1) | 0.005 (1) | −0.002 (1) |
C59 | 0.020 (1) | 0.015 (1) | 0.021 (1) | −0.001 (1) | 0.006 (1) | −0.002 (1) |
C60 | 0.030 (1) | 0.018 (1) | 0.028 (1) | −0.003 (1) | 0.005 (1) | 0.001 (1) |
C61 | 0.026 (1) | 0.020 (1) | 0.029 (1) | −0.003 (1) | 0.003 (1) | −0.005 (1) |
C62 | 0.029 (1) | 0.023 (1) | 0.035 (1) | −0.001 (1) | 0.012 (1) | −0.010 (1) |
Cl1—O2 | 1.447 (1) | C55—C56 | 1.384 (3) |
Cl1—O3 | 1.434 (2) | C56—C58 | 1.508 (3) |
Cl1—O4 | 1.439 (2) | C59—C61 | 1.527 (3) |
Cl1—O5 | 1.437 (2) | C59—C62 | 1.539 (3) |
Cl2—O6 | 1.438 (1) | C59—C60 | 1.540 (3) |
Cl2—O7 | 1.438 (2) | O1—HO1 | 0.81 (2) |
Cl2—O8 | 1.439 (2) | N11—HN11 | 0.950 |
Cl2—O9 | 1.432 (2) | N21—HN21 | 0.950 |
O1—C51 | 1.373 (2) | N31—HN31 | 0.950 |
N1—C17 | 1.461 (2) | N41—HN41 | 0.950 |
N1—C27 | 1.467 (3) | C53—H53 | 0.950 |
N1—C58 | 1.487 (2) | C55—H55 | 0.950 |
N2—C37 | 1.465 (2) | C57—H57a | 0.950 |
N2—C47 | 1.467 (2) | C57—H57b | 0.950 |
N2—C57 | 1.483 (2) | C58—H58a | 0.950 |
N11—C12 | 1.349 (3) | C58—H58b | 0.950 |
N11—C16 | 1.337 (3) | C12—H12 | 0.950 |
N21—C22 | 1.341 (3) | C13—H13 | 0.950 |
N21—C26 | 1.350 (3) | C14—H14 | 0.950 |
N31—C32 | 1.335 (3) | C15—H15 | 0.950 |
N31—C36 | 1.348 (3) | C17—H17a | 0.950 |
N41—C42 | 1.345 (2) | C17—H17b | 0.950 |
N41—C46 | 1.339 (2) | C22—H22 | 0.950 |
C12—C13 | 1.370 (3) | C23—H23 | 0.950 |
C13—C14 | 1.385 (3) | C24—H24 | 0.950 |
C14—C15 | 1.378 (3) | C25—H25 | 0.950 |
C15—C16 | 1.378 (3) | C27—H27a | 0.950 |
C16—C17 | 1.505 (3) | C27—H27b | 0.950 |
C22—C23 | 1.371 (3) | C32—H32 | 0.950 |
C23—C24 | 1.380 (3) | C33—H33 | 0.950 |
C24—C25 | 1.386 (3) | C34—H34 | 0.950 |
C25—C26 | 1.381 (3) | C35—H35 | 0.950 |
C26—C27 | 1.500 (3) | C37—H37a | 0.950 |
C32—C33 | 1.370 (3) | C37—H37b | 0.950 |
C33—C34 | 1.381 (3) | C42—H42 | 0.950 |
C34—C35 | 1.386 (3) | C43—H43 | 0.950 |
C35—C36 | 1.376 (3) | C44—H44 | 0.950 |
C36—C37 | 1.499 (3) | C45—H45 | 0.950 |
C42—C43 | 1.370 (3) | C47—H47a | 0.950 |
C43—C44 | 1.386 (3) | C47—H47b | 0.950 |
C44—C45 | 1.381 (3) | C60—H60a | 0.950 |
C45—C46 | 1.382 (3) | C60—H60b | 0.950 |
C46—C47 | 1.496 (3) | C60—H60c | 0.950 |
C51—C52 | 1.391 (3) | C61—H61a | 0.950 |
C51—C56 | 1.399 (3) | C61—H61b | 0.950 |
C52—C53 | 1.400 (3) | C61—H61c | 0.950 |
C52—C57 | 1.508 (3) | C62—H62a | 0.950 |
C53—C54 | 1.399 (3) | C62—H62b | 0.950 |
C54—C55 | 1.400 (3) | C62—H62c | 0.950 |
C54—C59 | 1.533 (3) | ||
O7i···O10 | 2.617 (13) | O1···N1 | 2.955 (2) |
O1···N41 | 2.982 (2) | O1···N2 | 3.192 (2) |
O2—Cl1—O3 | 109.3 (1) | C54—C53—H53 | 118.7 |
O2—Cl1—O4 | 109.39 (9) | C52—C53—H53 | 118.7 |
O2—Cl1—O5 | 108.72 (9) | C56—C55—H55 | 118.8 |
O3—Cl1—O4 | 110.5 (1) | C54—C55—H55 | 118.8 |
O3—Cl1—O5 | 109.4 (1) | H57a—C57—H57b | 109.5 |
O4—Cl1—O5 | 109.49 (9) | N2—C57—H57a | 108.0 |
O6—Cl2—O7 | 109.7 (1) | C52—C57—H57a | 108.0 |
O6—Cl2—O8 | 109.02 (9) | N2—C57—H57b | 108.0 |
O6—Cl2—O9 | 109.4 (1) | C52—C57—H57b | 108.0 |
O7—Cl2—O8 | 109.0 (1) | H58a—C58—H58b | 109.5 |
O7—Cl2—O9 | 110.4 (1) | N1—C58—H58a | 109.0 |
O8—Cl2—O9 | 109.3 (1) | C56—C58—H58a | 109.0 |
C17—N1—C27 | 111.9 (2) | N1—C58—H58b | 109.0 |
C58—N1—C17 | 110.9 (2) | C56—C58—H58b | 109.0 |
C58—N1—C27 | 111.6 (1) | N11—C12—H12 | 120.4 |
C37—N2—C47 | 110.1 (1) | C13—C12—H12 | 120.4 |
C57—N2—C37 | 109.1 (1) | C12—C13—H13 | 120.7 |
C57—N2—C47 | 111.3 (1) | C14—C13—H13 | 120.7 |
C12—N11—C16 | 123.7 (2) | C15—C14—H14 | 119.7 |
C22—N21—C26 | 123.6 (2) | C13—C14—H14 | 119.7 |
C32—N31—C36 | 123.0 (2) | C16—C15—H15 | 120.2 |
C42—N41—C46 | 123.4 (2) | C14—C15—H15 | 120.2 |
N11—C12—C13 | 119.2 (2) | H17a—C17—H17b | 109.5 |
C12—C13—C14 | 118.7 (2) | N1—C17—H17a | 108.8 |
C13—C14—C15 | 120.5 (2) | C16—C17—H17a | 108.8 |
C14—C15—C16 | 119.5 (2) | N1—C17—H17b | 108.8 |
N11—C16—C15 | 118.4 (2) | C16—C17—H17b | 108.8 |
N11—C16—C17 | 117.5 (2) | N21—C22—H22 | 120.1 |
C15—C16—C17 | 124.1 (2) | C23—C22—H22 | 120.1 |
N1—C17—C16 | 112.1 (2) | C22—C23—H23 | 120.6 |
N21—C22—C23 | 119.7 (2) | C24—C23—H23 | 120.6 |
C22—C23—C24 | 118.8 (2) | C23—C24—H24 | 120.0 |
C23—C24—C25 | 120.0 (2) | C25—C24—H24 | 120.0 |
C24—C25—C26 | 120.2 (2) | C26—C25—H25 | 119.9 |
N21—C26—C25 | 117.6 (2) | C24—C25—H25 | 119.9 |
N21—C26—C27 | 118.1 (2) | H27a—C27—H27b | 109.5 |
C25—C26—C27 | 124.1 (2) | N1—C27—H27a | 108.5 |
N1—C27—C26 | 113.4 (2) | C26—C27—H27a | 108.5 |
N31—C32—C33 | 120.8 (2) | N1—C27—H27b | 108.5 |
C32—C33—C34 | 118.2 (2) | C26—C27—H27b | 108.5 |
C33—C34—C35 | 119.8 (2) | N31—C32—H32 | 119.6 |
C34—C35—C36 | 120.4 (2) | C33—C32—H32 | 119.6 |
N31—C36—C35 | 117.8 (2) | C32—C33—H33 | 120.9 |
N31—C36—C37 | 117.0 (2) | C34—C33—H33 | 120.9 |
C35—C36—C37 | 125.1 (2) | C33—C34—H34 | 120.1 |
N2—C37—C36 | 112.6 (2) | C35—C34—H34 | 120.1 |
N41—C42—C43 | 119.5 (2) | C36—C35—H35 | 119.8 |
C42—C43—C44 | 119.1 (2) | C34—C35—H35 | 119.8 |
C43—C44—C45 | 119.7 (2) | H37a—C37—H37b | 109.5 |
C44—C45—C46 | 120.0 (2) | N2—C37—H37a | 108.7 |
N41—C46—C45 | 118.3 (2) | C36—C37—H37a | 108.7 |
N41—C46—C47 | 117.9 (2) | N2—C37—H37b | 108.7 |
C45—C46—C47 | 123.8 (2) | C36—C37—H37b | 108.7 |
N2—C47—C46 | 111.7 (2) | N41—C42—H42 | 120.2 |
O1—C51—C52 | 122.2 (2) | C43—C42—H42 | 120.2 |
O1—C51—C56 | 116.9 (2) | C42—C43—H43 | 120.5 |
C52—C51—C56 | 120.9 (2) | C44—C43—H43 | 120.5 |
C51—C52—C53 | 118.2 (2) | C45—C44—H44 | 120.2 |
C51—C52—C57 | 121.5 (2) | C43—C44—H44 | 120.1 |
C53—C52—C57 | 120.2 (2) | C44—C45—H45 | 120.0 |
C52—C53—C54 | 122.5 (2) | C46—C45—H45 | 120.0 |
C53—C54—C55 | 116.7 (2) | H47a—C47—H47b | 109.5 |
C53—C54—C59 | 123.4 (2) | N2—C47—H47a | 108.9 |
C55—C54—C59 | 119.8 (2) | C46—C47—H47a | 108.9 |
C54—C55—C56 | 122.5 (2) | N2—C47—H47b | 108.9 |
C51—C56—C55 | 118.8 (2) | C46—C47—H47b | 108.9 |
C55—C56—C58 | 121.5 (2) | H60a—C60—H60b | 109.4 |
C51—C56—C58 | 119.5 (2) | H60a—C60—H60c | 109.4 |
N2—C57—C52 | 115.2 (2) | C59—C60—H60a | 109.7 |
N1—C58—C56 | 111.2 (2) | H60b—C60—H60c | 109.5 |
C54—C59—C61 | 112.2 (2) | C59—C60—H60b | 109.4 |
C61—C59—C62 | 108.7 (2) | C59—C60—H60c | 109.4 |
C60—C59—C61 | 108.6 (2) | H61a—C61—H61b | 108.8 |
C54—C59—C62 | 109.4 (2) | H61a—C61—H61c | 108.8 |
C54—C59—C60 | 109.7 (2) | C59—C61—H61a | 112.2 |
C60—C59—C62 | 108.2 (2) | H61b—C61—H61c | 109.5 |
C51—O1—HO1 | 115 (2) | C59—C61—H61b | 108.8 |
C16—N11—HN11 | 118.2 | C59—C61—H61c | 108.8 |
C12—N11—HN11 | 118.1 | H62a—C62—H62b | 109.5 |
C22—N21—HN21 | 118.2 | H62a—C62—H62c | 109.5 |
C26—N21—HN21 | 118.2 | C59—C62—H62a | 109.4 |
C32—N31—HN31 | 118.5 | H62b—C62—H62c | 109.5 |
C36—N31—HN31 | 118.5 | C59—C62—H62b | 109.5 |
C46—N41—HN41 | 118.3 | C59—C62—H62c | 109.5 |
C42—N41—HN41 | 118.3 | ||
C51—C52—C57—N2 | −70.3 (2) | C51—C56—C58—N1 | −58.9 (2) |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—HN11···O1 | 0.95 | 1.98 | 2.861 (2) | 152.8 |
N21—HN21···Cl4 | 0.95 | 2.32 | 3.062 (2) | 134.8 |
N31—HN31···Cl3 | 0.95 | 2.16 | 3.045 (2) | 154.1 |
N41—HN41···Cl3 | 0.95 | 2.26 | 3.131 (2) | 151.5 |
O1—HO1···Cl4 | 0.81 (2) | 2.18 (3) | 2.938 (2) | 155 (2) |
Experimental details
Crystal data | |
Chemical formula | C36H44N6O4+·2Cl−·2ClO4−·0.132H2O |
Mr | 848.97 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 20.376 (1), 13.0504 (8), 15.8870 (9) |
β (°) | 110.491 (1) |
V (Å3) | 3957.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.40 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Integration (XPREP; Siemens, 1995) |
Tmin, Tmax | 0.885, 0.975 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 39525, 10979, 6374 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.037, 1.08 |
No. of reflections | 6374 |
No. of parameters | 506 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40 (5), −0.46 (5) |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Cascarano et al., 1996), KRYSTAL (Hazell, 1995), modified ORFLS (Reference? 1962), KRYSTAL, ORTEPIII (Burnett & Johnson, 1996), KRYSTAL, KRYSTAL.
C12—N11—C16 | 123.7 (2) | C42—N41—C46 | 123.4 (2) |
C22—N21—C26 | 123.6 (2) | O1—C51—C52 | 122.2 (2) |
C32—N31—C36 | 123.0 (2) | O1—C51—C56 | 116.9 (2) |
C51—C52—C57—N2 | −70.3 (2) | C51—C56—C58—N1 | −58.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—HN11···O1 | 0.95 | 1.98 | 2.861 (2) | 152.8 |
N21—HN21···Cl4 | 0.95 | 2.32 | 3.062 (2) | 134.8 |
N31—HN31···Cl3 | 0.95 | 2.16 | 3.045 (2) | 154.1 |
N41—HN41···Cl3 | 0.95 | 2.26 | 3.131 (2) | 151.5 |
O1—HO1···Cl4 | 0.81 (2) | 2.18 (3) | 2.938 (2) | 155 (2) |
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Compounds containing two transition metal ions have received considerable attention in the past two decades because of their potential reactivity in the activation of small molecules and catalysis of organic reactions, and as model systems for dimetallic enzymes (Reedijk, 1993; van der Beuken & Feringa, 1998). Several synthetic strategies for their preparation have been developed. These include self-asssembly methods, for example the spontaneous formation of dimetallic compounds with oxide and sulfide bridges, or the templated formation of suitable ditopic macrocyclic and acyclic ligands. The design of ligands containing two cavities suitable for metal binding is an important approach to a more controlled stepwise preparation of dimetallic compounds.
The title compound, bpbpH54+·2Cl-·2ClO4-.0.132H2O, (I), contains an example of such a preformed ditopic ligand. The compound bpbpH is an acyclic ditopic ligand precursor (it needs to be deprotonated in order to bind two metal ions); it has been used successfully by us for the preparation of dimetallic compounds. The ligand is normally septadentate, providing an amine and two pyridine donors to each metal ion in a dinuclear complex; the phenolate O atom `bridges' the two metal ions. The remaining coordination sphere of the metal ions is usually filled by small `exogenous' ligands, e.g. a typical formulation is [M2(bpbp)(CH3CO2)2](ClO4)2, M = a transition metal ion.
Interestingly bpbp- shows a remarkable ability to stabilize mixed-metal and mixed-valent compounds (Ghiladi et al., 1997, 1999). In the attempted preparation of one such compound from an acidic solution, we isolated a small amount of a colourless crystalline product, which has been shown, by X-ray diffraction, to be the double salt (I). The ligand is protonated at the pyridine N atoms and not at the tertiary N atoms as might be expected from their acidities (cf. pKa = 5.17 for pyridine and pKa = 11.72 for triethylamine). We have also observed this preference for protonation at the pyridine N atoms in salts of trispicolylamine (tpa), i.e. in (H3tpa)(SO4)(NO3) (Hazell et al., 1999) and in (H3tpa)2(HPO4)(ClO4)4·2H2O (Hazell & Toftlund, unpublished results).
The two Cl- ions are both hydrogen bonded (Fig. 1) to three pyridine N atoms and to the phenolic O atom of the same cation [Cl···N = 3.045 (2)–3.131 (2) Å, Cl···O = 2.938 (2) Å]; the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N···O = 2.861 (2) Å].
Bond distances and angles are generally similar to those in bpbp complexes, the exception being that the C—N(py)—C angles are in the range 123.0 (2)–123.7 (2)°, whereas in both coordinated and non-coordinated pyridine groups this angle is less than 120°. Mean values from the Cambridge Structural Database (Allen & Kennard, 1993): 117.8° for non-coordinated pyridine (5255 observations mean standard uncertainty 0.03), 118.6° for pyridine coordinated to a metal atom (10000 observations, mean standard uncertainty 0.02) and 122.6° for pyridinium compounds (901 observations, mean standard uncertainty 0.07). The molecule is not as symmetric as might have been expected: C51—O1 is bent towards N1 and the torsion angle C51—C52—C57—N2 is 11.4° larger than C51—C56—C58—N1, distortions which may be caused by repusion between N41 and O1 [O1···N41 = 2.982 (2) Å]. This result is interesting with respect to the apparent propensity of bpbp- to form unsymmetric dimetallic complexes, i.e. the incorporation of different metal ions in each cavity (Ghiladi et al.; 1997, 1999). A difference map showed a small peak which is interpreted as a partially occupied water site 2.62 (1) Å from one of the perchlorate O atoms.