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Bis(pyridine-2,6-dimethanol-
N,
O,
O')cobalt(II) disaccharinate dihydrate, [Co(C
7H
9NO
2)
2](C
7H
4NO
3S)
2·2H
2O, (I), and bis(pyridine-2,6-dimethanol-
N,
O,
O')copper(II) disaccharinate dihydrate, [Cu(C
7H
9NO
2)
2](C
7H
4NO
3S)
2·2H
2O, (II), collectively [
M(dmpy)
2](sac)
2·2H
2O (where
M is Co
II or Cu
II, sac is the saccharinate anion and dmpy is pyridine-2,6-dimethanol), are isostructural. The [
M(dmpy)
2]
2+ cations exhibit distorted octahedral geometry in which the two neutral dmpy species act as tripodal
N,
O,
O'-tridentate ligands. The crystal packing is determined by hydrogen bonding, as well as by weak pyridine-saccharinate
-
-stacking interactions.
Supporting information
CCDC references: 180130; 180131
Previously prepared tetraaquabis(saccharinato)cobalt(II) and copper(II)
dihydrates, [M(H2O)4(sac)2]·2H2O (1 mmol), were dissolved
in a mixture of methanol-2-propanol (1:1 v:v; 30 ml) and mixed with the dmpy
ligand (2 mmol) dissolved in methanol (15 ml) at room temperature. The
resulting solutions were left to stand at room temperature and allowed to
evaporate slowly over a few days for crystallization. Crystals of (I) and
(II), suitable for X-ray diffraction analysis, were collected by suction
filtration, washed with acetone and dried in air.
Hydroxyl and water H atoms were found in difference maps and were positionally
refined with geometric restraints (O—H = 0.82 Å for both hydroxyl and
water H atoms, and H···H = 1.30 Å for the water H atoms) and with
Uiso(H) = 1.5Ueq of the parent atom. The remaining H atoms
were placed in calculated positions 0.93 Å from their parent atoms with
Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.
(I) Bis(pyridine-2,6-dimethanol)cobalt(II) disaccharinate dihydrate
top
Crystal data top
[Co(C7H9NO2)2]·2C7H4O3S·2H2O | Z = 2 |
Mr = 737.61 | F(000) = 762 |
Triclinic, P1 | Dx = 1.559 Mg m−3 |
a = 8.1365 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.5177 (6) Å | Cell parameters from 4198 reflections |
c = 15.7558 (8) Å | θ = 2.7–29.9° |
α = 93.054 (1)° | µ = 0.75 mm−1 |
β = 97.494 (1)° | T = 298 K |
γ = 98.030 (1)° | Block, pale purple |
V = 1571.24 (13) Å3 | 0.46 × 0.42 × 0.21 mm |
Data collection top
Bruker SMART 1000 CCD area-detector diffractometer | 9108 independent reflections |
Radiation source: fine-focus sealed tube | 6843 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 30.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −11→10 |
Tmin = 0.716, Tmax = 0.854 | k = −17→17 |
19456 measured reflections | l = −22→22 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: mixed |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0533P)2] where P = (Fo2 + 2Fc2)/3 |
9108 reflections | (Δ/σ)max = 0.001 |
448 parameters | Δρmax = 0.30 e Å−3 |
10 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
[Co(C7H9NO2)2]·2C7H4O3S·2H2O | γ = 98.030 (1)° |
Mr = 737.61 | V = 1571.24 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1365 (4) Å | Mo Kα radiation |
b = 12.5177 (6) Å | µ = 0.75 mm−1 |
c = 15.7558 (8) Å | T = 298 K |
α = 93.054 (1)° | 0.46 × 0.42 × 0.21 mm |
β = 97.494 (1)° | |
Data collection top
Bruker SMART 1000 CCD area-detector diffractometer | 9108 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 6843 reflections with I > 2σ(I) |
Tmin = 0.716, Tmax = 0.854 | Rint = 0.020 |
19456 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 10 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.30 e Å−3 |
9108 reflections | Δρmin = −0.41 e Å−3 |
448 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | −0.26131 (3) | 0.312977 (16) | 0.669785 (13) | 0.03018 (6) | |
O1 | −0.13859 (16) | 0.45647 (9) | 0.74000 (8) | 0.0440 (3) | |
H1 | −0.055 (2) | 0.4479 (18) | 0.7757 (13) | 0.066* | |
O2 | −0.39229 (16) | 0.22318 (9) | 0.55628 (8) | 0.0453 (3) | |
H2 | −0.473 (2) | 0.1752 (16) | 0.5595 (15) | 0.068* | |
O3 | −0.03683 (17) | 0.25103 (11) | 0.65113 (9) | 0.0476 (3) | |
H3 | −0.034 (3) | 0.2138 (18) | 0.6080 (12) | 0.071* | |
O4 | −0.48982 (16) | 0.31145 (11) | 0.72428 (8) | 0.0479 (3) | |
H4 | −0.493 (3) | 0.3712 (14) | 0.7463 (15) | 0.072* | |
O1W | 1.0330 (2) | 0.14679 (13) | 0.51538 (10) | 0.0589 (4) | |
H1W1 | 0.973 (3) | 0.109 (2) | 0.4788 (15) | 0.088* | |
H2W1 | 1.118 (3) | 0.119 (2) | 0.5258 (17) | 0.088* | |
O2W | 0.42923 (19) | 0.49401 (12) | 0.78286 (9) | 0.0548 (3) | |
H1W2 | 0.496 (3) | 0.530 (2) | 0.8191 (14) | 0.082* | |
H2W2 | 0.350 (2) | 0.482 (2) | 0.8080 (15) | 0.082* | |
N1 | −0.25932 (17) | 0.42389 (10) | 0.57963 (8) | 0.0359 (3) | |
N2 | −0.23706 (17) | 0.20888 (10) | 0.76391 (8) | 0.0336 (3) | |
C1 | −0.1776 (2) | 0.52398 (13) | 0.60092 (11) | 0.0444 (4) | |
C2 | −0.1637 (3) | 0.59950 (16) | 0.54034 (14) | 0.0647 (6) | |
H2A | −0.1076 | 0.6692 | 0.5555 | 0.078* | |
C3 | −0.2351 (3) | 0.56873 (18) | 0.45678 (14) | 0.0725 (7) | |
H3A | −0.2263 | 0.6180 | 0.4149 | 0.087* | |
C4 | −0.3194 (3) | 0.46575 (17) | 0.43494 (12) | 0.0614 (6) | |
H4A | −0.3683 | 0.4446 | 0.3788 | 0.074* | |
C5 | −0.3292 (2) | 0.39471 (13) | 0.49877 (10) | 0.0416 (4) | |
C6 | −0.1028 (3) | 0.54806 (15) | 0.69364 (13) | 0.0621 (6) | |
H6A | 0.0176 | 0.5683 | 0.6977 | 0.075* | |
H6B | −0.1486 | 0.6083 | 0.7181 | 0.075* | |
C7 | −0.4141 (3) | 0.28008 (15) | 0.48207 (12) | 0.0578 (6) | |
H7A | −0.5328 | 0.2792 | 0.4637 | 0.069* | |
H7B | −0.3679 | 0.2447 | 0.4363 | 0.069* | |
C8 | −0.0933 (2) | 0.16691 (13) | 0.77976 (11) | 0.0427 (4) | |
C9 | −0.0680 (3) | 0.09946 (17) | 0.84518 (14) | 0.0655 (6) | |
H9 | 0.0325 | 0.0720 | 0.8564 | 0.079* | |
C10 | −0.1961 (4) | 0.07378 (18) | 0.89356 (15) | 0.0774 (8) | |
H10 | −0.1822 | 0.0283 | 0.9379 | 0.093* | |
C11 | −0.3427 (3) | 0.11469 (17) | 0.87659 (13) | 0.0655 (6) | |
H11 | −0.4297 | 0.0963 | 0.9084 | 0.079* | |
C12 | −0.3606 (2) | 0.18428 (13) | 0.81102 (11) | 0.0423 (4) | |
C13 | 0.0338 (2) | 0.19815 (16) | 0.72152 (13) | 0.0505 (5) | |
H13A | 0.1284 | 0.2460 | 0.7534 | 0.061* | |
H13B | 0.0744 | 0.1339 | 0.7003 | 0.061* | |
C14 | −0.5151 (2) | 0.23407 (16) | 0.78673 (13) | 0.0513 (5) | |
H14A | −0.6069 | 0.1778 | 0.7636 | 0.062* | |
H14B | −0.5455 | 0.2694 | 0.8375 | 0.062* | |
S1 | 0.23536 (5) | 0.28997 (4) | 1.03158 (3) | 0.04249 (11) | |
O5 | 0.12446 (15) | 0.43468 (10) | 0.84277 (7) | 0.0432 (3) | |
O6 | 0.2541 (2) | 0.17818 (12) | 1.02295 (11) | 0.0700 (4) | |
O7 | 0.33430 (17) | 0.35034 (12) | 1.10592 (9) | 0.0580 (4) | |
N3 | 0.26807 (17) | 0.34909 (13) | 0.94508 (9) | 0.0428 (3) | |
C15 | 0.13097 (19) | 0.38640 (12) | 0.91082 (10) | 0.0333 (3) | |
C16 | −0.01603 (18) | 0.36521 (12) | 0.95909 (9) | 0.0314 (3) | |
C17 | −0.1731 (2) | 0.39595 (14) | 0.94256 (11) | 0.0394 (4) | |
H17 | −0.2011 | 0.4353 | 0.8957 | 0.047* | |
C18 | −0.2881 (2) | 0.36609 (17) | 0.99832 (13) | 0.0521 (5) | |
H18 | −0.3945 | 0.3861 | 0.9889 | 0.063* | |
C19 | −0.2463 (3) | 0.30749 (19) | 1.06696 (14) | 0.0615 (6) | |
H19 | −0.3262 | 0.2874 | 1.1026 | 0.074* | |
C20 | −0.0892 (2) | 0.27735 (17) | 1.08474 (12) | 0.0537 (5) | |
H20 | −0.0610 | 0.2382 | 1.1317 | 0.064* | |
C21 | 0.0242 (2) | 0.30835 (13) | 1.02924 (11) | 0.0379 (3) | |
S2 | −0.77230 (5) | −0.12073 (3) | 0.71436 (3) | 0.03969 (10) | |
O8 | −0.65563 (14) | 0.07947 (9) | 0.56422 (7) | 0.0415 (3) | |
O9 | −0.86006 (17) | −0.22643 (11) | 0.68565 (11) | 0.0652 (4) | |
O10 | −0.8028 (2) | −0.07784 (13) | 0.79610 (10) | 0.0655 (4) | |
N4 | −0.80667 (16) | −0.03621 (11) | 0.64162 (9) | 0.0395 (3) | |
C22 | −0.66303 (18) | 0.00737 (11) | 0.61621 (10) | 0.0305 (3) | |
C23 | −0.51292 (17) | −0.04062 (11) | 0.65306 (9) | 0.0283 (3) | |
C24 | −0.35072 (19) | −0.02258 (13) | 0.63412 (11) | 0.0376 (3) | |
H24 | −0.3198 | 0.0277 | 0.5956 | 0.045* | |
C25 | −0.2355 (2) | −0.08199 (16) | 0.67445 (12) | 0.0480 (4) | |
H25 | −0.1256 | −0.0713 | 0.6626 | 0.058* | |
C26 | −0.2808 (2) | −0.15674 (17) | 0.73191 (13) | 0.0526 (5) | |
H26 | −0.2008 | −0.1954 | 0.7578 | 0.063* | |
C27 | −0.4424 (2) | −0.17522 (15) | 0.75165 (11) | 0.0439 (4) | |
H27 | −0.4731 | −0.2250 | 0.7906 | 0.053* | |
C28 | −0.55623 (19) | −0.11605 (12) | 0.71061 (10) | 0.0317 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.02952 (11) | 0.02995 (10) | 0.03102 (11) | 0.00422 (8) | 0.00297 (8) | 0.00550 (8) |
O1 | 0.0479 (7) | 0.0396 (6) | 0.0379 (6) | −0.0022 (5) | −0.0096 (5) | 0.0050 (5) |
O2 | 0.0502 (8) | 0.0369 (6) | 0.0419 (6) | −0.0099 (5) | −0.0029 (6) | 0.0069 (5) |
O3 | 0.0421 (7) | 0.0530 (8) | 0.0523 (8) | 0.0160 (6) | 0.0141 (6) | 0.0043 (6) |
O4 | 0.0374 (7) | 0.0644 (8) | 0.0452 (7) | 0.0156 (6) | 0.0089 (5) | 0.0042 (6) |
O1W | 0.0588 (10) | 0.0696 (10) | 0.0503 (8) | 0.0310 (8) | −0.0040 (7) | −0.0038 (7) |
O2W | 0.0490 (8) | 0.0627 (9) | 0.0547 (8) | 0.0052 (7) | 0.0178 (7) | 0.0046 (7) |
N1 | 0.0406 (8) | 0.0309 (6) | 0.0337 (7) | 0.0006 (5) | −0.0005 (6) | 0.0056 (5) |
N2 | 0.0382 (7) | 0.0280 (6) | 0.0332 (6) | 0.0038 (5) | 0.0021 (5) | 0.0006 (5) |
C1 | 0.0521 (10) | 0.0317 (8) | 0.0436 (9) | −0.0033 (7) | −0.0069 (8) | 0.0095 (7) |
C2 | 0.0805 (16) | 0.0386 (10) | 0.0643 (13) | −0.0138 (9) | −0.0119 (11) | 0.0202 (9) |
C3 | 0.0963 (18) | 0.0580 (12) | 0.0551 (12) | −0.0138 (12) | −0.0038 (12) | 0.0322 (10) |
C4 | 0.0795 (15) | 0.0600 (12) | 0.0373 (10) | −0.0092 (11) | −0.0038 (10) | 0.0184 (9) |
C5 | 0.0502 (10) | 0.0394 (8) | 0.0317 (8) | −0.0033 (7) | 0.0026 (7) | 0.0053 (7) |
C6 | 0.0868 (16) | 0.0329 (9) | 0.0531 (11) | −0.0098 (9) | −0.0226 (11) | 0.0074 (8) |
C7 | 0.0833 (15) | 0.0448 (10) | 0.0344 (9) | −0.0168 (10) | −0.0042 (9) | 0.0037 (8) |
C8 | 0.0529 (11) | 0.0336 (8) | 0.0394 (9) | 0.0143 (7) | −0.0082 (8) | −0.0037 (7) |
C9 | 0.0967 (18) | 0.0503 (11) | 0.0500 (11) | 0.0345 (12) | −0.0137 (12) | 0.0034 (9) |
C10 | 0.134 (2) | 0.0467 (11) | 0.0541 (13) | 0.0251 (13) | 0.0025 (14) | 0.0199 (10) |
C11 | 0.1007 (19) | 0.0483 (11) | 0.0462 (11) | −0.0067 (11) | 0.0206 (12) | 0.0114 (9) |
C12 | 0.0538 (11) | 0.0335 (8) | 0.0370 (8) | −0.0057 (7) | 0.0100 (8) | 0.0006 (7) |
C13 | 0.0380 (10) | 0.0590 (11) | 0.0541 (11) | 0.0228 (8) | −0.0062 (8) | −0.0113 (9) |
C14 | 0.0434 (10) | 0.0562 (11) | 0.0534 (11) | −0.0056 (8) | 0.0191 (9) | −0.0010 (9) |
S1 | 0.0353 (2) | 0.0483 (2) | 0.0445 (2) | 0.01009 (17) | −0.00064 (17) | 0.01368 (19) |
O5 | 0.0363 (6) | 0.0557 (7) | 0.0371 (6) | 0.0026 (5) | 0.0033 (5) | 0.0144 (5) |
O6 | 0.0735 (11) | 0.0510 (8) | 0.0906 (12) | 0.0266 (7) | 0.0059 (9) | 0.0185 (8) |
O7 | 0.0466 (8) | 0.0735 (9) | 0.0481 (7) | 0.0033 (7) | −0.0124 (6) | 0.0131 (7) |
N3 | 0.0290 (7) | 0.0575 (9) | 0.0445 (8) | 0.0098 (6) | 0.0071 (6) | 0.0125 (7) |
C15 | 0.0283 (7) | 0.0381 (8) | 0.0321 (7) | 0.0019 (6) | 0.0027 (6) | 0.0018 (6) |
C16 | 0.0265 (7) | 0.0348 (7) | 0.0309 (7) | 0.0008 (6) | 0.0025 (6) | −0.0012 (6) |
C17 | 0.0307 (8) | 0.0459 (9) | 0.0397 (8) | 0.0056 (7) | −0.0003 (7) | −0.0024 (7) |
C18 | 0.0304 (9) | 0.0692 (12) | 0.0549 (11) | 0.0042 (8) | 0.0085 (8) | −0.0098 (10) |
C19 | 0.0441 (11) | 0.0879 (16) | 0.0532 (12) | −0.0034 (10) | 0.0230 (9) | 0.0064 (11) |
C20 | 0.0477 (11) | 0.0692 (13) | 0.0449 (10) | −0.0002 (9) | 0.0128 (8) | 0.0177 (9) |
C21 | 0.0329 (8) | 0.0423 (8) | 0.0375 (8) | 0.0021 (6) | 0.0032 (6) | 0.0062 (7) |
S2 | 0.02830 (19) | 0.0427 (2) | 0.0519 (2) | 0.00645 (15) | 0.01251 (17) | 0.01875 (18) |
O8 | 0.0358 (6) | 0.0416 (6) | 0.0470 (7) | 0.0018 (5) | 0.0033 (5) | 0.0182 (5) |
O9 | 0.0427 (8) | 0.0483 (7) | 0.1003 (12) | −0.0110 (6) | 0.0042 (8) | 0.0254 (8) |
O10 | 0.0685 (10) | 0.0848 (10) | 0.0587 (9) | 0.0316 (8) | 0.0367 (8) | 0.0240 (8) |
N4 | 0.0253 (6) | 0.0438 (7) | 0.0518 (8) | 0.0067 (5) | 0.0061 (6) | 0.0186 (6) |
C22 | 0.0262 (7) | 0.0306 (7) | 0.0337 (7) | 0.0020 (5) | 0.0018 (6) | 0.0037 (6) |
C23 | 0.0229 (7) | 0.0303 (7) | 0.0303 (7) | 0.0026 (5) | 0.0015 (5) | −0.0007 (5) |
C24 | 0.0268 (7) | 0.0436 (8) | 0.0414 (9) | −0.0001 (6) | 0.0077 (6) | −0.0002 (7) |
C25 | 0.0252 (8) | 0.0634 (11) | 0.0553 (11) | 0.0097 (7) | 0.0049 (7) | −0.0022 (9) |
C26 | 0.0374 (10) | 0.0647 (12) | 0.0577 (11) | 0.0248 (9) | −0.0054 (8) | 0.0067 (9) |
C27 | 0.0417 (9) | 0.0496 (9) | 0.0431 (9) | 0.0153 (8) | 0.0027 (7) | 0.0131 (8) |
C28 | 0.0275 (7) | 0.0348 (7) | 0.0331 (7) | 0.0056 (6) | 0.0038 (6) | 0.0029 (6) |
Geometric parameters (Å, º) top
Co1—N2 | 2.0341 (12) | C11—C12 | 1.393 (3) |
Co1—N1 | 2.0385 (12) | C11—H11 | 0.9300 |
Co1—O1 | 2.1086 (12) | C12—C14 | 1.494 (3) |
Co1—O3 | 2.1295 (13) | C13—H13A | 0.9700 |
Co1—O2 | 2.1334 (12) | C13—H13B | 0.9700 |
Co1—O4 | 2.1455 (13) | C14—H14A | 0.9700 |
O1—C6 | 1.409 (2) | C14—H14B | 0.9700 |
O1—H1 | 0.846 (16) | S1—O6 | 1.4300 (15) |
O2—C7 | 1.406 (2) | S1—O7 | 1.4425 (15) |
O2—H2 | 0.835 (15) | S1—N3 | 1.6196 (14) |
O3—C13 | 1.420 (2) | S1—C21 | 1.7606 (17) |
O3—H3 | 0.808 (16) | O5—C15 | 1.2573 (18) |
O4—C14 | 1.431 (2) | N3—C15 | 1.330 (2) |
O4—H4 | 0.812 (16) | C15—C16 | 1.500 (2) |
O1W—H1W1 | 0.793 (16) | C16—C21 | 1.375 (2) |
O1W—H2W1 | 0.821 (16) | C16—C17 | 1.383 (2) |
O2W—H1W2 | 0.805 (16) | C17—C18 | 1.392 (2) |
O2W—H2W2 | 0.802 (16) | C17—H17 | 0.9300 |
N1—C5 | 1.335 (2) | C18—C19 | 1.372 (3) |
N1—C1 | 1.337 (2) | C18—H18 | 0.9300 |
N2—C12 | 1.338 (2) | C19—C20 | 1.381 (3) |
N2—C8 | 1.348 (2) | C19—H19 | 0.9300 |
C1—C2 | 1.383 (2) | C20—C21 | 1.383 (2) |
C1—C6 | 1.505 (3) | C20—H20 | 0.9300 |
C2—C3 | 1.380 (3) | S2—O9 | 1.4329 (14) |
C2—H2A | 0.9300 | S2—O10 | 1.4336 (15) |
C3—C4 | 1.376 (3) | S2—N4 | 1.6247 (13) |
C3—H3A | 0.9300 | S2—C28 | 1.7597 (15) |
C4—C5 | 1.380 (2) | O8—C22 | 1.2511 (17) |
C4—H4A | 0.9300 | N4—C22 | 1.3383 (19) |
C5—C7 | 1.497 (2) | C22—C23 | 1.499 (2) |
C6—H6A | 0.9700 | C23—C24 | 1.381 (2) |
C6—H6B | 0.9700 | C23—C28 | 1.3855 (19) |
C7—H7A | 0.9700 | C24—C25 | 1.388 (2) |
C7—H7B | 0.9700 | C24—H24 | 0.9300 |
C8—C9 | 1.380 (2) | C25—C26 | 1.383 (3) |
C8—C13 | 1.496 (3) | C25—H25 | 0.9300 |
C9—C10 | 1.382 (4) | C26—C27 | 1.381 (3) |
C9—H9 | 0.9300 | C26—H26 | 0.9300 |
C10—C11 | 1.363 (4) | C27—C28 | 1.383 (2) |
C10—H10 | 0.9300 | C27—H27 | 0.9300 |
| | | |
N2—Co1—N1 | 173.86 (5) | C12—C11—H11 | 120.4 |
N2—Co1—O1 | 98.82 (5) | N2—C12—C11 | 120.49 (19) |
N1—Co1—O1 | 76.85 (5) | N2—C12—C14 | 115.53 (14) |
N2—Co1—O3 | 76.87 (5) | C11—C12—C14 | 123.96 (18) |
N1—Co1—O3 | 99.01 (5) | O3—C13—C8 | 110.81 (14) |
O1—Co1—O3 | 95.06 (5) | O3—C13—H13A | 109.5 |
N2—Co1—O2 | 108.04 (5) | C8—C13—H13A | 109.5 |
N1—Co1—O2 | 76.36 (5) | O3—C13—H13B | 109.5 |
O1—Co1—O2 | 153.14 (4) | C8—C13—H13B | 109.5 |
O3—Co1—O2 | 91.06 (5) | H13A—C13—H13B | 108.1 |
N2—Co1—O4 | 76.86 (5) | O4—C14—C12 | 111.27 (14) |
N1—Co1—O4 | 107.66 (5) | O4—C14—H14A | 109.4 |
O1—Co1—O4 | 95.02 (5) | C12—C14—H14A | 109.4 |
O3—Co1—O4 | 152.99 (5) | O4—C14—H14B | 109.4 |
O2—Co1—O4 | 91.15 (5) | C12—C14—H14B | 109.4 |
C6—O1—Co1 | 117.35 (10) | H14A—C14—H14B | 108.0 |
C6—O1—H1 | 111.5 (16) | O6—S1—O7 | 114.91 (9) |
Co1—O1—H1 | 114.2 (16) | O6—S1—N3 | 111.20 (9) |
C7—O2—Co1 | 116.80 (10) | O7—S1—N3 | 110.62 (8) |
C7—O2—H2 | 113.0 (16) | O6—S1—C21 | 112.19 (9) |
Co1—O2—H2 | 120.0 (16) | O7—S1—C21 | 109.40 (9) |
C13—O3—Co1 | 114.65 (11) | N3—S1—C21 | 97.12 (7) |
C13—O3—H3 | 107.3 (18) | C15—N3—S1 | 110.60 (11) |
Co1—O3—H3 | 119.7 (18) | O5—C15—N3 | 122.65 (14) |
C14—O4—Co1 | 115.06 (11) | O5—C15—C16 | 122.56 (14) |
C14—O4—H4 | 108.5 (17) | N3—C15—C16 | 114.79 (13) |
Co1—O4—H4 | 109.4 (18) | C21—C16—C17 | 120.42 (15) |
H1W1—O1W—H2W1 | 106 (2) | C21—C16—C15 | 110.29 (13) |
H1W2—O2W—H2W2 | 101 (2) | C17—C16—C15 | 129.28 (14) |
C5—N1—C1 | 120.36 (13) | C16—C17—C18 | 117.83 (16) |
C5—N1—Co1 | 120.18 (10) | C16—C17—H17 | 121.1 |
C1—N1—Co1 | 119.30 (11) | C18—C17—H17 | 121.1 |
C12—N2—C8 | 120.24 (14) | C19—C18—C17 | 120.75 (18) |
C12—N2—Co1 | 120.49 (11) | C19—C18—H18 | 119.6 |
C8—N2—Co1 | 119.24 (11) | C17—C18—H18 | 119.6 |
N1—C1—C2 | 121.13 (16) | C18—C19—C20 | 121.98 (17) |
N1—C1—C6 | 115.98 (14) | C18—C19—H19 | 119.0 |
C2—C1—C6 | 122.88 (16) | C20—C19—H19 | 119.0 |
C3—C2—C1 | 118.27 (17) | C19—C20—C21 | 116.63 (17) |
C3—C2—H2A | 120.9 | C19—C20—H20 | 121.7 |
C1—C2—H2A | 120.9 | C21—C20—H20 | 121.7 |
C4—C3—C2 | 120.55 (17) | C16—C21—C20 | 122.37 (16) |
C4—C3—H3A | 119.7 | C16—C21—S1 | 107.17 (11) |
C2—C3—H3A | 119.7 | C20—C21—S1 | 130.45 (14) |
C3—C4—C5 | 118.09 (18) | O9—S2—O10 | 115.95 (10) |
C3—C4—H4A | 121.0 | O9—S2—N4 | 110.27 (8) |
C5—C4—H4A | 121.0 | O10—S2—N4 | 110.37 (8) |
N1—C5—C4 | 121.58 (16) | O9—S2—C28 | 110.42 (8) |
N1—C5—C7 | 115.67 (14) | O10—S2—C28 | 111.16 (9) |
C4—C5—C7 | 122.73 (16) | N4—S2—C28 | 97.07 (7) |
O1—C6—C1 | 110.11 (14) | C22—N4—S2 | 110.85 (10) |
O1—C6—H6A | 109.6 | O8—C22—N4 | 122.91 (14) |
C1—C6—H6A | 109.6 | O8—C22—C23 | 122.99 (13) |
O1—C6—H6B | 109.6 | N4—C22—C23 | 114.06 (12) |
C1—C6—H6B | 109.6 | C24—C23—C28 | 120.08 (14) |
H6A—C6—H6B | 108.2 | C24—C23—C22 | 129.11 (13) |
O2—C7—C5 | 110.86 (14) | C28—C23—C22 | 110.73 (12) |
O2—C7—H7A | 109.5 | C23—C24—C25 | 117.83 (15) |
C5—C7—H7A | 109.5 | C23—C24—H24 | 121.1 |
O2—C7—H7B | 109.5 | C25—C24—H24 | 121.1 |
C5—C7—H7B | 109.5 | C26—C25—C24 | 121.31 (16) |
H7A—C7—H7B | 108.1 | C26—C25—H25 | 119.3 |
N2—C8—C9 | 121.47 (19) | C24—C25—H25 | 119.3 |
N2—C8—C13 | 115.33 (14) | C27—C26—C25 | 121.42 (16) |
C9—C8—C13 | 123.20 (18) | C27—C26—H26 | 119.3 |
C8—C9—C10 | 118.2 (2) | C25—C26—H26 | 119.3 |
C8—C9—H9 | 120.9 | C26—C27—C28 | 116.70 (15) |
C10—C9—H9 | 120.9 | C26—C27—H27 | 121.6 |
C11—C10—C9 | 120.36 (19) | C28—C27—H27 | 121.6 |
C11—C10—H10 | 119.8 | C27—C28—C23 | 122.65 (15) |
C9—C10—H10 | 119.8 | C27—C28—S2 | 130.37 (12) |
C10—C11—C12 | 119.2 (2) | C23—C28—S2 | 106.94 (11) |
C10—C11—H11 | 120.4 | | |
| | | |
N2—Co1—O1—C6 | 169.81 (15) | C8—N2—C12—C11 | −0.4 (2) |
N1—Co1—O1—C6 | −5.75 (15) | Co1—N2—C12—C11 | −178.72 (14) |
O3—Co1—O1—C6 | 92.35 (15) | C8—N2—C12—C14 | −179.04 (15) |
O2—Co1—O1—C6 | −10.1 (2) | Co1—N2—C12—C14 | 2.6 (2) |
O4—Co1—O1—C6 | −112.74 (15) | C10—C11—C12—N2 | 1.5 (3) |
N2—Co1—O2—C7 | −176.76 (14) | C10—C11—C12—C14 | −179.9 (2) |
N1—Co1—O2—C7 | −1.21 (15) | Co1—O3—C13—C8 | 18.54 (19) |
O1—Co1—O2—C7 | 3.2 (2) | N2—C8—C13—O3 | −10.5 (2) |
O3—Co1—O2—C7 | −100.23 (15) | C9—C8—C13—O3 | 169.15 (17) |
O4—Co1—O2—C7 | 106.69 (15) | Co1—O4—C14—C12 | 9.89 (19) |
N2—Co1—O3—C13 | −15.86 (12) | N2—C12—C14—O4 | −8.2 (2) |
N1—Co1—O3—C13 | 159.49 (12) | C11—C12—C14—O4 | 173.17 (17) |
O1—Co1—O3—C13 | 82.04 (13) | O6—S1—N3—C15 | 118.12 (14) |
O2—Co1—O3—C13 | −124.14 (13) | O7—S1—N3—C15 | −112.92 (13) |
O4—Co1—O3—C13 | −29.5 (2) | C21—S1—N3—C15 | 0.95 (14) |
N2—Co1—O4—C14 | −6.86 (12) | S1—N3—C15—O5 | −179.33 (13) |
N1—Co1—O4—C14 | 177.46 (12) | S1—N3—C15—C16 | −0.05 (18) |
O1—Co1—O4—C14 | −104.76 (12) | O5—C15—C16—C21 | 178.09 (15) |
O3—Co1—O4—C14 | 6.80 (19) | N3—C15—C16—C21 | −1.2 (2) |
O2—Co1—O4—C14 | 101.41 (12) | O5—C15—C16—C17 | −3.1 (3) |
O1—Co1—N1—C5 | −179.19 (15) | N3—C15—C16—C17 | 177.64 (16) |
O3—Co1—N1—C5 | 87.68 (14) | C21—C16—C17—C18 | −0.9 (2) |
O2—Co1—N1—C5 | −1.22 (13) | C15—C16—C17—C18 | −179.63 (16) |
O4—Co1—N1—C5 | −88.04 (14) | C16—C17—C18—C19 | −0.4 (3) |
O1—Co1—N1—C1 | 5.35 (14) | C17—C18—C19—C20 | 1.2 (3) |
O3—Co1—N1—C1 | −87.78 (15) | C18—C19—C20—C21 | −0.6 (3) |
O2—Co1—N1—C1 | −176.69 (15) | C17—C16—C21—C20 | 1.5 (3) |
O4—Co1—N1—C1 | 96.50 (15) | C15—C16—C21—C20 | −179.55 (17) |
O1—Co1—N2—C12 | 95.39 (12) | C17—C16—C21—S1 | −177.24 (13) |
O3—Co1—N2—C12 | −171.43 (13) | C15—C16—C21—S1 | 1.72 (16) |
O2—Co1—N2—C12 | −84.64 (13) | C19—C20—C21—C16 | −0.7 (3) |
O4—Co1—N2—C12 | 2.25 (12) | C19—C20—C21—S1 | 177.68 (16) |
O1—Co1—N2—C8 | −82.99 (12) | O6—S1—C21—C16 | −118.01 (13) |
O3—Co1—N2—C8 | 10.19 (12) | O7—S1—C21—C16 | 113.24 (12) |
O2—Co1—N2—C8 | 96.98 (12) | N3—S1—C21—C16 | −1.61 (13) |
O4—Co1—N2—C8 | −176.13 (13) | O6—S1—C21—C20 | 63.4 (2) |
C5—N1—C1—C2 | 0.2 (3) | O7—S1—C21—C20 | −65.4 (2) |
Co1—N1—C1—C2 | 175.66 (17) | N3—S1—C21—C20 | 179.79 (19) |
C5—N1—C1—C6 | −179.65 (18) | O9—S2—N4—C22 | −120.44 (13) |
Co1—N1—C1—C6 | −4.2 (2) | O10—S2—N4—C22 | 110.15 (14) |
N1—C1—C2—C3 | −0.6 (4) | C28—S2—N4—C22 | −5.57 (13) |
C6—C1—C2—C3 | 179.2 (2) | S2—N4—C22—O8 | −175.79 (13) |
C1—C2—C3—C4 | 0.7 (4) | S2—N4—C22—C23 | 6.30 (18) |
C2—C3—C4—C5 | −0.3 (4) | O8—C22—C23—C24 | −4.9 (3) |
C1—N1—C5—C4 | 0.2 (3) | N4—C22—C23—C24 | 172.98 (16) |
Co1—N1—C5—C4 | −175.25 (17) | O8—C22—C23—C28 | 178.18 (14) |
C1—N1—C5—C7 | 178.71 (18) | N4—C22—C23—C28 | −3.91 (19) |
Co1—N1—C5—C7 | 3.3 (2) | C28—C23—C24—C25 | 0.0 (2) |
C3—C4—C5—N1 | −0.1 (4) | C22—C23—C24—C25 | −176.68 (16) |
C3—C4—C5—C7 | −178.5 (2) | C23—C24—C25—C26 | −0.1 (3) |
Co1—O1—C6—C1 | 5.2 (2) | C24—C25—C26—C27 | −0.1 (3) |
N1—C1—C6—O1 | −0.8 (3) | C25—C26—C27—C28 | 0.5 (3) |
C2—C1—C6—O1 | 179.4 (2) | C26—C27—C28—C23 | −0.7 (3) |
Co1—O2—C7—C5 | 3.1 (2) | C26—C27—C28—S2 | 176.60 (15) |
N1—C5—C7—O2 | −4.0 (3) | C24—C23—C28—C27 | 0.5 (2) |
C4—C5—C7—O2 | 174.5 (2) | C22—C23—C28—C27 | 177.70 (15) |
C12—N2—C8—C9 | −1.1 (3) | C24—C23—C28—S2 | −177.38 (12) |
Co1—N2—C8—C9 | 177.32 (14) | C22—C23—C28—S2 | −0.17 (15) |
C12—N2—C8—C13 | 178.57 (15) | O9—S2—C28—C27 | −59.69 (19) |
Co1—N2—C8—C13 | −3.05 (19) | O10—S2—C28—C27 | 70.47 (19) |
N2—C8—C9—C10 | 1.3 (3) | N4—S2—C28—C27 | −174.44 (17) |
C13—C8—C9—C10 | −178.3 (2) | O9—S2—C28—C23 | 117.96 (12) |
C8—C9—C10—C11 | −0.1 (3) | O10—S2—C28—C23 | −111.89 (12) |
C9—C10—C11—C12 | −1.2 (4) | N4—S2—C28—C23 | 3.21 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5 | 0.85 (2) | 1.72 (2) | 2.5658 (17) | 175 (2) |
O2—H2···O8 | 0.84 (2) | 1.79 (2) | 2.6192 (16) | 176 (2) |
O3—H3···O1Wi | 0.81 (2) | 1.83 (2) | 2.613 (2) | 164 (3) |
O4—H4···O2Wi | 0.81 (2) | 1.84 (2) | 2.620 (2) | 162 (3) |
O1W—H2W1···O8ii | 0.82 (2) | 2.00 (2) | 2.8064 (18) | 168 (3) |
O1W—H1W1···N4iii | 0.79 (2) | 2.25 (2) | 3.027 (2) | 166 (3) |
O2W—H2W2···O5 | 0.80 (2) | 2.00 (2) | 2.7861 (18) | 166 (3) |
O2W—H1W2···O7iv | 0.81 (2) | 2.09 (2) | 2.877 (2) | 168 (3) |
C17—H17···O1 | 0.93 | 2.59 | 3.357 (2) | 140 |
C20—H20···O10v | 0.93 | 2.55 | 3.294 (2) | 137 |
C27—H27···O7vi | 0.93 | 2.58 | 3.341 (2) | 139 |
Symmetry codes: (i) x−1, y, z; (ii) x+2, y, z; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x−1, −y, −z+2; (vi) −x, −y, −z+2. |
(II) Bis(pyridine-2,6-dimethanol)copper(II) disaccharinate dihydrate
top
Crystal data top
[Cu(C7H9NO2)2]·2C7H4O3S·2H2O | Z = 2 |
Mr = 742.22 | F(000) = 766 |
Triclinic, P1 | Dx = 1.570 Mg m−3 |
a = 8.1544 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4805 (5) Å | Cell parameters from 5581 reflections |
c = 15.7510 (7) Å | θ = 2.2–29.3° |
α = 93.195 (1)° | µ = 0.90 mm−1 |
β = 97.501 (1)° | T = 298 K |
γ = 97.877 (1)° | Rod, blue |
V = 1569.85 (12) Å3 | 0.52 × 0.30 × 0.19 mm |
Data collection top
Bruker SMART 1000 CCD area-detector diffractometer | 8915 independent reflections |
Radiation source: fine-focus sealed tube | 6477 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 30.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −8→11 |
Tmin = 0.731, Tmax = 0.843 | k = −17→16 |
13441 measured reflections | l = −22→14 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: mixed |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0497P)2] where P = (Fo2 + 2Fc2)/3 |
8915 reflections | (Δ/σ)max = 0.001 |
448 parameters | Δρmax = 0.36 e Å−3 |
10 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
[Cu(C7H9NO2)2]·2C7H4O3S·2H2O | γ = 97.877 (1)° |
Mr = 742.22 | V = 1569.85 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1544 (4) Å | Mo Kα radiation |
b = 12.4805 (5) Å | µ = 0.90 mm−1 |
c = 15.7510 (7) Å | T = 298 K |
α = 93.195 (1)° | 0.52 × 0.30 × 0.19 mm |
β = 97.501 (1)° | |
Data collection top
Bruker SMART 1000 CCD area-detector diffractometer | 8915 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 6477 reflections with I > 2σ(I) |
Tmin = 0.731, Tmax = 0.843 | Rint = 0.016 |
13441 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 10 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.36 e Å−3 |
8915 reflections | Δρmin = −0.30 e Å−3 |
448 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | −0.25895 (2) | 0.318117 (16) | 0.668457 (13) | 0.02893 (6) | |
O1 | −0.13777 (17) | 0.46034 (11) | 0.74270 (9) | 0.0428 (3) | |
H1 | −0.054 (2) | 0.454 (2) | 0.7753 (14) | 0.064* | |
O2 | −0.38258 (17) | 0.21909 (11) | 0.55525 (9) | 0.0433 (3) | |
H2 | −0.461 (3) | 0.1733 (17) | 0.5609 (16) | 0.065* | |
O3 | −0.02534 (18) | 0.25759 (12) | 0.65292 (11) | 0.0493 (4) | |
H3 | −0.019 (3) | 0.223 (2) | 0.6096 (13) | 0.074* | |
O4 | −0.49689 (19) | 0.32511 (14) | 0.71615 (10) | 0.0513 (4) | |
H4 | −0.496 (4) | 0.3828 (16) | 0.7394 (17) | 0.077* | |
O1W | 1.0341 (2) | 0.14736 (15) | 0.51569 (11) | 0.0611 (4) | |
H1W1 | 1.117 (3) | 0.121 (2) | 0.525 (2) | 0.092* | |
H2W1 | 0.969 (3) | 0.106 (2) | 0.4825 (17) | 0.092* | |
O2W | 0.4287 (2) | 0.50642 (14) | 0.78407 (11) | 0.0567 (4) | |
H1W2 | 0.348 (3) | 0.487 (2) | 0.8082 (17) | 0.085* | |
H2W2 | 0.492 (3) | 0.537 (2) | 0.8243 (15) | 0.085* | |
N1 | −0.25646 (18) | 0.42281 (11) | 0.58145 (9) | 0.0331 (3) | |
N2 | −0.24859 (18) | 0.21529 (11) | 0.75653 (9) | 0.0332 (3) | |
C1 | −0.1757 (3) | 0.52393 (14) | 0.60190 (13) | 0.0431 (5) | |
C2 | −0.1626 (3) | 0.59844 (17) | 0.54111 (16) | 0.0610 (7) | |
H2A | −0.1057 | 0.6681 | 0.5559 | 0.073* | |
C3 | −0.2355 (3) | 0.5677 (2) | 0.45776 (16) | 0.0649 (7) | |
H3A | −0.2289 | 0.6170 | 0.4157 | 0.078* | |
C4 | −0.3184 (3) | 0.46383 (18) | 0.43682 (14) | 0.0547 (6) | |
H4A | −0.3676 | 0.4421 | 0.3808 | 0.066* | |
C5 | −0.3269 (2) | 0.39301 (15) | 0.50049 (12) | 0.0385 (4) | |
C6 | −0.0989 (3) | 0.54927 (17) | 0.69462 (15) | 0.0654 (7) | |
H6A | 0.0215 | 0.5668 | 0.6980 | 0.079* | |
H6B | −0.1408 | 0.6119 | 0.7183 | 0.079* | |
C7 | −0.4134 (3) | 0.27830 (17) | 0.48323 (14) | 0.0585 (6) | |
H7A | −0.5328 | 0.2782 | 0.4690 | 0.070* | |
H7B | −0.3738 | 0.2441 | 0.4345 | 0.070* | |
C8 | −0.1087 (3) | 0.16958 (15) | 0.77560 (13) | 0.0458 (5) | |
C9 | −0.0944 (4) | 0.1005 (2) | 0.84053 (17) | 0.0729 (8) | |
H9 | 0.0039 | 0.0712 | 0.8540 | 0.087* | |
C10 | −0.2253 (5) | 0.0754 (2) | 0.88473 (18) | 0.0869 (10) | |
H10 | −0.2176 | 0.0280 | 0.9281 | 0.104* | |
C11 | −0.3677 (4) | 0.1199 (2) | 0.86536 (16) | 0.0751 (9) | |
H11 | −0.4580 | 0.1025 | 0.8950 | 0.090* | |
C12 | −0.3773 (3) | 0.19193 (16) | 0.80049 (13) | 0.0454 (5) | |
C13 | 0.0276 (3) | 0.19918 (19) | 0.72276 (15) | 0.0551 (6) | |
H13A | 0.1217 | 0.2427 | 0.7586 | 0.066* | |
H13B | 0.0650 | 0.1336 | 0.7014 | 0.066* | |
C14 | −0.5285 (3) | 0.24455 (19) | 0.77488 (16) | 0.0568 (6) | |
H14A | −0.6197 | 0.1897 | 0.7485 | 0.068* | |
H14B | −0.5625 | 0.2777 | 0.8257 | 0.068* | |
S1 | 0.23480 (6) | 0.28538 (4) | 1.02792 (3) | 0.04502 (12) | |
O5 | 0.12665 (16) | 0.43827 (11) | 0.84374 (9) | 0.0442 (3) | |
O6 | 0.2531 (2) | 0.17314 (14) | 1.01633 (13) | 0.0751 (5) | |
O7 | 0.33249 (19) | 0.34340 (14) | 1.10364 (10) | 0.0621 (4) | |
N3 | 0.26849 (19) | 0.34809 (15) | 0.94349 (11) | 0.0441 (4) | |
C15 | 0.1320 (2) | 0.38717 (14) | 0.91010 (12) | 0.0342 (4) | |
C16 | −0.0148 (2) | 0.36355 (14) | 0.95781 (11) | 0.0319 (4) | |
C17 | −0.1718 (2) | 0.39502 (16) | 0.94205 (13) | 0.0396 (4) | |
H17 | −0.1991 | 0.4368 | 0.8966 | 0.047* | |
C18 | −0.2869 (3) | 0.3621 (2) | 0.99638 (15) | 0.0529 (5) | |
H18 | −0.3929 | 0.3826 | 0.9875 | 0.064* | |
C19 | −0.2466 (3) | 0.2996 (2) | 1.06335 (16) | 0.0654 (7) | |
H19 | −0.3270 | 0.2770 | 1.0979 | 0.079* | |
C20 | −0.0896 (3) | 0.2698 (2) | 1.08022 (14) | 0.0560 (6) | |
H20 | −0.0614 | 0.2287 | 1.1259 | 0.067* | |
C21 | 0.0238 (2) | 0.30393 (15) | 1.02609 (12) | 0.0385 (4) | |
S2 | −0.77522 (6) | −0.11871 (4) | 0.71413 (3) | 0.04053 (12) | |
O8 | −0.65194 (16) | 0.08107 (11) | 0.56522 (9) | 0.0420 (3) | |
O9 | −0.86538 (19) | −0.22355 (13) | 0.68494 (13) | 0.0669 (5) | |
O10 | −0.8053 (2) | −0.07535 (15) | 0.79606 (11) | 0.0673 (5) | |
N4 | −0.80581 (17) | −0.03337 (13) | 0.64174 (11) | 0.0398 (4) | |
C22 | −0.6623 (2) | 0.00806 (13) | 0.61650 (11) | 0.0304 (3) | |
C23 | −0.51412 (19) | −0.04219 (13) | 0.65345 (11) | 0.0280 (3) | |
C24 | −0.3528 (2) | −0.02618 (15) | 0.63426 (12) | 0.0365 (4) | |
H24 | −0.3205 | 0.0239 | 0.5959 | 0.044* | |
C25 | −0.2401 (2) | −0.08810 (18) | 0.67469 (14) | 0.0473 (5) | |
H25 | −0.1306 | −0.0794 | 0.6626 | 0.057* | |
C26 | −0.2872 (2) | −0.16185 (18) | 0.73207 (15) | 0.0505 (5) | |
H26 | −0.2089 | −0.2017 | 0.7581 | 0.061* | |
C27 | −0.4484 (2) | −0.17771 (16) | 0.75161 (13) | 0.0438 (5) | |
H27 | −0.4806 | −0.2272 | 0.7905 | 0.053* | |
C28 | −0.5600 (2) | −0.11663 (14) | 0.71068 (11) | 0.0311 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.02817 (11) | 0.02750 (10) | 0.03069 (11) | 0.00306 (7) | 0.00258 (8) | 0.00444 (8) |
O1 | 0.0463 (8) | 0.0368 (7) | 0.0398 (8) | −0.0007 (6) | −0.0089 (6) | 0.0051 (6) |
O2 | 0.0460 (8) | 0.0348 (7) | 0.0448 (8) | −0.0074 (6) | 0.0006 (6) | 0.0099 (6) |
O3 | 0.0413 (8) | 0.0466 (8) | 0.0622 (10) | 0.0097 (6) | 0.0138 (7) | −0.0009 (7) |
O4 | 0.0403 (8) | 0.0667 (10) | 0.0482 (9) | 0.0151 (7) | 0.0064 (6) | −0.0030 (7) |
O1W | 0.0609 (11) | 0.0703 (11) | 0.0547 (10) | 0.0318 (9) | −0.0041 (8) | −0.0005 (8) |
O2W | 0.0512 (9) | 0.0635 (10) | 0.0561 (10) | 0.0026 (8) | 0.0165 (8) | 0.0035 (8) |
N1 | 0.0365 (8) | 0.0277 (7) | 0.0332 (8) | 0.0014 (6) | 0.0004 (6) | 0.0046 (6) |
N2 | 0.0400 (8) | 0.0271 (7) | 0.0305 (8) | 0.0021 (6) | 0.0018 (6) | −0.0001 (6) |
C1 | 0.0505 (11) | 0.0284 (9) | 0.0454 (11) | −0.0017 (8) | −0.0059 (9) | 0.0085 (8) |
C2 | 0.0742 (16) | 0.0353 (10) | 0.0644 (15) | −0.0108 (10) | −0.0107 (12) | 0.0179 (10) |
C3 | 0.0799 (17) | 0.0532 (13) | 0.0563 (15) | −0.0106 (12) | −0.0003 (12) | 0.0304 (11) |
C4 | 0.0717 (15) | 0.0542 (13) | 0.0332 (11) | −0.0039 (11) | −0.0026 (10) | 0.0139 (9) |
C5 | 0.0448 (10) | 0.0363 (9) | 0.0318 (9) | −0.0014 (8) | 0.0021 (8) | 0.0044 (7) |
C6 | 0.0938 (19) | 0.0315 (10) | 0.0560 (14) | −0.0112 (11) | −0.0260 (13) | 0.0081 (10) |
C7 | 0.0889 (17) | 0.0410 (11) | 0.0348 (11) | −0.0163 (11) | −0.0054 (11) | 0.0048 (9) |
C8 | 0.0619 (13) | 0.0332 (9) | 0.0392 (11) | 0.0164 (9) | −0.0109 (9) | −0.0047 (8) |
C9 | 0.120 (2) | 0.0489 (14) | 0.0489 (14) | 0.0346 (14) | −0.0175 (15) | 0.0053 (11) |
C10 | 0.161 (3) | 0.0493 (15) | 0.0500 (16) | 0.0199 (18) | 0.0040 (19) | 0.0180 (12) |
C11 | 0.124 (3) | 0.0504 (14) | 0.0475 (14) | −0.0185 (15) | 0.0301 (15) | 0.0059 (11) |
C12 | 0.0609 (13) | 0.0344 (10) | 0.0380 (11) | −0.0087 (9) | 0.0148 (9) | −0.0031 (8) |
C13 | 0.0417 (11) | 0.0622 (14) | 0.0596 (14) | 0.0256 (10) | −0.0101 (10) | −0.0149 (11) |
C14 | 0.0451 (12) | 0.0599 (14) | 0.0628 (15) | −0.0126 (10) | 0.0247 (11) | −0.0093 (11) |
S1 | 0.0386 (3) | 0.0511 (3) | 0.0461 (3) | 0.0110 (2) | −0.0006 (2) | 0.0155 (2) |
O5 | 0.0368 (7) | 0.0566 (8) | 0.0384 (7) | 0.0012 (6) | 0.0033 (6) | 0.0159 (6) |
O6 | 0.0818 (13) | 0.0533 (10) | 0.0959 (15) | 0.0295 (9) | 0.0067 (11) | 0.0208 (10) |
O7 | 0.0503 (9) | 0.0800 (11) | 0.0498 (9) | 0.0034 (8) | −0.0146 (7) | 0.0179 (8) |
N3 | 0.0295 (8) | 0.0612 (11) | 0.0443 (10) | 0.0103 (7) | 0.0074 (7) | 0.0140 (8) |
C15 | 0.0294 (8) | 0.0383 (9) | 0.0334 (9) | 0.0013 (7) | 0.0032 (7) | 0.0023 (7) |
C16 | 0.0284 (8) | 0.0346 (9) | 0.0308 (9) | 0.0004 (7) | 0.0033 (7) | −0.0010 (7) |
C17 | 0.0316 (9) | 0.0462 (10) | 0.0393 (10) | 0.0058 (8) | 0.0012 (8) | −0.0022 (8) |
C18 | 0.0321 (10) | 0.0717 (15) | 0.0540 (13) | 0.0057 (10) | 0.0089 (9) | −0.0067 (11) |
C19 | 0.0488 (13) | 0.0915 (19) | 0.0560 (15) | −0.0062 (13) | 0.0244 (11) | 0.0060 (13) |
C20 | 0.0530 (13) | 0.0725 (15) | 0.0421 (12) | −0.0024 (11) | 0.0118 (10) | 0.0177 (11) |
C21 | 0.0347 (9) | 0.0420 (10) | 0.0370 (10) | −0.0005 (7) | 0.0037 (7) | 0.0057 (8) |
S2 | 0.0297 (2) | 0.0421 (3) | 0.0535 (3) | 0.00588 (18) | 0.0123 (2) | 0.0196 (2) |
O8 | 0.0383 (7) | 0.0417 (7) | 0.0463 (8) | 0.0033 (6) | 0.0035 (6) | 0.0194 (6) |
O9 | 0.0431 (8) | 0.0493 (9) | 0.1040 (14) | −0.0104 (7) | 0.0030 (9) | 0.0273 (9) |
O10 | 0.0701 (11) | 0.0868 (12) | 0.0616 (11) | 0.0334 (9) | 0.0382 (9) | 0.0282 (9) |
N4 | 0.0250 (7) | 0.0444 (9) | 0.0520 (10) | 0.0068 (6) | 0.0042 (7) | 0.0192 (7) |
C22 | 0.0278 (8) | 0.0300 (8) | 0.0323 (9) | 0.0028 (6) | 0.0014 (6) | 0.0030 (7) |
C23 | 0.0250 (7) | 0.0278 (8) | 0.0299 (8) | 0.0028 (6) | 0.0015 (6) | −0.0004 (6) |
C24 | 0.0289 (8) | 0.0406 (10) | 0.0393 (10) | 0.0016 (7) | 0.0063 (7) | 0.0005 (8) |
C25 | 0.0275 (9) | 0.0588 (13) | 0.0561 (13) | 0.0114 (8) | 0.0042 (8) | −0.0006 (10) |
C26 | 0.0396 (11) | 0.0588 (13) | 0.0556 (13) | 0.0247 (9) | −0.0035 (9) | 0.0066 (10) |
C27 | 0.0450 (11) | 0.0438 (11) | 0.0449 (11) | 0.0149 (8) | 0.0017 (9) | 0.0135 (9) |
C28 | 0.0282 (8) | 0.0318 (8) | 0.0334 (9) | 0.0052 (6) | 0.0031 (7) | 0.0037 (7) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.9455 (14) | C11—C12 | 1.400 (3) |
Cu1—N2 | 1.9432 (15) | C11—H11 | 0.9300 |
Cu1—O1 | 2.1168 (13) | C12—C14 | 1.495 (3) |
Cu1—O2 | 2.1603 (14) | C13—H13A | 0.9700 |
Cu1—O3 | 2.1806 (14) | C13—H13B | 0.9700 |
Cu1—O4 | 2.1809 (15) | C14—H14A | 0.9700 |
O1—C6 | 1.402 (2) | C14—H14B | 0.9700 |
O1—H1 | 0.819 (16) | S1—O6 | 1.4331 (17) |
O2—C7 | 1.402 (2) | S1—O7 | 1.4418 (17) |
O2—H2 | 0.812 (16) | S1—N3 | 1.6153 (17) |
O3—C13 | 1.407 (3) | S1—C21 | 1.7638 (19) |
O3—H3 | 0.797 (16) | O5—C15 | 1.253 (2) |
O4—C14 | 1.424 (3) | N3—C15 | 1.333 (2) |
O4—H4 | 0.788 (16) | C15—C16 | 1.499 (2) |
O1W—H1W1 | 0.796 (16) | C16—C21 | 1.369 (2) |
O1W—H2W1 | 0.801 (17) | C16—C17 | 1.386 (2) |
O2W—H1W2 | 0.818 (17) | C17—C18 | 1.388 (3) |
O2W—H2W2 | 0.809 (17) | C17—H17 | 0.9300 |
N1—C5 | 1.338 (2) | C18—C19 | 1.379 (3) |
N1—C1 | 1.342 (2) | C18—H18 | 0.9300 |
N2—C12 | 1.339 (3) | C19—C20 | 1.379 (3) |
N2—C8 | 1.351 (2) | C19—H19 | 0.9300 |
C1—C2 | 1.375 (3) | C20—C21 | 1.379 (3) |
C1—C6 | 1.510 (3) | C20—H20 | 0.9300 |
C2—C3 | 1.379 (3) | S2—O9 | 1.4300 (16) |
C2—H2A | 0.9300 | S2—O10 | 1.4349 (17) |
C3—C4 | 1.378 (3) | S2—N4 | 1.6219 (15) |
C3—H3A | 0.9300 | S2—C28 | 1.7595 (17) |
C4—C5 | 1.376 (3) | O8—C22 | 1.252 (2) |
C4—H4A | 0.9300 | N4—C22 | 1.332 (2) |
C5—C7 | 1.500 (3) | C22—C23 | 1.502 (2) |
C6—H6A | 0.9700 | C23—C24 | 1.378 (2) |
C6—H6B | 0.9700 | C23—C28 | 1.379 (2) |
C7—H7A | 0.9700 | C24—C25 | 1.395 (3) |
C7—H7B | 0.9700 | C24—H24 | 0.9300 |
C8—C9 | 1.378 (3) | C25—C26 | 1.378 (3) |
C8—C13 | 1.492 (3) | C25—H25 | 0.9300 |
C9—C10 | 1.360 (4) | C26—C27 | 1.379 (3) |
C9—H9 | 0.9300 | C26—H26 | 0.9300 |
C10—C11 | 1.360 (4) | C27—C28 | 1.385 (2) |
C10—H10 | 0.9300 | C27—H27 | 0.9300 |
| | | |
N2—Cu1—N1 | 176.96 (6) | C12—C11—H11 | 120.2 |
N2—Cu1—O1 | 99.30 (6) | N2—C12—C11 | 120.3 (2) |
N1—Cu1—O1 | 79.10 (6) | N2—C12—C14 | 116.48 (18) |
N2—Cu1—O2 | 103.30 (5) | C11—C12—C14 | 123.2 (2) |
N1—Cu1—O2 | 78.30 (5) | O3—C13—C8 | 111.98 (16) |
O1—Cu1—O2 | 157.40 (5) | O3—C13—H13A | 109.2 |
N2—Cu1—O3 | 78.66 (6) | C8—C13—H13A | 109.2 |
N1—Cu1—O3 | 98.82 (6) | O3—C13—H13B | 109.2 |
O1—Cu1—O3 | 93.62 (6) | C8—C13—H13B | 109.2 |
O2—Cu1—O3 | 90.16 (6) | H13A—C13—H13B | 107.9 |
N2—Cu1—O4 | 78.92 (6) | O4—C14—C12 | 111.57 (17) |
N1—Cu1—O4 | 103.70 (6) | O4—C14—H14A | 109.3 |
O1—Cu1—O4 | 93.78 (6) | C12—C14—H14A | 109.3 |
O2—Cu1—O4 | 91.22 (6) | O4—C14—H14B | 109.3 |
O3—Cu1—O4 | 157.25 (6) | C12—C14—H14B | 109.3 |
C6—O1—Cu1 | 114.32 (12) | H14A—C14—H14B | 108.0 |
C6—O1—H1 | 107.8 (18) | O6—S1—O7 | 115.18 (10) |
Cu1—O1—H1 | 116.2 (18) | O6—S1—N3 | 111.26 (11) |
C7—O2—Cu1 | 113.55 (11) | O7—S1—N3 | 110.51 (10) |
C7—O2—H2 | 113.2 (18) | O6—S1—C21 | 112.10 (10) |
Cu1—O2—H2 | 117.7 (18) | O7—S1—C21 | 109.17 (10) |
C13—O3—Cu1 | 111.30 (12) | N3—S1—C21 | 97.19 (8) |
C13—O3—H3 | 109 (2) | C15—N3—S1 | 110.69 (13) |
Cu1—O3—H3 | 119 (2) | O5—C15—N3 | 122.64 (17) |
C14—O4—Cu1 | 111.55 (12) | O5—C15—C16 | 122.93 (15) |
C14—O4—H4 | 109 (2) | N3—C15—C16 | 114.42 (16) |
Cu1—O4—H4 | 109 (2) | C21—C16—C17 | 120.20 (17) |
H1W1—O1W—H2W1 | 108 (3) | C21—C16—C15 | 110.73 (15) |
H1W2—O2W—H2W2 | 100 (2) | C17—C16—C15 | 129.06 (17) |
C5—N1—C1 | 119.88 (16) | C16—C17—C18 | 117.73 (19) |
C5—N1—Cu1 | 120.43 (12) | C16—C17—H17 | 121.1 |
C1—N1—Cu1 | 119.59 (12) | C18—C17—H17 | 121.1 |
C12—N2—C8 | 119.64 (18) | C19—C18—C17 | 121.0 (2) |
C12—N2—Cu1 | 120.45 (13) | C19—C18—H18 | 119.5 |
C8—N2—Cu1 | 119.88 (14) | C17—C18—H18 | 119.5 |
N1—C1—C2 | 121.39 (19) | C20—C19—C18 | 121.4 (2) |
N1—C1—C6 | 115.88 (16) | C20—C19—H19 | 119.3 |
C2—C1—C6 | 122.72 (18) | C18—C19—H19 | 119.3 |
C1—C2—C3 | 118.7 (2) | C19—C20—C21 | 116.8 (2) |
C1—C2—H2A | 120.7 | C19—C20—H20 | 121.6 |
C3—C2—H2A | 120.7 | C21—C20—H20 | 121.6 |
C4—C3—C2 | 119.9 (2) | C16—C21—C20 | 122.76 (19) |
C4—C3—H3A | 120.0 | C16—C21—S1 | 106.93 (13) |
C2—C3—H3A | 120.0 | C20—C21—S1 | 130.30 (17) |
C5—C4—C3 | 118.7 (2) | O9—S2—O10 | 115.82 (12) |
C5—C4—H4A | 120.7 | O9—S2—N4 | 110.27 (10) |
C3—C4—H4A | 120.7 | O10—S2—N4 | 110.54 (10) |
N1—C5—C4 | 121.50 (17) | O9—S2—C28 | 110.59 (9) |
N1—C5—C7 | 116.32 (16) | O10—S2—C28 | 111.20 (10) |
C4—C5—C7 | 122.17 (18) | N4—S2—C28 | 96.82 (8) |
O1—C6—C1 | 110.48 (16) | C22—N4—S2 | 111.07 (11) |
O1—C6—H6A | 109.6 | O8—C22—N4 | 123.08 (15) |
C1—C6—H6A | 109.6 | O8—C22—C23 | 122.82 (15) |
O1—C6—H6B | 109.6 | N4—C22—C23 | 114.09 (15) |
C1—C6—H6B | 109.6 | C24—C23—C28 | 120.61 (15) |
H6A—C6—H6B | 108.1 | C24—C23—C22 | 128.85 (16) |
O2—C7—C5 | 110.67 (16) | C28—C23—C22 | 110.47 (14) |
O2—C7—H7A | 109.5 | C23—C24—C25 | 117.36 (18) |
C5—C7—H7A | 109.5 | C23—C24—H24 | 121.3 |
O2—C7—H7B | 109.5 | C25—C24—H24 | 121.3 |
C5—C7—H7B | 109.5 | C26—C25—C24 | 121.48 (18) |
H7A—C7—H7B | 108.1 | C26—C25—H25 | 119.3 |
N2—C8—C9 | 121.3 (2) | C24—C25—H25 | 119.3 |
N2—C8—C13 | 116.00 (18) | C25—C26—C27 | 121.26 (17) |
C9—C8—C13 | 122.7 (2) | C25—C26—H26 | 119.4 |
C10—C9—C8 | 119.4 (3) | C27—C26—H26 | 119.4 |
C10—C9—H9 | 120.3 | C26—C27—C28 | 116.94 (19) |
C8—C9—H9 | 120.3 | C26—C27—H27 | 121.5 |
C9—C10—C11 | 119.9 (2) | C28—C27—H27 | 121.5 |
C9—C10—H10 | 120.1 | C23—C28—C27 | 122.35 (17) |
C11—C10—H10 | 120.1 | C23—C28—S2 | 107.22 (12) |
C10—C11—C12 | 119.6 (3) | C27—C28—S2 | 130.37 (15) |
C10—C11—H11 | 120.2 | | |
| | | |
N2—Cu1—O1—C6 | 170.01 (16) | C8—N2—C12—C11 | −0.5 (3) |
N1—Cu1—O1—C6 | −7.37 (16) | Cu1—N2—C12—C11 | −178.41 (15) |
O2—Cu1—O1—C6 | −8.2 (2) | C8—N2—C12—C14 | −179.23 (17) |
O3—Cu1—O1—C6 | 90.92 (16) | Cu1—N2—C12—C14 | 2.9 (2) |
O4—Cu1—O1—C6 | −110.61 (16) | C10—C11—C12—N2 | 1.4 (3) |
N2—Cu1—O2—C7 | 176.33 (15) | C10—C11—C12—C14 | 180.0 (2) |
N1—Cu1—O2—C7 | −6.32 (15) | Cu1—O3—C13—C8 | 15.1 (2) |
O1—Cu1—O2—C7 | −5.5 (2) | N2—C8—C13—O3 | −9.1 (3) |
O3—Cu1—O2—C7 | −105.29 (15) | C9—C8—C13—O3 | 171.28 (19) |
O4—Cu1—O2—C7 | 97.42 (16) | Cu1—O4—C14—C12 | 10.9 (2) |
N2—Cu1—O3—C13 | −13.15 (13) | N2—C12—C14—O4 | −9.5 (3) |
N1—Cu1—O3—C13 | 165.13 (13) | C11—C12—C14—O4 | 171.8 (2) |
O1—Cu1—O3—C13 | 85.61 (13) | O6—S1—N3—C15 | 118.08 (16) |
O2—Cu1—O3—C13 | −116.69 (13) | O7—S1—N3—C15 | −112.65 (15) |
O4—Cu1—O3—C13 | −23.2 (2) | C21—S1—N3—C15 | 0.96 (16) |
N2—Cu1—O4—C14 | −7.69 (13) | S1—N3—C15—O5 | −179.35 (15) |
N1—Cu1—O4—C14 | 173.88 (13) | S1—N3—C15—C16 | −0.1 (2) |
O1—Cu1—O4—C14 | −106.44 (13) | O5—C15—C16—C21 | 178.15 (17) |
O2—Cu1—O4—C14 | 95.62 (14) | N3—C15—C16—C21 | −1.0 (2) |
O3—Cu1—O4—C14 | 2.3 (2) | O5—C15—C16—C17 | −3.1 (3) |
O1—Cu1—N1—C5 | −178.06 (15) | N3—C15—C16—C17 | 177.74 (18) |
O2—Cu1—N1—C5 | 1.60 (14) | C21—C16—C17—C18 | −1.3 (3) |
O3—Cu1—N1—C5 | 89.92 (15) | C15—C16—C17—C18 | −179.99 (18) |
O4—Cu1—N1—C5 | −86.79 (15) | C16—C17—C18—C19 | −0.5 (3) |
O1—Cu1—N1—C1 | 5.55 (15) | C17—C18—C19—C20 | 1.7 (4) |
O2—Cu1—N1—C1 | −174.79 (16) | C18—C19—C20—C21 | −1.1 (4) |
O3—Cu1—N1—C1 | −86.47 (15) | C17—C16—C21—C20 | 1.9 (3) |
O4—Cu1—N1—C1 | 96.82 (15) | C15—C16—C21—C20 | −179.15 (19) |
O1—Cu1—N2—C12 | 94.68 (14) | C17—C16—C21—S1 | −177.32 (14) |
O2—Cu1—N2—C12 | −86.02 (14) | C15—C16—C21—S1 | 1.59 (18) |
O3—Cu1—N2—C12 | −173.46 (15) | C19—C20—C21—C16 | −0.7 (3) |
O4—Cu1—N2—C12 | 2.61 (13) | C19—C20—C21—S1 | 178.37 (18) |
O1—Cu1—N2—C8 | −83.19 (14) | O6—S1—C21—C16 | −118.01 (15) |
O2—Cu1—N2—C8 | 96.12 (14) | O7—S1—C21—C16 | 113.15 (14) |
O3—Cu1—N2—C8 | 8.68 (13) | N3—S1—C21—C16 | −1.54 (15) |
O4—Cu1—N2—C8 | −175.25 (14) | O6—S1—C21—C20 | 62.8 (2) |
C5—N1—C1—C2 | −0.3 (3) | O7—S1—C21—C20 | −66.0 (2) |
Cu1—N1—C1—C2 | 176.13 (18) | N3—S1—C21—C20 | 179.3 (2) |
C5—N1—C1—C6 | −179.33 (19) | O9—S2—N4—C22 | −120.21 (15) |
Cu1—N1—C1—C6 | −2.9 (3) | O10—S2—N4—C22 | 110.44 (15) |
N1—C1—C2—C3 | 0.4 (4) | C28—S2—N4—C22 | −5.26 (15) |
C6—C1—C2—C3 | 179.4 (2) | S2—N4—C22—O8 | −175.19 (15) |
C1—C2—C3—C4 | −0.5 (4) | S2—N4—C22—C23 | 6.1 (2) |
C2—C3—C4—C5 | 0.3 (4) | O8—C22—C23—C24 | −5.8 (3) |
C1—N1—C5—C4 | 0.1 (3) | N4—C22—C23—C24 | 172.93 (17) |
Cu1—N1—C5—C4 | −176.23 (16) | O8—C22—C23—C28 | 177.35 (16) |
C1—N1—C5—C7 | 179.55 (19) | N4—C22—C23—C28 | −3.9 (2) |
Cu1—N1—C5—C7 | 3.2 (2) | C28—C23—C24—C25 | 0.2 (3) |
C3—C4—C5—N1 | −0.2 (3) | C22—C23—C24—C25 | −176.42 (17) |
C3—C4—C5—C7 | −179.5 (2) | C23—C24—C25—C26 | −0.5 (3) |
Cu1—O1—C6—C1 | 7.7 (3) | C24—C25—C26—C27 | 0.3 (3) |
N1—C1—C6—O1 | −3.5 (3) | C25—C26—C27—C28 | 0.3 (3) |
C2—C1—C6—O1 | 177.5 (2) | C24—C23—C28—C27 | 0.4 (3) |
Cu1—O2—C7—C5 | 9.2 (2) | C22—C23—C28—C27 | 177.56 (17) |
N1—C5—C7—O2 | −8.3 (3) | C24—C23—C28—S2 | −177.10 (13) |
C4—C5—C7—O2 | 171.1 (2) | C22—C23—C28—S2 | 0.06 (17) |
C12—N2—C8—C9 | −1.1 (3) | C26—C27—C28—C23 | −0.6 (3) |
Cu1—N2—C8—C9 | 176.81 (16) | C26—C27—C28—S2 | 176.25 (16) |
C12—N2—C8—C13 | 179.33 (17) | O9—S2—C28—C23 | 117.57 (14) |
Cu1—N2—C8—C13 | −2.8 (2) | O10—S2—C28—C23 | −112.29 (14) |
N2—C8—C9—C10 | 1.8 (3) | N4—S2—C28—C23 | 2.88 (14) |
C13—C8—C9—C10 | −178.6 (2) | O9—S2—C28—C27 | −59.7 (2) |
C8—C9—C10—C11 | −0.9 (4) | O10—S2—C28—C27 | 70.5 (2) |
C9—C10—C11—C12 | −0.6 (4) | N4—S2—C28—C27 | −174.34 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5 | 0.82 (2) | 1.75 (2) | 2.5639 (18) | 179 (3) |
O2—H2···O8 | 0.81 (2) | 1.82 (2) | 2.6267 (18) | 173 (3) |
O3—H3···O1Wi | 0.80 (2) | 1.84 (2) | 2.631 (2) | 171 (3) |
O4—H4···O2Wi | 0.79 (2) | 1.87 (2) | 2.629 (2) | 160 (3) |
O1W—H1W1···O8ii | 0.80 (2) | 2.04 (2) | 2.825 (2) | 168 (3) |
O1W—H2W1···N4iii | 0.80 (2) | 2.28 (2) | 3.052 (2) | 161 (3) |
O2W—H1W2···O5 | 0.82 (2) | 1.99 (2) | 2.791 (2) | 169 (3) |
O2W—H2W2···O7iv | 0.81 (2) | 2.08 (2) | 2.858 (2) | 160 (3) |
C17—H17···O1 | 0.93 | 2.56 | 3.324 (2) | 139 |
C20—H20···O10v | 0.93 | 2.53 | 3.289 (3) | 139 |
C27—H27···O7vi | 0.93 | 2.56 | 3.296 (2) | 136 |
Symmetry codes: (i) x−1, y, z; (ii) x+2, y, z; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x−1, −y, −z+2; (vi) −x, −y, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C7H9NO2)2]·2C7H4O3S·2H2O | [Cu(C7H9NO2)2]·2C7H4O3S·2H2O |
Mr | 737.61 | 742.22 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 8.1365 (4), 12.5177 (6), 15.7558 (8) | 8.1544 (4), 12.4805 (5), 15.7510 (7) |
α, β, γ (°) | 93.054 (1), 97.494 (1), 98.030 (1) | 93.195 (1), 97.501 (1), 97.877 (1) |
V (Å3) | 1571.24 (13) | 1569.85 (12) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.75 | 0.90 |
Crystal size (mm) | 0.46 × 0.42 × 0.21 | 0.52 × 0.30 × 0.19 |
|
Data collection |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.716, 0.854 | 0.731, 0.843 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19456, 9108, 6843 | 13441, 8915, 6477 |
Rint | 0.020 | 0.016 |
(sin θ/λ)max (Å−1) | 0.704 | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.094, 1.00 | 0.035, 0.090, 0.94 |
No. of reflections | 9108 | 8915 |
No. of parameters | 448 | 448 |
No. of restraints | 10 | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.41 | 0.36, −0.30 |
Selected geometric parameters (Å, º) for (I) topCo1—N2 | 2.0341 (12) | Co1—O3 | 2.1295 (13) |
Co1—N1 | 2.0385 (12) | Co1—O2 | 2.1334 (12) |
Co1—O1 | 2.1086 (12) | Co1—O4 | 2.1455 (13) |
| | | |
N2—Co1—N1 | 173.86 (5) | O1—Co1—O2 | 153.14 (4) |
N2—Co1—O1 | 98.82 (5) | O3—Co1—O2 | 91.06 (5) |
N1—Co1—O1 | 76.85 (5) | N2—Co1—O4 | 76.86 (5) |
N2—Co1—O3 | 76.87 (5) | N1—Co1—O4 | 107.66 (5) |
N1—Co1—O3 | 99.01 (5) | O1—Co1—O4 | 95.02 (5) |
O1—Co1—O3 | 95.06 (5) | O3—Co1—O4 | 152.99 (5) |
N2—Co1—O2 | 108.04 (5) | O2—Co1—O4 | 91.15 (5) |
N1—Co1—O2 | 76.36 (5) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5 | 0.846 (16) | 1.722 (16) | 2.5658 (17) | 175 (2) |
O2—H2···O8 | 0.835 (15) | 1.786 (16) | 2.6192 (16) | 176 (2) |
O3—H3···O1Wi | 0.808 (16) | 1.826 (17) | 2.613 (2) | 164 (3) |
O4—H4···O2Wi | 0.812 (16) | 1.835 (17) | 2.620 (2) | 162 (3) |
O1W—H2W1···O8ii | 0.821 (16) | 1.997 (17) | 2.8064 (18) | 168 (3) |
O1W—H1W1···N4iii | 0.793 (16) | 2.250 (17) | 3.027 (2) | 166 (3) |
O2W—H2W2···O5 | 0.802 (16) | 2.002 (16) | 2.7861 (18) | 166 (3) |
O2W—H1W2···O7iv | 0.805 (16) | 2.086 (17) | 2.877 (2) | 168 (3) |
C17—H17···O1 | 0.93 | 2.59 | 3.357 (2) | 140 |
C20—H20···O10v | 0.93 | 2.55 | 3.294 (2) | 137 |
C27—H27···O7vi | 0.93 | 2.58 | 3.341 (2) | 139 |
Symmetry codes: (i) x−1, y, z; (ii) x+2, y, z; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x−1, −y, −z+2; (vi) −x, −y, −z+2. |
Selected geometric parameters (Å, º) for (II) topCu1—N1 | 1.9455 (14) | Cu1—O2 | 2.1603 (14) |
Cu1—N2 | 1.9432 (15) | Cu1—O3 | 2.1806 (14) |
Cu1—O1 | 2.1168 (13) | Cu1—O4 | 2.1809 (15) |
| | | |
N2—Cu1—N1 | 176.96 (6) | O1—Cu1—O3 | 93.62 (6) |
N2—Cu1—O1 | 99.30 (6) | O2—Cu1—O3 | 90.16 (6) |
N1—Cu1—O1 | 79.10 (6) | N2—Cu1—O4 | 78.92 (6) |
N2—Cu1—O2 | 103.30 (5) | N1—Cu1—O4 | 103.70 (6) |
N1—Cu1—O2 | 78.30 (5) | O1—Cu1—O4 | 93.78 (6) |
O1—Cu1—O2 | 157.40 (5) | O2—Cu1—O4 | 91.22 (6) |
N2—Cu1—O3 | 78.66 (6) | O3—Cu1—O4 | 157.25 (6) |
N1—Cu1—O3 | 98.82 (6) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5 | 0.819 (16) | 1.745 (16) | 2.5639 (18) | 179 (3) |
O2—H2···O8 | 0.812 (16) | 1.820 (16) | 2.6267 (18) | 173 (3) |
O3—H3···O1Wi | 0.797 (16) | 1.842 (17) | 2.631 (2) | 171 (3) |
O4—H4···O2Wi | 0.788 (16) | 1.873 (18) | 2.629 (2) | 160 (3) |
O1W—H1W1···O8ii | 0.796 (16) | 2.041 (17) | 2.825 (2) | 168 (3) |
O1W—H2W1···N4iii | 0.801 (17) | 2.284 (19) | 3.052 (2) | 161 (3) |
O2W—H1W2···O5 | 0.818 (17) | 1.985 (17) | 2.791 (2) | 169 (3) |
O2W—H2W2···O7iv | 0.809 (17) | 2.084 (18) | 2.858 (2) | 160 (3) |
C17—H17···O1 | 0.93 | 2.56 | 3.324 (2) | 139 |
C20—H20···O10v | 0.93 | 2.53 | 3.289 (3) | 139 |
C27—H27···O7vi | 0.93 | 2.56 | 3.296 (2) | 136 |
Symmetry codes: (i) x−1, y, z; (ii) x+2, y, z; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x−1, −y, −z+2; (vi) −x, −y, −z+2. |
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The artificial sweetener saccharin (also known as 1,2-benzisothiazol-3(2H)-one 1,1-dioxide or o-benzosulfimide) is readily deprotonated to form the corresponding saccharinate anion (sac). The coordination behaviour of sac to metal ions depends on the presence of other co-ligands. Bulky ligands such as 1,10-phenathroline (phen; Deng et al., 2000, 2001; Williams et al., 2000; Yilmaz et al., 2001) and triethanolamine (tea; Topcu et al., 2001; Andac et al., 2001) prevent the coordination of sac to metal ions and so sac is present as a counter-ion in such complexes. The present study is part of our continuing research into the preparation and characterization of a series of mixed-ligand complexes of sac with N and O donor ligands and here we report the crystal structures of the pyridine-2,6-dimethanol (dmpy) complexes with cobalt and copper saccharinates, [Co(dmpy)2](sac)2·2H2O, (I), and [Cu(dmpy)2](sac)2·2H2O, (II). \sch
The structures of (I) and (II) are shown in Figs. 1 and 2, respectively. Tables 1–4 list selected geometrical data. These isostructural phases consist of a complex cation, two sac ions and two lattice water molecules. In the complex cations, the CoII or CuII ions are octahedrally coordinated by a pair of neutral dmpy ligands with no sac in the primary coordination sphere. Each dmpy ligand behaves as a tridentate ligand using all donor atoms, the amino N atom and both hydroxyl O atoms, and forms two five-membered metallocyclic chelate rings. The M—N bond lengths of the CoII complex, (I), are noticeably longer than those of the CuII complex, (II), while the M—O bond distances of (I) are somewhat shorter than those of (II).
The M—N bond distances in (II) are somewhat longer than those found in [Cu(dmpy)2](nif)2, where nif is the niflumate anion (Koman & Melnik, 1997), and similar to the corresponding distances in [Cu(pydca)(dmpy)], where pydca is pyridine-2,6-dicarboxylate (Koman et al., 2000), while the M—O bond distances are comparable with those observed in [Cu(dmpy)2](nif)2 and shorter than those found in [Cu(pydca)(dmpy)]. The larger deviations from regular octahedral geometry for the Cu phase are characteristic of the Jahn-Teller effect. The four M—O bonds forming the plane of the MO4N2 core are longer than the two M—N bonds occupying the axial positions, resulting in a `compressed' distorted octahedron around the metal ions.
Both dmpy ligands are essentially planar, with an average r.m.s. deviation of 0.057 Å in (I) and 0.065 Å in (II). Both hydroxyl O atoms deviate slightly from the dmpy planes. The planes of the two dmpy ligands are nearly perpendicular to each other, and the dihedral angles between the corresponding planes are 83.73 (3)° for both (I) and (II). The sac anions are also planar, with average r.m.s. deviations of 0.029 and 0.031 Å for (I) and (II), respectively.
In both complexes, the sac ions adopt a parallel alignment with each other and the dihedral angles between the corresponding planes are 16.02 (5) and 13.95 (6)° for (I) and (II), respectively. One of the pyridine rings (ring A = N2/C8—C12) is located between the phenyl rings (ring B = C16—C21 and ring C = C23—C28) of the two sac ions. The planes of rings A, B and C also adopt a parallel alignment and the dihedral angles between A and B, and A and C are 6.92 (12) and 11.39 (11)°, respectively, for (I), and 6.59 (14) and 9.36 (13)°, respectively, for (II). Additionally, the angle of the line passing through the centres of C—A—B to the plane of A is 159.86° for the both complexes. As a result, the phenyl rings of the sac ions and pyridine rings are connected by weak π–π interactions: A···B 3.6349 (11) and A···C 3.6093 (11) Å for (I), and A···B 3.6299 (13) and A···C 3.5844 (12) Å for (II).
The crystals exhibit a number of hydrogen bonds (Fig. 3). The packing and hydrogen-bonding schemes of compounds (I) and (II) are very similar. The H atoms of the hydroxyl groups of the dmpy ligands are involved in intermolecular hydrogen bonding with the water molecules and the carbonyl O atoms of the neighbouring sac ions, while the H atoms of the two water molecules form bifurcated hydrogen bonds with the negatively charged amine N atom and carbonyl and sulfonyl O atoms of the sac ions. Additionally, there are weak C—H···O interactions between phenyl H atoms and hydroxyl and sulfonyl O atoms. The crystal structures are stabilized by an infinite three-dimensional network of extensive hydrogen bonds and other intermolecular interactions.