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Reactions of the title free-base porphyrin compound (TPyP) with dysprosium trinitrate hexahydrate in different crystallization environments yielded two solid products, viz. [μ-5,15-bis(pyridin-1-ium-4-yl)-10,20-di-4-pyridylporphyrin]bis[aquatetranitratodysprosium(III)] benzene solvate, [Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6, (I), and 5,10,15,20-tetrakis(pyridin-1-ium-4-yl)porphyrin pentaaquadinitratodysprosate(III) pentanitrate diethanol solvate dihydrate, (C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O, (II). Compound (I) represents a 2:1 metal–porphyrin coordinated complex, which lies across a centre of inversion. Two trans-related pyridyl groups are involved in Dy coordination. The two other pyridyl substituents are protonated and involved in intermolecular hydrogen bonding along with the metal-coordinated water and nitrate ligands. Compound (II) represents an extended hydrogen-bonded assembly between the tetrakis(pyridin-1-ium-4-yl)porphyrin tetracation, the [Dy(NO3)2(H2O)5]+ cation and the free nitrate ions, as well as the ethanol and water solvent molecules. This report provides the first structural characterization of the exocyclic dysprosium complex with tetrapyridylporphyrin. It also demonstrates that charge balance can be readily achieved by protonation of the peripheral pyridyl functions, which then enhances their capacity in hydrogen bonding as H-atom donors rather than H-atom acceptors.
Supporting information
CCDC references: 790631; 790632
The porphyrin and lanthanoid salt reagents as well as all solvents were
obtained commercially. Compound (I) was obtained by dissolving dysprosium(III)
trinitrate hexahydrate (1.24 mmol) and TPyP (0.046 mmol) in a mixture of
ethanol (6 ml) and o-dichlorobenzene (8 ml). This solution was refluxed
overnight and filtered. Then it was placed in a tube and covered carefully
with a layer of benzene in order to induce crystallization of the product by
slow diffusion of benzene into the mother solution. Nice purple prisms of the
solid material, (I), were obtained after 5 months. Compound (II) was obtained
in more acidic conditions by dissolving Dy(NO3)3.6(H2O) (0.607 mmol),
TPyP (0.026 mmol) and 1,3.5-benzenetricarboxylic acid (0.030 mmol) in a
mixture of ethanol (12 ml) and o-dichlorobenzene (12 ml). The resulting
solution was refluxed for 12 h, filtered and left for crystallization by slow
evaporation. Diffraction quality crystals of (II) appeared at the bottom of
the tube after 40 d.
The H atoms bound to C atoms were located in calculated positions, and were
constrained to ride on their parent atoms with C—H distances of 0.95 and
0.98 Å and with Uiso(H) = 1.2 or 1.5 Ueq(C). Those bound
to O and N atoms were either located in difference Fourier maps or placed in
calculated positions to correspond to idealized hydrogen-bonding geometries,
with O—H and N—H distances within the range of 0.83–1.03 Å and
0.85–0.96 Å, respectively. Their atomic positions were not refined, and
they were constrained to ride on their parent atoms with Uiso(H) =
1.5 Ueq(carrier). In (I), the benzene crystallization solvent trapped
in the crystal lattice was found to be severely disordered such that it could
not be reliably modelled as discrete atoms. It is located on, and disordered
about, the centre of inversion at (0,0,1/2). For the final refinement its
contribution to the diffraction pattern was subtracted by the Squeeze
procedure, using PLATON (Spek, 2009). In (II) the two H atoms
bound to
N within the porphyrin core could not be located reliably. As some residual
electron density was observed near all the pyrrole N atoms, the H atoms bound
to them were assumed to be disordered between the four pyrrole rings, and
accordingly they were placed in calculated positions with N—H distances of
0.88 Å andUiso(H) = 1.2 Ueq(N).
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-III (Burnett & Johnson, 1996), Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) [µ-5,15-bis(pyridin-1-ium-4-yl)-10,20-di-4-
pyridylporphyrin]bis[aquatetranitratodysprosium(III)] benzene solvate
top
Crystal data top
[Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6 | Z = 1 |
Mr = 1477.82 | F(000) = 724 |
Triclinic, P1 | Dx = 1.644 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7897 (2) Å | Cell parameters from 4507 reflections |
b = 12.2577 (2) Å | θ = 1.4–27.1° |
c = 17.2316 (5) Å | µ = 2.58 mm−1 |
α = 70.1447 (10)° | T = 110 K |
β = 89.341 (1)° | Prism, purple |
γ = 75.3827 (16)° | 0.15 × 0.10 × 0.05 mm |
V = 1492.45 (6) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 6457 independent reflections |
Radiation source: fine-focus sealed tube | 5074 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.1°, θmin = 1.8° |
1 deg. ϕ and ω scans | h = 0→9 |
Absorption correction: multi-scan (Blessing, 1995) | k = −14→15 |
Tmin = 0.699, Tmax = 0.882 | l = −21→22 |
13999 measured reflections | |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0346P)2] where P = (Fo2 + 2Fc2)/3 |
6457 reflections | (Δ/σ)max = 0.001 |
379 parameters | Δρmax = 1.36 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
Crystal data top
[Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6 | γ = 75.3827 (16)° |
Mr = 1477.82 | V = 1492.45 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.7897 (2) Å | Mo Kα radiation |
b = 12.2577 (2) Å | µ = 2.58 mm−1 |
c = 17.2316 (5) Å | T = 110 K |
α = 70.1447 (10)° | 0.15 × 0.10 × 0.05 mm |
β = 89.341 (1)° | |
Data collection top
Nonius KappaCCD diffractometer | 6457 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5074 reflections with I > 2σ(I) |
Tmin = 0.699, Tmax = 0.882 | Rint = 0.054 |
13999 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.97 | Δρmax = 1.36 e Å−3 |
6457 reflections | Δρmin = −1.03 e Å−3 |
379 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. The structure contains also severely disordered benzene crystallization
solvent, which could not be reliably modeled by discrete atoms. It is located
on, and disordered about, crystallographic centers of inversion. Its
contribution to the diffraction data was subtracted by the Squeeze procedure,
using the PLATON software (Spek, 2003). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2728 (6) | 0.3326 (4) | 0.5960 (3) | 0.0215 (10) | |
C2 | 0.1662 (6) | 0.2578 (4) | 0.5839 (3) | 0.0281 (11) | |
H2 | 0.1204 | 0.2019 | 0.6260 | 0.034* | |
C3 | 0.1440 (6) | 0.2823 (4) | 0.5014 (3) | 0.0271 (11) | |
H3 | 0.0797 | 0.2459 | 0.4755 | 0.033* | |
C4 | 0.2331 (6) | 0.3720 (4) | 0.4594 (3) | 0.0220 (10) | |
C5 | 0.2514 (6) | 0.4171 (4) | 0.3747 (3) | 0.0220 (10) | |
C6 | 0.3575 (6) | 0.4952 (4) | 0.3365 (3) | 0.0217 (10) | |
C7 | 0.3675 (6) | 0.5434 (4) | 0.2473 (3) | 0.0254 (10) | |
H7 | 0.3058 | 0.5286 | 0.2063 | 0.031* | |
C8 | 0.4819 (6) | 0.6134 (4) | 0.2342 (3) | 0.0254 (10) | |
H8 | 0.5163 | 0.6571 | 0.1822 | 0.031* | |
C9 | 0.5422 (6) | 0.6086 (4) | 0.3152 (3) | 0.0199 (9) | |
C10 | 0.6628 (6) | 0.6701 (4) | 0.3280 (3) | 0.0191 (9) | |
N11 | 0.3067 (5) | 0.4004 (3) | 0.5196 (2) | 0.0212 (8) | |
H11 | 0.3750 | 0.4526 | 0.5076 | 0.025* | |
N12 | 0.4651 (5) | 0.5359 (3) | 0.3765 (2) | 0.0205 (8) | |
C13 | 0.1588 (6) | 0.3734 (4) | 0.3204 (2) | 0.0209 (10) | |
C14 | −0.0246 (6) | 0.3881 (4) | 0.3172 (3) | 0.0225 (10) | |
H14 | −0.0958 | 0.4252 | 0.3512 | 0.027* | |
C15 | −0.1021 (6) | 0.3477 (4) | 0.2637 (3) | 0.0227 (10) | |
H15 | −0.2272 | 0.3584 | 0.2621 | 0.027* | |
N16 | −0.0094 (5) | 0.2942 (3) | 0.2139 (2) | 0.0233 (8) | |
C17 | 0.1668 (6) | 0.2796 (4) | 0.2181 (3) | 0.0265 (10) | |
H17 | 0.2351 | 0.2426 | 0.1833 | 0.032* | |
C18 | 0.2552 (6) | 0.3157 (4) | 0.2707 (3) | 0.0253 (10) | |
H18 | 0.3811 | 0.3009 | 0.2726 | 0.030* | |
C19 | 0.7268 (6) | 0.7483 (4) | 0.2522 (2) | 0.0201 (9) | |
C20 | 0.6045 (7) | 0.8425 (4) | 0.1943 (3) | 0.0275 (11) | |
H20 | 0.4817 | 0.8591 | 0.2036 | 0.033* | |
C21 | 0.6621 (8) | 0.9121 (4) | 0.1229 (3) | 0.0339 (12) | |
H21 | 0.5789 | 0.9760 | 0.0824 | 0.041* | |
N22 | 0.8335 (7) | 0.8890 (4) | 0.1112 (2) | 0.0390 (12) | |
H22 | 0.8677 | 0.9348 | 0.0656 | 0.047* | |
C23 | 0.9597 (8) | 0.7988 (5) | 0.1657 (3) | 0.0381 (14) | |
H23 | 1.0816 | 0.7850 | 0.1548 | 0.046* | |
C24 | 0.9062 (7) | 0.7274 (4) | 0.2375 (3) | 0.0301 (11) | |
H24 | 0.9920 | 0.6640 | 0.2769 | 0.036* | |
Dy1 | −0.16769 (3) | 0.254801 (19) | 0.101320 (13) | 0.02266 (8) | |
O25 | −0.2795 (4) | 0.4577 (3) | 0.08919 (18) | 0.0258 (7) | |
H25A | −0.3644 | 0.5114 | 0.0450 | 0.031* | |
H25B | −0.2001 | 0.5031 | 0.0936 | 0.031* | |
N26 | −0.4919 (5) | 0.2577 (3) | 0.0150 (2) | 0.0263 (9) | |
O27 | −0.4881 (4) | 0.3514 (3) | 0.03221 (19) | 0.0286 (7) | |
O28 | −0.3643 (4) | 0.1658 (3) | 0.0483 (2) | 0.0290 (7) | |
O29 | −0.6091 (4) | 0.2586 (3) | −0.0314 (2) | 0.0338 (8) | |
N30 | −0.0376 (5) | 0.3841 (3) | −0.0494 (2) | 0.0259 (9) | |
O31 | −0.1794 (4) | 0.3517 (3) | −0.04998 (18) | 0.0281 (8) | |
O32 | 0.0434 (4) | 0.3574 (3) | 0.02102 (18) | 0.0284 (8) | |
O33 | 0.0176 (5) | 0.4394 (3) | −0.11420 (19) | 0.0324 (8) | |
N34 | 0.1371 (5) | 0.0616 (3) | 0.0877 (2) | 0.0263 (9) | |
O35 | −0.0091 (4) | 0.1066 (3) | 0.04046 (18) | 0.0240 (7) | |
O36 | 0.1508 (5) | 0.1072 (3) | 0.14148 (19) | 0.0334 (8) | |
O37 | 0.2524 (5) | −0.0201 (3) | 0.0783 (2) | 0.0372 (8) | |
N38 | −0.2955 (6) | 0.1028 (4) | 0.2415 (2) | 0.0327 (10) | |
O39 | −0.3617 (4) | 0.2172 (3) | 0.2115 (2) | 0.0303 (8) | |
O40 | −0.1591 (5) | 0.0617 (3) | 0.20781 (19) | 0.0309 (8) | |
O41 | −0.3601 (6) | 0.0392 (3) | 0.2978 (2) | 0.0551 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.021 (2) | 0.023 (2) | 0.019 (2) | −0.009 (2) | 0.0011 (18) | −0.0049 (19) |
C2 | 0.030 (3) | 0.031 (3) | 0.024 (3) | −0.016 (2) | −0.002 (2) | −0.006 (2) |
C3 | 0.033 (3) | 0.033 (3) | 0.019 (2) | −0.019 (2) | 0.000 (2) | −0.007 (2) |
C4 | 0.024 (2) | 0.024 (2) | 0.018 (2) | −0.009 (2) | −0.0048 (18) | −0.0051 (19) |
C5 | 0.021 (2) | 0.025 (2) | 0.022 (2) | −0.010 (2) | −0.0013 (19) | −0.008 (2) |
C6 | 0.023 (2) | 0.024 (2) | 0.017 (2) | −0.004 (2) | −0.0041 (18) | −0.0064 (19) |
C7 | 0.032 (3) | 0.030 (2) | 0.018 (2) | −0.015 (2) | 0.0002 (19) | −0.009 (2) |
C8 | 0.034 (3) | 0.031 (3) | 0.014 (2) | −0.017 (2) | 0.0044 (19) | −0.005 (2) |
C9 | 0.019 (2) | 0.026 (2) | 0.015 (2) | −0.007 (2) | 0.0016 (18) | −0.0074 (19) |
C10 | 0.018 (2) | 0.019 (2) | 0.018 (2) | −0.0074 (19) | 0.0020 (18) | −0.0021 (18) |
N11 | 0.026 (2) | 0.0253 (19) | 0.0144 (18) | −0.0142 (17) | −0.0008 (15) | −0.0045 (16) |
N12 | 0.022 (2) | 0.0233 (19) | 0.0176 (19) | −0.0106 (17) | 0.0006 (15) | −0.0060 (16) |
C13 | 0.032 (3) | 0.021 (2) | 0.009 (2) | −0.012 (2) | −0.0020 (18) | −0.0008 (18) |
C14 | 0.029 (3) | 0.023 (2) | 0.015 (2) | −0.009 (2) | −0.0044 (18) | −0.0028 (18) |
C15 | 0.025 (2) | 0.021 (2) | 0.018 (2) | −0.007 (2) | −0.0052 (19) | −0.0007 (19) |
N16 | 0.024 (2) | 0.026 (2) | 0.020 (2) | −0.0082 (18) | −0.0018 (16) | −0.0076 (17) |
C17 | 0.030 (3) | 0.028 (3) | 0.023 (2) | −0.010 (2) | 0.001 (2) | −0.010 (2) |
C18 | 0.023 (2) | 0.029 (2) | 0.025 (2) | −0.010 (2) | −0.0009 (19) | −0.009 (2) |
C19 | 0.032 (3) | 0.017 (2) | 0.013 (2) | −0.012 (2) | 0.0001 (18) | −0.0046 (18) |
C20 | 0.037 (3) | 0.027 (2) | 0.021 (2) | −0.016 (2) | −0.004 (2) | −0.006 (2) |
C21 | 0.051 (4) | 0.027 (3) | 0.028 (3) | −0.019 (3) | −0.007 (2) | −0.009 (2) |
N22 | 0.073 (4) | 0.045 (3) | 0.013 (2) | −0.042 (3) | 0.012 (2) | −0.009 (2) |
C23 | 0.049 (3) | 0.048 (3) | 0.040 (3) | −0.036 (3) | 0.024 (3) | −0.029 (3) |
C24 | 0.033 (3) | 0.030 (3) | 0.031 (3) | −0.016 (2) | 0.006 (2) | −0.011 (2) |
Dy1 | 0.02996 (13) | 0.02089 (12) | 0.01821 (12) | −0.00914 (9) | −0.00270 (8) | −0.00626 (8) |
O25 | 0.0329 (19) | 0.0191 (15) | 0.0244 (17) | −0.0080 (14) | −0.0076 (14) | −0.0053 (13) |
N26 | 0.034 (2) | 0.023 (2) | 0.025 (2) | −0.0110 (19) | 0.0028 (18) | −0.0095 (17) |
O27 | 0.036 (2) | 0.0220 (16) | 0.0297 (18) | −0.0087 (15) | −0.0054 (15) | −0.0102 (14) |
O28 | 0.0300 (19) | 0.0202 (16) | 0.0353 (19) | −0.0051 (15) | −0.0038 (15) | −0.0087 (15) |
O29 | 0.032 (2) | 0.043 (2) | 0.0336 (19) | −0.0151 (17) | −0.0078 (15) | −0.0182 (16) |
N30 | 0.037 (2) | 0.023 (2) | 0.021 (2) | −0.0115 (19) | −0.0024 (18) | −0.0080 (17) |
O31 | 0.038 (2) | 0.0290 (17) | 0.0205 (17) | −0.0191 (16) | −0.0021 (14) | −0.0057 (14) |
O32 | 0.0352 (19) | 0.0348 (18) | 0.0200 (17) | −0.0169 (16) | −0.0023 (14) | −0.0100 (14) |
O33 | 0.045 (2) | 0.0335 (19) | 0.0203 (18) | −0.0207 (17) | −0.0006 (15) | −0.0042 (15) |
N34 | 0.034 (2) | 0.026 (2) | 0.020 (2) | −0.013 (2) | 0.0033 (17) | −0.0069 (17) |
O35 | 0.0229 (17) | 0.0293 (17) | 0.0198 (16) | −0.0099 (14) | −0.0015 (13) | −0.0062 (14) |
O36 | 0.043 (2) | 0.0372 (19) | 0.0256 (18) | −0.0091 (17) | −0.0041 (15) | −0.0191 (16) |
O37 | 0.036 (2) | 0.037 (2) | 0.038 (2) | −0.0006 (18) | 0.0024 (17) | −0.0190 (17) |
N38 | 0.048 (3) | 0.030 (2) | 0.023 (2) | −0.017 (2) | 0.004 (2) | −0.0086 (19) |
O39 | 0.035 (2) | 0.0256 (18) | 0.0314 (19) | −0.0088 (16) | 0.0056 (15) | −0.0102 (15) |
O40 | 0.041 (2) | 0.0237 (17) | 0.0227 (17) | −0.0044 (16) | −0.0004 (16) | −0.0045 (14) |
O41 | 0.084 (3) | 0.043 (2) | 0.037 (2) | −0.030 (2) | 0.027 (2) | −0.0030 (19) |
Geometric parameters (Å, º) top
C1—N11 | 1.361 (5) | C20—C21 | 1.382 (7) |
C1—C10i | 1.395 (6) | C20—H20 | 0.9500 |
C1—C2 | 1.447 (6) | C21—N22 | 1.321 (7) |
C2—C3 | 1.354 (6) | C21—H21 | 0.9500 |
C2—H2 | 0.9500 | N22—C23 | 1.356 (7) |
C3—C4 | 1.431 (6) | N22—H22 | 0.8800 |
C3—H3 | 0.9500 | C23—C24 | 1.380 (7) |
C4—N11 | 1.374 (5) | C23—H23 | 0.9500 |
C4—C5 | 1.393 (6) | C24—H24 | 0.9500 |
C5—C6 | 1.412 (6) | Dy1—O25 | 2.355 (3) |
C5—C13 | 1.495 (5) | Dy1—O39 | 2.406 (3) |
C6—N12 | 1.373 (5) | Dy1—O28 | 2.434 (3) |
C6—C7 | 1.457 (6) | Dy1—O40 | 2.439 (3) |
C7—C8 | 1.352 (6) | Dy1—O32 | 2.451 (3) |
C7—H7 | 0.9500 | Dy1—O35 | 2.462 (3) |
C8—C9 | 1.456 (6) | Dy1—O31 | 2.462 (3) |
C8—H8 | 0.9500 | Dy1—O27 | 2.582 (3) |
C9—N12 | 1.374 (5) | Dy1—O36 | 2.613 (4) |
C9—C10 | 1.404 (6) | Dy1—N38 | 2.850 (4) |
C10—C1i | 1.395 (6) | Dy1—N30 | 2.870 (4) |
C10—C19 | 1.499 (6) | O25—H25A | 0.9496 |
N11—H11 | 0.9023 | O25—H25B | 0.9496 |
C13—C18 | 1.388 (6) | N26—O29 | 1.216 (4) |
C13—C14 | 1.394 (6) | N26—O28 | 1.263 (5) |
C14—C15 | 1.391 (5) | N26—O27 | 1.287 (4) |
C14—H14 | 0.9500 | N30—O33 | 1.230 (5) |
C15—N16 | 1.348 (6) | N30—O31 | 1.266 (5) |
C15—H15 | 0.9500 | N30—O32 | 1.273 (4) |
N16—C17 | 1.338 (6) | N34—O37 | 1.220 (5) |
N16—Dy1 | 2.551 (3) | N34—O36 | 1.252 (4) |
C17—C18 | 1.389 (6) | N34—O35 | 1.290 (5) |
C17—H17 | 0.9500 | N38—O41 | 1.214 (5) |
C18—H18 | 0.9500 | N38—O40 | 1.278 (5) |
C19—C20 | 1.386 (6) | N38—O39 | 1.284 (5) |
C19—C24 | 1.393 (7) | | |
| | | |
N11—C1—C10i | 126.8 (4) | O32—Dy1—O35 | 78.50 (10) |
N11—C1—C2 | 107.1 (4) | O25—Dy1—O31 | 80.06 (10) |
C10i—C1—C2 | 126.1 (4) | O39—Dy1—O31 | 140.67 (11) |
C3—C2—C1 | 107.1 (4) | O28—Dy1—O31 | 76.14 (10) |
C3—C2—H2 | 126.4 | O40—Dy1—O31 | 141.44 (10) |
C1—C2—H2 | 126.4 | O32—Dy1—O31 | 52.24 (9) |
C2—C3—C4 | 109.0 (4) | O35—Dy1—O31 | 70.49 (10) |
C2—C3—H3 | 125.5 | O25—Dy1—N16 | 70.85 (11) |
C4—C3—H3 | 125.5 | O39—Dy1—N16 | 78.07 (11) |
N11—C4—C5 | 126.3 (4) | O28—Dy1—N16 | 155.05 (11) |
N11—C4—C3 | 106.4 (4) | O40—Dy1—N16 | 85.02 (11) |
C5—C4—C3 | 127.2 (4) | O32—Dy1—N16 | 79.31 (10) |
C4—C5—C6 | 125.6 (4) | O35—Dy1—N16 | 120.20 (11) |
C4—C5—C13 | 117.1 (3) | O31—Dy1—N16 | 128.62 (10) |
C6—C5—C13 | 117.3 (4) | O25—Dy1—O27 | 66.05 (9) |
N12—C6—C5 | 125.9 (4) | O39—Dy1—O27 | 73.92 (11) |
N12—C6—C7 | 110.5 (3) | O28—Dy1—O27 | 50.84 (10) |
C5—C6—C7 | 123.6 (3) | O40—Dy1—O27 | 108.53 (10) |
C8—C7—C6 | 106.7 (4) | O32—Dy1—O27 | 111.46 (10) |
C8—C7—H7 | 126.7 | O35—Dy1—O27 | 109.73 (9) |
C6—C7—H7 | 126.7 | O31—Dy1—O27 | 66.75 (11) |
C7—C8—C9 | 106.7 (4) | N16—Dy1—O27 | 130.06 (11) |
C7—C8—H8 | 126.7 | O25—Dy1—O36 | 132.39 (10) |
C9—C8—H8 | 126.7 | O39—Dy1—O36 | 112.77 (11) |
N12—C9—C10 | 125.3 (4) | O28—Dy1—O36 | 110.00 (10) |
N12—C9—C8 | 110.5 (3) | O40—Dy1—O36 | 66.18 (11) |
C10—C9—C8 | 124.2 (4) | O32—Dy1—O36 | 71.78 (11) |
C1i—C10—C9 | 126.6 (4) | O35—Dy1—O36 | 50.15 (9) |
C1i—C10—C19 | 116.5 (3) | O31—Dy1—O36 | 104.29 (11) |
C9—C10—C19 | 116.8 (4) | N16—Dy1—O36 | 70.23 (11) |
C1—N11—C4 | 110.4 (3) | O27—Dy1—O36 | 159.49 (9) |
C1—N11—H11 | 127.3 | O25—Dy1—N38 | 110.38 (12) |
C4—N11—H11 | 122.1 | O39—Dy1—N38 | 26.61 (11) |
C9—N12—C6 | 105.6 (3) | O28—Dy1—N38 | 73.28 (11) |
C18—C13—C14 | 117.4 (4) | O40—Dy1—N38 | 26.54 (11) |
C18—C13—C5 | 120.3 (4) | O32—Dy1—N38 | 157.26 (11) |
C14—C13—C5 | 122.3 (4) | O35—Dy1—N38 | 100.54 (11) |
C15—C14—C13 | 119.1 (4) | O31—Dy1—N38 | 149.15 (10) |
C15—C14—H14 | 120.5 | N16—Dy1—N38 | 81.79 (11) |
C13—C14—H14 | 120.5 | O27—Dy1—N38 | 90.41 (11) |
N16—C15—C14 | 123.6 (4) | O36—Dy1—N38 | 90.00 (12) |
N16—C15—H15 | 118.2 | O25—Dy1—N30 | 76.23 (11) |
C14—C15—H15 | 118.2 | O39—Dy1—N30 | 158.31 (11) |
C17—N16—C15 | 116.7 (3) | O28—Dy1—N30 | 100.69 (10) |
C17—N16—Dy1 | 121.5 (3) | O40—Dy1—N30 | 147.97 (12) |
C15—N16—Dy1 | 121.1 (3) | O32—Dy1—N30 | 26.19 (9) |
N16—C17—C18 | 123.4 (4) | O35—Dy1—N30 | 72.60 (10) |
N16—C17—H17 | 118.3 | O31—Dy1—N30 | 26.05 (10) |
C18—C17—H17 | 118.3 | N16—Dy1—N30 | 104.24 (10) |
C17—C18—C13 | 119.7 (4) | O27—Dy1—N30 | 89.08 (11) |
C17—C18—H18 | 120.1 | O36—Dy1—N30 | 87.85 (11) |
C13—C18—H18 | 120.1 | N38—Dy1—N30 | 172.46 (10) |
C20—C19—C24 | 118.8 (4) | Dy1—O25—H25A | 120.4 |
C20—C19—C10 | 119.5 (4) | Dy1—O25—H25B | 120.0 |
C24—C19—C10 | 121.7 (4) | H25A—O25—H25B | 104.3 |
C21—C20—C19 | 119.7 (5) | O29—N26—O28 | 122.4 (3) |
C21—C20—H20 | 120.2 | O29—N26—O27 | 122.0 (4) |
C19—C20—H20 | 120.2 | O28—N26—O27 | 115.6 (3) |
N22—C21—C20 | 119.6 (5) | O29—N26—Dy1 | 169.4 (3) |
N22—C21—H21 | 120.2 | O28—N26—Dy1 | 54.83 (18) |
C20—C21—H21 | 120.2 | O27—N26—Dy1 | 61.6 (2) |
C21—N22—C23 | 123.6 (4) | N26—O27—Dy1 | 92.3 (2) |
C21—N22—H22 | 118.2 | N26—O28—Dy1 | 100.1 (2) |
C23—N22—H22 | 118.2 | O33—N30—O31 | 121.0 (3) |
N22—C23—C24 | 118.2 (5) | O33—N30—O32 | 122.1 (4) |
N22—C23—H23 | 120.9 | O31—N30—O32 | 116.9 (4) |
C24—C23—H23 | 120.9 | O33—N30—Dy1 | 179.7 (3) |
C23—C24—C19 | 120.2 (5) | O31—N30—Dy1 | 58.7 (2) |
C23—C24—H24 | 119.9 | O32—N30—Dy1 | 58.2 (2) |
C19—C24—H24 | 119.9 | N30—O31—Dy1 | 95.3 (2) |
O25—Dy1—O39 | 84.46 (11) | N30—O32—Dy1 | 95.6 (2) |
O25—Dy1—O28 | 116.89 (10) | O37—N34—O36 | 123.9 (4) |
O39—Dy1—O28 | 79.18 (11) | O37—N34—O35 | 120.1 (3) |
O25—Dy1—O40 | 135.09 (11) | O36—N34—O35 | 116.0 (4) |
O39—Dy1—O40 | 53.09 (11) | N34—O35—Dy1 | 100.0 (2) |
O28—Dy1—O40 | 73.14 (10) | N34—O36—Dy1 | 93.8 (3) |
O25—Dy1—O32 | 75.02 (11) | O41—N38—O40 | 123.1 (4) |
O39—Dy1—O32 | 153.41 (10) | O41—N38—O39 | 121.5 (5) |
O28—Dy1—O32 | 125.15 (10) | O40—N38—O39 | 115.4 (4) |
O40—Dy1—O32 | 137.92 (11) | O41—N38—Dy1 | 175.5 (3) |
O25—Dy1—O35 | 148.64 (10) | O40—N38—Dy1 | 58.5 (2) |
O39—Dy1—O35 | 125.43 (10) | O39—N38—Dy1 | 57.1 (2) |
O28—Dy1—O35 | 66.71 (10) | N38—O39—Dy1 | 96.3 (3) |
O40—Dy1—O35 | 76.26 (10) | N38—O40—Dy1 | 95.0 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O35ii | 0.88 | 2.26 | 2.926 (5) | 132 |
O25—H25A···O27iii | 0.95 | 1.86 | 2.784 (4) | 164 |
O25—H25B···O33iv | 0.95 | 1.83 | 2.762 (4) | 168 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x−1, −y+1, −z; (iv) −x, −y+1, −z. |
(II) 5,10,15,20-tetrakis(pyridin-1-ium-4-yl)porphyrin
pentaaquadinitratodysprosate(III) pentanitrate diethanol solvate dihydrate
top
Crystal data top
(C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O | Z = 2 |
Mr = 1437.54 | F(000) = 1462 |
Triclinic, P1 | Dx = 1.698 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8961 (2) Å | Cell parameters from 12265 reflections |
b = 12.9222 (2) Å | θ = 1.4–27.9° |
c = 18.5978 (3) Å | µ = 1.44 mm−1 |
α = 71.6843 (7)° | T = 110 K |
β = 80.9684 (8)° | Needle, purple |
γ = 73.3707 (7)° | 0.55 × 0.10 × 0.05 mm |
V = 2811.52 (8) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 13315 independent reflections |
Radiation source: fine-focus sealed tube | 11865 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.9°, θmin = 2.3° |
1 deg. ϕ & ω scans | h = 0→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = −15→16 |
Tmin = 0.512, Tmax = 0.932 | l = −23→24 |
47169 measured reflections | |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0428P)2 + 2.844P] where P = (Fo2 + 2Fc2)/3 |
13315 reflections | (Δ/σ)max = 0.002 |
813 parameters | Δρmax = 2.00 e Å−3 |
0 restraints | Δρmin = −1.62 e Å−3 |
Crystal data top
(C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O | γ = 73.3707 (7)° |
Mr = 1437.54 | V = 2811.52 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.8961 (2) Å | Mo Kα radiation |
b = 12.9222 (2) Å | µ = 1.44 mm−1 |
c = 18.5978 (3) Å | T = 110 K |
α = 71.6843 (7)° | 0.55 × 0.10 × 0.05 mm |
β = 80.9684 (8)° | |
Data collection top
Nonius KappaCCD diffractometer | 13315 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 11865 reflections with I > 2σ(I) |
Tmin = 0.512, Tmax = 0.932 | Rint = 0.044 |
47169 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | Δρmax = 2.00 e Å−3 |
13315 reflections | Δρmin = −1.62 e Å−3 |
813 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 | Occ. (<1) |
C1 | 0.18608 (19) | 0.0746 (2) | 0.32693 (13) | 0.0131 (5) | |
C2 | 0.09301 (19) | 0.1310 (2) | 0.28390 (14) | 0.0149 (5) | |
H2 | 0.0892 | 0.1369 | 0.2321 | 0.018* | |
C3 | 0.0111 (2) | 0.1748 (2) | 0.32993 (14) | 0.0161 (5) | |
H3 | −0.0597 | 0.2177 | 0.3159 | 0.019* | |
C4 | 0.05066 (18) | 0.1444 (2) | 0.40363 (13) | 0.0126 (5) | |
C5 | −0.00806 (19) | 0.1697 (2) | 0.46869 (13) | 0.0126 (5) | |
C6 | 0.02624 (19) | 0.1258 (2) | 0.54305 (13) | 0.0127 (5) | |
C7 | −0.03958 (19) | 0.1515 (2) | 0.60912 (14) | 0.0149 (5) | |
H7 | −0.1115 | 0.1979 | 0.6099 | 0.018* | |
C8 | 0.0210 (2) | 0.0969 (2) | 0.66893 (14) | 0.0159 (5) | |
H8 | −0.0005 | 0.0955 | 0.7204 | 0.019* | |
C9 | 0.12571 (19) | 0.0404 (2) | 0.63936 (13) | 0.0125 (5) | |
C10 | 0.21373 (19) | −0.0217 (2) | 0.68418 (13) | 0.0124 (5) | |
C11 | 0.31577 (19) | −0.0774 (2) | 0.65869 (13) | 0.0125 (5) | |
C12 | 0.40846 (19) | −0.1375 (2) | 0.70220 (14) | 0.0149 (5) | |
H12 | 0.4122 | −0.1454 | 0.7543 | 0.018* | |
C13 | 0.4899 (2) | −0.1810 (2) | 0.65582 (14) | 0.0150 (5) | |
H13 | 0.5601 | −0.2256 | 0.6700 | 0.018* | |
C14 | 0.45118 (19) | −0.1478 (2) | 0.58175 (13) | 0.0126 (5) | |
C15 | 0.51018 (18) | −0.1702 (2) | 0.51642 (14) | 0.0128 (5) | |
C16 | 0.47678 (19) | −0.1247 (2) | 0.44197 (13) | 0.0130 (5) | |
C17 | 0.5443 (2) | −0.1461 (2) | 0.37505 (14) | 0.0151 (5) | |
H17 | 0.6170 | −0.1903 | 0.3738 | 0.018* | |
C18 | 0.48353 (19) | −0.0910 (2) | 0.31525 (14) | 0.0148 (5) | |
H18 | 0.5056 | −0.0871 | 0.2635 | 0.018* | |
C19 | 0.37760 (19) | −0.0389 (2) | 0.34571 (13) | 0.0121 (4) | |
C20 | 0.28906 (19) | 0.0208 (2) | 0.30118 (13) | 0.0129 (5) | |
N21 | 0.15586 (16) | 0.08257 (17) | 0.39959 (11) | 0.0120 (4) | |
H21 | 0.1978 | 0.0524 | 0.4377 | 0.014* | 0.50 |
N22 | 0.12636 (16) | 0.05713 (17) | 0.56269 (11) | 0.0118 (4) | |
H22 | 0.1796 | 0.0297 | 0.5326 | 0.014* | 0.50 |
N23 | 0.34595 (16) | −0.08433 (17) | 0.58566 (11) | 0.0121 (4) | |
H23 | 0.3043 | −0.0530 | 0.5474 | 0.015* | 0.50 |
N24 | 0.37580 (16) | −0.05861 (17) | 0.42265 (11) | 0.0128 (4) | |
H24 | 0.3214 | −0.0341 | 0.4531 | 0.015* | 0.50 |
C25 | −0.11340 (19) | 0.2568 (2) | 0.45620 (13) | 0.0127 (5) | |
C26 | −0.1140 (2) | 0.3659 (2) | 0.41069 (14) | 0.0171 (5) | |
H26 | −0.0483 | 0.3831 | 0.3857 | 0.021* | |
C27 | −0.2099 (2) | 0.4481 (2) | 0.40207 (15) | 0.0190 (5) | |
H27 | −0.2106 | 0.5225 | 0.3713 | 0.023* | |
N28 | −0.30283 (17) | 0.42321 (19) | 0.43727 (12) | 0.0182 (4) | |
H28 | −0.3644 | 0.4821 | 0.4229 | 0.022* | |
C29 | −0.3059 (2) | 0.3191 (2) | 0.47957 (15) | 0.0184 (5) | |
H29 | −0.3732 | 0.3039 | 0.5025 | 0.022* | |
C30 | −0.21189 (19) | 0.2335 (2) | 0.49012 (14) | 0.0153 (5) | |
H30 | −0.2141 | 0.1595 | 0.5202 | 0.018* | |
C31 | 0.19750 (19) | −0.0302 (2) | 0.76687 (14) | 0.0142 (5) | |
C32 | 0.1699 (2) | 0.0650 (2) | 0.79307 (14) | 0.0169 (5) | |
H32 | 0.1628 | 0.1378 | 0.7580 | 0.020* | |
C33 | 0.1530 (2) | 0.0531 (2) | 0.87011 (15) | 0.0191 (5) | |
H33 | 0.1328 | 0.1177 | 0.8882 | 0.023* | |
N34 | 0.16514 (17) | −0.0500 (2) | 0.91918 (12) | 0.0187 (5) | |
H34 | 0.1452 | −0.0517 | 0.9675 | 0.022* | |
C35 | 0.1928 (2) | −0.1437 (2) | 0.89666 (15) | 0.0196 (5) | |
H35 | 0.2006 | −0.2154 | 0.9333 | 0.024* | |
C36 | 0.2097 (2) | −0.1362 (2) | 0.82055 (14) | 0.0179 (5) | |
H36 | 0.2297 | −0.2025 | 0.8044 | 0.022* | |
C37 | 0.61640 (19) | −0.2563 (2) | 0.52762 (13) | 0.0130 (5) | |
C38 | 0.6176 (2) | −0.3676 (2) | 0.56697 (14) | 0.0174 (5) | |
H38 | 0.5517 | −0.3876 | 0.5882 | 0.021* | |
C39 | 0.7145 (2) | −0.4486 (2) | 0.57502 (14) | 0.0174 (5) | |
H39 | 0.7157 | −0.5246 | 0.6021 | 0.021* | |
N40 | 0.80711 (16) | −0.41985 (18) | 0.54462 (12) | 0.0167 (4) | |
H40 | 0.8657 | −0.4701 | 0.5563 | 0.020* | |
C41 | 0.8094 (2) | −0.3135 (2) | 0.50728 (15) | 0.0180 (5) | |
H41 | 0.8768 | −0.2960 | 0.4873 | 0.022* | |
C42 | 0.7146 (2) | −0.2292 (2) | 0.49769 (14) | 0.0166 (5) | |
H42 | 0.7161 | −0.1537 | 0.4711 | 0.020* | |
C43 | 0.30547 (18) | 0.0287 (2) | 0.21861 (13) | 0.0133 (5) | |
C44 | 0.3304 (2) | −0.0677 (2) | 0.19423 (14) | 0.0163 (5) | |
H44 | 0.3362 | −0.1396 | 0.2302 | 0.020* | |
C45 | 0.3467 (2) | −0.0580 (2) | 0.11733 (14) | 0.0176 (5) | |
H45 | 0.3648 | −0.1233 | 0.1001 | 0.021* | |
N46 | 0.33671 (17) | 0.04407 (19) | 0.06738 (12) | 0.0165 (4) | |
H46 | 0.3542 | 0.0450 | 0.0151 | 0.020* | |
C47 | 0.3120 (2) | 0.1388 (2) | 0.08856 (14) | 0.0173 (5) | |
H47 | 0.3052 | 0.2097 | 0.0512 | 0.021* | |
C48 | 0.2964 (2) | 0.1331 (2) | 0.16457 (14) | 0.0161 (5) | |
H48 | 0.2795 | 0.1999 | 0.1800 | 0.019* | |
Dy1 | 0.702253 (9) | −0.533180 (10) | 0.860983 (6) | 0.01390 (4) | |
O49 | 0.79708 (15) | −0.69702 (15) | 0.81793 (10) | 0.0199 (4) | |
H49A | 0.8172 | −0.7634 | 0.8445 | 0.024* | |
H49B | 0.8423 | −0.6869 | 0.7747 | 0.024* | |
O50 | 0.53003 (14) | −0.40517 (16) | 0.85230 (11) | 0.0192 (4) | |
H50A | 0.4649 | −0.4177 | 0.8488 | 0.023* | |
H50B | 0.4989 | −0.3514 | 0.8703 | 0.023* | |
O51 | 0.60420 (15) | −0.66595 (16) | 0.92000 (10) | 0.0207 (4) | |
H51A | 0.5587 | −0.6801 | 0.8992 | 0.025* | |
H51B | 0.5921 | −0.6989 | 0.9706 | 0.025* | |
O52 | 0.61767 (15) | −0.53740 (16) | 0.75738 (10) | 0.0199 (4) | |
H52A | 0.6314 | −0.5968 | 0.7424 | 0.024* | |
H52B | 0.5453 | −0.4813 | 0.7409 | 0.024* | |
O53 | 0.84279 (15) | −0.63785 (17) | 0.94207 (11) | 0.0235 (4) | |
H53A | 0.9035 | −0.6593 | 0.9206 | 0.028* | |
H53B | 0.8528 | −0.6200 | 0.9806 | 0.028* | |
N54 | 0.81617 (19) | −0.4013 (2) | 0.73552 (13) | 0.0204 (5) | |
O55 | 0.71768 (15) | −0.36119 (17) | 0.75410 (11) | 0.0249 (4) | |
O56 | 0.86375 (16) | −0.49236 (17) | 0.78242 (12) | 0.0263 (4) | |
O57 | 0.86330 (19) | −0.3566 (2) | 0.67666 (12) | 0.0337 (5) | |
N58 | 0.67758 (18) | −0.43113 (19) | 0.98290 (12) | 0.0195 (5) | |
O59 | 0.64632 (15) | −0.51949 (16) | 0.99439 (11) | 0.0211 (4) | |
O60 | 0.71819 (16) | −0.39194 (16) | 0.91558 (10) | 0.0211 (4) | |
O61 | 0.67073 (18) | −0.38445 (17) | 1.03207 (11) | 0.0274 (4) | |
N62 | 0.44367 (17) | −0.14617 (19) | −0.07865 (12) | 0.0174 (4) | |
O63 | 0.44498 (17) | −0.24763 (16) | −0.07121 (11) | 0.0247 (4) | |
O64 | 0.44997 (18) | −0.11915 (18) | −0.02132 (11) | 0.0268 (4) | |
O65 | 0.43644 (17) | −0.07576 (17) | −0.14238 (11) | 0.0251 (4) | |
N66 | 0.33915 (17) | −0.38738 (19) | 0.73972 (12) | 0.0179 (4) | |
O67 | 0.25350 (15) | −0.32683 (18) | 0.71152 (12) | 0.0275 (4) | |
O68 | 0.42315 (15) | −0.41293 (16) | 0.69836 (11) | 0.0212 (4) | |
O69 | 0.34212 (15) | −0.42492 (18) | 0.81182 (11) | 0.0240 (4) | |
N70 | −0.50681 (18) | 0.63320 (18) | 0.35290 (12) | 0.0177 (4) | |
O71 | −0.42356 (16) | 0.64165 (17) | 0.30935 (11) | 0.0242 (4) | |
O72 | −0.59990 (15) | 0.67572 (16) | 0.32957 (11) | 0.0232 (4) | |
O73 | −0.49684 (15) | 0.58102 (17) | 0.42244 (10) | 0.0239 (4) | |
N74 | 0.09616 (18) | −0.0024 (2) | 1.08898 (12) | 0.0199 (5) | |
O75 | 0.13928 (17) | −0.09653 (17) | 1.07435 (11) | 0.0255 (4) | |
O76 | 0.07883 (19) | 0.08400 (18) | 1.03513 (12) | 0.0338 (5) | |
O77 | 0.07380 (17) | −0.0008 (2) | 1.15574 (11) | 0.0302 (5) | |
N78 | 0.98078 (18) | −0.62369 (19) | 0.65074 (13) | 0.0212 (5) | |
O79 | 0.88620 (15) | −0.63361 (17) | 0.67191 (11) | 0.0231 (4) | |
O80 | 1.05422 (18) | −0.66565 (19) | 0.69486 (13) | 0.0339 (5) | |
O81 | 1.00108 (15) | −0.56880 (17) | 0.58273 (11) | 0.0251 (4) | |
O82 | 1.03608 (16) | −0.69470 (18) | 0.86309 (12) | 0.0277 (4) | |
H82 | 1.0212 | −0.6644 | 0.8129 | 0.033* | |
C83 | 1.1105 (3) | −0.6398 (3) | 0.8749 (2) | 0.0410 (8) | |
H83A | 1.1611 | −0.6937 | 0.9126 | 0.049* | |
H83B | 1.0699 | −0.5769 | 0.8960 | 0.049* | |
C84 | 1.1733 (3) | −0.5954 (4) | 0.8043 (2) | 0.0482 (9) | |
H84A | 1.1235 | −0.5423 | 0.7666 | 0.072* | |
H84B | 1.2164 | −0.6578 | 0.7844 | 0.072* | |
H84C | 1.2218 | −0.5566 | 0.8147 | 0.072* | |
O85 | 0.15098 (16) | −0.38868 (18) | 0.91730 (12) | 0.0278 (5) | |
H85 | 0.2198 | −0.3971 | 0.8844 | 0.033* | |
C86 | 0.0596 (3) | −0.3396 (3) | 0.8703 (2) | 0.0396 (8) | |
H86A | 0.0640 | −0.3847 | 0.8352 | 0.048* | |
H86B | 0.0617 | −0.2621 | 0.8396 | 0.048* | |
C87 | −0.0442 (3) | −0.3365 (4) | 0.9190 (2) | 0.0474 (9) | |
H87A | −0.0508 | −0.2874 | 0.9512 | 0.071* | |
H87B | −0.0446 | −0.4128 | 0.9511 | 0.071* | |
H87C | −0.1053 | −0.3074 | 0.8867 | 0.071* | |
O88 | 0.35170 (16) | 0.12419 (17) | −0.08839 (11) | 0.0243 (4) | |
H88A | 0.3952 | 0.0699 | −0.1105 | 0.029* | |
H88B | 0.3799 | 0.1796 | −0.1038 | 0.029* | |
O89 | 0.44753 (16) | −0.69169 (17) | 0.84548 (11) | 0.0251 (4) | |
H89A | 0.3922 | −0.6344 | 0.8569 | 0.030* | |
H89B | 0.4507 | −0.6734 | 0.7911 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0152 (11) | 0.0133 (12) | 0.0108 (11) | −0.0024 (9) | −0.0010 (9) | −0.0042 (9) |
C2 | 0.0156 (11) | 0.0181 (12) | 0.0099 (11) | −0.0009 (9) | −0.0026 (9) | −0.0049 (9) |
C3 | 0.0136 (11) | 0.0187 (13) | 0.0119 (11) | 0.0010 (9) | −0.0022 (9) | −0.0029 (9) |
C4 | 0.0108 (10) | 0.0143 (12) | 0.0111 (11) | −0.0009 (9) | −0.0007 (9) | −0.0036 (9) |
C5 | 0.0116 (11) | 0.0129 (11) | 0.0123 (11) | −0.0013 (9) | −0.0005 (9) | −0.0041 (9) |
C6 | 0.0144 (11) | 0.0120 (11) | 0.0110 (11) | −0.0025 (9) | 0.0000 (9) | −0.0034 (9) |
C7 | 0.0122 (11) | 0.0185 (13) | 0.0130 (11) | −0.0014 (9) | 0.0010 (9) | −0.0064 (10) |
C8 | 0.0148 (11) | 0.0204 (13) | 0.0114 (11) | −0.0017 (9) | 0.0009 (9) | −0.0066 (10) |
C9 | 0.0140 (11) | 0.0115 (11) | 0.0109 (11) | −0.0022 (9) | 0.0005 (9) | −0.0031 (9) |
C10 | 0.0158 (11) | 0.0118 (11) | 0.0087 (10) | −0.0025 (9) | 0.0004 (9) | −0.0031 (9) |
C11 | 0.0143 (11) | 0.0121 (11) | 0.0104 (11) | −0.0025 (9) | 0.0002 (9) | −0.0037 (9) |
C12 | 0.0157 (11) | 0.0164 (12) | 0.0116 (11) | −0.0012 (9) | −0.0036 (9) | −0.0039 (9) |
C13 | 0.0146 (11) | 0.0154 (12) | 0.0127 (11) | 0.0007 (9) | −0.0046 (9) | −0.0033 (9) |
C14 | 0.0115 (10) | 0.0131 (12) | 0.0127 (11) | −0.0023 (9) | −0.0017 (9) | −0.0033 (9) |
C15 | 0.0110 (10) | 0.0126 (11) | 0.0135 (11) | −0.0010 (9) | −0.0004 (9) | −0.0041 (9) |
C16 | 0.0113 (11) | 0.0135 (12) | 0.0129 (11) | −0.0010 (9) | 0.0006 (9) | −0.0045 (9) |
C17 | 0.0146 (11) | 0.0153 (12) | 0.0135 (11) | −0.0001 (9) | 0.0009 (9) | −0.0057 (9) |
C18 | 0.0134 (11) | 0.0174 (12) | 0.0119 (11) | −0.0026 (9) | 0.0021 (9) | −0.0043 (9) |
C19 | 0.0126 (11) | 0.0130 (11) | 0.0101 (11) | −0.0021 (9) | 0.0003 (9) | −0.0042 (9) |
C20 | 0.0151 (11) | 0.0120 (11) | 0.0103 (11) | −0.0018 (9) | −0.0012 (9) | −0.0024 (9) |
N21 | 0.0107 (9) | 0.0141 (10) | 0.0089 (9) | −0.0001 (7) | 0.0006 (7) | −0.0034 (8) |
N22 | 0.0103 (9) | 0.0142 (10) | 0.0091 (9) | −0.0002 (7) | 0.0004 (7) | −0.0038 (8) |
N23 | 0.0104 (9) | 0.0143 (10) | 0.0101 (9) | −0.0005 (7) | −0.0007 (7) | −0.0038 (8) |
N24 | 0.0121 (9) | 0.0139 (10) | 0.0102 (9) | −0.0003 (8) | −0.0003 (7) | −0.0035 (8) |
C25 | 0.0125 (11) | 0.0155 (12) | 0.0108 (11) | −0.0009 (9) | −0.0017 (9) | −0.0065 (9) |
C26 | 0.0155 (12) | 0.0189 (13) | 0.0145 (12) | −0.0016 (10) | 0.0004 (9) | −0.0044 (10) |
C27 | 0.0208 (13) | 0.0175 (13) | 0.0153 (12) | −0.0009 (10) | −0.0021 (10) | −0.0035 (10) |
N28 | 0.0156 (10) | 0.0195 (11) | 0.0167 (10) | 0.0051 (8) | −0.0046 (8) | −0.0083 (9) |
C29 | 0.0123 (11) | 0.0249 (14) | 0.0185 (12) | −0.0021 (10) | 0.0003 (9) | −0.0100 (11) |
C30 | 0.0131 (11) | 0.0174 (12) | 0.0147 (11) | −0.0031 (9) | −0.0011 (9) | −0.0041 (10) |
C31 | 0.0123 (11) | 0.0159 (12) | 0.0124 (11) | −0.0004 (9) | −0.0015 (9) | −0.0038 (9) |
C32 | 0.0175 (12) | 0.0157 (12) | 0.0155 (12) | −0.0007 (9) | −0.0020 (9) | −0.0044 (10) |
C33 | 0.0180 (12) | 0.0222 (14) | 0.0178 (12) | −0.0010 (10) | −0.0027 (10) | −0.0099 (10) |
N34 | 0.0191 (11) | 0.0265 (12) | 0.0102 (10) | −0.0027 (9) | 0.0002 (8) | −0.0081 (9) |
C35 | 0.0202 (12) | 0.0212 (14) | 0.0149 (12) | −0.0042 (10) | 0.0000 (10) | −0.0033 (10) |
C36 | 0.0198 (12) | 0.0176 (13) | 0.0146 (12) | −0.0010 (10) | −0.0006 (10) | −0.0056 (10) |
C37 | 0.0123 (11) | 0.0147 (12) | 0.0115 (11) | 0.0009 (9) | −0.0005 (9) | −0.0070 (9) |
C38 | 0.0131 (11) | 0.0193 (13) | 0.0164 (12) | −0.0020 (9) | 0.0007 (9) | −0.0030 (10) |
C39 | 0.0177 (12) | 0.0157 (12) | 0.0158 (12) | −0.0010 (10) | −0.0015 (10) | −0.0033 (10) |
N40 | 0.0121 (10) | 0.0158 (11) | 0.0189 (11) | 0.0029 (8) | −0.0022 (8) | −0.0057 (9) |
C41 | 0.0139 (11) | 0.0205 (13) | 0.0183 (12) | −0.0035 (10) | 0.0015 (10) | −0.0056 (10) |
C42 | 0.0153 (11) | 0.0158 (12) | 0.0176 (12) | −0.0037 (9) | 0.0000 (9) | −0.0039 (10) |
C43 | 0.0100 (10) | 0.0169 (12) | 0.0107 (11) | −0.0004 (9) | −0.0007 (8) | −0.0037 (9) |
C44 | 0.0173 (12) | 0.0151 (12) | 0.0133 (12) | −0.0010 (9) | 0.0007 (9) | −0.0032 (9) |
C45 | 0.0189 (12) | 0.0192 (13) | 0.0152 (12) | −0.0028 (10) | 0.0015 (10) | −0.0088 (10) |
N46 | 0.0174 (10) | 0.0210 (11) | 0.0118 (10) | −0.0035 (8) | 0.0010 (8) | −0.0079 (8) |
C47 | 0.0189 (12) | 0.0164 (13) | 0.0142 (12) | −0.0039 (10) | −0.0007 (10) | −0.0016 (10) |
C48 | 0.0175 (12) | 0.0165 (12) | 0.0132 (11) | −0.0017 (9) | −0.0006 (9) | −0.0053 (10) |
Dy1 | 0.01412 (6) | 0.01434 (7) | 0.01207 (6) | −0.00234 (4) | 0.00030 (4) | −0.00387 (4) |
O49 | 0.0221 (9) | 0.0155 (9) | 0.0159 (9) | −0.0007 (7) | 0.0036 (7) | −0.0020 (7) |
O50 | 0.0136 (8) | 0.0206 (10) | 0.0253 (10) | 0.0001 (7) | −0.0003 (7) | −0.0137 (8) |
O51 | 0.0248 (10) | 0.0225 (10) | 0.0162 (9) | −0.0124 (8) | 0.0009 (7) | −0.0027 (7) |
O52 | 0.0219 (9) | 0.0204 (10) | 0.0177 (9) | 0.0007 (7) | −0.0043 (7) | −0.0100 (7) |
O53 | 0.0186 (9) | 0.0282 (11) | 0.0210 (10) | 0.0018 (8) | −0.0043 (7) | −0.0090 (8) |
N54 | 0.0259 (12) | 0.0226 (12) | 0.0164 (11) | −0.0129 (9) | 0.0046 (9) | −0.0073 (9) |
O55 | 0.0179 (9) | 0.0277 (11) | 0.0239 (10) | −0.0056 (8) | −0.0021 (8) | 0.0000 (8) |
O56 | 0.0210 (10) | 0.0190 (10) | 0.0304 (11) | −0.0025 (8) | 0.0076 (8) | −0.0024 (8) |
O57 | 0.0442 (13) | 0.0374 (13) | 0.0234 (11) | −0.0255 (11) | 0.0154 (10) | −0.0088 (9) |
N58 | 0.0226 (11) | 0.0197 (12) | 0.0149 (10) | −0.0026 (9) | −0.0013 (9) | −0.0057 (9) |
O59 | 0.0244 (10) | 0.0215 (10) | 0.0190 (9) | −0.0096 (8) | 0.0011 (8) | −0.0058 (8) |
O60 | 0.0305 (10) | 0.0198 (10) | 0.0130 (9) | −0.0098 (8) | 0.0016 (7) | −0.0032 (7) |
O61 | 0.0415 (12) | 0.0266 (11) | 0.0149 (9) | −0.0056 (9) | −0.0002 (8) | −0.0106 (8) |
N62 | 0.0186 (10) | 0.0222 (12) | 0.0130 (10) | −0.0068 (9) | 0.0020 (8) | −0.0071 (9) |
O63 | 0.0351 (11) | 0.0194 (10) | 0.0223 (10) | −0.0063 (8) | 0.0021 (8) | −0.0120 (8) |
O64 | 0.0429 (12) | 0.0286 (11) | 0.0147 (9) | −0.0149 (9) | 0.0019 (8) | −0.0107 (8) |
O65 | 0.0334 (11) | 0.0277 (11) | 0.0136 (9) | −0.0096 (9) | −0.0015 (8) | −0.0038 (8) |
N66 | 0.0174 (10) | 0.0181 (11) | 0.0193 (11) | −0.0040 (8) | −0.0020 (9) | −0.0072 (9) |
O67 | 0.0175 (9) | 0.0305 (11) | 0.0313 (11) | 0.0032 (8) | −0.0090 (8) | −0.0095 (9) |
O68 | 0.0177 (9) | 0.0236 (10) | 0.0204 (9) | −0.0013 (7) | 0.0018 (7) | −0.0089 (8) |
O69 | 0.0206 (9) | 0.0340 (12) | 0.0177 (9) | −0.0064 (8) | −0.0009 (7) | −0.0083 (8) |
N70 | 0.0211 (11) | 0.0133 (11) | 0.0176 (11) | −0.0011 (8) | −0.0025 (9) | −0.0054 (8) |
O71 | 0.0253 (10) | 0.0247 (11) | 0.0214 (10) | −0.0066 (8) | 0.0056 (8) | −0.0083 (8) |
O72 | 0.0218 (9) | 0.0195 (10) | 0.0269 (10) | 0.0022 (8) | −0.0104 (8) | −0.0073 (8) |
O73 | 0.0239 (10) | 0.0246 (10) | 0.0134 (9) | 0.0065 (8) | −0.0011 (7) | −0.0035 (8) |
N74 | 0.0169 (10) | 0.0281 (13) | 0.0154 (11) | −0.0053 (9) | 0.0026 (8) | −0.0091 (9) |
O75 | 0.0371 (11) | 0.0220 (10) | 0.0155 (9) | −0.0031 (9) | −0.0020 (8) | −0.0066 (8) |
O76 | 0.0453 (13) | 0.0254 (11) | 0.0205 (10) | 0.0018 (10) | −0.0006 (9) | −0.0032 (9) |
O77 | 0.0307 (11) | 0.0476 (14) | 0.0140 (9) | −0.0087 (10) | 0.0047 (8) | −0.0153 (9) |
N78 | 0.0214 (11) | 0.0172 (11) | 0.0206 (11) | 0.0031 (9) | −0.0040 (9) | −0.0055 (9) |
O79 | 0.0225 (10) | 0.0226 (10) | 0.0186 (9) | −0.0016 (8) | 0.0016 (8) | −0.0034 (8) |
O80 | 0.0308 (11) | 0.0330 (12) | 0.0330 (12) | 0.0044 (9) | −0.0167 (9) | −0.0071 (10) |
O81 | 0.0199 (9) | 0.0238 (10) | 0.0209 (10) | 0.0024 (8) | 0.0041 (8) | −0.0014 (8) |
O82 | 0.0238 (10) | 0.0277 (11) | 0.0293 (11) | −0.0024 (8) | −0.0030 (8) | −0.0080 (9) |
C83 | 0.0382 (18) | 0.044 (2) | 0.046 (2) | −0.0117 (15) | −0.0054 (16) | −0.0175 (17) |
C84 | 0.045 (2) | 0.062 (3) | 0.049 (2) | −0.0258 (19) | 0.0048 (17) | −0.025 (2) |
O85 | 0.0192 (9) | 0.0353 (12) | 0.0294 (11) | −0.0007 (8) | −0.0069 (8) | −0.0131 (9) |
C86 | 0.0320 (17) | 0.046 (2) | 0.0380 (19) | −0.0074 (15) | −0.0112 (14) | −0.0059 (16) |
C87 | 0.0287 (17) | 0.071 (3) | 0.047 (2) | −0.0189 (17) | 0.0013 (15) | −0.020 (2) |
O88 | 0.0316 (11) | 0.0239 (10) | 0.0178 (9) | −0.0105 (8) | 0.0024 (8) | −0.0056 (8) |
O89 | 0.0308 (11) | 0.0281 (11) | 0.0192 (10) | −0.0111 (9) | 0.0032 (8) | −0.0095 (8) |
Geometric parameters (Å, º) top
C1—N21 | 1.374 (3) | C41—H41 | 0.9500 |
C1—C20 | 1.399 (3) | C42—H42 | 0.9500 |
C1—C2 | 1.431 (3) | C43—C48 | 1.392 (3) |
C2—C3 | 1.359 (3) | C43—C44 | 1.393 (4) |
C2—H2 | 0.9500 | C44—C45 | 1.383 (3) |
C3—C4 | 1.435 (3) | C44—H44 | 0.9500 |
C3—H3 | 0.9500 | C45—N46 | 1.338 (3) |
C4—N21 | 1.367 (3) | C45—H45 | 0.9500 |
C4—C5 | 1.401 (3) | N46—C47 | 1.340 (3) |
C5—C6 | 1.409 (3) | N46—H46 | 0.9600 |
C5—C25 | 1.492 (3) | C47—C48 | 1.378 (3) |
C6—N22 | 1.370 (3) | C47—H47 | 0.9500 |
C6—C7 | 1.452 (3) | C48—H48 | 0.9500 |
C7—C8 | 1.345 (3) | Dy1—O51 | 2.3172 (18) |
C7—H7 | 0.9500 | Dy1—O50 | 2.3532 (17) |
C8—C9 | 1.454 (3) | Dy1—O53 | 2.3582 (18) |
C8—H8 | 0.9500 | Dy1—O52 | 2.3802 (18) |
C9—N22 | 1.372 (3) | Dy1—O60 | 2.4185 (19) |
C9—C10 | 1.408 (3) | Dy1—O49 | 2.4280 (18) |
C10—C11 | 1.397 (3) | Dy1—O56 | 2.4372 (19) |
C10—C31 | 1.492 (3) | Dy1—O55 | 2.507 (2) |
C11—N23 | 1.377 (3) | Dy1—O59 | 2.5196 (19) |
C11—C12 | 1.437 (3) | Dy1—N54 | 2.892 (2) |
C12—C13 | 1.359 (3) | Dy1—N58 | 2.897 (2) |
C12—H12 | 0.9500 | O49—H49A | 0.8329 |
C13—C14 | 1.433 (3) | O49—H49B | 0.9132 |
C13—H13 | 0.9500 | O50—H50A | 0.9151 |
C14—N23 | 1.374 (3) | O50—H50B | 0.8368 |
C14—C15 | 1.394 (3) | O51—H51A | 0.8394 |
C15—C16 | 1.407 (3) | O51—H51B | 0.9118 |
C15—C37 | 1.494 (3) | O52—H52A | 0.8598 |
C16—N24 | 1.368 (3) | O52—H52B | 1.0263 |
C16—C17 | 1.456 (3) | O53—H53A | 0.8346 |
C17—C18 | 1.347 (3) | O53—H53B | 0.8564 |
C17—H17 | 0.9500 | N54—O57 | 1.223 (3) |
C18—C19 | 1.453 (3) | N54—O55 | 1.265 (3) |
C18—H18 | 0.9500 | N54—O56 | 1.277 (3) |
C19—N24 | 1.370 (3) | N58—O61 | 1.224 (3) |
C19—C20 | 1.406 (3) | N58—O59 | 1.263 (3) |
C20—C43 | 1.492 (3) | N58—O60 | 1.283 (3) |
N21—H21 | 0.8800 | N62—O64 | 1.242 (3) |
N22—H22 | 0.8800 | N62—O65 | 1.245 (3) |
N23—H23 | 0.8800 | N62—O63 | 1.270 (3) |
N24—H24 | 0.8800 | N66—O67 | 1.240 (3) |
C25—C26 | 1.396 (4) | N66—O68 | 1.252 (3) |
C25—C30 | 1.396 (3) | N66—O69 | 1.277 (3) |
C26—C27 | 1.374 (4) | N70—O71 | 1.249 (3) |
C26—H26 | 0.9500 | N70—O72 | 1.252 (3) |
C27—N28 | 1.346 (3) | N70—O73 | 1.264 (3) |
C27—H27 | 0.9500 | N74—O76 | 1.235 (3) |
N28—C29 | 1.336 (4) | N74—O77 | 1.235 (3) |
N28—H28 | 0.9349 | N74—O75 | 1.279 (3) |
C29—C30 | 1.379 (3) | N78—O80 | 1.239 (3) |
C29—H29 | 0.9500 | N78—O79 | 1.251 (3) |
C30—H30 | 0.9500 | N78—O81 | 1.269 (3) |
C31—C32 | 1.397 (4) | O82—C83 | 1.423 (4) |
C31—C36 | 1.401 (4) | O82—H82 | 0.9192 |
C32—C33 | 1.381 (4) | C83—C84 | 1.472 (5) |
C32—H32 | 0.9500 | C83—H83A | 0.9900 |
C33—N34 | 1.340 (4) | C83—H83B | 0.9900 |
C33—H33 | 0.9500 | C84—H84A | 0.9800 |
N34—C35 | 1.339 (4) | C84—H84B | 0.9800 |
N34—H34 | 0.8903 | C84—H84C | 0.9800 |
C35—C36 | 1.375 (4) | O85—C86 | 1.450 (4) |
C35—H35 | 0.9500 | O85—H85 | 0.9950 |
C36—H36 | 0.9500 | C86—C87 | 1.491 (5) |
C37—C38 | 1.390 (4) | C86—H86A | 0.9900 |
C37—C42 | 1.395 (3) | C86—H86B | 0.9900 |
C38—C39 | 1.375 (3) | C87—H87A | 0.9800 |
C38—H38 | 0.9500 | C87—H87B | 0.9800 |
C39—N40 | 1.339 (3) | C87—H87C | 0.9800 |
C39—H39 | 0.9500 | O88—H88A | 0.9271 |
N40—C41 | 1.337 (3) | O88—H88B | 0.8452 |
N40—H40 | 0.8496 | O89—H89A | 0.9226 |
C41—C42 | 1.377 (3) | O89—H89B | 0.9605 |
| | | |
N21—C1—C20 | 125.6 (2) | C47—N46—H46 | 121.5 |
N21—C1—C2 | 107.1 (2) | N46—C47—C48 | 119.8 (2) |
C20—C1—C2 | 127.3 (2) | N46—C47—H47 | 120.1 |
C3—C2—C1 | 108.2 (2) | C48—C47—H47 | 120.1 |
C3—C2—H2 | 125.9 | C47—C48—C43 | 119.5 (2) |
C1—C2—H2 | 125.9 | C47—C48—H48 | 120.3 |
C2—C3—C4 | 107.7 (2) | C43—C48—H48 | 120.3 |
C2—C3—H3 | 126.2 | O51—Dy1—O50 | 83.77 (7) |
C4—C3—H3 | 126.2 | O51—Dy1—O53 | 89.82 (7) |
N21—C4—C5 | 125.9 (2) | O50—Dy1—O53 | 144.32 (6) |
N21—C4—C3 | 107.4 (2) | O51—Dy1—O52 | 78.20 (7) |
C5—C4—C3 | 126.7 (2) | O50—Dy1—O52 | 70.58 (6) |
C4—C5—C6 | 126.1 (2) | O53—Dy1—O52 | 142.08 (6) |
C4—C5—C25 | 116.1 (2) | O51—Dy1—O60 | 123.86 (6) |
C6—C5—C25 | 117.7 (2) | O50—Dy1—O60 | 75.63 (6) |
N22—C6—C5 | 125.2 (2) | O53—Dy1—O60 | 79.16 (7) |
N22—C6—C7 | 110.8 (2) | O52—Dy1—O60 | 137.02 (6) |
C5—C6—C7 | 123.9 (2) | O51—Dy1—O49 | 75.13 (7) |
C8—C7—C6 | 106.7 (2) | O50—Dy1—O49 | 137.69 (6) |
C8—C7—H7 | 126.7 | O53—Dy1—O49 | 72.73 (7) |
C6—C7—H7 | 126.7 | O52—Dy1—O49 | 69.45 (6) |
C7—C8—C9 | 106.6 (2) | O60—Dy1—O49 | 146.16 (7) |
C7—C8—H8 | 126.7 | O51—Dy1—O56 | 147.01 (7) |
C9—C8—H8 | 126.7 | O50—Dy1—O56 | 123.87 (7) |
N22—C9—C10 | 125.5 (2) | O53—Dy1—O56 | 77.20 (7) |
N22—C9—C8 | 110.7 (2) | O52—Dy1—O56 | 93.52 (7) |
C10—C9—C8 | 123.8 (2) | O60—Dy1—O56 | 83.76 (7) |
C11—C10—C9 | 126.1 (2) | O49—Dy1—O56 | 72.09 (7) |
C11—C10—C31 | 116.2 (2) | O51—Dy1—O55 | 147.18 (6) |
C9—C10—C31 | 117.6 (2) | O50—Dy1—O55 | 72.45 (6) |
N23—C11—C10 | 125.5 (2) | O53—Dy1—O55 | 122.64 (7) |
N23—C11—C12 | 107.0 (2) | O52—Dy1—O55 | 72.80 (7) |
C10—C11—C12 | 127.5 (2) | O60—Dy1—O55 | 72.23 (7) |
C13—C12—C11 | 108.1 (2) | O49—Dy1—O55 | 107.76 (6) |
C13—C12—H12 | 125.9 | O56—Dy1—O55 | 51.53 (6) |
C11—C12—H12 | 125.9 | O51—Dy1—O59 | 72.78 (6) |
C12—C13—C14 | 107.9 (2) | O50—Dy1—O59 | 75.60 (6) |
C12—C13—H13 | 126.0 | O53—Dy1—O59 | 68.99 (6) |
C14—C13—H13 | 126.0 | O52—Dy1—O59 | 137.25 (6) |
N23—C14—C15 | 125.7 (2) | O60—Dy1—O59 | 51.76 (6) |
N23—C14—C13 | 107.4 (2) | O49—Dy1—O59 | 129.27 (6) |
C15—C14—C13 | 126.8 (2) | O56—Dy1—O59 | 127.42 (7) |
C14—C15—C16 | 126.5 (2) | O55—Dy1—O59 | 120.51 (7) |
C14—C15—C37 | 116.4 (2) | O51—Dy1—N54 | 155.91 (6) |
C16—C15—C37 | 117.0 (2) | O50—Dy1—N54 | 98.26 (7) |
N24—C16—C15 | 125.0 (2) | O53—Dy1—N54 | 101.53 (7) |
N24—C16—C17 | 110.7 (2) | O52—Dy1—N54 | 79.88 (7) |
C15—C16—C17 | 124.2 (2) | O60—Dy1—N54 | 79.50 (6) |
C18—C17—C16 | 106.7 (2) | O49—Dy1—N54 | 87.93 (6) |
C18—C17—H17 | 126.6 | O56—Dy1—N54 | 25.98 (7) |
C16—C17—H17 | 126.6 | O55—Dy1—N54 | 25.85 (6) |
C17—C18—C19 | 106.3 (2) | O59—Dy1—N54 | 131.09 (6) |
C17—C18—H18 | 126.8 | O51—Dy1—N58 | 98.26 (7) |
C19—C18—H18 | 126.8 | O50—Dy1—N58 | 74.15 (6) |
N24—C19—C20 | 125.5 (2) | O53—Dy1—N58 | 72.13 (6) |
N24—C19—C18 | 111.0 (2) | O52—Dy1—N58 | 144.72 (6) |
C20—C19—C18 | 123.5 (2) | O60—Dy1—N58 | 25.98 (6) |
C1—C20—C19 | 126.1 (2) | O49—Dy1—N58 | 144.23 (6) |
C1—C20—C43 | 116.3 (2) | O56—Dy1—N58 | 106.10 (7) |
C19—C20—C43 | 117.6 (2) | O55—Dy1—N58 | 96.62 (7) |
C4—N21—C1 | 109.68 (19) | O59—Dy1—N58 | 25.77 (6) |
C4—N21—H21 | 125.2 | N54—Dy1—N58 | 105.40 (6) |
C1—N21—H21 | 125.2 | Dy1—O49—H49A | 127.5 |
C6—N22—C9 | 105.12 (19) | Dy1—O49—H49B | 118.2 |
C6—N22—H22 | 127.4 | H49A—O49—H49B | 108.6 |
C9—N22—H22 | 127.4 | Dy1—O50—H50A | 128.2 |
C14—N23—C11 | 109.53 (19) | Dy1—O50—H50B | 134.8 |
C14—N23—H23 | 125.2 | H50A—O50—H50B | 91.3 |
C11—N23—H23 | 125.2 | Dy1—O51—H51A | 124.7 |
C16—N24—C19 | 105.17 (19) | Dy1—O51—H51B | 128.8 |
C16—N24—H24 | 127.4 | H51A—O51—H51B | 104.7 |
C19—N24—H24 | 127.4 | Dy1—O52—H52A | 122.0 |
C26—C25—C30 | 118.6 (2) | Dy1—O52—H52B | 121.0 |
C26—C25—C5 | 119.4 (2) | H52A—O52—H52B | 113.5 |
C30—C25—C5 | 122.0 (2) | Dy1—O53—H53A | 115.8 |
C27—C26—C25 | 119.8 (2) | Dy1—O53—H53B | 123.4 |
C27—C26—H26 | 120.1 | H53A—O53—H53B | 107.8 |
C25—C26—H26 | 120.1 | O57—N54—O55 | 122.7 (2) |
N28—C27—C26 | 119.9 (2) | O57—N54—O56 | 121.8 (2) |
N28—C27—H27 | 120.0 | O55—N54—O56 | 115.5 (2) |
C26—C27—H27 | 120.0 | O57—N54—Dy1 | 170.23 (19) |
C29—N28—C27 | 122.0 (2) | O55—N54—Dy1 | 59.79 (12) |
C29—N28—H28 | 124.1 | O56—N54—Dy1 | 56.70 (12) |
C27—N28—H28 | 113.2 | N54—O55—Dy1 | 94.36 (15) |
N28—C29—C30 | 120.4 (2) | N54—O56—Dy1 | 97.32 (14) |
N28—C29—H29 | 119.8 | O61—N58—O59 | 123.2 (2) |
C30—C29—H29 | 119.8 | O61—N58—O60 | 120.9 (2) |
C29—C30—C25 | 119.3 (2) | O59—N58—O60 | 115.8 (2) |
C29—C30—H30 | 120.4 | O61—N58—Dy1 | 176.54 (19) |
C25—C30—H30 | 120.4 | O59—N58—Dy1 | 60.16 (12) |
C32—C31—C36 | 118.3 (2) | O60—N58—Dy1 | 55.68 (12) |
C32—C31—C10 | 121.9 (2) | N58—O59—Dy1 | 94.06 (14) |
C36—C31—C10 | 119.8 (2) | N58—O60—Dy1 | 98.33 (15) |
C33—C32—C31 | 119.8 (2) | O64—N62—O65 | 121.1 (2) |
C33—C32—H32 | 120.1 | O64—N62—O63 | 118.7 (2) |
C31—C32—H32 | 120.1 | O65—N62—O63 | 120.2 (2) |
N34—C33—C32 | 119.6 (2) | O67—N66—O68 | 120.8 (2) |
N34—C33—H33 | 120.2 | O67—N66—O69 | 119.9 (2) |
C32—C33—H33 | 120.2 | O68—N66—O69 | 119.3 (2) |
C35—N34—C33 | 122.6 (2) | O71—N70—O72 | 121.7 (2) |
C35—N34—H34 | 121.7 | O71—N70—O73 | 119.1 (2) |
C33—N34—H34 | 115.2 | O72—N70—O73 | 119.2 (2) |
N34—C35—C36 | 120.0 (2) | O76—N74—O77 | 122.5 (2) |
N34—C35—H35 | 120.0 | O76—N74—O75 | 118.1 (2) |
C36—C35—H35 | 120.0 | O77—N74—O75 | 119.4 (2) |
C35—C36—C31 | 119.7 (2) | O80—N78—O79 | 121.4 (2) |
C35—C36—H36 | 120.1 | O80—N78—O81 | 119.7 (2) |
C31—C36—H36 | 120.1 | O79—N78—O81 | 118.9 (2) |
C38—C37—C42 | 118.8 (2) | C83—O82—H82 | 106.4 |
C38—C37—C15 | 119.2 (2) | O82—C83—C84 | 112.3 (3) |
C42—C37—C15 | 121.9 (2) | O82—C83—H83A | 109.1 |
C39—C38—C37 | 119.8 (2) | C84—C83—H83A | 109.1 |
C39—C38—H38 | 120.1 | O82—C83—H83B | 109.1 |
C37—C38—H38 | 120.1 | C84—C83—H83B | 109.1 |
N40—C39—C38 | 119.8 (2) | H83A—C83—H83B | 107.9 |
N40—C39—H39 | 120.1 | C83—C84—H84A | 109.5 |
C38—C39—H39 | 120.1 | C83—C84—H84B | 109.5 |
C41—N40—C39 | 122.1 (2) | H84A—C84—H84B | 109.5 |
C41—N40—H40 | 120.4 | C83—C84—H84C | 109.5 |
C39—N40—H40 | 116.7 | H84A—C84—H84C | 109.5 |
N40—C41—C42 | 120.3 (2) | H84B—C84—H84C | 109.5 |
N40—C41—H41 | 119.8 | C86—O85—H85 | 109.6 |
C42—C41—H41 | 119.8 | O85—C86—C87 | 110.0 (3) |
C41—C42—C37 | 119.1 (2) | O85—C86—H86A | 109.7 |
C41—C42—H42 | 120.4 | C87—C86—H86A | 109.7 |
C37—C42—H42 | 120.4 | O85—C86—H86B | 109.7 |
C48—C43—C44 | 118.9 (2) | C87—C86—H86B | 109.7 |
C48—C43—C20 | 120.2 (2) | H86A—C86—H86B | 108.2 |
C44—C43—C20 | 120.8 (2) | C86—C87—H87A | 109.5 |
C45—C44—C43 | 119.6 (2) | C86—C87—H87B | 109.5 |
C45—C44—H44 | 120.2 | H87A—C87—H87B | 109.5 |
C43—C44—H44 | 120.2 | C86—C87—H87C | 109.5 |
N46—C45—C44 | 119.5 (2) | H87A—C87—H87C | 109.5 |
N46—C45—H45 | 120.3 | H87B—C87—H87C | 109.5 |
C44—C45—H45 | 120.3 | H88A—O88—H88B | 106.0 |
C45—N46—C47 | 122.7 (2) | H89A—O89—H89B | 103.9 |
C45—N46—H46 | 115.6 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N28—H28···O73 | 0.93 | 1.82 | 2.727 (3) | 164 |
N34—H34···O75 | 0.89 | 1.88 | 2.743 (3) | 162 |
N40—H40···O81 | 0.85 | 1.88 | 2.722 (3) | 174 |
N46—H46···O88 | 0.96 | 1.87 | 2.749 (3) | 150 |
O49—H49A···O75i | 0.83 | 1.96 | 2.776 (3) | 167 |
O49—H49B···O79 | 0.91 | 1.87 | 2.744 (3) | 159 |
O50—H50A···O69 | 0.92 | 1.86 | 2.748 (3) | 163 |
O50—H50B···O63ii | 0.84 | 1.90 | 2.724 (3) | 168 |
O51—H51A···O89 | 0.84 | 1.93 | 2.769 (3) | 173 |
O51—H51B···O63iii | 0.91 | 1.82 | 2.726 (3) | 174 |
O52—H52A···O72iv | 0.86 | 2.06 | 2.834 (3) | 149 |
O52—H52B···O68 | 1.03 | 1.74 | 2.744 (3) | 164 |
O53—H53A···O82 | 0.83 | 1.89 | 2.719 (3) | 174 |
O53—H53B···O85i | 0.86 | 1.93 | 2.759 (3) | 163 |
O82—H82···O80 | 0.92 | 2.17 | 3.011 (3) | 151 |
O85—H85···O69 | 1.00 | 1.94 | 2.923 (3) | 170 |
O88—H88A···O65 | 0.93 | 2.05 | 2.924 (3) | 156 |
O88—H88B···O89v | 0.85 | 2.00 | 2.840 (3) | 172 |
Symmetry codes: (i) −x+1, −y−1, −z+2; (ii) x, y, z+1; (iii) −x+1, −y−1, −z+1; (iv) −x, −y, −z+1; (v) x, y+1, z−1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6 | (C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O |
Mr | 1477.82 | 1437.54 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 7.7897 (2), 12.2577 (2), 17.2316 (5) | 12.8961 (2), 12.9222 (2), 18.5978 (3) |
α, β, γ (°) | 70.1447 (10), 89.341 (1), 75.3827 (16) | 71.6843 (7), 80.9684 (8), 73.3707 (7) |
V (Å3) | 1492.45 (6) | 2811.52 (8) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.58 | 1.44 |
Crystal size (mm) | 0.15 × 0.10 × 0.05 | 0.55 × 0.10 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.699, 0.882 | 0.512, 0.932 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13999, 6457, 5074 | 47169, 13315, 11865 |
Rint | 0.054 | 0.044 |
(sin θ/λ)max (Å−1) | 0.641 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.083, 0.97 | 0.034, 0.082, 1.04 |
No. of reflections | 6457 | 13315 |
No. of parameters | 379 | 813 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.36, −1.03 | 2.00, −1.62 |
Selected bond lengths (Å) for (I) topDy1—O25 | 2.355 (3) | Dy1—O35 | 2.462 (3) |
Dy1—O39 | 2.406 (3) | Dy1—O31 | 2.462 (3) |
Dy1—O28 | 2.434 (3) | Dy1—O27 | 2.582 (3) |
Dy1—O40 | 2.439 (3) | Dy1—O36 | 2.613 (4) |
Dy1—O32 | 2.451 (3) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O35i | 0.88 | 2.26 | 2.926 (5) | 132 |
O25—H25A···O27ii | 0.95 | 1.86 | 2.784 (4) | 164 |
O25—H25B···O33iii | 0.95 | 1.83 | 2.762 (4) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x−1, −y+1, −z; (iii) −x, −y+1, −z. |
Selected bond lengths (Å) for (II) topDy1—O51 | 2.3172 (18) | Dy1—O49 | 2.4280 (18) |
Dy1—O50 | 2.3532 (17) | Dy1—O56 | 2.4372 (19) |
Dy1—O53 | 2.3582 (18) | Dy1—O55 | 2.507 (2) |
Dy1—O52 | 2.3802 (18) | Dy1—O59 | 2.5196 (19) |
Dy1—O60 | 2.4185 (19) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N28—H28···O73 | 0.93 | 1.82 | 2.727 (3) | 164 |
N34—H34···O75 | 0.89 | 1.88 | 2.743 (3) | 162 |
N40—H40···O81 | 0.85 | 1.88 | 2.722 (3) | 174 |
N46—H46···O88 | 0.96 | 1.87 | 2.749 (3) | 150 |
O49—H49A···O75i | 0.83 | 1.96 | 2.776 (3) | 167 |
O49—H49B···O79 | 0.91 | 1.87 | 2.744 (3) | 159 |
O50—H50A···O69 | 0.92 | 1.86 | 2.748 (3) | 163 |
O50—H50B···O63ii | 0.84 | 1.90 | 2.724 (3) | 168 |
O51—H51A···O89 | 0.84 | 1.93 | 2.769 (3) | 173 |
O51—H51B···O63iii | 0.91 | 1.82 | 2.726 (3) | 174 |
O52—H52A···O72iv | 0.86 | 2.06 | 2.834 (3) | 149 |
O52—H52B···O68 | 1.03 | 1.74 | 2.744 (3) | 164 |
O53—H53A···O82 | 0.83 | 1.89 | 2.719 (3) | 174 |
O53—H53B···O85i | 0.86 | 1.93 | 2.759 (3) | 163 |
O82—H82···O80 | 0.92 | 2.17 | 3.011 (3) | 151 |
O85—H85···O69 | 1.00 | 1.94 | 2.923 (3) | 170 |
O88—H88A···O65 | 0.93 | 2.05 | 2.924 (3) | 156 |
O88—H88B···O89v | 0.85 | 2.00 | 2.840 (3) | 172 |
Symmetry codes: (i) −x+1, −y−1, −z+2; (ii) x, y, z+1; (iii) −x+1, −y−1, −z+1; (iv) −x, −y, −z+1; (v) x, y+1, z−1. |
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The tetra(4-pyridyl)porphyrin ligand (TPyP) is characterized by rigid square-planar geometry, bears multiple diverging molecular recognition sites for metal coordination as well as hydrogen bonding, and consequently reveals an extraordinarily rich supramolecular chemistry. Of particular interest is the coordination polymerization of this scaffold through exocyclic metal ion connectors. A survey of the literature indicates that the TPyP moiety provides an excellent building block for the formation of extended hybrid coordination polymers of diverse topologies when reacted with exocyclic transition metal ion connectors such as Ag (e.g. Carlucci et al., 2003), Cd (e.g. Zheng et al., 2007), Cu (e.g. Ohmura et al., 2006), Fe (Hagrman et al., 1999), Hg and Pb (Sharma et al., 1999) ions. Structures with exocyclic coordination to the TPyP macroring of selected transition metals in discrete complexes have been reported as well (e.g. Kon et al., 2006). Only a few coordination polymers and molecular complexes of lanthanoid (Ln) ions with simple bipyridyl ligands are known (Sharma & Rogers, 1999), but analogous compounds with the TPyP unit have not been explored until recently. This could be due to the oxophilic nature of the lanthanoid ions and their much lower tendency to coordinate to aromatic pyridyl sites. In recent studies newer types of framework solids were obtained (Lipstman & Goldberg, 2010) by reacting the TPyP with various aqua nitrate salts of lanthanoid f-metals. Those materials are characterized by open architectures of three-dimensional connectivity, which are sustained either by a combination of coordination polymerization in one direction and hydrogen bonding in the other directions, or by hydrogen-bonding interactions between the organic and inorganic components in all three dimensions. Direct coordination bonding between a lanthanoid ion and the pyridyl sites of TPyP has been observed thus far for La, Nd, Sm, Gd and Tb ions (Lipstman & Goldberg, 2009, 2010). Direct insertion of the lanthanoids into the centre of the porphyrin core is unlikely due to the relatively large size of these ions. Only a small number of double-decker-type compounds in which the Ln ions are sandwiched between, and coordinated by, the central pyrrole rings of two TPyPs has been observed (Ikeda et al., 2000).
Within the context of our continuing investigations on porphyrin framework solids (Goldberg, 2008) and on the supramolecular hybrid assemblies of the TPyP with lanthanoid ions, we describe here the structures of two new solid products, (I) and (II), obtained by reacting the porphyrin ligand with dysprosium nitrate hexahydrate, DyIII(NO3)3.6(H2O), in different crystallization conditions. It should be noticed that the large excess of the aqua nitrate salt in the reaction creates acidic conditions which promote protonation of the TPyP Lewis base, accompanied by insertion of additional nitrate ions into the solid products. This has been observed in earlier studies of the tetranitrato lanthanide complexes with TPyP (Lipstman & Goldberg, 2009, 2010) as well as with 4,4'-bipyridine (Sharma & Rogers, 1999). Compound (I) provides another example of this. Here, two trans-related pyridyl groups of the TPyP component become protonated, while the other two pyridyl functions engage in coordinative bonds with two Dy metal centres. The ORTEP structure of this product, [Dy3+(NO3-)4(H2O)]2.(TPyPH2)2+, is illustrated in Fig. 1. The porphyrin core in the formed metallo-organic complex is essentially planar. The Dy ion doubly coordinates to the four nitrate ions and singly to a water molecule (Table 1), being thus characterized by a coordination number of 9 (typical of lanthanoid metal ions in their most common oxidation state of 3+). The crystal packing of (I) involves hydrogen-bonding interactions between neighbouring units of the complex, utilizing the water ligand and pyridinium fragments as H-atom donors and the metal-coordinated nitrate ions as H-atom acceptors (Table 2). It reveals columnar organization of the organic and inorganic components along the a axis of the crystal (Fig. 2). The porphyrin entities are stacked along a in an offset-stacked manner, as commonly observed in a large variety of tetraarylporphyrin compounds (Byrn et al., 1993). The interstitial voids between the porphyrin columns entrap disordered molecules of the benzene crystallization solvent. The inorganic [Dy3+(NO3-)4(H2O)] components displaced along the a axis at (x,1/2,0) are hydrogen bonded to one another across inversion centres at (0,1/2,0) and (1/2,1/2,0); the (TPyPH2)2+ entity located across the inversion centre at (1/2,1/2,1/2) takes part in hydrogen bonding with adjacent units of the coordination complex near the (1,1,0) and (0,0,1) corners of the unit cell (Table 2).
In more acidic conditions, due to the presence of benzenetricarboxylic acid in the crystallization mixture, a full protonation of the peripheral pyridyl groups of the TPyP has occurred in compound (II). Moreover, in such conditions the basic nitrate anions have comparable tendency to be present in either a free or a metal-coordinated state, due to the competing ion-pairing and coordination interactions. In an aqueous protic environment this leads also to crystallization of the product in a solvated form of complex composition: [Dy3+(NO3-)2(H2O)5].(TPyPH4)4+.5(NO3-).2EtOH.2H2O (Fig. 3). The Dy ion in (II) is also nine-coordinate, linking singly to five molecules of water and doubly to two nitrate ions (Table 3). Given the large number of potential O—H and N—H H-atom donor and the nitrate H-atom acceptor sites, the supramolecular organization in this structure is netted by a large number of O—H···O and N—H···O hydrogen bonds (Table 4). Fig. 4 illustrates the hydrogen-bonded crystal packing of (II). It also shows that the protonated pyridyl sites of the (TPyPH4)4+ residue are not available for metal coordination, being involved in charge-assisted hydrogen bonds with the surrounding nitrate ions and water molecules. The conformation of the porphyrin macrocycle in (II) is essentially planar. The observed crystal packing exhibit segregated zones of the porphyrin and the metal-complex fragment parallel to the (ac) plane of the crystal, the former being centred at y = 0 and the latter clustering around y = 1/2.
In summary, we report here on yet another example of previously rarely observed direct exocyclic coordination adducts of TPyP and lanthanoid ions (Lipstman & Goldberg, 2009, 2010). Structures in which the TPyP entity is involved in supramolecular hydrogen bonding through their pyridyl groups are also scarce (Koner & Goldberg, 2009, 2010; Langford & Woodward, 2007; Kim et al., 2005). While it is expected in crystal engineering that the pyridyl N sites will normally engage in hydrogen bonds as H-atom acceptors with complementary H-atom donors, in structures (I) and (II) the protonated pyridyl sites adopt and [an?] opposite H-atom donating function.