Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045667/tk2189sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045667/tk2189Isup2.hkl |
CCDC reference: 663621
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.032
- wR factor = 0.085
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT215_ALERT_3_B Disordered F5 has ADP max/min Ratio ....... 4.80 PLAT215_ALERT_3_B Disordered F5' has ADP max/min Ratio ....... 4.80 PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.90 Ratio PLAT220_ALERT_2_B Large Non-Solvent F Ueq(max)/Ueq(min) ... 3.66 Ratio
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.62 mm PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT213_ALERT_2_C Atom F2 has ADP max/min Ratio ............. 3.50 prola PLAT213_ALERT_2_C Atom C11 has ADP max/min Ratio ............. 3.80 prola PLAT213_ALERT_2_C Atom F10 has ADP max/min Ratio ............. 3.20 prola PLAT213_ALERT_2_C Atom F10A has ADP max/min Ratio ............. 3.20 prola PLAT213_ALERT_2_C Atom F10B has ADP max/min Ratio ............. 3.20 prola PLAT213_ALERT_2_C Atom F10C has ADP max/min Ratio ............. 3.20 prola PLAT213_ALERT_2_C Atom C17' has ADP max/min Ratio ............. 3.80 prola PLAT215_ALERT_3_C Disordered F6 has ADP max/min Ratio ....... 3.10 PLAT215_ALERT_3_C Disordered F6' has ADP max/min Ratio ....... 3.10 PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.43 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for F5 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for F5' PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C19' PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT301_ALERT_3_C Main Residue Disorder ......................... 20.00 Perc. PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 11.60 Deg. F4' -C16 -F4 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 18.40 Deg. F5 -C16 -F5' 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 0.00 Deg. F6' -C16 -F6 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 3.00 Deg. C28 -C29 -C28' 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 28.50 Deg. F12B -C32 -F11A 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 30.20 Deg. F12B -C32 -F12C 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 21.90 Deg. F10A -C32 -F10 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 24.20 Deg. F10A -C32 -F11B 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 29.20 Deg. F10 -C32 -F10C 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 42.60 Deg. F11B -C32 -F11C 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 20.70 Deg. F12C -C32 -F12 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 33.60 Deg. F12A -C32 -F12 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 32.30 Deg. F10C -C32 -F10B 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 26.50 Deg. F12A -C32 -F10B 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 24.90 Deg. F11A -C32 -F11 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 21.80 Deg. F11C -C32 -F11 1.555 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 76
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 36 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 31 ALERT type 2 Indicator that the structure model may be wrong or deficient 8 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
All chemicals were of analytical grade and were used without further purification. Complex (I) was prepared according to method C in Bauer et al., 1964. Pale-yellow products were obtained. Purification by recrystallization was accomplished by room temperature evaporation of a CH2Cl2 solution of (I). Single crystal suitable for X-ray analysis were obtained from an EtOH solution of (I); m. pt. 422 K.
Two of the four thienyl rings as well as the four CF3 groups are disordered. The positional disorder of F atoms, F4, F5 and F6, was modelled anisotropically over two positions with site occupancy factors for the primed and unprimed atoms equalling 0.5 (from refinement). The F10, F11 and F12 atoms were modelled over four positions with the site occupancy factors of 0.472, 0.274, 0.099 and 0.156 for atoms (F10, F11, F12), (F10A, F11A, F12A), (F10B, F11B, F12B) and (F10C, F11C, F12C), respectively, as determined from least-squares refinement; of these, the F10, F11, & F12 atoms were refined with anisotropic displacement parameters.
Two of the four thienyl rings were disordered and modelled anisotropically over two orientations with refined occupancy factors of S3:S3'=0.668 (5):0.332 and S4:S4'=0.656 (4):0.344, respectively, obtained from least-squares refinement.
The N1—H atom was located by difference Fourier synthesis and refined without constraint so that N—H = 0.87 Å. The C-bound H atoms were included in the riding model approximation with C—H = 0.95 - 0.98 Å, and with Uiso(H) = 1.2Ueq(C). The highest residual electron density peak is 0.78 Å from the Eu atom, and the deepest hole is 0.62 Å from the S2 atom.
The structure of the title complex, [DMAP][Eu(TTA)4] (I), Fig. 1, shows the trivalent Eu cation to be 8-coordinated by eight O atoms derived from four chelating β-diketonate ligands. The coordination polyhedron can be best described as a distorted tetragonal antiprism in which the square planes are defined by the O1, O2, O5 & O6 atoms and the atoms O3, O4, O7 & O8. The 4-dimethylaminopyridinium cation forms a N—H···O hydrogen bond to the O6 atom (Table 1). Complex (I) has intensive photoluminescence (PL) at room temperature. The corresponding 4-aminopyridinium complex, [4-aminopyridinium][Eu(TTA)4] has mechanoluminescence (ML) properties (Chen et al., 2001), which was attributed to the disorder in the thienyl rings and CF3 groups (Sweeting & Rheingold, 1987). However, (I) also has disorder in the thienyl rings and CF3 groups (see Experimental) but does not exhibit ML.
For the corresponding 4-aminopyridinium complex, see Chen et al. (2001). For related literature, see: Bauer et al. (1964); Sweeting & Rheingold (1987).
Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1998); software used to prepare material for publication: SHELXTL (Siemens, 1998).
Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level. H atoms have been omitted for clarity. |
(C7H11N2)[Eu(C8H4F3O2S)4] | Dx = 1.738 Mg m−3 |
Mr = 1159.83 | Melting point: 422 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 77909 reflections |
a = 20.0202 (4) Å | θ = 3.0–27.5° |
b = 18.9160 (3) Å | µ = 1.71 mm−1 |
c = 23.4108 (4) Å | T = 93 K |
V = 8865.7 (3) Å3 | Block, light yellow |
Z = 8 | 0.62 × 0.45 × 0.23 mm |
F(000) = 4592 |
Rigaku R-AXIS RAPID diffractometer | 10137 independent reflections |
Radiation source: Rotating Anode | 9604 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | h = −25→21 |
Tmin = 0.418, Tmax = 0.695 | k = −24→24 |
82834 measured reflections | l = −30→30 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0426P)2 + 19.8P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.002 |
10137 reflections | Δρmax = 1.29 e Å−3 |
725 parameters | Δρmin = −1.10 e Å−3 |
76 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00046 (5) |
(C7H11N2)[Eu(C8H4F3O2S)4] | V = 8865.7 (3) Å3 |
Mr = 1159.83 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 20.0202 (4) Å | µ = 1.71 mm−1 |
b = 18.9160 (3) Å | T = 93 K |
c = 23.4108 (4) Å | 0.62 × 0.45 × 0.23 mm |
Rigaku R-AXIS RAPID diffractometer | 10137 independent reflections |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | 9604 reflections with I > 2σ(I) |
Tmin = 0.418, Tmax = 0.695 | Rint = 0.048 |
82834 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 76 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0426P)2 + 19.8P] where P = (Fo2 + 2Fc2)/3 |
10137 reflections | Δρmax = 1.29 e Å−3 |
725 parameters | Δρmin = −1.10 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Eu | 0.597426 (6) | 0.721987 (6) | 0.360975 (5) | 0.01510 (6) | |
S1 | 0.60799 (4) | 0.57483 (4) | 0.17677 (3) | 0.03073 (16) | |
S2 | 0.39615 (5) | 0.83825 (6) | 0.44619 (5) | 0.0506 (3) | |
F1 | 0.39394 (12) | 0.59604 (15) | 0.43360 (8) | 0.0594 (7) | |
F2 | 0.34744 (12) | 0.57253 (18) | 0.35390 (9) | 0.0750 (10) | |
F3 | 0.35621 (11) | 0.67993 (16) | 0.38226 (13) | 0.0737 (8) | |
F7 | 0.58142 (9) | 0.56142 (11) | 0.53956 (8) | 0.0405 (5) | |
F8 | 0.65626 (10) | 0.63695 (11) | 0.56345 (7) | 0.0402 (5) | |
F9 | 0.68492 (10) | 0.53054 (10) | 0.54391 (7) | 0.0390 (5) | |
O1 | 0.57171 (10) | 0.64663 (11) | 0.28185 (8) | 0.0270 (4) | |
O2 | 0.49679 (9) | 0.66181 (10) | 0.38064 (8) | 0.0228 (4) | |
O3 | 0.52853 (9) | 0.79803 (11) | 0.41529 (8) | 0.0232 (4) | |
O4 | 0.66577 (9) | 0.79900 (10) | 0.41878 (8) | 0.0220 (4) | |
O5 | 0.68395 (9) | 0.63666 (10) | 0.35019 (8) | 0.0215 (4) | |
O6 | 0.61699 (9) | 0.65975 (10) | 0.45317 (7) | 0.0199 (4) | |
O7 | 0.53810 (9) | 0.79814 (11) | 0.29734 (8) | 0.0243 (4) | |
O8 | 0.67192 (8) | 0.76383 (10) | 0.29028 (7) | 0.0172 (3) | |
N1 | 0.53190 (12) | 0.78441 (13) | 0.03754 (10) | 0.0228 (5) | |
N2 | 0.37594 (13) | 0.73141 (14) | 0.14289 (10) | 0.0276 (5) | |
C1 | 0.5848 (2) | 0.5117 (2) | 0.12886 (14) | 0.0430 (8) | |
H1 | 0.6112 | 0.4979 | 0.0970 | 0.052* | |
C2 | 0.5244 (2) | 0.4834 (2) | 0.14134 (15) | 0.0509 (10) | |
H2 | 0.5039 | 0.4477 | 0.1189 | 0.061* | |
C3 | 0.49566 (16) | 0.51149 (15) | 0.18959 (11) | 0.0280 (6) | |
H3 | 0.4534 | 0.4972 | 0.2041 | 0.034* | |
C4 | 0.53614 (15) | 0.56404 (15) | 0.21516 (11) | 0.0246 (5) | |
C5 | 0.52640 (13) | 0.60478 (14) | 0.26746 (11) | 0.0218 (5) | |
C6 | 0.46612 (14) | 0.59541 (16) | 0.29869 (11) | 0.0273 (6) | |
H6 | 0.4315 | 0.5675 | 0.2826 | 0.033* | |
C7 | 0.45655 (14) | 0.62543 (16) | 0.35122 (11) | 0.0251 (6) | |
C8 | 0.38772 (15) | 0.61804 (15) | 0.37990 (10) | 0.0425 (9) | |
C9 | 0.3482 (2) | 0.8823 (3) | 0.4915 (2) | 0.0627 (13) | |
H9 | 0.3008 | 0.8809 | 0.4903 | 0.075* | |
C10 | 0.3826 (3) | 0.9204 (2) | 0.5301 (2) | 0.0659 (14) | |
H10 | 0.3606 | 0.9472 | 0.5587 | 0.079* | |
C11 | 0.45524 (16) | 0.91853 (16) | 0.52591 (13) | 0.0331 (7) | |
H11 | 0.4870 | 0.9434 | 0.5483 | 0.040* | |
C12 | 0.46776 (16) | 0.86778 (15) | 0.47749 (13) | 0.0300 (6) | |
C13 | 0.53184 (14) | 0.84155 (14) | 0.45560 (11) | 0.0231 (5) | |
C14 | 0.59243 (15) | 0.86281 (16) | 0.48075 (12) | 0.0279 (6) | |
H14 | 0.5916 | 0.8957 | 0.5114 | 0.034* | |
C15 | 0.65323 (14) | 0.83693 (15) | 0.46199 (11) | 0.0243 (5) | |
C16 | 0.71490 (14) | 0.85150 (14) | 0.49939 (11) | 0.0351 (7) | |
C21 | 0.70624 (11) | 0.58265 (12) | 0.37441 (10) | 0.0169 (5) | |
C22 | 0.69243 (12) | 0.56499 (14) | 0.43225 (11) | 0.0198 (5) | |
H22 | 0.7125 | 0.5239 | 0.4481 | 0.024* | |
C23 | 0.65101 (12) | 0.60529 (14) | 0.46600 (10) | 0.0190 (5) | |
C24 | 0.64375 (11) | 0.58252 (12) | 0.52873 (10) | 0.0281 (6) | |
C29 | 0.54665 (12) | 0.82280 (13) | 0.24797 (10) | 0.0205 (5) | |
C30 | 0.60626 (13) | 0.81424 (15) | 0.21592 (11) | 0.0217 (5) | |
H30 | 0.6073 | 0.8295 | 0.1773 | 0.026* | |
C31 | 0.66273 (12) | 0.78427 (13) | 0.23958 (10) | 0.0178 (5) | |
C32 | 0.72446 (12) | 0.77568 (12) | 0.20115 (9) | 0.0268 (6) | |
C33 | 0.49300 (14) | 0.72594 (14) | 0.11988 (12) | 0.0227 (5) | |
H33 | 0.5021 | 0.6975 | 0.1524 | 0.027* | |
C34 | 0.54349 (13) | 0.74485 (15) | 0.08441 (11) | 0.0231 (5) | |
H34 | 0.5878 | 0.7300 | 0.0927 | 0.028* | |
C35 | 0.46985 (14) | 0.80629 (16) | 0.02486 (11) | 0.0251 (5) | |
H35 | 0.4628 | 0.8338 | −0.0086 | 0.030* | |
C36 | 0.41688 (14) | 0.79004 (16) | 0.05877 (12) | 0.0242 (5) | |
H36 | 0.3735 | 0.8065 | 0.0492 | 0.029* | |
C37 | 0.42670 (13) | 0.74846 (14) | 0.10856 (10) | 0.0199 (5) | |
C38 | 0.38690 (17) | 0.68721 (18) | 0.19277 (14) | 0.0374 (7) | |
H38A | 0.4021 | 0.6403 | 0.1806 | 0.045* | |
H38B | 0.3451 | 0.6826 | 0.2142 | 0.045* | |
H38C | 0.4209 | 0.7089 | 0.2172 | 0.045* | |
C39 | 0.30806 (14) | 0.7547 (2) | 0.12963 (15) | 0.0341 (7) | |
H39A | 0.3072 | 0.8064 | 0.1264 | 0.041* | |
H39B | 0.2777 | 0.7397 | 0.1602 | 0.041* | |
H39C | 0.2937 | 0.7337 | 0.0934 | 0.041* | |
S3 | 0.76027 (15) | 0.55120 (13) | 0.26924 (11) | 0.0207 (5) | 0.668 (4) |
C17 | 0.8112 (8) | 0.4800 (7) | 0.2609 (5) | 0.021 (3) | 0.668 (4) |
H17 | 0.8333 | 0.4683 | 0.2263 | 0.025* | 0.668 (4) |
C18 | 0.8162 (7) | 0.4416 (8) | 0.3103 (5) | 0.022 (2) | 0.668 (4) |
H18 | 0.8384 | 0.3974 | 0.3127 | 0.026* | 0.668 (4) |
C19 | 0.7845 (7) | 0.4749 (6) | 0.3580 (5) | 0.0195 (18) | 0.668 (4) |
H19 | 0.7870 | 0.4585 | 0.3963 | 0.023* | 0.668 (4) |
C20 | 0.74887 (11) | 0.53566 (11) | 0.34022 (8) | 0.0169 (5) | 0.668 (4) |
S4 | 0.41641 (14) | 0.8617 (2) | 0.25791 (17) | 0.0364 (8) | 0.656 (5) |
C25 | 0.3827 (7) | 0.9126 (9) | 0.2054 (5) | 0.032 (3) | 0.656 (5) |
H25 | 0.3361 | 0.9218 | 0.2045 | 0.039* | 0.656 (5) |
C26 | 0.4241 (5) | 0.9401 (11) | 0.1645 (7) | 0.033 (3) | 0.656 (5) |
H26 | 0.4135 | 0.9747 | 0.1364 | 0.039* | 0.656 (5) |
C27 | 0.4867 (5) | 0.9055 (8) | 0.1732 (4) | 0.031 (3) | 0.656 (5) |
H27 | 0.5228 | 0.9101 | 0.1472 | 0.037* | 0.656 (5) |
C28 | 0.4912 (6) | 0.864 (2) | 0.2234 (13) | 0.0240 (17) | 0.656 (5) |
F4 | 0.7630 (6) | 0.8826 (11) | 0.4694 (7) | 0.025 (2) | 0.50 |
F5 | 0.7102 (15) | 0.8890 (16) | 0.5472 (8) | 0.085 (4) | 0.50 |
F6 | 0.738 (8) | 0.792 (5) | 0.522 (8) | 0.0916 (12) | 0.50 |
F10 | 0.7128 (4) | 0.7831 (6) | 0.14554 (14) | 0.045 (2) | 0.472 (7) |
F11 | 0.7484 (3) | 0.7097 (2) | 0.2073 (3) | 0.0290 (12) | 0.472 (7) |
F12 | 0.7734 (3) | 0.8167 (4) | 0.2210 (4) | 0.0457 (18) | 0.472 (7) |
S3' | 0.7835 (4) | 0.4610 (3) | 0.3669 (3) | 0.0217 (11) | 0.332 (4) |
C17' | 0.8212 (15) | 0.4430 (17) | 0.3035 (6) | 0.030 (7) | 0.332 (4) |
H17' | 0.8537 | 0.4071 | 0.2977 | 0.036* | 0.332 (4) |
C18' | 0.7980 (17) | 0.4876 (16) | 0.2619 (10) | 0.022 (3) | 0.332 (4) |
H18' | 0.8033 | 0.4779 | 0.2224 | 0.026* | 0.332 (4) |
C19' | 0.7653 (14) | 0.5498 (12) | 0.2824 (4) | 0.042 (8) | 0.332 (4) |
H19' | 0.7564 | 0.5919 | 0.2615 | 0.050* | 0.332 (4) |
C20' | 0.74887 (11) | 0.53566 (11) | 0.34022 (8) | 0.0169 (5) | 0.332 (4) |
S4' | 0.4999 (3) | 0.9122 (4) | 0.1631 (3) | 0.0231 (10) | 0.344 (5) |
C25' | 0.4167 (5) | 0.929 (2) | 0.1690 (14) | 0.032 (6) | 0.344 (5) |
H25' | 0.3939 | 0.9483 | 0.1371 | 0.038* | 0.344 (5) |
C26' | 0.3811 (14) | 0.9151 (17) | 0.2177 (10) | 0.031 (4) | 0.344 (5) |
H26' | 0.3388 | 0.9326 | 0.2294 | 0.037* | 0.344 (5) |
C27' | 0.4254 (7) | 0.8673 (10) | 0.2461 (10) | 0.027 (5) | 0.344 (5) |
H27' | 0.4123 | 0.8416 | 0.2791 | 0.033* | 0.344 (5) |
C28' | 0.4902 (11) | 0.861 (4) | 0.222 (3) | 0.0240 (17) | 0.344 (5) |
F4' | 0.7693 (6) | 0.8701 (11) | 0.4706 (7) | 0.037 (4) | 0.50 |
F5' | 0.6989 (15) | 0.9023 (15) | 0.5362 (9) | 0.085 (4) | 0.50 |
F6' | 0.738 (8) | 0.792 (5) | 0.522 (8) | 0.0916 (12) | 0.50 |
F10A | 0.7067 (9) | 0.7574 (9) | 0.1485 (3) | 0.045 (2) | 0.274 (5) |
F11A | 0.7679 (5) | 0.7273 (5) | 0.2187 (4) | 0.0290 (12) | 0.274 (5) |
F12A | 0.7570 (6) | 0.8368 (4) | 0.1960 (6) | 0.0457 (18) | 0.274 (5) |
F10B | 0.7361 (11) | 0.8384 (5) | 0.1770 (10) | 0.0447 (4) | 0.099 (5) |
F11B | 0.7135 (8) | 0.7314 (9) | 0.1580 (6) | 0.0290 (12) | 0.099 (5) |
F12B | 0.7814 (6) | 0.7573 (14) | 0.2261 (7) | 0.0457 (18) | 0.099 (5) |
F10C | 0.7226 (11) | 0.8152 (12) | 0.1542 (7) | 0.045 (2) | 0.156 (7) |
F11C | 0.7331 (8) | 0.7072 (3) | 0.1903 (7) | 0.0290 (12) | 0.156 (7) |
F12C | 0.7822 (6) | 0.7938 (14) | 0.2251 (10) | 0.0457 (18) | 0.156 (7) |
H1N | 0.5629 (19) | 0.798 (2) | 0.0139 (16) | 0.036 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Eu | 0.01078 (8) | 0.01810 (8) | 0.01641 (8) | 0.00051 (4) | 0.00067 (4) | −0.00262 (4) |
S1 | 0.0312 (4) | 0.0349 (4) | 0.0261 (3) | 0.0025 (3) | 0.0008 (3) | −0.0050 (3) |
S2 | 0.0327 (4) | 0.0486 (6) | 0.0705 (7) | 0.0121 (4) | 0.0194 (4) | 0.0144 (5) |
F1 | 0.0613 (14) | 0.0929 (19) | 0.0240 (9) | −0.0511 (13) | 0.0071 (9) | −0.0015 (10) |
F2 | 0.0443 (13) | 0.143 (3) | 0.0381 (11) | −0.0603 (16) | 0.0124 (10) | −0.0339 (14) |
F3 | 0.0276 (11) | 0.102 (2) | 0.091 (2) | 0.0076 (13) | 0.0156 (12) | −0.0096 (17) |
F7 | 0.0346 (10) | 0.0516 (12) | 0.0353 (10) | 0.0055 (9) | 0.0185 (8) | 0.0140 (9) |
F8 | 0.0487 (11) | 0.0538 (12) | 0.0182 (8) | 0.0156 (9) | −0.0056 (7) | −0.0067 (8) |
F9 | 0.0433 (11) | 0.0482 (12) | 0.0254 (8) | 0.0211 (9) | 0.0091 (7) | 0.0135 (8) |
O1 | 0.0211 (9) | 0.0323 (11) | 0.0275 (10) | −0.0061 (8) | 0.0037 (8) | −0.0129 (8) |
O2 | 0.0188 (9) | 0.0296 (10) | 0.0200 (8) | −0.0077 (7) | −0.0003 (7) | −0.0015 (7) |
O3 | 0.0203 (9) | 0.0272 (10) | 0.0222 (9) | 0.0053 (8) | 0.0034 (7) | −0.0040 (7) |
O4 | 0.0201 (9) | 0.0260 (10) | 0.0199 (8) | −0.0049 (7) | 0.0025 (7) | −0.0060 (7) |
O5 | 0.0227 (9) | 0.0206 (9) | 0.0213 (8) | 0.0063 (7) | 0.0064 (7) | 0.0032 (7) |
O6 | 0.0154 (8) | 0.0259 (9) | 0.0186 (8) | 0.0041 (7) | 0.0020 (7) | −0.0014 (7) |
O7 | 0.0176 (9) | 0.0365 (11) | 0.0186 (9) | 0.0092 (8) | −0.0017 (7) | −0.0015 (8) |
O8 | 0.0135 (8) | 0.0209 (9) | 0.0173 (8) | −0.0008 (7) | −0.0029 (6) | 0.0009 (7) |
N1 | 0.0189 (11) | 0.0314 (13) | 0.0182 (10) | −0.0043 (9) | 0.0057 (9) | −0.0001 (9) |
N2 | 0.0202 (12) | 0.0327 (13) | 0.0299 (13) | −0.0003 (10) | 0.0084 (9) | 0.0018 (10) |
C1 | 0.060 (2) | 0.043 (2) | 0.0259 (15) | 0.0079 (17) | 0.0065 (15) | −0.0089 (14) |
C2 | 0.072 (3) | 0.045 (2) | 0.0353 (18) | −0.017 (2) | −0.0010 (17) | −0.0150 (15) |
C3 | 0.0364 (15) | 0.0262 (14) | 0.0215 (12) | −0.0120 (12) | −0.0059 (11) | −0.0002 (10) |
C4 | 0.0313 (14) | 0.0242 (13) | 0.0181 (12) | 0.0016 (11) | −0.0064 (10) | −0.0005 (10) |
C5 | 0.0243 (13) | 0.0204 (12) | 0.0208 (12) | 0.0012 (10) | −0.0073 (10) | −0.0001 (9) |
C6 | 0.0257 (13) | 0.0363 (16) | 0.0198 (12) | −0.0111 (12) | −0.0066 (10) | −0.0002 (11) |
C7 | 0.0225 (13) | 0.0327 (15) | 0.0200 (12) | −0.0090 (11) | −0.0038 (10) | 0.0049 (10) |
C8 | 0.0318 (16) | 0.068 (3) | 0.0276 (15) | −0.0248 (17) | 0.0035 (13) | −0.0087 (15) |
C9 | 0.044 (2) | 0.063 (3) | 0.081 (3) | 0.023 (2) | 0.035 (2) | 0.021 (2) |
C10 | 0.074 (3) | 0.053 (3) | 0.071 (3) | 0.026 (2) | 0.049 (3) | 0.005 (2) |
C11 | 0.0384 (16) | 0.0310 (15) | 0.0298 (14) | 0.0119 (13) | 0.0288 (13) | 0.0072 (12) |
C12 | 0.0351 (16) | 0.0225 (14) | 0.0325 (14) | 0.0069 (12) | 0.0168 (12) | 0.0036 (11) |
C13 | 0.0294 (14) | 0.0174 (12) | 0.0226 (12) | 0.0029 (10) | 0.0117 (10) | 0.0027 (9) |
C14 | 0.0349 (15) | 0.0243 (14) | 0.0246 (13) | −0.0074 (11) | 0.0131 (11) | −0.0071 (11) |
C15 | 0.0278 (14) | 0.0260 (14) | 0.0192 (12) | −0.0108 (11) | 0.0049 (10) | −0.0029 (10) |
C16 | 0.0389 (17) | 0.0465 (19) | 0.0199 (13) | −0.0188 (14) | 0.0010 (12) | −0.0048 (12) |
C21 | 0.0121 (10) | 0.0171 (11) | 0.0216 (11) | −0.0004 (9) | 0.0009 (9) | −0.0032 (9) |
C22 | 0.0184 (12) | 0.0211 (12) | 0.0199 (11) | 0.0022 (9) | 0.0023 (9) | 0.0010 (9) |
C23 | 0.0161 (11) | 0.0238 (13) | 0.0169 (11) | −0.0020 (9) | 0.0008 (9) | 0.0007 (9) |
C24 | 0.0283 (14) | 0.0357 (16) | 0.0202 (12) | 0.0087 (12) | 0.0052 (10) | 0.0045 (11) |
C29 | 0.0178 (12) | 0.0251 (13) | 0.0187 (11) | 0.0061 (10) | −0.0071 (9) | −0.0064 (10) |
C30 | 0.0196 (12) | 0.0308 (14) | 0.0147 (11) | 0.0054 (10) | −0.0045 (9) | −0.0029 (10) |
C31 | 0.0146 (11) | 0.0222 (12) | 0.0166 (11) | 0.0009 (9) | −0.0018 (9) | −0.0034 (9) |
C32 | 0.0163 (12) | 0.0425 (17) | 0.0214 (13) | 0.0063 (11) | −0.0006 (10) | 0.0003 (11) |
C33 | 0.0207 (13) | 0.0273 (14) | 0.0201 (12) | 0.0035 (10) | 0.0019 (10) | 0.0024 (10) |
C34 | 0.0158 (12) | 0.0316 (14) | 0.0217 (12) | 0.0014 (10) | 0.0007 (9) | −0.0029 (10) |
C35 | 0.0271 (13) | 0.0303 (14) | 0.0178 (11) | 0.0012 (11) | −0.0003 (10) | 0.0017 (10) |
C36 | 0.0181 (12) | 0.0303 (14) | 0.0244 (13) | 0.0025 (11) | −0.0018 (10) | 0.0011 (11) |
C37 | 0.0165 (12) | 0.0227 (13) | 0.0204 (12) | −0.0014 (9) | 0.0030 (9) | −0.0012 (10) |
C38 | 0.0379 (17) | 0.0353 (17) | 0.0391 (17) | 0.0011 (14) | 0.0202 (14) | 0.0118 (13) |
C39 | 0.0142 (13) | 0.0458 (19) | 0.0422 (17) | −0.0004 (13) | 0.0076 (12) | −0.0040 (14) |
S3 | 0.0214 (9) | 0.0209 (7) | 0.0198 (7) | −0.0003 (5) | 0.0043 (7) | −0.0022 (5) |
C17 | 0.014 (7) | 0.023 (3) | 0.027 (3) | 0.001 (3) | 0.011 (3) | −0.005 (2) |
C18 | 0.017 (4) | 0.017 (4) | 0.031 (3) | 0.005 (3) | 0.003 (3) | 0.006 (3) |
C19 | 0.020 (3) | 0.013 (4) | 0.025 (4) | −0.003 (3) | 0.006 (3) | −0.003 (2) |
C20 | 0.0157 (11) | 0.0171 (12) | 0.0178 (11) | −0.0011 (9) | 0.0022 (9) | −0.0018 (9) |
S4 | 0.0205 (7) | 0.0557 (16) | 0.0331 (13) | 0.0192 (9) | −0.0067 (8) | −0.0065 (9) |
C25 | 0.029 (4) | 0.050 (5) | 0.019 (5) | 0.026 (3) | −0.010 (3) | −0.010 (4) |
C26 | 0.039 (4) | 0.034 (7) | 0.025 (4) | 0.009 (4) | −0.007 (3) | 0.000 (3) |
C27 | 0.017 (4) | 0.045 (6) | 0.031 (6) | 0.013 (4) | −0.003 (3) | −0.017 (3) |
C28 | 0.0202 (13) | 0.032 (4) | 0.0197 (18) | 0.0102 (15) | −0.0070 (12) | −0.007 (2) |
F4 | 0.013 (3) | 0.031 (5) | 0.031 (3) | −0.008 (4) | −0.006 (2) | 0.005 (3) |
F5 | 0.030 (8) | 0.165 (9) | 0.061 (6) | −0.020 (4) | −0.003 (4) | −0.081 (7) |
F6 | 0.108 (2) | 0.084 (2) | 0.0825 (19) | −0.0538 (18) | −0.0709 (19) | 0.0522 (16) |
F10 | 0.035 (3) | 0.086 (7) | 0.0133 (11) | 0.030 (5) | 0.0074 (11) | 0.016 (2) |
F11 | 0.019 (3) | 0.0490 (19) | 0.019 (3) | 0.0160 (17) | −0.0099 (17) | −0.0033 (16) |
F12 | 0.0167 (19) | 0.061 (4) | 0.060 (3) | −0.011 (2) | 0.0093 (17) | −0.018 (3) |
S3' | 0.0210 (16) | 0.017 (2) | 0.027 (2) | 0.0032 (17) | −0.0002 (13) | −0.0028 (13) |
C17' | 0.025 (9) | 0.027 (12) | 0.038 (10) | −0.002 (7) | 0.019 (7) | −0.021 (8) |
C18' | 0.007 (10) | 0.041 (9) | 0.018 (6) | −0.006 (5) | 0.004 (4) | −0.006 (6) |
C19' | 0.029 (7) | 0.039 (10) | 0.058 (15) | 0.011 (6) | −0.016 (9) | −0.030 (9) |
C20' | 0.0157 (11) | 0.0171 (12) | 0.0178 (11) | −0.0011 (9) | 0.0022 (9) | −0.0018 (9) |
S4' | 0.018 (2) | 0.0314 (14) | 0.0198 (16) | 0.0093 (14) | −0.0012 (15) | −0.0003 (11) |
C25' | 0.030 (8) | 0.033 (11) | 0.033 (11) | 0.010 (7) | −0.019 (7) | 0.006 (6) |
C26' | 0.032 (7) | 0.045 (8) | 0.017 (8) | 0.009 (6) | −0.002 (6) | −0.012 (7) |
C27' | 0.037 (9) | 0.009 (5) | 0.035 (11) | −0.003 (5) | −0.009 (6) | −0.005 (5) |
C28' | 0.0202 (13) | 0.032 (4) | 0.0197 (18) | 0.0102 (15) | −0.0070 (12) | −0.007 (2) |
F4' | 0.027 (4) | 0.051 (9) | 0.032 (4) | 0.010 (3) | −0.003 (3) | −0.004 (4) |
F5' | 0.030 (8) | 0.165 (9) | 0.061 (6) | −0.020 (4) | −0.003 (4) | −0.081 (7) |
F6' | 0.108 (2) | 0.084 (2) | 0.0825 (19) | −0.0538 (18) | −0.0709 (19) | 0.0522 (16) |
F10A | 0.035 (3) | 0.086 (7) | 0.0133 (11) | 0.030 (5) | 0.0074 (11) | 0.016 (2) |
F11A | 0.019 (3) | 0.0490 (19) | 0.019 (3) | 0.0160 (17) | −0.0099 (17) | −0.0033 (16) |
F12A | 0.0167 (19) | 0.061 (4) | 0.060 (3) | −0.011 (2) | 0.0093 (17) | −0.018 (3) |
F10B | 0.0349 (5) | 0.0858 (5) | 0.0133 (4) | 0.0300 (6) | 0.0074 (4) | 0.0159 (6) |
F11B | 0.019 (3) | 0.0490 (19) | 0.019 (3) | 0.0160 (17) | −0.0099 (17) | −0.0033 (16) |
F12B | 0.0167 (19) | 0.061 (4) | 0.060 (3) | −0.011 (2) | 0.0093 (17) | −0.018 (3) |
F10C | 0.035 (3) | 0.086 (7) | 0.0133 (11) | 0.030 (5) | 0.0074 (11) | 0.016 (2) |
F11C | 0.019 (3) | 0.0490 (19) | 0.019 (3) | 0.0160 (17) | −0.0099 (17) | −0.0033 (16) |
F12C | 0.0167 (19) | 0.061 (4) | 0.060 (3) | −0.011 (2) | 0.0093 (17) | −0.018 (3) |
Eu—O2 | 2.3594 (18) | C23—C24 | 1.537 (3) |
Eu—O3 | 2.3639 (18) | C29—C30 | 1.419 (4) |
Eu—O8 | 2.3642 (17) | C29—C28 | 1.4700 (19) |
Eu—O5 | 2.3810 (18) | C29—C28' | 1.470 (2) |
Eu—O7 | 2.3885 (19) | C30—C31 | 1.381 (3) |
Eu—O1 | 2.3935 (18) | C30—H30 | 0.9500 |
Eu—O4 | 2.4135 (18) | C31—C32 | 1.537 (3) |
Eu—O6 | 2.4896 (18) | C32—F12B | 1.327 (3) |
S1—C1 | 1.703 (4) | C32—F11A | 1.327 (3) |
S1—C4 | 1.708 (3) | C32—F10A | 1.328 (3) |
S2—C9 | 1.655 (4) | C32—F12C | 1.330 (3) |
S2—C12 | 1.704 (4) | C32—F10 | 1.330 (3) |
F1—C8 | 1.330 (2) | C32—F11B | 1.330 (3) |
F2—C8 | 1.327 (2) | C32—F10C | 1.331 (3) |
F3—C8 | 1.331 (3) | C32—F11C | 1.331 (3) |
F7—C24 | 1.335 (2) | C32—F12A | 1.333 (3) |
F8—C24 | 1.335 (2) | C32—F12 | 1.334 (3) |
F9—C24 | 1.331 (2) | C32—F10B | 1.334 (3) |
O1—C5 | 1.250 (3) | C32—F11 | 1.344 (3) |
O2—C7 | 1.264 (3) | C33—C34 | 1.356 (4) |
O3—C13 | 1.254 (3) | C33—C37 | 1.419 (4) |
O4—C15 | 1.265 (3) | C33—H33 | 0.9500 |
O5—C21 | 1.251 (3) | C34—H34 | 0.9500 |
O6—C23 | 1.271 (3) | C35—C36 | 1.360 (4) |
O7—C29 | 1.258 (3) | C35—H35 | 0.9500 |
O8—C31 | 1.262 (3) | C36—C37 | 1.420 (4) |
N1—C35 | 1.343 (4) | C36—H36 | 0.9500 |
N1—C34 | 1.348 (4) | C38—H38A | 0.9800 |
N1—H1N | 0.87 (4) | C38—H38B | 0.9800 |
N2—C37 | 1.335 (3) | C38—H38C | 0.9800 |
N2—C38 | 1.453 (4) | C39—H39A | 0.9800 |
N2—C39 | 1.462 (4) | C39—H39B | 0.9800 |
C1—C2 | 1.354 (6) | C39—H39C | 0.9800 |
C1—H1 | 0.9500 | S3—C17 | 1.700 (3) |
C2—C3 | 1.374 (5) | S3—C20 | 1.703 (2) |
C2—H2 | 0.9500 | C17—C18 | 1.369 (3) |
C3—C4 | 1.415 (4) | C17—H17 | 0.9500 |
C3—H3 | 0.9500 | C18—C19 | 1.429 (3) |
C4—C5 | 1.460 (4) | C18—H18 | 0.9500 |
C5—C6 | 1.422 (4) | C19—C20 | 1.416 (3) |
C6—C7 | 1.368 (4) | C19—H19 | 0.9500 |
C6—H6 | 0.9500 | S4—C25 | 1.701 (3) |
C7—C8 | 1.539 (4) | S4—C28 | 1.702 (3) |
C9—C10 | 1.346 (7) | C25—C26 | 1.369 (3) |
C9—H9 | 0.9500 | C25—H25 | 0.9500 |
C10—C11 | 1.457 (6) | C26—C27 | 1.429 (3) |
C10—H10 | 0.9500 | C26—H26 | 0.9500 |
C11—C12 | 1.507 (4) | C27—C28 | 1.418 (3) |
C11—H11 | 0.9500 | C27—H27 | 0.9500 |
C12—C13 | 1.468 (4) | S3'—C17' | 1.699 (3) |
C13—C14 | 1.407 (4) | C17'—C18' | 1.369 (3) |
C14—C15 | 1.383 (4) | C17'—H17' | 0.9500 |
C14—H14 | 0.9500 | C18'—C19' | 1.430 (3) |
C15—C16 | 1.539 (4) | C18'—H18' | 0.9500 |
C16—F4' | 1.328 (3) | C19'—H19' | 0.9500 |
C16—F4 | 1.329 (3) | S4'—C28' | 1.699 (3) |
C16—F5 | 1.329 (3) | S4'—C25' | 1.699 (3) |
C16—F5' | 1.329 (3) | C25'—C26' | 1.369 (3) |
C16—F6' | 1.330 (3) | C25'—H25' | 0.9500 |
C16—F6 | 1.330 (3) | C26'—C27' | 1.430 (3) |
C21—C22 | 1.422 (3) | C26'—H26' | 0.9500 |
C21—C20 | 1.4694 (13) | C27'—C28' | 1.421 (3) |
C22—C23 | 1.376 (3) | C27'—H27' | 0.9500 |
C22—H22 | 0.9500 | ||
O2—Eu—O3 | 71.96 (7) | F12B—C32—F11A | 28.5 (10) |
O2—Eu—O8 | 146.80 (6) | F12B—C32—F10A | 124.8 (11) |
O3—Eu—O8 | 122.74 (6) | F11A—C32—F10A | 106.4 (7) |
O2—Eu—O5 | 108.35 (7) | F12B—C32—F12C | 30.2 (13) |
O3—Eu—O5 | 153.38 (6) | F11A—C32—F12C | 58.6 (12) |
O8—Eu—O5 | 72.17 (6) | F10A—C32—F12C | 133.7 (13) |
O2—Eu—O7 | 89.32 (7) | F12B—C32—F10 | 127.5 (9) |
O3—Eu—O7 | 71.24 (7) | F11A—C32—F10 | 119.3 (5) |
O8—Eu—O7 | 71.04 (6) | F10A—C32—F10 | 21.9 (8) |
O5—Eu—O7 | 134.78 (6) | F12C—C32—F10 | 122.5 (13) |
O2—Eu—O1 | 71.34 (6) | F12B—C32—F11B | 108.1 (7) |
O3—Eu—O1 | 130.78 (7) | F11A—C32—F11B | 84.7 (7) |
O8—Eu—O1 | 78.07 (6) | F10A—C32—F11B | 24.2 (9) |
O5—Eu—O1 | 70.77 (7) | F12C—C32—F11B | 128.7 (13) |
O7—Eu—O1 | 76.67 (7) | F10—C32—F11B | 45.1 (8) |
O2—Eu—O4 | 131.75 (6) | F12B—C32—F10C | 122.4 (13) |
O3—Eu—O4 | 70.25 (7) | F11A—C32—F10C | 131.4 (10) |
O8—Eu—O4 | 80.37 (6) | F10A—C32—F10C | 51.1 (12) |
O5—Eu—O4 | 93.22 (7) | F12C—C32—F10C | 103.2 (16) |
O7—Eu—O4 | 105.52 (7) | F10—C32—F10C | 29.2 (10) |
O1—Eu—O4 | 156.25 (6) | F11B—C32—F10C | 73.8 (12) |
O2—Eu—O6 | 74.75 (6) | F12B—C32—F11C | 73.6 (12) |
O3—Eu—O6 | 85.02 (6) | F11A—C32—F11C | 45.8 (8) |
O8—Eu—O6 | 131.75 (6) | F10A—C32—F11C | 66.7 (9) |
O5—Eu—O6 | 69.94 (6) | F12C—C32—F11C | 102.6 (12) |
O7—Eu—O6 | 154.71 (6) | F10—C32—F11C | 86.4 (7) |
O1—Eu—O6 | 115.04 (7) | F11B—C32—F11C | 42.6 (10) |
O4—Eu—O6 | 73.15 (6) | F10C—C32—F11C | 113.1 (11) |
C1—S1—C4 | 91.91 (16) | F12B—C32—F12A | 81.3 (9) |
C9—S2—C12 | 92.7 (2) | F11A—C32—F12A | 107.9 (5) |
C5—O1—Eu | 137.88 (18) | F10A—C32—F12A | 105.8 (7) |
C7—O2—Eu | 134.49 (17) | F12C—C32—F12A | 52.4 (13) |
C13—O3—Eu | 140.66 (18) | F10—C32—F12A | 84.6 (7) |
C15—O4—Eu | 132.68 (17) | F11B—C32—F12A | 123.9 (9) |
C21—O5—Eu | 139.92 (15) | F10C—C32—F12A | 56.7 (13) |
C23—O6—Eu | 132.25 (15) | F11C—C32—F12A | 139.7 (8) |
C29—O7—Eu | 136.81 (16) | F12B—C32—F12 | 50.8 (10) |
C31—O8—Eu | 132.00 (16) | F11A—C32—F12 | 79.2 (5) |
C35—N1—C34 | 120.7 (2) | F10A—C32—F12 | 132.2 (9) |
C35—N1—H1N | 115 (2) | F12C—C32—F12 | 20.7 (11) |
C34—N1—H1N | 124 (2) | F10—C32—F12 | 114.1 (5) |
C37—N2—C38 | 120.5 (3) | F11B—C32—F12 | 138.8 (8) |
C37—N2—C39 | 120.4 (2) | F10C—C32—F12 | 88.9 (12) |
C38—N2—C39 | 119.0 (2) | F11C—C32—F12 | 122.5 (7) |
C2—C1—S1 | 112.2 (3) | F12A—C32—F12 | 33.6 (6) |
C2—C1—H1 | 123.9 | F12B—C32—F10B | 105.7 (8) |
S1—C1—H1 | 123.9 | F11A—C32—F10B | 129.0 (9) |
C1—C2—C3 | 113.5 (3) | F10A—C32—F10B | 83.4 (9) |
C1—C2—H2 | 123.2 | F12C—C32—F10B | 78.4 (15) |
C3—C2—H2 | 123.2 | F10—C32—F10B | 61.4 (11) |
C2—C3—C4 | 112.3 (3) | F11B—C32—F10B | 105.4 (8) |
C2—C3—H3 | 123.9 | F10C—C32—F10B | 32.3 (11) |
C4—C3—H3 | 123.9 | F11C—C32—F10B | 139.5 (11) |
C3—C4—C5 | 130.5 (3) | F12A—C32—F10B | 26.5 (9) |
C3—C4—S1 | 110.1 (2) | F12—C32—F10B | 60.2 (11) |
C5—C4—S1 | 119.4 (2) | F12B—C32—F11 | 53.3 (11) |
O1—C5—C6 | 123.8 (2) | F11A—C32—F11 | 24.9 (4) |
O1—C5—C4 | 117.6 (2) | F10A—C32—F11 | 87.4 (7) |
C6—C5—C4 | 118.6 (2) | F12C—C32—F11 | 83.3 (12) |
C7—C6—C5 | 122.0 (2) | F10—C32—F11 | 105.4 (4) |
C7—C6—H6 | 119.0 | F11B—C32—F11 | 63.7 (8) |
C5—C6—H6 | 119.0 | F10C—C32—F11 | 128.3 (10) |
O2—C7—C6 | 128.8 (3) | F11C—C32—F11 | 21.8 (6) |
O2—C7—C8 | 112.5 (2) | F12A—C32—F11 | 129.8 (5) |
C6—C7—C8 | 118.7 (2) | F12—C32—F11 | 103.9 (4) |
F2—C8—F1 | 106.7 (2) | F10B—C32—F11 | 143.9 (8) |
F2—C8—F3 | 107.5 (3) | C34—C33—C37 | 120.2 (2) |
F1—C8—F3 | 106.3 (3) | C34—C33—H33 | 119.9 |
F2—C8—C7 | 113.8 (2) | C37—C33—H33 | 119.9 |
F1—C8—C7 | 110.9 (2) | N1—C34—C33 | 121.1 (2) |
F3—C8—C7 | 111.3 (2) | N1—C34—H34 | 119.5 |
C10—C9—S2 | 113.7 (3) | C33—C34—H34 | 119.5 |
C10—C9—H9 | 123.2 | N1—C35—C36 | 121.5 (3) |
S2—C9—H9 | 123.2 | N1—C35—H35 | 119.2 |
C9—C10—C11 | 117.0 (3) | C36—C35—H35 | 119.2 |
C9—C10—H10 | 121.5 | C35—C36—C37 | 119.8 (3) |
C11—C10—H10 | 121.5 | C35—C36—H36 | 120.1 |
C10—C11—C12 | 103.4 (3) | C37—C36—H36 | 120.1 |
C10—C11—H11 | 128.3 | N2—C37—C33 | 121.8 (2) |
C12—C11—H11 | 128.3 | N2—C37—C36 | 121.5 (3) |
C13—C12—C11 | 128.6 (3) | C33—C37—C36 | 116.7 (2) |
C13—C12—S2 | 118.3 (2) | N2—C38—H38A | 109.5 |
C11—C12—S2 | 113.1 (2) | N2—C38—H38B | 109.5 |
O3—C13—C14 | 123.2 (2) | H38A—C38—H38B | 109.5 |
O3—C13—C12 | 116.0 (3) | N2—C38—H38C | 109.5 |
C14—C13—C12 | 120.7 (2) | H38A—C38—H38C | 109.5 |
C15—C14—C13 | 121.6 (3) | H38B—C38—H38C | 109.5 |
C15—C14—H14 | 119.2 | N2—C39—H39A | 109.5 |
C13—C14—H14 | 119.2 | N2—C39—H39B | 109.5 |
O4—C15—C14 | 129.0 (3) | H39A—C39—H39B | 109.5 |
O4—C15—C16 | 113.4 (2) | N2—C39—H39C | 109.5 |
C14—C15—C16 | 117.5 (2) | H39A—C39—H39C | 109.5 |
F4'—C16—F4 | 11.6 (19) | H39B—C39—H39C | 109.5 |
F4'—C16—F5 | 110 (2) | C17—S3—C20 | 93.2 (4) |
F4—C16—F5 | 105 (2) | C18—C17—S3 | 111.6 (7) |
F4'—C16—F5' | 110 (2) | C18—C17—H17 | 124.2 |
F4—C16—F5' | 101 (2) | S3—C17—H17 | 124.2 |
F5—C16—F5' | 18.4 (18) | C17—C18—C19 | 113.2 (9) |
F4'—C16—F6' | 98 (8) | C17—C18—H18 | 123.4 |
F4—C16—F6' | 109 (8) | C19—C18—H18 | 123.4 |
F5—C16—F6' | 98 (9) | C20—C19—C18 | 110.6 (7) |
F5'—C16—F6' | 116 (9) | C20—C19—H19 | 124.7 |
F4'—C16—F6 | 98 (8) | C18—C19—H19 | 124.7 |
F4—C16—F6 | 109 (8) | C19—C20—C21 | 128.6 (5) |
F5—C16—F6 | 98 (9) | C19—C20—S3 | 111.0 (5) |
F5'—C16—F6 | 116 (9) | C21—C20—S3 | 120.33 (18) |
F6'—C16—F6 | 0 (10) | C25—S4—C28 | 89.6 (5) |
F4'—C16—C15 | 114.6 (9) | C26—C25—S4 | 118.8 (11) |
F4—C16—C15 | 111.1 (8) | C26—C25—H25 | 120.6 |
F5—C16—C15 | 121.2 (11) | S4—C25—H25 | 120.6 |
F5'—C16—C15 | 107.8 (10) | C25—C26—C27 | 104.8 (13) |
F6'—C16—C15 | 111 (7) | C25—C26—H26 | 127.6 |
F6—C16—C15 | 111 (7) | C27—C26—H26 | 127.6 |
O5—C21—C22 | 123.66 (19) | C28—C27—C26 | 115.5 (10) |
O5—C21—C20 | 117.0 (2) | C28—C27—H27 | 122.2 |
C22—C21—C20 | 119.3 (2) | C26—C27—H27 | 122.2 |
C23—C22—C21 | 122.3 (2) | C27—C28—C29 | 131.7 (6) |
C23—C22—H22 | 118.9 | C27—C28—S4 | 110.4 (5) |
C21—C22—H22 | 118.9 | C29—C28—S4 | 117.8 (3) |
O6—C23—C22 | 129.5 (2) | C18'—C17'—S3' | 110.3 (15) |
O6—C23—C24 | 113.7 (2) | C18'—C17'—H17' | 124.9 |
C22—C23—C24 | 116.8 (2) | S3'—C17'—H17' | 124.9 |
F9—C24—F7 | 107.9 (2) | C17'—C18'—C19' | 115 (2) |
F9—C24—F8 | 106.9 (2) | C17'—C18'—H18' | 122.4 |
F7—C24—F8 | 106.9 (2) | C19'—C18'—H18' | 122.4 |
F9—C24—C23 | 113.80 (19) | C18'—C19'—H19' | 127.2 |
F7—C24—C23 | 110.72 (19) | C28'—S4'—C25' | 85.9 (10) |
F8—C24—C23 | 110.3 (2) | C26'—C25'—S4' | 123 (2) |
O7—C29—C30 | 123.9 (2) | C26'—C25'—H25' | 118.6 |
O7—C29—C28 | 116.9 (5) | S4'—C25'—H25' | 118.6 |
C30—C29—C28 | 119.2 (5) | C25'—C26'—C27' | 101 (2) |
O7—C29—C28' | 117.2 (10) | C25'—C26'—H26' | 129.7 |
C30—C29—C28' | 118.9 (10) | C27'—C26'—H26' | 129.7 |
C28—C29—C28' | 3 (6) | C28'—C27'—C26' | 116 (2) |
C31—C30—C29 | 121.6 (2) | C28'—C27'—H27' | 122.1 |
C31—C30—H30 | 119.2 | C26'—C27'—H27' | 122.1 |
C29—C30—H30 | 119.2 | C27'—C28'—C29 | 125.5 (12) |
O8—C31—C30 | 128.5 (2) | C27'—C28'—S4' | 112.1 (13) |
O8—C31—C32 | 113.6 (2) | C29—C28'—S4' | 121.9 (4) |
C30—C31—C32 | 117.8 (2) | ||
O2—Eu—O1—C5 | 1.7 (3) | S2—C12—C13—C14 | −178.4 (2) |
O3—Eu—O1—C5 | −42.0 (3) | O3—C13—C14—C15 | 0.4 (4) |
O8—Eu—O1—C5 | −165.2 (3) | C12—C13—C14—C15 | 177.9 (3) |
O5—Eu—O1—C5 | 119.8 (3) | Eu—O4—C15—C14 | −21.0 (5) |
O7—Eu—O1—C5 | −92.1 (3) | Eu—O4—C15—C16 | 155.28 (17) |
O4—Eu—O1—C5 | 169.6 (2) | C13—C14—C15—O4 | 8.0 (5) |
O6—Eu—O1—C5 | 64.1 (3) | C13—C14—C15—C16 | −168.1 (2) |
O3—Eu—O2—C7 | 133.8 (3) | O4—C15—C16—F4' | 45.6 (11) |
O8—Eu—O2—C7 | 11.0 (3) | C14—C15—C16—F4' | −137.7 (11) |
O5—Eu—O2—C7 | −74.3 (3) | O4—C15—C16—F4 | 57.6 (10) |
O7—Eu—O2—C7 | 63.3 (3) | C14—C15—C16—F4 | −125.7 (11) |
O1—Eu—O2—C7 | −12.8 (3) | O4—C15—C16—F5 | −178 (2) |
O4—Eu—O2—C7 | 173.7 (2) | C14—C15—C16—F5 | −2 (2) |
O6—Eu—O2—C7 | −136.5 (3) | O4—C15—C16—F5' | 167.9 (18) |
O2—Eu—O3—C13 | 138.9 (3) | C14—C15—C16—F5' | −15.4 (18) |
O8—Eu—O3—C13 | −74.3 (3) | O4—C15—C16—F6' | −64 (9) |
O5—Eu—O3—C13 | 43.8 (4) | C14—C15—C16—F6' | 113 (9) |
O7—Eu—O3—C13 | −125.5 (3) | O4—C15—C16—F6 | −64 (9) |
O1—Eu—O3—C13 | −177.6 (3) | C14—C15—C16—F6 | 113 (9) |
O4—Eu—O3—C13 | −10.5 (3) | Eu—O5—C21—C22 | −18.8 (4) |
O6—Eu—O3—C13 | 63.4 (3) | Eu—O5—C21—C20 | 161.13 (18) |
O2—Eu—O4—C15 | −23.4 (3) | O5—C21—C22—C23 | 2.3 (4) |
O3—Eu—O4—C15 | 17.0 (2) | C20—C21—C22—C23 | −177.6 (2) |
O8—Eu—O4—C15 | 147.1 (3) | Eu—O6—C23—C22 | 4.7 (4) |
O5—Eu—O4—C15 | −141.6 (2) | Eu—O6—C23—C24 | −175.31 (14) |
O7—Eu—O4—C15 | 80.0 (3) | C21—C22—C23—O6 | 3.5 (4) |
O1—Eu—O4—C15 | 172.1 (2) | C21—C22—C23—C24 | −176.5 (2) |
O6—Eu—O4—C15 | −73.7 (2) | O6—C23—C24—F9 | −172.8 (2) |
O2—Eu—O5—C21 | −46.7 (3) | C22—C23—C24—F9 | 7.1 (3) |
O3—Eu—O5—C21 | 39.5 (3) | O6—C23—C24—F7 | 65.4 (3) |
O8—Eu—O5—C21 | 168.2 (3) | C22—C23—C24—F7 | −114.6 (2) |
O7—Eu—O5—C21 | −154.9 (2) | O6—C23—C24—F8 | −52.7 (3) |
O1—Eu—O5—C21 | −108.5 (3) | C22—C23—C24—F8 | 127.3 (2) |
O4—Eu—O5—C21 | 89.4 (3) | Eu—O7—C29—C30 | −6.9 (4) |
O6—Eu—O5—C21 | 18.7 (3) | Eu—O7—C29—C28 | 174 (2) |
O2—Eu—O6—C23 | 106.0 (2) | Eu—O7—C29—C28' | 171 (4) |
O3—Eu—O6—C23 | 178.7 (2) | O7—C29—C30—C31 | −7.3 (4) |
O8—Eu—O6—C23 | −50.8 (2) | C28—C29—C30—C31 | 172 (2) |
O5—Eu—O6—C23 | −10.5 (2) | C28'—C29—C30—C31 | 175 (4) |
O7—Eu—O6—C23 | 158.7 (2) | Eu—O8—C31—C30 | 27.7 (4) |
O1—Eu—O6—C23 | 45.6 (2) | Eu—O8—C31—C32 | −154.24 (15) |
O4—Eu—O6—C23 | −110.5 (2) | C29—C30—C31—O8 | −3.4 (4) |
O2—Eu—O7—C29 | −134.9 (3) | C29—C30—C31—C32 | 178.7 (2) |
O3—Eu—O7—C29 | 154.0 (3) | C35—N1—C34—C33 | 0.2 (4) |
O8—Eu—O7—C29 | 17.8 (2) | C37—C33—C34—N1 | −0.8 (4) |
O5—Eu—O7—C29 | −19.3 (3) | C34—N1—C35—C36 | 0.6 (4) |
O1—Eu—O7—C29 | −63.9 (3) | N1—C35—C36—C37 | −0.6 (4) |
O4—Eu—O7—C29 | 91.7 (3) | C38—N2—C37—C33 | −1.6 (4) |
O6—Eu—O7—C29 | 175.0 (2) | C39—N2—C37—C33 | −179.2 (3) |
O2—Eu—O8—C31 | 29.9 (3) | C38—N2—C37—C36 | 178.3 (3) |
O3—Eu—O8—C31 | −78.2 (2) | C39—N2—C37—C36 | 0.7 (4) |
O5—Eu—O8—C31 | 126.3 (2) | C34—C33—C37—N2 | −179.3 (3) |
O7—Eu—O8—C31 | −26.9 (2) | C34—C33—C37—C36 | 0.8 (4) |
O1—Eu—O8—C31 | 52.9 (2) | C35—C36—C37—N2 | −180.0 (3) |
O4—Eu—O8—C31 | −137.1 (2) | C35—C36—C37—C33 | −0.1 (4) |
O6—Eu—O8—C31 | 165.9 (2) | C20—S3—C17—C18 | 4.1 (15) |
C4—S1—C1—C2 | 0.2 (3) | S3—C17—C18—C19 | −7 (2) |
S1—C1—C2—C3 | −0.3 (5) | C17—C18—C19—C20 | 7 (2) |
C1—C2—C3—C4 | 0.2 (5) | C18—C19—C20—C21 | 176.0 (9) |
C2—C3—C4—C5 | −177.2 (3) | C18—C19—C20—S3 | −3.8 (15) |
C2—C3—C4—S1 | 0.0 (4) | O5—C21—C20—C19 | 174.5 (10) |
C1—S1—C4—C3 | −0.1 (2) | C22—C21—C20—C19 | −5.6 (10) |
C1—S1—C4—C5 | 177.4 (2) | O5—C21—C20—S3 | −5.7 (3) |
Eu—O1—C5—C6 | 6.7 (4) | C22—C21—C20—S3 | 174.2 (2) |
Eu—O1—C5—C4 | −174.05 (19) | C17—S3—C20—C19 | −0.1 (11) |
C3—C4—C5—O1 | 177.2 (3) | C17—S3—C20—C21 | −179.9 (7) |
S1—C4—C5—O1 | 0.3 (3) | C28—S4—C25—C26 | −7 (2) |
C3—C4—C5—C6 | −3.4 (4) | S4—C25—C26—C27 | 10 (2) |
S1—C4—C5—C6 | 179.6 (2) | C25—C26—C27—C28 | −9 (3) |
O1—C5—C6—C7 | −8.3 (5) | C26—C27—C28—C29 | −178 (4) |
C4—C5—C6—C7 | 172.4 (3) | C26—C27—C28—S4 | 4 (4) |
Eu—O2—C7—C6 | 16.2 (5) | O7—C29—C28—C27 | 171 (4) |
Eu—O2—C7—C8 | −161.58 (18) | C30—C29—C28—C27 | −8 (6) |
C5—C6—C7—O2 | −2.8 (5) | C28'—C29—C28—C27 | −92 (22) |
C5—C6—C7—C8 | 174.8 (3) | O7—C29—C28—S4 | −11 (4) |
O2—C7—C8—F2 | −171.5 (3) | C30—C29—C28—S4 | 170 (2) |
C6—C7—C8—F2 | 10.5 (4) | C28'—C29—C28—S4 | 86 (15) |
O2—C7—C8—F1 | −51.2 (3) | C25—S4—C28—C27 | 1 (3) |
C6—C7—C8—F1 | 130.8 (3) | C25—S4—C28—C29 | −177 (3) |
O2—C7—C8—F3 | 66.9 (3) | S3'—C17'—C18'—C19' | 18 (4) |
C6—C7—C8—F3 | −111.1 (3) | C28'—S4'—C25'—C26' | 16 (5) |
C12—S2—C9—C10 | 0.8 (4) | S4'—C25'—C26'—C27' | −18 (4) |
S2—C9—C10—C11 | 1.2 (5) | C25'—C26'—C27'—C28' | 10 (6) |
C9—C10—C11—C12 | −2.7 (5) | C26'—C27'—C28'—C29 | 171 (6) |
C10—C11—C12—C13 | −176.1 (3) | C26'—C27'—C28'—S4' | 0 (8) |
C10—C11—C12—S2 | 3.2 (3) | O7—C29—C28'—C27' | −5 (10) |
C9—S2—C12—C13 | 177.0 (3) | C30—C29—C28'—C27' | 173 (6) |
C9—S2—C12—C11 | −2.5 (3) | C28—C29—C28'—C27' | −89 (24) |
Eu—O3—C13—C14 | 5.4 (4) | O7—C29—C28'—S4' | 166 (5) |
Eu—O3—C13—C12 | −172.08 (19) | C30—C29—C28'—S4' | −16 (9) |
C11—C12—C13—O3 | 178.5 (3) | C28—C29—C28'—S4' | 81 (12) |
S2—C12—C13—O3 | −0.8 (3) | C25'—S4'—C28'—C27' | −8 (6) |
C11—C12—C13—C14 | 0.9 (4) | C25'—S4'—C28'—C29 | −179 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O6i | 0.87 (4) | 1.96 (4) | 2.814 (3) | 168 (4) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)[Eu(C8H4F3O2S)4] |
Mr | 1159.83 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 93 |
a, b, c (Å) | 20.0202 (4), 18.9160 (3), 23.4108 (4) |
V (Å3) | 8865.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.62 × 0.45 × 0.23 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Numerical (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.418, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 82834, 10137, 9604 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.085, 1.00 |
No. of reflections | 10137 |
No. of parameters | 725 |
No. of restraints | 76 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0426P)2 + 19.8P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.29, −1.10 |
Computer programs: RAPID-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O6i | 0.87 (4) | 1.96 (4) | 2.814 (3) | 168 (4) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
The structure of the title complex, [DMAP][Eu(TTA)4] (I), Fig. 1, shows the trivalent Eu cation to be 8-coordinated by eight O atoms derived from four chelating β-diketonate ligands. The coordination polyhedron can be best described as a distorted tetragonal antiprism in which the square planes are defined by the O1, O2, O5 & O6 atoms and the atoms O3, O4, O7 & O8. The 4-dimethylaminopyridinium cation forms a N—H···O hydrogen bond to the O6 atom (Table 1). Complex (I) has intensive photoluminescence (PL) at room temperature. The corresponding 4-aminopyridinium complex, [4-aminopyridinium][Eu(TTA)4] has mechanoluminescence (ML) properties (Chen et al., 2001), which was attributed to the disorder in the thienyl rings and CF3 groups (Sweeting & Rheingold, 1987). However, (I) also has disorder in the thienyl rings and CF3 groups (see Experimental) but does not exhibit ML.