Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103029470/av1158sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029470/av1158Isup2.hkl |
CCDC reference: 235313
LaCl3·6H2O (0.5 mmol), 2-fluorobenzoic acid (1.5 mmol) and 4,4'-bipyridine (0.5 mmol) were dissolved separately in appropriate amounts of ethanol. The ethanol solution of 2-fluorobenzoic acid was controlled to pH 6–7 with an aqueous solution of NaOH (2 mol dm−3), and then the ethanol solutions of 4,4'-bipyridine and LaCl3 were added dropwise. The mixture was heated under reflux with stirring for 2 h, and the resulting white minor precipitate was filtered off. Single crystals were obtained from the mother liquor after one month at room temperature.
H atoms were placed at calculated positions, with C—H distances of 0.93 Å and O—Hwater distance of 0.85 Å. Please check computer programs used.
Data collection: SMART (Bruker, 1997); cell refinement: SMART); data reduction: SAINT (Bruker, 1997; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Fig. 1. A view of complex (I), with the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level. |
[La(C7H4FO2)6(C10H8N2)2(H2O)2] | Z = 2 |
Mr = 730.42 | F(000) = 724 |
Triclinic, P1 | Dx = 1.698 Mg m−3 |
a = 9.746 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.780 (7) Å | Cell parameters from 986 reflections |
c = 13.315 (7) Å | θ = 3.2–28.0° |
α = 113.132 (9)° | µ = 1.57 mm−1 |
β = 104.763 (9)° | T = 293 K |
γ = 96.916 (9)° | Prism, white |
V = 1428.6 (13) Å3 | 0.20 × 0.18 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 6871 independent reflections |
Radiation source: fine-focus sealed tube | 5931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 28.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→13 |
Tmin = 0.728, Tmax = 0.834 | k = −15→16 |
13305 measured reflections | l = −17→16 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0392P)2] where P = (Fo2 + 2Fc2)/3 |
6871 reflections | (Δ/σ)max = 0.002 |
397 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
[La(C7H4FO2)6(C10H8N2)2(H2O)2] | γ = 96.916 (9)° |
Mr = 730.42 | V = 1428.6 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.746 (5) Å | Mo Kα radiation |
b = 12.780 (7) Å | µ = 1.57 mm−1 |
c = 13.315 (7) Å | T = 293 K |
α = 113.132 (9)° | 0.20 × 0.18 × 0.12 mm |
β = 104.763 (9)° |
Bruker SMART CCD area-detector diffractometer | 6871 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5931 reflections with I > 2σ(I) |
Tmin = 0.728, Tmax = 0.834 | Rint = 0.032 |
13305 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.77 e Å−3 |
6871 reflections | Δρmin = −1.02 e Å−3 |
397 parameters |
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 | ||
La1 | 0.270721 (16) | 0.462748 (14) | 0.474272 (14) | 0.01955 (6) | |
C1 | 0.5566 (3) | 0.7307 (3) | 0.5589 (3) | 0.0267 (6) | |
C2 | 0.4994 (3) | 0.8372 (3) | 0.5770 (3) | 0.0267 (6) | |
C3 | 0.5894 (4) | 0.9501 (3) | 0.6337 (3) | 0.0356 (8) | |
C4 | 0.5366 (4) | 1.0488 (3) | 0.6504 (4) | 0.0454 (9) | |
H4 | 0.6003 | 1.1232 | 0.6886 | 0.055* | |
C5 | 0.3877 (5) | 1.0351 (4) | 0.6096 (4) | 0.0504 (10) | |
H5 | 0.3500 | 1.1007 | 0.6201 | 0.061* | |
C6 | 0.2943 (4) | 0.9246 (4) | 0.5532 (4) | 0.0489 (10) | |
H6 | 0.1937 | 0.9157 | 0.5256 | 0.059* | |
C7 | 0.3493 (3) | 0.8275 (3) | 0.5378 (3) | 0.0374 (8) | |
H7 | 0.2849 | 0.7535 | 0.5002 | 0.045* | |
C8 | 0.5667 (3) | 0.4954 (3) | 0.7183 (3) | 0.0260 (6) | |
C9 | 0.5893 (3) | 0.4608 (3) | 0.8161 (3) | 0.0277 (7) | |
C10 | 0.7051 (4) | 0.5192 (4) | 0.9196 (3) | 0.0411 (9) | |
C11 | 0.7232 (5) | 0.4870 (4) | 1.0083 (4) | 0.0556 (11) | |
H11 | 0.8009 | 0.5294 | 1.0772 | 0.067* | |
C12 | 0.6252 (5) | 0.3915 (4) | 0.9941 (4) | 0.0574 (12) | |
H12 | 0.6376 | 0.3680 | 1.0530 | 0.069* | |
C13 | 0.5093 (5) | 0.3307 (4) | 0.8935 (4) | 0.0588 (12) | |
H13 | 0.4432 | 0.2659 | 0.8842 | 0.071* | |
C14 | 0.4903 (4) | 0.3657 (3) | 0.8054 (3) | 0.0422 (9) | |
H14 | 0.4101 | 0.3249 | 0.7381 | 0.051* | |
C15 | −0.0091 (3) | 0.6065 (3) | 0.4011 (3) | 0.0234 (6) | |
C16 | −0.0020 (3) | 0.6741 (3) | 0.3320 (3) | 0.0255 (6) | |
C17 | −0.0702 (4) | 0.7648 (3) | 0.3408 (3) | 0.0376 (8) | |
C18 | −0.0586 (5) | 0.8265 (4) | 0.2762 (4) | 0.0523 (11) | |
H18 | −0.1055 | 0.8869 | 0.2829 | 0.063* | |
C19 | 0.0215 (5) | 0.7987 (4) | 0.2027 (4) | 0.0499 (10) | |
H19 | 0.0292 | 0.8402 | 0.1598 | 0.060* | |
C20 | 0.0906 (4) | 0.7093 (4) | 0.1927 (3) | 0.0463 (9) | |
H20 | 0.1453 | 0.6905 | 0.1430 | 0.056* | |
C21 | 0.0791 (3) | 0.6470 (3) | 0.2561 (3) | 0.0332 (7) | |
H21 | 0.1258 | 0.5864 | 0.2482 | 0.040* | |
C22 | −0.0008 (4) | 0.2862 (3) | 0.1763 (3) | 0.0398 (8) | |
H22 | 0.0315 | 0.3567 | 0.1744 | 0.048* | |
C23 | −0.1093 (4) | 0.1992 (3) | 0.0790 (3) | 0.0421 (9) | |
H23 | −0.1483 | 0.2120 | 0.0146 | 0.050* | |
C24 | −0.1592 (4) | 0.0927 (3) | 0.0788 (3) | 0.0355 (8) | |
C25 | −0.0939 (4) | 0.0806 (3) | 0.1780 (4) | 0.0469 (10) | |
H25 | −0.1228 | 0.0106 | 0.1819 | 0.056* | |
C26 | 0.0135 (4) | 0.1721 (3) | 0.2707 (3) | 0.0444 (9) | |
H26 | 0.0559 | 0.1614 | 0.3358 | 0.053* | |
C27 | −0.5196 (4) | −0.0661 (4) | −0.1615 (3) | 0.0477 (10) | |
H27 | −0.5966 | −0.0469 | −0.2027 | 0.057* | |
C28 | −0.3986 (4) | 0.0242 (3) | −0.0806 (3) | 0.0422 (9) | |
H28 | −0.3953 | 0.1013 | −0.0689 | 0.051* | |
C29 | −0.2835 (4) | −0.0022 (3) | −0.0179 (3) | 0.0393 (8) | |
C30 | −0.2942 (5) | −0.1199 (4) | −0.0431 (4) | 0.0616 (13) | |
H30 | −0.2182 | −0.1426 | −0.0051 | 0.074* | |
C31 | −0.4198 (5) | −0.2026 (4) | −0.1256 (4) | 0.0678 (14) | |
H31 | −0.4254 | −0.2808 | −0.1412 | 0.081* | |
F1 | 0.7359 (2) | 0.9671 (2) | 0.6771 (3) | 0.0684 (8) | |
F2 | 0.8003 (3) | 0.6157 (3) | 0.9376 (2) | 0.0808 (10) | |
F3 | −0.1461 (3) | 0.8002 (3) | 0.4148 (3) | 0.0728 (8) | |
N1 | 0.0599 (3) | 0.2759 (2) | 0.2716 (2) | 0.0344 (6) | |
N2 | −0.5319 (4) | −0.1780 (3) | −0.1835 (3) | 0.0544 (9) | |
O1 | 0.4742 (3) | 0.63668 (19) | 0.5411 (2) | 0.0348 (5) | |
O2 | 0.6865 (2) | 0.7367 (2) | 0.5615 (2) | 0.0451 (7) | |
O3 | 0.4358 (2) | 0.4812 (2) | 0.6617 (2) | 0.0367 (6) | |
O4 | 0.6770 (2) | 0.5342 (2) | 0.69945 (19) | 0.0334 (5) | |
O5 | 0.0632 (2) | 0.5309 (2) | 0.3915 (2) | 0.0323 (5) | |
O6 | −0.0876 (2) | 0.6291 (2) | 0.4651 (2) | 0.0323 (5) | |
O7 | 0.2306 (2) | 0.6321 (2) | 0.6405 (2) | 0.0421 (6) | |
H7A | 0.2930 | 0.6952 | 0.6915 | 0.063* | |
H7B | 0.1487 | 0.6292 | 0.6521 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.01654 (8) | 0.02040 (9) | 0.02189 (9) | 0.00551 (6) | 0.00559 (6) | 0.00969 (7) |
C1 | 0.0306 (15) | 0.0216 (15) | 0.0230 (16) | 0.0047 (12) | 0.0033 (12) | 0.0089 (13) |
C2 | 0.0269 (14) | 0.0245 (16) | 0.0282 (16) | 0.0079 (12) | 0.0075 (12) | 0.0117 (13) |
C3 | 0.0313 (16) | 0.0267 (17) | 0.044 (2) | 0.0072 (13) | 0.0090 (14) | 0.0131 (15) |
C4 | 0.051 (2) | 0.0247 (18) | 0.054 (2) | 0.0108 (16) | 0.0135 (18) | 0.0133 (17) |
C5 | 0.059 (2) | 0.039 (2) | 0.057 (3) | 0.0292 (19) | 0.018 (2) | 0.022 (2) |
C6 | 0.0383 (19) | 0.049 (2) | 0.055 (3) | 0.0221 (18) | 0.0062 (17) | 0.021 (2) |
C7 | 0.0288 (16) | 0.0347 (19) | 0.040 (2) | 0.0079 (14) | 0.0034 (14) | 0.0125 (16) |
C8 | 0.0284 (14) | 0.0274 (16) | 0.0214 (15) | 0.0094 (12) | 0.0086 (12) | 0.0091 (13) |
C9 | 0.0293 (15) | 0.0324 (17) | 0.0234 (16) | 0.0127 (13) | 0.0103 (12) | 0.0118 (13) |
C10 | 0.0366 (18) | 0.052 (2) | 0.0305 (19) | 0.0040 (16) | 0.0062 (15) | 0.0192 (17) |
C11 | 0.055 (2) | 0.080 (3) | 0.031 (2) | 0.014 (2) | 0.0047 (18) | 0.030 (2) |
C12 | 0.076 (3) | 0.079 (3) | 0.049 (3) | 0.037 (3) | 0.031 (2) | 0.048 (3) |
C13 | 0.067 (3) | 0.060 (3) | 0.070 (3) | 0.015 (2) | 0.029 (2) | 0.044 (3) |
C14 | 0.0419 (19) | 0.043 (2) | 0.043 (2) | 0.0046 (16) | 0.0116 (16) | 0.0242 (18) |
C15 | 0.0173 (12) | 0.0259 (16) | 0.0243 (15) | 0.0041 (11) | 0.0018 (11) | 0.0120 (13) |
C16 | 0.0228 (13) | 0.0277 (16) | 0.0269 (16) | 0.0053 (12) | 0.0033 (12) | 0.0164 (13) |
C17 | 0.0377 (17) | 0.043 (2) | 0.044 (2) | 0.0172 (16) | 0.0159 (16) | 0.0272 (18) |
C18 | 0.063 (3) | 0.052 (3) | 0.068 (3) | 0.027 (2) | 0.024 (2) | 0.047 (2) |
C19 | 0.058 (2) | 0.056 (3) | 0.051 (2) | 0.010 (2) | 0.016 (2) | 0.042 (2) |
C20 | 0.049 (2) | 0.058 (3) | 0.041 (2) | 0.0101 (19) | 0.0191 (18) | 0.029 (2) |
C21 | 0.0334 (16) | 0.0365 (19) | 0.0333 (18) | 0.0093 (14) | 0.0122 (14) | 0.0180 (15) |
C22 | 0.0447 (19) | 0.035 (2) | 0.0325 (19) | −0.0035 (15) | 0.0073 (15) | 0.0145 (16) |
C23 | 0.045 (2) | 0.044 (2) | 0.0290 (19) | −0.0007 (16) | 0.0064 (15) | 0.0156 (17) |
C24 | 0.0330 (16) | 0.0293 (18) | 0.0322 (19) | 0.0047 (14) | 0.0066 (14) | 0.0052 (15) |
C25 | 0.046 (2) | 0.0275 (19) | 0.053 (2) | 0.0004 (16) | −0.0043 (18) | 0.0187 (18) |
C26 | 0.0420 (19) | 0.034 (2) | 0.042 (2) | −0.0015 (16) | −0.0069 (16) | 0.0177 (17) |
C27 | 0.043 (2) | 0.055 (3) | 0.028 (2) | 0.0016 (18) | 0.0034 (16) | 0.0098 (18) |
C28 | 0.045 (2) | 0.043 (2) | 0.0271 (19) | 0.0019 (16) | 0.0065 (15) | 0.0100 (16) |
C29 | 0.0357 (17) | 0.0340 (19) | 0.0337 (19) | 0.0030 (15) | 0.0069 (14) | 0.0050 (15) |
C30 | 0.046 (2) | 0.037 (2) | 0.067 (3) | 0.0091 (18) | −0.002 (2) | 0.003 (2) |
C31 | 0.062 (3) | 0.027 (2) | 0.071 (3) | 0.0022 (19) | 0.003 (2) | −0.007 (2) |
F1 | 0.0302 (11) | 0.0322 (12) | 0.115 (2) | 0.0022 (9) | 0.0051 (12) | 0.0180 (13) |
F2 | 0.0689 (17) | 0.093 (2) | 0.0478 (16) | −0.0325 (15) | −0.0131 (13) | 0.0336 (15) |
F3 | 0.0911 (19) | 0.083 (2) | 0.102 (2) | 0.0613 (17) | 0.0645 (18) | 0.0655 (18) |
N1 | 0.0325 (14) | 0.0311 (16) | 0.0324 (16) | 0.0024 (12) | 0.0055 (12) | 0.0117 (13) |
N2 | 0.051 (2) | 0.049 (2) | 0.0313 (18) | −0.0053 (16) | 0.0070 (15) | −0.0042 (15) |
O1 | 0.0450 (13) | 0.0224 (11) | 0.0365 (13) | 0.0027 (10) | 0.0174 (11) | 0.0115 (10) |
O2 | 0.0258 (11) | 0.0282 (13) | 0.0698 (19) | 0.0080 (10) | 0.0063 (12) | 0.0159 (13) |
O3 | 0.0274 (11) | 0.0529 (16) | 0.0337 (13) | 0.0130 (10) | 0.0072 (10) | 0.0238 (12) |
O4 | 0.0283 (11) | 0.0468 (15) | 0.0255 (12) | 0.0056 (10) | 0.0085 (9) | 0.0178 (11) |
O5 | 0.0352 (11) | 0.0376 (13) | 0.0368 (13) | 0.0206 (10) | 0.0148 (10) | 0.0236 (11) |
O6 | 0.0308 (11) | 0.0343 (13) | 0.0435 (14) | 0.0128 (9) | 0.0202 (10) | 0.0226 (11) |
O7 | 0.0297 (11) | 0.0370 (14) | 0.0438 (15) | 0.0060 (10) | 0.0160 (11) | 0.0007 (11) |
La1—O5 | 2.471 (2) | C15—O6 | 1.260 (4) |
La1—O1 | 2.480 (2) | C15—C16 | 1.497 (4) |
La1—O6i | 2.488 (2) | C16—C17 | 1.384 (5) |
La1—O3 | 2.504 (2) | C16—C21 | 1.402 (4) |
La1—O4ii | 2.506 (2) | C17—F3 | 1.351 (4) |
La1—O2ii | 2.510 (3) | C17—C18 | 1.391 (5) |
La1—O7 | 2.572 (3) | C18—C19 | 1.370 (6) |
La1—N1 | 2.852 (3) | C18—H18 | 0.9300 |
La1—O1ii | 2.942 (3) | C19—C20 | 1.374 (6) |
La1—C1ii | 3.108 (3) | C19—H19 | 0.9300 |
C1—O2 | 1.250 (4) | C20—C21 | 1.383 (5) |
C1—O1 | 1.262 (4) | C20—H20 | 0.9300 |
C1—C2 | 1.489 (4) | C21—H21 | 0.9300 |
C1—La1ii | 3.108 (3) | C22—N1 | 1.321 (4) |
C2—C3 | 1.386 (4) | C22—C23 | 1.385 (5) |
C2—C7 | 1.395 (4) | C22—H22 | 0.9300 |
C3—F1 | 1.351 (4) | C23—C24 | 1.388 (5) |
C3—C4 | 1.378 (5) | C23—H23 | 0.9300 |
C4—C5 | 1.376 (5) | C24—C25 | 1.389 (5) |
C4—H4 | 0.9300 | C24—C29 | 1.490 (5) |
C5—C6 | 1.377 (6) | C25—C26 | 1.378 (5) |
C5—H5 | 0.9300 | C25—H25 | 0.9300 |
C6—C7 | 1.372 (5) | C26—N1 | 1.343 (5) |
C6—H6 | 0.9300 | C26—H26 | 0.9300 |
C7—H7 | 0.9300 | C27—N2 | 1.326 (6) |
C8—O4 | 1.253 (4) | C27—C28 | 1.389 (5) |
C8—O3 | 1.255 (4) | C27—H27 | 0.9300 |
C8—C9 | 1.507 (4) | C28—C29 | 1.381 (5) |
C9—C10 | 1.388 (5) | C28—H28 | 0.9300 |
C9—C14 | 1.392 (5) | C29—C30 | 1.390 (6) |
C10—F2 | 1.348 (4) | C30—C31 | 1.383 (6) |
C10—C11 | 1.375 (5) | C30—H30 | 0.9300 |
C11—C12 | 1.371 (6) | C31—N2 | 1.315 (6) |
C11—H11 | 0.9300 | C31—H31 | 0.9300 |
C12—C13 | 1.368 (6) | O1—La1ii | 2.942 (3) |
C12—H12 | 0.9300 | O2—La1ii | 2.510 (3) |
C13—C14 | 1.391 (6) | O4—La1ii | 2.506 (2) |
C13—H13 | 0.9300 | O6—La1i | 2.488 (2) |
C14—H14 | 0.9300 | O7—H7A | 0.8497 |
C15—O5 | 1.248 (4) | O7—H7B | 0.8506 |
O5—La1—O1 | 99.84 (9) | C12—C11—C10 | 119.2 (4) |
O5—La1—O6i | 83.20 (8) | C12—C11—H11 | 120.4 |
O1—La1—O6i | 143.64 (8) | C10—C11—H11 | 120.4 |
O5—La1—O3 | 142.72 (8) | C13—C12—C11 | 120.3 (4) |
O1—La1—O3 | 75.43 (8) | C13—C12—H12 | 119.9 |
O6i—La1—O3 | 80.53 (8) | C11—C12—H12 | 119.9 |
O5—La1—O4ii | 78.17 (8) | C12—C13—C14 | 120.0 (4) |
O1—La1—O4ii | 71.69 (8) | C12—C13—H13 | 120.0 |
O6i—La1—O4ii | 143.01 (8) | C14—C13—H13 | 120.0 |
O3—La1—O4ii | 131.59 (8) | C13—C14—C9 | 121.2 (4) |
O5—La1—O2ii | 133.53 (8) | C13—C14—H14 | 119.4 |
O1—La1—O2ii | 122.16 (8) | C9—C14—H14 | 119.4 |
O6i—La1—O2ii | 74.58 (8) | O5—C15—O6 | 124.1 (3) |
O3—La1—O2ii | 73.03 (9) | O5—C15—C16 | 117.8 (3) |
O4ii—La1—O2ii | 95.77 (9) | O6—C15—C16 | 118.1 (3) |
O5—La1—O7 | 71.51 (9) | C17—C16—C21 | 117.7 (3) |
O1—La1—O7 | 72.89 (8) | C17—C16—C15 | 123.0 (3) |
O6i—La1—O7 | 73.90 (8) | C21—C16—C15 | 119.3 (3) |
O3—La1—O7 | 71.81 (9) | F3—C17—C16 | 122.0 (3) |
O4ii—La1—O7 | 127.77 (9) | F3—C17—C18 | 117.0 (3) |
O2ii—La1—O7 | 135.76 (10) | C16—C17—C18 | 121.0 (3) |
O5—La1—N1 | 68.32 (9) | C19—C18—C17 | 120.3 (4) |
O1—La1—N1 | 142.92 (8) | C19—C18—H18 | 119.8 |
O6i—La1—N1 | 71.99 (9) | C17—C18—H18 | 119.8 |
O3—La1—N1 | 135.31 (9) | C18—C19—C20 | 119.8 (4) |
O4ii—La1—N1 | 71.49 (9) | C18—C19—H19 | 120.1 |
O2ii—La1—N1 | 66.16 (9) | C20—C19—H19 | 120.1 |
O7—La1—N1 | 129.38 (8) | C19—C20—C21 | 120.3 (4) |
O5—La1—O1ii | 151.13 (7) | C19—C20—H20 | 119.9 |
O1—La1—O1ii | 76.33 (9) | C21—C20—H20 | 119.9 |
O6i—La1—O1ii | 117.06 (7) | C20—C21—C16 | 120.9 (3) |
O3—La1—O1ii | 64.85 (8) | C20—C21—H21 | 119.5 |
O4ii—La1—O1ii | 73.46 (7) | C16—C21—H21 | 119.5 |
O2ii—La1—O1ii | 46.53 (7) | N1—C22—C23 | 124.5 (3) |
O7—La1—O1ii | 131.64 (7) | N1—C22—H22 | 117.8 |
N1—La1—O1ii | 97.23 (8) | C23—C22—H22 | 117.8 |
O5—La1—C1ii | 148.13 (8) | C22—C23—C24 | 119.2 (4) |
O1—La1—C1ii | 99.86 (9) | C22—C23—H23 | 120.4 |
O6i—La1—C1ii | 95.35 (9) | C24—C23—H23 | 120.4 |
O3—La1—C1ii | 67.12 (8) | C23—C24—C25 | 116.6 (3) |
O4ii—La1—C1ii | 84.57 (8) | C23—C24—C29 | 122.9 (3) |
O2ii—La1—C1ii | 22.67 (8) | C25—C24—C29 | 120.4 (3) |
O7—La1—C1ii | 138.75 (9) | C26—C25—C24 | 120.1 (3) |
N1—La1—C1ii | 80.90 (9) | C26—C25—H25 | 119.9 |
O1ii—La1—C1ii | 23.87 (7) | C24—C25—H25 | 119.9 |
O2—C1—O1 | 121.3 (3) | N1—C26—C25 | 123.3 (4) |
O2—C1—C2 | 118.7 (3) | N1—C26—H26 | 118.4 |
O1—C1—C2 | 120.0 (3) | C25—C26—H26 | 118.4 |
O2—C1—La1ii | 50.69 (16) | N2—C27—C28 | 123.9 (4) |
O1—C1—La1ii | 70.64 (18) | N2—C27—H27 | 118.0 |
C2—C1—La1ii | 169.4 (2) | C28—C27—H27 | 118.0 |
C3—C2—C7 | 116.4 (3) | C29—C28—C27 | 119.0 (4) |
C3—C2—C1 | 123.0 (3) | C29—C28—H28 | 120.5 |
C7—C2—C1 | 120.7 (3) | C27—C28—H28 | 120.5 |
F1—C3—C4 | 117.0 (3) | C28—C29—C30 | 117.2 (3) |
F1—C3—C2 | 120.0 (3) | C28—C29—C24 | 120.9 (3) |
C4—C3—C2 | 123.0 (3) | C30—C29—C24 | 121.7 (4) |
C5—C4—C3 | 118.7 (3) | C31—C30—C29 | 118.9 (4) |
C5—C4—H4 | 120.7 | C31—C30—H30 | 120.6 |
C3—C4—H4 | 120.7 | C29—C30—H30 | 120.6 |
C4—C5—C6 | 120.2 (4) | N2—C31—C30 | 124.5 (4) |
C4—C5—H5 | 119.9 | N2—C31—H31 | 117.8 |
C6—C5—H5 | 119.9 | C30—C31—H31 | 117.8 |
C7—C6—C5 | 120.1 (4) | C22—N1—C26 | 116.3 (3) |
C7—C6—H6 | 119.9 | C22—N1—La1 | 123.3 (2) |
C5—C6—H6 | 119.9 | C26—N1—La1 | 120.4 (2) |
C6—C7—C2 | 121.6 (3) | C31—N2—C27 | 116.5 (3) |
C6—C7—H7 | 119.2 | C1—O1—La1 | 166.6 (2) |
C2—C7—H7 | 119.2 | C1—O1—La1ii | 85.49 (19) |
O4—C8—O3 | 125.7 (3) | La1—O1—La1ii | 103.67 (9) |
O4—C8—C9 | 118.6 (3) | C1—O2—La1ii | 106.6 (2) |
O3—C8—C9 | 115.6 (3) | C8—O3—La1 | 143.8 (2) |
C10—C9—C14 | 116.5 (3) | C8—O4—La1ii | 135.3 (2) |
C10—C9—C8 | 123.7 (3) | C15—O5—La1 | 150.2 (2) |
C14—C9—C8 | 119.9 (3) | C15—O6—La1i | 143.4 (2) |
F2—C10—C11 | 117.8 (3) | La1—O7—H7A | 127.7 |
F2—C10—C9 | 119.3 (3) | La1—O7—H7B | 121.6 |
C11—C10—C9 | 122.8 (4) | H7A—O7—H7B | 110.6 |
O2—C1—C2—C3 | −22.4 (5) | O6i—La1—N1—C22 | 134.1 (3) |
O1—C1—C2—C3 | 157.8 (3) | O3—La1—N1—C22 | −171.0 (3) |
La1ii—C1—C2—C3 | −23.9 (13) | O4ii—La1—N1—C22 | −39.9 (3) |
O2—C1—C2—C7 | 158.3 (3) | O2ii—La1—N1—C22 | −145.2 (3) |
O1—C1—C2—C7 | −21.5 (5) | O7—La1—N1—C22 | 84.2 (3) |
La1ii—C1—C2—C7 | 156.8 (10) | O1ii—La1—N1—C22 | −109.8 (3) |
C7—C2—C3—F1 | 178.2 (3) | C1ii—La1—N1—C22 | −127.2 (3) |
C1—C2—C3—F1 | −1.1 (5) | O5—La1—N1—C26 | −133.3 (3) |
C7—C2—C3—C4 | −0.7 (5) | O1—La1—N1—C26 | 149.4 (3) |
C1—C2—C3—C4 | 180.0 (3) | O6i—La1—N1—C26 | −43.6 (3) |
F1—C3—C4—C5 | −178.6 (4) | O3—La1—N1—C26 | 11.3 (3) |
C2—C3—C4—C5 | 0.3 (6) | O4ii—La1—N1—C26 | 142.4 (3) |
C3—C4—C5—C6 | 0.0 (6) | O2ii—La1—N1—C26 | 37.1 (3) |
C4—C5—C6—C7 | 0.2 (7) | O7—La1—N1—C26 | −93.5 (3) |
C5—C6—C7—C2 | −0.6 (6) | O1ii—La1—N1—C26 | 72.6 (3) |
C3—C2—C7—C6 | 0.8 (5) | C1ii—La1—N1—C26 | 55.1 (3) |
C1—C2—C7—C6 | −179.8 (4) | C30—C31—N2—C27 | 1.5 (8) |
O4—C8—C9—C10 | 35.4 (5) | C28—C27—N2—C31 | −1.4 (6) |
O3—C8—C9—C10 | −145.2 (3) | O2—C1—O1—La1 | −133.9 (8) |
O4—C8—C9—C14 | −144.9 (3) | C2—C1—O1—La1 | 45.9 (11) |
O3—C8—C9—C14 | 34.6 (4) | La1ii—C1—O1—La1 | −133.7 (9) |
C14—C9—C10—F2 | −176.6 (4) | O2—C1—O1—La1ii | −0.1 (3) |
C8—C9—C10—F2 | 3.2 (6) | C2—C1—O1—La1ii | 179.7 (3) |
C14—C9—C10—C11 | −0.3 (6) | O5—La1—O1—C1 | −18.6 (9) |
C8—C9—C10—C11 | 179.4 (4) | O6i—La1—O1—C1 | −110.5 (9) |
F2—C10—C11—C12 | 177.8 (4) | O3—La1—O1—C1 | −160.7 (9) |
C9—C10—C11—C12 | 1.6 (7) | O4ii—La1—O1—C1 | 55.3 (9) |
C10—C11—C12—C13 | −1.3 (7) | O2ii—La1—O1—C1 | 140.6 (9) |
C11—C12—C13—C14 | −0.1 (7) | O7—La1—O1—C1 | −85.6 (9) |
C12—C13—C14—C9 | 1.4 (7) | N1—La1—O1—C1 | 48.3 (10) |
C10—C9—C14—C13 | −1.1 (6) | O1ii—La1—O1—C1 | 132.2 (10) |
C8—C9—C14—C13 | 179.1 (4) | C1ii—La1—O1—C1 | 136.2 (9) |
O5—C15—C16—C17 | −176.0 (3) | O5—La1—O1—La1ii | −150.76 (8) |
O6—C15—C16—C17 | 4.1 (4) | O6i—La1—O1—La1ii | 117.35 (11) |
O5—C15—C16—C21 | 2.8 (4) | O3—La1—O1—La1ii | 67.13 (8) |
O6—C15—C16—C21 | −177.1 (3) | O4ii—La1—O1—La1ii | −76.81 (8) |
C21—C16—C17—F3 | −177.5 (3) | O2ii—La1—O1—La1ii | 8.43 (12) |
C15—C16—C17—F3 | 1.4 (5) | O7—La1—O1—La1ii | 142.21 (10) |
C21—C16—C17—C18 | 0.1 (5) | N1—La1—O1—La1ii | −83.86 (14) |
C15—C16—C17—C18 | 178.9 (3) | O1ii—La1—O1—La1ii | 0.0 |
F3—C17—C18—C19 | 177.4 (4) | C1ii—La1—O1—La1ii | 4.06 (9) |
C16—C17—C18—C19 | −0.3 (6) | O1—C1—O2—La1ii | 0.2 (4) |
C17—C18—C19—C20 | 0.1 (7) | C2—C1—O2—La1ii | −179.6 (2) |
C18—C19—C20—C21 | 0.2 (6) | O4—C8—O3—La1 | 18.3 (6) |
C19—C20—C21—C16 | −0.4 (6) | C9—C8—O3—La1 | −161.2 (3) |
C17—C16—C21—C20 | 0.2 (5) | O5—La1—O3—C8 | −135.0 (4) |
C15—C16—C21—C20 | −178.7 (3) | O1—La1—O3—C8 | −47.8 (4) |
N1—C22—C23—C24 | −0.5 (6) | O6i—La1—O3—C8 | 159.7 (4) |
C22—C23—C24—C25 | −0.7 (6) | O4ii—La1—O3—C8 | 0.5 (4) |
C22—C23—C24—C29 | 174.9 (3) | O2ii—La1—O3—C8 | 83.0 (4) |
C23—C24—C25—C26 | 0.6 (6) | O7—La1—O3—C8 | −124.3 (4) |
C29—C24—C25—C26 | −175.1 (4) | N1—La1—O3—C8 | 107.6 (4) |
C24—C25—C26—N1 | 0.5 (7) | O1ii—La1—O3—C8 | 33.7 (4) |
N2—C27—C28—C29 | −0.5 (6) | C1ii—La1—O3—C8 | 59.7 (4) |
C27—C28—C29—C30 | 2.2 (6) | O3—C8—O4—La1ii | −26.9 (5) |
C27—C28—C29—C24 | −173.1 (3) | C9—C8—O4—La1ii | 152.5 (2) |
C23—C24—C29—C28 | −32.6 (5) | O6—C15—O5—La1 | −69.7 (5) |
C25—C24—C29—C28 | 142.8 (4) | C16—C15—O5—La1 | 110.4 (4) |
C23—C24—C29—C30 | 152.3 (4) | O1—La1—O5—C15 | −52.3 (4) |
C25—C24—C29—C30 | −32.3 (6) | O6i—La1—O5—C15 | 91.0 (4) |
C28—C29—C30—C31 | −2.2 (7) | O3—La1—O5—C15 | 26.5 (5) |
C24—C29—C30—C31 | 173.1 (4) | O4ii—La1—O5—C15 | −121.1 (4) |
C29—C30—C31—N2 | 0.3 (8) | O2ii—La1—O5—C15 | 152.2 (4) |
C23—C22—N1—C26 | 1.6 (6) | O7—La1—O5—C15 | 15.8 (4) |
C23—C22—N1—La1 | −176.2 (3) | N1—La1—O5—C15 | 164.3 (4) |
C25—C26—N1—C22 | −1.6 (6) | O1ii—La1—O5—C15 | −131.8 (4) |
C25—C26—N1—La1 | 176.3 (3) | C1ii—La1—O5—C15 | −179.8 (4) |
O5—La1—N1—C22 | 44.3 (3) | O5—C15—O6—La1i | −44.0 (5) |
O1—La1—N1—C22 | −32.9 (3) | C16—C15—O6—La1i | 135.9 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···N2iii | 0.85 | 2.02 | 2.855 (4) | 168 |
O7—H7B···O5i | 0.85 | 2.50 | 3.158 (4) | 135 |
C5—H5···F3iv | 0.93 | 2.52 | 3.379 (5) | 153 |
C26—H26···O2ii | 0.93 | 2.44 | 2.950 (4) | 115 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z+1; (iv) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [La(C7H4FO2)6(C10H8N2)2(H2O)2] |
Mr | 730.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.746 (5), 12.780 (7), 13.315 (7) |
α, β, γ (°) | 113.132 (9), 104.763 (9), 96.916 (9) |
V (Å3) | 1428.6 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.57 |
Crystal size (mm) | 0.20 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.728, 0.834 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13305, 6871, 5931 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.080, 1.08 |
No. of reflections | 6871 |
No. of parameters | 397 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −1.02 |
Computer programs: SMART (Bruker, 1997), SMART), SAINT (Bruker, 1997, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···N2i | 0.85 | 2.02 | 2.855 (4) | 168 |
O7—H7B···O5ii | 0.85 | 2.50 | 3.158 (4) | 135 |
C5—H5···F3iii | 0.93 | 2.52 | 3.379 (5) | 153 |
C26—H26···O2iv | 0.93 | 2.44 | 2.950 (4) | 115 |
Symmetry codes: (i) x+1, y+1, z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
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Rare earth carboxylate complexes with aromatic diamines, such as 1,10-phenanthroline and 2,2'-bipyridine, have been studied extensively. These lanthanide complexes display a variety of structural types, high stability and intense fluorescence characteristics. However, few rare earth carboxylate complexes with 4,4'-bipyridine have been reported. This paper reports the structure of the title complex, determined by single-crystal X-ray diffraction analysis.
Each La3+ ion is coordinated by seven O atoms and one N atom from a 4,4'-bipyridine molecule, where six of the O atoms (O1, O1A, O2A, O3, O4A and O5) are from different 2-fluorobenzoate groups and the seventh (O7) is from the water molecule. Carboxylate groups adopt three coordination modes, viz. unidentate, bidentate-bridging and bidentate-chelating. Two La3+ ions form a dimeric molecule with four bridging carboxylate groups. The O5/C15/O6 carboxylate groups are in the unidentate mode, with one atom (O5) coordinated to the La3+ ion. The O3/C8/O4 groups are in the bridging mode, in which two O atoms coordinate to two different La3+ ions. The O1/C1/O2 groups are in the chelating-bridging mode, in which two O atoms chelate one La3+ ion and one of the O atoms is linked to another La3+ ion. La—Ocarboxy distances in the title complex range from 2.471 (2) to 2.942 (3) Å [mean 2.569 Å]. The O—La—O angles range from 71.51 (9) to 143.64 (8)°. One N atom from a 4,4'-bipyridine molecule is coordinated to the La3+ ion; this conformation contrasts with that of the [Eu(DBM)3.1/2(4,4'-bipy)] complex, in which two N atoms from 4,4'-bipyridine link two Eu3+ ions to result in an infinite polymeric chain (Wang et al., 1995). The La1—N1 bond distance is 2.852 (3) Å. Each La3+ ion is also coordinated by a water molecule, the La—Owater bond distance being 2.572 (3) Å.
Hydrogen bonds exist between two dimeric molecules, involving the non-coordinated N atom of the 4,4'-bipyridine group of one dimeric molecule and the H atom of the coordinated water molecule of another dimer. (O—H···N = 2.019 Å and O—H···N = 167.9°). An infinite one-dimensional dimeric supramolecular chain is formed, linked by the hydrogen bonds.