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The title complex, [La2(C12H8N2)2(C6H5CO2)6], has a binuclear cage structure in which two La atoms are bridged by four benzoate ions with an La...La distance of 4.1143 (3) Å. The complex has a center of symmetry. The benzoate groups coordinate each LaIII atom in three different ways.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002963/ob6029sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002963/ob6029Isup2.hkl
Contains datablock I

CCDC reference: 159835

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.024
  • wR factor = 0.060
  • Data-to-parameter ratio = 12.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.546 0.734 Tmin' and Tmax expected: 0.614 0.734 RR' = 0.890 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Lanthanide complexes play an important role in special materials having optical, electronic, magnetic and biological importance (Deborah et al., 2000; Farrugia et al., 2000). The varied coordination modes of lanthanide elements and carboxylate groups also stimulated our interest in this work.

In the title compound, (I), two La atoms are bridged by four benzoate groups, forming a binuclear cage structure with Ci symmetry. Among them, two benzoate groups also behave as chelating ligands to the La atoms. Another benzoate ion and a 1,10-phenanthroline (phen) molecule chelate with each La atom in the terminal position of the cage. The irregular nine-coordinate environment of the La atom is completed by six O and two N atoms. The La—O bond lengths are in the range of 2.4460 (19) to 2.860 (2) Å (Table 1). The La—N1 and La—N2 bond lengths are 2.704 (2) and 2.756 (2) Å, respectively. The distance between the two La atoms is 4.1143 (3) Å. These values are slightly longer than in the SmIII–benzoate complex Sm2(C12H8N2)2(C6H5CO2)6 (Niu et al., 1999) due to the effect of the Lanthanide contraction.

Experimental top

La(NO3)3 (0.5 mmol) in methanol (30 ml) was added dropwise to a solution (methanol–H2O, 1:1, 30 ml) of phen (0.5 mmol) and benzoic acid (1.5 mmol). The mixture was heated and refluxed for 10 h to give a pink solution. The solution was filtered at room temperature and crystals of (I) were obtained after 6 d.

Refinement top

The positions of all H atoms were generated geometrically (C—H distance fixed at 0.96 Å), and allowed to ride on their respective parent C atoms.

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Tetra-µ-benzoato-O:O'-bis[(benzoato-O,O')(1,10-phenanthroline-N,N')- lanthanum(III)] top
Crystal data top
[La2(C7H5O2)6(C12H8N2)2]Z = 1
Mr = 1364.92F(000) = 679
Triclinic, P1Dx = 1.585 Mg m3
a = 10.9356 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.9818 (2) ÅCell parameters from 120 reflections
c = 12.4945 (3) Åθ = 1.7–25.0°
α = 104.888 (1)°µ = 1.54 mm1
β = 93.268 (1)°T = 293 K
γ = 113.402 (1)°Plane, pink
V = 1428.48 (5) Å30.31 × 0.21 × 0.20 mm
Data collection top
Siemens Smart CCD
diffractometer
4901 independent reflections
Radiation source: fine-focus sealed tube4427 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.546, Tmax = 0.734k = 1314
7321 measured reflectionsl = 149
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.060 w = 1/[σ2(Fo2) + (0.0302P)2 + 0.0941P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.017
4901 reflectionsΔρmax = 0.61 e Å3
380 parametersΔρmin = 0.59 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0022 (4)
Crystal data top
[La2(C7H5O2)6(C12H8N2)2]γ = 113.402 (1)°
Mr = 1364.92V = 1428.48 (5) Å3
Triclinic, P1Z = 1
a = 10.9356 (2) ÅMo Kα radiation
b = 11.9818 (2) ŵ = 1.54 mm1
c = 12.4945 (3) ÅT = 293 K
α = 104.888 (1)°0.31 × 0.21 × 0.20 mm
β = 93.268 (1)°
Data collection top
Siemens Smart CCD
diffractometer
4901 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
4427 reflections with I > 2σ(I)
Tmin = 0.546, Tmax = 0.734Rint = 0.019
7321 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.060H-atom parameters constrained
S = 1.04Δρmax = 0.61 e Å3
4901 reflectionsΔρmin = 0.59 e Å3
380 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
La0.135359 (14)0.064305 (13)0.147434 (12)0.03130 (7)
O10.1594 (2)0.14151 (19)0.06398 (19)0.0532 (6)
O20.00697 (19)0.14069 (18)0.05750 (17)0.0420 (5)
O30.24532 (19)0.13991 (19)0.00349 (17)0.0444 (5)
O40.09329 (19)0.09061 (19)0.15456 (17)0.0469 (5)
O50.0776 (2)0.18940 (18)0.32531 (17)0.0470 (5)
O60.27652 (19)0.28549 (18)0.27926 (17)0.0465 (5)
N10.1939 (2)0.0122 (2)0.3216 (2)0.0414 (5)
N20.3883 (2)0.0725 (2)0.1963 (2)0.0392 (5)
C10.1033 (3)0.0481 (3)0.3865 (3)0.0499 (7)
H10.03000.02740.38260.060*
C20.1123 (4)0.1156 (3)0.4605 (3)0.0578 (9)
H20.04850.13610.50680.069*
C30.2159 (4)0.1506 (3)0.4635 (3)0.0581 (9)
H30.22120.19880.50970.070*
C40.3144 (3)0.1146 (3)0.3973 (3)0.0485 (7)
C50.4279 (4)0.1459 (3)0.3971 (3)0.0612 (9)
H50.43530.19640.44020.073*
C60.5232 (4)0.1043 (3)0.3364 (3)0.0616 (9)
H60.59590.12590.33840.074*
C70.5155 (3)0.0267 (3)0.2683 (3)0.0468 (7)
C80.6144 (3)0.0214 (3)0.2047 (3)0.0568 (9)
H80.69120.00590.20770.068*
C90.5985 (3)0.0902 (3)0.1392 (3)0.0547 (8)
H90.66310.12130.09610.066*
C100.4830 (3)0.1140 (3)0.1375 (3)0.0481 (7)
H100.47280.16160.09230.058*
C110.4034 (3)0.0023 (3)0.2620 (2)0.0385 (6)
C120.3009 (3)0.0423 (3)0.3277 (2)0.0398 (6)
C250.0702 (3)0.1973 (3)0.0226 (2)0.0367 (6)
C260.0376 (3)0.3331 (2)0.0848 (2)0.0365 (6)
C270.1281 (3)0.3832 (3)0.0642 (3)0.0476 (7)
H270.20960.33130.01450.057*
C280.0972 (4)0.5099 (3)0.1173 (3)0.0587 (9)
H280.15870.54290.10480.070*
C290.0246 (4)0.5869 (3)0.1887 (3)0.0632 (10)
H290.04580.67250.22350.076*
C300.1146 (4)0.5389 (3)0.2091 (3)0.0605 (9)
H300.19690.59200.25740.073*
C310.0839 (3)0.4112 (3)0.1578 (3)0.0471 (7)
H310.14490.37830.17250.057*
C320.2088 (3)0.1552 (2)0.0936 (2)0.0370 (6)
C330.3104 (3)0.2564 (2)0.1341 (2)0.0377 (6)
C340.4448 (3)0.3183 (3)0.0809 (3)0.0550 (8)
H340.47240.29720.02020.066*
C350.5378 (4)0.4113 (4)0.1178 (3)0.0698 (11)
H350.62790.45180.08190.084*
C360.4993 (4)0.4443 (3)0.2060 (3)0.0671 (10)
H360.56230.50830.22930.081*
C370.3676 (4)0.3829 (3)0.2601 (3)0.0650 (10)
H370.34120.40490.32070.078*
C380.2730 (3)0.2881 (3)0.2254 (3)0.0500 (8)
H380.18390.24580.26380.060*
C390.1889 (3)0.2858 (3)0.3417 (2)0.0376 (6)
C400.2195 (3)0.4036 (3)0.4372 (2)0.0392 (6)
C410.1209 (4)0.4147 (3)0.4977 (3)0.0545 (8)
H410.03350.34950.47770.065*
C420.1520 (5)0.5227 (4)0.5882 (3)0.0714 (11)
H420.08530.53030.62840.086*
C430.2805 (5)0.6179 (4)0.6181 (3)0.0759 (12)
H430.30110.68970.67940.091*
C440.3795 (4)0.6087 (3)0.5587 (3)0.0670 (10)
H440.46710.67350.58000.080*
C450.3483 (3)0.5025 (3)0.4670 (3)0.0495 (7)
H450.41450.49740.42500.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La0.03122 (10)0.02742 (10)0.03333 (10)0.01076 (7)0.00642 (6)0.00887 (6)
O10.0514 (12)0.0375 (11)0.0609 (14)0.0211 (10)0.0101 (11)0.0000 (10)
O20.0470 (11)0.0388 (10)0.0498 (12)0.0256 (9)0.0116 (9)0.0169 (9)
O30.0410 (11)0.0505 (12)0.0467 (12)0.0173 (9)0.0155 (9)0.0252 (10)
O40.0388 (11)0.0417 (11)0.0498 (12)0.0056 (9)0.0094 (9)0.0154 (10)
O50.0474 (12)0.0368 (11)0.0471 (12)0.0112 (9)0.0145 (10)0.0070 (9)
O60.0421 (11)0.0410 (11)0.0468 (12)0.0127 (9)0.0131 (10)0.0048 (9)
N10.0445 (13)0.0411 (13)0.0405 (13)0.0191 (11)0.0098 (11)0.0138 (11)
N20.0354 (12)0.0356 (12)0.0413 (13)0.0123 (10)0.0056 (10)0.0082 (10)
C10.0551 (18)0.0504 (18)0.0489 (18)0.0235 (15)0.0165 (15)0.0194 (15)
C20.073 (2)0.0526 (19)0.0503 (19)0.0245 (18)0.0204 (17)0.0221 (16)
C30.078 (2)0.0501 (19)0.0495 (19)0.0255 (18)0.0083 (17)0.0245 (16)
C40.0556 (18)0.0397 (16)0.0453 (17)0.0193 (14)0.0024 (14)0.0093 (14)
C50.074 (2)0.059 (2)0.060 (2)0.0384 (19)0.0013 (19)0.0198 (18)
C60.062 (2)0.056 (2)0.071 (2)0.0390 (18)0.0004 (19)0.0062 (18)
C70.0469 (17)0.0409 (16)0.0472 (17)0.0227 (14)0.0018 (14)0.0003 (13)
C80.0467 (18)0.0541 (19)0.064 (2)0.0283 (16)0.0054 (16)0.0013 (17)
C90.0417 (16)0.0553 (19)0.056 (2)0.0181 (15)0.0131 (15)0.0027 (16)
C100.0431 (16)0.0448 (17)0.0496 (18)0.0136 (13)0.0102 (14)0.0114 (14)
C110.0384 (15)0.0311 (14)0.0358 (15)0.0127 (12)0.0031 (12)0.0008 (12)
C120.0446 (16)0.0347 (14)0.0361 (15)0.0172 (13)0.0011 (12)0.0052 (12)
C250.0342 (14)0.0330 (14)0.0453 (16)0.0158 (12)0.0123 (13)0.0122 (12)
C260.0423 (15)0.0316 (14)0.0386 (15)0.0164 (12)0.0115 (12)0.0135 (12)
C270.0500 (17)0.0427 (16)0.0526 (18)0.0246 (14)0.0092 (14)0.0106 (14)
C280.079 (2)0.0486 (18)0.062 (2)0.0418 (18)0.0163 (19)0.0147 (17)
C290.096 (3)0.0342 (16)0.055 (2)0.0294 (18)0.009 (2)0.0045 (15)
C300.069 (2)0.0392 (17)0.055 (2)0.0125 (16)0.0056 (17)0.0052 (15)
C310.0499 (17)0.0406 (16)0.0471 (17)0.0162 (14)0.0016 (14)0.0139 (14)
C320.0379 (15)0.0320 (14)0.0421 (16)0.0140 (12)0.0165 (13)0.0126 (12)
C330.0400 (15)0.0294 (13)0.0440 (16)0.0137 (12)0.0164 (12)0.0116 (12)
C340.0477 (18)0.0550 (19)0.0517 (19)0.0067 (15)0.0088 (15)0.0238 (16)
C350.050 (2)0.063 (2)0.070 (2)0.0059 (17)0.0113 (18)0.0255 (19)
C360.067 (2)0.050 (2)0.081 (3)0.0103 (18)0.032 (2)0.0337 (19)
C370.075 (2)0.063 (2)0.078 (3)0.032 (2)0.028 (2)0.048 (2)
C380.0489 (17)0.0478 (17)0.065 (2)0.0228 (15)0.0172 (16)0.0313 (16)
C390.0419 (15)0.0328 (14)0.0357 (15)0.0141 (13)0.0027 (12)0.0105 (12)
C400.0545 (17)0.0350 (14)0.0311 (14)0.0217 (13)0.0043 (12)0.0119 (12)
C410.070 (2)0.0488 (18)0.0497 (19)0.0295 (16)0.0184 (16)0.0156 (15)
C420.112 (3)0.075 (3)0.050 (2)0.062 (3)0.027 (2)0.0160 (19)
C430.126 (4)0.055 (2)0.046 (2)0.051 (3)0.007 (2)0.0020 (17)
C440.082 (3)0.0412 (18)0.057 (2)0.0186 (18)0.017 (2)0.0014 (16)
C450.0537 (18)0.0404 (16)0.0464 (18)0.0157 (14)0.0025 (14)0.0098 (14)
Geometric parameters (Å, º) top
La—O2i2.4460 (19)C6—C71.433 (5)
La—O32.4685 (19)C7—C111.404 (4)
La—O4i2.4756 (18)C7—C81.404 (5)
La—O62.5173 (19)C8—C91.351 (5)
La—O12.542 (2)C9—C101.402 (5)
La—O52.6048 (19)C11—C121.438 (4)
La—N12.704 (2)C25—C261.495 (4)
La—N22.756 (2)C26—C311.382 (4)
La—O22.860 (2)C26—C271.388 (4)
O1—C251.249 (3)C27—C281.382 (4)
O2—C251.272 (3)C28—C291.373 (5)
O2—Lai2.4460 (19)C29—C301.364 (5)
O3—C321.255 (4)C30—C311.389 (4)
O4—C321.259 (3)C32—C331.506 (4)
O4—Lai2.4756 (18)C33—C381.382 (4)
O5—C391.262 (3)C33—C341.386 (4)
O6—C391.270 (3)C34—C351.379 (4)
N1—C11.325 (4)C35—C361.361 (6)
N1—C121.358 (4)C36—C371.365 (5)
N2—C101.314 (4)C37—C381.385 (4)
N2—C111.363 (4)C39—C401.498 (4)
C1—C21.399 (5)C40—C411.380 (4)
C2—C31.357 (5)C40—C451.383 (4)
C3—C41.395 (5)C41—C421.388 (5)
C4—C121.416 (4)C42—C431.364 (6)
C4—C51.432 (5)C43—C441.371 (6)
C5—C61.334 (5)C44—C451.382 (4)
O2i—La—O372.52 (7)C2—C3—C4120.2 (3)
O2i—La—O4i79.10 (7)C3—C4—C12117.6 (3)
O3—La—O4i134.26 (7)C3—C4—C5123.5 (3)
O2i—La—O691.19 (7)C12—C4—C5118.8 (3)
O3—La—O687.38 (7)C6—C5—C4121.5 (3)
O4i—La—O6128.87 (6)C5—C6—C7121.2 (3)
O2i—La—O1126.03 (7)C11—C7—C8117.1 (3)
O3—La—O187.45 (7)C11—C7—C6119.5 (3)
O4i—La—O181.04 (7)C8—C7—C6123.3 (3)
O6—La—O1138.47 (7)C9—C8—C7120.3 (3)
O2i—La—O580.24 (7)C8—C9—C10118.8 (3)
O3—La—O5129.53 (7)N2—C10—C9123.4 (3)
O4i—La—O577.79 (6)N2—C11—C7122.4 (3)
O6—La—O551.07 (6)N2—C11—C12118.4 (3)
O1—La—O5141.97 (7)C7—C11—C12119.3 (3)
O2i—La—N1148.16 (7)N1—C12—C4121.8 (3)
O3—La—N1138.33 (7)N1—C12—C11118.5 (3)
O4i—La—N179.48 (7)C4—C12—C11119.6 (3)
O6—La—N184.22 (7)O1—C25—O2121.0 (2)
O1—La—N172.91 (7)O1—C25—C26118.8 (3)
O5—La—N172.40 (7)O2—C25—C26120.2 (3)
O2i—La—N2148.23 (7)C31—C26—C27119.5 (3)
O3—La—N278.28 (7)C31—C26—C25121.1 (3)
O4i—La—N2131.77 (7)C27—C26—C25119.3 (3)
O6—La—N275.01 (7)C28—C27—C26120.1 (3)
O1—La—N263.59 (7)C29—C28—C27119.8 (3)
O5—La—N2110.24 (7)C30—C29—C28120.6 (3)
N1—La—N260.11 (7)C29—C30—C31120.2 (3)
O2i—La—O278.60 (6)C26—C31—C30119.7 (3)
O3—La—O273.34 (6)O3—C32—O4124.9 (2)
O4i—La—O266.31 (6)O3—C32—C33118.2 (2)
O6—La—O2160.12 (7)O4—C32—C33116.9 (3)
O1—La—O247.49 (6)C38—C33—C34118.5 (3)
O5—La—O2141.02 (6)C38—C33—C32121.2 (3)
N1—La—O2113.37 (6)C34—C33—C32120.3 (3)
N2—La—O2104.95 (6)C35—C34—C33120.3 (3)
C25—O1—La103.24 (17)C36—C35—C34120.8 (3)
C25—O2—Lai170.92 (18)C35—C36—C37119.6 (3)
C25—O2—La87.49 (16)C36—C37—C38120.6 (3)
Lai—O2—La101.40 (6)C33—C38—C37120.2 (3)
C32—O3—La136.59 (17)O5—C39—O6121.6 (2)
C32—O4—Lai139.76 (18)O5—C39—C40119.5 (3)
C39—O5—La91.70 (16)O6—C39—C40118.9 (2)
C39—O6—La95.59 (16)C41—C40—C45119.1 (3)
C1—N1—C12118.2 (3)C41—C40—C39120.8 (3)
C1—N1—La120.1 (2)C45—C40—C39120.1 (3)
C12—N1—La119.95 (18)C40—C41—C42120.1 (3)
C10—N2—C11118.1 (3)C43—C42—C41120.0 (4)
C10—N2—La121.6 (2)C42—C43—C44120.6 (3)
C11—N2—La118.13 (17)C43—C44—C45119.6 (4)
N1—C1—C2123.3 (3)C44—C45—C40120.6 (3)
C3—C2—C1118.8 (3)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[La2(C7H5O2)6(C12H8N2)2]
Mr1364.92
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)10.9356 (2), 11.9818 (2), 12.4945 (3)
α, β, γ (°)104.888 (1), 93.268 (1), 113.402 (1)
V3)1428.48 (5)
Z1
Radiation typeMo Kα
µ (mm1)1.54
Crystal size (mm)0.31 × 0.21 × 0.20
Data collection
DiffractometerSiemens Smart CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.546, 0.734
No. of measured, independent and
observed [I > 2σ(I)] reflections
7321, 4901, 4427
Rint0.019
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.060, 1.04
No. of reflections4901
No. of parameters380
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.61, 0.59

Computer programs: SMART (Siemens, 1994), SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
La—O2i2.4460 (19)La—O52.6048 (19)
La—O32.4685 (19)La—N12.704 (2)
La—O4i2.4756 (18)La—N22.756 (2)
La—O62.5173 (19)La—O22.860 (2)
La—O12.542 (2)
O2i—La—O372.52 (7)O1—La—N172.91 (7)
O2i—La—O4i79.10 (7)O5—La—N172.40 (7)
O3—La—O4i134.26 (7)O2i—La—N2148.23 (7)
O2i—La—O691.19 (7)O3—La—N278.28 (7)
O3—La—O687.38 (7)O4i—La—N2131.77 (7)
O4i—La—O6128.87 (6)O6—La—N275.01 (7)
O2i—La—O1126.03 (7)O1—La—N263.59 (7)
O3—La—O187.45 (7)O5—La—N2110.24 (7)
O4i—La—O181.04 (7)N1—La—N260.11 (7)
O6—La—O1138.47 (7)O2i—La—O278.60 (6)
O2i—La—O580.24 (7)O3—La—O273.34 (6)
O3—La—O5129.53 (7)O4i—La—O266.31 (6)
O4i—La—O577.79 (6)O6—La—O2160.12 (7)
O6—La—O551.07 (6)O1—La—O247.49 (6)
O1—La—O5141.97 (7)O5—La—O2141.02 (6)
O2i—La—N1148.16 (7)N1—La—O2113.37 (6)
O3—La—N1138.33 (7)N2—La—O2104.95 (6)
O4i—La—N179.48 (7)Lai—O2—La101.40 (6)
O6—La—N184.22 (7)
Symmetry code: (i) x, y, z.
 

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