The title compound, [La2(C8H3NO6)2(C8H4NO6)2(H2O)6]·2H2O, consists of dimeric units related by an inversion center. The two LaIII atoms are linked by two bridging bidentate carboxylate groups and two monodentate carboxylate groups. Each LaIII atom is nine-coordinated by six O atoms from five different carboxylate groups and three from water molecules. Hydrogen bonds between the water molecules and between the solvent water and a carboxylate O atom are observed in the structure. In the crystal packing, there are slipped π–π stacking interactions between the parallel benzene rings. Both hydrogen-bonding and π–π interactions combine to stabilize the three-dimensional supramolecular network.
Supporting information
CCDC reference: 279505
A solution of LaCl3 (0.0245 g, 0.10 mmol) in water (5 ml) was added dropwise with constant stirring to an aqueous solution (5 ml) of 3-nitro-1,2-benzenedicarboxylic acid (0.0211 g, 0.1 mmol). The pH of the mixture was adjusted to 3–4 with 0.1 M NaOH solution; the resulting mixture was then transferred into a Teflon-lined stainless steel vessel, which was sealed and heated to 423 K for 72 h, then cooled to room temperature. The reaction mixture was then filtered and single crystals were obtained from the filtrate at room temperature after a few days.
H atoms attached to C atoms were placed at calculated positions (C—H = 0.93 Å) and allowed to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)]. Water and hydroxy H atoms were located in a difference map and refined with O—H distances restrained to 0.85 (3) Å and with Uiso(H) = 1.2Ueq(O). [Should the O-atom positional parameters have s.u. values if they were restrained, or were they constrained?]
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.
Bis(µ-3-nitro-1,2-benzenedicarboxylato) -
κ8O1,
O2:
O2,
O3;O
3,
O2:
O2,
O1 -bis[triaqua(3-nitro-2-carboxybenzoato-
κ2O,
O')lanthanum(III)] dihydrate
top
Crystal data top
C32H26La2N4O30·2H2O | Z = 1 |
Mr = 1260.42 | F(000) = 620 |
Triclinic, P1 | Dx = 1.986 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1700 (12) Å | Cell parameters from 3775 reflections |
b = 8.9036 (13) Å | θ = 2.6–26.4° |
c = 15.279 (2) Å | µ = 2.12 mm−1 |
α = 100.828 (2)° | T = 294 K |
β = 90.935 (2)° | Block, colourless |
γ = 104.581 (2)° | 0.24 × 0.22 × 0.18 mm |
V = 1054.1 (3) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3711 independent reflections |
Radiation source: fine-focus sealed tube | 3350 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 0 pixels mm-1 | θmax = 25.0°, θmin = 2.4° |
ϕ and ω scans | h = −9→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→10 |
Tmin = 0.593, Tmax = 0.683 | l = −18→17 |
5399 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0292P)2 + 0.3043P] where P = (Fo2 + 2Fc2)/3 |
3711 reflections | (Δ/σ)max = 0.002 |
316 parameters | Δρmax = 0.89 e Å−3 |
10 restraints | Δρmin = −0.90 e Å−3 |
Crystal data top
C32H26La2N4O30·2H2O | γ = 104.581 (2)° |
Mr = 1260.42 | V = 1054.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.1700 (12) Å | Mo Kα radiation |
b = 8.9036 (13) Å | µ = 2.12 mm−1 |
c = 15.279 (2) Å | T = 294 K |
α = 100.828 (2)° | 0.24 × 0.22 × 0.18 mm |
β = 90.935 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3711 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3350 reflections with I > 2σ(I) |
Tmin = 0.593, Tmax = 0.683 | Rint = 0.020 |
5399 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 10 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.89 e Å−3 |
3711 reflections | Δρmin = −0.90 e Å−3 |
316 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 | |
La1 | 0.34827 (2) | 1.11284 (2) | 0.432118 (11) | 0.01815 (7) | |
O1 | 0.5449 (3) | 0.6661 (3) | 0.42591 (15) | 0.0306 (6) | |
O2 | 0.4094 (3) | 0.8523 (2) | 0.44534 (14) | 0.0223 (5) | |
O3 | 0.1013 (3) | 0.8889 (3) | 0.36665 (15) | 0.0275 (5) | |
O4 | 0.0006 (3) | 0.6439 (3) | 0.39096 (16) | 0.0355 (6) | |
O5 | −0.1211 (4) | 0.6744 (5) | 0.2175 (2) | 0.0733 (11) | |
O6 | −0.1027 (4) | 0.5290 (4) | 0.0935 (2) | 0.0689 (10) | |
O7 | 0.0699 (3) | 1.1806 (3) | 0.18173 (17) | 0.0399 (6) | |
H7 | 0.0413 | 1.2382 | 0.2268 | 0.048* | |
O8 | 0.2526 (3) | 1.1769 (3) | 0.28850 (15) | 0.0318 (6) | |
O9 | 0.5234 (3) | 1.0325 (3) | 0.30701 (14) | 0.0251 (5) | |
O10 | 0.6224 (3) | 1.2202 (3) | 0.22793 (16) | 0.0325 (6) | |
O11 | 0.7250 (4) | 0.9261 (4) | 0.1595 (2) | 0.0529 (8) | |
O12 | 0.6708 (4) | 0.7706 (4) | 0.0315 (2) | 0.0628 (9) | |
O13 | 0.1303 (3) | 1.2612 (3) | 0.45670 (16) | 0.0362 (6) | |
H13A | 0.0664 | 1.2677 | 0.4136 | 0.043* | |
H13B | 0.0954 | 1.2842 | 0.5088 | 0.043* | |
O14 | 0.2093 (3) | 1.0307 (3) | 0.57479 (16) | 0.0368 (6) | |
H14A | 0.2748 | 1.0121 | 0.6131 | 0.044* | |
H14B | 0.1224 | 1.0583 | 0.5951 | 0.044* | |
O15 | 0.5579 (3) | 1.3571 (3) | 0.39953 (17) | 0.0362 (6) | |
H15A | 0.5802 | 1.3266 | 0.3426 | 0.043* | |
H15B | 0.5572 | 1.4552 | 0.4157 | 0.043* | |
N1 | −0.0437 (4) | 0.6025 (4) | 0.1666 (2) | 0.0344 (7) | |
N2 | 0.6315 (4) | 0.8588 (4) | 0.0936 (2) | 0.0367 (8) | |
C1 | 0.4406 (4) | 0.7302 (3) | 0.3973 (2) | 0.0210 (7) | |
C2 | 0.3578 (4) | 0.6653 (4) | 0.3053 (2) | 0.0218 (7) | |
C3 | 0.4488 (4) | 0.5905 (4) | 0.2421 (2) | 0.0286 (8) | |
H3 | 0.5569 | 0.5849 | 0.2585 | 0.034* | |
C4 | 0.3813 (5) | 0.5249 (4) | 0.1561 (2) | 0.0333 (8) | |
H4 | 0.4440 | 0.4769 | 0.1147 | 0.040* | |
C5 | 0.2212 (5) | 0.5309 (4) | 0.1318 (2) | 0.0323 (8) | |
H5 | 0.1739 | 0.4860 | 0.0741 | 0.039* | |
C6 | 0.1308 (4) | 0.6043 (4) | 0.1941 (2) | 0.0253 (7) | |
C7 | 0.1957 (4) | 0.6740 (3) | 0.2816 (2) | 0.0200 (7) | |
C8 | 0.0885 (4) | 0.7411 (4) | 0.3522 (2) | 0.0233 (7) | |
C9 | 0.1923 (4) | 1.1311 (4) | 0.2119 (2) | 0.0242 (7) | |
C10 | 0.2529 (4) | 1.0165 (4) | 0.1444 (2) | 0.0262 (7) | |
C11 | 0.1452 (5) | 0.9338 (4) | 0.0698 (2) | 0.0347 (9) | |
H11 | 0.0373 | 0.9489 | 0.0641 | 0.042* | |
C12 | 0.1969 (6) | 0.8303 (4) | 0.0047 (3) | 0.0419 (10) | |
H12 | 0.1242 | 0.7754 | −0.0448 | 0.050* | |
C13 | 0.3567 (5) | 0.8079 (4) | 0.0130 (2) | 0.0383 (9) | |
H13 | 0.3937 | 0.7400 | −0.0316 | 0.046* | |
C14 | 0.4622 (5) | 0.8876 (4) | 0.0886 (2) | 0.0290 (8) | |
C15 | 0.4149 (4) | 0.9938 (4) | 0.1558 (2) | 0.0247 (7) | |
C16 | 0.5329 (4) | 1.0895 (4) | 0.2369 (2) | 0.0222 (7) | |
O16 | 0.9405 (3) | 0.3283 (3) | 0.31491 (17) | 0.0379 (6) | |
H16A | 0.8347 | 0.2834 | 0.3121 | 0.046* | |
H16B | 0.9685 | 0.4284 | 0.3331 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.02274 (11) | 0.01593 (10) | 0.01637 (11) | 0.00892 (7) | −0.00133 (7) | −0.00043 (7) |
O1 | 0.0374 (14) | 0.0262 (12) | 0.0292 (13) | 0.0191 (11) | −0.0094 (11) | −0.0052 (10) |
O2 | 0.0301 (12) | 0.0174 (11) | 0.0202 (11) | 0.0116 (9) | 0.0005 (9) | −0.0016 (9) |
O3 | 0.0244 (12) | 0.0203 (12) | 0.0352 (14) | 0.0084 (10) | −0.0034 (10) | −0.0041 (10) |
O4 | 0.0453 (16) | 0.0251 (13) | 0.0365 (14) | 0.0112 (12) | 0.0204 (12) | 0.0030 (11) |
O5 | 0.049 (2) | 0.117 (3) | 0.051 (2) | 0.046 (2) | −0.0153 (16) | −0.023 (2) |
O6 | 0.066 (2) | 0.084 (2) | 0.0435 (19) | 0.0270 (19) | −0.0302 (16) | −0.0271 (17) |
O7 | 0.0416 (16) | 0.0495 (16) | 0.0328 (14) | 0.0261 (13) | −0.0090 (12) | −0.0001 (12) |
O8 | 0.0393 (14) | 0.0432 (15) | 0.0185 (13) | 0.0229 (12) | −0.0011 (11) | 0.0033 (11) |
O9 | 0.0301 (13) | 0.0275 (12) | 0.0207 (12) | 0.0135 (10) | 0.0042 (10) | 0.0038 (10) |
O10 | 0.0351 (14) | 0.0272 (13) | 0.0312 (14) | 0.0003 (11) | 0.0032 (11) | 0.0065 (11) |
O11 | 0.0406 (17) | 0.067 (2) | 0.0507 (19) | 0.0276 (15) | −0.0028 (14) | −0.0082 (16) |
O12 | 0.065 (2) | 0.071 (2) | 0.0522 (19) | 0.0370 (18) | 0.0161 (16) | −0.0141 (17) |
O13 | 0.0448 (15) | 0.0524 (16) | 0.0211 (13) | 0.0326 (13) | 0.0046 (11) | 0.0042 (11) |
O14 | 0.0363 (14) | 0.0479 (16) | 0.0314 (14) | 0.0182 (12) | 0.0088 (11) | 0.0104 (12) |
O15 | 0.0503 (16) | 0.0185 (12) | 0.0386 (15) | 0.0109 (11) | 0.0113 (12) | −0.0003 (11) |
N1 | 0.0394 (18) | 0.0333 (17) | 0.0266 (17) | 0.0093 (14) | −0.0092 (14) | −0.0028 (14) |
N2 | 0.049 (2) | 0.0325 (17) | 0.0320 (18) | 0.0180 (16) | 0.0131 (16) | 0.0041 (15) |
C1 | 0.0243 (17) | 0.0170 (15) | 0.0213 (17) | 0.0063 (13) | 0.0005 (13) | 0.0017 (13) |
C2 | 0.0293 (18) | 0.0177 (15) | 0.0163 (16) | 0.0061 (13) | 0.0005 (13) | −0.0013 (13) |
C3 | 0.0284 (19) | 0.0274 (18) | 0.030 (2) | 0.0113 (15) | 0.0034 (15) | −0.0003 (15) |
C4 | 0.044 (2) | 0.034 (2) | 0.0213 (18) | 0.0159 (17) | 0.0082 (16) | −0.0028 (15) |
C5 | 0.048 (2) | 0.0279 (19) | 0.0159 (17) | 0.0074 (17) | 0.0003 (16) | −0.0034 (14) |
C6 | 0.0307 (18) | 0.0205 (16) | 0.0220 (17) | 0.0039 (14) | −0.0030 (14) | 0.0015 (14) |
C7 | 0.0232 (17) | 0.0173 (15) | 0.0186 (16) | 0.0047 (13) | 0.0009 (13) | 0.0021 (13) |
C8 | 0.0206 (17) | 0.0251 (18) | 0.0218 (17) | 0.0084 (14) | −0.0047 (14) | −0.0045 (14) |
C9 | 0.0237 (17) | 0.0274 (17) | 0.0236 (19) | 0.0081 (14) | −0.0006 (14) | 0.0091 (14) |
C10 | 0.0337 (19) | 0.0264 (18) | 0.0200 (17) | 0.0093 (15) | 0.0021 (14) | 0.0060 (14) |
C11 | 0.040 (2) | 0.035 (2) | 0.030 (2) | 0.0098 (17) | −0.0089 (17) | 0.0079 (17) |
C12 | 0.058 (3) | 0.032 (2) | 0.029 (2) | 0.0080 (19) | −0.0128 (19) | −0.0035 (17) |
C13 | 0.057 (3) | 0.033 (2) | 0.0223 (19) | 0.0111 (19) | 0.0024 (18) | 0.0000 (16) |
C14 | 0.038 (2) | 0.0265 (18) | 0.0219 (18) | 0.0086 (16) | 0.0048 (15) | 0.0036 (14) |
C15 | 0.0310 (19) | 0.0231 (17) | 0.0195 (17) | 0.0041 (14) | 0.0031 (14) | 0.0067 (14) |
C16 | 0.0197 (16) | 0.0266 (18) | 0.0218 (18) | 0.0109 (14) | 0.0056 (13) | 0.0011 (14) |
O16 | 0.0327 (14) | 0.0293 (13) | 0.0505 (16) | 0.0120 (11) | −0.0011 (12) | −0.0003 (12) |
Geometric parameters (Å, º) top
La1—O13 | 2.466 (2) | O15—H15A | 0.90 |
La1—O3 | 2.491 (2) | O15—H15B | 0.86 |
La1—O9 | 2.511 (2) | N1—C6 | 1.475 (4) |
La1—O8 | 2.528 (2) | N2—C14 | 1.473 (5) |
La1—O2 | 2.535 (2) | C1—C2 | 1.495 (4) |
La1—O15 | 2.543 (2) | C1—La1i | 2.998 (3) |
La1—O1i | 2.610 (2) | C2—C7 | 1.392 (4) |
La1—O14 | 2.615 (2) | C2—C3 | 1.400 (4) |
La1—O2i | 2.622 (2) | C3—C4 | 1.378 (5) |
La1—C1i | 2.998 (3) | C3—H3 | 0.9300 |
O1—C1 | 1.253 (4) | C4—C5 | 1.370 (5) |
O1—La1i | 2.610 (2) | C4—H4 | 0.9300 |
O2—C1 | 1.277 (4) | C5—C6 | 1.382 (5) |
O2—La1i | 2.622 (2) | C5—H5 | 0.9300 |
O3—C8 | 1.270 (4) | C6—C7 | 1.398 (4) |
O4—C8 | 1.228 (4) | C7—C8 | 1.529 (4) |
O5—N1 | 1.203 (4) | C9—C10 | 1.491 (5) |
O6—N1 | 1.207 (4) | C10—C11 | 1.393 (5) |
O7—C9 | 1.300 (4) | C10—C15 | 1.401 (5) |
O7—H7 | 0.85 | C11—C12 | 1.372 (5) |
O8—C9 | 1.216 (4) | C11—H11 | 0.9300 |
O9—C16 | 1.264 (4) | C12—C13 | 1.376 (6) |
O10—C16 | 1.242 (4) | C12—H12 | 0.9300 |
O11—N2 | 1.214 (4) | C13—C14 | 1.389 (5) |
O12—N2 | 1.215 (4) | C13—H13 | 0.9300 |
O13—H13A | 0.85 | C14—C15 | 1.390 (5) |
O13—H13B | 0.85 | C15—C16 | 1.530 (5) |
O14—H14A | 0.85 | O16—H16A | 0.85 |
O14—H14B | 0.85 | O16—H16B | 0.85 |
| | | |
O13—La1—O3 | 83.15 (8) | La1—O15—H15B | 128.5 |
O13—La1—O9 | 137.27 (7) | H15A—O15—H15B | 115.9 |
O3—La1—O9 | 90.76 (7) | O5—N1—O6 | 122.7 (3) |
O13—La1—O8 | 68.51 (8) | O5—N1—C6 | 118.9 (3) |
O3—La1—O8 | 74.03 (8) | O6—N1—C6 | 118.4 (3) |
O9—La1—O8 | 69.16 (7) | O11—N2—O12 | 123.6 (3) |
O13—La1—O2 | 142.64 (8) | O11—N2—C14 | 118.0 (3) |
O3—La1—O2 | 70.17 (7) | O12—N2—C14 | 118.5 (3) |
O9—La1—O2 | 70.57 (7) | O1—C1—O2 | 120.3 (3) |
O8—La1—O2 | 124.64 (7) | O1—C1—C2 | 119.2 (3) |
O13—La1—O15 | 90.13 (8) | O2—C1—C2 | 120.5 (3) |
O3—La1—O15 | 143.53 (8) | O1—C1—La1i | 60.06 (16) |
O9—La1—O15 | 70.31 (7) | O2—C1—La1i | 60.70 (16) |
O8—La1—O15 | 70.18 (8) | C2—C1—La1i | 171.1 (2) |
O2—La1—O15 | 126.81 (8) | C7—C2—C3 | 119.9 (3) |
O13—La1—O1i | 73.44 (8) | C7—C2—C1 | 122.8 (3) |
O3—La1—O1i | 142.38 (8) | C3—C2—C1 | 117.3 (3) |
O9—La1—O1i | 126.34 (8) | C4—C3—C2 | 121.3 (3) |
O8—La1—O1i | 121.22 (8) | C4—C3—H3 | 119.4 |
O2—La1—O1i | 112.94 (7) | C2—C3—H3 | 119.4 |
O15—La1—O1i | 66.82 (8) | C5—C4—C3 | 119.7 (3) |
O13—La1—O14 | 76.51 (8) | C5—C4—H4 | 120.2 |
O3—La1—O14 | 77.96 (8) | C3—C4—H4 | 120.2 |
O9—La1—O14 | 143.32 (8) | C4—C5—C6 | 119.2 (3) |
O8—La1—O14 | 137.10 (8) | C4—C5—H5 | 120.4 |
O2—La1—O14 | 72.77 (7) | C6—C5—H5 | 120.4 |
O15—La1—O14 | 135.12 (8) | C5—C6—C7 | 122.8 (3) |
O1i—La1—O14 | 68.30 (8) | C5—C6—N1 | 117.6 (3) |
O13—La1—O2i | 121.50 (7) | C7—C6—N1 | 119.5 (3) |
O3—La1—O2i | 133.32 (7) | C2—C7—C6 | 117.1 (3) |
O9—La1—O2i | 92.98 (7) | C2—C7—C8 | 120.3 (3) |
O8—La1—O2i | 149.00 (8) | C6—C7—C8 | 122.2 (3) |
O2—La1—O2i | 67.47 (8) | O4—C8—O3 | 126.6 (3) |
O15—La1—O2i | 80.12 (8) | O4—C8—C7 | 115.2 (3) |
O1i—La1—O2i | 49.59 (7) | O3—C8—C7 | 118.2 (3) |
O14—La1—O2i | 71.68 (8) | O8—C9—O7 | 122.2 (3) |
O13—La1—C1i | 96.79 (8) | O8—C9—C10 | 123.5 (3) |
O3—La1—C1i | 142.74 (8) | O7—C9—C10 | 114.3 (3) |
O9—La1—C1i | 112.33 (8) | C11—C10—C15 | 121.0 (3) |
O8—La1—C1i | 140.52 (8) | C11—C10—C9 | 118.5 (3) |
O2—La1—C1i | 89.75 (8) | C15—C10—C9 | 120.5 (3) |
O15—La1—C1i | 73.57 (8) | C12—C11—C10 | 120.6 (4) |
O1i—La1—C1i | 24.58 (7) | C12—C11—H11 | 119.7 |
O14—La1—C1i | 65.99 (8) | C10—C11—H11 | 119.7 |
O2i—La1—C1i | 25.14 (7) | C11—C12—C13 | 119.8 (3) |
C1—O1—La1i | 95.36 (18) | C11—C12—H12 | 120.1 |
C1—O2—La1 | 140.9 (2) | C13—C12—H12 | 120.1 |
C1—O2—La1i | 94.15 (18) | C12—C13—C14 | 119.4 (4) |
La1—O2—La1i | 112.53 (8) | C12—C13—H13 | 120.3 |
C8—O3—La1 | 129.1 (2) | C14—C13—H13 | 120.3 |
C9—O7—H7 | 105.4 | C13—C14—C15 | 122.5 (3) |
C9—O8—La1 | 149.0 (2) | C13—C14—N2 | 116.9 (3) |
C16—O9—La1 | 122.26 (19) | C15—C14—N2 | 120.5 (3) |
La1—O13—H13A | 121.6 | C14—C15—C10 | 116.6 (3) |
La1—O13—H13B | 120.7 | C14—C15—C16 | 123.3 (3) |
H13A—O13—H13B | 115.3 | C10—C15—C16 | 120.1 (3) |
La1—O14—H14A | 116.1 | O10—C16—O9 | 126.7 (3) |
La1—O14—H14B | 123.0 | O10—C16—C15 | 115.8 (3) |
H14A—O14—H14B | 115.7 | O9—C16—C15 | 117.4 (3) |
La1—O15—H15A | 103.4 | H16A—O16—H16B | 115.9 |
| | | |
O13—La1—O2—C1 | 117.7 (3) | O2—C1—C2—C3 | 149.2 (3) |
O3—La1—O2—C1 | 70.6 (3) | C7—C2—C3—C4 | 0.2 (5) |
O9—La1—O2—C1 | −27.6 (3) | C1—C2—C3—C4 | 178.9 (3) |
O8—La1—O2—C1 | 17.8 (3) | C2—C3—C4—C5 | −0.9 (5) |
O15—La1—O2—C1 | −72.3 (3) | C3—C4—C5—C6 | 0.7 (5) |
O1i—La1—O2—C1 | −149.8 (3) | C4—C5—C6—C7 | 0.1 (5) |
O14—La1—O2—C1 | 153.7 (3) | C4—C5—C6—N1 | −177.5 (3) |
O2i—La1—O2—C1 | −129.5 (4) | O5—N1—C6—C5 | −175.2 (4) |
C1i—La1—O2—C1 | −141.4 (3) | O6—N1—C6—C5 | 4.5 (5) |
O13—La1—O2—La1i | −112.87 (12) | O5—N1—C6—C7 | 7.1 (5) |
O3—La1—O2—La1i | −159.93 (10) | O6—N1—C6—C7 | −173.2 (3) |
O9—La1—O2—La1i | 101.89 (9) | C3—C2—C7—C6 | 0.7 (5) |
O8—La1—O2—La1i | 147.28 (8) | C1—C2—C7—C6 | −178.0 (3) |
O15—La1—O2—La1i | 57.15 (12) | C3—C2—C7—C8 | 174.1 (3) |
O1i—La1—O2—La1i | −20.32 (11) | C1—C2—C7—C8 | −4.6 (5) |
O14—La1—O2—La1i | −76.84 (9) | C5—C6—C7—C2 | −0.8 (5) |
O2i—La1—O2—La1i | 0.0 | N1—C6—C7—C2 | 176.8 (3) |
C1i—La1—O2—La1i | −11.96 (9) | C5—C6—C7—C8 | −174.1 (3) |
O13—La1—O3—C8 | −161.3 (3) | N1—C6—C7—C8 | 3.5 (5) |
O9—La1—O3—C8 | 61.1 (3) | La1—O3—C8—O4 | 111.4 (3) |
O8—La1—O3—C8 | 129.1 (3) | La1—O3—C8—C7 | −66.6 (4) |
O2—La1—O3—C8 | −7.9 (3) | C2—C7—C8—O4 | −88.7 (4) |
O15—La1—O3—C8 | 117.8 (3) | C6—C7—C8—O4 | 84.4 (4) |
O1i—La1—O3—C8 | −110.1 (3) | C2—C7—C8—O3 | 89.6 (4) |
O14—La1—O3—C8 | −83.7 (3) | C6—C7—C8—O3 | −97.3 (4) |
O2i—La1—O3—C8 | −33.7 (3) | La1—O8—C9—O7 | 132.3 (4) |
C1i—La1—O3—C8 | −69.1 (3) | La1—O8—C9—C10 | −48.7 (6) |
O13—La1—O8—C9 | −122.6 (5) | O8—C9—C10—C11 | 159.7 (3) |
O3—La1—O8—C9 | −33.8 (4) | O7—C9—C10—C11 | −21.2 (5) |
O9—La1—O8—C9 | 63.3 (4) | O8—C9—C10—C15 | −20.7 (5) |
O2—La1—O8—C9 | 17.4 (5) | O7—C9—C10—C15 | 158.4 (3) |
O15—La1—O8—C9 | 139.1 (4) | C15—C10—C11—C12 | −1.4 (5) |
O1i—La1—O8—C9 | −176.0 (4) | C9—C10—C11—C12 | 178.2 (3) |
O14—La1—O8—C9 | −85.0 (4) | C10—C11—C12—C13 | −0.1 (6) |
O2i—La1—O8—C9 | 121.6 (4) | C11—C12—C13—C14 | 1.7 (6) |
C1i—La1—O8—C9 | 163.5 (4) | C12—C13—C14—C15 | −1.9 (6) |
O13—La1—O9—C16 | 11.8 (3) | C12—C13—C14—N2 | 180.0 (3) |
O3—La1—O9—C16 | 92.5 (2) | O11—N2—C14—C13 | −179.3 (3) |
O8—La1—O9—C16 | 19.9 (2) | O12—N2—C14—C13 | 1.4 (5) |
O2—La1—O9—C16 | 161.1 (2) | O11—N2—C14—C15 | 2.6 (5) |
O15—La1—O9—C16 | −55.6 (2) | O12—N2—C14—C15 | −176.7 (3) |
O1i—La1—O9—C16 | −94.2 (2) | C13—C14—C15—C10 | 0.5 (5) |
O14—La1—O9—C16 | 163.2 (2) | N2—C14—C15—C10 | 178.5 (3) |
O2i—La1—O9—C16 | −134.0 (2) | C13—C14—C15—C16 | −176.4 (3) |
C1i—La1—O9—C16 | −117.5 (2) | N2—C14—C15—C16 | 1.6 (5) |
La1i—O1—C1—O2 | −8.1 (3) | C11—C10—C15—C14 | 1.1 (5) |
La1i—O1—C1—C2 | 169.8 (2) | C9—C10—C15—C14 | −178.5 (3) |
La1—O2—C1—O1 | 142.4 (3) | C11—C10—C15—C16 | 178.2 (3) |
La1i—O2—C1—O1 | 8.1 (3) | C9—C10—C15—C16 | −1.4 (5) |
La1—O2—C1—C2 | −35.5 (5) | La1—O9—C16—O10 | 79.6 (4) |
La1i—O2—C1—C2 | −169.8 (3) | La1—O9—C16—C15 | −96.2 (3) |
La1—O2—C1—La1i | 134.4 (3) | C14—C15—C16—O10 | 89.6 (4) |
O1—C1—C2—C7 | 150.0 (3) | C10—C15—C16—O10 | −87.3 (4) |
O2—C1—C2—C7 | −32.1 (5) | C14—C15—C16—O9 | −94.1 (4) |
O1—C1—C2—C3 | −28.7 (4) | C10—C15—C16—O9 | 89.0 (4) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O16ii | 0.85 | 1.76 | 2.599 (4) | 168 |
O13—H13A···O16ii | 0.85 | 2.04 | 2.881 (4) | 169 |
O13—H13B···O4iii | 0.85 | 1.82 | 2.659 (3) | 169 |
O14—H14A···O9i | 0.85 | 2.19 | 3.036 (3) | 170 |
O14—H14B···O3iii | 0.85 | 2.07 | 2.916 (4) | 174 |
O15—H15A···O10 | 0.90 | 1.91 | 2.794 (4) | 168 |
O15—H15B···O1iv | 0.86 | 1.88 | 2.734 (4) | 168 |
O16—H16A···O10v | 0.85 | 2.04 | 2.756 (4) | 142 |
O16—H16B···O4vi | 0.85 | 1.91 | 2.747 (4) | 169 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y+1, z; (iii) −x, −y+2, −z+1; (iv) x, y+1, z; (v) x, y−1, z; (vi) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | C32H26La2N4O30·2H2O |
Mr | 1260.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 8.1700 (12), 8.9036 (13), 15.279 (2) |
α, β, γ (°) | 100.828 (2), 90.935 (2), 104.581 (2) |
V (Å3) | 1054.1 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.12 |
Crystal size (mm) | 0.24 × 0.22 × 0.18 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.593, 0.683 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5399, 3711, 3350 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.059, 1.06 |
No. of reflections | 3711 |
No. of parameters | 316 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.89, −0.90 |
Selected bond lengths (Å) topLa1—O13 | 2.466 (2) | La1—O14 | 2.615 (2) |
La1—O3 | 2.491 (2) | La1—O2i | 2.622 (2) |
La1—O9 | 2.511 (2) | O7—C9 | 1.300 (4) |
La1—O8 | 2.528 (2) | O8—C9 | 1.216 (4) |
La1—O2 | 2.535 (2) | O9—C16 | 1.264 (4) |
La1—O15 | 2.543 (2) | O10—C16 | 1.242 (4) |
La1—O1i | 2.610 (2) | | |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O16ii | 0.85 | 1.761 | 2.599 (4) | 168 |
O13—H13A···O16ii | 0.85 | 2.039 | 2.881 (4) | 169 |
O13—H13B···O4iii | 0.85 | 1.815 | 2.659 (3) | 169 |
O14—H14B···O3iii | 0.85 | 2.066 | 2.916 (4) | 174 |
O15—H15B···O1iv | 0.86 | 1.883 | 2.734 (4) | 168 |
O16—H16A···O10v | 0.85 | 2.036 | 2.756 (4) | 142 |
O16—H16B···O4vi | 0.85 | 1.906 | 2.747 (4) | 169 |
Symmetry codes: (ii) x−1, y+1, z; (iii) −x, −y+2, −z+1; (iv) x, y+1, z; (v) x, y−1, z; (vi) x+1, y, z. |
Rare-earth carboxylates show an intriguing variety of crystal structures as a result of the usually high coordination number of the metal ions and the many types of coordination displayed by carboxylate ligands in such complexes. Dimeric and polymeric forms are most frequently observed for these compounds (Quchi et al., 1988). Such complexes can be used as starting materials in a wide range of applications in materials science including superconductors, magnetic materials, catalysts and luminescent probes (Seo et al., 2000). There are some reports on the complexes of lanthanides with 3-nitro-1,2-benzenedicarboxylic acid (Brzyska & Kloc, 1992a,b; Makushova et al., 1989). We report here the preparation and crystal structure of the title compound: [La2(HL)2(L)2(H2O)6]·2H2O, (I), where L is (C8H3NO6).
The asymmetric unit of complex (I) consists of two La atoms, two L ligands, two HL ligands, six coordinated water molecules and two solvent water molecules (Fig. 1). Each La atom is coordinated by six O atoms of five different carboxylate groups and by three O atoms of water molecules. They adopt a distorted tricapped trigonal–prismatic arrangement, with atoms O3, O9, O2A, O13, O14 and O15 filling the vertexes and atoms O1A, O2 and O8 capping the rectangular faces (Fig. 2). A similar coordination environment was observed previously for lanthanoid(III) complexes, such as [La2(pyridine-3,4-dicarboxylic acid)2(NO3)2(H2O)3] (Qin et al., 2006) and [Ln2(4,5-imidazoledicarboxylate)2(H2O)3]·1.5H2O (Ln = Sm and Eu; Qin et al., 2005). The La—Ocarboxylate bond distances range from 2.491 (2) to 2.622 (2) Å (mean 2.549 Å), and those of the La—Oaqua bonds from 2.466 (2) to 2.615 (2) Å (mean 2.541 Å), all of which are within the range of those observed for other nine-coordinate LaIII complexes with oxygen donor ligands (Kiritsis et al., 1998; Pan et al., 2000; Qin et al., 2006). The resulting La···La intradimer separation is 4.289 (s.u.?) Å. It is noteworthy that complex (I) contains both protonated (HL) and deprotonated (L) groups. The HL ligand adopts a bis(monodentate) coordination mode, in which the distances within the acid group are significantly different [C9—O7 = 1.300 (4) and C9—O8 = 1.216 (4) Å, and C16—O9 = 1.264 (4) and C16—O10 = 1.242 (4) Å], despite the fact that one is an acid group and the other is a carboxylate group. The L ligand adopts a bidentate chelating–monodentate coordination mode, which acts as a µ2-bridge through one µ3-bridging O atom [O2(1 − x, 2 − y, 1 − z)] and two monodentate O atoms (O1 and O3) to link two LaIII atoms. The coordination mode contrasts with that in the [La2(pyridine-3,4-dicarboxylic acid)2(NO3)2(H2O)3] complex, in which the carboxylate groups adopt two kinds of coordination modes: one is monodentate–bidentate, and the other is chelating–bidentate (Qin et al., 2006).
In the HL ligand, one carboxylate group shows a distortion from the molecular plane; the dihedral angle between the planes of the benzene ring (C2–C7; plane I) and the carboxylate group atoms (O1/C1/O2; plane II) is 30.49°. The other carboxylate group is almost perpendicular to the molecular plane; the dihedral angle between plane I and the plane formed by the carboxylate group atoms O3, C8 and O4 is 87.38°. These features are similar to those in the L ligand, in which the dihedral angle between the C10–C15 (plane IV) and O8/C9/O7 planes is 21.10°, and that between plane IV and the O10/C16/O9 plane is 89.21°. Within each ligand, the nitro groups are almost coplanar with the benzene ring; the dihedral angle between plane I and the N1/O5/O6 plane is 6.36°, and that between plane IV and the N2/O11/O12 plane is 2.72°. Finally, the dihedral angle between the two benzene rings (planes I and IV) is 12.38°.
Intermolecular hydrogen bonds [O3carboxylate···O14aqua, O4carboxylate···O13aqua, O7carboxylate···O16water and O13aqua···O16water; Table 2] bridge the molecules, forming an infinite chain along the a axis, and intermolecular hydrogen bonds between O15aqua and O1carboxylate and between O16water and O4carboxylate generate an infinite chain along the b axis. The solvent water molecule O16 in the structure is in a tetrahedral environment with one water–water interaction, two water–caboxylate interactions involving O atoms of the HL ligand and one water–carboxylate interaction with an O atom of the L ligand. There are slipped π–π stacking interactions between the parallel benzene rings of the HL lignds with a distance of C13···C14 = 3.404 Å (Fig. 3), which interlink molecules into an infinite one-dimensional chain along the c axis and further interconnect a two-dimensional structure into a three-dimensional supramolecular network (Fig.4).