Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112002247/ku3062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112002247/ku3062Isup2.hkl |
CCDC reference: 873873
A mixture of La2O3 (0. 215 g, 0.66 mmol) and crotonic acid (0.344 g, 4.0 mmol) was dissolved in water (200 ml), followed by the addition of adenine (0.089 g, 0.66 mmol) dissolved in ethanol (?? ml). The resultant mixture was refluxed for 24 h and filtered. The filtrate was left to stand at room temperature. On standing, colourless crystals suitable for single X-ray diffraction analysis appeared, which were used without further processing. All the reagents and solvents were commercially available and were used without additional purification.
One of the crotonate units (trailing number 3) appeared with its tail disordered in two sets of dissimilar populations, which refined to 0.615 (4) and 0.385 (4). Similarity restraints were applied to the chemically equivalent bond lengths and angles involving the disordered C atoms, while the anisotropic displacement factors of the two positions of each disordered atom were constrained to be equal [instructions SADI 0.01 and EADP in SHELXTL (Sheldrick, 2008)]. As a result of the disorder, the angles at atom C13, which is bonded to both disordered and nondisordered atoms, ended up having slightly unrealistic values.
H atoms in the ordered part of the structure were clearly seen in a difference Fourier map, but were treated differently in the refinement: H atoms on C atoms were repositioned at their expected locations, and allowed to ride both in coordinates and in isotropic displacement parameters [Uiso(H) = 1.2Ueq(C) and C—H = 0.95 Å for methine H atoms and Uiso(H) = 1.5Ueq(C) and C—H = 0.98 Å for methyl H atoms]. H atoms attached to N and O atoms were refined with a restrained N—H distance of 0.85 (1) Å and free Uiso(H) values.
The checkCIF procedure gave a type B alert on the Hirshfeld test involving the La1—O23 pair. Even if not always genuine, this type of alert may be caused by a wrong assignment of some of the intervening atomic species. The careful synthetic conditions, as well as a variety of refinement trials with different atomic assignments, proved the alert was, in this case, an artifact.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 20080 and PLATON (Spek, 2009).
[La(C4H5O2)3(H2O)2]·C5H5N5·H2O | Z = 2 |
Mr = 583.34 | F(000) = 584 |
Triclinic, P1 | Dx = 1.664 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9484 (11) Å | Cell parameters from 6882 reflections |
b = 11.4743 (14) Å | θ = 3.4–26.0° |
c = 12.3985 (15) Å | µ = 1.89 mm−1 |
α = 68.978 (2)° | T = 150 K |
β = 84.418 (2)° | Blocks, colourless |
γ = 78.501 (2)° | 0.46 × 0.25 × 0.18 mm |
V = 1164.0 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 4569 independent reflections |
Radiation source: fine-focus sealed tube | 4445 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.010 |
CCD rotation images, thin slices scans | θmax = 26.0°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −10→11 |
Tmin = 0.79, Tmax = 0.89 | k = −12→14 |
6882 measured reflections | l = −14→15 |
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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.9326P] where P = (Fo2 + 2Fc2)/3 |
4569 reflections | (Δ/σ)max = 0.003 |
339 parameters | Δρmax = 0.93 e Å−3 |
27 restraints | Δρmin = −0.61 e Å−3 |
[La(C4H5O2)3(H2O)2]·C5H5N5·H2O | γ = 78.501 (2)° |
Mr = 583.34 | V = 1164.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9484 (11) Å | Mo Kα radiation |
b = 11.4743 (14) Å | µ = 1.89 mm−1 |
c = 12.3985 (15) Å | T = 150 K |
α = 68.978 (2)° | 0.46 × 0.25 × 0.18 mm |
β = 84.418 (2)° |
Bruker SMART CCD area-detector diffractometer | 4569 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 4445 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.89 | Rint = 0.010 |
6882 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 27 restraints |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.93 e Å−3 |
4569 reflections | Δρmin = −0.61 e Å−3 |
339 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
La1 | 0.258113 (12) | 0.469516 (10) | 0.505134 (9) | 0.01609 (5) | |
O11 | 0.51850 (17) | 0.52119 (15) | 0.38310 (14) | 0.0204 (3) | |
O21 | 0.34019 (17) | 0.49029 (16) | 0.29089 (14) | 0.0233 (3) | |
C11 | 0.4771 (2) | 0.4981 (2) | 0.29785 (18) | 0.0190 (4) | |
C21 | 0.5959 (3) | 0.4753 (2) | 0.2121 (2) | 0.0240 (5) | |
H21 | 0.6869 | 0.5087 | 0.2048 | 0.029* | |
C31 | 0.5814 (3) | 0.4112 (3) | 0.1457 (2) | 0.0314 (5) | |
H31 | 0.4857 | 0.3862 | 0.1482 | 0.038* | |
C41 | 0.7037 (4) | 0.3744 (3) | 0.0664 (3) | 0.0479 (8) | |
H41A | 0.6672 | 0.4091 | −0.0129 | 0.072* | |
H41B | 0.7291 | 0.2817 | 0.0907 | 0.072* | |
H41C | 0.7948 | 0.4083 | 0.0695 | 0.072* | |
O12 | 0.26433 (17) | 0.70966 (15) | 0.45845 (14) | 0.0225 (3) | |
O22 | 0.12796 (17) | 0.62492 (15) | 0.61462 (14) | 0.0209 (3) | |
C12 | 0.1885 (2) | 0.7178 (2) | 0.5477 (2) | 0.0214 (4) | |
C22 | 0.1698 (3) | 0.8367 (2) | 0.5730 (2) | 0.0307 (5) | |
H22 | 0.2180 | 0.9033 | 0.5219 | 0.037* | |
C32 | 0.0909 (3) | 0.8553 (3) | 0.6616 (2) | 0.0333 (6) | |
H32 | 0.0443 | 0.7875 | 0.7125 | 0.040* | |
C42 | 0.0674 (4) | 0.9747 (3) | 0.6898 (3) | 0.0516 (8) | |
H42A | 0.1167 | 0.9572 | 0.7625 | 0.077* | |
H42B | −0.0421 | 1.0049 | 0.6978 | 0.077* | |
H42C | 0.1122 | 1.0398 | 0.6275 | 0.077* | |
O13 | −0.01923 (17) | 0.41021 (15) | 0.61065 (14) | 0.0212 (3) | |
O23 | 0.19047 (19) | 0.31923 (16) | 0.70748 (14) | 0.0272 (4) | |
C13 | 0.0487 (3) | 0.3291 (2) | 0.69897 (19) | 0.0205 (4) | |
C23" | −0.0654 (9) | 0.2537 (8) | 0.7743 (6) | 0.0239 (9) | 0.385 (4) |
H23" | −0.1689 | 0.2754 | 0.7523 | 0.029* | 0.385 (4) |
C33" | −0.0257 (7) | 0.1580 (5) | 0.8704 (5) | 0.0260 (7) | 0.385 (4) |
H33" | 0.0784 | 0.1371 | 0.8907 | 0.031* | 0.385 (4) |
C43" | −0.1350 (9) | 0.0799 (8) | 0.9496 (7) | 0.0412 (9) | 0.385 (4) |
H43A | −0.1127 | −0.0058 | 0.9461 | 0.062* | 0.385 (4) |
H43B | −0.2397 | 0.1194 | 0.9254 | 0.062* | 0.385 (4) |
H43C | −0.1239 | 0.0753 | 1.0289 | 0.062* | 0.385 (4) |
C23' | −0.0187 (5) | 0.2417 (5) | 0.8037 (4) | 0.0239 (9) | 0.615 (4) |
H23' | 0.0415 | 0.1992 | 0.8703 | 0.029* | 0.615 (4) |
C33' | −0.1585 (4) | 0.2211 (4) | 0.8074 (3) | 0.0260 (7) | 0.615 (4) |
H33' | −0.2176 | 0.2662 | 0.7406 | 0.031* | 0.615 (4) |
C43' | −0.2320 (6) | 0.1325 (5) | 0.9085 (4) | 0.0412 (9) | 0.615 (4) |
H43D | −0.3287 | 0.1779 | 0.9293 | 0.062* | 0.615 (4) |
H43E | −0.1641 | 0.0995 | 0.9742 | 0.062* | 0.615 (4) |
H43F | −0.2515 | 0.0619 | 0.8882 | 0.062* | 0.615 (4) |
N1 | 0.3744 (2) | 0.14894 (19) | 0.02733 (17) | 0.0256 (4) | |
N2 | 0.2275 (2) | 0.28142 (19) | 0.10650 (18) | 0.0249 (4) | |
H2 | 0.162 (3) | 0.343 (2) | 0.113 (3) | 0.047 (10)* | |
N3 | 0.3158 (2) | 0.18264 (19) | 0.30451 (17) | 0.0262 (4) | |
N4 | 0.5099 (2) | −0.00355 (19) | 0.32845 (17) | 0.0261 (4) | |
N5 | 0.5979 (3) | −0.0788 (2) | 0.17952 (18) | 0.0308 (5) | |
H5A | 0.656 (3) | −0.142 (2) | 0.225 (2) | 0.040 (9)* | |
H5B | 0.591 (4) | −0.081 (3) | 0.1127 (14) | 0.034 (8)* | |
C1 | 0.2685 (3) | 0.2507 (2) | 0.0098 (2) | 0.0266 (5) | |
H1 | 0.2246 | 0.2983 | −0.0633 | 0.032* | |
C2 | 0.3154 (3) | 0.1915 (2) | 0.1933 (2) | 0.0214 (4) | |
C3 | 0.4154 (3) | 0.0832 (2) | 0.3644 (2) | 0.0279 (5) | |
H3 | 0.4209 | 0.0716 | 0.4438 | 0.034* | |
C4 | 0.5065 (3) | 0.0070 (2) | 0.2162 (2) | 0.0232 (5) | |
C5 | 0.4051 (3) | 0.1104 (2) | 0.14338 (19) | 0.0220 (4) | |
O1W | 0.44769 (18) | 0.26588 (15) | 0.53948 (15) | 0.0237 (3) | |
H1WA | 0.435 (4) | 0.1905 (14) | 0.575 (2) | 0.039 (9)* | |
H1WB | 0.5398 (15) | 0.261 (3) | 0.553 (3) | 0.039 (8)* | |
O2W | 0.16734 (17) | 0.30103 (15) | 0.45501 (14) | 0.0216 (3) | |
H2WA | 0.218 (3) | 0.276 (3) | 0.404 (2) | 0.042 (9)* | |
H2WB | 0.0770 (16) | 0.324 (3) | 0.431 (2) | 0.028 (7)* | |
O3W | 0.0578 (2) | 0.47256 (18) | 0.17762 (16) | 0.0313 (4) | |
H3WB | −0.002 (3) | 0.444 (3) | 0.234 (2) | 0.047 (10)* | |
H3WA | 0.129 (4) | 0.492 (4) | 0.205 (4) | 0.073 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.01078 (7) | 0.01818 (8) | 0.02088 (8) | −0.00018 (5) | −0.00168 (5) | −0.00963 (5) |
O11 | 0.0146 (7) | 0.0246 (8) | 0.0242 (8) | −0.0016 (6) | −0.0020 (6) | −0.0118 (7) |
O21 | 0.0141 (7) | 0.0320 (9) | 0.0257 (8) | −0.0030 (6) | −0.0023 (6) | −0.0125 (7) |
C11 | 0.0175 (10) | 0.0162 (10) | 0.0216 (10) | −0.0006 (8) | −0.0028 (8) | −0.0053 (8) |
C21 | 0.0163 (10) | 0.0308 (12) | 0.0222 (11) | −0.0024 (9) | −0.0005 (9) | −0.0068 (9) |
C31 | 0.0292 (13) | 0.0359 (14) | 0.0300 (13) | −0.0029 (11) | 0.0008 (10) | −0.0146 (11) |
C41 | 0.0499 (18) | 0.060 (2) | 0.0345 (15) | 0.0071 (15) | 0.0020 (14) | −0.0273 (15) |
O12 | 0.0164 (7) | 0.0217 (8) | 0.0298 (8) | −0.0005 (6) | −0.0021 (6) | −0.0106 (7) |
O22 | 0.0148 (7) | 0.0229 (8) | 0.0282 (8) | −0.0010 (6) | −0.0009 (6) | −0.0140 (7) |
C12 | 0.0100 (9) | 0.0253 (11) | 0.0308 (12) | 0.0008 (8) | −0.0070 (8) | −0.0124 (9) |
C22 | 0.0273 (12) | 0.0263 (12) | 0.0419 (14) | −0.0059 (10) | −0.0003 (11) | −0.0155 (11) |
C32 | 0.0343 (14) | 0.0305 (13) | 0.0415 (15) | −0.0012 (11) | −0.0039 (12) | −0.0216 (12) |
C42 | 0.064 (2) | 0.0419 (17) | 0.062 (2) | −0.0014 (15) | −0.0027 (17) | −0.0375 (16) |
O13 | 0.0142 (7) | 0.0241 (8) | 0.0257 (8) | 0.0009 (6) | −0.0011 (6) | −0.0113 (7) |
O23 | 0.0200 (8) | 0.0310 (9) | 0.0267 (8) | 0.0046 (7) | −0.0050 (7) | −0.0093 (7) |
C13 | 0.0217 (11) | 0.0177 (10) | 0.0225 (11) | −0.0006 (8) | 0.0025 (9) | −0.0098 (9) |
C23" | 0.028 (3) | 0.0259 (17) | 0.017 (2) | −0.004 (2) | −0.0047 (17) | −0.0058 (17) |
C33" | 0.0274 (17) | 0.0255 (16) | 0.0265 (16) | −0.0079 (13) | 0.0029 (13) | −0.0101 (13) |
C43" | 0.044 (2) | 0.040 (2) | 0.037 (2) | −0.0182 (18) | 0.0061 (17) | −0.0066 (18) |
C23' | 0.028 (3) | 0.0259 (17) | 0.017 (2) | −0.004 (2) | −0.0047 (17) | −0.0058 (17) |
C33' | 0.0274 (17) | 0.0255 (16) | 0.0265 (16) | −0.0079 (13) | 0.0029 (13) | −0.0101 (13) |
C43' | 0.044 (2) | 0.040 (2) | 0.037 (2) | −0.0182 (18) | 0.0061 (17) | −0.0066 (18) |
N1 | 0.0294 (10) | 0.0243 (10) | 0.0212 (10) | 0.0015 (8) | −0.0020 (8) | −0.0086 (8) |
N2 | 0.0259 (10) | 0.0206 (10) | 0.0265 (10) | 0.0047 (8) | −0.0047 (8) | −0.0097 (8) |
N3 | 0.0299 (11) | 0.0255 (10) | 0.0249 (10) | 0.0030 (8) | −0.0026 (8) | −0.0146 (8) |
N4 | 0.0289 (11) | 0.0258 (10) | 0.0233 (10) | 0.0038 (8) | −0.0059 (8) | −0.0115 (8) |
N5 | 0.0353 (12) | 0.0308 (11) | 0.0227 (10) | 0.0133 (9) | −0.0069 (9) | −0.0135 (9) |
C1 | 0.0309 (12) | 0.0251 (11) | 0.0230 (11) | 0.0002 (10) | −0.0048 (9) | −0.0091 (9) |
C2 | 0.0198 (10) | 0.0194 (10) | 0.0244 (11) | 0.0000 (8) | −0.0012 (9) | −0.0088 (9) |
C3 | 0.0344 (13) | 0.0272 (12) | 0.0224 (11) | 0.0037 (10) | −0.0061 (10) | −0.0122 (10) |
C4 | 0.0224 (11) | 0.0234 (11) | 0.0234 (11) | 0.0005 (9) | −0.0014 (9) | −0.0098 (9) |
C5 | 0.0226 (11) | 0.0226 (11) | 0.0215 (11) | −0.0015 (9) | 0.0011 (9) | −0.0102 (9) |
O1W | 0.0131 (7) | 0.0203 (8) | 0.0365 (9) | 0.0002 (6) | −0.0036 (7) | −0.0096 (7) |
O2W | 0.0126 (7) | 0.0279 (8) | 0.0301 (9) | −0.0003 (6) | −0.0022 (6) | −0.0183 (7) |
O3W | 0.0365 (11) | 0.0291 (9) | 0.0291 (9) | −0.0004 (8) | 0.0020 (8) | −0.0149 (8) |
La1—O1W | 2.5229 (16) | C23"—C33" | 1.319 (6) |
La1—O2W | 2.5239 (16) | C23"—H23" | 0.9500 |
La1—O13i | 2.5562 (16) | C33"—C43" | 1.501 (6) |
La1—O23 | 2.5789 (17) | C33"—H33" | 0.9500 |
La1—O11ii | 2.5802 (15) | C43"—H43A | 0.9800 |
La1—O12 | 2.6156 (16) | C43"—H43B | 0.9800 |
La1—O21 | 2.6246 (16) | C43"—H43C | 0.9800 |
La1—O22 | 2.6419 (15) | C23'—C33' | 1.312 (5) |
La1—O11 | 2.7002 (16) | C23'—H23' | 0.9500 |
La1—O13 | 2.7815 (16) | C33'—C43' | 1.493 (5) |
La1—C12 | 3.015 (2) | C33'—H33' | 0.9500 |
La1—C11 | 3.037 (2) | C43'—H43D | 0.9800 |
O11—C11 | 1.281 (3) | C43'—H43E | 0.9800 |
O21—C11 | 1.260 (3) | C43'—H43F | 0.9800 |
C11—C21 | 1.482 (3) | N1—C1 | 1.313 (3) |
C21—C31 | 1.316 (3) | N1—C5 | 1.383 (3) |
C21—H21 | 0.9500 | N2—C1 | 1.365 (3) |
C31—C41 | 1.500 (3) | N2—C2 | 1.373 (3) |
C31—H31 | 0.9500 | N2—H2 | 0.852 (10) |
C41—H41A | 0.9800 | N3—C3 | 1.328 (3) |
C41—H41B | 0.9800 | N3—C2 | 1.346 (3) |
C41—H41C | 0.9800 | N4—C3 | 1.346 (3) |
O12—C12 | 1.263 (3) | N4—C4 | 1.355 (3) |
O22—C12 | 1.275 (3) | N5—C4 | 1.332 (3) |
C12—C22 | 1.481 (3) | N5—H5A | 0.851 (10) |
C22—C32 | 1.307 (3) | N5—H5B | 0.847 (10) |
C22—H22 | 0.9500 | C1—H1 | 0.9500 |
C32—C42 | 1.503 (3) | C2—C5 | 1.383 (3) |
C32—H32 | 0.9500 | C3—H3 | 0.9500 |
C42—H42A | 0.9800 | C4—C5 | 1.417 (3) |
C42—H42B | 0.9800 | O1W—H1WA | 0.843 (10) |
C42—H42C | 0.9800 | O1W—H1WB | 0.845 (10) |
O13—C13 | 1.268 (3) | O2W—H2WA | 0.844 (10) |
O23—C13 | 1.262 (3) | O2W—H2WB | 0.847 (10) |
C13—C23' | 1.487 (4) | O3W—H3WB | 0.845 (10) |
C13—C23" | 1.501 (6) | O3W—H3WA | 0.848 (10) |
O1W—La1—O2W | 65.02 (5) | C31—C41—H41C | 109.5 |
O1W—La1—O13i | 139.60 (5) | H41A—C41—H41C | 109.5 |
O2W—La1—O13i | 76.63 (5) | H41B—C41—H41C | 109.5 |
O1W—La1—O23 | 74.01 (5) | C12—O12—La1 | 95.67 (13) |
O2W—La1—O23 | 78.82 (6) | C12—O22—La1 | 94.11 (13) |
O13i—La1—O23 | 111.59 (5) | O12—C12—O22 | 120.3 (2) |
O1W—La1—O11ii | 72.08 (5) | O12—C12—C22 | 119.2 (2) |
O2W—La1—O11ii | 136.12 (5) | O22—C12—C22 | 120.5 (2) |
O13i—La1—O11ii | 147.25 (5) | O12—C12—La1 | 59.69 (11) |
O23—La1—O11ii | 81.12 (5) | O22—C12—La1 | 60.93 (11) |
O1W—La1—O12 | 137.58 (5) | C22—C12—La1 | 174.31 (16) |
O2W—La1—O12 | 148.87 (5) | C32—C22—C12 | 123.8 (2) |
O13i—La1—O12 | 74.71 (5) | C32—C22—H22 | 118.1 |
O23—La1—O12 | 123.30 (5) | C12—C22—H22 | 118.1 |
O11ii—La1—O12 | 73.25 (5) | C22—C32—C42 | 125.6 (3) |
O1W—La1—O21 | 79.99 (5) | C22—C32—H32 | 117.2 |
O2W—La1—O21 | 70.36 (5) | C42—C32—H32 | 117.2 |
O13i—La1—O21 | 75.46 (5) | C32—C42—H42A | 109.5 |
O23—La1—O21 | 145.94 (5) | C32—C42—H42B | 109.5 |
O11ii—La1—O21 | 111.46 (5) | H42A—C42—H42B | 109.5 |
O12—La1—O21 | 90.75 (5) | C32—C42—H42C | 109.5 |
O1W—La1—O22 | 140.03 (5) | H42A—C42—H42C | 109.5 |
O2W—La1—O22 | 133.15 (5) | H42B—C42—H42C | 109.5 |
O13i—La1—O22 | 76.68 (5) | C13—O13—La1i | 152.84 (14) |
O23—La1—O22 | 76.23 (5) | C13—O13—La1 | 90.70 (13) |
O11ii—La1—O22 | 77.51 (5) | La1i—O13—La1 | 116.46 (6) |
O12—La1—O22 | 49.50 (5) | C13—O23—La1 | 100.51 (13) |
O21—La1—O22 | 136.33 (5) | O23—C13—O13 | 120.2 (2) |
O1W—La1—O11 | 70.77 (5) | O23—C13—C23' | 111.6 (2) |
O2W—La1—O11 | 108.80 (5) | O13—C13—C23' | 128.1 (3) |
O13i—La1—O11 | 112.73 (5) | O23—C13—C23" | 131.7 (3) |
O23—La1—O11 | 135.58 (5) | O13—C13—C23" | 108.0 (3) |
O11ii—La1—O11 | 62.97 (6) | O23—C13—La1 | 55.66 (11) |
O12—La1—O11 | 72.13 (5) | O13—C13—La1 | 64.92 (11) |
O21—La1—O11 | 48.84 (5) | C23'—C13—La1 | 166.6 (2) |
O22—La1—O11 | 116.83 (5) | C23"—C13—La1 | 168.1 (3) |
O1W—La1—O13 | 108.48 (5) | C33"—C23"—C13 | 121.7 (6) |
O2W—La1—O13 | 65.81 (5) | C33"—C23"—H23" | 119.2 |
O13i—La1—O13 | 63.54 (6) | C13—C23"—H23" | 119.2 |
O23—La1—O13 | 48.12 (5) | C23"—C33"—C43" | 124.0 (6) |
O11ii—La1—O13 | 123.04 (5) | C23"—C33"—H33" | 118.0 |
O12—La1—O13 | 110.60 (5) | C43"—C33"—H33" | 118.0 |
O21—La1—O13 | 124.96 (5) | C33'—C23'—C13 | 122.3 (4) |
O22—La1—O13 | 67.95 (5) | C33'—C23'—H23' | 118.8 |
O11—La1—O13 | 173.72 (4) | C13—C23'—H23' | 118.8 |
O1W—La1—C12 | 144.35 (5) | C23'—C33'—C43' | 125.1 (4) |
O2W—La1—C12 | 149.50 (5) | C23'—C33'—H33' | 117.4 |
O13i—La1—C12 | 75.79 (5) | C43'—C33'—H33' | 117.4 |
O23—La1—C12 | 99.53 (6) | C33'—C43'—H43D | 109.5 |
O11ii—La1—C12 | 72.29 (5) | C33'—C43'—H43E | 109.5 |
O12—La1—C12 | 24.64 (6) | H43D—C43'—H43E | 109.5 |
O21—La1—C12 | 114.35 (6) | C33'—C43'—H43F | 109.5 |
O22—La1—C12 | 24.96 (6) | H43D—C43'—H43F | 109.5 |
O11—La1—C12 | 93.76 (5) | H43E—C43'—H43F | 109.5 |
O13—La1—C12 | 90.18 (5) | C1—N1—C5 | 104.12 (19) |
O1W—La1—C11 | 70.77 (6) | C1—N2—C2 | 105.92 (19) |
O2W—La1—C11 | 87.33 (5) | C1—N2—H2 | 128 (2) |
O13i—La1—C11 | 96.13 (5) | C2—N2—H2 | 126 (2) |
O23—La1—C11 | 144.77 (5) | C3—N3—C2 | 111.4 (2) |
O11ii—La1—C11 | 87.13 (5) | C3—N4—C4 | 118.3 (2) |
O12—La1—C11 | 83.88 (5) | C4—N5—H5A | 122 (2) |
O21—La1—C11 | 24.33 (5) | C4—N5—H5B | 122 (2) |
O22—La1—C11 | 133.27 (5) | H5A—N5—H5B | 115 (3) |
O11—La1—C11 | 24.92 (5) | N1—C1—N2 | 113.6 (2) |
O13—La1—C11 | 148.80 (5) | N1—C1—H1 | 123.2 |
C12—La1—C11 | 108.32 (6) | N2—C1—H1 | 123.2 |
C11—O11—La1ii | 147.07 (14) | N3—C2—N2 | 127.7 (2) |
C11—O11—La1 | 92.43 (12) | N3—C2—C5 | 126.4 (2) |
La1ii—O11—La1 | 117.03 (6) | N2—C2—C5 | 105.9 (2) |
C11—O21—La1 | 96.51 (13) | N3—C3—N4 | 129.2 (2) |
O21—C11—O11 | 120.18 (19) | N3—C3—H3 | 115.4 |
O21—C11—C21 | 121.8 (2) | N4—C3—H3 | 115.4 |
O11—C11—C21 | 118.00 (19) | N5—C4—N4 | 119.1 (2) |
O21—C11—La1 | 59.15 (11) | N5—C4—C5 | 123.2 (2) |
O11—C11—La1 | 62.65 (11) | N4—C4—C5 | 117.7 (2) |
C21—C11—La1 | 164.82 (15) | C2—C5—N1 | 110.4 (2) |
C31—C21—C11 | 123.1 (2) | C2—C5—C4 | 117.1 (2) |
C31—C21—H21 | 118.4 | N1—C5—C4 | 132.5 (2) |
C11—C21—H21 | 118.4 | La1—O1W—H1WA | 129 (2) |
C21—C31—C41 | 125.2 (3) | La1—O1W—H1WB | 121 (2) |
C21—C31—H31 | 117.4 | H1WA—O1W—H1WB | 101 (3) |
C41—C31—H31 | 117.4 | La1—O2W—H2WA | 117 (2) |
C31—C41—H41A | 109.5 | La1—O2W—H2WB | 113 (2) |
C31—C41—H41B | 109.5 | H2WA—O2W—H2WB | 104 (3) |
H41A—C41—H41B | 109.5 | H3WB—O3W—H3WA | 106 (4) |
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 |
N2—H2···O3W | 0.85 (1) | 1.96 (2) | 2.774 (3) | 159 (3) |
N5—H5A···O23iii | 0.85 (1) | 2.15 (1) | 2.970 (3) | 162 (3) |
N5—H5B···N1iv | 0.85 (1) | 2.12 (2) | 2.927 (3) | 159 (3) |
O1W—H1WA···N4iii | 0.84 (1) | 2.03 (2) | 2.831 (3) | 158 (3) |
O1W—H1WB···O12ii | 0.85 (1) | 1.83 (1) | 2.651 (2) | 162 (3) |
O2W—H2WA···N3 | 0.84 (1) | 1.95 (1) | 2.776 (2) | 167 (3) |
O2W—H2WB···O22i | 0.85 (1) | 1.89 (1) | 2.733 (2) | 177 (3) |
O3W—H3WA···O21 | 0.85 (1) | 2.25 (2) | 3.082 (3) | 166 (4) |
O3W—H3WB···O22i | 0.85 (1) | 2.07 (1) | 2.914 (3) | 173 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [La(C4H5O2)3(H2O)2]·C5H5N5·H2O |
Mr | 583.34 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.9484 (11), 11.4743 (14), 12.3985 (15) |
α, β, γ (°) | 68.978 (2), 84.418 (2), 78.501 (2) |
V (Å3) | 1164.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.89 |
Crystal size (mm) | 0.46 × 0.25 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) |
Tmin, Tmax | 0.79, 0.89 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6882, 4569, 4445 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.057, 1.05 |
No. of reflections | 4569 |
No. of parameters | 339 |
No. of restraints | 27 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.93, −0.61 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 20080 and PLATON (Spek, 2009).
La1—O1W | 2.5229 (16) | La1—O12 | 2.6156 (16) |
La1—O2W | 2.5239 (16) | La1—O21 | 2.6246 (16) |
La1—O13i | 2.5562 (16) | La1—O22 | 2.6419 (15) |
La1—O23 | 2.5789 (17) | La1—O11 | 2.7002 (16) |
La1—O11ii | 2.5802 (15) | La1—O13 | 2.7815 (16) |
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 |
N2—H2···O3W | 0.852 (10) | 1.962 (16) | 2.774 (3) | 159 (3) |
N5—H5A···O23iii | 0.851 (10) | 2.149 (14) | 2.970 (3) | 162 (3) |
N5—H5B···N1iv | 0.847 (10) | 2.119 (15) | 2.927 (3) | 159 (3) |
O1W—H1WA···N4iii | 0.843 (10) | 2.033 (16) | 2.831 (3) | 158 (3) |
O1W—H1WB···O12ii | 0.845 (10) | 1.833 (14) | 2.651 (2) | 162 (3) |
O2W—H2WA···N3 | 0.844 (10) | 1.947 (13) | 2.776 (2) | 167 (3) |
O2W—H2WB···O22i | 0.847 (10) | 1.887 (10) | 2.733 (2) | 177 (3) |
O3W—H3WA···O21 | 0.848 (10) | 2.254 (15) | 3.082 (3) | 166 (4) |
O3W—H3WB···O22i | 0.845 (10) | 2.073 (11) | 2.914 (3) | 173 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z. |
Homonuclear systems with ligands that serve as molecular bridges between metal centres have received considerable attention over the years (Fujita et al., 1994; Lu & Babb, 2001; Thompson, 2002). A point of interest in these systems is the possibility to introduce extra ligands as bridges and thus obtain grid structures and/or clusters, which are appealing not only structurally, but also for their potential application, e.g. in ion exchange, catalysis, molecular absorption, optical, electronic and magnetic areas (Ma et al., 2000; Wang et al., 2002; Xu et al., 2002; Benelli & Gatteschi, 2002; Pan et al., 2004). We have for some time focused our attention on the efficiency of crotonic acid (Hcrot or but-2-enoic acid) to couple LnIII ions and as a result we have described the synthesis, structural and magnetic characterization of a number of lanthanide complexes displaying these types of bridges (Rizzi et al., 2003; Baggio et al., 2003, 2005; Atria et al., 2004; Muñoz et al., 2005; Perec et al., 2008).
In parallel, our investigation on carboxylate complexes showed us that the incorporation of some purine derivatives (in our case, 2,6-diaminopurine, dap) might facilitate crystallization, either through their inclusion as neutral cocrystallization agents (Atria et al., 2009), or as counter-ions (Atria, Morel et al., 2011) or even as coordinating ligands (Atria, Corsini et al., 2011; Atria, Garland et al., 2011).
We present herein our first result with adenine (ade), a close relative to dap which a preliminary literature search [Cambridge Structural Database (CSD), Version 5.32; Allen, 2002] had shown to be equally versatile and which in conjunction with crotonic acid led to the title La complex formulated as {[Ln(crot)3(H2O)2].ade.H2O}n, (I). In this complex, the adenine molecule appears unbound, but fulfils an esential role in crystal stabilization.
Fig. 1 shows the asymmetric unit of (I), consisting of an La1 cation, three crotonate anions and two coordinated water molecules determining the neutral complex, completed by an external adenine and one hydration water molecule. The three crotonate anions (distinguished by their trailing numbers 1, 2 and 3) act in a chelating way. Units 1 and 3 have in addition one of their carboxylate O atoms (O11 and O13) shared by neigbouring coordination polyhedra (Fig. 1), thus giving rise to chains which evolve along [100]. In addition to the eight sites thus provided by the carboxylate O atoms to the La environment, there are two extra water O atoms, completing a tenfold coordination. These latter La—Oaq bonds are very similar in length, as well as the shortest in the whole set (Table 1); those coming from crotonate anions, instead, present a broader span [2.556 (2)–2.781 (2) Å]. The whole coordination assembly resembles a slightly distorted bicapped square antiprism (Fig. 1, inset), with atoms O11 and O13 at the apices, defining an almost straight vertical axis [O11—La1—O13 = 173.72 (4) °].
As stated, the µ2κ3 binding modes displayed by the crot1 and crot3 ligands generate a one-dimensional structure parallel to [100]. Fig. 2 shows a partial view of one of these [La(crot)3(H2O)2] chains. The main motifs are the two different (LaO)2 loops (A and B in Fig. 2), leading to La1···La1 intercationic distances of La1···La1i = 4.5394 (6) and La1···La1ii = 4.5036 (6) Å [symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x+1, -y + 1, -z + 1], and giving the chain a slightly twisted character as measured by the La1i···La1···La1ii angle of 163.40 (2)° and an interplanar dihedral angle of 38.42 (2)°.
These loops, flanked by two chelating carboxylate groups, act as the only covalent links in the chain. This is a rather unusual fact in Ln–carboxylate chains, where the vast majority of the reported cases present triple or even more complex bridging schemes: out of about 270 polymeric structures with Ln–carboxylate motifs found in the CSD, only seven (the present structure included) show this very simple linking motif. Surprisingly, in three of them the ligand involved is precisely the crotonate anion (Atria et al., 2004; Baggio et al., 2005, and this work).
The neutral adenine molecule (hereafter ade0) does not show any unusual feature from a metrical point of view (see, for instance, Mahapatra et al., 2008), and the distribution of single/double bonds within the ring system corresponds to the most frequent disposition found for the molecule. In fact, ade0 can present two possible prototropic states, with protonation at either N1 or N2 [see (a) and (b) in Scheme 2]. A search of the CSD disclosed 24 appearences of an ade0 unit, one-third of which correspond to (a) and two-thirds to (b) thus confirming the present case as corresponding to the most frequent state.
The molecule does not take part in coordination but, in conjunction with the solvent water, it plays an important role in the general cohesion. Both molecules generate a hydrogen-bonded two-dimensional structure which serves as the interchain linking agent (see below). The array presents a strikingly planar character (the r.m.s. deviation from the least-squares plane for non-H atoms is 0.10 Å) and lies almost exactly on the crystallographic (220) plane. Planarity is the result of a whole family of inversion centres at r1 and r2 being embedded into the array [r1 = (1/2,0,0) + (1/2,-1/2,0) n; r2 = (0,0,1/2) m; n and m are integers]. This characteristic guarantees that the adenine molecules are parallel to each other (the result of centrosymmetry) and coplanar (the result of embedding). Fig. 3(a) shows in projection the way in which the adenine–water (220) planes intersect the La–crotonate [100] chains, at a slanting angle of 146.0°.
The dense hydrogen-bonding network has the carboxylate O atoms as acceptors and the adenine and water (coordinated as well as hydration) H atoms as donors, generating a number of hydrogen-bonding loops. Full details are given in Table 2, and a general view of the way in which this happens is given in Fig. 3(b) [for a survey of graph-set nomenclature of hydrogen-bonding loops, see Bernstein et al. (1995)]. Three of the generated loops are centrosymmetric and internal to the chains, thus reinforcing their internal cohesion. They involve the three different water molecules in the asymmetric unit, viz. the two coordinated water molecules (in Fig. 2, loop A {[O12—La1—O1W—H1WB···] plus its image at (-x+1, -y+1, -z+1)} and loop B {[O22—La1—O2W—H2WB···] plus its image at -x, -y+1, -z+1}, both with graph-set motif R22(8)) and the unbound water solvent molecule (loop C, graph-set motif R44(12), {[O22—La1—O21···H3WA—O3W—H3WB···] plus its image at -x, -y+1, -z+1}).
On the other hand, neighbouring [100] chains in the structure are one unit cell apart in either the b or c directions, and thus occupy only sparsely the available space in the crystal; the remaining hydrogen bonds serve to link these otherwise non-interacting structures, to define a tight three-dimensional network. These interactions fully involve the adenine N and H atoms. Three of these loops are also centrosymmetric {D [R88(24)], E [R22(10)] and F [R44(16)] in Fig. 3b}, while the remaining two loops lie in general positions {G [R22(8)] and H [R22(10)] in Fig. 3b}.