catena-Poly[[aqua[(2,4-dichlorophenoxy)acetato]neodymium(III)]-di-μ-(2,4-dichlorophenoxy)acetato]
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702154X/zl2021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702154X/zl2021Isup2.hkl |
CCDC reference: 650541
A mixture of Nd2O3 (0.5 mmol), 2,4-dichlorophenoxyacetic acid (1 mmol) and H2O (10 ml) in the presence of HClO4 (0.385 mmol) was stirred vigorously for 20 min and then sealed in a Teflon-lined stainless-steel autoclave (20 ml, capacity). The autoclave was heated to and maintained at 433 K for 7 days, and then cooled to room temperature at 5 K h-1. The crystal were obtained in ca 46% yield based on Nd.
Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å, and with Uiso(H) = 1.2 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.85 Å and H···H = 1.39 Å, each within a standard deviation of 0.01 Å
2,4-Dichlorophenoxyacetic acid is an important biologically active compound that has been commonly used in herbicides and plant-growth agents. The monophenoxyacetate group has versatile bonding modes to metal ions and easily forms simple complexes (Dendrinou-Samara et al., 2001; Psomas et al., 2000). Recently, we obtained the one-dimensional neodymium polymer (I), its crystal structure is reported here.
The NdIII centre is in a distorted tricapped trigonal prismatic geometry, defined by eight O atoms from five 2,4-dichlorophenoxyacetate ligands and one water molecule (Fig. 1). Coordination bond lengths, angles and torsion angles at the NdIII atom are given in Table 1. The 2,4-dichlorophenoxyacetate ligands exhibit two different types of coordination modes: One of the ligands is coordinating only to one of the neodymium centers (O7, O8), the other two carboxylate ligands are linking the neodym centers in a µ2 way via the carboxylate atoms
O2 and O4 to form chains parallel to the c axis with a Nd···Nd distance of 4.172 (3) Å. The oxygen atoms of the non-bridging 2,4-dichlorophenoxyacetate ligand are forming hydrogen bonds with the coordinated water molecules of neighboring entities with the H-bonds extending parallel to the main polymeric chain (see Table 2 for numerical values). The chains as a whole are also involved in π···π stacking interactions of some of the phenyl rings (C11 to C16) with neigboring chains to form a ruffly layer perpendicular to the b axis (Fig. 2). The centroid-centroid distance between phenyl groups (at -1 + x, y, -1 + z) and the offset are 3.719 (2) and 0.060 (2) Å, respectively, indicating a normal π···π stacking interaction (Lee et al., 2007).
Related literature: Dendrinou-Samara et al. (2001); Lee et al. (2007); Psomas et al. (2000).
Data collection: APEXII (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.
[Nd(C8H5Cl2O3)3(H2O)] | F(000) = 1612 |
Mr = 822.32 | Dx = 1.871 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8000 reflections |
a = 10.1801 (2) Å | θ = 1.7–26.0° |
b = 35.4768 (6) Å | µ = 2.38 mm−1 |
c = 8.1456 (2) Å | T = 293 K |
β = 97.144 (1)° | Platelet, purple |
V = 2919.00 (10) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 5617 independent reflections |
Radiation source: fine-focus sealed tube | 5062 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
φ and ω scans | θmax = 26.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.566, Tmax = 0.626 | k = −43→43 |
31522 measured reflections | l = −10→8 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0401P)2 + 2.8846P] where P = (Fo2 + 2Fc2)/3 |
5617 reflections | (Δ/σ)max = 0.001 |
370 parameters | Δρmax = 0.74 e Å−3 |
3 restraints | Δρmin = −1.54 e Å−3 |
[Nd(C8H5Cl2O3)3(H2O)] | V = 2919.00 (10) Å3 |
Mr = 822.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.1801 (2) Å | µ = 2.38 mm−1 |
b = 35.4768 (6) Å | T = 293 K |
c = 8.1456 (2) Å | 0.25 × 0.20 × 0.20 mm |
β = 97.144 (1)° |
Bruker APEXII area-detector diffractometer | 5617 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5062 reflections with I > 2σ(I) |
Tmin = 0.566, Tmax = 0.626 | Rint = 0.038 |
31522 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 3 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | Δρmax = 0.74 e Å−3 |
5617 reflections | Δρmin = −1.54 e Å−3 |
370 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 | ||
C1 | 0.2331 (3) | 0.23189 (10) | 0.4591 (5) | 0.0211 (8) | |
C2 | 0.1116 (4) | 0.22703 (12) | 0.3335 (5) | 0.0310 (9) | |
H2A | 0.0752 | 0.2516 | 0.3022 | 0.037* | |
H2B | 0.1370 | 0.2151 | 0.2350 | 0.037* | |
C3 | 0.0273 (4) | 0.16667 (11) | 0.3963 (5) | 0.0284 (8) | |
C4 | 0.1374 (4) | 0.14754 (13) | 0.3584 (6) | 0.0456 (12) | |
H4 | 0.2118 | 0.1609 | 0.3359 | 0.055* | |
C5 | 0.1378 (5) | 0.10843 (14) | 0.3535 (8) | 0.0592 (15) | |
H5 | 0.2119 | 0.0957 | 0.3260 | 0.071* | |
C6 | 0.0302 (5) | 0.08870 (13) | 0.3888 (8) | 0.0546 (13) | |
C7 | −0.0803 (4) | 0.10688 (13) | 0.4312 (7) | 0.0470 (12) | |
H7 | −0.1530 | 0.0932 | 0.4570 | 0.056* | |
C8 | −0.0809 (4) | 0.14578 (12) | 0.4346 (5) | 0.0337 (9) | |
C9 | 0.7044 (3) | 0.22777 (10) | 0.9310 (5) | 0.0234 (8) | |
C10 | 0.8244 (4) | 0.22184 (12) | 1.0600 (5) | 0.0300 (9) | |
H10A | 0.8602 | 0.2462 | 1.0970 | 0.036* | |
H10B | 0.7969 | 0.2089 | 1.1550 | 0.036* | |
C11 | 0.9044 (4) | 0.16244 (11) | 0.9735 (5) | 0.0298 (9) | |
C12 | 0.7919 (4) | 0.14320 (13) | 1.0026 (6) | 0.0422 (11) | |
H12 | 0.7219 | 0.1563 | 1.0389 | 0.051* | |
C13 | 0.7817 (5) | 0.10486 (15) | 0.9785 (7) | 0.0569 (14) | |
H13 | 0.7057 | 0.0923 | 1.0003 | 0.068* | |
C14 | 0.8829 (6) | 0.08520 (14) | 0.9227 (8) | 0.0597 (15) | |
C15 | 0.9975 (5) | 0.10342 (14) | 0.8931 (7) | 0.0536 (13) | |
H15 | 1.0669 | 0.0900 | 0.8569 | 0.064* | |
C16 | 1.0074 (4) | 0.14191 (13) | 0.9182 (6) | 0.0400 (10) | |
C17 | 0.4793 (3) | 0.15799 (11) | 0.6587 (5) | 0.0292 (9) | |
C18 | 0.5042 (5) | 0.11663 (12) | 0.6386 (6) | 0.0456 (11) | |
H18A | 0.5941 | 0.1105 | 0.6851 | 0.055* | |
H18B | 0.4440 | 0.1021 | 0.6972 | 0.055* | |
C19 | 0.5380 (4) | 0.07433 (12) | 0.4211 (6) | 0.0426 (11) | |
C20 | 0.6068 (5) | 0.04845 (12) | 0.5265 (7) | 0.0518 (13) | |
H20 | 0.6182 | 0.0528 | 0.6399 | 0.062* | |
C21 | 0.6589 (5) | 0.01595 (14) | 0.4636 (9) | 0.0635 (16) | |
H21 | 0.7055 | −0.0012 | 0.5348 | 0.076* | |
C22 | 0.6413 (6) | 0.00947 (13) | 0.2979 (9) | 0.0632 (16) | |
C23 | 0.5724 (6) | 0.03446 (14) | 0.1902 (8) | 0.0604 (15) | |
H23 | 0.5605 | 0.0297 | 0.0770 | 0.072* | |
C24 | 0.5212 (5) | 0.06667 (13) | 0.2532 (7) | 0.0493 (12) | |
Cl1 | −0.21982 (12) | 0.16884 (4) | 0.4836 (2) | 0.0636 (4) | |
Cl2 | 0.02712 (19) | 0.03967 (4) | 0.3748 (3) | 0.1027 (7) | |
Cl3 | 1.15126 (13) | 0.16473 (4) | 0.8836 (2) | 0.0710 (4) | |
Cl4 | 0.8703 (2) | 0.03676 (4) | 0.8933 (3) | 0.1017 (7) | |
Cl5 | 0.43592 (16) | 0.09847 (4) | 0.11576 (19) | 0.0678 (4) | |
Cl6 | 0.7043 (2) | −0.03135 (4) | 0.2194 (3) | 0.1014 (7) | |
Nd1 | 0.469125 (17) | 0.237244 (5) | 0.69698 (2) | 0.01875 (8) | |
O1 | 0.2348 (2) | 0.21996 (8) | 0.6017 (3) | 0.0319 (6) | |
O2 | 0.3345 (2) | 0.24889 (8) | 0.4157 (3) | 0.0265 (6) | |
O3 | 0.0130 (2) | 0.20488 (7) | 0.3960 (4) | 0.0309 (6) | |
O4 | 0.6009 (3) | 0.24198 (8) | 0.9835 (3) | 0.0290 (4) | |
O5 | 0.7074 (2) | 0.22086 (8) | 0.7852 (3) | 0.0290 (4) | |
O6 | 0.9254 (2) | 0.20022 (8) | 0.9956 (3) | 0.0318 (6) | |
O7 | 0.4680 (3) | 0.17038 (8) | 0.8010 (4) | 0.0334 (6) | |
O8 | 0.4773 (3) | 0.17940 (7) | 0.5340 (3) | 0.0320 (6) | |
O9 | 0.4849 (3) | 0.10728 (8) | 0.4683 (4) | 0.0457 (8) | |
O1W | 0.4630 (4) | 0.30741 (9) | 0.7056 (4) | 0.0515 (9) | |
H1W | 0.469 (6) | 0.3196 (12) | 0.790 (3) | 0.062* | |
H2W | 0.459 (6) | 0.3203 (12) | 0.623 (3) | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0169 (16) | 0.0262 (18) | 0.019 (2) | −0.0013 (13) | −0.0007 (13) | −0.0043 (15) |
C2 | 0.0232 (18) | 0.038 (2) | 0.030 (2) | −0.0101 (15) | −0.0027 (16) | 0.0029 (18) |
C3 | 0.0244 (17) | 0.036 (2) | 0.023 (2) | −0.0037 (15) | −0.0033 (15) | −0.0031 (17) |
C4 | 0.028 (2) | 0.047 (3) | 0.063 (3) | −0.0041 (18) | 0.007 (2) | −0.008 (2) |
C5 | 0.039 (3) | 0.050 (3) | 0.089 (5) | 0.009 (2) | 0.015 (3) | −0.014 (3) |
C6 | 0.052 (3) | 0.035 (3) | 0.076 (4) | 0.002 (2) | 0.005 (3) | −0.002 (3) |
C7 | 0.038 (2) | 0.043 (3) | 0.061 (3) | −0.0049 (19) | 0.012 (2) | 0.007 (2) |
C8 | 0.031 (2) | 0.039 (2) | 0.032 (3) | −0.0024 (16) | 0.0099 (17) | 0.0012 (19) |
C9 | 0.0224 (17) | 0.0220 (17) | 0.026 (2) | −0.0018 (13) | 0.0043 (15) | 0.0018 (15) |
C10 | 0.0260 (18) | 0.038 (2) | 0.024 (2) | 0.0082 (16) | −0.0042 (15) | −0.0044 (17) |
C11 | 0.0283 (18) | 0.038 (2) | 0.023 (2) | 0.0069 (16) | 0.0002 (15) | 0.0042 (17) |
C12 | 0.033 (2) | 0.048 (3) | 0.046 (3) | 0.0035 (18) | 0.0047 (19) | 0.005 (2) |
C13 | 0.047 (3) | 0.054 (3) | 0.069 (4) | −0.005 (2) | 0.005 (2) | 0.010 (3) |
C14 | 0.076 (4) | 0.035 (3) | 0.065 (4) | 0.003 (2) | −0.005 (3) | 0.002 (2) |
C15 | 0.059 (3) | 0.045 (3) | 0.059 (4) | 0.019 (2) | 0.013 (3) | −0.002 (2) |
C16 | 0.037 (2) | 0.046 (3) | 0.038 (3) | 0.0091 (19) | 0.0081 (19) | 0.007 (2) |
C17 | 0.0269 (18) | 0.0267 (19) | 0.034 (3) | 0.0001 (14) | 0.0028 (16) | 0.0013 (18) |
C18 | 0.064 (3) | 0.029 (2) | 0.044 (3) | 0.001 (2) | 0.006 (2) | 0.002 (2) |
C19 | 0.043 (2) | 0.030 (2) | 0.057 (3) | −0.0062 (18) | 0.013 (2) | −0.010 (2) |
C20 | 0.058 (3) | 0.030 (2) | 0.066 (4) | 0.001 (2) | 0.005 (2) | −0.002 (2) |
C21 | 0.059 (3) | 0.036 (3) | 0.096 (5) | 0.004 (2) | 0.010 (3) | −0.002 (3) |
C22 | 0.065 (3) | 0.030 (3) | 0.101 (5) | −0.002 (2) | 0.032 (3) | −0.016 (3) |
C23 | 0.076 (4) | 0.041 (3) | 0.068 (4) | −0.004 (3) | 0.025 (3) | −0.014 (3) |
C24 | 0.054 (3) | 0.034 (2) | 0.062 (4) | −0.005 (2) | 0.016 (2) | −0.004 (2) |
Cl1 | 0.0447 (6) | 0.0503 (7) | 0.1041 (12) | 0.0008 (5) | 0.0424 (7) | 0.0047 (7) |
Cl2 | 0.0892 (12) | 0.0357 (8) | 0.184 (2) | 0.0034 (7) | 0.0217 (12) | −0.0074 (10) |
Cl3 | 0.0502 (7) | 0.0626 (8) | 0.1090 (13) | 0.0091 (6) | 0.0447 (8) | 0.0078 (8) |
Cl4 | 0.1212 (15) | 0.0392 (8) | 0.1399 (19) | 0.0014 (9) | −0.0025 (13) | −0.0050 (9) |
Cl5 | 0.0964 (11) | 0.0528 (8) | 0.0534 (9) | 0.0074 (7) | 0.0063 (7) | −0.0100 (7) |
Cl6 | 0.1208 (15) | 0.0460 (8) | 0.1457 (19) | 0.0169 (9) | 0.0498 (13) | −0.0285 (10) |
Nd1 | 0.02001 (11) | 0.02489 (12) | 0.01098 (13) | −0.00004 (7) | 0.00042 (7) | 0.00037 (7) |
O1 | 0.0294 (13) | 0.0506 (17) | 0.0148 (15) | −0.0125 (12) | −0.0001 (10) | 0.0018 (13) |
O2 | 0.0164 (11) | 0.0347 (13) | 0.0280 (16) | −0.0028 (10) | 0.0016 (10) | −0.0024 (12) |
O3 | 0.0204 (12) | 0.0331 (15) | 0.0389 (18) | −0.0065 (10) | 0.0019 (11) | 0.0011 (13) |
O4 | 0.0265 (9) | 0.0502 (12) | 0.0100 (10) | 0.0078 (8) | 0.0011 (7) | −0.0052 (9) |
O5 | 0.0265 (9) | 0.0502 (12) | 0.0100 (10) | 0.0078 (8) | 0.0011 (7) | −0.0052 (9) |
O6 | 0.0221 (12) | 0.0384 (15) | 0.0341 (17) | 0.0068 (11) | 0.0009 (11) | −0.0033 (13) |
O7 | 0.0439 (16) | 0.0305 (14) | 0.0259 (17) | −0.0006 (12) | 0.0047 (12) | 0.0042 (12) |
O8 | 0.0422 (15) | 0.0278 (14) | 0.0263 (16) | 0.0043 (11) | 0.0051 (12) | −0.0006 (12) |
O9 | 0.0546 (19) | 0.0334 (16) | 0.048 (2) | 0.0087 (14) | 0.0006 (15) | −0.0100 (15) |
O1W | 0.091 (3) | 0.0291 (17) | 0.035 (2) | 0.0007 (16) | 0.012 (2) | −0.0003 (14) |
C1—O1 | 1.235 (5) | C15—H15 | 0.9300 |
C1—O2 | 1.282 (4) | C16—Cl3 | 1.727 (5) |
C1—C2 | 1.514 (5) | C17—O7 | 1.258 (5) |
C2—O3 | 1.418 (4) | C17—O8 | 1.266 (5) |
C2—H2A | 0.9700 | C17—C18 | 1.501 (6) |
C2—H2B | 0.9700 | C18—O9 | 1.416 (6) |
C3—O3 | 1.364 (5) | C18—H18A | 0.9700 |
C3—C4 | 1.378 (6) | C18—H18B | 0.9700 |
C3—C8 | 1.394 (5) | C19—O9 | 1.363 (5) |
C4—C5 | 1.388 (7) | C19—C24 | 1.384 (7) |
C4—H4 | 0.9300 | C19—C20 | 1.386 (7) |
C5—C6 | 1.361 (7) | C20—C21 | 1.393 (7) |
C5—H5 | 0.9300 | C20—H20 | 0.9300 |
C6—C7 | 1.377 (7) | C21—C22 | 1.359 (9) |
C6—Cl2 | 1.743 (5) | C21—H21 | 0.9300 |
C7—C8 | 1.380 (6) | C22—C23 | 1.376 (8) |
C7—H7 | 0.9300 | C22—Cl6 | 1.738 (5) |
C8—Cl1 | 1.724 (4) | C23—C24 | 1.381 (7) |
C9—O5 | 1.217 (5) | C23—H23 | 0.9300 |
C9—O4 | 1.288 (4) | C24—Cl5 | 1.743 (6) |
C9—C10 | 1.524 (5) | Nd1—O2i | 2.430 (3) |
C10—O6 | 1.434 (4) | Nd1—O4ii | 2.439 (3) |
C10—H10A | 0.9700 | Nd1—O8 | 2.451 (3) |
C10—H10B | 0.9700 | Nd1—O1W | 2.491 (3) |
C11—O6 | 1.366 (5) | Nd1—O1 | 2.492 (2) |
C11—C12 | 1.379 (6) | Nd1—O5 | 2.511 (2) |
C11—C16 | 1.396 (6) | Nd1—O7 | 2.519 (3) |
C12—C13 | 1.376 (7) | Nd1—O4 | 2.549 (3) |
C12—H12 | 0.9300 | Nd1—O2 | 2.553 (3) |
C13—C14 | 1.367 (8) | O2—Nd1ii | 2.430 (3) |
C13—H13 | 0.9300 | O4—Nd1i | 2.439 (3) |
C14—C15 | 1.381 (8) | O1W—H1W | 0.811 (19) |
C14—Cl4 | 1.737 (5) | O1W—H2W | 0.807 (19) |
C15—C16 | 1.382 (7) | ||
O1—C1—O2 | 120.2 (3) | C19—C20—H20 | 119.8 |
O1—C1—C2 | 120.8 (3) | C21—C20—H20 | 119.8 |
O2—C1—C2 | 119.0 (3) | C22—C21—C20 | 119.7 (5) |
O3—C2—C1 | 112.1 (3) | C22—C21—H21 | 120.1 |
O3—C2—H2A | 109.2 | C20—C21—H21 | 120.1 |
C1—C2—H2A | 109.2 | C21—C22—C23 | 121.2 (5) |
O3—C2—H2B | 109.2 | C21—C22—Cl6 | 119.8 (5) |
C1—C2—H2B | 109.2 | C23—C22—Cl6 | 119.0 (5) |
H2A—C2—H2B | 107.9 | C22—C23—C24 | 118.8 (6) |
O3—C3—C4 | 125.4 (4) | C22—C23—H23 | 120.6 |
O3—C3—C8 | 116.2 (3) | C24—C23—H23 | 120.6 |
C4—C3—C8 | 118.4 (4) | C23—C24—C19 | 121.6 (5) |
C3—C4—C5 | 120.3 (4) | C23—C24—Cl5 | 118.5 (5) |
C3—C4—H4 | 119.9 | C19—C24—Cl5 | 119.9 (4) |
C5—C4—H4 | 119.9 | O2i—Nd1—O4ii | 150.72 (10) |
C6—C5—C4 | 120.2 (4) | O2i—Nd1—O8 | 128.82 (9) |
C6—C5—H5 | 119.9 | O4ii—Nd1—O8 | 78.94 (9) |
C4—C5—H5 | 119.9 | O2i—Nd1—O1W | 76.03 (11) |
C5—C6—C7 | 121.1 (4) | O4ii—Nd1—O1W | 74.69 (11) |
C5—C6—Cl2 | 120.5 (4) | O8—Nd1—O1W | 148.70 (10) |
C7—C6—Cl2 | 118.4 (4) | O2i—Nd1—O1 | 70.88 (9) |
C6—C7—C8 | 118.6 (4) | O4ii—Nd1—O1 | 116.28 (9) |
C6—C7—H7 | 120.7 | O8—Nd1—O1 | 73.80 (9) |
C8—C7—H7 | 120.7 | O1W—Nd1—O1 | 103.20 (11) |
C7—C8—C3 | 121.4 (4) | O2i—Nd1—O5 | 116.76 (8) |
C7—C8—Cl1 | 119.0 (3) | O4ii—Nd1—O5 | 71.11 (9) |
C3—C8—Cl1 | 119.6 (3) | O8—Nd1—O5 | 82.21 (9) |
O5—C9—O4 | 121.6 (3) | O1W—Nd1—O5 | 104.47 (11) |
O5—C9—C10 | 122.0 (3) | O1—Nd1—O5 | 152.33 (10) |
O4—C9—C10 | 116.3 (3) | O2i—Nd1—O7 | 85.27 (9) |
O6—C10—C9 | 111.8 (3) | O4ii—Nd1—O7 | 123.39 (9) |
O6—C10—H10A | 109.3 | O8—Nd1—O7 | 52.82 (9) |
C9—C10—H10A | 109.3 | O1W—Nd1—O7 | 158.46 (10) |
O6—C10—H10B | 109.3 | O1—Nd1—O7 | 80.13 (9) |
C9—C10—H10B | 109.3 | O5—Nd1—O7 | 74.37 (9) |
H10A—C10—H10B | 107.9 | O2i—Nd1—O4 | 66.17 (8) |
O6—C11—C12 | 125.6 (4) | O4ii—Nd1—O4 | 111.05 (9) |
O6—C11—C16 | 116.3 (4) | O8—Nd1—O4 | 120.11 (9) |
C12—C11—C16 | 118.1 (4) | O1W—Nd1—O4 | 85.44 (10) |
C13—C12—C11 | 120.9 (4) | O1—Nd1—O4 | 132.52 (9) |
C13—C12—H12 | 119.5 | O5—Nd1—O4 | 51.21 (8) |
C11—C12—H12 | 119.5 | O7—Nd1—O4 | 77.18 (9) |
C14—C13—C12 | 120.3 (5) | O2i—Nd1—O2 | 109.66 (8) |
C14—C13—H13 | 119.8 | O4ii—Nd1—O2 | 65.98 (8) |
C12—C13—H13 | 119.8 | O8—Nd1—O2 | 72.55 (9) |
C13—C14—C15 | 120.4 (5) | O1W—Nd1—O2 | 81.43 (10) |
C13—C14—Cl4 | 120.3 (5) | O1—Nd1—O2 | 51.24 (8) |
C15—C14—Cl4 | 119.2 (4) | O5—Nd1—O2 | 133.31 (8) |
C14—C15—C16 | 119.0 (5) | O7—Nd1—O2 | 115.44 (9) |
C14—C15—H15 | 120.5 | O4—Nd1—O2 | 166.86 (9) |
C16—C15—H15 | 120.5 | C1—O1—Nd1 | 96.3 (2) |
C15—C16—C11 | 121.3 (4) | C1—O2—Nd1ii | 147.6 (2) |
C15—C16—Cl3 | 119.1 (4) | C1—O2—Nd1 | 92.1 (2) |
C11—C16—Cl3 | 119.6 (3) | Nd1ii—O2—Nd1 | 113.70 (9) |
O7—C17—O8 | 122.3 (4) | C3—O3—C2 | 118.1 (3) |
O7—C17—C18 | 118.6 (4) | C9—O4—Nd1i | 154.2 (2) |
O8—C17—C18 | 119.0 (4) | C9—O4—Nd1 | 91.6 (2) |
O9—C18—C17 | 109.3 (4) | Nd1i—O4—Nd1 | 113.52 (10) |
O9—C18—H18A | 109.8 | C9—O5—Nd1 | 95.3 (2) |
C17—C18—H18A | 109.8 | C11—O6—C10 | 117.8 (3) |
O9—C18—H18B | 109.8 | C17—O7—Nd1 | 90.8 (2) |
C17—C18—H18B | 109.8 | C17—O8—Nd1 | 93.8 (2) |
H18A—C18—H18B | 108.3 | C19—O9—C18 | 117.7 (4) |
O9—C19—C24 | 116.3 (4) | Nd1—O1W—H1W | 124 (3) |
O9—C19—C20 | 125.6 (5) | Nd1—O1W—H2W | 123 (3) |
C24—C19—C20 | 118.2 (4) | H1W—O1W—H2W | 113 (3) |
C19—C20—C21 | 120.5 (5) | ||
O1—C1—C2—O3 | −5.7 (5) | O2i—Nd1—O2—Nd1ii | 155.20 (14) |
O2—C1—C2—O3 | 174.8 (3) | O4ii—Nd1—O2—Nd1ii | 6.46 (9) |
O3—C3—C4—C5 | −176.3 (5) | O8—Nd1—O2—Nd1ii | −78.96 (12) |
C8—C3—C4—C5 | 2.1 (7) | O1W—Nd1—O2—Nd1ii | 83.44 (13) |
C3—C4—C5—C6 | −1.1 (9) | O1—Nd1—O2—Nd1ii | −161.91 (17) |
C4—C5—C6—C7 | −0.5 (9) | O5—Nd1—O2—Nd1ii | −18.41 (18) |
C4—C5—C6—Cl2 | 177.4 (5) | O7—Nd1—O2—Nd1ii | −110.62 (11) |
C5—C6—C7—C8 | 1.1 (9) | O4—Nd1—O2—Nd1ii | 86.1 (3) |
Cl2—C6—C7—C8 | −176.9 (4) | C4—C3—O3—C2 | 7.8 (6) |
C6—C7—C8—C3 | 0.0 (8) | C8—C3—O3—C2 | −170.5 (3) |
C6—C7—C8—Cl1 | 178.8 (4) | C1—C2—O3—C3 | −79.9 (4) |
O3—C3—C8—C7 | 176.9 (4) | O5—C9—O4—Nd1i | 173.1 (4) |
C4—C3—C8—C7 | −1.6 (7) | C10—C9—O4—Nd1i | −9.7 (7) |
O3—C3—C8—Cl1 | −1.8 (5) | O5—C9—O4—Nd1 | 5.1 (4) |
C4—C3—C8—Cl1 | 179.7 (3) | C10—C9—O4—Nd1 | −177.7 (3) |
O5—C9—C10—O6 | −12.6 (5) | O2i—Nd1—O4—C9 | 167.9 (2) |
O4—C9—C10—O6 | 170.1 (3) | O4ii—Nd1—O4—C9 | −43.72 (17) |
O6—C11—C12—C13 | −179.0 (4) | O8—Nd1—O4—C9 | 45.5 (2) |
C16—C11—C12—C13 | 0.3 (7) | O1W—Nd1—O4—C9 | −115.4 (2) |
C11—C12—C13—C14 | −1.0 (8) | O1—Nd1—O4—C9 | 140.9 (2) |
C12—C13—C14—C15 | 1.3 (9) | O5—Nd1—O4—C9 | −2.70 (19) |
C12—C13—C14—Cl4 | 179.7 (4) | O7—Nd1—O4—C9 | 77.4 (2) |
C13—C14—C15—C16 | −1.0 (8) | O2—Nd1—O4—C9 | −118.1 (3) |
Cl4—C14—C15—C16 | −179.4 (4) | O2i—Nd1—O4—Nd1i | −6.45 (9) |
C14—C15—C16—C11 | 0.4 (8) | O4ii—Nd1—O4—Nd1i | 141.95 (15) |
C14—C15—C16—Cl3 | 179.3 (4) | O8—Nd1—O4—Nd1i | −128.87 (11) |
O6—C11—C16—C15 | 179.3 (4) | O1W—Nd1—O4—Nd1i | 70.29 (13) |
C12—C11—C16—C15 | 0.0 (7) | O1—Nd1—O4—Nd1i | −33.46 (18) |
O6—C11—C16—Cl3 | 0.5 (5) | O5—Nd1—O4—Nd1i | −177.03 (17) |
C12—C11—C16—Cl3 | −178.9 (3) | O7—Nd1—O4—Nd1i | −96.91 (12) |
O7—C17—C18—O9 | 167.3 (3) | O2—Nd1—O4—Nd1i | 67.6 (4) |
O8—C17—C18—O9 | −16.3 (5) | O4—C9—O5—Nd1 | −5.2 (4) |
O9—C19—C20—C21 | −178.8 (4) | C10—C9—O5—Nd1 | 177.7 (3) |
C24—C19—C20—C21 | 0.9 (7) | O2i—Nd1—O5—C9 | −6.8 (2) |
C19—C20—C21—C22 | −0.5 (8) | O4ii—Nd1—O5—C9 | 142.5 (2) |
C20—C21—C22—C23 | −0.1 (8) | O8—Nd1—O5—C9 | −136.6 (2) |
C20—C21—C22—Cl6 | −179.2 (4) | O1W—Nd1—O5—C9 | 74.6 (2) |
C21—C22—C23—C24 | 0.3 (8) | O1—Nd1—O5—C9 | −106.7 (3) |
Cl6—C22—C23—C24 | 179.3 (4) | O7—Nd1—O5—C9 | −83.1 (2) |
C22—C23—C24—C19 | 0.2 (8) | O4—Nd1—O5—C9 | 2.9 (2) |
C22—C23—C24—Cl5 | 179.2 (4) | O2—Nd1—O5—C9 | 166.5 (2) |
O9—C19—C24—C23 | 178.9 (4) | C12—C11—O6—C10 | 2.3 (6) |
C20—C19—C24—C23 | −0.8 (7) | C16—C11—O6—C10 | −177.0 (4) |
O9—C19—C24—Cl5 | 0.0 (6) | C9—C10—O6—C11 | −73.9 (4) |
C20—C19—C24—Cl5 | −179.7 (4) | O8—C17—O7—Nd1 | −4.8 (4) |
O2—C1—O1—Nd1 | −3.9 (4) | C18—C17—O7—Nd1 | 171.5 (3) |
C2—C1—O1—Nd1 | 176.7 (3) | O2i—Nd1—O7—C17 | 151.1 (2) |
O2i—Nd1—O1—C1 | 139.4 (2) | O4ii—Nd1—O7—C17 | −35.4 (2) |
O4ii—Nd1—O1—C1 | −9.7 (3) | O8—Nd1—O7—C17 | 2.6 (2) |
O8—Nd1—O1—C1 | −78.2 (2) | O1W—Nd1—O7—C17 | −179.3 (3) |
O1W—Nd1—O1—C1 | 69.5 (2) | O1—Nd1—O7—C17 | 79.7 (2) |
O5—Nd1—O1—C1 | −109.2 (3) | O5—Nd1—O7—C17 | −89.4 (2) |
O7—Nd1—O1—C1 | −132.2 (2) | O4—Nd1—O7—C17 | −142.3 (2) |
O4—Nd1—O1—C1 | 165.5 (2) | O2—Nd1—O7—C17 | 41.6 (2) |
O2—Nd1—O1—C1 | 2.1 (2) | O7—C17—O8—Nd1 | 4.9 (4) |
O1—C1—O2—Nd1ii | 147.7 (3) | C18—C17—O8—Nd1 | −171.4 (3) |
C2—C1—O2—Nd1ii | −32.8 (6) | O2i—Nd1—O8—C17 | −44.6 (2) |
O1—C1—O2—Nd1 | 3.7 (4) | O4ii—Nd1—O8—C17 | 145.8 (2) |
C2—C1—O2—Nd1 | −176.8 (3) | O1W—Nd1—O8—C17 | 178.8 (2) |
O2i—Nd1—O2—C1 | −44.94 (17) | O1—Nd1—O8—C17 | −92.4 (2) |
O4ii—Nd1—O2—C1 | 166.3 (2) | O5—Nd1—O8—C17 | 73.7 (2) |
O8—Nd1—O2—C1 | 80.9 (2) | O7—Nd1—O8—C17 | −2.6 (2) |
O1W—Nd1—O2—C1 | −116.7 (2) | O4—Nd1—O8—C17 | 37.8 (2) |
O1—Nd1—O2—C1 | −2.06 (19) | O2—Nd1—O8—C17 | −146.1 (2) |
O5—Nd1—O2—C1 | 141.5 (2) | C24—C19—O9—C18 | −177.9 (4) |
O7—Nd1—O2—C1 | 49.2 (2) | C20—C19—O9—C18 | 1.8 (6) |
O4—Nd1—O2—C1 | −114.0 (4) | C17—C18—O9—C19 | 161.7 (4) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O8i | 0.81 (2) | 1.98 (3) | 2.702 (4) | 148 (4) |
O1W—H2W···Cl5i | 0.81 (2) | 2.89 (4) | 3.422 (4) | 125 (4) |
O1W—H2W···O7ii | 0.81 (2) | 2.66 (2) | 3.395 (5) | 152 (4) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Nd(C8H5Cl2O3)3(H2O)] |
Mr | 822.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.1801 (2), 35.4768 (6), 8.1456 (2) |
β (°) | 97.144 (1) |
V (Å3) | 2919.00 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.38 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.566, 0.626 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31522, 5617, 5062 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.088, 1.23 |
No. of reflections | 5617 |
No. of parameters | 370 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.74, −1.54 |
Computer programs: APEXII (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.
Nd1—O2i | 2.430 (3) | Nd1—O5 | 2.511 (2) |
Nd1—O4ii | 2.439 (3) | Nd1—O7 | 2.519 (3) |
Nd1—O8 | 2.451 (3) | Nd1—O4 | 2.549 (3) |
Nd1—O1W | 2.491 (3) | Nd1—O2 | 2.553 (3) |
Nd1—O1 | 2.492 (2) | ||
O8—Nd1—O1W | 148.70 (10) | O1W—Nd1—O4 | 85.44 (10) |
O8—Nd1—O1 | 73.80 (9) | O1—Nd1—O4 | 132.52 (9) |
O1W—Nd1—O1 | 103.20 (11) | O5—Nd1—O4 | 51.21 (8) |
O8—Nd1—O5 | 82.21 (9) | O7—Nd1—O4 | 77.18 (9) |
O1W—Nd1—O5 | 104.47 (11) | O8—Nd1—O2 | 72.55 (9) |
O1—Nd1—O5 | 152.33 (10) | O1W—Nd1—O2 | 81.43 (10) |
O8—Nd1—O7 | 52.82 (9) | O1—Nd1—O2 | 51.24 (8) |
O1W—Nd1—O7 | 158.46 (10) | O5—Nd1—O2 | 133.31 (8) |
O1—Nd1—O7 | 80.13 (9) | O7—Nd1—O2 | 115.44 (9) |
O5—Nd1—O7 | 74.37 (9) | O4—Nd1—O2 | 166.86 (9) |
O8—Nd1—O4 | 120.11 (9) | C1—O1—Nd1 | 96.3 (2) |
C1—C2—O3—C3 | −79.9 (4) | C17—C18—O9—C19 | 161.7 (4) |
C9—C10—O6—C11 | −73.9 (4) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O8i | 0.811 (19) | 1.98 (3) | 2.702 (4) | 148 (4) |
O1W—H2W···Cl5i | 0.807 (19) | 2.89 (4) | 3.422 (4) | 125 (4) |
O1W—H2W···O7ii | 0.807 (19) | 2.66 (2) | 3.395 (5) | 152 (4) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
2,4-Dichlorophenoxyacetic acid is an important biologically active compound that has been commonly used in herbicides and plant-growth agents. The monophenoxyacetate group has versatile bonding modes to metal ions and easily forms simple complexes (Dendrinou-Samara et al., 2001; Psomas et al., 2000). Recently, we obtained the one-dimensional neodymium polymer (I), its crystal structure is reported here.
The NdIII centre is in a distorted tricapped trigonal prismatic geometry, defined by eight O atoms from five 2,4-dichlorophenoxyacetate ligands and one water molecule (Fig. 1). Coordination bond lengths, angles and torsion angles at the NdIII atom are given in Table 1. The 2,4-dichlorophenoxyacetate ligands exhibit two different types of coordination modes: One of the ligands is coordinating only to one of the neodymium centers (O7, O8), the other two carboxylate ligands are linking the neodym centers in a µ2 way via the carboxylate atoms
O2 and O4 to form chains parallel to the c axis with a Nd···Nd distance of 4.172 (3) Å. The oxygen atoms of the non-bridging 2,4-dichlorophenoxyacetate ligand are forming hydrogen bonds with the coordinated water molecules of neighboring entities with the H-bonds extending parallel to the main polymeric chain (see Table 2 for numerical values). The chains as a whole are also involved in π···π stacking interactions of some of the phenyl rings (C11 to C16) with neigboring chains to form a ruffly layer perpendicular to the b axis (Fig. 2). The centroid-centroid distance between phenyl groups (at -1 + x, y, -1 + z) and the offset are 3.719 (2) and 0.060 (2) Å, respectively, indicating a normal π···π stacking interaction (Lee et al., 2007).