Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019010/ci2363sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019010/ci2363Isup2.hkl |
CCDC reference: 646638
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.033
- wR factor = 0.083
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ce1
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Hill et al. (2004); Kitagawa & Kitaura (2004); Long et al. (2000, 2001, 2002, 2004); Ma et al. (2005); Yaghi et al. (2003).
A mixture of CeCl3.6H2O (0.20 mmol), 4,4'-bipyridine N,N'-dioxide (0.40 mmol) and water (10 ml) was stirred at ca 323 K for 3 h and then filtered. The filtrate was kept at room temperature and yellow crystals of the title compound (yield 53%, based on Ce) were obtained after several days.
The water H atoms were located in difference Fourier maps, and refined with O—H distances restrained at 0.85 Å and Uiso = 1.2Ueq(O). The remaining H atoms were positioned geometrically, with C—H = 0.93 Å, and were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C)
Recently, inorganic-organic coordination compounds attracted considerable attention due to their fascinating structure and potential applications as functional materials (Kitagawa & Kitaura, 2004; Yaghi et al., 2003). Multidentate O-donor ligands have been employed extensively as organic spacers in the construction of extended networks. 4,4'-Bipyridine N,N'-dioxide (L), a typical bridge ligand, can coordinate to lanthanide metal ions in five possible modes, and generate some predicted, controlled structural frameworks, including one-dimensional chains, two-dimensional layer, and three-dimensional network (Hill et al., 2004; Long et al., 2000, 2001, 2002, 2004; Ma et al., 2005). We report here the synthesis and crystal structure of the title compound, (I).
As illustrated in Fig. 1, in compound (I), each CeIII atom is coordinated by six O atoms [Ce—O = 2.454 (3)–2.545 (3) Å] from three L ligands and three water molecules, and two chloride ions [Ce—Cl = 2.8277 (9) and 2.8721 (9) Å] in a distorted tetragonal antiprism geometry. The interesting feature of (I) is that the asymmetric unit contains two L ligands, which exhibit two different coordination modes. One of the L acts as a bridging ligand, linking two CeIII ions, with a Ce···Cei distance of 13.1324 (8) Å [symmetry code: (i) x + 1, y - 1, z], and the other acts a terminal ligand. As a result of this coordination a linear polymeric chain is formed (Fig. 2), similar to that in catena-[bis(µ2-4,4'-bipyridine N,N'-dioxide)-tris (nitrato)-terbium(III)] (Long et al., 2002) but different from the wave-like chain in catena-[(µ2-4,4'-bipyridine N,N'-dioxide)-(methanol)-\ tris(nitrato)-terbium(III)] (Long et al., 2002). The pyridine rings in the L ligand are not coplanar; the dihedral angle between the N1- and N2-pyridine rings is 14.2 (2)° and that between the N3- and N4-pyridine rings is 10.5 (2)°.
In the polymeric chain, weak face-to face π-π interactions are observed between the adjacent bridging and terminal L ligands, with Cg3···Cg2i and Cg4···Cg1i distances of 3.596 (2) and 3.888 (2) Å, respectively (Cg1, Cg2, Cg3 and Cg4 denote the centroids of the N1/C1—C5, N2/C6—C10, N3/C11—C15 and N4/C16—C20 rings, respectively). The neighboring chains are cross-linked by O—H···O and O—H···Cl hydrogen bonds, involving three coordinated water molecules, one lattice water molecule, one uncoordinated chloride ion and the uncoordinated O atom of the L ligand (Table 1), forming a three-dimensional hydrogen-bonded network, as shown in Fig.3.
For related literature, see: Hill et al. (2004); Kitagawa & Kitaura (2004); Long et al. (2000, 2001, 2002, 2004); Ma et al. (2005); Yaghi et al. (2003).
Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[CeCl2(C10H8N2O2)2(H2O)3]Cl·H2O) | Z = 2 |
Mr = 694.90 | F(000) = 690 |
Triclinic, P1 | Dx = 1.813 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6677 (1) Å | Cell parameters from 3563 reflections |
b = 10.4584 (3) Å | θ = 2.3–27.5° |
c = 14.7861 (3) Å | µ = 2.16 mm−1 |
α = 83.362 (5)° | T = 293 K |
β = 73.027 (4)° | Prism, orange |
γ = 86.190 (6)° | 0.45 × 0.22 × 0.10 mm |
V = 1272.63 (6) Å3 |
Rigaku Mercury CCD diffractometer | 5698 independent reflections |
Radiation source: fine-focus sealed tube | 5315 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −11→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | k = −13→9 |
Tmin = 0.444, Tmax = 0.813 | l = −19→19 |
9756 measured reflections |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0423P)2 + 2.1096P] where P = (Fo2 + 2Fc2)/3 |
5698 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 1.31 e Å−3 |
0 restraints | Δρmin = −1.13 e Å−3 |
[CeCl2(C10H8N2O2)2(H2O)3]Cl·H2O) | γ = 86.190 (6)° |
Mr = 694.90 | V = 1272.63 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6677 (1) Å | Mo Kα radiation |
b = 10.4584 (3) Å | µ = 2.16 mm−1 |
c = 14.7861 (3) Å | T = 293 K |
α = 83.362 (5)° | 0.45 × 0.22 × 0.10 mm |
β = 73.027 (4)° |
Rigaku Mercury CCD diffractometer | 5698 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | 5315 reflections with I > 2σ(I) |
Tmin = 0.444, Tmax = 0.813 | Rint = 0.019 |
9756 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.31 e Å−3 |
5698 reflections | Δρmin = −1.13 e Å−3 |
325 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 | ||
Ce1 | 0.00594 (2) | 0.441087 (16) | 0.796133 (12) | 0.01936 (7) | |
Cl1 | −0.11177 (11) | 0.19676 (8) | 0.88064 (7) | 0.03122 (19) | |
Cl2 | 0.09043 (12) | 0.67876 (8) | 0.84625 (6) | 0.03285 (19) | |
Cl3 | 0.10399 (16) | 0.85283 (13) | 0.58040 (9) | 0.0563 (3) | |
O1 | −0.2380 (4) | 0.5682 (3) | 0.7862 (2) | 0.0387 (7) | |
O2 | −0.8044 (3) | 1.3811 (2) | 0.8983 (2) | 0.0350 (6) | |
O3 | 0.7408 (4) | −0.5185 (3) | 0.5485 (2) | 0.0378 (6) | |
O4 | 0.2428 (3) | 0.3201 (3) | 0.6970 (2) | 0.0373 (6) | |
O5 | −0.1189 (4) | 0.3598 (3) | 0.6824 (2) | 0.0464 (8) | |
H5A | −0.0935 | 0.2845 | 0.6653 | 0.056* | |
H5B | −0.1466 | 0.3972 | 0.6351 | 0.056* | |
O6 | −0.1698 (3) | 0.4586 (3) | 0.96565 (18) | 0.0332 (6) | |
H6A | −0.1812 | 0.5220 | 0.9984 | 0.040* | |
H6B | −0.1465 | 0.3917 | 0.9983 | 0.040* | |
O7 | 0.1258 (4) | 0.5682 (2) | 0.63959 (18) | 0.0385 (7) | |
H7B | 0.1148 | 0.6482 | 0.6236 | 0.046* | |
H7A | 0.1731 | 0.5393 | 0.5867 | 0.046* | |
O8 | −0.0742 (3) | 0.10277 (19) | 0.62206 (14) | 0.0154 (4) | |
H8A | −0.0028 | 0.0725 | 0.6485 | 0.018* | |
H8B | −0.0526 | 0.0870 | 0.5645 | 0.018* | |
N1 | −0.3048 (4) | 0.6797 (3) | 0.8165 (2) | 0.0291 (7) | |
N2 | −0.7157 (4) | 1.2713 (3) | 0.8993 (2) | 0.0271 (6) | |
N3 | 0.3114 (4) | 0.2040 (3) | 0.6792 (2) | 0.0259 (6) | |
N4 | 0.6763 (4) | −0.4033 (3) | 0.5714 (2) | 0.0284 (6) | |
C1 | −0.2279 (5) | 0.7893 (4) | 0.7815 (3) | 0.0357 (9) | |
H1 | −0.1242 | 0.7867 | 0.7399 | 0.043* | |
C2 | −0.4516 (5) | 0.6817 (4) | 0.8794 (3) | 0.0416 (10) | |
H2 | −0.5020 | 0.6048 | 0.9059 | 0.050* | |
C3 | −0.3012 (5) | 0.9058 (4) | 0.8068 (3) | 0.0335 (8) | |
H3 | −0.2455 | 0.9810 | 0.7825 | 0.040* | |
C4 | −0.5281 (5) | 0.7971 (4) | 0.9050 (3) | 0.0394 (10) | |
H4 | −0.6304 | 0.7972 | 0.9483 | 0.047* | |
C5 | −0.4557 (4) | 0.9133 (3) | 0.8673 (2) | 0.0236 (7) | |
C6 | −0.5413 (4) | 1.0395 (3) | 0.8856 (2) | 0.0232 (7) | |
C7 | −0.4733 (4) | 1.1541 (3) | 0.8356 (3) | 0.0299 (8) | |
H7 | −0.3675 | 1.1530 | 0.7966 | 0.036* | |
C8 | −0.6954 (4) | 1.0496 (4) | 0.9479 (3) | 0.0297 (8) | |
H8 | −0.7416 | 0.9769 | 0.9859 | 0.036* | |
C9 | −0.5622 (5) | 1.2680 (4) | 0.8442 (3) | 0.0320 (8) | |
H9 | −0.5157 | 1.3437 | 0.8114 | 0.038* | |
C10 | −0.7813 (5) | 1.1658 (4) | 0.9543 (3) | 0.0313 (8) | |
H10 | −0.8841 | 1.1712 | 0.9966 | 0.038* | |
C11 | 0.4609 (5) | 0.1976 (4) | 0.6179 (3) | 0.0304 (8) | |
H11 | 0.5140 | 0.2728 | 0.5895 | 0.037* | |
C12 | 0.2344 (4) | 0.0960 (3) | 0.7219 (3) | 0.0282 (7) | |
H12 | 0.1312 | 0.1022 | 0.7637 | 0.034* | |
C13 | 0.5353 (4) | 0.0786 (3) | 0.5975 (3) | 0.0290 (7) | |
H13 | 0.6372 | 0.0748 | 0.5540 | 0.035* | |
C14 | 0.3065 (4) | −0.0234 (4) | 0.7045 (3) | 0.0276 (7) | |
H14 | 0.2523 | −0.0971 | 0.7355 | 0.033* | |
C15 | 0.4602 (4) | −0.0351 (3) | 0.6406 (2) | 0.0231 (7) | |
C16 | 0.5370 (4) | −0.1637 (3) | 0.6185 (2) | 0.0246 (7) | |
C17 | 0.6976 (5) | −0.1775 (4) | 0.5648 (3) | 0.0343 (8) | |
H17 | 0.7603 | −0.1053 | 0.5437 | 0.041* | |
C18 | 0.4512 (5) | −0.2754 (4) | 0.6482 (3) | 0.0338 (8) | |
H18 | 0.3443 | −0.2705 | 0.6851 | 0.041* | |
C19 | 0.7645 (5) | −0.2979 (4) | 0.5423 (3) | 0.0361 (9) | |
H19 | 0.8719 | −0.3057 | 0.5067 | 0.043* | |
C20 | 0.5208 (5) | −0.3933 (4) | 0.6241 (3) | 0.0368 (9) | |
H20 | 0.4602 | −0.4668 | 0.6443 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.02181 (11) | 0.01415 (10) | 0.02068 (10) | 0.00357 (7) | −0.00417 (7) | −0.00329 (6) |
Cl1 | 0.0306 (4) | 0.0229 (4) | 0.0348 (4) | −0.0044 (3) | −0.0010 (4) | −0.0006 (3) |
Cl2 | 0.0440 (5) | 0.0219 (4) | 0.0313 (4) | −0.0052 (4) | −0.0082 (4) | −0.0018 (3) |
Cl3 | 0.0570 (7) | 0.0563 (7) | 0.0524 (7) | −0.0063 (6) | −0.0124 (6) | 0.0020 (6) |
O1 | 0.0418 (16) | 0.0312 (14) | 0.0461 (16) | 0.0220 (12) | −0.0178 (13) | −0.0154 (12) |
O2 | 0.0448 (16) | 0.0252 (13) | 0.0402 (15) | 0.0187 (12) | −0.0205 (13) | −0.0144 (11) |
O3 | 0.0529 (17) | 0.0228 (13) | 0.0358 (14) | 0.0162 (12) | −0.0107 (13) | −0.0102 (11) |
O4 | 0.0410 (16) | 0.0239 (13) | 0.0414 (15) | 0.0138 (12) | −0.0041 (12) | −0.0098 (11) |
O5 | 0.078 (2) | 0.0238 (13) | 0.0532 (18) | 0.0115 (14) | −0.0437 (18) | −0.0115 (13) |
O6 | 0.0428 (15) | 0.0281 (13) | 0.0260 (13) | 0.0021 (11) | −0.0042 (11) | −0.0084 (10) |
O7 | 0.0617 (19) | 0.0198 (12) | 0.0246 (13) | 0.0018 (12) | 0.0009 (12) | −0.0012 (10) |
O8 | 0.0277 (11) | 0.0113 (9) | 0.0100 (9) | −0.0060 (8) | −0.0094 (8) | 0.0005 (7) |
N1 | 0.0283 (15) | 0.0276 (15) | 0.0313 (15) | 0.0147 (12) | −0.0096 (13) | −0.0084 (12) |
N2 | 0.0329 (16) | 0.0223 (14) | 0.0302 (15) | 0.0113 (12) | −0.0149 (13) | −0.0112 (12) |
N3 | 0.0283 (15) | 0.0237 (14) | 0.0255 (14) | 0.0099 (12) | −0.0070 (12) | −0.0096 (11) |
N4 | 0.0368 (17) | 0.0217 (14) | 0.0265 (14) | 0.0096 (12) | −0.0098 (13) | −0.0063 (12) |
C1 | 0.0287 (19) | 0.033 (2) | 0.035 (2) | 0.0093 (16) | 0.0029 (16) | 0.0026 (16) |
C2 | 0.033 (2) | 0.0256 (19) | 0.057 (3) | −0.0006 (16) | 0.0026 (19) | −0.0050 (18) |
C3 | 0.0281 (19) | 0.0261 (18) | 0.038 (2) | 0.0042 (15) | 0.0001 (16) | 0.0053 (15) |
C4 | 0.0263 (19) | 0.0262 (19) | 0.055 (3) | 0.0031 (15) | 0.0064 (17) | −0.0089 (17) |
C5 | 0.0246 (16) | 0.0227 (16) | 0.0233 (16) | 0.0061 (13) | −0.0077 (13) | −0.0023 (13) |
C6 | 0.0228 (16) | 0.0239 (16) | 0.0229 (15) | 0.0047 (13) | −0.0074 (13) | −0.0036 (13) |
C7 | 0.0231 (17) | 0.0258 (18) | 0.040 (2) | 0.0023 (14) | −0.0086 (15) | −0.0034 (15) |
C8 | 0.0294 (18) | 0.0284 (18) | 0.0264 (17) | 0.0065 (15) | −0.0031 (14) | 0.0006 (14) |
C9 | 0.033 (2) | 0.0234 (17) | 0.041 (2) | −0.0006 (15) | −0.0128 (17) | −0.0020 (15) |
C10 | 0.0299 (19) | 0.035 (2) | 0.0257 (17) | 0.0105 (16) | −0.0047 (14) | −0.0058 (15) |
C11 | 0.0308 (19) | 0.0241 (17) | 0.0305 (18) | 0.0030 (14) | −0.0012 (15) | −0.0013 (14) |
C12 | 0.0239 (17) | 0.0266 (17) | 0.0324 (18) | 0.0036 (14) | −0.0037 (14) | −0.0104 (14) |
C13 | 0.0246 (17) | 0.0265 (17) | 0.0313 (18) | 0.0064 (14) | −0.0009 (14) | −0.0069 (14) |
C14 | 0.0261 (17) | 0.0249 (17) | 0.0308 (18) | 0.0006 (14) | −0.0053 (14) | −0.0067 (14) |
C15 | 0.0228 (16) | 0.0217 (16) | 0.0255 (16) | 0.0037 (13) | −0.0075 (13) | −0.0069 (13) |
C16 | 0.0260 (17) | 0.0212 (16) | 0.0267 (16) | 0.0038 (13) | −0.0072 (14) | −0.0065 (13) |
C17 | 0.0250 (18) | 0.0266 (18) | 0.049 (2) | 0.0024 (15) | −0.0045 (16) | −0.0122 (17) |
C18 | 0.0271 (19) | 0.0249 (18) | 0.042 (2) | 0.0018 (15) | 0.0017 (16) | −0.0047 (16) |
C19 | 0.0257 (18) | 0.031 (2) | 0.048 (2) | 0.0072 (15) | −0.0038 (17) | −0.0124 (17) |
C20 | 0.038 (2) | 0.0220 (18) | 0.044 (2) | 0.0005 (16) | −0.0013 (17) | −0.0039 (16) |
Ce1—O1 | 2.454 (3) | C2—H2 | 0.93 |
Ce1—O5 | 2.498 (3) | C3—C5 | 1.380 (5) |
Ce1—O7 | 2.504 (3) | C3—H3 | 0.93 |
Ce1—O4 | 2.508 (3) | C4—C5 | 1.386 (5) |
Ce1—O2i | 2.544 (3) | C4—H4 | 0.93 |
Ce1—O6 | 2.545 (3) | C5—C6 | 1.484 (4) |
Ce1—Cl1 | 2.8277 (9) | C6—C8 | 1.389 (5) |
Ce1—Cl2 | 2.8721 (9) | C6—C7 | 1.402 (5) |
O1—N1 | 1.332 (4) | C7—C9 | 1.373 (5) |
O2—N2 | 1.340 (4) | C7—H7 | 0.93 |
O3—N4 | 1.332 (4) | C8—C10 | 1.380 (5) |
O4—N3 | 1.336 (4) | C8—H8 | 0.93 |
O5—H5A | 0.85 | C9—H9 | 0.93 |
O5—H5B | 0.85 | C10—H10 | 0.93 |
O6—H6A | 0.85 | C11—C13 | 1.387 (5) |
O6—H6B | 0.85 | C11—H11 | 0.93 |
O7—H7B | 0.85 | C12—C14 | 1.377 (5) |
O7—H7A | 0.85 | C12—H12 | 0.93 |
O8—H8A | 0.85 | C13—C15 | 1.389 (5) |
O8—H8B | 0.85 | C13—H13 | 0.93 |
N1—C1 | 1.337 (5) | C14—C15 | 1.397 (5) |
N1—C2 | 1.340 (5) | C14—H14 | 0.93 |
N2—C9 | 1.343 (5) | C15—C16 | 1.488 (4) |
N2—C10 | 1.344 (5) | C16—C18 | 1.384 (5) |
N3—C12 | 1.345 (5) | C16—C17 | 1.395 (5) |
N3—C11 | 1.350 (5) | C17—C19 | 1.385 (5) |
N4—C19 | 1.339 (5) | C17—H17 | 0.93 |
N4—C20 | 1.350 (5) | C18—C20 | 1.374 (5) |
C1—C3 | 1.375 (5) | C18—H18 | 0.93 |
C1—H1 | 0.93 | C19—H19 | 0.93 |
C2—C4 | 1.375 (5) | C20—H20 | 0.93 |
O1—Ce1—O5 | 68.28 (9) | N1—C2—H2 | 119.9 |
O1—Ce1—O7 | 82.33 (10) | C4—C2—H2 | 119.9 |
O5—Ce1—O7 | 74.47 (10) | C1—C3—C5 | 121.3 (4) |
O1—Ce1—O4 | 141.78 (10) | C1—C3—H3 | 119.3 |
O5—Ce1—O4 | 79.52 (10) | C5—C3—H3 | 119.3 |
O7—Ce1—O4 | 69.30 (9) | C2—C4—C5 | 121.3 (4) |
O1—Ce1—O2i | 144.12 (9) | C2—C4—H4 | 119.4 |
O5—Ce1—O2i | 144.07 (8) | C5—C4—H4 | 119.4 |
O7—Ce1—O2i | 115.80 (10) | C3—C5—C4 | 116.3 (3) |
O4—Ce1—O2i | 73.45 (9) | C3—C5—C6 | 121.1 (3) |
O1—Ce1—O6 | 72.90 (9) | C4—C5—C6 | 122.5 (3) |
O5—Ce1—O6 | 117.92 (10) | C8—C6—C7 | 116.8 (3) |
O7—Ce1—O6 | 143.72 (8) | C8—C6—C5 | 122.1 (3) |
O4—Ce1—O6 | 143.38 (9) | C7—C6—C5 | 120.9 (3) |
O2i—Ce1—O6 | 75.39 (9) | C9—C7—C6 | 120.2 (3) |
O1—Ce1—Cl1 | 103.72 (8) | C9—C7—H7 | 119.9 |
O5—Ce1—Cl1 | 74.42 (8) | C6—C7—H7 | 119.9 |
O7—Ce1—Cl1 | 143.21 (6) | C10—C8—C6 | 121.1 (4) |
O4—Ce1—Cl1 | 86.13 (7) | C10—C8—H8 | 119.5 |
O2i—Ce1—Cl1 | 80.49 (7) | C6—C8—H8 | 119.5 |
O6—Ce1—Cl1 | 70.10 (6) | N2—C9—C7 | 120.8 (4) |
O1—Ce1—Cl2 | 82.29 (7) | N2—C9—H9 | 119.6 |
O5—Ce1—Cl2 | 140.34 (7) | C7—C9—H9 | 119.6 |
O7—Ce1—Cl2 | 75.80 (7) | N2—C10—C8 | 119.8 (3) |
O4—Ce1—Cl2 | 113.29 (7) | N2—C10—H10 | 120.1 |
O2i—Ce1—Cl2 | 73.59 (6) | C8—C10—H10 | 120.1 |
O6—Ce1—Cl2 | 74.96 (6) | N3—C11—C13 | 119.8 (3) |
Cl1—Ce1—Cl2 | 140.64 (3) | N3—C11—H11 | 120.1 |
N1—O1—Ce1 | 134.5 (2) | C13—C11—H11 | 120.1 |
N2—O2—Ce1ii | 125.79 (19) | N3—C12—C14 | 120.7 (3) |
N3—O4—Ce1 | 145.4 (2) | N3—C12—H12 | 119.6 |
Ce1—O5—H5A | 119.7 | C14—C12—H12 | 119.6 |
Ce1—O5—H5B | 132.0 | C11—C13—C15 | 121.2 (3) |
H5A—O5—H5B | 101.3 | C11—C13—H13 | 119.4 |
Ce1—O6—H6A | 128.0 | C15—C13—H13 | 119.4 |
Ce1—O6—H6B | 105.8 | C12—C14—C15 | 120.7 (3) |
H6A—O6—H6B | 108.1 | C12—C14—H14 | 119.7 |
Ce1—O7—H7B | 129.1 | C15—C14—H14 | 119.7 |
Ce1—O7—H7A | 127.5 | C13—C15—C14 | 116.8 (3) |
H7B—O7—H7A | 102.5 | C13—C15—C16 | 122.0 (3) |
H8A—O8—H8B | 113.1 | C14—C15—C16 | 121.2 (3) |
O1—N1—C1 | 120.0 (3) | C18—C16—C17 | 116.6 (3) |
O1—N1—C2 | 119.6 (3) | C18—C16—C15 | 121.6 (3) |
C1—N1—C2 | 120.4 (3) | C17—C16—C15 | 121.8 (3) |
O2—N2—C9 | 119.2 (3) | C19—C17—C16 | 120.6 (4) |
O2—N2—C10 | 120.0 (3) | C19—C17—H17 | 119.7 |
C9—N2—C10 | 120.8 (3) | C16—C17—H17 | 119.7 |
O4—N3—C12 | 120.9 (3) | C20—C18—C16 | 121.4 (4) |
O4—N3—C11 | 118.3 (3) | C20—C18—H18 | 119.3 |
C12—N3—C11 | 120.8 (3) | C16—C18—H18 | 119.3 |
O3—N4—C19 | 120.5 (3) | N4—C19—C17 | 120.8 (4) |
O3—N4—C20 | 119.4 (3) | N4—C19—H19 | 119.6 |
C19—N4—C20 | 120.1 (3) | C17—C19—H19 | 119.6 |
N1—C1—C3 | 120.4 (3) | N4—C20—C18 | 120.5 (4) |
N1—C1—H1 | 119.8 | N4—C20—H20 | 119.7 |
C3—C1—H1 | 119.8 | C18—C20—H20 | 119.7 |
N1—C2—C4 | 120.2 (4) | ||
O5—Ce1—O1—N1 | −168.3 (4) | C8—C6—C7—C9 | −4.6 (5) |
O7—Ce1—O1—N1 | −92.1 (3) | C5—C6—C7—C9 | 171.5 (3) |
O4—Ce1—O1—N1 | −133.7 (3) | C7—C6—C8—C10 | 4.8 (5) |
O2i—Ce1—O1—N1 | 32.2 (4) | C5—C6—C8—C10 | −171.2 (3) |
O6—Ce1—O1—N1 | 61.1 (3) | O2—N2—C9—C7 | −173.0 (3) |
Cl1—Ce1—O1—N1 | 124.9 (3) | C10—N2—C9—C7 | 6.3 (5) |
Cl2—Ce1—O1—N1 | −15.5 (3) | C6—C7—C9—N2 | −0.8 (6) |
O1—Ce1—O4—N3 | −108.8 (4) | O2—N2—C10—C8 | 173.3 (3) |
O5—Ce1—O4—N3 | −76.3 (4) | C9—N2—C10—C8 | −6.0 (5) |
O7—Ce1—O4—N3 | −153.5 (4) | C6—C8—C10—N2 | 0.3 (6) |
O2i—Ce1—O4—N3 | 79.8 (4) | O4—N3—C11—C13 | −179.7 (3) |
O6—Ce1—O4—N3 | 47.0 (5) | C12—N3—C11—C13 | 1.1 (5) |
Cl1—Ce1—O4—N3 | −1.5 (4) | O4—N3—C12—C14 | −179.0 (3) |
Cl2—Ce1—O4—N3 | 143.1 (4) | C11—N3—C12—C14 | 0.2 (5) |
Ce1—O1—N1—C1 | 64.5 (5) | N3—C11—C13—C15 | −1.6 (6) |
Ce1—O1—N1—C2 | −117.8 (4) | N3—C12—C14—C15 | −1.1 (5) |
Ce1ii—O2—N2—C9 | 94.6 (4) | C11—C13—C15—C14 | 0.7 (5) |
Ce1ii—O2—N2—C10 | −84.7 (4) | C11—C13—C15—C16 | 179.1 (3) |
Ce1—O4—N3—C12 | 5.9 (6) | C12—C14—C15—C13 | 0.6 (5) |
Ce1—O4—N3—C11 | −173.3 (3) | C12—C14—C15—C16 | −177.8 (3) |
O1—N1—C1—C3 | 175.0 (4) | C13—C15—C16—C18 | −168.2 (4) |
C2—N1—C1—C3 | −2.7 (6) | C14—C15—C16—C18 | 10.2 (5) |
O1—N1—C2—C4 | −174.3 (4) | C13—C15—C16—C17 | 10.0 (5) |
C1—N1—C2—C4 | 3.4 (7) | C14—C15—C16—C17 | −171.7 (3) |
N1—C1—C3—C5 | −0.9 (6) | C18—C16—C17—C19 | 0.6 (6) |
N1—C2—C4—C5 | −0.6 (7) | C15—C16—C17—C19 | −177.7 (4) |
C1—C3—C5—C4 | 3.5 (6) | C17—C16—C18—C20 | −1.1 (6) |
C1—C3—C5—C6 | −172.9 (4) | C15—C16—C18—C20 | 177.2 (4) |
C2—C4—C5—C3 | −2.8 (6) | O3—N4—C19—C17 | 179.0 (4) |
C2—C4—C5—C6 | 173.5 (4) | C20—N4—C19—C17 | −0.7 (6) |
C3—C5—C6—C8 | −178.5 (3) | C16—C17—C19—N4 | 0.3 (6) |
C4—C5—C6—C8 | 5.3 (5) | O3—N4—C20—C18 | −179.5 (4) |
C3—C5—C6—C7 | 5.6 (5) | C19—N4—C20—C18 | 0.2 (6) |
C4—C5—C6—C7 | −170.5 (4) | C16—C18—C20—N4 | 0.7 (7) |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O8 | 0.85 | 2.06 | 2.896 (3) | 170 |
O5—H5B···O3ii | 0.85 | 1.93 | 2.763 (4) | 167 |
O6—H6A···O2iii | 0.85 | 1.90 | 2.716 (4) | 161 |
O6—H6B···Cl2iv | 0.85 | 2.50 | 3.214 (3) | 142 |
O7—H7A···O3v | 0.85 | 1.95 | 2.778 (4) | 164 |
O7—H7B···Cl3 | 0.85 | 2.17 | 3.014 (3) | 176 |
O8—H8B···Cl3vi | 0.85 | 2.32 | 3.059 (2) | 145 |
Symmetry codes: (ii) x−1, y+1, z; (iii) −x−1, −y+2, −z+2; (iv) −x, −y+1, −z+2; (v) −x+1, −y, −z+1; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CeCl2(C10H8N2O2)2(H2O)3]Cl·H2O) |
Mr | 694.90 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6677 (1), 10.4584 (3), 14.7861 (3) |
α, β, γ (°) | 83.362 (5), 73.027 (4), 86.190 (6) |
V (Å3) | 1272.63 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.16 |
Crystal size (mm) | 0.45 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2004) |
Tmin, Tmax | 0.444, 0.813 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9756, 5698, 5315 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.084, 1.06 |
No. of reflections | 5698 |
No. of parameters | 325 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.31, −1.13 |
Computer programs: CrystalClear (Rigaku/MSC, 2004), CrystalClear, SHELXTL (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O8 | 0.85 | 2.06 | 2.896 (3) | 170 |
O5—H5B···O3i | 0.85 | 1.93 | 2.763 (4) | 167 |
O6—H6A···O2ii | 0.85 | 1.90 | 2.716 (4) | 161 |
O6—H6B···Cl2iii | 0.85 | 2.50 | 3.214 (3) | 142 |
O7—H7A···O3iv | 0.85 | 1.95 | 2.778 (4) | 164 |
O7—H7B···Cl3 | 0.85 | 2.17 | 3.014 (3) | 176 |
O8—H8B···Cl3v | 0.85 | 2.32 | 3.059 (2) | 145 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x−1, −y+2, −z+2; (iii) −x, −y+1, −z+2; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Recently, inorganic-organic coordination compounds attracted considerable attention due to their fascinating structure and potential applications as functional materials (Kitagawa & Kitaura, 2004; Yaghi et al., 2003). Multidentate O-donor ligands have been employed extensively as organic spacers in the construction of extended networks. 4,4'-Bipyridine N,N'-dioxide (L), a typical bridge ligand, can coordinate to lanthanide metal ions in five possible modes, and generate some predicted, controlled structural frameworks, including one-dimensional chains, two-dimensional layer, and three-dimensional network (Hill et al., 2004; Long et al., 2000, 2001, 2002, 2004; Ma et al., 2005). We report here the synthesis and crystal structure of the title compound, (I).
As illustrated in Fig. 1, in compound (I), each CeIII atom is coordinated by six O atoms [Ce—O = 2.454 (3)–2.545 (3) Å] from three L ligands and three water molecules, and two chloride ions [Ce—Cl = 2.8277 (9) and 2.8721 (9) Å] in a distorted tetragonal antiprism geometry. The interesting feature of (I) is that the asymmetric unit contains two L ligands, which exhibit two different coordination modes. One of the L acts as a bridging ligand, linking two CeIII ions, with a Ce···Cei distance of 13.1324 (8) Å [symmetry code: (i) x + 1, y - 1, z], and the other acts a terminal ligand. As a result of this coordination a linear polymeric chain is formed (Fig. 2), similar to that in catena-[bis(µ2-4,4'-bipyridine N,N'-dioxide)-tris (nitrato)-terbium(III)] (Long et al., 2002) but different from the wave-like chain in catena-[(µ2-4,4'-bipyridine N,N'-dioxide)-(methanol)-\ tris(nitrato)-terbium(III)] (Long et al., 2002). The pyridine rings in the L ligand are not coplanar; the dihedral angle between the N1- and N2-pyridine rings is 14.2 (2)° and that between the N3- and N4-pyridine rings is 10.5 (2)°.
In the polymeric chain, weak face-to face π-π interactions are observed between the adjacent bridging and terminal L ligands, with Cg3···Cg2i and Cg4···Cg1i distances of 3.596 (2) and 3.888 (2) Å, respectively (Cg1, Cg2, Cg3 and Cg4 denote the centroids of the N1/C1—C5, N2/C6—C10, N3/C11—C15 and N4/C16—C20 rings, respectively). The neighboring chains are cross-linked by O—H···O and O—H···Cl hydrogen bonds, involving three coordinated water molecules, one lattice water molecule, one uncoordinated chloride ion and the uncoordinated O atom of the L ligand (Table 1), forming a three-dimensional hydrogen-bonded network, as shown in Fig.3.