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Acta Cryst. (2007). E63, m1666    [ doi:10.1107/S1600536807022519 ]

Poly[[diaquatris[[mu]4-(p-phenylenedioxy)diacetato]dipraseodymium(III)] dihydrate]

R.-H. Zeng, Y.-C. Qiu, Y.-P. Cai, J.-Z. Wu and H. Deng

Abstract top

The title praseodymium coordination polymer, {[Pr2(C10H8O6)3(H2O)2]·2H2O}n, was obtained by the hydrothermal reaction of Pr(NO3)3 with (p-phenylenedioxy)diacetic acid in alkaline aqueous solution. Each PrIII atom is coordinated by nine O atoms, eight from four (p-phenylenedioxy)diacetate ligands and one from a water molecule, displaying a tricapped trigonal prismatic geometry. There is a centre of symmetry at the mid-point of the Pr...Pr vector. The bridging ligands crosslink the metal ions to form a three-dimensional network, with channels running along the c axis in which the uncoordinated water molecules are located. The crystal structure is stabilized by intermolecular O-H...O hydrogen-bonding interactions.

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Tao et al., 2000; Choi & Jeon, 2003). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metal ions and the bridging building blocks, as well as on the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. As a building block, (p-phenylenedioxy)diacetic acid (1,4-BDOA) is an excellent candidate for the construction of supramolecular complexes (Qiu et al., 2006). Recently, we obtained the title novel coordination polymer, (I), by the reaction of praseodymium nitrate, (p-phenylenedioxy)diacetic acid in alkaline aqueous solution, and its crystal structure is reported here.

In (I), each PrIII ion is coordinated by nine oxygen atoms, eight from four 1,4-BDOA2- ligands and one from a water molecule (Fig. 1). The coordination environment around the PrIII ion can be described as a tri-capped-trigonal prismatic geometry with O—Pr—O bond angles ranging from 47.76 (8) to 149.67 (8) Å. Pairs of Pr ions are bridged by the dianionic ligands at a distance of 4.188 (3) Å to form helical chains which are further cross-linked by the ligands into a three-dimensional supramolecular network (Fig. 2) with channels running along the c axis hosting the uncoordinated water molecules. The crystal structure is stabilized by intermolecular O—H···O hydrogen bonding interactions.

Related literature top

For related literature, see: Choi & Jeon (2003); Qiu et al. (2006); Tao et al. (2000).

Experimental top

A mixture of Pr(NO3)3 (0.5 mmol), (p-phenylenedioxy)diacetic acid (0.75 mmol), NaOH (1.5 mmol) and H2O (10 ml) was placed in a 20 ml Teflon reactor, which was heated at 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. Crystals were obtained after washing with water and drying in air.

Refinement top

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 = 0.82 or 0.85 Å and H···H = 1.29 or 1.39 Å, each within a standard deviation of 0.01 Å.

Computing details top

Data collection: APEX2 (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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atomic-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the symmetry operator (1 - x, -y, 2 - z).
[Figure 2] Fig. 2. The molecular packing of (I), showing the intermolecular hydrogen bonding interactions as the broken lines.
Poly[[diaquatris[µ4-(p-phenylenedioxy)diacetato]dipraseodymium(III)] dihydrate] top
Crystal data top
[Pr2(C10H8O6)3(H2O)2]·2H2OF(000) = 1012
Mr = 1026.38Dx = 1.959 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3500 reflections
a = 12.1685 (3) Åθ = 1.7–28.0°
b = 16.9339 (4) ŵ = 2.86 mm−1
c = 8.9299 (2) ÅT = 293 K
β = 108.956 (1)°Block, colourless
V = 1740.30 (7) Å30.18 × 0.15 × 0.12 mm
Z = 2
Data collection top
Bruker APEXII area-detector
diffractometer		4182 independent reflections
Radiation source: fine-focus sealed tube3381 reflections with I > 2σ(I)
graphiteRint = 0.036
φ and ω scansθmax = 28.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.607, Tmax = 0.715k = −17→22
14677 measured reflectionsl = −11→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0304P)2 + 2.8471P]
where P = (Fo2 + 2Fc2)/3
4182 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.62 e Å−3
6 restraintsΔρmin = −0.81 e Å−3
Crystal data top
[Pr2(C10H8O6)3(H2O)2]·2H2OV = 1740.30 (7) Å3
Mr = 1026.38Z = 2
Monoclinic, P21/cMo Kα radiation
a = 12.1685 (3) ŵ = 2.86 mm−1
b = 16.9339 (4) ÅT = 293 K
c = 8.9299 (2) Å0.18 × 0.15 × 0.12 mm
β = 108.956 (1)°
Data collection top
Bruker APEXII area-detector
diffractometer		4182 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3381 reflections with I > 2σ(I)
Tmin = 0.607, Tmax = 0.715Rint = 0.036
14677 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.62 e Å−3
S = 1.03Δρmin = −0.81 e Å−3
4182 reflectionsAbsolute structure: ?
244 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.3882 (3)0.2982 (2)1.0544 (4)0.0214 (7)
C20.2921 (3)0.2998 (2)0.8969 (4)0.0230 (8)
H2A0.22190.32140.90970.028*
H2B0.31440.33290.82290.028*
C30.1633 (3)0.2069 (2)0.7228 (4)0.0198 (7)
C40.1125 (3)0.2595 (2)0.6019 (5)0.0274 (8)
H40.14790.30770.59670.033*
C50.0081 (3)0.2397 (2)0.4888 (5)0.0289 (9)
H5−0.02680.27490.40750.035*
C6−0.0447 (3)0.1683 (2)0.4949 (4)0.0218 (8)
C70.0062 (3)0.1167 (2)0.6184 (4)0.0262 (8)
H7−0.02950.06870.62440.031*
C80.1099 (3)0.1363 (2)0.7325 (4)0.0240 (8)
H80.14370.10190.81590.029*
C9−0.1944 (3)0.0758 (2)0.3755 (4)0.0270 (8)
H9A−0.21510.06950.47090.032*
H9B−0.13530.03690.37810.032*
C10−0.3006 (3)0.0605 (2)0.2326 (4)0.0227 (8)
C110.3538 (3)0.0272 (2)1.1574 (4)0.0254 (8)
C120.3027 (4)−0.0132 (3)1.2703 (5)0.0414 (11)
H12A0.2934−0.06901.24430.050*
H12B0.3569−0.00861.37700.050*
C130.1003 (4)0.0075 (3)1.1304 (5)0.0352 (10)
C140.0010 (4)0.0502 (3)1.1204 (5)0.0368 (10)
H140.00160.08421.20240.044*
C150.0980 (4)−0.0433 (3)1.0079 (5)0.0377 (10)
H150.1636−0.07271.01260.045*
O10.4518 (3)0.23847 (17)1.0882 (3)0.0385 (8)
O20.3992 (2)0.35833 (16)1.1385 (3)0.0284 (6)
O30.2716 (2)0.22057 (15)0.8373 (3)0.0241 (6)
O4−0.1475 (2)0.15296 (16)0.3742 (3)0.0272 (6)
O5−0.3176 (2)−0.01103 (16)0.2027 (3)0.0281 (6)
O6−0.3610 (2)0.11699 (16)0.1607 (3)0.0312 (6)
O70.3150 (2)0.09148 (16)1.0965 (3)0.0318 (6)
O80.4394 (2)−0.00571 (16)1.1333 (3)0.0282 (6)
O90.1936 (3)0.0180 (2)1.2671 (3)0.0414 (8)
O1W0.6001 (3)0.2096 (2)0.8741 (4)0.0525 (10)
O2W0.7480 (3)0.2822 (2)0.1433 (4)0.0648 (11)
Pr10.451486 (16)0.116370 (11)0.92970 (2)0.01832 (7)
H1W0.62020.22630.79860.022*
H2W0.55620.24090.89260.022*
H3W0.78940.24560.13000.022*
H4W0.68050.28070.07270.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0247 (19)0.019 (2)0.0184 (16)0.0007 (15)0.0038 (14)0.0004 (15)
C20.027 (2)0.0151 (19)0.0206 (17)−0.0004 (15)−0.0008 (15)−0.0047 (14)
C30.0137 (16)0.0204 (19)0.0200 (16)0.0001 (14)−0.0021 (13)−0.0060 (14)
C40.023 (2)0.021 (2)0.031 (2)−0.0068 (16)−0.0009 (16)0.0024 (16)
C50.023 (2)0.026 (2)0.0268 (19)−0.0029 (17)−0.0073 (16)0.0071 (16)
C60.0156 (17)0.022 (2)0.0199 (16)−0.0023 (15)−0.0047 (13)−0.0043 (15)
C70.0225 (19)0.023 (2)0.0248 (18)−0.0062 (16)−0.0034 (15)0.0009 (16)
C80.0203 (18)0.022 (2)0.0217 (17)−0.0001 (15)−0.0038 (14)0.0033 (15)
C90.0236 (19)0.020 (2)0.0262 (19)−0.0056 (16)−0.0076 (15)0.0021 (16)
C100.0204 (18)0.025 (2)0.0185 (17)−0.0065 (16)0.0009 (14)0.0007 (15)
C110.0240 (19)0.027 (2)0.0238 (18)−0.0021 (16)0.0052 (15)−0.0027 (16)
C120.040 (3)0.044 (3)0.042 (2)0.001 (2)0.016 (2)0.018 (2)
C130.037 (2)0.033 (3)0.043 (2)−0.007 (2)0.024 (2)0.005 (2)
C140.042 (3)0.031 (2)0.047 (3)−0.007 (2)0.028 (2)−0.007 (2)
C150.036 (2)0.031 (3)0.056 (3)0.0017 (19)0.028 (2)0.002 (2)
O10.0356 (17)0.0254 (17)0.0343 (16)0.0095 (13)−0.0166 (13)−0.0140 (13)
O20.0379 (16)0.0199 (15)0.0197 (12)0.0014 (12)−0.0012 (11)−0.0079 (11)
O30.0192 (13)0.0168 (14)0.0249 (13)−0.0007 (10)−0.0084 (10)−0.0051 (10)
O40.0201 (13)0.0207 (15)0.0271 (13)−0.0082 (11)−0.0110 (11)0.0041 (11)
O50.0237 (14)0.0196 (15)0.0321 (14)−0.0063 (11)−0.0032 (12)−0.0030 (11)
O60.0239 (14)0.0246 (16)0.0300 (14)−0.0006 (12)−0.0122 (12)0.0044 (12)
O70.0388 (16)0.0234 (15)0.0392 (16)0.0103 (13)0.0208 (13)0.0093 (13)
O80.0252 (14)0.0282 (16)0.0279 (14)0.0072 (12)0.0039 (12)0.0005 (12)
O90.0360 (17)0.055 (2)0.0406 (17)−0.0066 (15)0.0231 (15)0.0001 (15)
O1W0.050 (2)0.065 (3)0.0345 (17)−0.0256 (18)0.0027 (15)0.0144 (16)
O2W0.053 (2)0.067 (3)0.056 (2)−0.012 (2)−0.0079 (18)0.011 (2)
Pr10.01760 (11)0.01524 (11)0.01758 (10)−0.00029 (8)−0.00054 (7)0.00020 (8)
Geometric parameters (Å, °) top
C1—O21.246 (4)C12—H12A0.9700
C1—O11.250 (4)C12—H12B0.9700
C1—C21.509 (5)C13—O91.383 (5)
C2—O31.435 (4)C13—C151.385 (6)
C2—H2A0.9700C13—C141.385 (6)
C2—H2B0.9700C14—C15i1.372 (6)
C3—C81.377 (5)C14—H140.9300
C3—C41.382 (5)C15—C14i1.372 (6)
C3—O31.400 (4)C15—H150.9300
C4—C51.382 (5)O1—Pr12.505 (3)
C4—H40.9300O2—Pr1ii2.505 (2)
C5—C61.378 (5)O3—Pr12.723 (2)
C5—H50.9300O5—Pr1iii2.446 (3)
C6—O41.385 (4)O6—Pr1iv2.531 (3)
C6—C71.386 (5)O7—Pr12.600 (3)
C7—C81.380 (5)O8—Pr1v2.465 (3)
C7—H70.9300O8—Pr12.788 (3)
C8—H80.9300O1W—Pr12.568 (3)
C9—O41.427 (4)O1W—H1W0.8374
C9—C101.514 (5)O1W—H2W0.8059
C9—H9A0.9700O2W—H3W0.8319
C9—H9B0.9700O2W—H4W0.8582
C10—O51.244 (4)Pr1—O5iii2.446 (3)
C10—O61.249 (4)Pr1—O8v2.465 (3)
C11—O71.241 (5)Pr1—O2vi2.505 (2)
C11—O81.260 (4)Pr1—O6vii2.531 (3)
C11—C121.510 (5)Pr1—H2W2.5404
C12—O91.420 (5)
O2—C1—O1125.3 (3)C2—O3—Pr1117.86 (19)
O2—C1—C2116.5 (3)C6—O4—C9115.3 (3)
O1—C1—C2118.1 (3)C10—O5—Pr1iii148.5 (2)
O3—C2—C1108.5 (3)C10—O6—Pr1iv129.8 (2)
O3—C2—H2A110.0C11—O7—Pr199.8 (2)
C1—C2—H2A110.0C11—O8—Pr1v155.7 (3)
O3—C2—H2B110.0C11—O8—Pr190.3 (2)
C1—C2—H2B110.0Pr1v—O8—Pr1105.58 (9)
H2A—C2—H2B108.4C13—O9—C12117.6 (3)
C8—C3—C4120.6 (3)Pr1—O1W—H1W140.5
C8—C3—O3116.7 (3)Pr1—O1W—H2W79.0
C4—C3—O3122.7 (3)H1W—O1W—H2W109.3
C3—C4—C5119.0 (4)H3W—O2W—H4W110.7
C3—C4—H4120.5O5iii—Pr1—O8v70.05 (9)
C5—C4—H4120.5O5iii—Pr1—O1138.91 (10)
C6—C5—C4120.9 (3)O8v—Pr1—O1148.69 (9)
C6—C5—H5119.5O5iii—Pr1—O2vi73.65 (9)
C4—C5—H5119.5O8v—Pr1—O2vi82.36 (9)
C5—C6—O4116.7 (3)O1—Pr1—O2vi113.49 (9)
C5—C6—C7119.4 (3)O5iii—Pr1—O6vii132.82 (9)
O4—C6—C7123.9 (3)O8v—Pr1—O6vii77.26 (9)
C8—C7—C6120.0 (4)O1—Pr1—O6vii72.56 (9)
C8—C7—H7120.0O2vi—Pr1—O6vii134.67 (10)
C6—C7—H7120.0O5iii—Pr1—O1W139.07 (10)
C3—C8—C7120.0 (3)O8v—Pr1—O1W87.60 (11)
C3—C8—H8120.0O1—Pr1—O1W74.31 (12)
C7—C8—H8120.0O2vi—Pr1—O1W69.60 (9)
O4—C9—C10112.6 (3)O6vii—Pr1—O1W69.51 (10)
O4—C9—H9A109.1O5iii—Pr1—O773.11 (9)
C10—C9—H9A109.1O8v—Pr1—O7119.94 (9)
O4—C9—H9B109.1O1—Pr1—O772.20 (10)
C10—C9—H9B109.1O2vi—Pr1—O7128.92 (9)
H9A—C9—H9B107.8O6vii—Pr1—O796.22 (9)
O5—C10—O6127.3 (3)O1W—Pr1—O7146.24 (11)
O5—C10—C9112.6 (3)O5iii—Pr1—O388.99 (8)
O6—C10—C9120.0 (3)O8v—Pr1—O3149.67 (8)
O7—C11—O8122.1 (4)O1—Pr1—O359.33 (8)
O7—C11—C12120.6 (4)O2vi—Pr1—O370.52 (8)
O8—C11—C12117.2 (4)O6vii—Pr1—O3131.89 (8)
O9—C12—C11113.8 (4)O1W—Pr1—O395.18 (10)
O9—C12—H12A108.8O7—Pr1—O371.23 (8)
C11—C12—H12A108.8O5iii—Pr1—O866.83 (8)
O9—C12—H12B108.8O8v—Pr1—O874.42 (9)
C11—C12—H12B108.8O1—Pr1—O8103.55 (9)
H12A—C12—H12B107.7O2vi—Pr1—O8138.96 (8)
O9—C13—C15125.3 (4)O6vii—Pr1—O872.30 (8)
O9—C13—C14116.0 (4)O1W—Pr1—O8140.50 (9)
C15—C13—C14118.7 (4)O7—Pr1—O847.76 (8)
C15i—C14—C13121.4 (4)O3—Pr1—O8118.08 (8)
C15i—C14—H14119.3O5iii—Pr1—H2W145.7
C13—C14—H14119.3O8v—Pr1—H2W105.7
C14i—C15—C13119.9 (4)O1—Pr1—H2W58.7
C14i—C15—H15120.1O2vi—Pr1—H2W72.0
C13—C15—H15120.1O6vii—Pr1—H2W75.2
C1—O1—Pr1130.1 (2)O1W—Pr1—H2W18.1
C1—O2—Pr1ii135.0 (2)O7—Pr1—H2W130.5
C3—O3—C2115.8 (3)O3—Pr1—H2W79.1
C3—O3—Pr1126.0 (2)O8—Pr1—H2W146.6
Symmetry codes: (i) −x, −y, −z+2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z+1; (iv) x−1, y, z−1; (v) −x+1, −y, −z+2; (vi) x, −y+1/2, z−1/2; (vii) x+1, y, z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2Wii0.842.403.149 (5)149
O1W—H2W···O10.812.473.064 (5)131
O2W—H3W···O4viii0.832.592.992 (5)111
O2W—H4W···O1Wix0.862.102.778 (5)135
Symmetry codes: (ii) x, −y+1/2, z+1/2; (viii) x+1, y, z; (ix) x, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2Wi0.842.403.149 (5)149
O1W—H2W···O10.812.473.064 (5)131
O2W—H3W···O4ii0.832.592.992 (5)111
O2W—H4W···O1Wiii0.862.102.778 (5)135
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, y, z; (iii) x, y, z−1.
Acknowledgements top

The authors acknowledge South China Normal University for supporting this work.

references
References top

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