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Acta Cryst. (2009). E65, m208-m209    [ doi:10.1107/S1600536809001718 ]

catena-Poly[[[tetraaquapraseodymium(III)]-di-[mu]-nicotinato-[kappa]2O:N;[kappa]2O:N-disilver(I)-di-[mu]-nicotinato-[kappa]2N:O;[kappa]2N:O] perchlorate monohydrate]

B. Guan, C.-H. Zhang and W.-D. Song

Abstract top

In the title compound, {[Ag2Pr(C6H4NO2)4(H2O)4]ClO4·H2O}n, the PrIII atom, lying on a twofold rotation axis, has a distorted square-antiprismatic coordination geometry, defined by four O atoms from four nicotinate (nic) ligands and four water molecules. The AgI atom is coordinated in an almost linear fashion by two pyridyl N atoms from two nicotinate ligands. The linear coordination is augmented by weak interactions with three O atoms from one perchlorate anion, one uncoordinated water molecule and one carboxylate group. Two Pr atoms link two {Ag(nic)2}+ units into a ring, which is further extended into an infinite zigzag chain by sharing the Pr atoms. These chains are further connected into a three-dimensional network via weak Ag...O interactions, O-H...O hydrogen bonds, Ag...Ag interactions [3.357 (2) Å] and [pi]-[pi] interactions between the pyridyl rings [centroid-centroid distance = 3.685 (4) Å].

Comment top

Nicotinic acid is a multifunctional bridging ligand possessing of O and N donors, which can thus be utilized to construct lanthanide–transition heterometallic complexes, via carboxylate O atoms binding to lanthanides and N atoms binding to transition metal ions such as AgI or CuI (Cheng et al., 2007a,b; Luo et al., 2006, 2007). On the basis of above considerations, we chose nicotinic acid, PrIII and AgI metal ions as building blocks. A new one-dimensional 4 d–4f coordination polymer was obtained from the hydrothermal treatment of Pr6O11, AgNO3, perchloric acid and nicotinic acid in water.

In the title compound (Fig. 1), the PrIII atom, lying on a twofold rotation axis, has a distorted square-antiprismatic coordination geometry, defined by four O atoms from four nicotinate (nic) ligands and four water molecules. The perchlorate anion lies on a mirror plane and the uncoordinated water molecule lies on a twofold rotation axis. The AgI atom is coordinated in an almost linear fashion by two pyridyl N atoms from two nic ligands. The linear coordination are augmented by weak Ag···O interactions with one O atom from the ClO4- anion, one O atom from the uncoordinated water molecule and one carboxylate O atom from the nic ligand (Table 1). The Ag atom also exhibits an argentophilic interaction, with an Ag···Ag distance of 3.357 (1) Å. The pyridyl rings of the nic ligands coordinating to the Ag atom are almost coplanar and have a dihedral angle of 1.74 (2)°. Two Pr atoms link two Ag(nic)2+ units into a ring, which are further extended into an infinite zigzag chain by sharing the common Pr atoms (Fig. 2). These chains are further connected into a three-dimensional network via the weak Ag···O interactions, O—H···O hydrogen bonds (Table 2), weak Ag···Ag interactions and π–π interactions occurring between the pyridyl rings of neighboring nic ligands [centroid–centroid distance = 3.685 (4) Å].

Related literature top

For general background, see: Cheng et al. (2007a,b); Luo et al. (2006, 2007).

Experimental top

A mixture of Pr6O11 (0.170 g, 0.5 mmol), AgNO3 (0.169 g, 1 mmol), nicotinic acid (0.123 g, 1 mmol), HClO4 (0.12 ml) and H2O (10 ml) was placed in a 23 ml Teflon-lined reactor, which was heated to 433 K for 3 d and then cooled to room temperature at a rate of 10 K h-1. The pale-purple plate crystals obtained were washed with water and dried in air (yield 46% based on Pr).

Refinement top

H atoms on C atoms were positioned geometrically and treated as riding on the parent C atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of water molecules were located in difference Fourier maps and fixed in the refinements, with Uiso(H) = 1.5Ueq(O). The highest residual electron density was found 1.09 Å from atom Pr1 and the deepest hole 0.76 Å from atom Cl1.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, extended to show the Pr and Ag coordination environments. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1/2 - x, 3/2 - y, 1 - z; (ii) x, 1/2 + y, 3/2 - z; (iii) 1/2 - x, y, 1/2 - z; (viii) x, 3/2 - y, -1/2 + z; (ix) -x, y, z.]
[Figure 2] Fig. 2. View of the zigzag chain in the title compound.
catena-Poly[[[tetraaquapraseodymium(III)]-di-µ-nicotinato- κ2O:N;κ2O:N-disilver(I)-di-µ-nicotinato- κ2N:O;κ2N:O] perchlorate monohydrate] top
Crystal data top
[Ag2Pr(C6H4NO2)4(H2O)4]ClO4·H2OF(000) = 4032
Mr = 1034.59Dx = 2.060 Mg m−3
Orthorhombic, CmcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2Cell parameters from 3121 reflections
a = 35.396 (3) Åθ = 1.4–28°
b = 12.3733 (10) ŵ = 2.76 mm−1
c = 15.2324 (13) ÅT = 273 K
V = 6671.2 (10) Å3Plate, pale purple
Z = 80.30 × 0.25 × 0.22 mm
Data collection top
Bruker APEXII CCD
diffractometer		3065 independent reflections
Radiation source: fine-focus sealed tube2478 reflections with I > 2σ(I)
graphiteRint = 0.049
φ and ω scansθmax = 25.2°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −28→42
Tmin = 0.453, Tmax = 0.552k = −13→14
16336 measured reflectionsl = −18→18
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0479P)2 + 31.5675P]
where P = (Fo2 + 2Fc2)/3
3065 reflections(Δ/σ)max < 0.001
227 parametersΔρmax = 1.56 e Å−3
27 restraintsΔρmin = −0.86 e Å−3
Crystal data top
[Ag2Pr(C6H4NO2)4(H2O)4]ClO4·H2OV = 6671.2 (10) Å3
Mr = 1034.59Z = 8
Orthorhombic, CmcaMo Kα radiation
a = 35.396 (3) ŵ = 2.76 mm−1
b = 12.3733 (10) ÅT = 273 K
c = 15.2324 (13) Å0.30 × 0.25 × 0.22 mm
Data collection top
Bruker APEXII CCD
diffractometer		3065 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2478 reflections with I > 2σ(I)
Tmin = 0.453, Tmax = 0.552Rint = 0.049
16336 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.036 w = 1/[σ2(Fo2) + (0.0479P)2 + 31.5675P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.097Δρmax = 1.56 e Å−3
S = 1.06Δρmin = −0.86 e Å−3
3065 reflectionsAbsolute structure: ?
227 parametersFlack parameter: ?
27 restraintsRogers parameter: ?
H-atom parameters constrained
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pr10.25001.08315 (12)0.25000.0216 (5)
Ag10.11088 (6)0.60988 (15)0.56463 (12)0.0439 (6)
C20.1570 (6)0.8876 (17)0.4208 (13)0.031 (5)
C60.1963 (6)0.9230 (16)0.3979 (13)0.027 (4)
C30.1260 (7)0.943 (2)0.3901 (17)0.048 (6)
H30.12921.00380.35550.058*
C10.1508 (6)0.7976 (18)0.4725 (13)0.033 (5)
H10.17160.76070.49450.040*
C40.0904 (8)0.908 (2)0.411 (2)0.067 (9)
H40.06920.94390.38990.081*
C50.0867 (7)0.816 (2)0.4631 (18)0.054 (7)
H50.06250.79270.47820.065*
N10.1163 (5)0.7608 (15)0.4925 (12)0.040 (5)
O10.2002 (4)0.9976 (12)0.3439 (9)0.035 (3)
O20.2235 (4)0.8725 (12)0.4344 (9)0.033 (3)
N20.1025 (5)0.4681 (15)0.6456 (12)0.037 (4)
C70.1323 (6)0.4144 (16)0.6770 (14)0.032 (5)
H70.15630.43850.66100.038*
C110.0685 (8)0.434 (2)0.669 (2)0.057 (8)
H110.04740.47180.64890.069*
Cl10.00000.6849 (10)0.5898 (10)0.080 (4)
O70.00000.803 (3)0.588 (4)0.150 (19)
O60.00000.647 (5)0.685 (4)0.25 (4)
C80.1300 (6)0.3255 (16)0.7316 (13)0.030 (5)
C90.0945 (7)0.292 (2)0.7558 (19)0.057 (8)
H90.09140.23440.79410.069*
C100.0631 (8)0.346 (3)0.723 (3)0.082 (12)
H100.03880.32320.73620.098*
C120.1652 (6)0.2676 (16)0.7619 (13)0.028 (4)
O30.1962 (4)0.3019 (12)0.7341 (9)0.032 (3)
O40.1611 (4)0.1878 (13)0.8104 (11)0.044 (4)
O1W0.2180 (4)0.9435 (12)0.1603 (9)0.035 (4)
H1W0.23730.91950.12950.053*
H2W0.19960.89180.18070.053*
O2W0.2515 (5)1.1653 (13)0.3996 (10)0.046 (4)
H3W0.26151.23940.41100.069*
H4W0.24541.14090.44860.069*
O3W0.1776 (8)0.50000.50000.080 (10)
H5W0.19200.50100.45830.120*
O50.0324 (9)0.643 (3)0.565 (3)0.19 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pr10.0227 (9)0.0223 (8)0.0199 (8)0.0000.0012 (6)0.000
Ag10.0482 (12)0.0376 (11)0.0458 (11)−0.0044 (9)0.0028 (8)0.0151 (8)
C20.035 (12)0.033 (11)0.024 (10)0.001 (10)0.006 (9)0.001 (9)
C60.032 (12)0.025 (10)0.023 (10)0.000 (9)0.005 (9)−0.004 (8)
C30.038 (14)0.051 (15)0.054 (15)0.000 (12)0.009 (12)0.023 (12)
C10.034 (12)0.038 (12)0.028 (10)−0.003 (10)0.003 (9)0.004 (10)
C40.035 (15)0.07 (2)0.09 (2)0.003 (14)0.004 (15)0.043 (17)
C50.034 (14)0.060 (17)0.069 (18)−0.005 (13)0.012 (12)0.023 (14)
N10.039 (11)0.040 (11)0.040 (10)−0.002 (9)0.006 (8)0.014 (9)
O10.034 (8)0.032 (8)0.037 (8)0.000 (7)0.005 (6)0.013 (7)
O20.029 (8)0.038 (8)0.031 (8)0.000 (7)0.000 (6)0.005 (7)
N20.034 (11)0.033 (10)0.045 (11)0.000 (8)0.002 (8)0.010 (8)
C70.030 (12)0.028 (11)0.037 (12)−0.006 (9)0.001 (9)0.001 (9)
C110.037 (15)0.054 (17)0.08 (2)0.006 (12)0.003 (13)0.029 (15)
Cl10.040 (6)0.070 (8)0.130 (11)0.0000.0000.009 (7)
O70.17 (5)0.09 (3)0.19 (5)0.0000.0000.04 (3)
O60.45 (13)0.14 (5)0.15 (6)0.0000.0000.02 (4)
C80.030 (12)0.024 (11)0.036 (12)−0.002 (9)0.004 (9)0.001 (9)
C90.034 (14)0.054 (16)0.08 (2)−0.002 (12)0.005 (13)0.042 (15)
C100.029 (15)0.08 (2)0.13 (3)0.000 (15)0.004 (17)0.06 (2)
C120.026 (11)0.028 (11)0.031 (11)0.000 (9)0.003 (8)−0.005 (9)
O30.027 (8)0.031 (8)0.037 (8)−0.005 (6)0.002 (6)−0.005 (6)
O40.031 (9)0.044 (10)0.056 (10)0.005 (7)0.007 (7)0.023 (8)
O1W0.029 (8)0.035 (8)0.041 (9)−0.006 (6)0.006 (7)−0.009 (7)
O2W0.071 (12)0.044 (10)0.024 (8)−0.021 (9)0.013 (8)−0.010 (7)
O3W0.047 (16)0.15 (3)0.040 (14)0.0000.000−0.002 (17)
O50.07 (2)0.14 (3)0.35 (6)0.04 (2)0.07 (3)0.12 (3)
Geometric parameters (Å, °) top
Pr1—O3i2.390 (14)N2—C111.32 (3)
Pr1—O1W2.477 (14)N2—C71.34 (3)
Pr1—O2W2.495 (14)C7—C81.38 (3)
Pr1—O12.504 (13)C7—H70.9300
Ag1—N22.165 (18)C11—C101.37 (4)
Ag1—N12.175 (18)C11—H110.9300
Ag1—O4ii2.777 (16)Cl1—O5iv1.31 (3)
Ag1—O52.81 (3)Cl1—O51.31 (3)
Ag1—O3W2.90 (2)Cl1—O71.46 (4)
Ag1—Ag1iii3.357 (2)Cl1—O61.52 (5)
C2—C31.37 (3)C8—C91.37 (3)
C2—C11.38 (3)C8—C121.51 (3)
C2—C61.50 (3)C9—C101.39 (4)
C6—O11.24 (2)C9—H90.9300
C6—O21.27 (3)C10—H100.9300
C3—C41.37 (4)C12—O41.24 (2)
C3—H30.9300C12—O31.25 (2)
C1—N11.34 (3)O1W—H1W0.88
C1—H10.9300O1W—H2W0.97
C4—C51.39 (4)O2W—H3W1.00
C4—H40.9300O2W—H4W0.83
C5—N11.33 (3)O3W—H5W0.82
C5—H50.9300
O3i—Pr1—O3v106.9 (7)C3—C4—H4120.8
O3i—Pr1—O1W146.7 (5)C5—C4—H4120.8
O3v—Pr1—O1W89.7 (5)N1—C5—C4123 (2)
O3i—Pr1—O1Wvi89.7 (5)N1—C5—H5118.7
O3v—Pr1—O1Wvi146.7 (5)C4—C5—H5118.7
O1W—Pr1—O1Wvi91.5 (7)C5—N1—C1118 (2)
O3i—Pr1—O2W69.4 (5)C5—N1—Ag1122.9 (16)
O3v—Pr1—O2W82.3 (5)C1—N1—Ag1119.1 (15)
O1W—Pr1—O2W142.9 (5)C6—O1—Pr1140.4 (13)
O1Wvi—Pr1—O2W76.7 (5)C11—N2—C7118 (2)
O3i—Pr1—O2Wvi82.3 (5)C11—N2—Ag1122.3 (16)
O3v—Pr1—O2Wvi69.4 (5)C7—N2—Ag1119.9 (14)
O1W—Pr1—O2Wvi76.7 (5)N2—C7—C8124 (2)
O1Wvi—Pr1—O2Wvi142.9 (5)N2—C7—H7117.8
O2W—Pr1—O2Wvi131.9 (7)C8—C7—H7117.8
O3i—Pr1—O1139.0 (5)N2—C11—C10123 (2)
O3v—Pr1—O175.5 (5)N2—C11—H11118.7
O1W—Pr1—O172.5 (5)C10—C11—H11118.7
O1Wvi—Pr1—O173.2 (5)O5iv—Cl1—O5122 (4)
O2W—Pr1—O170.5 (5)O5iv—Cl1—O7113.2 (18)
O2Wvi—Pr1—O1132.8 (5)O5—Cl1—O7113.2 (18)
O3i—Pr1—O1vi75.5 (5)O5iv—Cl1—O698 (2)
O3v—Pr1—O1vi139.0 (5)O5—Cl1—O698 (2)
O1W—Pr1—O1vi73.2 (5)O7—Cl1—O6109 (3)
O1Wvi—Pr1—O1vi72.5 (5)C9—C8—C7117 (2)
O2W—Pr1—O1vi132.8 (5)C9—C8—C12122.1 (19)
O2Wvi—Pr1—O1vi70.5 (5)C7—C8—C12120.9 (19)
O1—Pr1—O1vi129.9 (7)C8—C9—C10119 (2)
N2—Ag1—N1174.6 (7)C8—C9—H9120.3
N2—Ag1—Ag1iii71.2 (5)C10—C9—H9120.3
N1—Ag1—Ag1iii113.5 (5)C11—C10—C9119 (3)
C3—C2—C1118 (2)C11—C10—H10120.5
C3—C2—C6121.2 (19)C9—C10—H10120.5
C1—C2—C6121 (2)O4—C12—O3124.9 (19)
O1—C6—O2124.6 (19)O4—C12—C8117.7 (18)
O1—C6—C2118.3 (19)O3—C12—C8117.4 (18)
O2—C6—C2117.1 (17)C12—O3—Pr1i150.2 (13)
C4—C3—C2120 (2)Pr1—O1W—H1W100.1
C4—C3—H3119.9Pr1—O1W—H2W126.4
C2—C3—H3119.9H1W—O1W—H2W118.2
N1—C1—C2123 (2)Pr1—O2W—H3W122.7
N1—C1—H1118.3Pr1—O2W—H4W131.7
C2—C1—H1118.3H3W—O2W—H4W105.6
C3—C4—C5118 (3)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) x, y+1/2, −z+3/2; (iii) x, −y+1, −z+1; (iv) −x, y, z; (v) x, −y+3/2, z−1/2; (vi) −x+1/2, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2vi0.881.792.67 (2)179
O1W—H2W···O4iii0.971.682.63 (2)163
O2W—H3W···O2vii1.001.772.77 (2)176
O2W—H4W···O2viii0.831.952.76 (2)162
O3W—H5W···O1Wix0.822.152.91 (2)157
Symmetry codes: (vi) −x+1/2, y, −z+1/2; (iii) x, −y+1, −z+1; (vii) −x+1/2, y+1/2, z; (viii) x, −y+2, −z+1; (ix) x, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Pr1—O3i2.390 (14)Ag1—N12.175 (18)
Pr1—O1W2.477 (14)Ag1—O4ii2.777 (16)
Pr1—O2W2.495 (14)Ag1—O52.81 (3)
Pr1—O12.504 (13)Ag1—O3W2.90 (2)
Ag1—N22.165 (18)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) x, y+1/2, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2iii0.881.792.67 (2)179
O1W—H2W···O4iv0.971.682.63 (2)163
O2W—H3W···O2v1.001.772.77 (2)176
O2W—H4W···O2vi0.831.952.76 (2)162
O3W—H5W···O1Wvii0.822.152.91 (2)157
Symmetry codes: (iii) −x+1/2, y, −z+1/2; (iv) x, −y+1, −z+1; (v) −x+1/2, y+1/2, z; (vi) x, −y+2, −z+1; (vii) x, y−1/2, −z+1/2.
Acknowledgements top

The authors acknowledge Guangdong Ocean University for supporting this work.

references
References top

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