[Cd(phen)2{MoO4}]·H2O, a one dimensional coordination polymer with bridging molybdate groups

metal-organic papers

m1840

4(C12H8N2)2]H2O doi:10.1107/S1600536805026073 Acta Cryst.(2005). E61, m1840–m1842 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

[Cd(phen)

{MoO

}]

H

O, a one-dimensional

coordination polymer with bridging molybdate

groups

Xiuli Bai,a,bYing Luaand Enbo Wanga*

a

Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China, andb_{Department of} Chemistry Changchun Teacher’s College, Changchun 130032, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 283 K

Mean(C–C) = 0.007 A˚

Rfactor = 0.038

wRfactor = 0.128

Data-to-parameter ratio = 15.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

In the title compound,catena -poly[[bis(1,10-phenanthroline)-cadmium(II)]--tetraoxomolybdato], {[CdMoO4(C12H8N2)2

]-H2O}n, the Cd

II

ion has a distorted octahedral geometry, defined by four N atoms of two chelating phen (phenanthro-line) ligands and two O atoms from two MoO4tetrahedra. The

MoVIatom has a distorted tetrahedral geometry, defined by two terminal O atoms and two bridging (to Cd) O atoms. The compound exhibits a one-dimensional corrugated chain structure, and is further extended into a three-dimensional

inorganic–organic hybrid compound via hydrogen-bonding

and weaker–bonding interactions.

Comment

In the past decade, organic–inorganic hybrid materials have attracted extensive attention due to their potential applica-tions in catalysis, magnetism, electron conductivity and photochemistry as well as their interesting structural features (Gouzerh & Proust, 1998; Hagrmanet al., 1999; Hagrman & Zubieta, 1999). Hydrothermal methods are a key technique for preparing such materials (Yaghi & Li, 1995).

One topic of interest to us is the integration of metal– organic complexes with molybdenum oxide moieties into a single hybrid structure. A variety of such phases have been

prepared and characterized including [Mn(phen)(H2

O)-MoO4]H2O (phen is 1,10-phenanthroline; Zhanget al., 2004),

[Cu(phen)MoO4]H2O (Hagrman & Zubieta, 1999) and

[FeCl(2,20_-bpy)MoO

4] (2,20-bpy is 2,20-bipyridine; Zapf et al.,

1998). In these complexes, the organonitrogen components act not only as charge compensators and space-filling constituents, but also as ligands bonded directly to a secondary metal center. We report here the synthesis and structure of the title compound, (I), a new one-dimensional coordination polymer containing {MoO4} tetrahedra and [Cd(phen)2O2] octahedra.

As shown in Fig. 1, there is one crystallographically inde-pendent Cd center and one Mo atom in the asymmetric unit. The octahedral coordination environment about Cd is defined (Table 1) by four N atoms from two chelating phen ligands, and two O atoms from two {MoO4} tetrahedra. The average

Cd—N distance is 2.400 (4) A˚ , and the Cd—O bond lengths are 2.211 (3) and 2.191 (3) A˚ . The Mo atom, residing in a tetrahedral environment, is coordinated by two terminal O atoms and two bridging O atoms, with Mo—O bond lengths in the range 1.731 (4)0–1.762 (3) A˚ . The {CdO2N4} octahedra

and {MoO4} tetrahedra are connected by corner-sharing O

atoms to form a one-dimensional chain, which is similar to the nickel–molybdate chains in [Ni(3,40_-bipyridine)

2MoO4]3H2O

(LaDucaet al., 2002). In (I), adjacent chains are held together

via two types of supramolecular interactions. One involves O—H O hydrogen bonds arising from the non-coordinated water molecule (Table 2). The other involves weak aromatic

—stacking of the phen groups; the close contact distance

between adjacent aromatic rings of phen is 3.841 A˚ . (I) is finally extended into a three-dimensional structure by these weak interactions (Fig. 3).

Experimental

A mixture of Cd(NO3)28H2O (0.5 mmol), Na2MoO42H2O (0.5 mmol), 1,10-phenanthroline (0.6 mmol) and water (10 ml) was stirred for 20 min in air. The mixture was then transferred to a 23 ml Teflon reactor and kept at 433 K for 72 h under autogenous pressure. Crystals of (I) suitable for X-ray analysis were obtained after the reactor had been cooled and opened.

Crystal data

[CdMoO4(C12H8N2)2]H2O

Mr= 650.76 Monoclinic,P2₁=c a= 13.901 (3) A˚

b= 15.370 (3) A˚

c= 10.742 (2) A˚ = 101.61 (3) V= 2248.2 (8) A˚3

Z= 4

Dx= 1.923 Mg m

3

MoKradiation

Cell parameters from 20706 reflections

= 3.0–27.5

= 1.55 mm1

T= 283 (2) K Block, colorless 0.340.280.26 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

oscillation scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995)

Tmin= 0.611,Tmax= 0.668

20706 measured reflections

5060 independent reflections 4251 reflections withI> 2(I)

Rint= 0.047

max= 27.5 h=18!16

k=19!19

l=13!13

metal-organic papers

Acta Cryst.(2005). E61, m1840–m1842 Baiet al. _[CdMoO

4(C12H8N2)2]H2O

m1841

A view of the building units of (I), showing 50% probability displacement ellipsoids (H atoms omitted for clarity). Atom O2Ais generated by the symmetry code (x,1

2y,z 1

2). H atoms have been omitted.

Figure 2

A view of the one-dimensonal chain formed by alternating {MoO4}

tetrahedra and [CdN2O2] units. H atoms have been omitted.

Figure 3

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.038}

wR(F2) = 0.128

S= 1.01 5060 reflections 318 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.09P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.60 e A˚ 3

min=0.98 e A˚ 3

Table 1

Selected bond lengths (A˚ ).

Cd1—O2 2.191 (3)

Cd1—O1 2.211 (3)

Cd1—N2 2.374 (4)

Cd1—N3 2.375 (4)

Cd1—N1 2.390 (4)

Cd1—N4 2.457 (4)

Mo2—O3 1.730 (3)

Mo2—O4 1.746 (3)

Mo2—O2i

1.762 (3)

Mo2—O1 1.763 (3)

Symmetry code: (i)x;yþ1 2;z

1 2.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O1W—H1 O4 0.85 1.91 2.743 (5) 165

O1W—H2 O3ii

0.85 1.93 2.739 (6) 158

Symmetry code: (ii)xþ2;y;z.

C-bound H atoms were placed in idealized positions (C—H = 0.93 A˚ ) and refined as riding with the constraintUiso(H) = 1.2Ueq

applied. The water H atoms were positioned geometrically (O—H = 0.85 A˚ ) and refined as riding, withUiso(H) values freely refined.

Data collection: PROCESS-AUTO (Rigaku, 1998); cell

refine-ment: PROCESS-AUTO; data reduction: PROCESS-AUTO;

program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication:SHELXL97.

This work was supported financially by the National Natural Science Foundation of China (No. 20371011).

References

Bruker (1998). SHELXTL. Version 5.16. Bruker AXS Inc., Madison, Wisconsin, USA.

Gouzerh, P. & Proust, A. (1998).Chem. Rev.98, 77–112.

Hagrman, P.-J., Hagrman, D. & Zubieta, J. (1999).Angew. Chem. Int. Ed.38, 2638–2684.

Hagrman, P. J. & Zubieta, J. (1999).Inorg. Chem.38, 4480–4485. Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan. Rigaku (1998).PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. LaDuca, R. L. Jr, Desiak, M., Rarig, R. S. Jr & Zubieta, J. (2002).Inorg. Chim.

Acta,332, 79–86.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Yaghi, O.-M. & Li, H.-L. (1995).J. Am. Chem. Soc.117, 10401–10402. Zapf, P.-J., Hammond, R.-P., Haushalter, R.-C. & Zubieta, J. (1998).Chem.

Mater.10, 1366–1373.

Zhang, Q.-Z., Lu, C.-Z., Yang, W.-B., Chen, S.-M., Yu, Y.-Q., He, X., Yan, Y., Liu, J.-H., Xu, X.-J., Xia, C.-K., Wu, X.-Y. & Chen, L.-J. (2004).J. Solid State Chem.177, 2862–2866.

metal-organic papers

m1842

supporting information

sup-1

Acta Cryst. (2005). E61, m1840–m1842

supporting information

Acta Cryst. (2005). E61, m1840–m1842 [https://doi.org/10.1107/S1600536805026073]

[Cd(phen)

{MoO

}]

·

H

O, a one-dimensional coordination polymer with

bridging molybdate groups

Xiuli Bai, Ying Lu and Enbo Wang

catena-poly[[bis(1,10-phenanthroline)cadmium(II)]-µ-tetraoxomolybdato]

Crystal data

[CdMoO4(C12H8N2)2]·H2O

Mr = 650.76

Monoclinic, P21/c

Hall symbol: -P 2ybc a = 13.901 (3) Å b = 15.370 (3) Å c = 10.742 (2) Å β = 101.61 (3)° V = 2248.2 (8) Å3

Z = 4

F(000) = 1280 Dx = 1.923 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 20706 reflections θ = 3.0–27.5°

µ = 1.55 mm−1

T = 283 K Block, colorless 0.34 × 0.28 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Radiation source: Rotation anode Graphite monochromator

Detector resolution: 0.01 pixels mm-1

oscillation scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.611, Tmax = 0.668

20706 measured reflections 5060 independent reflections 4251 reflections with I > 2σ(I) Rint = 0.047

θmax = 27.5°, θmin = 3.0°

h = −18→16 k = −19→19 l = −13→13

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.038}

wR(F2_{) = 0.128}

S = 1.01 5060 reflections 318 parameters 2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.09P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.60 e Å−3

supporting information

sup-2

Acta Cryst. (2005). E61, m1840–m1842 Special details

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

supporting information

sup-3

Acta Cryst. (2005). E61, m1840–m1842

C14 0.9756 (3) 0.1102 (3) 0.7320 (4) 0.0257 (9) H14A 1.0064 0.1475 0.7960 0.031* C15 0.9773 (3) 0.0227 (3) 0.7515 (4) 0.0246 (9) H15A 1.0076 −0.0002 0.8297 0.030* C16 0.9325 (3) −0.0330 (3) 0.6516 (4) 0.0200 (8) C17 0.9345 (4) −0.1262 (3) 0.6628 (4) 0.0255 (10) H17A 0.9644 −0.1514 0.7395 0.031* C18 0.8940 (3) −0.1777 (3) 0.5651 (4) 0.0259 (9) H18A 0.8989 −0.2378 0.5735 0.031* C19 0.8430 (3) −0.1399 (3) 0.4469 (4) 0.0213 (9) C20 0.7995 (3) −0.1906 (3) 0.3418 (4) 0.0255 (9) H20A 0.8026 −0.2510 0.3465 0.031* C21 0.7527 (4) −0.1507 (3) 0.2330 (4) 0.0275 (10) H21A 0.7251 −0.1835 0.1619 0.033* C22 0.7467 (3) −0.0597 (3) 0.2294 (4) 0.0255 (9) H22A 0.7135 −0.0333 0.1553 0.031* C23 0.8361 (3) −0.0493 (3) 0.4343 (4) 0.0171 (8) C24 0.8839 (3) 0.0061 (3) 0.5375 (3) 0.0179 (8)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-4

Acta Cryst. (2005). E61, m1840–m1842

C16 0.018 (2) 0.027 (2) 0.0159 (17) 0.0026 (16) 0.0061 (17) 0.0045 (15) C17 0.030 (3) 0.027 (2) 0.018 (2) 0.0046 (18) 0.0009 (19) 0.0065 (16) C18 0.028 (2) 0.021 (2) 0.027 (2) 0.0033 (18) 0.0028 (19) 0.0065 (17) C19 0.023 (2) 0.026 (2) 0.0168 (19) 0.0005 (16) 0.0089 (18) 0.0040 (15) C20 0.029 (2) 0.019 (2) 0.028 (2) 0.0016 (18) 0.0046 (19) 0.0010 (17) C21 0.034 (3) 0.027 (2) 0.021 (2) −0.0033 (19) 0.005 (2) −0.0037 (16) C22 0.030 (2) 0.025 (2) 0.0197 (19) 0.0011 (18) 0.0003 (18) 0.0033 (16) C23 0.0137 (19) 0.024 (2) 0.0160 (18) 0.0016 (15) 0.0080 (16) 0.0020 (15) C24 0.0141 (19) 0.026 (2) 0.0146 (17) 0.0008 (15) 0.0052 (16) 0.0020 (15)

Geometric parameters (Å, º)

Cd1—O2 2.191 (3) C6—C7 1.429 (7) Cd1—O1 2.211 (3) C6—H6A 0.9300 Cd1—N2 2.374 (4) C7—C12 1.407 (6) Cd1—N3 2.375 (4) C7—C8 1.420 (7) Cd1—N1 2.390 (4) C8—C9 1.338 (8) Cd1—N4 2.457 (4) C8—H8A 0.9300 Mo2—O3 1.730 (3) C9—C10 1.404 (7) Mo2—O4 1.746 (3) C9—H9A 0.9300 Mo2—O2i _{1.762 (3) C10—H10A 0.9300}

Mo2—O1 1.763 (3) C11—C12 1.453 (6) O1W—H1 0.8501 C13—C14 1.393 (7) O1W—H2 0.8500 C13—H13A 0.9300 O2—Mo2ii _{1.762 (3) C14—C15 1.360 (7)}

N1—C22 1.323 (5) C14—H14A 0.9300 N1—C23 1.368 (5) C15—C16 1.416 (6) N2—C13 1.332 (6) C15—H15A 0.9300 N2—C24 1.354 (6) C16—C24 1.409 (5) N3—C1 1.337 (6) C16—C17 1.437 (6) N3—C11 1.364 (6) C17—C18 1.344 (7) N4—C10 1.325 (6) C17—H17A 0.9300 N4—C12 1.351 (6) C18—C19 1.446 (6) C1—C2 1.376 (8) C18—H18A 0.9300 C1—H1A 0.9300 C19—C23 1.400 (6) C2—C3 1.357 (8) C19—C20 1.405 (6) C2—H2A 0.9300 C20—C21 1.364 (6) C3—C4 1.408 (7) C20—H20A 0.9300 C3—H3A 0.9300 C21—C22 1.401 (6) C4—C11 1.406 (7) C21—H21A 0.9300 C4—C5 1.422 (7) C22—H22A 0.9300 C5—C6 1.340 (8) C23—C24 1.449 (5) C5—H5A 0.9300

supporting information

sup-5

Acta Cryst. (2005). E61, m1840–m1842

O1—Cd1—N3 87.75 (13) C9—C8—H8A 119.9 N2—Cd1—N3 146.91 (13) C7—C8—H8A 119.9 O2—Cd1—N1 163.27 (12) C8—C9—C10 119.3 (5) O1—Cd1—N1 90.70 (12) C8—C9—H9A 120.4 N2—Cd1—N1 70.17 (12) C10—C9—H9A 120.4 N3—Cd1—N1 92.54 (13) N4—C10—C9 122.7 (5) O2—Cd1—N4 88.48 (12) N4—C10—H10A 118.7 O1—Cd1—N4 156.46 (13) C9—C10—H10A 118.7 N2—Cd1—N4 83.91 (12) N3—C11—C4 122.7 (4) N3—Cd1—N4 69.15 (13) N3—C11—C12 117.6 (4) N1—Cd1—N4 94.61 (12) C4—C11—C12 119.7 (4) O3—Mo2—O4 110.96 (19) N4—C12—C7 122.4 (4) O3—Mo2—O2i _{110.48 (17) N4—C12—C11 119.1 (4)}

O4—Mo2—O2i _{108.00 (16) C7—C12—C11 118.5 (4)}

O3—Mo2—O1 108.39 (17) N2—C13—C14 123.1 (4) O4—Mo2—O1 109.16 (17) N2—C13—H13A 118.4 O2i_{—Mo2—O1 109.84 (16) C14—C13—H13A 118.4}

Mo2—O1—Cd1 155.5 (2) C15—C14—C13 119.4 (4) H1—O1W—H2 115.4 C15—C14—H14A 120.3 Mo2ii_{—O2—Cd1 152.79 (19) C13—C14—H14A 120.3}

supporting information

sup-6

Acta Cryst. (2005). E61, m1840–m1842

C5—C6—H6A 119.2 N2—C24—C23 119.0 (4) C7—C6—H6A 119.2 C16—C24—C23 118.7 (4)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1W—H1···O4 0.85 1.91 2.743 (5) 165 O1W—H2···O3iii _{0.85 1.93 2.739 (6) 158}