CdHPO3 with a channel structure

inorganic papers

Acta Cryst.(2007). E63, i105–i107 doi:10.1107/S1600536807010483 Wanget al. _CdHPO

3

i105

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

CdHPO

with a channel structure

Li Wang, Tian-You Song, Jia-Ning Xu and Su-Hua Shi*

College of Chemistry, Jilin University, Jiefang Road 2519, Changchun, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(P–O) = 0.003 A˚

Rfactor = 0.027

wRfactor = 0.067

Data-to-parameter ratio = 13.9

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

Received 7 December 2006 Accepted 5 March 2007

#2007 International Union of Crystallography

All rights reserved

Cadmium phosphite, CdHPO3, was obtained by mild

hydro-thermal synthesis. The construction of the three-dimensional framework structure may be viewed as an assembly of distorted CdO6 octahedra and HPO3 tetrahedra which leads

to the formation of channels along [001]. The crystal structure is isotypic with CdSO3-III and is a new example of the

stereochemical equivalence of the P-bonded H atom in HPO32 and the electron lone pair in XO32 oxoanions (X

= SIVor SeIV).

Comment

Recently, compounds containing the tetrahedral phosphite group, HPO3

2

, have been investigated as alternative candi-dates for a possible replacement of phosphates in their various applications. Like the corresponding phosphates, transition metal phosphites exhibit a multi-faceted crystal chemistry with the formation of one-dimensional chain structures, two-dimensional layer structures or three-two-dimensional framework structures (Shiehet al., 1990; Zakharovaet al., 1994; Sghyaret al., 1991; Sapina et al., 1989; Liu et al., 2005). However, the number of structurally well characterized transition metal phosphites is much smaller than that of the corresponding phosphates. In the course of studies of the formation of novel transition metal phosphites, we have successfully employed

Figure 1

The CdO6octahedron and an attached PO3H tetrahedron in the structure

of (I), with displacement ellipsoids drawn at the 50% probability level. The H atom is shown as a sphere of arbitrary radius. [Symmetry codes: (i) 1x,y,z(ii)2

3y, 2 3+xy,

1

3z(iii) 1

3+xy, 2 3+x,

1 3z(iv) 1

3+y, 2 3x+y,

2

hydrothermal methods and have prepared anhydrous cadmium phosphite, CdHPO3, (I). Its structure is isotypic with

CdSO3-III (Engelen et al., 1987), and therefore (I) can be

viewed as another example of the stereochemical equivalence of the P-bonded H atom in HPO3

2

and the electron lone pair in XO3

2

oxoanions (X = SIV or SeIV) (Corbridge, 1956; Gattow, 1958; Weisset al., 1966; Handlovicˇ, 1969; Andersenet al., 1984; Engelenet al., 1987; Boldtet al., 2000).

In the asymmetric unit of compound (I) there are one Cd, one P, one H and three O sites (Fig. 1). The Cd atom has a distorted octahedral coordination by six O atoms, with Cd—O bond lengths ranging from 2.233 (3) to 2.353 (3) A˚ (Table 1). The P atom is in a distorted tetrahedral coordination by three O atoms, with P—O bond lengths between 1.521 (3) and 1.529 (3) A˚ , and by one H atom, with a bond length of 1.38 (5) A˚ , in good agreement with other phosphite structures reported previously (Bonaviaet al., 1995). The existence of a P—H bond is verified by IR spectroscopy, which reveals a characteristic strong absorption at 2402 cm1(Shiet al., 2004). The construction of the three-dimensional framework structure in compound (I) may be viewed as an assembly of CdO6 octahedra and distorted HPO3 tetrahedra sharing

corners and edges. The CdO6octahedra share edges with O2

and O3 as bridging atoms, which leads to the formation of pseudo-helical chains. Adjacent chains are linked by HPO3

tetrahedra to construct a three-dimensional framework with channels along [001], as shown in Fig. 2. The free space within the channels is slightly reduced because the H atoms of the phosphite tetrahedra protrude towards the centre of the channels.

Experimental

Compound (I) was prepared from a reaction mixture consisting of CdCl22.5H2O, H3PO3, ethylenediamine and water in a molar ratio of

1:12:2:444. A typical reaction batch consisted of CdCl22.5H2O

(0.228 g), H3PO3(1.0 g), ethylenediamine (0.10 ml) and water (8 ml).

The mixture was stirred for 30 min at room temperature, transferred to a 23 ml PTFE-lined stainless steel autoclave with a filling capacity of 50% and heated at 443 K for 5 d under autogenous pressure. Fine colourless crystals of (I) with rod or block-like habit were filtered off, washed with water and dried at room temperature (yield 60% based on Cd).

Crystal data

CdHPO3 Mr= 192.39

Trigonal,R3 a= 13.509 (2) A˚ c= 8.379 (2) A˚ V= 1324.3 (4) A˚3

Z= 18

MoKradiation

= 7.73 mm1 T= 293 (2) K 0.200.200.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer Absorption correction: none 2018 measured reflections

679 independent reflections 660 reflections withI> 2(I) Rint= 0.024

Refinement

R[F2_{> 2(F}2_{)] = 0.027} wR(F2_{) = 0.067} S= 1.03 679 reflections

49 parameters

All H-atom parameters refined

max= 0.92 e A˚ 3

min=3.51 e A˚ 3

Table 1

Selected geometric parameters (A˚ ,_).

Cd1—O1 2.233 (3)

Cd1—O3i 2.275 (3)

Cd1—O2ii 2.322 (3) Cd1—O3iii 2.325 (3) Cd1—O1iv 2.333 (3) Cd1—O2v 2.353 (3)

P1—O3 1.521 (3)

P1—O2 1.523 (3)

P1—O1 1.529 (3)

P1—H1 1.38 (5)

O3—P1—O2 111.91 (16)

O3—P1—O1 111.73 (16)

O2—P1—O1 111.22 (17)

O3—P1—H1 109 (2)

O2—P1—H1 107 (2)

O1—P1—H1 105 (2)

Symmetry codes: (i) xþ1;y;z; (ii) yþ2 3;xy

2 3;zþ

1 3; (iii) xy1

3;x23;zþ31; (iv)yþ13;xþyþ23;zþ23; (v)xþyþ1;xþ1;z.

The H atom was located in a difference Fourier map and refined freely. The deepest hole in the final Fourier map is 0.02 A˚ away from Cd.

Data collection:SMART(Bruker, 2003); cell refinement: SAINT-Plus(Bruker, 2003); data reduction:SAINT-Plus; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 2003) and DIAMOND (Brandenburg, 2005);

software used to prepare material for publication:SHELXL97.

This work was supported by the State Basic Research Project (grant No. G2000077507) and the National Science Foundation of China (grant Nos. 29873017 and 20101004).

References

Andersen, L., Lindqvist, O. & Moret, J. (1984).Acta Cryst.C40, 586–589. Boldt, K., Engelen, B., Pantho¨fer, M. & Unterweide, K. (2000).Eur. J. Inorg.

Chem.pp. 2071–2075.

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Figure 2

Bonavia, G., Debord, J., Haushalter, R. C., Rose, D. & Zubieta, J. (1995). Chem. Mater.7, 1995–1998.

Brandenburg, K. (2005).DIAMOND. Release 3.1. Crystal Impact GbR, Bonn, Germany.

Bruker (2003).SMART,SAINT,SHELXTLandSADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Corbridge, D. E. C. (1956).Acta Cryst.9, 991–994.

Engelen, B., Buchmeier, W. & Lutz, H. D. (1987).Z. Naturforsch. Teil B,42, 37–41.

Gattow, G. (1958).Acta Cryst.11, 377–383. Handlovicˇ, M. (1969).Acta Cryst.B25, 227–231.

Liu, W., Chen, H. H., Yang, X. X. & Zhao, J. T. (2005).Eur. J. Inorg. Chem.pp. 946–951.

Sapina, F., Gomez-Romero, P., Marcos, M. D., Amoros, P., Ibanez, R., Beltran, D., Navarro, R., Rillo, C. & Lera, F. (1989).Eur. J. Solid State Inorg. Chem.

26, 603–617.

Sghyar, M., Durand, J., Cot, L. & Rafiq, M. (1991).Acta Cryst.C47, 2515–2517. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Shieh, M., Martin, K. J., Squattrito, P. J. & Clearfield, A. (1990).Inorg. Chem.

29, 958–963.

Shi, S. H., Qian, W., Li, G. H., Wang, L., Yuan, H. M., Xu, J. N., Zhu, G. S., Song, T. Y. & Qiu, S. L. (2004).J. Solid State Chem.177, 3038–3044. Weiss, R., Wendling, J.-P. & Grandjean, D. (1966).Acta Cryst.20, 563–566. Zakharova, B. S., Ilyukhin, A. B. & Chudinova, N. N. (1994).Zh. Neorg. Khim.

39, 1443–1445. (In Russian.)

inorganic papers

Acta Cryst.(2007). E63, i105–i107 Wanget al. _CdHPO

supporting information

sup-1 Acta Cryst. (2007). E63, i105–i107

supporting information

Acta Cryst. (2007). E63, i105–i107 [https://doi.org/10.1107/S1600536807010483]

CdHPO

with a channel structure

Li Wang, Tian-You Song, Jia-Ning Xu and Su-Hua Shi

Cadmium phosphate(III)

Crystal data CdHPO3 Mr = 192.39 Hexagonal, R3 Hall symbol: -R 3 a = 13.509 (2) Å c = 8.379 (2) Å V = 1324.3 (4) Å3 Z = 18

F(000) = 1584

Dx = 4.342 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2109 reflections θ = 3.0–27.3°

µ = 7.73 mm−1 T = 293 K Block, colourless 0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

2018 measured reflections 679 independent reflections

660 reflections with I > 2σ(I) Rint = 0.024

θmax = 27.4°, θmin = 3.0° h = −10→17

k = −17→17 l = −9→10

Refinement Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.027} wR(F2_{) = 0.067} S = 1.03 679 reflections 49 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.055P)2 + 5.8207P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.012 Δρmax = 0.92 e Å−3 Δρmin = −3.51 e Å−3

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.

supporting information

sup-2 Acta Cryst. (2007). E63, i105–i107

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

Cd1 0.44451 (2) 0.06208 (2) 0.23950 (3) 0.00916 (16)

P1 0.68801 (8) 0.16748 (8) 0.04639 (11) 0.0072 (2)

O1 0.6343 (2) 0.1537 (2) 0.2114 (3) 0.0114 (5)

O3 0.6532 (2) 0.0525 (2) −0.0300 (3) 0.0131 (6)

O2 0.8174 (2) 0.2440 (2) 0.0533 (3) 0.0135 (6)

H1 0.646 (5) 0.224 (5) −0.043 (6) 0.016*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cd1 0.00783 (19) 0.00993 (19) 0.0091 (2) 0.00400 (12) −0.00008 (8) 0.00032 (8)

P1 0.0065 (4) 0.0077 (4) 0.0078 (4) 0.0039 (3) −0.0001 (3) −0.0001 (3)

O1 0.0094 (12) 0.0139 (13) 0.0111 (12) 0.0059 (11) 0.0005 (9) −0.0013 (10)

O3 0.0154 (13) 0.0108 (13) 0.0128 (13) 0.0064 (11) −0.0026 (11) −0.0023 (10)

O2 0.0076 (13) 0.0126 (13) 0.0164 (13) 0.0022 (10) 0.0018 (10) −0.0040 (11)

Geometric parameters (Å, º)

Cd1—O1 2.233 (3) P1—O1 1.529 (3)

Cd1—O3i _{2.275 (3) P1—H1 1.38 (5)}

Cd1—O2ii _{2.322 (3) O1—Cd1}vi _{2.333 (3)}

Cd1—O3iii _{2.325 (3) O3—Cd1}i _{2.275 (3)}

Cd1—O1iv _{2.333 (3) O3—Cd1}vii _{2.324 (3)}

Cd1—O2v _{2.353 (3) O2—Cd1}viii _{2.322 (3)}

P1—O3 1.521 (3) O2—Cd1ix _{2.354 (3)}

P1—O2 1.523 (3)

O1—Cd1—O3i _{114.21 (10) O3—P1—O2 111.91 (16)}

O1—Cd1—O2ii _{98.53 (10) O3—P1—O1 111.73 (16)}

O3i_—Cd1—O2ii _{91.52 (10) O2—P1—O1 111.22 (17)}

O1—Cd1—O3iii _{159.24 (10) O3—P1—H1 109 (2)}

O3i_—Cd1—O3iii _{85.76 (3) O2—P1—H1 107 (2)}

O2ii_—Cd1—O3iii _{74.24 (10) O1—P1—H1 105 (2)}

O1—Cd1—O1iv _{83.21 (13) P1—O1—Cd1 120.41 (16)}

O3i_—Cd1—O1iv _{159.60 (10) P1—O1—Cd1}vi _{118.53 (15)}

O2ii_—Cd1—O1iv _{96.41 (9) Cd1—O1—Cd1}vi _{109.52 (11)}

O3iii_—Cd1—O1iv _{78.41 (10) P1—O3—Cd1}i _{142.90 (17)}

O1—Cd1—O2v _{91.92 (10) P1—O3—Cd1}vii _{114.33 (15)}

O3i_—Cd1—O2v _{74.57 (10) Cd1}i_—O3—Cd1vii _{102.68 (11)}

O2ii_—Cd1—O2v _{165.19 (10) P1—O2—Cd1}viii _{126.47 (16)}

O3iii_—Cd1—O2v _{99.24 (10) P1—O2—Cd1}ix _{131.89 (16)}

O1iv_—Cd1—O2v _{95.21 (10) Cd1}viii_—O2—Cd1ix _{100.37 (10)}

Symmetry codes: (i) −x+1, −y, −z; (ii) −y+2/3, x−y−2/3, z+1/3; (iii) x−y−1/3, x−2/3, −z+1/3; (iv) y+1/3, −x+y+2/3, −z+2/3; (v) −x+y+1, −x+1, z; (vi)