supplementary materials
Disodium tricopper(II) tetrakis[selenate(IV)] tetrahydrate
The title compound, Na2Cu3(SeO3)4(H2O)4, has been prepared under hydrothermal conditions. The crystal structure contains a three-dimensional anionic framework made up from distorted [CuO4(H2O)2] octahedra (
symmetry), [CuO4(H2O)] square pyramids and trigonal-pyramidal SeO3 units sharing common corners. The connectivity among these units leads to four- and eight-membered polyhedral rings, which by edge-sharing interconnect into walls. A rhombus-like 16-membered polyhedral ring channel system with a longest length of approximately 14.0 Å and a shortest length of 5.3 Å is enclosed by such walls along the a axis. The water molecules attached to the Cu atoms, as well as the electron lone pairs of the SeIV atoms, protrude into these channels. The seven-coordinated Na+ counter-cations occupy the remaining free space of the 16-membered polyhedral ring channels. An intricate network of O-H
O hydrogen bonds further consolidates the three-dimensional structure.
The title compound was synthesized under hydrothermal conditions. A mixture of
Na2SeO3 and CuSO4.5H2O in a molar ratio of 1:1 was placed in a
Teflon-lined stainless steel autoclave and heated to 443 K for 5 d, cooled
at 2 K/h to 373 K, and finally cooled to room temperature. Light blue crystals
with a rod-like habit were obtained. Cu, Se and Na contents were analyzed using
ICP-AES (Varian Vista, radial observation): Obs./calc. mass%: Cu, 23.33/23.91;
Se, 38.70/39.23; Na, 5.63/5.42.
Charge balance considerations and bond valence sum (BVS) calculations indicate
that atoms O5 and O6 belong to water molecules. For the metal atoms, the
oxidation states of +2 for Cu ions (BVS Cu1: +2.05 and Cu2: +2.01), +4 for the
Se ions (BVS Se1: +4.01 and Se2: +4.06) and +1 for the Na ions (BVS Na1: +1.02)
were confirmed. The hydrogen atoms of the water molecules were located from
difference Fourier maps and were refined with distance restraints of d(O—H)
= 0.80 (8)–0.89 (8) Å and a common Uiso parameter of 0.05 Å2.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Crystal Impact, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).
disodium tricopper(II) tetrakis[selenate(IV)] tetrahydrate
top
Crystal data top
| Na2Cu3(SeO3)4(H2O)4 | F(000) = 762 |
| Mr = 816.50 | Dx = 3.661 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 986 reflections |
| a = 5.2218 (5) Å | θ = 2.6–22.8° |
| b = 8.9863 (6) Å | µ = 14.24 mm−1 |
| c = 15.7960 (11) Å | T = 296 K |
| β = 92.071 (4)° | Rod, light blue |
| V = 740.74 (10) Å3 | 0.15 × 0.10 × 0.10 mm |
| Z = 2 | |
Data collection top
Bruker SMART CCD
diffractometer | 2142 independent reflections |
| Radiation source: fine-focus sealed tube | 2065 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| ω scans | θmax = 30.0°, θmin = 2.6° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004) | h = −7→7 |
| Tmin = 0.204, Tmax = 0.250 | k = −12→12 |
| 6010 measured reflections | l = −21→22 |
Refinement top
| 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) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0202P)2 + 3.7977P]
where P = (Fo2 + 2Fc2)/3 |
| 2142 reflections | (Δ/σ)max = 0.001 |
| 115 parameters | Δρmax = 0.77 e Å−3 |
| 0 restraints | Δρmin = −1.02 e Å−3 |
Crystal data top
| Na2Cu3(SeO3)4(H2O)4 | V = 740.74 (10) Å3 |
| Mr = 816.50 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.2218 (5) Å | µ = 14.24 mm−1 |
| b = 8.9863 (6) Å | T = 296 K |
| c = 15.7960 (11) Å | 0.15 × 0.10 × 0.10 mm |
| β = 92.071 (4)° | |
Data collection top
Bruker SMART CCD
diffractometer | 2142 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004) | 2065 reflections with I > 2σ(I) |
| Tmin = 0.204, Tmax = 0.250 | Rint = 0.027 |
| 6010 measured reflections | θmax = 30.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.068 | Δρmax = 0.77 e Å−3 |
| S = 1.12 | Δρmin = −1.02 e Å−3 |
| 2142 reflections | Absolute structure: ? |
| 115 parameters | Flack parameter: ? |
| 0 restraints | Rogers 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 F^2^ 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 F^2^. 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 F^2^ 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| | x | y | z | Uiso*/Ueq | |
| Se1 | 0.20254 (7) | 0.28287 (4) | 0.09687 (2) | 0.01090 (10) | |
| Se2 | −0.79415 (7) | 0.53958 (5) | 0.27304 (2) | 0.01476 (11) | |
| Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.01381 (14) | |
| Cu2 | −0.29891 (8) | 0.42910 (6) | 0.17116 (3) | 0.01266 (11) | |
| O1 | −1.0733 (5) | 0.4403 (4) | 0.27181 (18) | 0.0207 (6) | |
| O2 | −0.0088 (5) | 0.4276 (3) | 0.09497 (18) | 0.0153 (5) | |
| O3 | −0.5831 (5) | 0.4016 (3) | 0.24757 (18) | 0.0165 (5) | |
| O4 | 0.1289 (6) | 0.2058 (3) | 0.00011 (18) | 0.0166 (5) | |
| O5 | −0.3653 (7) | 0.6725 (4) | 0.1392 (2) | 0.0209 (6) | |
| O6 | 0.2781 (6) | −0.0756 (4) | 0.07804 (19) | 0.0199 (6) | |
| O7 | 0.4702 (5) | 0.3793 (3) | 0.07309 (17) | 0.0149 (5) | |
| O8 | −0.7371 (6) | 0.5600 (4) | 0.3773 (2) | 0.0272 (7) | |
| Na1 | 0.7415 (3) | 0.3619 (2) | −0.04070 (11) | 0.0226 (4) | |
| H1 | −0.277 (15) | 0.707 (9) | 0.104 (5) | 0.050* | |
| H2 | −0.372 (14) | 0.748 (9) | 0.174 (5) | 0.050* | |
| H4 | 0.226 (15) | −0.063 (9) | 0.131 (5) | 0.050* | |
| H3 | 0.437 (15) | −0.049 (9) | 0.088 (5) | 0.050* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Se1 | 0.01040 (17) | 0.01286 (18) | 0.00949 (17) | −0.00189 (12) | 0.00133 (12) | −0.00064 (12) |
| Se2 | 0.01172 (18) | 0.0176 (2) | 0.01500 (18) | 0.00083 (13) | 0.00180 (13) | −0.00071 (14) |
| Cu1 | 0.0139 (3) | 0.0124 (3) | 0.0149 (3) | −0.0023 (2) | −0.0030 (2) | −0.0004 (2) |
| Cu2 | 0.0085 (2) | 0.0195 (2) | 0.0101 (2) | 0.00022 (17) | 0.00143 (15) | −0.00087 (17) |
| O1 | 0.0097 (12) | 0.0415 (19) | 0.0110 (12) | −0.0042 (12) | 0.0007 (10) | −0.0034 (12) |
| O2 | 0.0107 (12) | 0.0208 (14) | 0.0146 (12) | 0.0036 (10) | 0.0042 (10) | 0.0019 (11) |
| O3 | 0.0137 (12) | 0.0207 (14) | 0.0152 (12) | 0.0002 (11) | 0.0044 (10) | 0.0009 (11) |
| O4 | 0.0211 (14) | 0.0166 (13) | 0.0121 (12) | −0.0080 (11) | 0.0015 (10) | −0.0022 (10) |
| O5 | 0.0298 (16) | 0.0117 (14) | 0.0215 (15) | −0.0011 (12) | 0.0048 (13) | −0.0013 (11) |
| O6 | 0.0177 (14) | 0.0280 (17) | 0.0138 (13) | 0.0011 (12) | −0.0030 (11) | −0.0043 (12) |
| O7 | 0.0099 (11) | 0.0215 (14) | 0.0135 (12) | −0.0054 (10) | 0.0010 (9) | −0.0021 (11) |
| O8 | 0.0190 (14) | 0.045 (2) | 0.0176 (14) | −0.0028 (14) | 0.0012 (12) | −0.0149 (14) |
| Na1 | 0.0193 (8) | 0.0307 (10) | 0.0177 (8) | 0.0015 (7) | 0.0015 (6) | 0.0005 (7) |
Geometric parameters (Å, °) top
| Se1—O7 | 1.698 (3) | Cu2—O1iii | 1.947 (3) |
| Se1—O2 | 1.705 (3) | Cu2—O3 | 1.962 (3) |
| Se1—O4 | 1.709 (3) | Cu2—O2 | 1.968 (3) |
| Se2—O8 | 1.673 (3) | Cu2—O7iv | 1.980 (3) |
| Se2—O1 | 1.708 (3) | Cu2—O5 | 2.268 (3) |
| Se2—O3 | 1.717 (3) | Na1—O7 | 2.333 (4) |
| Cu1—O4 | 1.968 (3) | Na1—O5v | 2.482 (4) |
| Cu1—O4i | 1.968 (3) | Na1—O2vi | 2.519 (4) |
| Cu1—O6 | 1.990 (3) | Na1—O4iii | 2.526 (4) |
| Cu1—O6i | 1.990 (3) | Na1—O2iii | 2.537 (3) |
| Cu1—O8ii | 2.475 (3) | Na1—O7vi | 2.618 (4) |
| Cu1—O8ii | 2.475 (3) | Na1—O6vii | 2.641 (4) |
| | | |
| O7—Se1—O2 | 98.30 (14) | Cu2—O5—H2 | 129 (5) |
| O7—Se1—O4 | 99.75 (13) | Na1v—O5—H2 | 116 (5) |
| O2—Se1—O4 | 99.71 (14) | H1—O5—H2 | 100 (7) |
| O8—Se2—O1 | 100.95 (16) | Cu1—O6—Na1vii | 99.94 (13) |
| O8—Se2—O3 | 102.54 (16) | Cu1—O6—H4 | 107 (5) |
| O1—Se2—O3 | 100.08 (15) | Na1vii—O6—H4 | 109 (5) |
| O4—Cu1—O4i | 180.00 (6) | Cu1—O6—H3 | 133 (5) |
| O4—Cu1—O6 | 94.50 (13) | Na1vii—O6—H3 | 110 (5) |
| O4i—Cu1—O6 | 85.50 (13) | H4—O6—H3 | 97 (7) |
| O4—Cu1—O6i | 85.50 (13) | Se1—O7—Cu2iii | 115.16 (15) |
| O4i—Cu1—O6i | 94.50 (13) | Se1—O7—Na1 | 131.60 (16) |
| O6—Cu1—O6i | 180.00 (14) | Cu2iii—O7—Na1 | 104.37 (12) |
| O1iii—Cu2—O3 | 87.30 (12) | Se1—O7—Na1vi | 98.71 (13) |
| O1iii—Cu2—O2 | 92.48 (12) | Cu2iii—O7—Na1vi | 101.13 (12) |
| O3—Cu2—O2 | 172.34 (13) | Na1—O7—Na1vi | 99.95 (12) |
| O1iii—Cu2—O7iv | 169.80 (14) | O7—Na1—O5v | 90.14 (12) |
| O3—Cu2—O7iv | 90.00 (12) | O7—Na1—O2vi | 124.83 (13) |
| O2—Cu2—O7iv | 88.88 (11) | O5v—Na1—O2vi | 108.41 (12) |
| O1iii—Cu2—O5 | 102.39 (14) | O7—Na1—O4iii | 110.09 (12) |
| O3—Cu2—O5 | 98.36 (13) | O5v—Na1—O4iii | 134.38 (13) |
| O2—Cu2—O5 | 89.17 (12) | O2vi—Na1—O4iii | 93.18 (11) |
| O7iv—Cu2—O5 | 87.73 (12) | O7—Na1—O2iii | 69.01 (10) |
| Se2—O1—Cu2iv | 121.82 (17) | O5v—Na1—O2iii | 158.39 (13) |
| Se1—O2—Cu2 | 120.42 (16) | O2vi—Na1—O2iii | 80.72 (11) |
| Se1—O2—Na1vi | 102.26 (13) | O4iii—Na1—O2iii | 62.06 (10) |
| Cu2—O2—Na1vi | 130.61 (15) | O7—Na1—O7vi | 80.06 (12) |
| Se1—O2—Na1iv | 98.62 (14) | O5v—Na1—O7vi | 70.66 (11) |
| Cu2—O2—Na1iv | 97.75 (12) | O2vi—Na1—O7vi | 60.11 (10) |
| Na1vi—O2—Na1iv | 99.28 (11) | O4iii—Na1—O7vi | 150.69 (12) |
| Se2—O3—Cu2 | 124.02 (17) | O2iii—Na1—O7vi | 99.14 (11) |
| Se1—O4—Cu1 | 116.58 (15) | O7—Na1—O6vii | 102.55 (12) |
| Se1—O4—Na1iv | 98.94 (14) | O5v—Na1—O6vii | 73.44 (11) |
| Cu1—O4—Na1iv | 104.54 (13) | O2vi—Na1—O6vii | 132.30 (12) |
| Cu2—O5—Na1v | 97.49 (13) | O4iii—Na1—O6vii | 62.63 (11) |
| Cu2—O5—H1 | 116 (6) | O2iii—Na1—O6vii | 115.47 (12) |
| Na1v—O5—H1 | 94 (5) | O7vi—Na1—O6vii | 144.02 (11) |
| Symmetry codes: (i) −x, −y, −z; (ii) −x−1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z; (vii) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O5—H1···O4v | 0.80 (8) | 2.00 (8) | 2.786 (4) | 168 (7) |
| O5—H2···O3viii | 0.87 (8) | 1.88 (8) | 2.746 (4) | 174 (7) |
| O6—H3···O8ix | 0.87 (8) | 1.91 (8) | 2.758 (5) | 163 (7) |
| O6—H4···O1ii | 0.89 (8) | 1.76 (8) | 2.641 (4) | 169 (8) |
| Symmetry codes: (v) −x, −y+1, −z; (viii) −x−1, y+1/2, −z+1/2; (ix) −x, y−1/2, −z+1/2; (ii) −x−1, y−1/2, −z+1/2. |
Table 1
Selected geometric parameters (Å) top| Se1—O7 | 1.698 (3) | Cu1—O6 | 1.990 (3) |
| Se1—O2 | 1.705 (3) | Cu1—O8i | 2.475 (3) |
| Se1—O4 | 1.709 (3) | Cu2—O1ii | 1.947 (3) |
| Se2—O8 | 1.673 (3) | Cu2—O3 | 1.962 (3) |
| Se2—O1 | 1.708 (3) | Cu2—O2 | 1.968 (3) |
| Se2—O3 | 1.717 (3) | Cu2—O7iii | 1.980 (3) |
| Cu1—O4 | 1.968 (3) | Cu2—O5 | 2.268 (3) |
| Symmetry codes: (i) −x−1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1, y, z. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O5—H1···O4iv | 0.80 (8) | 2.00 (8) | 2.786 (4) | 168 (7) |
| O5—H2···O3v | 0.87 (8) | 1.88 (8) | 2.746 (4) | 174 (7) |
| O6—H3···O8vi | 0.87 (8) | 1.91 (8) | 2.758 (5) | 163 (7) |
| O6—H4···O1i | 0.89 (8) | 1.76 (8) | 2.641 (4) | 169 (8) |
| Symmetry codes: (iv) −x, −y+1, −z; (v) −x−1, y+1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2; (i) −x−1, y−1/2, −z+1/2. |
This work was supported by the opening project of the State Key Laboratory of
High Performance Ceramics and Superfine Microstructure (grant No.
SKL200706SIC).
Asai, T. & Kiriyama, R. (1973). Bull. Chem. Soc. Jpn, 46, 2395–2401.
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Crystal Impact (2004). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Giester, G. (1991). Monatsh. Chem. 122, 229–234.
Iskhakova, L. D. & Kozlova, N. P. (1995). Kristallografiya, 40, 635–638.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
![[Figure 1]](./wm2197fig1thm.gif)
![[Figure 2]](./wm2197fig2thm.gif)
![[Figure 3]](./wm2197fig3thm.gif)
Studies of hydrous copper selenites and selenates with three-dimensional frameworks have been reported previously, e.g. by Asai & Kiriyama (1973), Giester (1991) and Iskhakova & Kozlova (1995). Among the corresponding structures various polyhedral ring channel systems are established. The current article presents the result of the single-crystal X-ray analysis of a new sodium copper selenite, Na2Cu3(SeO3)4(H2O)4, (I), with a 16-membered polydedral ring channel system.
In the asymmetric unit of (I) there are two crystallographically distinct copper atoms. The six-coordinated Cu1 site is a typical Jahn-Teller ion with a distorted, tetragonally elongated octahedral [Cu1O4(H2O)2] coordination, whereas Cu2 is surrounded by five O-atoms, leading to a distorted square-pyramidal [Cu2O4(H2O)] environment. The two independent selenium atoms are coordinated by three oxygen atoms, forming the characteristic trigonal-pyramidal SeO32- anion (Fig. 1).
The square-pyramidal [Cu2O4(H2O)] units share its basal O atoms with four neighboring SeO3 units leading to chains of corner-shared four-membered polyhedral rings running along [100]. The [Cu1O4(H2O)2] units are located between such parallel chains and bridge them via Cu—O—Se bonds into an open framework. The water molecules attached to Cu1 and Cu2 as well as the electron lone-pairs of the selenium(IV) atoms protrude into the free space of this network (Fig. 2).
The basic features of the structure could also be described as the assemblage of linear chains of Cu and Se centres leading to 4-membered and 8-membered rings that interconnect by edge-sharing into two similar wavy layer packings extending along [011] and [011], respectively. Such layers intersect at the Cu(1) sites, eventually forming a rhombus-like 16-membered ring channel system extending along the a axis with the biggest length of approximately 14.0 Å and the smallest length of 5.3 Å (Fig.3).
The Na+ counter cations are coordinated by seven oxygen atoms and occupy the central space of the 16-membered ring polyhedral channels to keep the structural stability and satisfy the charge balance. An intricate network of O—H···O hydrogen bonds further consolidates the three-dimensional structure (Table 2).