metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Poly[propane-1,3-diyldi­ammonium tetra-μ-selenito-trizinc dihydrate]

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aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 27 June 2006; accepted 29 June 2006; online 11 August 2006)

The title compound, (C3H12N2)[Zn3(SeO3)4]·2H2O, is built up from organic cations, {[Zn3(SeO3)4]2−}n macroanionic sheets and water mol­ecules. The inorganic component of the structure is notable for incorporating both octa­hedrally and tetra­hedrally coordinated Zn atoms. A network of N—H⋯O and O—H⋯O hydrogen bonds helps to establish the layered structure. The six-coordinate Zn atom has site symmetry [\overline{1}], and one C and the two water O atoms have site symmetry m.

Comment

Organically templated inorganic networks have been intensively studied in the last few years and a vast variety of new structures have been described (Cheetham et al., 1999[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268-3292.]). Many zinc-containing compounds have been reported, with a large majority of these containing tetra­hedral ZnO4 groups in combination with phosphate, hydrogen phosphite, arsenate, selenite, etc., oxo-anions (e.g. Ritchie & Harrison, 2004[Ritchie, L. K. & Harrison, W. T. A. (2004). Acta Cryst. C60, m634-m636.]). Here, we describe the synthesis and structure of the title compound, (C3H12N2)[Zn3(SeO3)4]·2H2O, (I)[link] (Fig. 1[link]), which contains both octa­hdral and tetra­hedral Zn centres. Compound (I)[link] is quite distict from (C3H12N2)[Zn(SeO3)2] (Millange et al., 2004[Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Férey, G. (2004). Solid State Sci. 6, 229-233.]), which contains chains built up from vertex-sharing ZnO4 tetra­hedra and SeO3 pyramids.

[Scheme 1]

There are two Zn sites in (I)[link]. Atom Zn1 (site symmetry [\overline{1}]) adopts a fairly regular octa­bedral coordination (Table 1[link]) with a mean Zn—O distance of 2.109 (2) Å [range of cis bond angles is 85.85 (9)–94.65 (9)°]. Atom Zn2 is the central atom of a somewhat distorted ZnO4 tetra­hedron, with a mean Zn—O distance of 1.964 (2) Å and O—Zn—O angles varying from 102.48 (10) to 122.01 (10)° (spread = 19.5°).

The two selenite groups in (I)[link] show the usual pyramidal geometry, with mean Se—O values of 1.695 (2) and 1.693 (2) Å for the Se1- and Se2-centred polyhedra, respectively. The O—Se—O bond angles are clustered into the very narrow range of 101.35 (12)–102.52 (11)° (spread = 1.2°). The unobserved lone pair of the SeIV atom is presumed to point in the direction of the fourth tetra­hedral vertex (Verma, 1999[Verma, V. P. (1999). Thermochim. Acta, 327, 63-102.]). Atoms Se1 and Se2 are displaced from the planes of their three attached O atoms by 0.7472 (14) and 0.7564 (14) Å, respectively.

There are six framework O atoms in (I)[link]. Atom O1 is terminal to Se1 and does not bond to Zn, whereas atoms O2, O4 and O5 are bicoordinate to one Se and one Zn atom, with a mean Zn—O—Se angle of 128.1 (2)°. Finally, atoms O3 and O6 are tricoordinate to two Zn and one Se atom. The bond-angle sums for O3 and O6 are 359.5 and 353.6°, respectively. The Se1—O1 bond length is slightly shorter than the bonds between Se and O2, O4 and O5, whilst the Se—O bond lengths for the tricoordinate O atoms are significantly longer.

The complete organic cation is generated by mirror symmetry, with atom C2 lying on the reflecting plane. Otherwise its geometrical parameters are normal. Two uncoordinated water mol­ecules complete the structure of (I)[link]. Both water O atoms (O7 and O8) have site symmetry m. The H atoms attached to O8 also lie in the reflecting plane.

The polyhedral connectivity in (I)[link] results in distinctive infinite macroanionic sheets of stoichiometry [Zn3(SeO3)4]n2n which propagate in (010). Considered in isolation, the Zn1O6 and Zn2O4 groups form chains that propagate along [100]. Each Zn1O6 octa­hedron is linked to two neighbouring Zn1O6 moieties by a pair of Zn2O4 tetra­hdra, forming `four-ring' (four-polyhedra) loops. The chains are crosslinked along [001] by the Se2 atoms, forming a sheet. Finally, the Se1–O1 ­fragments are attached to the four-ring loops, both above and below the plane (Fig. 3[link]).

The organic cation and water mol­ecules occupy the inter-layer regions of the structure and inter­act with the inorganic sheets by way of N—H⋯O and O—H⋯O hydrogen bonds (Table 2[link]). Each –NH3+ moiety makes two simple N—H⋯O links and one bifurcated N—H⋯(O,O) link, thus serving as a pillar or bridge between the (010) inorganic layers. This pillaring via hydrogen bonds is quite different from the direct ligand-like Zn—N bond that can occur in some networks containing Zn (Ritchie & Harrison, 2004[Ritchie, L. K. & Harrison, W. T. A. (2004). Acta Cryst. C60, m634-m636.]).

The O7 water mol­ecule in (I)[link] also bridges the layers, in an O1⋯H—O7—H⋯O1([x, {1\over2}-y, z]) configuration. Finally, the O8 water mol­ecule behaves in a similar way, but the acceptor O atoms are parts of O7 water mol­ecules and not framework O atoms. It is notable that the terminal (non-Zn bound) O1 atom accepts three hydrogen bonds.

Compound (I)[link] complements a handful of other templated phases containing octa­hedral Zn atoms. The novel phase (C6H17N3)2[Zn7(PO4)6] (Kongshaug et al., 2000[Kongshaug, K. O., Fjellvag, H. & Lillerud, K. P. (2000). Microporous Mesoporous Mater. 39, 341-350.]) contains ZnO6 groups incorporated into a chabazite-like tetra­hdral ZnO4/PO4 framework [C6H17N32+ is the 1-(2-amino­ethyl)­piper­azin­ium dication]. The partially cobalt-substituted phase (C4H12N2)[Zn3−xCox(HPO3)4(H2O)2] (x ≃ 0.83; Shi et al., 2004[Shi, S., Quin, W., Li, G., Wang, L., Yuan, H., Xu, J., Zhu, G., Song, T. & Qiu, S. (2004). J. Solid State Chem. 177, 3038-3044.]) contains trans-Zn(H2O)2O4 octa­hedra as part of a three-dimensional architecture incorporating the organic cations (C4H12N22+ is the piperazinium dication).

[Figure 1]
Figure 1
View of a fragment of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x + 1, y, z; (ii) −x, 1 − y, 1 − z; (iii) 1 − x, 1 − y, 1 − z; (iv) x − 1, y, z; (v) 1 − x, 1 − y, 2 − z; (vi) x, [{3\over 2}] − y, z.]
[Figure 2]
Figure 2
A view of part of an (010) macroanionic layer in (I)[link], with the ZnO6 and ZnO4 groups represented by polyhedra.
[Figure 3]
Figure 3
The unit-cell packing in (I)[link], viewed down [100]. Polyhedral drawing conventions are as in Fig. 2[link]. Hydrogen bonds are indicated by dashed lines.

Experimental

A mixture of 1,3-diamino­propane (0.37 g, 5 mmol), aqueous 0.5 M `H2SeO3' solution (i.e. dissolved SeO2; 20 ml, 10 mmol) and ZnO (0.407 g, 5 mmol) was heated to 353 K for 2 d in a plastic bottle. Product recovery by vacuum filtration and rinsing with water and acetone yielded blocks of (I)[link] accompanied by some white powder.

Crystal data
  • (C3H12N2)[Zn3(SeO3)4]·2H2O

  • Mr = 816.12

  • Monoclinic, P 21 /m

  • a = 4.9345 (3) Å

  • b = 22.9848 (13) Å

  • c = 8.3987 (5) Å

  • β = 104.623 (1)°

  • V = 921.71 (9) Å3

  • Z = 2

  • Dx = 2.941 Mg m−3

  • Mo Kα radiation

  • μ = 11.84 mm−1

  • T = 293 (2) K

  • Block, colourless

  • 0.21 × 0.15 × 0.06 mm

Data collection
  • Bruker SMART1000 CCD area-detector diffractometer

  • ω scans

  • Absorption correction: multi-scan (SADABS; Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.175, Tmax = 0.494

  • 7902 measured reflections

  • 3219 independent reflections

  • 2404 reflections with I > 2σ(I)

  • Rint = 0.038

  • θmax = 32.7°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.064

  • S = 0.93

  • 3219 reflections

  • 126 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0246P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.08 e Å−3

  • Δρmin = −0.83 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • Extinction coefficient: 0.0040 (3)

Table 1
Selected geometric parameters (Å, °)

Zn1—O2i 2.048 (2) 
Zn1—O3 2.136 (2)
Zn1—O6 2.144 (2)
Zn2—O4ii 1.941 (2)
Zn2—O5 1.946 (2)
Zn2—O3 1.958 (2)
Zn2—O6iii 2.011 (2)
Se1—O1 1.674 (2)
Se1—O2 1.682 (2)
Se1—O3 1.730 (2)
Se2—O4 1.681 (2)
Se2—O5 1.682 (2)
Se2—O6 1.715 (2)
Se1—O2—Zn1iii 130.32 (13)
Se1—O3—Zn2 121.61 (12)
Se1—O3—Zn1 117.55 (11)
Zn2—O3—Zn1 120.34 (11)
Se2—O4—Zn2ii 126.44 (13)
Se2—O5—Zn2 127.57 (14)
Se2—O6—Zn2i 117.85 (11)
Se2—O6—Zn1 118.24 (11)
Zn2i—O6—Zn1 117.48 (11)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O5 0.89 2.26 3.081 (4) 153
N1—H1⋯O4iii 0.89 2.33 2.868 (4) 119
N1—H2⋯O1iv 0.89 2.11 2.974 (4) 165
N1—H3⋯O1ii 0.89 1.97 2.857 (4) 174
O7—H4⋯O1 0.90 1.90 2.800 (4) 180
O8—H5⋯O7 0.86 2.12 2.972 (9) 172
O8—H6⋯O7i 0.97 2.02 2.988 (8) 179
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z; (iv) -x, -y+1, -z+2.

O-bound H atoms were located in a difference map and refined as riding in their as-found relative locations, with O—H distances in the range 0.86–0.97 Å. H atoms bonded to C or N atoms were placed in idealized locations, with C—H = 0.97 Å and N—H = 0.91 Å, and refined as riding, allowing the –NH3 group to rotate but not tilt. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.

Data collection: SMART (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and ATOMS (Dowty, 2002[Dowty, E. (2002). ATOMS for Windows. Version 6.2. Shape Software, Kingsport, Tennessee, USA. URL: https://www.shapesoftware.com .]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Organically templated inorganic networks have been intensively studied in the last few years and a vast variety of new structures have been described (Cheetham et al., 1999). Many zinc-containing compounds have been reported, with a large majority of these containing tetrahedral ZnO4 groups in combination with phosphate, hydrogen phosphite, arsenate, selenite etc. oxo-anions (e.g. Ritchie & Harrison, 2004). Here, we describe the synthesis and structure of the title compound, (I), (C3H12N2)·Zn3(SeO3)4·2H2O (Fig. 1), which contains both octahdral and tetrahedral Zn centres. Compound (I) is quite distict from (C3H12N2)·Zn(SeO3)2 (Millange et al., 2004), which contains chains built up from vertex-sharing ZnO4 tetrahedra and SeO3 pyramids.

There are two Zn sites in (I). Atom Zn1 (site symmetry 1) adopts a fairly regular octabedral coordination (Table 1) with a mean Zn—O distance of 2.109 (2) Å [spread of cis bond angles = 85.85 (9)–94.65 (9)°]. Atom Zn2 is the central atom of a somewhat distorted ZnO4 tetrahedron, with a mean Zn—O distance of 1.964 (2) Å and O—Zn—O angles varying from 102.48 (10) to 122.01 (10)° (spread = 19.5°).

The two selenite groups in (I) show the usual pyramidal geometry, with mean Se—O values of 1.695 (2) and 1.693 (2) Å for the Se1- and Se2-centred polyhedra, respectively. The O—Se—O bond angles are clustered into the very narrow range of 101.35 (12)–102.52 (11)° (spread = 1.2°). The unobserved lone pair of the SeIV atom is presumed to point in the direction of the fourth tetrahedral vertex (Verma, 1999). Atoms Se1 and Se2 are displaced from the planes of their three attached O atoms by 0.7472 (14) and 0.7564 (14) Å, respectively.

There are six framework O atoms in (I). Atom O1 is terminal to Se1 and does not bond to Zn, whereas atoms O2, O4 and O5 are bi-coordinate to one Se and one Zn, with a mean Zn—O—Se of 128.1 (2)°. Finally, atoms O3 and O6 are tri-coordinate to two Zn and one Se. The bond-angle sums for O3 and O6 are 359.5 and 353.6°, respectively. The Se1—O1 bond length is slightly shorter than the bonds between Se and O2, O4 and O5, whilst the Se—O bond lengths for the tri-coordinate O atoms are significantly longer.

The complete organic cation is generated by mirror symmetry, with atom C2 lying on the reflecting plane. Otherwise its geometrical parameters are normal. Two uncoordinated water molecules complete the structure of (I). Both water O atoms (O7 and O8) have site symmetry m. The H atoms attached to O8 also lie in the reflecting plane.

The polyhedral connectivity in (I) results in distinctive infinite macroanionic sheets of stoichiometry [Zn3(SeO3)4]n2n- which propagate in (010). Considered in isolation, the Zn1O6 and Zn2O4 groups form chains that propagate along [100]. Each Zn1O6 octahedron is linked to two neighbouring Zn1O6 moieties by a pair of Zn2O4 tetrahdra, forming `four-ring' (four-polyhedra) loops. The chains are crosslinked along [001] by the Se2 atoms, to form a sheet. Finally, the Se1—O1 fragments are attached to the four-ring loops, both above and below the plane (Fig. 3).

The organic cation and water molecules occupy the inter-layer regions of the structure and interact with the inorganic sheets by way of N—H···O and O—H···O hydrogen bonds (Table 2). Each –NH3+ moiety makes two simple N—H···O links and one bifurcated N—H···(O,O) link, thus serving as a pillar or bridge between the (010) inorganic layers. This pillaring via hydrogen bonds is quite different from the direct ligand-like Zn—N bond that can occur in some networks containing Zn (Ritchie & Harrison, 2004).

The O7 water molecule in (I) also bridges the layers, in an O1···H—O7—H···O1 [Symmetry code?] configuration. Finally, the O8 water molecule behaves in a similar way, but the acceptor O atoms are parts of O7 water molecules and not framework O atoms. It is notable that the terminal (non-Zn bound) O1 atom accepts three hydrogen bonds.

Compound (I) complements a handful of other templated phases containing octahedral Zn atoms. The novel phase (C6H17N3)2·Zn7(PO4)6 (Kongshaug et al., 2000) contains ZnO6 groups incorporated into a chabazite-like tetrahdral ZnO4/PO4 framework [C6H17N32+ is the 1-(2-aminoethyl)piperazinium dication]. The partially cobalt-substituted phase (C4H12N2)·Zn3 - xCox(HPO3)4(H2O)2 (x 0.83; Shi et al., 2004) contains trans-Zn(H2O)2O4 octahedra as part of a three-dimensional architecture incorporating the organic cations (C4H12N22+ is the piperazinium dication).

Experimental top

A mixture of 1,3 diaminopropane (0.37 g, 5 mmol), aqueous? 0.5 M `H2SeO3' solution (i.e. dissolved SeO2; 20 ml, 10 mmol) and ZnO (0.407 g, 5 mmol) was heated to 353 K for 2 d in a plastic bottle. Product recovery by vacuum filtration and rinsing with water and acetone yielded blocks of (I) accompanied by some white powder.

Refinement top

O-bound H atoms were located in a difference map and refined as riding in their as-found relative locations, with O—H distances in the range 0.86–0.97 Å. H atoms bonded to C or N atoms were placed in idealized locations, with C—H = 0.97 and N—H = 0.91 Å, and refined as riding, allowing the –NH3 group to rotate but not tilt. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of a fragment of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x + 1, y, z; (ii) -x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1 - z; (iv) x - 1, y, z; (v) 1 - x, 1 - y, 2 - z; (vi) x, 3/2 - y, z.]
[Figure 2] Fig. 2. A view of part of an (010) macroanionic layer in (I), with the ZnO6 and ZnO4 groups represented by polyhedra.
[Figure 3] Fig. 3. The unit-cell packing in (I), viewed down [100]. Polyhedral drawing conventions as in Fig. 2. Hydrogen bonds are indicated by dashed lines.
Propane-1,3-diyldiammonium tetra-µ-selenito-trizinc dihydrate top
Crystal data top
(C3H12N20[Zn3(SeO3)4]·2H2OF(000) = 772
Mr = 816.12Dx = 2.941 Mg m3
MonoclinicP21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 2685 reflections
a = 4.9345 (3) Åθ = 3.1–32.5°
b = 22.9848 (13) ŵ = 11.84 mm1
c = 8.3987 (5) ÅT = 293 K
β = 104.623 (1)°Block, colourless
V = 921.71 (9) Å30.21 × 0.15 × 0.06 mm
Z = 2
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
3219 independent reflections
Radiation source: fine-focus sealed tube2404 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scansθmax = 32.7°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 76
Tmin = 0.175, Tmax = 0.494k = 3429
7902 measured reflectionsl = 912
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033 w = 1/[σ2(Fo2) + (0.0246P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.064(Δ/σ)max = 0.001
S = 0.93Δρmax = 1.08 e Å3
3219 reflectionsΔρmin = 0.83 e Å3
126 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0040 (3)
Primary atom site location: structure-invariant direct methods
Crystal data top
(C3H12N20[Zn3(SeO3)4]·2H2OV = 921.71 (9) Å3
Mr = 816.12Z = 2
MonoclinicP21/mMo Kα radiation
a = 4.9345 (3) ŵ = 11.84 mm1
b = 22.9848 (13) ÅT = 293 K
c = 8.3987 (5) Å0.21 × 0.15 × 0.06 mm
β = 104.623 (1)°
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
3219 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
2404 reflections with I > 2σ(I)
Tmin = 0.175, Tmax = 0.494Rint = 0.038
7902 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 0.93Δρmax = 1.08 e Å3
3219 reflectionsΔρmin = 0.83 e Å3
126 parameters
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
Zn10.50000.50000.50000.01443 (11)
Zn20.13449 (8)0.489408 (17)0.81307 (4)0.01677 (10)
Se10.01254 (7)0.401400 (14)0.50464 (4)0.01495 (8)
Se20.65495 (7)0.579245 (14)0.84141 (4)0.01457 (8)
O10.0795 (5)0.34728 (10)0.6423 (3)0.0248 (6)
O20.3157 (5)0.41983 (10)0.5085 (3)0.0226 (5)
O30.2089 (5)0.45788 (10)0.6117 (3)0.0171 (5)
O40.8708 (5)0.57246 (10)1.0305 (3)0.0211 (5)
O50.3453 (5)0.56087 (11)0.8768 (3)0.0236 (5)
O60.7369 (5)0.51810 (10)0.7463 (3)0.0178 (5)
N10.3533 (6)0.64265 (13)1.1687 (3)0.0240 (6)
H10.32190.61151.10380.036*
H20.24470.64121.23860.036*
H30.53230.64331.22470.036*
C10.2884 (9)0.69580 (16)1.0670 (5)0.0316 (9)
H1A0.09190.69551.00840.038*
H1B0.39810.69590.98610.038*
C20.3503 (12)0.75001.1694 (6)0.0290 (12)
H2A0.54620.75001.22900.035*
H2B0.23890.75001.24940.035*
O70.0285 (11)0.25000.4353 (6)0.0576 (14)
H40.00580.28140.50130.069*
O80.3811 (14)0.25000.2297 (7)0.092 (2)
H50.24900.25000.28000.111*
H60.57400.25000.29530.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0146 (3)0.0160 (3)0.0128 (2)0.0005 (2)0.00366 (17)0.00143 (19)
Zn20.0168 (2)0.0197 (2)0.01422 (18)0.00056 (14)0.00467 (13)0.00078 (14)
Se10.01639 (17)0.01547 (16)0.01322 (14)0.00075 (12)0.00417 (11)0.00126 (12)
Se20.01591 (17)0.01570 (16)0.01243 (14)0.00070 (12)0.00418 (11)0.00056 (11)
O10.0292 (15)0.0153 (12)0.0274 (13)0.0008 (10)0.0024 (10)0.0066 (10)
O20.0143 (12)0.0179 (12)0.0364 (14)0.0023 (9)0.0079 (10)0.0009 (10)
O30.0189 (12)0.0193 (12)0.0146 (11)0.0045 (9)0.0070 (8)0.0044 (9)
O40.0219 (13)0.0262 (13)0.0139 (11)0.0055 (10)0.0020 (9)0.0013 (9)
O50.0186 (13)0.0258 (13)0.0295 (13)0.0039 (10)0.0119 (10)0.0088 (11)
O60.0163 (12)0.0233 (12)0.0132 (10)0.0026 (9)0.0024 (8)0.0056 (9)
N10.0259 (17)0.0238 (16)0.0208 (14)0.0047 (12)0.0034 (12)0.0008 (12)
C10.040 (2)0.025 (2)0.026 (2)0.0006 (16)0.0015 (16)0.0025 (15)
C20.037 (3)0.024 (3)0.023 (3)0.0000.002 (2)0.000
O70.099 (4)0.027 (2)0.044 (3)0.0000.013 (3)0.000
O80.082 (5)0.144 (7)0.056 (4)0.0000.027 (3)0.000
Geometric parameters (Å, º) top
Zn1—O2i2.048 (2)Se2—O61.715 (2)
Zn1—O2ii2.048 (2)N1—C11.479 (4)
Zn1—O32.136 (2)N1—H10.8900
Zn1—O3iii2.136 (2)N1—H20.8900
Zn1—O62.144 (2)N1—H30.8900
Zn1—O6iii2.144 (2)C1—C21.501 (4)
Zn2—O4iv1.941 (2)C1—H1A0.9700
Zn2—O51.946 (2)C1—H1B0.9700
Zn2—O31.958 (2)C2—C1vi1.501 (4)
Zn2—O6v2.011 (2)C2—H2A0.9700
Se1—O11.674 (2)C2—H2B0.9700
Se1—O21.682 (2)O7—H40.90
Se1—O31.730 (2)O8—H50.86
Se2—O41.681 (2)O8—H60.97
Se2—O51.682 (2)
O2i—Zn1—O2ii180.0Se1—O3—Zn2121.61 (12)
O2i—Zn1—O394.65 (9)Se1—O3—Zn1117.55 (11)
O2ii—Zn1—O385.35 (9)Zn2—O3—Zn1120.34 (11)
O2i—Zn1—O3iii85.35 (9)Se2—O4—Zn2iv126.44 (13)
O2ii—Zn1—O3iii94.65 (9)Se2—O5—Zn2127.57 (14)
O3—Zn1—O3iii180.0Se2—O6—Zn2ii117.85 (11)
O2i—Zn1—O689.32 (9)Se2—O6—Zn1118.24 (11)
O2ii—Zn1—O690.68 (9)Zn2ii—O6—Zn1117.48 (11)
O3—Zn1—O685.85 (8)C1—N1—H1109.5
O3iii—Zn1—O694.15 (8)C1—N1—H2109.5
O2i—Zn1—O6iii90.68 (9)H1—N1—H2109.5
O2ii—Zn1—O6iii89.32 (9)C1—N1—H3109.5
O3—Zn1—O6iii94.15 (8)H1—N1—H3109.5
O3iii—Zn1—O6iii85.85 (8)H2—N1—H3109.5
O6—Zn1—O6iii180.0N1—C1—C2111.8 (3)
O4iv—Zn2—O5122.01 (10)N1—C1—H1A109.2
O4iv—Zn2—O3110.55 (10)C2—C1—H1A109.2
O5—Zn2—O3110.25 (10)N1—C1—H1B109.2
O4iv—Zn2—O6v104.50 (10)C2—C1—H1B109.2
O5—Zn2—O6v102.48 (10)H1A—C1—H1B107.9
O3—Zn2—O6v105.24 (9)C1—C2—C1vi112.2 (4)
O1—Se1—O2101.36 (13)C1—C2—H2A109.2
O1—Se1—O3102.22 (11)C1vi—C2—H2A109.2
O2—Se1—O3102.52 (11)C1—C2—H2B109.2
O4—Se2—O5101.35 (12)C1vi—C2—H2B109.2
O4—Se2—O6101.33 (11)H2A—C2—H2B107.9
O5—Se2—O6102.01 (11)H5—O8—H6118.4
Se1—O2—Zn1v130.32 (13)
O1—Se1—O2—Zn1v140.13 (17)O5—Se2—O4—Zn2iv41.76 (19)
O3—Se1—O2—Zn1v34.7 (2)O6—Se2—O4—Zn2iv63.11 (19)
O1—Se1—O3—Zn262.42 (16)O4—Se2—O5—Zn2107.11 (17)
O2—Se1—O3—Zn242.33 (16)O6—Se2—O5—Zn22.78 (19)
O1—Se1—O3—Zn1125.66 (14)O4iv—Zn2—O5—Se2102.74 (18)
O2—Se1—O3—Zn1129.59 (13)O3—Zn2—O5—Se229.5 (2)
O4iv—Zn2—O3—Se152.67 (16)O6v—Zn2—O5—Se2141.11 (16)
O5—Zn2—O3—Se1169.45 (13)O4—Se2—O6—Zn2ii33.08 (16)
O6v—Zn2—O3—Se159.62 (15)O5—Se2—O6—Zn2ii137.43 (14)
O4iv—Zn2—O3—Zn1135.62 (12)O4—Se2—O6—Zn1175.73 (13)
O5—Zn2—O3—Zn12.26 (15)O5—Se2—O6—Zn171.38 (15)
O6v—Zn2—O3—Zn1112.09 (12)O2i—Zn1—O6—Se28.82 (14)
O2i—Zn1—O3—Se1119.42 (13)O2ii—Zn1—O6—Se2171.18 (14)
O2ii—Zn1—O3—Se160.58 (13)O3—Zn1—O6—Se285.90 (14)
O6—Zn1—O3—Se1151.60 (13)O3iii—Zn1—O6—Se294.10 (14)
O6iii—Zn1—O3—Se128.40 (13)O2i—Zn1—O6—Zn2ii142.49 (13)
O2i—Zn1—O3—Zn252.61 (13)O2ii—Zn1—O6—Zn2ii37.51 (13)
O2ii—Zn1—O3—Zn2127.39 (13)O3—Zn1—O6—Zn2ii122.80 (13)
O6—Zn1—O3—Zn236.37 (12)O3iii—Zn1—O6—Zn2ii57.20 (13)
O6iii—Zn1—O3—Zn2143.63 (12)N1—C1—C2—C1vi179.3 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y+1, z+1; (iv) x+1, y+1, z+2; (v) x1, y, z; (vi) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.892.263.081 (4)153
N1—H1···O4v0.892.332.868 (4)119
N1—H2···O1vii0.892.112.974 (4)165
N1—H3···O1iv0.891.972.857 (4)174
O7—H4···O10.901.902.800 (4)180
O8—H5···O70.862.122.972 (9)172
O8—H6···O7ii0.972.022.988 (8)179
Symmetry codes: (ii) x+1, y, z; (iv) x+1, y+1, z+2; (v) x1, y, z; (vii) x, y+1, z+2.

Experimental details

Crystal data
Chemical formula(C3H12N20[Zn3(SeO3)4]·2H2O
Mr816.12
Crystal system, space groupMonoclinicP21/m
Temperature (K)293
a, b, c (Å)4.9345 (3), 22.9848 (13), 8.3987 (5)
β (°) 104.623 (1)
V3)921.71 (9)
Z2
Radiation typeMo Kα
µ (mm1)11.84
Crystal size (mm)0.21 × 0.15 × 0.06
Data collection
DiffractometerBruker SMART1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.175, 0.494
No. of measured, independent and
observed [I > 2σ(I)] reflections
7902, 3219, 2404
Rint0.038
(sin θ/λ)max1)0.759
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.064, 0.93
No. of reflections3219
No. of parameters126
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.08, 0.83

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 2002), SHELXL97.

Selected geometric parameters (Å, º) top
Zn1—O2i2.048 (2)Se1—O11.674 (2)
Zn1—O32.136 (2)Se1—O21.682 (2)
Zn1—O62.144 (2)Se1—O31.730 (2)
Zn2—O4ii1.941 (2)Se2—O41.681 (2)
Zn2—O51.946 (2)Se2—O51.682 (2)
Zn2—O31.958 (2)Se2—O61.715 (2)
Zn2—O6iii2.011 (2)
Se1—O2—Zn1iii130.32 (13)Se2—O5—Zn2127.57 (14)
Se1—O3—Zn2121.61 (12)Se2—O6—Zn2i117.85 (11)
Se1—O3—Zn1117.55 (11)Se2—O6—Zn1118.24 (11)
Zn2—O3—Zn1120.34 (11)Zn2i—O6—Zn1117.48 (11)
Se2—O4—Zn2ii126.44 (13)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z+2; (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.892.263.081 (4)153
N1—H1···O4iii0.892.332.868 (4)119
N1—H2···O1iv0.892.112.974 (4)165
N1—H3···O1ii0.891.972.857 (4)174
O7—H4···O10.901.902.800 (4)180
O8—H5···O70.862.122.972 (9)172
O8—H6···O7i0.972.022.988 (8)179
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z+2; (iii) x1, y, z; (iv) x, y+1, z+2.
 

References

First citationBruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268–3292.  Web of Science CrossRef CAS Google Scholar
First citationDowty, E. (2002). ATOMS for Windows. Version 6.2. Shape Software, Kingsport, Tennessee, USA. URL: https://www.shapesoftware.comGoogle Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationKongshaug, K. O., Fjellvag, H. & Lillerud, K. P. (2000). Microporous Mesoporous Mater. 39, 341–350.  Web of Science CSD CrossRef CAS Google Scholar
First citationMillange, F., Serre, C., Cabourdin, T., Marrot, J. & Férey, G. (2004). Solid State Sci. 6, 229–233.  Web of Science CSD CrossRef CAS Google Scholar
First citationRitchie, L. K. & Harrison, W. T. A. (2004). Acta Cryst. C60, m634–m636.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationShi, S., Quin, W., Li, G., Wang, L., Yuan, H., Xu, J., Zhu, G., Song, T. & Qiu, S. (2004). J. Solid State Chem. 177, 3038–3044.  CSD CrossRef CAS Google Scholar
First citationVerma, V. P. (1999). Thermochim. Acta, 327, 63–102.  Web of Science CrossRef CAS Google Scholar

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