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

Ritchie, L.K.; Harrison, W.T.A.

doi:10.1107/S010827010602508X

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 9| September 2006| Pages m413-m415

doi:10.1107/S010827010602508X

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

Lyndsey K. Ritchie ^a and William T. A. Harrison ^a ^*

^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 ). 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, (C₃H₁₂N₂)[Zn₃(SeO₃)₄]·2H₂O, (I) (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 $[\overline{1}]$ ) adopts a fairly regular octabedral coordination (Table 1) 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) 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 Se^IV 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 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). 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, forming 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( $[x, {1\over2}-y, z]$ ) 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) 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)[Zn_3−xCo_x(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).

Figure 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, $[{3\over 2}]$ − y, z.]

Figure 2
A view of part of an (010) macroanionic layer in (I)

, with the ZnO₆ and ZnO₄ groups represented by polyhedra.

Figure 3
The unit-cell packing in (I)

, viewed down [100]. Polyhedral drawing conventions are as in Fig. 2

. 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) accompanied by some white powder.

Crystal data

(C₃H₁₂N₂)[Zn₃(SeO₃)₄]·2H₂O
M_r = 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
D_x = 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 ) T_min = 0.175, T_max = 0.494
7902 measured reflections
3219 independent reflections
2404 reflections with I > 2σ(I)
R_int = 0.038
θ_max = 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(F_o²) + (0.0246P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.83 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
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	D⋯A	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⋯O1^iv	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 U_iso(H) = 1.2U_eq(carrier) was applied in all cases.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S010827010602508X/gd3033sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827010602508X/gd3033Isup2.hkl

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 Se^IV 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 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)·Zn_{3 -} _xCo_x(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.

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

	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.]
	Fig. 2. A view of part of an (010) macroanionic layer in (I), with the ZnO₆ and ZnO₄ groups represented by polyhedra.
	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]·2H₂O	F(000) = 772
M_r = 816.12	D_x = 2.941 Mg m⁻³
MonoclinicP2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2685 reflections
a = 4.9345 (3) Å	θ = 3.1–32.5°
b = 22.9848 (13) Å	µ = 11.84 mm⁻¹
c = 8.3987 (5) Å	T = 293 K
β = 104.623 (1)°	Block, colourless
V = 921.71 (9) Å³	0.21 × 0.15 × 0.06 mm
Z = 2

Data collection top

Bruker SMART1000 CCD area-detector diffractometer	3219 independent reflections
Radiation source: fine-focus sealed tube	2404 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 32.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −7→6
T_min = 0.175, T_max = 0.494	k = −34→29
7902 measured reflections	l = −9→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0246P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.064	(Δ/σ)_max = 0.001
S = 0.93	Δρ_max = 1.08 e Å⁻³
3219 reflections	Δρ_min = −0.83 e Å⁻³
126 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0040 (3)
Primary atom site location: structure-invariant direct methods

Crystal data top

(C₃H₁₂N₂₀[Zn₃(SeO₃)₄]·2H₂O	V = 921.71 (9) Å³
M_r = 816.12	Z = 2
MonoclinicP2₁/m	Mo Kα radiation
a = 4.9345 (3) Å	µ = 11.84 mm⁻¹
b = 22.9848 (13) Å	T = 293 K
c = 8.3987 (5) Å	0.21 × 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)
T_min = 0.175, T_max = 0.494	R_int = 0.038
7902 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 0.93	Δρ_max = 1.08 e Å⁻³
3219 reflections	Δρ_min = −0.83 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.5000	0.5000	0.01443 (11)
Zn2	0.13449 (8)	0.489408 (17)	0.81307 (4)	0.01677 (10)
Se1	0.01254 (7)	0.401400 (14)	0.50464 (4)	0.01495 (8)
Se2	0.65495 (7)	0.579245 (14)	0.84141 (4)	0.01457 (8)
O1	0.0795 (5)	0.34728 (10)	0.6423 (3)	0.0248 (6)
O2	−0.3157 (5)	0.41983 (10)	0.5085 (3)	0.0226 (5)
O3	0.2089 (5)	0.45788 (10)	0.6117 (3)	0.0171 (5)
O4	0.8708 (5)	0.57246 (10)	1.0305 (3)	0.0211 (5)
O5	0.3453 (5)	0.56087 (11)	0.8768 (3)	0.0236 (5)
O6	0.7369 (5)	0.51810 (10)	0.7463 (3)	0.0178 (5)
N1	0.3533 (6)	0.64265 (13)	1.1687 (3)	0.0240 (6)
H1	0.3219	0.6115	1.1038	0.036*
H2	0.2447	0.6412	1.2386	0.036*
H3	0.5323	0.6433	1.2247	0.036*
C1	0.2884 (9)	0.69580 (16)	1.0670 (5)	0.0316 (9)
H1A	0.0919	0.6955	1.0084	0.038*
H1B	0.3981	0.6959	0.9861	0.038*
C2	0.3503 (12)	0.7500	1.1694 (6)	0.0290 (12)
H2A	0.5462	0.7500	1.2290	0.035*
H2B	0.2389	0.7500	1.2494	0.035*
O7	−0.0285 (11)	0.2500	0.4353 (6)	0.0576 (14)
H4	0.0058	0.2814	0.5013	0.069*
O8	0.3811 (14)	0.2500	0.2297 (7)	0.092 (2)
H5	0.2490	0.2500	0.2800	0.111*
H6	0.5740	0.2500	0.2953	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0146 (3)	0.0160 (3)	0.0128 (2)	−0.0005 (2)	0.00366 (17)	−0.00143 (19)
Zn2	0.0168 (2)	0.0197 (2)	0.01422 (18)	0.00056 (14)	0.00467 (13)	−0.00078 (14)
Se1	0.01639 (17)	0.01547 (16)	0.01322 (14)	0.00075 (12)	0.00417 (11)	−0.00126 (12)
Se2	0.01591 (17)	0.01570 (16)	0.01243 (14)	−0.00070 (12)	0.00418 (11)	−0.00056 (11)
O1	0.0292 (15)	0.0153 (12)	0.0274 (13)	0.0008 (10)	0.0024 (10)	0.0066 (10)
O2	0.0143 (12)	0.0179 (12)	0.0364 (14)	0.0023 (9)	0.0079 (10)	0.0009 (10)
O3	0.0189 (12)	0.0193 (12)	0.0146 (11)	−0.0045 (9)	0.0070 (8)	−0.0044 (9)
O4	0.0219 (13)	0.0262 (13)	0.0139 (11)	−0.0055 (10)	0.0020 (9)	0.0013 (9)
O5	0.0186 (13)	0.0258 (13)	0.0295 (13)	−0.0039 (10)	0.0119 (10)	−0.0088 (11)
O6	0.0163 (12)	0.0233 (12)	0.0132 (10)	0.0026 (9)	0.0024 (8)	−0.0056 (9)
N1	0.0259 (17)	0.0238 (16)	0.0208 (14)	−0.0047 (12)	0.0034 (12)	−0.0008 (12)
C1	0.040 (2)	0.025 (2)	0.026 (2)	0.0006 (16)	0.0015 (16)	0.0025 (15)
C2	0.037 (3)	0.024 (3)	0.023 (3)	0.000	0.002 (2)	0.000
O7	0.099 (4)	0.027 (2)	0.044 (3)	0.000	0.013 (3)	0.000
O8	0.082 (5)	0.144 (7)	0.056 (4)	0.000	0.027 (3)	0.000

Geometric parameters (Å, º) top

Zn1—O2ⁱ	2.048 (2)	Se2—O6	1.715 (2)
Zn1—O2ⁱⁱ	2.048 (2)	N1—C1	1.479 (4)
Zn1—O3	2.136 (2)	N1—H1	0.8900
Zn1—O3ⁱⁱⁱ	2.136 (2)	N1—H2	0.8900
Zn1—O6	2.144 (2)	N1—H3	0.8900
Zn1—O6ⁱⁱⁱ	2.144 (2)	C1—C2	1.501 (4)
Zn2—O4^iv	1.941 (2)	C1—H1A	0.9700
Zn2—O5	1.946 (2)	C1—H1B	0.9700
Zn2—O3	1.958 (2)	C2—C1^vi	1.501 (4)
Zn2—O6^v	2.011 (2)	C2—H2A	0.9700
Se1—O1	1.674 (2)	C2—H2B	0.9700
Se1—O2	1.682 (2)	O7—H4	0.90
Se1—O3	1.730 (2)	O8—H5	0.86
Se2—O4	1.681 (2)	O8—H6	0.97
Se2—O5	1.682 (2)

O2ⁱ—Zn1—O2ⁱⁱ	180.0	Se1—O3—Zn2	121.61 (12)
O2ⁱ—Zn1—O3	94.65 (9)	Se1—O3—Zn1	117.55 (11)
O2ⁱⁱ—Zn1—O3	85.35 (9)	Zn2—O3—Zn1	120.34 (11)
O2ⁱ—Zn1—O3ⁱⁱⁱ	85.35 (9)	Se2—O4—Zn2^iv	126.44 (13)
O2ⁱⁱ—Zn1—O3ⁱⁱⁱ	94.65 (9)	Se2—O5—Zn2	127.57 (14)
O3—Zn1—O3ⁱⁱⁱ	180.0	Se2—O6—Zn2ⁱⁱ	117.85 (11)
O2ⁱ—Zn1—O6	89.32 (9)	Se2—O6—Zn1	118.24 (11)
O2ⁱⁱ—Zn1—O6	90.68 (9)	Zn2ⁱⁱ—O6—Zn1	117.48 (11)
O3—Zn1—O6	85.85 (8)	C1—N1—H1	109.5
O3ⁱⁱⁱ—Zn1—O6	94.15 (8)	C1—N1—H2	109.5
O2ⁱ—Zn1—O6ⁱⁱⁱ	90.68 (9)	H1—N1—H2	109.5
O2ⁱⁱ—Zn1—O6ⁱⁱⁱ	89.32 (9)	C1—N1—H3	109.5
O3—Zn1—O6ⁱⁱⁱ	94.15 (8)	H1—N1—H3	109.5
O3ⁱⁱⁱ—Zn1—O6ⁱⁱⁱ	85.85 (8)	H2—N1—H3	109.5
O6—Zn1—O6ⁱⁱⁱ	180.0	N1—C1—C2	111.8 (3)
O4^iv—Zn2—O5	122.01 (10)	N1—C1—H1A	109.2
O4^iv—Zn2—O3	110.55 (10)	C2—C1—H1A	109.2
O5—Zn2—O3	110.25 (10)	N1—C1—H1B	109.2
O4^iv—Zn2—O6^v	104.50 (10)	C2—C1—H1B	109.2
O5—Zn2—O6^v	102.48 (10)	H1A—C1—H1B	107.9
O3—Zn2—O6^v	105.24 (9)	C1—C2—C1^vi	112.2 (4)
O1—Se1—O2	101.36 (13)	C1—C2—H2A	109.2
O1—Se1—O3	102.22 (11)	C1^vi—C2—H2A	109.2
O2—Se1—O3	102.52 (11)	C1—C2—H2B	109.2
O4—Se2—O5	101.35 (12)	C1^vi—C2—H2B	109.2
O4—Se2—O6	101.33 (11)	H2A—C2—H2B	107.9
O5—Se2—O6	102.01 (11)	H5—O8—H6	118.4
Se1—O2—Zn1^v	130.32 (13)

O1—Se1—O2—Zn1^v	140.13 (17)	O5—Se2—O4—Zn2^iv	41.76 (19)
O3—Se1—O2—Zn1^v	34.7 (2)	O6—Se2—O4—Zn2^iv	−63.11 (19)
O1—Se1—O3—Zn2	−62.42 (16)	O4—Se2—O5—Zn2	−107.11 (17)
O2—Se1—O3—Zn2	42.33 (16)	O6—Se2—O5—Zn2	−2.78 (19)
O1—Se1—O3—Zn1	125.66 (14)	O4^iv—Zn2—O5—Se2	102.74 (18)
O2—Se1—O3—Zn1	−129.59 (13)	O3—Zn2—O5—Se2	−29.5 (2)
O4^iv—Zn2—O3—Se1	52.67 (16)	O6^v—Zn2—O5—Se2	−141.11 (16)
O5—Zn2—O3—Se1	−169.45 (13)	O4—Se2—O6—Zn2ⁱⁱ	−33.08 (16)
O6^v—Zn2—O3—Se1	−59.62 (15)	O5—Se2—O6—Zn2ⁱⁱ	−137.43 (14)
O4^iv—Zn2—O3—Zn1	−135.62 (12)	O4—Se2—O6—Zn1	175.73 (13)
O5—Zn2—O3—Zn1	2.26 (15)	O5—Se2—O6—Zn1	71.38 (15)
O6^v—Zn2—O3—Zn1	112.09 (12)	O2ⁱ—Zn1—O6—Se2	8.82 (14)
O2ⁱ—Zn1—O3—Se1	119.42 (13)	O2ⁱⁱ—Zn1—O6—Se2	−171.18 (14)
O2ⁱⁱ—Zn1—O3—Se1	−60.58 (13)	O3—Zn1—O6—Se2	−85.90 (14)
O6—Zn1—O3—Se1	−151.60 (13)	O3ⁱⁱⁱ—Zn1—O6—Se2	94.10 (14)
O6ⁱⁱⁱ—Zn1—O3—Se1	28.40 (13)	O2ⁱ—Zn1—O6—Zn2ⁱⁱ	−142.49 (13)
O2ⁱ—Zn1—O3—Zn2	−52.61 (13)	O2ⁱⁱ—Zn1—O6—Zn2ⁱⁱ	37.51 (13)
O2ⁱⁱ—Zn1—O3—Zn2	127.39 (13)	O3—Zn1—O6—Zn2ⁱⁱ	122.80 (13)
O6—Zn1—O3—Zn2	36.37 (12)	O3ⁱⁱⁱ—Zn1—O6—Zn2ⁱⁱ	−57.20 (13)
O6ⁱⁱⁱ—Zn1—O3—Zn2	−143.63 (12)	N1—C1—C2—C1^vi	179.3 (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) x−1, y, z; (vi) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.89	2.26	3.081 (4)	153
N1—H1···O4^v	0.89	2.33	2.868 (4)	119
N1—H2···O1^vii	0.89	2.11	2.974 (4)	165
N1—H3···O1^iv	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···O7ⁱⁱ	0.97	2.02	2.988 (8)	179

Symmetry codes: (ii) x+1, y, z; (iv) −x+1, −y+1, −z+2; (v) x−1, y, z; (vii) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂₀[Zn₃(SeO₃)₄]·2H₂O
M_r	816.12
Crystal system, space group	MonoclinicP2₁/m
Temperature (K)	293
a, b, c (Å)	4.9345 (3), 22.9848 (13), 8.3987 (5)
β (°)	104.623 (1)
V (Å³)	921.71 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.84
Crystal size (mm)	0.21 × 0.15 × 0.06

Data collection
Diffractometer	Bruker SMART1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.175, 0.494
No. of measured, independent and observed [I > 2σ(I)] reflections	7902, 3219, 2404
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.064, 0.93
No. of reflections	3219
No. of parameters	126
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—O2ⁱ	2.048 (2)	Se1—O1	1.674 (2)
Zn1—O3	2.136 (2)	Se1—O2	1.682 (2)
Zn1—O6	2.144 (2)	Se1—O3	1.730 (2)
Zn2—O4ⁱⁱ	1.941 (2)	Se2—O4	1.681 (2)
Zn2—O5	1.946 (2)	Se2—O5	1.682 (2)
Zn2—O3	1.958 (2)	Se2—O6	1.715 (2)
Zn2—O6ⁱⁱⁱ	2.011 (2)

Se1—O2—Zn1ⁱⁱⁱ	130.32 (13)	Se2—O5—Zn2	127.57 (14)
Se1—O3—Zn2	121.61 (12)	Se2—O6—Zn2ⁱ	117.85 (11)
Se1—O3—Zn1	117.55 (11)	Se2—O6—Zn1	118.24 (11)
Zn2—O3—Zn1	120.34 (11)	Zn2ⁱ—O6—Zn1	117.48 (11)
Se2—O4—Zn2ⁱⁱ	126.44 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···O1^iv	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.

References

Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268–3292. Web of Science CrossRef CAS Google Scholar
Dowty, E. (2002). ATOMS for Windows. Version 6.2. Shape Software, Kingsport, Tennessee, USA. URL: https://www.shapesoftware.com . Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kongshaug, K. O., Fjellvag, H. & Lillerud, K. P. (2000). Microporous Mesoporous Mater. 39, 341–350. Web of Science CSD CrossRef CAS Google Scholar
Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Férey, G. (2004). Solid State Sci. 6, 229–233. Web of Science CSD CrossRef CAS Google Scholar
Ritchie, L. K. & Harrison, W. T. A. (2004). Acta Cryst. C60, m634–m636. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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. CSD CrossRef CAS Google Scholar
Verma, V. P. (1999). Thermochim. Acta, 327, 63–102. Web of Science CrossRef CAS Google Scholar

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ISSN: 2053-2296

Volume 62| Part 9| September 2006| Pages m413-m415

doi:10.1107/S010827010602508X

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

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

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

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