β-[H2N(CH2)2NH2]0.5[ZnHPO3], a second modification of ethyl­ene­diamine zinc hydrogen phosphite

Gordon, L.E.; Harrison, W.T.A.

doi:10.1107/S0108270104027039

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 12| December 2004| Pages m637-m639

doi:10.1107/S0108270104027039

β-[H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃], a second modification of ethylenediamine zinc hydrogen phosphite

Laura E. Gordon ^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 28 September 2004; accepted 25 October 2004; online 11 November 2004)

The title compound, poly[dizinc(II)-μ-ethylenediamine-di-μ-(hydrogen phosphito)], β-[H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] or [Zn₂(HPO₃)₂(C₂H₈N₂)]_n, is a hybrid organic/inorganic solid built up from ethylenediamine molecules (which lie about inversion centres), Zn²⁺ cations (coordinated by three O atoms and one N atom) and HPO₃²⁻ hydrogen phosphite groups. The organic species bond to the Zn atom as unprotonated ligands, acting as bridges between infinite ZnHPO₃ layers that propagate as very buckled (001) sheets. The zincophosphite sheets contain polyhedral four- and eight-membered rings in a 4.8² topology. β-[H₂N(CH₂)₂NH₂]_0.5·ZnHPO₃ complements the previously described α modification of the same stoichiometry [Rodgers & Harrison (2000 ). Chem. Commun. pp. 2385–2386].

Comment

Among the myriad variety of organically templated inorganic networks (Cheetham et al., 1999 ), a small but distinctive family contains tetrahedral ZnO₃N and pyramidal SeO₃ or pseudo-pyramidal HPO₃ building blocks. The inorganic moieties share vertices, as Zn—O—Se or Zn—O—P bonds, thereby forming an infinite sheet. The linear-chain diamine organic species bonds directly to zinc as a ligand via each N atom, thus acting as a `pillar' between the inorganic sheets. Both modifications of ethylenediamine zinc selenite, [H₂N(CH₂)₂NH₂]_0.5·ZnSeO₃ (Choudhury et al., 2002 ; Millange et al., 2004 ), contain such sheets of ZnO₃N and SeO₃ groups, fused into a three-dimensional network by the ethylenediamine moieties bonding to the Zn atoms via each NH₂ group. These modifications differ in the topological connectivity (O'Keeffe & Hyde, 1996 ) of the Zn and Se nodal atoms; the first (Choudhury et al., 2002) is based on 6³ inorganic sheets (each nodal atom participates in three six-membered rings), whereas the second (Millange et al., 2004) contains 4.8² sheets. The 1,4-diaminobenzene template in [C₆N₂H₈]_0.5[ZnHPO₃] (Kirkpatrick & Harrison, 2004 ) acts in a similar way to ethylenediamine in the zinc selenite phases; in this case, 6³ polyhedral sheets built up from ZnO₃N and HPO₃ units arise. Conversely, in [H₂N(CH₂)₄NH₂]_0.5[ZnHPO₃] (Ritchie & Harrison, 2004 ), 4.8² polyhedral sheets arise from the ZnO₃N and HPO₃ units. Finally, [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000; hereafter known as the α modification of this stoichiometry) has a novel structure based on 4.8² sheets in which two independent networks form an interpenetrating array akin to some coordination polymers.

We describe here the title compound, (I), which crystallizes as a second, β, modification of [H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃]. Compound (I) (Fig. 1) is built up from neutral unprotonated ethylenediamine [H₂N(CH₂)₂NH₂ or C₂H₈N₂] molecules, Zn²⁺ cations and HPO₃²⁻ hydrogen phosphite groups. Each complete ethylenediamine entity is generated from a half-molecule H₂NCH₂– fragment by inversion symmetry. However, these entities differ significantly in their conformations (Table 1); in the N1-containing molecule, atoms Zn1 and C1^v (see Table 1 for symmetry code) are gauche, whereas in the N2-containing molecule, the equivalent pair of atoms, Zn2 and C2^vi, are close to anti. Both the N atoms of each H₂N(CH₂)₂NH₂ molecule make ligand-like bonds to zinc by formal donation of their lone pair of electrons, as observed for the related systems (Rodgers & Harrison, 2000; Kirkpatrick & Harrison, 2004) noted above. The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.931 (10) Å], each of which form bridges to P atoms of nearby HPO₃²⁻ groups [mean Zn—O—P = 135.1 (6)°]. The pseudo-pyramidal HPO₃²⁻ moieties have typical (Kirkpatrick & Harrison, 2004) geometric parameters, with a mean P—O distance of 1.513 (10) Å and a mean O—P—O angle of 112.9 (7)°. Both distinct HPO₃²⁻ groups form bridges to three nearby zinc cations. As usual, the PH moieties do not interact with any nearby chemical species.

The polyhedral building units in (I) thus consist of ZnO₃N and HPO₃ tetrahedra, linked by way of the O atoms. These units form sheets, built up from strictly alternating Zn- and P-centred moieties, which propagate in the (001) plane. Every tetrahedral node (i.e. the Zn and P atoms) participates in one four-atom loop (composed of the asymmetric unit atoms) and two eight-atom loops (Fig. 2), thus generating a 4.8² sheet topology (O'Keeffe & Hyde, 1996).

The organic species crosslink the (001) ZnHPO₃ sheets in a Zn—b—Zn (b is the organic bridge) fashion, as shown in Fig. 3, resulting in a hybrid `pillared' structure in which the inorganic and organic components of the structure alternate along [001]. In principle, this arrangement represents an unusual kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I), unlike the case of organically pillared zirconyl phosphates (Alberti et al., 1999 ), the presence of the P—H bond protruding into the channel region and the steric bulk of the ethylenediamine moieties means that there is no possibility of ingress by other chemical species. Finally, the ethylenediamine –NH₂ groups in (I) participate in N—H⋯O hydrogen bonds (Table 2), all of which are close to linear (mean H—H⋯O = 172°). These hydrogen bonds appear to help to anchor the organic moiety to an eight-membered ring window in the zinc hydrogen phosphite layer, in a similar way to the behaviour of ethylenediamine in α-[H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] (Rodgers & Harrison, 2000). However, the zincophosphite eight-membered ring pores in (I) are distinctly flattened, whereas in α-[H₂N(CH₂)₂NH₂]_0.5[ZnHPO₃] they are far more regular. The recently reported ethylenediammonium zinc hydrogen phosphite [H₃N(CH₂)₂NH₃][Zn₂(HPO₃)₃] (Lin et al., 2004 ) is a more conventional templated network (Cheetham et al., 1999), in which the organic species is protonated and interacts with the inorganic component by way of N—H⋯O hydrogen bonds. Interestingly, a 4.8² network topology is formed by the [Zn₂(HPO₃)₃]²⁻ sheets.

Figure 1
A view of a fragment of (I

), showing the different conformations of the N1 and N2 ethylenediamine species. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii. The symmetry codes are as given in Table 1

Figure 2
A view of a fragment of a ZnHPO₃ layer in (I

), showing the topological connectivity of the Zn (large spheres) and P (small spheres) tetrahedral nodes into 4.8² sheets. The lines linking the Zn and P nodes represent Zn—O—P bridges, which are not linear (see Table 1

Figure 3
The unit-cell packing in (I

), in a polyhedral representation (ZnO₃N groups: light shading; HPO₃ groups: dark shading; ethylenediamine molecules in ball-and-stick representation). All H atoms, except the hydrogen phosphite H1 and H2 species, have been omitted for clarity.

Experimental

A mixture of zinc oxide (3.00 g), phosphorus acid (H₃PO₃, 2.02 g) and ethylenediamine (1.48 g) (molar ratio 2:3:2) was shaken in distilled water (20 ml) in a 60 ml HDPE (high-density polyethylene) bottle for a few minutes, resulting in the formation of a white slurry. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown fans of needle- and blade-like crystals of (I) accompanied by some undissolved zinc oxide.

Crystal data

[Zn₂(HPO₃)₂(C₂H₈N₂)]
M_r = 350.80
Monoclinic, P2₁/c
a = 8.3609 (4) Å
b = 7.9369 (4) Å
c = 15.8259 (7) Å
β = 104.689 (1)°
V = 1015.88 (8) Å³
Z = 4
D_x = 2.294 Mg m⁻³
Mo Kα radiation
Cell parameters from 5099 reflections
θ = 2.5–27.4°
μ = 5.04 mm⁻¹
T = 293 (2) K
Slab, colourless
0.33 × 0.30 × 0.11 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.287, T_max = 0.607
7093 measured reflections
2309 independent reflections
2075 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.5°
h = −10 → 8
k = −9 → 10
l = −20 → 20

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.171
S = 1.28
2309 reflections
128 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0155P)² + 26.0795P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.01 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0028 (5)

Table 1
Selected geometric parameters (Å, °)

Zn1—O1	1.929 (8)
Zn1—O3	1.932 (8)
Zn1—O2	1.932 (8)
Zn1—N1	2.016 (8)
Zn2—O6	1.923 (7)
Zn2—O5	1.934 (8)
Zn2—O4	1.938 (8)
Zn2—N2	2.021 (8)
P1—O5	1.497 (8)
P1—O3	1.518 (9)
P1—O2ⁱ	1.519 (7)
P2—O6	1.511 (8)
P2—O1	1.513 (8)
P2—O4ⁱⁱ	1.519 (8)

P2—O1—Zn1	141.0 (5)
P1ⁱⁱⁱ—O2—Zn1	128.8 (5)
P1—O3—Zn1	134.9 (5)
P2^iv—O4—Zn2	133.3 (5)
P1—O5—Zn2	143.6 (6)
P2—O6—Zn2	128.9 (5)

Zn1—N1—C1—C1^v	−64.8 (13)
Zn2—N2—C2—C2^vi	170.1 (11)
Symmetry codes: (i) $[-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ ; (ii) $[1-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (iii) $[-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (iv) $[1-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ ; (v) -x,1-y,2-z; (vi) 1-x,1-y,1-z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.90	2.20	3.099 (11)	173
N1—H1B⋯O4ⁱⁱⁱ	0.90	2.10	2.984 (11)	167
N2—H2A⋯O2^iv	0.90	2.11	2.995 (11)	170
N2—H2B⋯O6ⁱⁱ	0.90	2.14	3.038 (12)	177
Symmetry codes: (i) $[-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ ; (ii) $[1-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (iii) $[-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (iv) $[1-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ .

Several crystals of (I) were examined, and the diffraction quality was rather poor in all cases, with some peaks showing signs of being `smeared' or split. All H atoms were placed in idealized locations and refined as riding on their carrier atoms (P—H = 1.32 Å, N—H = 0.90 Å and C—H = 0.97 Å). For all H atoms, the constraint U_iso(H) = 1.2U_eq(carrier atom) was applied. The maximum difference peak is 1.22 Å from atom H2A.

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; molecular graphics: ORTEP-3 (Farrugia, 1997 ) and ATOMS (Shape Software, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270104027039/gg1223sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104027039/gg1223Isup2.hkl

Comment top

Among the myriad variety of organically templated inorganic networks (Cheetham et al., 1999) a small but distinctive family contains tetrahedral ZnO₃N and pyramidal SeO₃ or pseudo-pyramidal HPO₃ building blocks. The inorganic moieties share vertices, as Zn—O—Se or Zn—O—P bonds, thereby forming an infinite sheet. The linear-chain diamine organic species bonds directly to zinc as a ligand via each N atom, thus acting as a `pillar' between the inorganic sheets. Both modifications of ethylenediamine zinc selenite, [H₂N(CH₂)₂NH₂]_0.5·ZnSeO₃ (Choudhury et al., 2002; Millange et al., 2004), contain such sheets of ZnO₃N and SeO₃ groups fused into a three-dimensional network by the ethylenediamine moieties bonding to Zn via each NH₂ group. These modifications differ in the topological connectivity (O'Keeffe & Hyde, 1996) of the Zn and Se nodal atoms; the first (Choudhury et al., 2002) is based on 6³ inorganic sheets (each nodal atom participates in three six-membered rings) whereas the second (Millange et al., 2004) contains 4.8² sheets. The 1,4-diaminobenzene template in [C₆N₂H₈]_0.5·ZnHPO₃ (Kirkpatrick & Harrison, 2004) acts in a similar way to ethylenediamine in the zinc selenite phases; in this case, 6³ polyhedral sheets built up from ZnO₃N and HPO₃ units arise. Conversely, in [H₂N(CH₂)₄NH₂]_0.5·ZnHPO₃ (Ritchie & Harrison, 2004), 4.8² polyhedral sheets arise from the ZnO₃N and HPO₃ units. Finally, [H₂N(CH₂)₂NH₂]_0.5·ZnHPO₃ (Rodgers & Harrison, 2000; hereafter known as the α modification of this stoichiometry) has a novel structure based on 4.8² sheets in which two independent networks form an interpenetrating array akin to some coordination polymers.

We describe here the title compound, (I), which crystallizes as a second, β, modification of [H₂N(CH₂)₂NH₂]_0.5·ZnHPO₃. Compound (I) (Fig. 1) is built up from neutral unprotonated ethylenediamine [H₂N(CH₂)₂NH₂ or C₂H₈N₂] molecules, Zn²⁺ cations and HPO₃²⁻ hydrogen phosphite groups. Each complete ethylenediamine entity is generated from a half-molecule H₂NCH₂ fragment by inversion symmetry. However, these entities differ significantly in their conformations (Table 1); in the N1-containing molecule, atoms Zn1 and C1^v (see Table 1 for symmetry code) are gauche, whereas in the N2-containing molecule, the equivalent pair of atoms, Zn2 and C2^vi, are close to anti. Both the N atoms of each H₂N(CH₂)₂NH₂ molecule make ligand-like bonds to zinc by formal donation of their lone pair of electrons, as observed for the related systems (Rodgers & Harrison, 2000; Kirkpatrick & Harrison, 2004) noted above. The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.931 (10) Å], each of which form bridges to P atoms of nearby HPO₃²⁻ groups [mean Zn—O—P = 135.1(s.u.?)°]. The pseudo-pyramidal HPO₃²⁻ moieties have typical (Kirkpatrick & Harrison, 2004) geometric parameters, with a mean P—O distance of 1.513 (10) Å, and a mean O—P—O angle of 112.9 (7)°. Both distinct HPO₃²⁻ groups form bridges to three nearby zinc cations. As usual, the P—H moieties do not interact with any nearby chemical species.

The polyhedral building units in (I) thus consist of ZnO₃N and HPO₃ tetrahedra, linked by way of the O atoms. These units form sheets, built up from strictly alternating Zn- and P-centred moieties, which propagate in the (001) plane. Every tetrahedral node (i.e. the Zn and P atoms) participates in one four-atom loop (composed of the asymmetric-unit atoms) and two eight-atom loops (Fig. 2), thus generating a 4.8² sheet topology (O'Keeffe & Hyde, 1996).

The organic species crosslink the (001) ZnHPO₃ sheets in a Zn—b—Zn (b is the organic bridge) fashion, as shown in Fig. 3, resulting in a hybrid `pillared' structure in which the inorganic and organic components of the structure alternate along [001]. In principle, this arrangement represents an unusual kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I), unlike the case of organically pillared zirconyl phosphates (Alberti et al., 1999), the presence of the P–H bond protruding into the channel region and the steric bulk of the ethylenediamine moieties means that there is no possibility of ingress by other chemical species. Finally, the ethylenediamine –NH₂ groups in (I) participate in N—H···O hydrogen bonds (Table 2), all of which are close to linear (mean H—H···O = 172°). These hydrogen bonds appear to help to anchor the organic moiety to an eight-membered ring window in the zinc hydrogen phosphite layer, in a similar way to the behaviour of ethylenediamine in α-[H₂N(CH₂)₂NH₂]_0.5·ZnHPO₃ (Rodgers & Harrison, 2000). However, the zincophosphite eight-membered ring pores in (I) are distinctly flattened, whereas in α-[H₂N(CH₂)₂NH₂]_0.5·ZnHPO₃ they are far more regular. The recently reported ethylenediammonium zinc hydrogen phosphite [H₃N(CH₂)₂NH₃]·Zn₂(HPO₃)₃ (Lin et al., 2004) is a more conventional templated network (Cheetham et al., 1999), in which the organic species is protonated and interacts with the inorganic component by way of N—H···O hydrogen bonds. Interestingly, a 4.8² network topology is formed by the [Zn₂(HPO₃)₃]²⁻ sheets.

Experimental top

A mixture of zinc oxide (3.00 g), phosphorus acid (H₃PO₃, 2.02 g) and ethylenediamine (1.48 g) (molar ratio 2:3:2) was shaken in distilled water (20 ml) in a 60 ml HDPE bottle for a few minutes, resulting in the formation of a white slurry. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown fans of needle- and blade-like crystals of (I) accompanied by some undissolved zinc oxide.

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; molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 2003); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. A view of a fragment of (I), showing the different conformations of the N1 and N2 ethylenediamine species. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii. (Symmetry codes as in Table 1.)
	Fig. 2. A view of a fragment of a ZnHPO₃ layer in (I), showing the topologial connectivity of the Zn (large spheres) and P (small spheres) tetrahedral nodes into 4.8² sheets. The lines linking the Zn and P nodes represent Zn—O—P bridges, which are not linear (see Table 1).
	Fig. 3. The unit-cell packing in (I), in a polyhedral representation (ZnO₃N groups: light shading; HPO₃ groups: dark shading; ethylenediamine molecules in ball and stick representation). All H atoms, except the hydrogen phosphite H1 and H2 species, have been omitted for clarity.

poly[dizinc(II)-µ-ethylenediamine-di-µ-(hydrogen phosphito)] top

Crystal data top

[Zn₂(HPO₃)₂(C₂H₈N₂)]	F(000) = 696
M_r = 350.80	D_x = 2.294 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5099 reflections
a = 8.3609 (4) Å	θ = 2.5–27.4°
b = 7.9369 (4) Å	µ = 5.04 mm⁻¹
c = 15.8259 (7) Å	T = 293 K
β = 104.689 (1)°	Slab, colourless
V = 1015.88 (8) Å³	0.33 × 0.30 × 0.11 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	2309 independent reflections
Radiation source: fine-focus sealed tube	2075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→8
T_min = 0.287, T_max = 0.607	k = −9→10
7093 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.064	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.0155P)² + 26.0795P] where P = (F_o² + 2F_c²)/3
S = 1.28	(Δ/σ)_max = 0.001
2309 reflections	Δρ_max = 1.23 e Å⁻³
128 parameters	Δρ_min = −1.01 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (5)

Crystal data top

[Zn₂(HPO₃)₂(C₂H₈N₂)]	V = 1015.88 (8) Å³
M_r = 350.80	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3609 (4) Å	µ = 5.04 mm⁻¹
b = 7.9369 (4) Å	T = 293 K
c = 15.8259 (7) Å	0.33 × 0.30 × 0.11 mm
β = 104.689 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2309 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	2075 reflections with I > 2σ(I)
T_min = 0.287, T_max = 0.607	R_int = 0.031
7093 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.28	w = 1/[σ²(F_o²) + (0.0155P)² + 26.0795P] where P = (F_o² + 2F_c²)/3
2309 reflections	Δρ_max = 1.23 e Å⁻³
128 parameters	Δρ_min = −1.01 e Å⁻³

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	0.11474 (14)	0.38756 (15)	0.83143 (7)	0.0235 (3)
Zn2	0.38904 (14)	0.68996 (14)	0.68286 (7)	0.0230 (3)
P1	0.0169 (3)	0.5316 (3)	0.63692 (16)	0.0213 (5)
H1	−0.0418	0.4539	0.5617	0.026*
P2	0.4857 (3)	0.5427 (3)	0.87062 (16)	0.0220 (5)
H2	0.5634	0.6090	0.9464	0.026*
O1	0.3405 (9)	0.4468 (13)	0.8874 (6)	0.045 (2)
O2	0.1208 (9)	0.1473 (9)	0.8516 (6)	0.0372 (19)
O3	0.0580 (11)	0.3934 (11)	0.7053 (5)	0.0409 (19)
O4	0.3895 (10)	0.9280 (10)	0.6555 (5)	0.0359 (18)
O5	0.1630 (9)	0.6304 (12)	0.6262 (6)	0.043 (2)
O6	0.4385 (11)	0.6892 (10)	0.8084 (5)	0.0370 (18)
N1	−0.0377 (10)	0.5380 (10)	0.8779 (5)	0.0222 (16)
H1A	−0.0448	0.6370	0.8494	0.027*
H1B	−0.1390	0.4912	0.8632	0.027*
C1	0.0031 (14)	0.5758 (13)	0.9738 (6)	0.029 (2)
H1C	0.1130	0.6244	0.9916	0.034*
H1D	−0.0746	0.6583	0.9850	0.034*
N2	0.5245 (10)	0.5470 (11)	0.6212 (5)	0.0238 (17)
H2A	0.6267	0.5907	0.6302	0.029*
H2B	0.5338	0.4421	0.6435	0.029*
C2	0.4463 (12)	0.5392 (15)	0.5258 (6)	0.031 (2)
H2C	0.4180	0.6526	0.5044	0.037*
H2D	0.3444	0.4753	0.5163	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0245 (6)	0.0229 (6)	0.0247 (6)	0.0007 (5)	0.0091 (4)	0.0014 (4)
Zn2	0.0252 (6)	0.0221 (6)	0.0235 (6)	0.0007 (4)	0.0094 (4)	0.0005 (4)
P1	0.0228 (11)	0.0203 (12)	0.0212 (11)	−0.0004 (10)	0.0063 (9)	−0.0021 (9)
P2	0.0232 (12)	0.0227 (12)	0.0202 (11)	−0.0003 (10)	0.0057 (9)	−0.0020 (9)
O1	0.027 (4)	0.064 (6)	0.044 (5)	−0.007 (4)	0.010 (3)	0.016 (4)
O2	0.028 (4)	0.021 (4)	0.068 (6)	0.001 (3)	0.021 (4)	0.008 (4)
O3	0.062 (5)	0.033 (4)	0.029 (4)	0.002 (4)	0.014 (4)	−0.005 (3)
O4	0.034 (4)	0.030 (4)	0.048 (5)	−0.002 (3)	0.017 (3)	−0.002 (4)
O5	0.025 (4)	0.049 (5)	0.055 (5)	−0.004 (4)	0.010 (4)	0.011 (4)
O6	0.062 (5)	0.025 (4)	0.024 (4)	0.007 (4)	0.012 (4)	−0.003 (3)
N1	0.029 (4)	0.018 (4)	0.021 (4)	0.000 (3)	0.007 (3)	0.005 (3)
C1	0.042 (6)	0.023 (5)	0.024 (5)	−0.003 (4)	0.013 (4)	−0.002 (4)
N2	0.023 (4)	0.023 (4)	0.027 (4)	−0.001 (3)	0.007 (3)	−0.005 (3)
C2	0.026 (5)	0.042 (6)	0.023 (5)	0.007 (5)	0.004 (4)	0.000 (4)

Geometric parameters (Å, º) top

Zn1—O1	1.929 (8)	P2—H2	1.3200
Zn1—O3	1.932 (8)	O2—P1ⁱⁱⁱ	1.519 (7)
Zn1—O2	1.932 (8)	O4—P2^iv	1.519 (8)
Zn1—N1	2.016 (8)	N1—C1	1.499 (12)
Zn2—O6	1.923 (7)	N1—H1A	0.9000
Zn2—O5	1.934 (8)	N1—H1B	0.9000
Zn2—O4	1.938 (8)	C1—C1^v	1.469 (19)
Zn2—N2	2.021 (8)	C1—H1C	0.9700
P1—O5	1.497 (8)	C1—H1D	0.9700
P1—O3	1.518 (9)	N2—C2	1.486 (12)
P1—O2ⁱ	1.519 (7)	N2—H2A	0.9000
P1—H1	1.3200	N2—H2B	0.9000
P2—O6	1.511 (8)	C2—C2^vi	1.494 (19)
P2—O1	1.513 (8)	C2—H2C	0.9700
P2—O4ⁱⁱ	1.519 (8)	C2—H2D	0.9700

O1—Zn1—O3	115.1 (4)	P2^iv—O4—Zn2	133.3 (5)
O1—Zn1—O2	100.5 (4)	P1—O5—Zn2	143.6 (6)
O3—Zn1—O2	100.6 (4)	P2—O6—Zn2	128.9 (5)
O1—Zn1—N1	108.9 (4)	C1—N1—Zn1	119.0 (6)
O3—Zn1—N1	110.5 (3)	C1—N1—H1A	107.6
O2—Zn1—N1	121.1 (3)	Zn1—N1—H1A	107.6
O6—Zn2—O5	114.0 (4)	C1—N1—H1B	107.6
O6—Zn2—O4	102.8 (3)	Zn1—N1—H1B	107.6
O5—Zn2—O4	101.1 (4)	H1A—N1—H1B	107.0
O6—Zn2—N2	119.8 (3)	C1^v—C1—N1	112.1 (10)
O5—Zn2—N2	103.9 (4)	C1^v—C1—H1C	109.2
O4—Zn2—N2	114.0 (3)	N1—C1—H1C	109.2
O5—P1—O3	114.6 (5)	C1^v—C1—H1D	109.2
O5—P1—O2ⁱ	111.2 (5)	N1—C1—H1D	109.2
O3—P1—O2ⁱ	113.1 (5)	H1C—C1—H1D	107.9
O5—P1—H1	105.7	C2—N2—Zn2	111.0 (6)
O3—P1—H1	105.7	C2—N2—H2A	109.4
O2ⁱ—P1—H1	105.7	Zn2—N2—H2A	109.4
O6—P2—O1	114.4 (5)	C2—N2—H2B	109.4
O6—P2—O4ⁱⁱ	111.6 (5)	Zn2—N2—H2B	109.4
O1—P2—O4ⁱⁱ	112.5 (5)	H2A—N2—H2B	108.0
O6—P2—H2	105.8	N2—C2—C2^vi	113.7 (10)
O1—P2—H2	105.8	N2—C2—H2C	108.8
O4ⁱⁱ—P2—H2	105.8	C2^vi—C2—H2C	108.8
P2—O1—Zn1	141.0 (5)	N2—C2—H2D	108.8
P1ⁱⁱⁱ—O2—Zn1	128.8 (5)	C2^vi—C2—H2D	108.8
P1—O3—Zn1	134.9 (5)	H2C—C2—H2D	107.7

O6—P2—O1—Zn1	29.8 (12)	O2ⁱ—P1—O5—Zn2	109.7 (10)
O4ⁱⁱ—P2—O1—Zn1	−98.9 (10)	O6—Zn2—O5—P1	−28.0 (11)
O3—Zn1—O1—P2	22.6 (12)	O4—Zn2—O5—P1	−137.5 (10)
O2—Zn1—O1—P2	129.7 (10)	N2—Zn2—O5—P1	104.1 (10)
N1—Zn1—O1—P2	−102.1 (10)	O1—P2—O6—Zn2	−86.1 (8)
O1—Zn1—O2—P1ⁱⁱⁱ	149.6 (7)	O4ⁱⁱ—P2—O6—Zn2	43.2 (8)
O3—Zn1—O2—P1ⁱⁱⁱ	−92.1 (7)	O5—Zn2—O6—P2	83.7 (8)
N1—Zn1—O2—P1ⁱⁱⁱ	29.9 (9)	O4—Zn2—O6—P2	−167.9 (7)
O5—P1—O3—Zn1	75.9 (9)	N2—Zn2—O6—P2	−40.3 (8)
O2ⁱ—P1—O3—Zn1	−53.1 (9)	O1—Zn1—N1—C1	−41.9 (7)
O1—Zn1—O3—P1	−78.3 (9)	O3—Zn1—N1—C1	−169.3 (7)
O2—Zn1—O3—P1	174.6 (8)	O2—Zn1—N1—C1	73.7 (8)
N1—Zn1—O3—P1	45.5 (9)	Zn1—N1—C1—C1^v	−64.8 (13)
O6—Zn2—O4—P2^iv	102.1 (7)	O6—Zn2—N2—C2	168.8 (7)
O5—Zn2—O4—P2^iv	−139.9 (7)	O5—Zn2—N2—C2	40.1 (8)
N2—Zn2—O4—P2^iv	−29.1 (8)	O4—Zn2—N2—C2	−69.0 (8)
O3—P1—O5—Zn2	−20.1 (12)	Zn2—N2—C2—C2^vi	170.1 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.90	2.20	3.099 (11)	173
N1—H1B···O4ⁱⁱⁱ	0.90	2.10	2.984 (11)	167
N2—H2A···O2^iv	0.90	2.11	2.995 (11)	170
N2—H2B···O6ⁱⁱ	0.90	2.14	3.038 (12)	177

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

Experimental details

Crystal data
Chemical formula	[Zn₂(HPO₃)₂(C₂H₈N₂)]
M_r	350.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3609 (4), 7.9369 (4), 15.8259 (7)
β (°)	104.689 (1)
V (Å³)	1015.88 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.04
Crystal size (mm)	0.33 × 0.30 × 0.11

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.287, 0.607
No. of measured, independent and observed [I > 2σ(I)] reflections	7093, 2309, 2075
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.171, 1.28
No. of reflections	2309
No. of parameters	128
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0155P)² + 26.0795P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.23, −1.01

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 2003).

Selected geometric parameters (Å, º) top

Zn1—O1	1.929 (8)	Zn2—N2	2.021 (8)
Zn1—O3	1.932 (8)	P1—O5	1.497 (8)
Zn1—O2	1.932 (8)	P1—O3	1.518 (9)
Zn1—N1	2.016 (8)	P1—O2ⁱ	1.519 (7)
Zn2—O6	1.923 (7)	P2—O6	1.511 (8)
Zn2—O5	1.934 (8)	P2—O1	1.513 (8)
Zn2—O4	1.938 (8)	P2—O4ⁱⁱ	1.519 (8)

P2—O1—Zn1	141.0 (5)	P2^iv—O4—Zn2	133.3 (5)
P1ⁱⁱⁱ—O2—Zn1	128.8 (5)	P1—O5—Zn2	143.6 (6)
P1—O3—Zn1	134.9 (5)	P2—O6—Zn2	128.9 (5)

Zn1—N1—C1—C1^v	−64.8 (13)	Zn2—N2—C2—C2^vi	170.1 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.90	2.20	3.099 (11)	173
N1—H1B···O4ⁱⁱⁱ	0.90	2.10	2.984 (11)	167
N2—H2A···O2^iv	0.90	2.11	2.995 (11)	170
N2—H2B···O6ⁱⁱ	0.90	2.14	3.038 (12)	177

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

Acknowledgements

The authors thank Jillian Johnstone for experimental assistance.

References

Alberti, G., Brunet, E., Dionigi, M., Juanes, O., Mata, M. J., Rodriguez-Ubis, J. C. & Vivani, R. (1999). Angew. Chem. Int. Ed. 38, 3351–3353. Web of Science CrossRef CAS Google Scholar
Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269–3292. Web of Science CrossRef Google Scholar
Choudhury, A., Kumar, U. D. & Rao, C. N. R. (2002). Angew. Chem. Int. Ed. 41, 158–161. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–565. CrossRef CAS IUCr Journals Google Scholar
Fu, W., Shi, Z., Li, G., Znang, D., Dong, W., Chen, X. & Feng, S. (2004). Solid State Sci. 6, 225–228. Web of Science CSD CrossRef CAS Google Scholar
Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593–598. CSD CrossRef CAS Google Scholar
Lin, Z. E., Zhang, J., Zheng, S. T. & Yang, G. Y. (2004). Solid State Sci. 6, 371–376. Web of Science CSD CrossRef CAS Google Scholar
Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Féret, G. (2004). Solid State Sci. 6, 229–233. Web of Science CSD CrossRef CAS Google Scholar
O'Keeffe, M. & Hyde, B. G. (1996). Crystal Structures 1. Patterns and Symmetry, p. 357. Washington, DC: Mineralogical Society of America. 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
Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385–2386. Web of Science CrossRef Google Scholar
Shape Software (2003). ATOMS. Version 6.0. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 12| December 2004| Pages m637-m639

doi:10.1107/S0108270104027039

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search term		doi		Advanced search
Author		volume	page

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