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CHEMISTRY
ISSN: 2053-2296

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

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[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]). Chem. Commun. pp. 2385–2386].

Comment

Among the myriad variety of organically templated inorganic networks (Cheetham et al., 1999[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269-3292.]), 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[Choudhury, A., Kumar, U. D. & Rao, C. N. R. (2002). Angew. Chem. Int. Ed. 41, 158-161.]; Millange et al., 2004[Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Féret, G. (2004). Solid State Sci. 6, 229-233.]), 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[O'Keeffe, M. & Hyde, B. G. (1996). Crystal Structures 1. Patterns and Symmetry, p. 357. Washington, DC: Mineralogical Society of America.]) of the Zn and Se nodal atoms; the first (Choudhury et al., 2002[Choudhury, A., Kumar, U. D. & Rao, C. N. R. (2002). Angew. Chem. Int. Ed. 41, 158-161.]) is based on 63 inorganic sheets (each nodal atom participates in three six-membered rings), whereas the second (Millange et al., 2004[Millange, F., Serre, C., Cabourdin, T., Marrot, J. & Féret, G. (2004). Solid State Sci. 6, 229-233.]) contains 4.82 sheets. The 1,4-di­amino­benzene template in [C6N2H8]0.5[ZnHPO3] (Kirkpatrick & Harrison, 2004[Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593-598.]) 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[Ritchie, L. K. & Harrison, W. T. A. (2004). Acta Cryst. C60, m634-m636.]), 4.82 polyhedral sheets arise from the ZnO3N and HPO3 units. Finally, [H2N(CH2)2NH2]0.5[ZnHPO3] (Rodgers & Harrison, 2000[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]; 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.

[Scheme 1]

We describe here the title compound, (I[link]), which crystallizes as a second, β, modification of [H2N(CH2)2NH2]0.5[ZnHPO3]. Compound (I[link]) (Fig. 1[link]) 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[link]); in the N1-containing mol­ecule, atoms Zn1 and C1v (see Table 1[link] for symmetry code) are gauche, whereas in the N2-containing mol­ecule, the equivalent pair of atoms, Zn2 and C2vi, 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[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]; Kirkpatrick & Harrison, 2004[Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593-598.]) 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[Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593-598.]) 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[link]) 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[link]), thus generating a 4.82 sheet topology (O'Keeffe & Hyde, 1996[O'Keeffe, M. & Hyde, B. G. (1996). Crystal Structures 1. Patterns and Symmetry, p. 357. Washington, DC: Mineralogical Society of America.]).

The organic species crosslink the (001) ZnHPO3 sheets in a Zn—b—Zn (b is the organic bridge) fashion, as shown in Fig. 3[link], 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[link]), unlike the case of organically pillared zirconyl phosphates (Alberti et al., 1999[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.]), 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[link]) participate in N—H⋯O hydrogen bonds (Table 2[link]), 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[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]). However, the zincophosphite eight-membered ring pores in (I[link]) 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[Lin, Z. E., Zhang, J., Zheng, S. T. & Yang, G. Y. (2004). Solid State Sci. 6, 371-376.]) is a more conventional templated network (Cheetham et al., 1999[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269-3292.]), 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]
Figure 1
A view of a fragment of (I[link]), 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[link].
[Figure 2]
Figure 2
A view of a fragment of a ZnHPO3 layer in (I[link]), 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[link]).
[Figure 3]
Figure 3
The unit-cell packing in (I[link]), 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[link]) accompanied by some undissolved zinc oxide.

Crystal data
  • [Zn2(HPO3)2(C2H8N2)]

  • Mr = 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

  • Dx = 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[Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.287, Tmax = 0.607

  • 7093 measured reflections

  • 2309 independent reflections

  • 2075 reflections with I > 2σ(I)

  • Rint = 0.031

  • θmax = 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(Fo2) + (0.0155P)2 + 26.0795P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.23 e Å−3

  • Δρmin = −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)
P2iv—O4—Zn2 133.3 (5)
P1—O5—Zn2 143.6 (6)
P2—O6—Zn2 128.9 (5)
Zn1—N1—C1—C1v −64.8 (13)
Zn2—N2—C2—C2vi 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 DA 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⋯O2iv 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[link]) 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 Uiso(H) = 1.2Ueq(carrier atom) was applied. The maximum difference peak is 1.22 Å from atom H2A.

Data collection: SMART (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). 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; molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565-565.]) and ATOMS (Shape Software, 2003[Shape Software (2003). ATOMS. Version 6.0. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 C1v (see Table 1 for symmetry code) are gauche, whereas in the N2-containing molecule, the equivalent pair of atoms, Zn2 and C2vi, 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.

Refinement top

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 Uiso(H) = 1.2Ueq(carrier atom) was applied. The maximum difference peak is 1.22 Å from atom H2A.

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
[Figure 1] 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.)
[Figure 2] 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).
[Figure 3] 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
Mr = 350.80Dx = 2.294 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5099 reflections
a = 8.3609 (4) Åθ = 2.5–27.4°
b = 7.9369 (4) ŵ = 5.04 mm1
c = 15.8259 (7) ÅT = 293 K
β = 104.689 (1)°Slab, colourless
V = 1015.88 (8) Å30.33 × 0.30 × 0.11 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer
2309 independent reflections
Radiation source: fine-focus sealed tube2075 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 108
Tmin = 0.287, Tmax = 0.607k = 910
7093 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.171 w = 1/[σ2(Fo2) + (0.0155P)2 + 26.0795P]
where P = (Fo2 + 2Fc2)/3
S = 1.28(Δ/σ)max = 0.001
2309 reflectionsΔρmax = 1.23 e Å3
128 parametersΔρmin = 1.01 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0028 (5)
Crystal data top
[Zn2(HPO3)2(C2H8N2)]V = 1015.88 (8) Å3
Mr = 350.80Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3609 (4) ŵ = 5.04 mm1
b = 7.9369 (4) ÅT = 293 K
c = 15.8259 (7) Å0.33 × 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)
Tmin = 0.287, Tmax = 0.607Rint = 0.031
7093 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.171H-atom parameters constrained
S = 1.28 w = 1/[σ2(Fo2) + (0.0155P)2 + 26.0795P]
where P = (Fo2 + 2Fc2)/3
2309 reflectionsΔρmax = 1.23 e Å3
128 parametersΔρmin = 1.01 e Å3
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
Zn10.11474 (14)0.38756 (15)0.83143 (7)0.0235 (3)
Zn20.38904 (14)0.68996 (14)0.68286 (7)0.0230 (3)
P10.0169 (3)0.5316 (3)0.63692 (16)0.0213 (5)
H10.04180.45390.56170.026*
P20.4857 (3)0.5427 (3)0.87062 (16)0.0220 (5)
H20.56340.60900.94640.026*
O10.3405 (9)0.4468 (13)0.8874 (6)0.045 (2)
O20.1208 (9)0.1473 (9)0.8516 (6)0.0372 (19)
O30.0580 (11)0.3934 (11)0.7053 (5)0.0409 (19)
O40.3895 (10)0.9280 (10)0.6555 (5)0.0359 (18)
O50.1630 (9)0.6304 (12)0.6262 (6)0.043 (2)
O60.4385 (11)0.6892 (10)0.8084 (5)0.0370 (18)
N10.0377 (10)0.5380 (10)0.8779 (5)0.0222 (16)
H1A0.04480.63700.84940.027*
H1B0.13900.49120.86320.027*
C10.0031 (14)0.5758 (13)0.9738 (6)0.029 (2)
H1C0.11300.62440.99160.034*
H1D0.07460.65830.98500.034*
N20.5245 (10)0.5470 (11)0.6212 (5)0.0238 (17)
H2A0.62670.59070.63020.029*
H2B0.53380.44210.64350.029*
C20.4463 (12)0.5392 (15)0.5258 (6)0.031 (2)
H2C0.41800.65260.50440.037*
H2D0.34440.47530.51630.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0245 (6)0.0229 (6)0.0247 (6)0.0007 (5)0.0091 (4)0.0014 (4)
Zn20.0252 (6)0.0221 (6)0.0235 (6)0.0007 (4)0.0094 (4)0.0005 (4)
P10.0228 (11)0.0203 (12)0.0212 (11)0.0004 (10)0.0063 (9)0.0021 (9)
P20.0232 (12)0.0227 (12)0.0202 (11)0.0003 (10)0.0057 (9)0.0020 (9)
O10.027 (4)0.064 (6)0.044 (5)0.007 (4)0.010 (3)0.016 (4)
O20.028 (4)0.021 (4)0.068 (6)0.001 (3)0.021 (4)0.008 (4)
O30.062 (5)0.033 (4)0.029 (4)0.002 (4)0.014 (4)0.005 (3)
O40.034 (4)0.030 (4)0.048 (5)0.002 (3)0.017 (3)0.002 (4)
O50.025 (4)0.049 (5)0.055 (5)0.004 (4)0.010 (4)0.011 (4)
O60.062 (5)0.025 (4)0.024 (4)0.007 (4)0.012 (4)0.003 (3)
N10.029 (4)0.018 (4)0.021 (4)0.000 (3)0.007 (3)0.005 (3)
C10.042 (6)0.023 (5)0.024 (5)0.003 (4)0.013 (4)0.002 (4)
N20.023 (4)0.023 (4)0.027 (4)0.001 (3)0.007 (3)0.005 (3)
C20.026 (5)0.042 (6)0.023 (5)0.007 (5)0.004 (4)0.000 (4)
Geometric parameters (Å, º) top
Zn1—O11.929 (8)P2—H21.3200
Zn1—O31.932 (8)O2—P1iii1.519 (7)
Zn1—O21.932 (8)O4—P2iv1.519 (8)
Zn1—N12.016 (8)N1—C11.499 (12)
Zn2—O61.923 (7)N1—H1A0.9000
Zn2—O51.934 (8)N1—H1B0.9000
Zn2—O41.938 (8)C1—C1v1.469 (19)
Zn2—N22.021 (8)C1—H1C0.9700
P1—O51.497 (8)C1—H1D0.9700
P1—O31.518 (9)N2—C21.486 (12)
P1—O2i1.519 (7)N2—H2A0.9000
P1—H11.3200N2—H2B0.9000
P2—O61.511 (8)C2—C2vi1.494 (19)
P2—O11.513 (8)C2—H2C0.9700
P2—O4ii1.519 (8)C2—H2D0.9700
O1—Zn1—O3115.1 (4)P2iv—O4—Zn2133.3 (5)
O1—Zn1—O2100.5 (4)P1—O5—Zn2143.6 (6)
O3—Zn1—O2100.6 (4)P2—O6—Zn2128.9 (5)
O1—Zn1—N1108.9 (4)C1—N1—Zn1119.0 (6)
O3—Zn1—N1110.5 (3)C1—N1—H1A107.6
O2—Zn1—N1121.1 (3)Zn1—N1—H1A107.6
O6—Zn2—O5114.0 (4)C1—N1—H1B107.6
O6—Zn2—O4102.8 (3)Zn1—N1—H1B107.6
O5—Zn2—O4101.1 (4)H1A—N1—H1B107.0
O6—Zn2—N2119.8 (3)C1v—C1—N1112.1 (10)
O5—Zn2—N2103.9 (4)C1v—C1—H1C109.2
O4—Zn2—N2114.0 (3)N1—C1—H1C109.2
O5—P1—O3114.6 (5)C1v—C1—H1D109.2
O5—P1—O2i111.2 (5)N1—C1—H1D109.2
O3—P1—O2i113.1 (5)H1C—C1—H1D107.9
O5—P1—H1105.7C2—N2—Zn2111.0 (6)
O3—P1—H1105.7C2—N2—H2A109.4
O2i—P1—H1105.7Zn2—N2—H2A109.4
O6—P2—O1114.4 (5)C2—N2—H2B109.4
O6—P2—O4ii111.6 (5)Zn2—N2—H2B109.4
O1—P2—O4ii112.5 (5)H2A—N2—H2B108.0
O6—P2—H2105.8N2—C2—C2vi113.7 (10)
O1—P2—H2105.8N2—C2—H2C108.8
O4ii—P2—H2105.8C2vi—C2—H2C108.8
P2—O1—Zn1141.0 (5)N2—C2—H2D108.8
P1iii—O2—Zn1128.8 (5)C2vi—C2—H2D108.8
P1—O3—Zn1134.9 (5)H2C—C2—H2D107.7
O6—P2—O1—Zn129.8 (12)O2i—P1—O5—Zn2109.7 (10)
O4ii—P2—O1—Zn198.9 (10)O6—Zn2—O5—P128.0 (11)
O3—Zn1—O1—P222.6 (12)O4—Zn2—O5—P1137.5 (10)
O2—Zn1—O1—P2129.7 (10)N2—Zn2—O5—P1104.1 (10)
N1—Zn1—O1—P2102.1 (10)O1—P2—O6—Zn286.1 (8)
O1—Zn1—O2—P1iii149.6 (7)O4ii—P2—O6—Zn243.2 (8)
O3—Zn1—O2—P1iii92.1 (7)O5—Zn2—O6—P283.7 (8)
N1—Zn1—O2—P1iii29.9 (9)O4—Zn2—O6—P2167.9 (7)
O5—P1—O3—Zn175.9 (9)N2—Zn2—O6—P240.3 (8)
O2i—P1—O3—Zn153.1 (9)O1—Zn1—N1—C141.9 (7)
O1—Zn1—O3—P178.3 (9)O3—Zn1—N1—C1169.3 (7)
O2—Zn1—O3—P1174.6 (8)O2—Zn1—N1—C173.7 (8)
N1—Zn1—O3—P145.5 (9)Zn1—N1—C1—C1v64.8 (13)
O6—Zn2—O4—P2iv102.1 (7)O6—Zn2—N2—C2168.8 (7)
O5—Zn2—O4—P2iv139.9 (7)O5—Zn2—N2—C240.1 (8)
N2—Zn2—O4—P2iv29.1 (8)O4—Zn2—N2—C269.0 (8)
O3—P1—O5—Zn220.1 (12)Zn2—N2—C2—C2vi170.1 (11)
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, 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···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.203.099 (11)173
N1—H1B···O4iii0.902.102.984 (11)167
N2—H2A···O2iv0.902.112.995 (11)170
N2—H2B···O6ii0.902.143.038 (12)177
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Zn2(HPO3)2(C2H8N2)]
Mr350.80
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.3609 (4), 7.9369 (4), 15.8259 (7)
β (°) 104.689 (1)
V3)1015.88 (8)
Z4
Radiation typeMo Kα
µ (mm1)5.04
Crystal size (mm)0.33 × 0.30 × 0.11
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.287, 0.607
No. of measured, independent and
observed [I > 2σ(I)] reflections
7093, 2309, 2075
Rint0.031
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.171, 1.28
No. of reflections2309
No. of parameters128
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0155P)2 + 26.0795P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)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—O11.929 (8)Zn2—N22.021 (8)
Zn1—O31.932 (8)P1—O51.497 (8)
Zn1—O21.932 (8)P1—O31.518 (9)
Zn1—N12.016 (8)P1—O2i1.519 (7)
Zn2—O61.923 (7)P2—O61.511 (8)
Zn2—O51.934 (8)P2—O11.513 (8)
Zn2—O41.938 (8)P2—O4ii1.519 (8)
P2—O1—Zn1141.0 (5)P2iv—O4—Zn2133.3 (5)
P1iii—O2—Zn1128.8 (5)P1—O5—Zn2143.6 (6)
P1—O3—Zn1134.9 (5)P2—O6—Zn2128.9 (5)
Zn1—N1—C1—C1v64.8 (13)Zn2—N2—C2—C2vi170.1 (11)
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, 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···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.203.099 (11)173
N1—H1B···O4iii0.902.102.984 (11)167
N2—H2A···O2iv0.902.112.995 (11)170
N2—H2B···O6ii0.902.143.038 (12)177
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2.
 

Acknowledgements

The authors thank Jillian Johnstone for experimental assistance.

References

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