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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Butane-1,4-di­amine zinc(II) hydrogen phosphite

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

(Received 25 August 2004; accepted 4 October 2004; online 11 November 2004)

The title compound, poly[zinc(II)-μ-butane-1,4-diamine-μ-(hydrogen phosphito)] (C4H12N2)0.5[ZnHPO3], is a hybrid organic–inorganic solid built up from 1,4-di­amino­butane mol­ecules, Zn2+ cations (coordinated by three O atoms and one N atom) and HPO32− hydrogen phosphite groups. The organic species bonds to the Zn atom as an unprotonated ligand, resulting in it acting as a bridge between infinite ZnHPO3 layers, which propagate in (100). The complete butane-1,4-diamine species is generated from a H2N(CH2)2– half mol­ecule by inversion symmetry. The zincophosphite sheets contain polyhedral four- and eight-membered rings in a 4.82 topology.

Comment

The title compound, [H2N(CH2)4NH2]0.5[ZnHPO3], (I[link]), is another example of the rapidly expanding family of organically templated zinc hydrogen phosphite (ZnHPO) networks (Kirkpatrick & Harrison, 2004[Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593-598.], and references therein; Fu et al., 2004[Fu, W., Shi, Z., Li, G., Zhang, D., Dong, W., Chen, X. & Feng, S. (2004). Solid State Sci. 6, 225-228.]) and is the first reported ZnHPO compound to incorporate butane-1,4-diamine as the organic species. Compound (I[link]) was prepared in single-crystal form by a typical mild-condition solution-mediated reaction (Cheetham et al., 1999[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269-3292.]).

[Scheme 1]

Compound (I[link]) (Fig. 1[link]) is built up from neutral unprotonated butane-1,4-diamine [H2N(CH2)4NH2] mol­ecules, Zn2+ cations and HPO32− hydrogen phosphite groups. Each complete butane-1,4-diamine entity is generated from a half-mol­ecule H2N(CH2)2– fragment by inversion symmetry (Table 1[link]). The N atom makes a ligand-like bond to the Zn atom by formal donation of its lone pair of electrons, as seen in related systems (Rodgers & Harrison, 2000[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]). The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.943 (2) Å], all of which form bridges to nearby HPO32− groups [mean Zn—O—P = 131.3 (2)°]. The pseudo-pyramidal HPO32− moiety has typical geometrical parameters, with a mean P—O distance of 1.518 (2) Å and a mean O—P—O angle of 112.48 (9)° (Kirkpatrick & Harrison, 2004[Kirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593-598.]). Its three O atoms all make bridges to nearby zinc cations. As usual, the P—H moiety does 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 (100) plane. Every tetrahedral node (i.e. the Zn and P atoms) participates in one four-membered ring (generated by inversion symmetry) and two eight-membered rings (Fig. 2[link]), and this topology is classed as a 4.82 sheet (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 (100) 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 alternate along [100]. In principle, this arrangement represents a novel kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I[link]), the presence of the P—H bond protruding into the channel region and the highly twisted conformation of the 1,4-di­amino­butane moiety mean that there is no possibility of ingress by other chemical species. Finally, the butane-1,4-diamine NH2 groups in (I[link]) participate in N—H⋯O hydrogen bonds (Table 2[link]), of which one (via H3) is simple and one (via H2) is bifurcated (Fig. 4[link]). 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 [H2N(CH2)2NH2]0.5[ZnHPO3] (Rodgers & Harrison, 2000[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]). Here, however, the zincophosphite 8-ring pores are highly flattened, whereas in [H2N(CH2)2NH2]0.5[ZnHPO3] they are far more regular.

Compound (I[link]) complements several other `pillared' networks built up from ZnO3Nl (Nl = ligand amine N atom) tetrahedra and pyramidal or pseudo-pyramidal inorganic oxy­anions. 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 sheets of ZnO3N and SeO3 groups fused into a three-dimensional network by the ethyl­ene­di­amine moieties bonding to the Zn atom from each end of the H2N(CH2)2NH2 species. The first of these (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.]) is based on 4.82 sheets, as seen here for (I[link]). 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 [H2N(CH2)2NH2]0.5[ZnSeO3] phases; in this case, 63 polyhedral sheets arise. Finally, [H2N(CH2)2NH2]0.5[ZnHPO3] (Rodgers & Harrison, 2000[Rodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385-2386.]) has a novel structure based on 4.82 sheets in which two independent networks form an interpenetrating array akin to coordination polymers.

[Figure 1]
Figure 1
A view of a fragment of (I[link]) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radii. Symmetry codes are as in Table 1[link].
[Figure 2]
Figure 2
A view down [100] of a fragment of a ZnHPO3 layer in (I[link]), showing the topologial connectivity of the Zn (large spheres) and P (small spheres) tetrahedral nodes into 4.82 sheets. Atoms labelled with an asterisk (*) are at the symmetry position (2 − x, 1 − y, 1 − z). The lines linking the Zn and P atoms represent Zn—O—P bridges, which are not linear (see Table 1[link]).
[Figure 3]
Figure 3
The unit-cell packing in (I[link]), viewed down [001], in a polyhedral representation (ZnO3N groups: dark shading; HPO3 groups: light shading). All H atoms, except for atom H1, have been omitted for clarity.
[Figure 4]
Figure 4
A polyhedral view of a fragment of a (100) ZnHPO3 layer in (I[link]), showing the N—H⋯O bonds associated with a flattened 8-ring window. Symmetry codes are as in Table 2[link].

Experimental

Zinc oxide, phos­pho­rus acid (H3PO3) and butane-1,4-diamine in a 1:2:2 molar ratio were shaken in distilled water (25 ml) in a 60 ml HDPE bottle for a few minutes until a white slurry formed. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered off hot by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown block-like crystals of (I[link]). An ATOMS (Shape Software, 1999[Shape Software (1999). ATOMS. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA.]) simulation of the X-ray powder pattern of (I[link]), based on the single-crystal structure described here, was in excellent agreement with the measured data, indicating phase purity.

Crystal data
  • (C4H12N2)0.5[ZnHPO3]

  • Mr = 189.43

  • Monoclinic, P21/c

  • a = 8.4713 (4) Å

  • b = 8.2489 (4) Å

  • c = 8.0805 (4) Å

  • β = 96.093 (1)°

  • V = 561.47 (5) Å3

  • Z = 4

  • Dx = 2.241 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3298 reflections

  • θ = 2.5–32.2°

  • μ = 4.57 mm−1

  • T = 293 (2) K

  • Slab, colourless

  • 0.32 × 0.30 × 0.13 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 = 0.323, Tmax = 0.588

  • 5407 measured reflections

  • 1964 independent reflections

  • 1667 reflections with I > 2σ(I)

  • Rint = 0.017

  • θmax = 32.2°

  • h = −12 → 12

  • k = −5 → 12

  • l = −12 → 11

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.019

  • wR(F2) = 0.049

  • S = 1.07

  • 1964 reflections

  • 74 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0259P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.002

  • Δρmax = 0.44 e Å−3

  • Δρmin = −0.32 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.0032 (7)

Table 1
Selected geometric parameters (Å, °)

Zn1—O1 1.9331 (11)
Zn1—O3i 1.9427 (11)
Zn1—O2ii 1.9539 (11)
Zn1—N1 2.0260 (12)
P1—O1 1.5140 (11)
P1—O3 1.5152 (12)
P1—O2 1.5254 (11)
   
P1—O1—Zn1 135.21 (7)
P1—O2—Zn1ii 124.08 (7)
P1—O3—Zn1iii 134.49 (7)
C1—N1—Zn1 116.33 (9)
Zn1—N1—C1—C2 −57.62 (14)
N1—C1—C2—C2iv −61.9 (2)
C1—C2—C2iv—C1iv 180.0
Symmetry codes: (i) [x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]; (ii) 2-x,1-y,1-z; (iii) [x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]; (iv) 1-x,1-y,-z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H2⋯O2v 0.90 2.47 3.2107 (17) 140
N1—H2⋯O3vi 0.90 2.57 3.1143 (16) 119
N1—H3⋯O2vii 0.90 2.29 3.1501 (15) 160
Symmetry codes: (v) [x,{\script{3\over 2}}-y,z-{\script{1\over 2}}]; (vi) [2-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]; (vii) x,y,z-1.

All H atoms were placed in idealized positions and refined as riding on their carrier atoms [P—H = 1.32 Å, N—H = 0.90 Å, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(parent atom)].

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 (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 (Shape Software, 1999[Shape Software (1999). ATOMS. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound, [H2N(CH2)4NH2]0.5[ZnHPO3], (I), is another example of the rapidly expanding family of organically templated zinc hydrogen phosphite (ZnHPO) networks (Kirkpatrick & Harrison, 2004, and references therein; Fu et al., 2004) and is the first reported ZnHPO compound to incorporate 1,4-diaminobutane as the organic species. Compound (I) was prepared in single-crystal form by a typical mild-condition solution-mediated reaction (Cheetham et al., 1999).

Compound (I) (Fig. 1) is built up from neutral unprotonated 1,4-diaminobutane [H2N(CH2)4NH2 or C4H12N2] molecules, Zn2+ cations, and HPO32− hydrogen phosphite groups. Each complete 1,4-diaminobutane entity is generated from a half-molecule [H2N(CH2)2] fragment by inversion symmetry (Table 1). The N atom makes a ligand-like bond to zinc by formal donation of its lone pair of electrons, as seen in related systems (Rodgers & Harrison, 2000). The tetrahedral zinc coordination is completed by three O atoms [mean Zn—O = 1.943 (2) Å], all of which form bridges to nearby HPO32− groups [mean Zn—O—P = 131.3 (2)°]. The pseudo-pyramidal HPO32− moiety has typical geometrical parameters, with a mean P—O distance of 1.518 (2) Å, and a mean O—P—O angle of 112.48 (9)° (Kirkpatrick & Harrison, 2004, and references therein). Its three O atoms all make bridges to nearby zinc cations. As usual, the P—H moiety does 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 (100) plane. Every tetrahedral node (i.e. the Zn and P atoms) participates in one four-membered ring (generated by inversion symmetry) and two eight-membered rings (Fig. 2), and this topology is classed as a 4.82 sheet (O'Keeffe & Hyde, 1996).

The organic species crosslink the (100) 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 alternate along [100]. In principle, this arrangement represents a novel kind of microporosity, with the channels bounded by both inorganic and organic surfaces. However, in (I), the presence of the P–H bond protruding into the channel region and the highly twisted conformation of the 1,4-diaminobutane moiety means that there is no possibility of ingress by other chemical species. Finally, the 1,4-diaminobutane –NH2 groups in (I) participate in N—H···O hydrogen bonds (Table 2), of which one (via H3) is simple and one (via H2) is bifurcated (Fig. 4). 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 [H2N(CH2)2NH2]0.5[ZnHPO3] (Rodgers & Harrison, 2000). Here, however, the zincophosphate eight-ring pores are highly flattened, whereas in [H2N(CH2)2NH2]0.5[ZnHPO3] they are far more regular.

Compound (I) complements several other `pillared' networks built up from ZnO3Nl (Nl = ligand amine N atom) tetrahedra and pyramidal or pseudo-pyramidal inorganic oxyanions. Both modifications of ethylenediamine zinc selenite, [H2N(CH2)2NH2]0.5[ZnSeO3] (Choudhury et al., 2002; Millange et al., 2004), contain sheets of ZnO3N and SeO3 groups fused into a three-dimensional network by the ethylenediamine moieties bonding to Zn from each end of the H2N(CH2)2NH2 species. The first of these (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) is based on 4.82 sheets, as seen here for (I). The 1,4-diaminobenzene template in [C6N2H8]0.5[ZnHPO3] (Kirkpatrick & Harrison, 2004) acts in a similar way to ethylenediamine in the [H2N(CH2)2NH2]0.5[ZnSeO3] phases; in this case 63 polyhedral sheets arise. Finally, [H2N(CH2)2NH2]0.5[ZnHPO3] (Rodgers & Harrison, 2000) has a novel structure based on 4.82 sheets in which two independent networks from an interpenetrating array akin to coordination polymers.

Experimental top

Zinc oxide, phosphorus acid (H3PO3) and 1,4-diaminobutane in a 1:2:2 molar ratio were shaken in distilled water (25 ml) in a 60 ml HDPE bottle for a few minutes until a white slurry formed. The bottle was then placed in an oven at 353 K for 2 d. The solid product was filtered hot by suction filtration using a Buchner funnel and rinsed with water and acetone, resulting in intergrown block-like crystals of (I). An ATOMS (Shape Software, 1999) simulation of the X-ray powder pattern of (I) based on the single-crystal structure described here, was in excellent agreement with the measured data, indicating phase purity.

Refinement top

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, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(parent atom)].

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 (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of a fragment of (I) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius. Symmetry codes are as in Table 1.
[Figure 2] Fig. 2. A view down [100] 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. Atoms labeled with an asterisk (*) are at the symmetry position (2 − x, 1 − y, 1 − z). The lines linking the Zn and P atoms represent Zn—O—P bridges, which are not linear (see Table 1).
[Figure 3] Fig. 3. The unit-cell packing in (I), viewed down [001], in a polyhedral representation (ZnO3N groups: dark shading; HPO3 groups: light shading). All H atoms, except atom H1, have been omitted for clarity.
[Figure 4] Fig. 4. A polyhedral view of a fragment of a (100) ZnHPO3 layer in (I), showing the N—H···O bonds associated with a flattened eight-ring window. Symmetry codes are as in Table 2.
Butane-1,4-diamine zinc(II) hydrogen phosphite top
Crystal data top
(C4H12N2)0.5[ZnHPO3]F(000) = 380
Mr = 189.43Dx = 2.241 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3298 reflections
a = 8.4713 (4) Åθ = 2.5–32.2°
b = 8.2489 (4) ŵ = 4.57 mm1
c = 8.0805 (4) ÅT = 293 K
β = 96.093 (1)°Slab, colourless
V = 561.47 (5) Å30.32 × 0.30 × 0.13 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer
1964 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ω scansθmax = 32.2°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1212
Tmin = 0.323, Tmax = 0.588k = 512
5407 measured reflectionsl = 1211
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)] = 0.019H-atom parameters constrained
wR(F2) = 0.049 w = 1/[σ2(Fo2) + (0.0259P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
1964 reflectionsΔρmax = 0.44 e Å3
74 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0032 (7)
Crystal data top
(C4H12N2)0.5[ZnHPO3]V = 561.47 (5) Å3
Mr = 189.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.4713 (4) ŵ = 4.57 mm1
b = 8.2489 (4) ÅT = 293 K
c = 8.0805 (4) Å0.32 × 0.30 × 0.13 mm
β = 96.093 (1)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1964 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1667 reflections with I > 2σ(I)
Tmin = 0.323, Tmax = 0.588Rint = 0.017
5407 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.049H-atom parameters constrained
S = 1.07Δρmax = 0.44 e Å3
1964 reflectionsΔρmin = 0.32 e Å3
74 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
Zn10.897600 (18)0.46510 (2)0.218542 (18)0.02079 (6)
P10.80502 (4)0.38978 (5)0.58340 (4)0.01849 (8)
H10.66290.35260.62490.022*
O10.77922 (14)0.46180 (16)0.41029 (13)0.0341 (3)
O20.87536 (13)0.51177 (15)0.71268 (13)0.0292 (2)
O30.89785 (15)0.23256 (13)0.58785 (15)0.0340 (3)
N10.79215 (13)0.63445 (15)0.06227 (14)0.0216 (2)
H20.85340.72390.06940.026*
H30.78980.59680.04250.026*
C10.62758 (16)0.68278 (19)0.09135 (18)0.0255 (3)
H40.58920.76250.00850.031*
H50.63060.73390.19980.031*
C20.51209 (16)0.54297 (19)0.08398 (16)0.0243 (3)
H60.41020.58300.11100.029*
H70.54960.46450.16850.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02292 (9)0.01930 (9)0.01926 (9)0.00246 (6)0.00184 (5)0.00111 (6)
P10.01839 (15)0.02006 (17)0.01691 (15)0.00126 (13)0.00140 (11)0.00077 (12)
O10.0351 (6)0.0467 (8)0.0206 (5)0.0139 (5)0.0030 (4)0.0097 (5)
O20.0231 (5)0.0312 (6)0.0319 (6)0.0012 (4)0.0032 (4)0.0115 (4)
O30.0484 (7)0.0190 (5)0.0363 (6)0.0068 (5)0.0134 (5)0.0076 (5)
N10.0189 (5)0.0203 (6)0.0250 (5)0.0029 (4)0.0001 (4)0.0030 (5)
C10.0216 (6)0.0242 (7)0.0298 (7)0.0025 (6)0.0010 (5)0.0025 (6)
C20.0195 (6)0.0322 (8)0.0212 (6)0.0025 (6)0.0020 (4)0.0019 (6)
Geometric parameters (Å, º) top
Zn1—O11.9331 (11)N1—C11.4924 (18)
Zn1—O3i1.9427 (11)N1—H20.9000
Zn1—O2ii1.9539 (11)N1—H30.9000
Zn1—N12.0260 (12)C1—C21.509 (2)
P1—O11.5140 (11)C1—H40.9700
P1—O31.5152 (12)C1—H50.9700
P1—O21.5254 (11)C2—C2iv1.526 (3)
P1—H11.3200C2—H60.9700
O2—Zn1ii1.9539 (11)C2—H70.9700
O3—Zn1iii1.9427 (11)
O1—Zn1—O3i117.03 (5)Zn1—N1—H2108.2
O1—Zn1—O2ii110.62 (5)C1—N1—H3108.2
O3i—Zn1—O2ii100.29 (5)Zn1—N1—H3108.2
O1—Zn1—N1106.10 (5)H2—N1—H3107.4
O3i—Zn1—N1105.41 (5)N1—C1—C2113.71 (12)
O2ii—Zn1—N1117.75 (5)N1—C1—H4108.8
O1—P1—O3112.42 (7)C2—C1—H4108.8
O1—P1—O2112.43 (7)N1—C1—H5108.8
O3—P1—O2112.60 (7)C2—C1—H5108.8
O1—P1—H1106.3H4—C1—H5107.7
O3—P1—H1106.3C1—C2—C2iv114.55 (15)
O2—P1—H1106.3C1—C2—H6108.6
P1—O1—Zn1135.21 (7)C2iv—C2—H6108.6
P1—O2—Zn1ii124.08 (7)C1—C2—H7108.6
P1—O3—Zn1iii134.49 (7)C2iv—C2—H7108.6
C1—N1—Zn1116.33 (9)H6—C2—H7107.6
C1—N1—H2108.2
O3—P1—O1—Zn132.09 (14)O2—P1—O3—Zn1iii84.33 (12)
O2—P1—O1—Zn196.23 (12)O1—Zn1—N1—C118.17 (11)
O3i—Zn1—O1—P175.42 (13)O3i—Zn1—N1—C1106.60 (10)
O2ii—Zn1—O1—P138.56 (13)O2ii—Zn1—N1—C1142.64 (9)
N1—Zn1—O1—P1167.34 (11)Zn1—N1—C1—C257.62 (14)
O1—P1—O2—Zn1ii93.89 (10)N1—C1—C2—C2iv61.9 (2)
O3—P1—O2—Zn1ii34.34 (11)C1—C2—C2iv—C1iv180.0
O1—P1—O3—Zn1iii147.44 (10)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1, z+1; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2···O2v0.902.473.2107 (17)140
N1—H2···O3vi0.902.573.1143 (16)119
N1—H3···O2vii0.902.293.1501 (15)160
Symmetry codes: (v) x, y+3/2, z1/2; (vi) x+2, y+1/2, z+1/2; (vii) x, y, z1.

Experimental details

Crystal data
Chemical formula(C4H12N2)0.5[ZnHPO3]
Mr189.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.4713 (4), 8.2489 (4), 8.0805 (4)
β (°) 96.093 (1)
V3)561.47 (5)
Z4
Radiation typeMo Kα
µ (mm1)4.57
Crystal size (mm)0.32 × 0.30 × 0.13
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.323, 0.588
No. of measured, independent and
observed [I > 2σ(I)] reflections
5407, 1964, 1667
Rint0.017
(sin θ/λ)max1)0.750
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.049, 1.07
No. of reflections1964
No. of parameters74
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.32

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

Selected geometric parameters (Å, º) top
Zn1—O11.9331 (11)P1—O11.5140 (11)
Zn1—O3i1.9427 (11)P1—O31.5152 (12)
Zn1—O2ii1.9539 (11)P1—O21.5254 (11)
Zn1—N12.0260 (12)
P1—O1—Zn1135.21 (7)P1—O3—Zn1iii134.49 (7)
P1—O2—Zn1ii124.08 (7)C1—N1—Zn1116.33 (9)
Zn1—N1—C1—C257.62 (14)C1—C2—C2iv—C1iv180.0
N1—C1—C2—C2iv61.9 (2)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+2, y+1, z+1; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H2···O2v0.902.473.2107 (17)140
N1—H2···O3vi0.902.573.1143 (16)119
N1—H3···O2vii0.902.293.1501 (15)160
Symmetry codes: (v) x, y+3/2, z1/2; (vi) x+2, y+1/2, z+1/2; (vii) x, y, z1.
 

References

First citationBruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3269–3292.  Web of Science CrossRef Google Scholar
First citationChoudhury, A., Kumar, U. D. & Rao, C. N. R. (2002). Angew. Chem. Int. Ed. 41, 158–161.  Web of Science CSD CrossRef CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFu, W., Shi, Z., Li, G., Zhang, D., Dong, W., Chen, X. & Feng, S. (2004). Solid State Sci. 6, 225–228.  Web of Science CSD CrossRef CAS Google Scholar
First citationKirkpatrick, A. & Harrison, W. T. A. (2004). Solid State Sci. 6, 593–598.  CSD CrossRef CAS Google Scholar
First citationMillange, F., Serre, C., Cabourdin, T., Marrot, J. & Féret, G. (2004). Solid State Sci. 6, 229–233.  Web of Science CSD CrossRef CAS Google Scholar
First citationO'Keeffe, M. & Hyde, B. G. (1996). Crystal Structures 1. Patterns and Symmetry, p. 357. Washington, DC: Mineralogical Society of America.  Google Scholar
First citationRodgers, J. A. & Harrison, W. T. A. (2000). Chem. Commun. pp. 2385–2386.  Web of Science CrossRef Google Scholar
First citationShape Software (1999). ATOMS. Shape Software, 525 Hidden Valley Road, Kingsport, Tennessee, USA.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar

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