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Acta Cryst. (2007). E63, m1925    [ doi:10.1107/S1600536807028140 ]

Poly[ethylenediammonium di-[mu]4-phosphatodizincate(II)]

J.-X. Pan and G.-Y. Yang

Abstract top

In the title compound, (C2H10N2)[ZnPO4]2, alternating ZnO4 [Zn-O = 1.899 (5)-1.940 (6) Å] and PO4 [P-O = 1.525 (6)-1.539 (6) Å] tetrahedra are linked through their vertices to generate a three-dimensional zeolite-like framework with perpendicular six- and eight-membered ring channels. The disordered ethylenediammonium dications are located in the eight-membered ring channels near the twofold axes. The C atom and H atoms attached to C and N are disordered over two positions in a ratio of 0.55:0.45. All atoms are located in general positions.

Comment top

Organically templated metal phosphates have attracted considerable attention in recent years because of their potential applications in catalysis, ion exchange and separation (Davis & Lobo, 1992). Among these, zinc phosphates constitute an important family and compounds with zero-, one-, two- and three-dimensional architectures have been isolated (Cheetham et al., 1999; Rao et al., 2001). In the course of our studies of open-framework zinc phosphates, we have got the title compound with zeolite DFT topology. The asymmetric unit of compound (I) is composed of half of a diprotonated ethylenediamine cation and a [ZnPO4]- anion (Fig. 1). The Zn and P atoms both adopt tetrahedral coordination with dav(Zn—O) = 1.921 (6) Å and dav(P—O) = 1.532 (6) Å. Each Zn atom makes four Zn—O—P links to nearby P atoms via bicoordinate O atom bridges and vice versa, thus a fully connected alternating three-dimensional framework arises. The compound consists of 4-, 6-, and 8-rings and its framework topology is identical to that of UCSB-3, ACP-3 (Bu, Feng, Gier, Zhao et al., 1998; Bu, Feng, Gier & Stucky, 1998) and [Fe0.4Zn0.6PO4]2.[NH3CH2CH2NH3] (Zhao et al., 2005). The anionic [ZnPO4]- framework encloses a system of fairly regular 8-ring (i.e. eight tetrahedral centres made up of four ZnO4 and four PO4 units) channels propagating along [001] direction (Fig. 2) (approximate atom-to-atom dimensions = 7.36 × 4.63 Å). These intersect with the 8-ring channels (dimensions ~ 7.18 × 3.56 Å) which propagate along [110] and [-110] directions (Fig. 3). The diprotonated ethylenediamine molecules are located at the center of 8-ring channels viewed along the c axis. Two nitrogen atoms are ordered, whereas two carbon atoms each have two possible locations, as illustrated in Fig. 1. The twofold axis (1/4, 1/4, z) along the c axis passes through ethylenediamine molecules in both orientations. The template molecules form N—H···O type hydrogen bonds with the oxygen atoms of the framework (Table 1).

Related literature top

The title compound has a zeolite DFT topology and its framework is identical to UCSB-3 (ZnAsO and GaGeO), ACP-3 (CoAlPO) (Bu, Feng, Gier, Zhao et al., 1998; Bu, Feng, Gier & Stucky, 1998) and [Fe0.4Zn0.6PO4]2.[NH3CH2CH2NH3] (Zhao et al., 2005). For general background, see: Davis & Lobo (1992); Cheetham et al. (1999); Rao et al. (2001).

Experimental top

The title compound was prepared by hydrothermal synthesis from a mixture of ZnO (0.162 g, 2 mmol), diethylenetriamine (0.22 ml, 2 mmol), 85% H3PO4 (0.20 ml, 3 mmol) and 37% HCl (1 ml) in H2O (3.6 ml). The mixture was sealed in a Teflon autoclave, heated at 433 K for 4 d, and cooled. The resulting product, containing colorless prismlike single crystals, was filtered, washed with distilled water, and then dried at ambient temperature (87% yield based on Zn).

Refinement top

All the hydrogen atoms were positioned geometrically (the C—H and N—H bonds were fixed at 0.97 and 0.89 Å, respectively) and refined in the riding mode, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(N). The C1 atom in dication was treated as disordered between two positions with occupancies of 0.55 and 0.45, respectively. Subsequently, the H atoms attached to atoms C1 and N1 were treated as disordered too.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 40% probability level. Two orientations of diprotonated ethylenediamine are also shown. H atoms have been omitted. Symmetry codes are as in Table 1.
[Figure 2] Fig. 2. Polyhedral view of the structure of the title compound along the [001] direction showing the 8-ring channels. Dotted lines indicate hydrogen-bonding interactions and H atoms have been omitted. Color code: ZnO4 tetrahedra, magenta; PO4 tetrahedra, green; N, blue; C, gray.
[Figure 3] Fig. 3. Polyhedral view of the eight-ring channels along the [110] direction in the title compound. Color key is as in Fig. 2.
Poly[ethylenediammonium di-µ4-phosphatodizincate(II)] top
Crystal data top
(C2H10N2)[ZnPO4]2Dx = 2.642 Mg m−3
Mr = 382.80Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/nCell parameters from 36 reflections
a = 10.3940 (8) Åθ = 2.8–25.0°
c = 8.9094 (10) ŵ = 5.35 mm−1
V = 962.53 (15) Å3T = 293 K
Z = 4Prism, colorless
F(000) = 7600.12 × 0.12 × 0.10 mm
Data collection top
Siemens SMART CCD
diffractometer		841 independent reflections
Radiation source: fine-focus sealed tube616 reflections with I > 2σ(I)
graphiteRint = 0.056
φ and ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: mulit-scan
(SADABS; Sheldrick, 1996)		h = −11→12
Tmin = 0.566, Tmax = 0.617k = −12→8
2819 measured reflectionsl = −10→6
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0595P)2 + 6.4771P]
where P = (Fo2 + 2Fc2)/3
841 reflections(Δ/σ)max < 0.001
55 parametersΔρmax = 0.67 e Å−3
0 restraintsΔρmin = −0.66 e Å−3
Crystal data top
(C2H10N2)[ZnPO4]2Z = 4
Mr = 382.80Mo Kα radiation
Tetragonal, P42/nµ = 5.35 mm−1
a = 10.3940 (8) ÅT = 293 K
c = 8.9094 (10) Å0.12 × 0.12 × 0.10 mm
V = 962.53 (15) Å3
Data collection top
Siemens SMART CCD
diffractometer		841 independent reflections
Absorption correction: mulit-scan
(SADABS; Sheldrick, 1996)		616 reflections with I > 2σ(I)
Tmin = 0.566, Tmax = 0.617Rint = 0.056
2819 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.128Δρmax = 0.67 e Å−3
S = 1.04Δρmin = −0.66 e Å−3
841 reflectionsAbsolute structure: ?
55 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
Zn11.11040 (8)0.87230 (8)0.33996 (9)0.0193 (3)
P11.11143 (19)0.59342 (19)0.2006 (2)0.0180 (5)
O11.0614 (7)0.7318 (6)0.2109 (7)0.0461 (18)
O21.0612 (6)0.8386 (6)0.5432 (6)0.0293 (14)
O30.9986 (6)1.0023 (6)0.2537 (7)0.0354 (16)
O41.2829 (5)0.9291 (6)0.3159 (6)0.0369 (16)
N11.3804 (7)1.1268 (7)0.5038 (9)0.032 (16)
H1A1.41381.08140.57900.047*0.45
H2A1.44221.17260.45980.047*0.45
H3A1.34541.07360.43710.047*0.45
H1B1.41461.08090.42950.047*0.55
H2B1.34801.07390.57270.047*0.55
H3B1.44101.17570.54540.047*0.55
C11.2800 (17)1.2149 (16)0.5630 (2)0.025 (7)0.45
H4A1.21291.16540.61200.030*0.45
H5A1.31751.27250.63660.030*0.45
C21.2739 (2)1.2120 (2)0.4420 (3)0.051 (8)0.55
H4B1.35661.21990.39240.061*0.55
H5B1.22681.13830.40400.061*0.55
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0177 (5)0.0194 (6)0.0206 (5)0.0019 (4)0.0008 (4)0.0003 (4)
P10.0178 (11)0.0171 (11)0.0190 (10)−0.0038 (8)−0.0008 (8)−0.0025 (8)
O10.067 (5)0.028 (4)0.044 (4)0.007 (3)−0.008 (3)−0.014 (3)
O20.036 (4)0.032 (3)0.020 (3)−0.007 (3)0.000 (3)−0.003 (3)
O30.046 (4)0.033 (4)0.027 (3)0.024 (3)−0.005 (3)−0.004 (3)
O40.019 (3)0.060 (4)0.032 (3)−0.009 (3)0.008 (3)−0.006 (3)
N10.026 (4)0.030 (4)0.039 (4)0.006 (4)−0.003 (3)−0.002 (3)
C10.024 (11)0.018 (12)0.031 (15)0.010 (8)−0.016 (8)−0.016 (7)
C20.048 (15)0.052 (17)0.053 (18)0.006 (10)0.001 (10)−0.002 (10)
Geometric parameters (Å, °) top
Zn1—O41.900 (6)N1—H2A0.8900
Zn1—O21.914 (6)N1—H3A0.8900
Zn1—O11.927 (6)N1—H1B0.8900
Zn1—O31.941 (6)N1—H2B0.8900
P1—O4i1.522 (6)N1—H3B0.8900
P1—O2ii1.532 (6)C1—C1vi0.9599
P1—O11.532 (7)C1—C21.0803
P1—O3iii1.538 (6)C1—C2vi1.4329
O2—P1iv1.532 (6)C1—H4A0.9700
O3—P1v1.538 (6)C1—H5A0.9700
O4—P1i1.522 (6)C2—C2vi0.9332
N1—C11.4852C2—C1vi1.4329
N1—C21.5208C2—H4B0.9700
N1—H1A0.8900C2—H5B0.9700
O4—Zn1—O2114.6 (2)C1—N1—H3B89.8
O4—Zn1—O1114.7 (3)C2—N1—H3B109.5
O2—Zn1—O1110.8 (3)H1A—N1—H3B73.3
O4—Zn1—O3107.7 (3)H2A—N1—H3B50.8
O2—Zn1—O3110.0 (3)H3A—N1—H3B157.3
O1—Zn1—O397.7 (3)H1B—N1—H3B109.5
O4i—P1—O2ii109.8 (3)H2B—N1—H3B109.5
O4i—P1—O1110.4 (4)C1vi—C1—C289.0
O2ii—P1—O1112.0 (4)C1vi—C1—C2vi48.9
O4i—P1—O3iii104.9 (4)C2—C1—C2vi40.6
O2ii—P1—O3iii110.9 (3)C1vi—C1—N1157.7
O1—P1—O3iii108.5 (4)C2—C1—N170.7
P1—O1—Zn1131.1 (4)C2vi—C1—N1109.5
P1iv—O2—Zn1138.2 (4)C1vi—C1—H4A86.3
P1v—O3—Zn1141.3 (4)C2—C1—H4A113.1
P1i—O4—Zn1135.2 (4)C2vi—C1—H4A109.8
C1—N1—C242.1N1—C1—H4A109.8
C1—N1—H1A109.5C1vi—C1—H5A78.0
C2—N1—H1A149.9C2—C1—H5A135.7
C1—N1—H2A109.5C2vi—C1—H5A109.8
C2—N1—H2A93.1N1—C1—H5A109.8
H1A—N1—H2A109.5H4A—C1—H5A108.2
C1—N1—H3A109.5C2vi—C2—C190.4
C2—N1—H3A79.8C2vi—C2—C1vi48.9
H1A—N1—H3A109.5C1—C2—C1vi42.0
H2A—N1—H3A109.5C2vi—C2—N1151.7
C1—N1—H1B151.1C1—C2—N167.2
C2—N1—H1B109.5C1vi—C2—N1108.7
H1A—N1—H1B96.9C2vi—C2—H4B113.6
H2A—N1—H1B70.8C1—C2—H4B113.6
H3A—N1—H1B48.2C1vi—C2—H4B130.1
C1—N1—H2B82.5N1—C2—H4B64.5
C2—N1—H2B109.5C2vi—C2—H5B113.6
H1A—N1—H2B45.7C1—C2—H5B113.6
H2A—N1—H2B155.1C1vi—C2—H5B118.9
H3A—N1—H2B85.5N1—C2—H5B91.9
H1B—N1—H2B109.5H4B—C2—H5B110.8
Symmetry codes: (i) −x+5/2, −y+3/2, z; (ii) −y+2, x−1/2, z−1/2; (iii) y, −x+3/2, −z+1/2; (iv) y+1/2, −x+2, z+1/2; (v) −y+3/2, x, −z+1/2; (vi) −x+5/2, −y+5/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3iv0.891.992.874 (6)172
N1—H2A···O2vii0.892.122.924 (6)149
N1—H3A···O40.891.962.838 (6)168
N1—H3A···O3viii0.892.452.920 (7)113
N1—H1B···O3viii0.892.032.920 (7)173
N1—H1B···O40.892.322.838 (6)117
N1—H2B···O1iv0.892.233.101 (7)168
N1—H2B···O3iv0.892.402.874 (6)114
N1—H3B···O2vii0.892.252.924 (6)133
N1—H3B···O1vii0.892.573.345 (7)146
Symmetry codes: (iv) y+1/2, −x+2, z+1/2; (vii) x+1/2, y+1/2, −z+1; (viii) −y+5/2, x, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.891.992.874 (6)172
N1—H2A···O2ii0.892.122.924 (6)149
N1—H3A···O40.891.962.838 (6)168
N1—H3A···O3iii0.892.452.920 (7)113
N1—H1B···O3iii0.892.032.920 (7)173
N1—H1B···O40.892.322.838 (6)117
N1—H2B···O1i0.892.233.101 (7)168
N1—H2B···O3i0.892.402.874 (6)114
N1—H3B···O2ii0.892.252.924 (6)133
N1—H3B···O1ii0.892.573.345 (7)146
Symmetry codes: (i) y+1/2, −x+2, z+1/2; (ii) x+1/2, y+1/2, −z+1; (iii) −y+5/2, x, −z+1/2.
Acknowledgements top

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China.

references
References top

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