Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028140/cv2252sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028140/cv2252Isup2.hkl |
CCDC reference: 654774
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (P-O) = 0.007 Å
- Disorder in main residue
- R factor = 0.047
- wR factor = 0.128
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Zn1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 4.00 Perc. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.50 Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 42.10 Deg. C1 -N1 -C2 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 40.60 Deg. C2 -C1 -C2 1.555 1.555 2.775 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 42.00 Deg. C1 -C2 -C1 1.555 1.555 2.775
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.950 Tmax scaled 0.586 Tmin scaled 0.538 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
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).
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.
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).
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).
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.
(C2H10N2)[ZnPO4]2 | Dx = 2.642 Mg m−3 |
Mr = 382.80 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P42/n | Cell parameters from 36 reflections |
a = 10.3940 (8) Å | θ = 2.8–25.0° |
c = 8.9094 (10) Å | µ = 5.35 mm−1 |
V = 962.53 (15) Å3 | T = 293 K |
Z = 4 | Prism, colorless |
F(000) = 760 | 0.12 × 0.12 × 0.10 mm |
Siemens SMART CCD diffractometer | 841 independent reflections |
Radiation source: fine-focus sealed tube | 616 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
φ and ω scans | θmax = 25.0°, θmin = 2.8° |
Absorption correction: mulit-scan (SADABS; Sheldrick, 1996) | h = −11→12 |
Tmin = 0.566, Tmax = 0.617 | k = −12→8 |
2819 measured reflections | l = −10→6 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-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 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
(C2H10N2)[ZnPO4]2 | Z = 4 |
Mr = 382.80 | Mo Kα radiation |
Tetragonal, P42/n | µ = 5.35 mm−1 |
a = 10.3940 (8) Å | T = 293 K |
c = 8.9094 (10) Å | 0.12 × 0.12 × 0.10 mm |
V = 962.53 (15) Å3 |
Siemens SMART CCD diffractometer | 841 independent reflections |
Absorption correction: mulit-scan (SADABS; Sheldrick, 1996) | 616 reflections with I > 2σ(I) |
Tmin = 0.566, Tmax = 0.617 | Rint = 0.056 |
2819 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.67 e Å−3 |
841 reflections | Δρmin = −0.66 e Å−3 |
55 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 1.11040 (8) | 0.87230 (8) | 0.33996 (9) | 0.0193 (3) | |
P1 | 1.11143 (19) | 0.59342 (19) | 0.2006 (2) | 0.0180 (5) | |
O1 | 1.0614 (7) | 0.7318 (6) | 0.2109 (7) | 0.0461 (18) | |
O2 | 1.0612 (6) | 0.8386 (6) | 0.5432 (6) | 0.0293 (14) | |
O3 | 0.9986 (6) | 1.0023 (6) | 0.2537 (7) | 0.0354 (16) | |
O4 | 1.2829 (5) | 0.9291 (6) | 0.3159 (6) | 0.0369 (16) | |
N1 | 1.3804 (7) | 1.1268 (7) | 0.5038 (9) | 0.032 (16) | |
H1A | 1.4138 | 1.0814 | 0.5790 | 0.047* | 0.45 |
H2A | 1.4422 | 1.1726 | 0.4598 | 0.047* | 0.45 |
H3A | 1.3454 | 1.0736 | 0.4371 | 0.047* | 0.45 |
H1B | 1.4146 | 1.0809 | 0.4295 | 0.047* | 0.55 |
H2B | 1.3480 | 1.0739 | 0.5727 | 0.047* | 0.55 |
H3B | 1.4410 | 1.1757 | 0.5454 | 0.047* | 0.55 |
C1 | 1.2800 (17) | 1.2149 (16) | 0.5630 (2) | 0.025 (7) | 0.45 |
H4A | 1.2129 | 1.1654 | 0.6120 | 0.030* | 0.45 |
H5A | 1.3175 | 1.2725 | 0.6366 | 0.030* | 0.45 |
C2 | 1.2739 (2) | 1.2120 (2) | 0.4420 (3) | 0.051 (8) | 0.55 |
H4B | 1.3566 | 1.2199 | 0.3924 | 0.061* | 0.55 |
H5B | 1.2268 | 1.1383 | 0.4040 | 0.061* | 0.55 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0177 (5) | 0.0194 (6) | 0.0206 (5) | 0.0019 (4) | 0.0008 (4) | 0.0003 (4) |
P1 | 0.0178 (11) | 0.0171 (11) | 0.0190 (10) | −0.0038 (8) | −0.0008 (8) | −0.0025 (8) |
O1 | 0.067 (5) | 0.028 (4) | 0.044 (4) | 0.007 (3) | −0.008 (3) | −0.014 (3) |
O2 | 0.036 (4) | 0.032 (3) | 0.020 (3) | −0.007 (3) | 0.000 (3) | −0.003 (3) |
O3 | 0.046 (4) | 0.033 (4) | 0.027 (3) | 0.024 (3) | −0.005 (3) | −0.004 (3) |
O4 | 0.019 (3) | 0.060 (4) | 0.032 (3) | −0.009 (3) | 0.008 (3) | −0.006 (3) |
N1 | 0.026 (4) | 0.030 (4) | 0.039 (4) | 0.006 (4) | −0.003 (3) | −0.002 (3) |
C1 | 0.024 (11) | 0.018 (12) | 0.031 (15) | 0.010 (8) | −0.016 (8) | −0.016 (7) |
C2 | 0.048 (15) | 0.052 (17) | 0.053 (18) | 0.006 (10) | 0.001 (10) | −0.002 (10) |
Zn1—O4 | 1.900 (6) | N1—H2A | 0.8900 |
Zn1—O2 | 1.914 (6) | N1—H3A | 0.8900 |
Zn1—O1 | 1.927 (6) | N1—H1B | 0.8900 |
Zn1—O3 | 1.941 (6) | N1—H2B | 0.8900 |
P1—O4i | 1.522 (6) | N1—H3B | 0.8900 |
P1—O2ii | 1.532 (6) | C1—C1vi | 0.9599 |
P1—O1 | 1.532 (7) | C1—C2 | 1.0803 |
P1—O3iii | 1.538 (6) | C1—C2vi | 1.4329 |
O2—P1iv | 1.532 (6) | C1—H4A | 0.9700 |
O3—P1v | 1.538 (6) | C1—H5A | 0.9700 |
O4—P1i | 1.522 (6) | C2—C2vi | 0.9332 |
N1—C1 | 1.4852 | C2—C1vi | 1.4329 |
N1—C2 | 1.5208 | C2—H4B | 0.9700 |
N1—H1A | 0.8900 | C2—H5B | 0.9700 |
O4—Zn1—O2 | 114.6 (2) | C1—N1—H3B | 89.8 |
O4—Zn1—O1 | 114.7 (3) | C2—N1—H3B | 109.5 |
O2—Zn1—O1 | 110.8 (3) | H1A—N1—H3B | 73.3 |
O4—Zn1—O3 | 107.7 (3) | H2A—N1—H3B | 50.8 |
O2—Zn1—O3 | 110.0 (3) | H3A—N1—H3B | 157.3 |
O1—Zn1—O3 | 97.7 (3) | H1B—N1—H3B | 109.5 |
O4i—P1—O2ii | 109.8 (3) | H2B—N1—H3B | 109.5 |
O4i—P1—O1 | 110.4 (4) | C1vi—C1—C2 | 89.0 |
O2ii—P1—O1 | 112.0 (4) | C1vi—C1—C2vi | 48.9 |
O4i—P1—O3iii | 104.9 (4) | C2—C1—C2vi | 40.6 |
O2ii—P1—O3iii | 110.9 (3) | C1vi—C1—N1 | 157.7 |
O1—P1—O3iii | 108.5 (4) | C2—C1—N1 | 70.7 |
P1—O1—Zn1 | 131.1 (4) | C2vi—C1—N1 | 109.5 |
P1iv—O2—Zn1 | 138.2 (4) | C1vi—C1—H4A | 86.3 |
P1v—O3—Zn1 | 141.3 (4) | C2—C1—H4A | 113.1 |
P1i—O4—Zn1 | 135.2 (4) | C2vi—C1—H4A | 109.8 |
C1—N1—C2 | 42.1 | N1—C1—H4A | 109.8 |
C1—N1—H1A | 109.5 | C1vi—C1—H5A | 78.0 |
C2—N1—H1A | 149.9 | C2—C1—H5A | 135.7 |
C1—N1—H2A | 109.5 | C2vi—C1—H5A | 109.8 |
C2—N1—H2A | 93.1 | N1—C1—H5A | 109.8 |
H1A—N1—H2A | 109.5 | H4A—C1—H5A | 108.2 |
C1—N1—H3A | 109.5 | C2vi—C2—C1 | 90.4 |
C2—N1—H3A | 79.8 | C2vi—C2—C1vi | 48.9 |
H1A—N1—H3A | 109.5 | C1—C2—C1vi | 42.0 |
H2A—N1—H3A | 109.5 | C2vi—C2—N1 | 151.7 |
C1—N1—H1B | 151.1 | C1—C2—N1 | 67.2 |
C2—N1—H1B | 109.5 | C1vi—C2—N1 | 108.7 |
H1A—N1—H1B | 96.9 | C2vi—C2—H4B | 113.6 |
H2A—N1—H1B | 70.8 | C1—C2—H4B | 113.6 |
H3A—N1—H1B | 48.2 | C1vi—C2—H4B | 130.1 |
C1—N1—H2B | 82.5 | N1—C2—H4B | 64.5 |
C2—N1—H2B | 109.5 | C2vi—C2—H5B | 113.6 |
H1A—N1—H2B | 45.7 | C1—C2—H5B | 113.6 |
H2A—N1—H2B | 155.1 | C1vi—C2—H5B | 118.9 |
H3A—N1—H2B | 85.5 | N1—C2—H5B | 91.9 |
H1B—N1—H2B | 109.5 | H4B—C2—H5B | 110.8 |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3iv | 0.89 | 1.99 | 2.874 (6) | 172 |
N1—H2A···O2vii | 0.89 | 2.12 | 2.924 (6) | 149 |
N1—H3A···O4 | 0.89 | 1.96 | 2.838 (6) | 168 |
N1—H3A···O3viii | 0.89 | 2.45 | 2.920 (7) | 113 |
N1—H1B···O3viii | 0.89 | 2.03 | 2.920 (7) | 173 |
N1—H1B···O4 | 0.89 | 2.32 | 2.838 (6) | 117 |
N1—H2B···O1iv | 0.89 | 2.23 | 3.101 (7) | 168 |
N1—H2B···O3iv | 0.89 | 2.40 | 2.874 (6) | 114 |
N1—H3B···O2vii | 0.89 | 2.25 | 2.924 (6) | 133 |
N1—H3B···O1vii | 0.89 | 2.57 | 3.345 (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. |
Experimental details
Crystal data | |
Chemical formula | (C2H10N2)[ZnPO4]2 |
Mr | 382.80 |
Crystal system, space group | Tetragonal, P42/n |
Temperature (K) | 293 |
a, c (Å) | 10.3940 (8), 8.9094 (10) |
V (Å3) | 962.53 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.35 |
Crystal size (mm) | 0.12 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD |
Absorption correction | Mulit-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.566, 0.617 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2819, 841, 616 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.128, 1.04 |
No. of reflections | 841 |
No. of parameters | 55 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.66 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.89 | 1.99 | 2.874 (6) | 172 |
N1—H2A···O2ii | 0.89 | 2.12 | 2.924 (6) | 149 |
N1—H3A···O4 | 0.89 | 1.96 | 2.838 (6) | 168 |
N1—H3A···O3iii | 0.89 | 2.45 | 2.920 (7) | 113 |
N1—H1B···O3iii | 0.89 | 2.03 | 2.920 (7) | 173 |
N1—H1B···O4 | 0.89 | 2.32 | 2.838 (6) | 117 |
N1—H2B···O1i | 0.89 | 2.23 | 3.101 (7) | 168 |
N1—H2B···O3i | 0.89 | 2.40 | 2.874 (6) | 114 |
N1—H3B···O2ii | 0.89 | 2.25 | 2.924 (6) | 133 |
N1—H3B···O1ii | 0.89 | 2.57 | 3.345 (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. |
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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).