The title compound contains HPO3 pseudo-pyramids [dav(P—O) = 1.516 (2) Å], ZnO4 tetrahedra [dav(Zn—O) = 1.939 (2) Å], and trans-ZnO2(H2O)4 octahedra. These building units link together by way of Zn—O—P bridges [θav = 128.1°], resulting in a layered structure.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (P-O) = 0.002 Å
- R factor = 0.026
- wR factor = 0.074
- Data-to-parameter ratio = 26.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.232 0.547
Tmin and Tmax expected: 0.183 0.503
RR = 1.167
Please check that your absorption correction is appropriate.
PLAT_420 Alert C D-H Without Acceptor P(2) - H(2) ?
PLAT_420 Alert C D-H Without Acceptor P(3) - H(3) ?
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: H11 N1 O11 P3 Zn2.5
Atom count from _chemical_formula_moiety:H88 N20 O4
ABSTM_02 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 0.919
Tmax scaled 0.503 Tmin scaled 0.213
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Crystal data top
(NH4)2Zn5(HPO3)6·4H2O | F(000) = 452 |
Mr = 457.43 | Dx = 2.469 Mg m−3 |
Triclinic, P1 | Melting point: decomposes before melting K |
a = 7.2263 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7728 (4) Å | Cell parameters from 3972 reflections |
c = 10.2349 (5) Å | θ = 2.5–32.4° |
α = 63.409 (1)° | µ = 5.29 mm−1 |
β = 87.162 (1)° | T = 293 K |
γ = 72.969 (1)° | Chunky plate, colourless |
V = 615.18 (5) Å3 | 0.39 × 0.28 × 0.13 mm |
Z = 2 | |
Data collection top
Bruker SMART 1000 CCD diffractometer | 4274 independent reflections |
Radiation source: fine-focus sealed tube | 3646 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
ω scans | θmax = 32.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −10→9 |
Tmin = 0.232, Tmax = 0.547 | k = −13→14 |
6425 measured reflections | l = −15→15 |
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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0457P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4274 reflections | Δρmax = 0.74 e Å−3 |
161 parameters | Δρmin = −0.64 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: 0.0101 (10) |
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 | Uiso*/Ueq | |
N1 | 0.2216 (3) | 0.0432 (3) | −0.1527 (2) | 0.0323 (4) | |
H4 | 0.0901 | 0.0626 | −0.1832 | 0.039* | |
H5 | 0.3153 | 0.0389 | −0.1983 | 0.039* | |
H6 | 0.2653 | −0.0598 | −0.0947 | 0.039* | |
H7 | 0.2341 | 0.0888 | −0.0898 | 0.039* | |
Zn1 | 0.33591 (3) | 0.70373 (3) | 0.33542 (2) | 0.02207 (7) | |
Zn2 | 0.36418 (3) | 0.35646 (3) | −0.01856 (2) | 0.02207 (7) | |
Zn3 | 0.5000 | 0.0000 | 0.5000 | 0.02457 (8) | |
P1 | 0.76267 (7) | 0.49691 (6) | 0.34845 (5) | 0.02117 (10) | |
H1 | 0.9357 | 0.4953 | 0.3861 | 0.025* | |
P2 | 0.23711 (8) | 0.59235 (7) | 0.11813 (6) | 0.02365 (11) | |
H2 | 0.0574 | 0.6545 | 0.0550 | 0.028* | |
P3 | 0.24927 (7) | 0.06249 (6) | 0.20335 (5) | 0.01984 (10) | |
H3 | 0.1040 | 0.1587 | 0.2343 | 0.024* | |
O1 | 0.6177 (2) | 0.65059 (19) | 0.3397 (2) | 0.0319 (3) | |
O2 | 0.7265 (3) | 0.34607 (19) | 0.46569 (17) | 0.0351 (4) | |
O3 | 0.7754 (3) | 0.4894 (2) | 0.20445 (17) | 0.0364 (4) | |
O4 | 0.3106 (3) | 0.42325 (19) | 0.13484 (17) | 0.0324 (3) | |
O5 | 0.3533 (2) | 0.7013 (2) | 0.01944 (19) | 0.0323 (3) | |
O6 | 0.2266 (3) | 0.5857 (2) | 0.2685 (2) | 0.0414 (4) | |
O7 | 0.2957 (2) | 0.15858 (18) | 0.04834 (15) | 0.0265 (3) | |
O8 | 0.1819 (2) | −0.07397 (18) | 0.21001 (17) | 0.0274 (3) | |
O9 | 0.4199 (3) | 0.0023 (2) | 0.31444 (18) | 0.0340 (4) | |
O10 | 0.2921 (3) | 0.2245 (2) | 0.4567 (2) | 0.0510 (5) | |
H8 | 0.3268 | 0.2750 | 0.4848 | 0.061* | |
H9 | 0.2797 | 0.3058 | 0.3576 | 0.061* | |
O11 | 0.6953 (4) | 0.1300 (3) | 0.3727 (3) | 0.0661 (7) | |
H10 | 0.7417 | 0.1837 | 0.3945 | 0.079* | |
H11 | 0.6129 | 0.2208 | 0.2671 | 0.079* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0287 (9) | 0.0375 (11) | 0.0332 (10) | −0.0132 (8) | 0.0030 (7) | −0.0161 (9) |
Zn1 | 0.02774 (13) | 0.01781 (11) | 0.01966 (11) | −0.00815 (9) | 0.00385 (9) | −0.00705 (9) |
Zn2 | 0.02897 (13) | 0.01842 (12) | 0.01929 (11) | −0.01069 (9) | 0.00455 (9) | −0.00702 (9) |
Zn3 | 0.03317 (19) | 0.02149 (16) | 0.02000 (15) | −0.00807 (13) | −0.00420 (13) | −0.00968 (13) |
P1 | 0.0217 (2) | 0.0181 (2) | 0.0202 (2) | −0.00656 (18) | 0.00270 (17) | −0.00547 (18) |
P2 | 0.0237 (2) | 0.0237 (2) | 0.0278 (2) | −0.0112 (2) | 0.00540 (19) | −0.0131 (2) |
P3 | 0.0243 (2) | 0.0155 (2) | 0.0177 (2) | −0.00576 (17) | −0.00058 (17) | −0.00565 (17) |
O1 | 0.0296 (8) | 0.0216 (7) | 0.0431 (9) | −0.0055 (6) | 0.0028 (7) | −0.0147 (7) |
O2 | 0.0637 (12) | 0.0225 (8) | 0.0216 (7) | −0.0202 (8) | 0.0127 (7) | −0.0087 (6) |
O3 | 0.0484 (10) | 0.0284 (8) | 0.0192 (7) | −0.0023 (7) | 0.0044 (7) | −0.0056 (6) |
O4 | 0.0533 (10) | 0.0239 (8) | 0.0237 (7) | −0.0148 (7) | 0.0073 (7) | −0.0124 (6) |
O5 | 0.0310 (8) | 0.0238 (8) | 0.0386 (9) | −0.0124 (6) | 0.0093 (7) | −0.0094 (7) |
O6 | 0.0604 (12) | 0.0510 (11) | 0.0409 (9) | −0.0385 (10) | 0.0248 (9) | −0.0334 (9) |
O7 | 0.0409 (9) | 0.0217 (7) | 0.0202 (6) | −0.0175 (6) | 0.0033 (6) | −0.0074 (6) |
O8 | 0.0273 (7) | 0.0191 (7) | 0.0307 (7) | −0.0104 (6) | −0.0039 (6) | −0.0043 (6) |
O9 | 0.0418 (9) | 0.0332 (9) | 0.0267 (7) | −0.0054 (7) | −0.0110 (7) | −0.0156 (7) |
O10 | 0.0651 (13) | 0.0243 (9) | 0.0544 (12) | 0.0010 (9) | −0.0233 (10) | −0.0161 (9) |
O11 | 0.111 (2) | 0.0719 (16) | 0.0597 (14) | −0.0694 (16) | 0.0384 (14) | −0.0449 (13) |
Geometric parameters (Å, º) top
N1—H4 | 0.9525 | Zn3—O11 | 2.166 (2) |
N1—H5 | 0.8048 | P1—O3 | 1.5050 (17) |
N1—H6 | 0.8733 | P1—O2 | 1.5140 (16) |
N1—H7 | 0.9526 | P1—O1 | 1.5260 (17) |
Zn1—O6 | 1.9283 (16) | P1—H1 | 1.3200 |
Zn1—O2i | 1.9325 (15) | P2—O6 | 1.5104 (18) |
Zn1—O1 | 1.9462 (17) | P2—O4 | 1.5114 (16) |
Zn1—O8ii | 1.9583 (15) | P2—O5 | 1.5281 (16) |
Zn2—O3iii | 1.9079 (16) | P2—H2 | 1.3200 |
Zn2—O4 | 1.9365 (15) | P3—O9 | 1.5079 (16) |
Zn2—O7 | 1.9480 (14) | P3—O7 | 1.5197 (15) |
Zn2—O5iii | 1.9529 (17) | P3—O8 | 1.5219 (15) |
Zn3—O9iv | 2.0014 (14) | P3—H3 | 1.3200 |
Zn3—O9 | 2.0014 (14) | O10—H8 | 0.7717 |
Zn3—O10 | 2.1290 (19) | O10—H9 | 0.9566 |
Zn3—O10iv | 2.1290 (19) | O11—H10 | 0.8084 |
Zn3—O11iv | 2.166 (2) | O11—H11 | 1.0981 |
| | | |
H4—N1—H5 | 128.6 | O3—P1—O2 | 109.52 (10) |
H4—N1—H6 | 105.4 | O3—P1—O1 | 113.71 (10) |
H5—N1—H6 | 91.0 | O2—P1—O1 | 113.08 (10) |
H4—N1—H7 | 113.4 | O3—P1—H1 | 106.7 |
H5—N1—H7 | 109.5 | O2—P1—H1 | 106.7 |
H6—N1—H7 | 102.7 | O1—P1—H1 | 106.7 |
O6—Zn1—O2i | 108.41 (7) | O6—P2—O4 | 109.10 (10) |
O6—Zn1—O1 | 114.27 (8) | O6—P2—O5 | 112.87 (10) |
O2i—Zn1—O1 | 106.63 (8) | O4—P2—O5 | 113.41 (10) |
O6—Zn1—O8ii | 102.07 (8) | O6—P2—H2 | 107.0 |
O2i—Zn1—O8ii | 107.23 (7) | O4—P2—H2 | 107.0 |
O1—Zn1—O8ii | 117.79 (7) | O5—P2—H2 | 107.0 |
O3iii—Zn2—O4 | 114.23 (7) | O9—P3—O7 | 111.59 (10) |
O3iii—Zn2—O7 | 109.52 (7) | O9—P3—O8 | 111.91 (9) |
O4—Zn2—O7 | 106.65 (6) | O7—P3—O8 | 109.55 (8) |
O3iii—Zn2—O5iii | 114.45 (8) | O9—P3—H3 | 107.9 |
O4—Zn2—O5iii | 104.69 (7) | O7—P3—H3 | 107.9 |
O7—Zn2—O5iii | 106.73 (7) | O8—P3—H3 | 107.9 |
O9iv—Zn3—O9 | 180.0 | P1—O1—Zn1 | 127.86 (10) |
O9iv—Zn3—O10 | 85.46 (7) | P1—O2—Zn1i | 129.28 (10) |
O9—Zn3—O10 | 94.54 (7) | P1—O3—Zn2iii | 128.74 (11) |
O9iv—Zn3—O10iv | 94.54 (7) | P2—O4—Zn2 | 127.96 (10) |
O9—Zn3—O10iv | 85.46 (7) | P2—O5—Zn2iii | 126.35 (10) |
O10—Zn3—O10iv | 180.0 | P2—O6—Zn1 | 125.97 (10) |
O9iv—Zn3—O11iv | 86.14 (8) | P3—O7—Zn2 | 124.65 (8) |
O9—Zn3—O11iv | 93.86 (8) | P3—O8—Zn1v | 119.29 (9) |
O10—Zn3—O11iv | 91.57 (10) | P3—O9—Zn3 | 143.17 (12) |
O10iv—Zn3—O11iv | 88.43 (10) | Zn3—O10—H8 | 114.5 |
O9iv—Zn3—O11 | 93.86 (8) | Zn3—O10—H9 | 114.5 |
O9—Zn3—O11 | 86.14 (8) | H8—O10—H9 | 90.9 |
O10—Zn3—O11 | 88.43 (10) | Zn3—O11—H10 | 125.1 |
O10iv—Zn3—O11 | 91.57 (10) | Zn3—O11—H11 | 106.4 |
O11iv—Zn3—O11 | 180.0 (2) | H10—O11—H11 | 101.0 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z+1; (v) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O8vi | 0.95 | 1.96 | 2.904 (2) | 170 |
N1—H5···O9vii | 0.80 | 2.23 | 3.035 (3) | 174 |
N1—H6···O5v | 0.87 | 2.00 | 2.865 (3) | 173 |
N1—H7···O7 | 0.95 | 1.94 | 2.887 (2) | 172 |
O10—H8···O1i | 0.77 | 2.31 | 3.022 (3) | 154 |
O10—H9···O4 | 0.96 | 2.08 | 3.004 (3) | 162 |
O10—H9···O6 | 0.96 | 2.38 | 3.069 (3) | 129 |
O11—H10···O2 | 0.81 | 2.00 | 2.742 (2) | 153 |
O11—H11···O4 | 1.10 | 2.43 | 3.410 (3) | 148 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (v) x, y−1, z; (vi) −x, −y, −z; (vii) −x+1, −y, −z. |