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NaZn(H2PO3)3·H2O contains zigzag chains of edge-sharing alternating NaO6 [dav(Na-O) = 2.452 (2) Å] and ZnO6 [dav(Zn-O) = 2.104 (2) Å] octahedra, crosslinked by H2PO3 pseudo-pyramids [dav(P-OZn) = 1.501 (2) Å and dav(P-OH) = 1.572 (2) Å]. It is isostructural with NaM(H2PO3)3·H2O (M = Mn, Co).
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (P-O) = 0.001 Å
- R factor = 0.025
- wR factor = 0.057
- Data-to-parameter ratio = 26.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor P(1) - H(1) ?
PLAT_420 Alert C D-H Without Acceptor P(2) - H(2) ?
PLAT_420 Alert C D-H Without Acceptor P(3) - H(3) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Solutions I and II were made up as follows. I: NaOH (2.5 mmol) + H3PO3 (2.5 mmol) in 10 ml water; II: ZnO (2.5 mmol) + H3PO3 (1.5 mmol) in 10 ml
water. They were mixed in a 1:1.5 ratio, stirred for 6 h, and the resulting
clear solution was left to stand at room temperature. After two weeks,
colourless lozenge-shaped crystals of the title compound were recovered by
filtration and washing with 80% ethanol solution.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); 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
NaZn(H2PO3)3·H2O | Dx = 2.342 Mg m−3 |
Mr = 349.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 5338 reflections |
a = 9.0609 (4) Å | θ = 2.7–32.5° |
b = 14.7671 (6) Å | µ = 3.04 mm−1 |
c = 14.8106 (6) Å | T = 298 K |
V = 1981.71 (14) Å3 | Cut chunk, colourless |
Z = 8 | 0.23 × 0.20 × 0.13 mm |
F(000) = 1392 | |
Data collection top
Bruker SMART 1000 CCD diffractometer | 3585 independent reflections |
Radiation source: fine-focus sealed tube | 2756 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 32.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −7→13 |
Tmin = 0.541, Tmax = 0.693 | k = −18→22 |
16277 measured reflections | l = −22→21 |
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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0263P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.001 |
3585 reflections | Δρmax = 0.42 e Å−3 |
137 parameters | Δρmin = −0.38 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: 0.00347 (18) |
Crystal data top
NaZn(H2PO3)3·H2O | V = 1981.71 (14) Å3 |
Mr = 349.33 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.0609 (4) Å | µ = 3.04 mm−1 |
b = 14.7671 (6) Å | T = 298 K |
c = 14.8106 (6) Å | 0.23 × 0.20 × 0.13 mm |
Data collection top
Bruker SMART 1000 CCD diffractometer | 3585 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2756 reflections with I > 2σ(I) |
Tmin = 0.541, Tmax = 0.693 | Rint = 0.044 |
16277 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.42 e Å−3 |
3585 reflections | Δρmin = −0.38 e Å−3 |
137 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 | x | y | z | Uiso*/Ueq | |
Na1 | 0.06203 (9) | 0.15826 (5) | 0.43140 (6) | 0.02699 (18) | |
Zn1 | 0.44787 (2) | 0.159229 (13) | 0.454618 (13) | 0.01433 (6) | |
P1 | 0.23667 (5) | 0.22366 (3) | 0.61899 (3) | 0.01382 (9) | |
H1 | 0.2280 | 0.1417 | 0.6543 | 0.017* | |
P2 | 0.46060 (5) | 0.03033 (3) | 0.26273 (3) | 0.01518 (9) | |
H2 | 0.3152 | 0.0348 | 0.2601 | 0.018* | |
P3 | 0.27067 (5) | −0.03047 (3) | 0.49123 (3) | 0.01535 (9) | |
H3 | 0.2504 | −0.0383 | 0.5791 | 0.018* | |
O1 | 0.38120 (13) | 0.22998 (8) | 0.57018 (9) | 0.0189 (3) | |
O2 | 0.51353 (15) | 0.10242 (9) | 0.32712 (9) | 0.0230 (3) | |
O3 | 0.59411 (14) | 0.08450 (8) | 0.53245 (9) | 0.0203 (3) | |
O4 | 0.27611 (13) | 0.06871 (8) | 0.47007 (9) | 0.0201 (3) | |
O5 | 0.59986 (13) | 0.26144 (8) | 0.43594 (8) | 0.0183 (3) | |
O6 | 0.28586 (14) | 0.23966 (8) | 0.38093 (9) | 0.0224 (3) | |
H6A | 0.2888 | 0.2343 | 0.3236 | 0.027* | |
H6B | 0.3061 | 0.2903 | 0.3913 | 0.027* | |
O7 | 0.23906 (14) | 0.29349 (10) | 0.69963 (9) | 0.0254 (3) | |
H7 | 0.1625 | 0.3354 | 0.6943 | 0.030* | |
O8 | 0.50331 (17) | −0.06669 (9) | 0.29648 (10) | 0.0321 (3) | |
H8 | 0.4824 | −0.0728 | 0.3541 | 0.039* | |
O9 | 0.51572 (15) | 0.03950 (9) | 0.16814 (9) | 0.0227 (3) | |
O10 | 0.13259 (16) | −0.07348 (9) | 0.44355 (11) | 0.0336 (4) | |
H10 | 0.0985 | −0.0378 | 0.3994 | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Na1 | 0.0220 (4) | 0.0275 (4) | 0.0315 (4) | 0.0084 (3) | −0.0075 (3) | −0.0132 (3) |
Zn1 | 0.01300 (9) | 0.01432 (10) | 0.01566 (10) | −0.00044 (8) | 0.00002 (7) | −0.00097 (7) |
P1 | 0.01267 (19) | 0.01518 (19) | 0.0136 (2) | 0.00119 (16) | 0.00018 (15) | 0.00091 (16) |
P2 | 0.0156 (2) | 0.0168 (2) | 0.0132 (2) | −0.00082 (17) | 0.00099 (15) | −0.00083 (16) |
P3 | 0.01327 (19) | 0.0142 (2) | 0.0186 (2) | −0.00023 (17) | −0.00110 (15) | 0.00196 (16) |
O1 | 0.0145 (6) | 0.0221 (6) | 0.0201 (6) | −0.0023 (5) | 0.0033 (5) | −0.0054 (5) |
O2 | 0.0243 (7) | 0.0248 (7) | 0.0200 (7) | −0.0057 (6) | 0.0024 (5) | −0.0068 (5) |
O3 | 0.0225 (6) | 0.0175 (6) | 0.0208 (7) | 0.0077 (5) | 0.0002 (5) | 0.0017 (5) |
O4 | 0.0146 (6) | 0.0118 (5) | 0.0341 (8) | 0.0001 (5) | −0.0019 (5) | −0.0001 (5) |
O5 | 0.0158 (6) | 0.0183 (6) | 0.0208 (6) | −0.0037 (5) | 0.0050 (5) | −0.0049 (5) |
O6 | 0.0307 (7) | 0.0190 (6) | 0.0175 (7) | 0.0034 (6) | −0.0042 (5) | −0.0019 (5) |
O7 | 0.0239 (7) | 0.0353 (8) | 0.0170 (7) | 0.0116 (6) | −0.0054 (5) | −0.0091 (6) |
O8 | 0.0532 (10) | 0.0197 (7) | 0.0234 (7) | 0.0066 (7) | 0.0065 (6) | 0.0051 (6) |
O9 | 0.0309 (7) | 0.0219 (6) | 0.0153 (6) | 0.0013 (6) | 0.0053 (5) | 0.0009 (5) |
O10 | 0.0295 (8) | 0.0177 (6) | 0.0536 (10) | −0.0083 (6) | −0.0220 (7) | 0.0109 (6) |
Geometric parameters (Å, º) top
Na1—O5i | 2.3203 (14) | P1—H1 | 1.32 |
Na1—O1i | 2.3257 (14) | P2—O9 | 1.4935 (13) |
Na1—O9ii | 2.3292 (15) | P2—O2 | 1.5075 (13) |
Na1—O4 | 2.4165 (14) | P2—O8 | 1.5659 (14) |
Na1—O6 | 2.4733 (16) | P2—H2 | 1.32 |
Na1—O10iii | 2.8473 (18) | P3—O4 | 1.4985 (13) |
Zn1—O5 | 2.0618 (12) | P3—O3iv | 1.5035 (13) |
Zn1—O4 | 2.0643 (12) | P3—O10 | 1.5708 (14) |
Zn1—O3 | 2.0743 (12) | P3—H3 | 1.32 |
Zn1—O1 | 2.0942 (12) | O6—H6A | 0.8530 |
Zn1—O2 | 2.1503 (13) | O6—H6B | 0.7846 |
Zn1—O6 | 2.1810 (13) | O7—H7 | 0.9327 |
P1—O1 | 1.4987 (13) | O8—H8 | 0.8793 |
P1—O5i | 1.4990 (13) | O10—H10 | 0.8943 |
P1—O7 | 1.5780 (14) | | |
| | | |
O5i—Na1—O1i | 75.52 (5) | O9—P2—O2 | 115.02 (8) |
O5i—Na1—O9ii | 161.33 (6) | O9—P2—O8 | 107.44 (8) |
O1i—Na1—O9ii | 113.64 (5) | O2—P2—O8 | 111.44 (8) |
O5i—Na1—O4 | 87.73 (5) | O9—P2—H2 | 107.5 |
O1i—Na1—O4 | 162.99 (6) | O2—P2—H2 | 107.5 |
O9ii—Na1—O4 | 83.26 (5) | O8—P2—H2 | 107.5 |
O5i—Na1—O6 | 83.48 (5) | O4—P3—O3iv | 116.30 (8) |
O1i—Na1—O6 | 103.28 (5) | O4—P3—O10 | 109.11 (7) |
O9ii—Na1—O6 | 108.81 (6) | O3iv—P3—O10 | 109.24 (8) |
O4—Na1—O6 | 71.30 (5) | O4—P3—H3 | 107.3 |
O5i—Na1—O10iii | 76.43 (5) | O3iv—P3—H3 | 107.3 |
O1i—Na1—O10iii | 83.24 (5) | O10—P3—H3 | 107.3 |
O9ii—Na1—O10iii | 88.23 (5) | P1—O1—Zn1 | 127.97 (7) |
O4—Na1—O10iii | 95.87 (5) | P2—O2—Zn1 | 137.98 (8) |
O6—Na1—O10iii | 156.66 (5) | P3iv—O3—Zn1 | 132.32 (8) |
O5—Zn1—O4 | 172.96 (5) | P3—O4—Zn1 | 132.91 (8) |
O5—Zn1—O3 | 92.14 (5) | P1v—O5—Zn1 | 137.11 (8) |
O4—Zn1—O3 | 94.33 (5) | P1—O1—Na1v | 131.65 (7) |
O5—Zn1—O1 | 86.40 (5) | Zn1—O1—Na1v | 98.20 (5) |
O4—Zn1—O1 | 90.86 (5) | P3—O4—Na1 | 123.92 (7) |
O3—Zn1—O1 | 89.74 (5) | Zn1—O4—Na1 | 102.97 (5) |
O5—Zn1—O2 | 89.02 (5) | P1v—O5—Na1v | 120.44 (7) |
O4—Zn1—O2 | 93.06 (5) | Zn1—O5—Na1v | 99.31 (5) |
O3—Zn1—O2 | 95.95 (5) | Zn1—O6—Na1 | 97.82 (5) |
O1—Zn1—O2 | 172.82 (5) | Zn1—O6—H6A | 115.2 |
O5—Zn1—O6 | 89.07 (5) | Na1—O6—H6A | 106.3 |
O4—Zn1—O6 | 84.30 (5) | Zn1—O6—H6B | 105.2 |
O3—Zn1—O6 | 176.21 (5) | Na1—O6—H6B | 126.5 |
O1—Zn1—O6 | 86.74 (5) | H6A—O6—H6B | 106.1 |
O2—Zn1—O6 | 87.66 (5) | P1—O7—H7 | 111.1 |
O1—P1—O5i | 116.85 (8) | P2—O8—H8 | 110.5 |
O1—P1—O7 | 108.21 (7) | P2—O9—Na1vi | 136.24 (8) |
O5i—P1—O7 | 109.04 (7) | P3—O10—Na1iii | 112.25 (8) |
O1—P1—H1 | 107.5 | P3—O10—H10 | 111.5 |
O5i—P1—H1 | 107.5 | Na1iii—O10—H10 | 121.4 |
O7—P1—H1 | 107.5 | | |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) x+1/2, −y+1/2, −z+1; (vi) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7vii | 0.85 | 1.93 | 2.7622 (19) | 163 |
O6—H6B···O10viii | 0.78 | 2.23 | 3.0034 (19) | 171 |
O7—H7···O2i | 0.93 | 1.66 | 2.5875 (18) | 170 |
O8—H8···O3iv | 0.88 | 1.83 | 2.696 (2) | 170 |
O10—H10···O9ii | 0.89 | 1.69 | 2.5771 (19) | 169 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+1/2; (iv) −x+1, −y, −z+1; (vii) x, −y+1/2, z−1/2; (viii) −x+1/2, y+1/2, z. |
Experimental details
Crystal data |
Chemical formula | NaZn(H2PO3)3·H2O |
Mr | 349.33 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 9.0609 (4), 14.7671 (6), 14.8106 (6) |
V (Å3) | 1981.71 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.04 |
Crystal size (mm) | 0.23 × 0.20 × 0.13 |
|
Data collection |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.541, 0.693 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16277, 3585, 2756 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.057, 0.94 |
No. of reflections | 3585 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.38 |
Selected geometric parameters (Å, º) topNa1—O5i | 2.3203 (14) | Zn1—O6 | 2.1810 (13) |
Na1—O1i | 2.3257 (14) | P1—O1 | 1.4987 (13) |
Na1—O9ii | 2.3292 (15) | P1—O5i | 1.4990 (13) |
Na1—O4 | 2.4165 (14) | P1—O7 | 1.5780 (14) |
Na1—O6 | 2.4733 (16) | P2—O9 | 1.4935 (13) |
Na1—O10iii | 2.8473 (18) | P2—O2 | 1.5075 (13) |
Zn1—O5 | 2.0618 (12) | P2—O8 | 1.5659 (14) |
Zn1—O4 | 2.0643 (12) | P3—O4 | 1.4985 (13) |
Zn1—O3 | 2.0743 (12) | P3—O3iv | 1.5035 (13) |
Zn1—O1 | 2.0942 (12) | P3—O10 | 1.5708 (14) |
Zn1—O2 | 2.1503 (13) | | |
| | | |
P1—O1—Zn1 | 127.97 (7) | P3—O4—Zn1 | 132.91 (8) |
P2—O2—Zn1 | 137.98 (8) | P1v—O5—Zn1 | 137.11 (8) |
P3iv—O3—Zn1 | 132.32 (8) | | |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7vi | 0.85 | 1.93 | 2.7622 (19) | 163.1 |
O6—H6B···O10vii | 0.78 | 2.23 | 3.0034 (19) | 170.8 |
O7—H7···O2i | 0.93 | 1.66 | 2.5875 (18) | 170.4 |
O8—H8···O3iv | 0.88 | 1.83 | 2.696 (2) | 170.1 |
O10—H10···O9ii | 0.89 | 1.69 | 2.5771 (19) | 169.0 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+1/2; (iv) −x+1, −y, −z+1; (vi) x, −y+1/2, z−1/2; (vii) −x+1/2, y+1/2, z. |
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Only a few mixed-metal phosphites containing sodium and a transition metal have been reported, including the isostructural NaCo(H2PO3)3·H2O (Kratochvil et al., 1982) and NaMn(H2PO3)3·H2O (Chmelikova et al., 1986). Here, we report the synthesis and structure of the third member of this family, NaZn(H2PO3)3·H2O, as part of our ongoing investigations of Na—M—H3PO3 (M = divalent transition metal) systems.
The zinc cation is octahedrally coordinated with dav(Zn—O) = 2.104 (2) Å. Five of the O atoms bridge to phosphite P atoms (θav = 133.7°) and the remaining atom (O6) is part of a water molecule. A similar average Zn—O distance of 2.115 Å is found in in Zn(H2PO3)2·3H2O (Ortiz-Avila et al., 1989).
The three unique PIII atoms are coordinated by three O atoms in pseudo-pyramidal geometry, with a terminal H atom [d(P—H) = 1.32 Å] occupying the fourth tetrahedral vertex. P1 and P3 possess one P—OH vertex and make two P—O—Zn bridges; P2 has one terminal P═O9 bond, one P—OH bond, and makes one P—O—Zn link. The average P—-OZn and P—OH bond lengths are 1.501 (2) and 1.572 (2) Å, respectively. These P—O and P—OH distances are similar to their equivalent values in NaMn(H2PO3)3·H2O and NaCo(H2PO3)3·H2O (1.500 and 1.574 Å, and 1.496 and 1.567 Å, respectively).
The Na1 coordination can be described as distorted octahedral with one Na—O vertex significantly longer than the other five. The bond-valence sum (Brown, 1996) for sodium of 1.15 (ideal value = 1.00) indicates that its valence is satisfied by this coordination. The average Na—O separation of 2.452 (2) Å is similar to that found in NaMn(H2PO3)3·H2O (2.442 Å) and NaCo(H2PO3)3·H2O (2.443 Å).
The polyhedral connectivity in NaZn(H2PO3)3·H2O consists of zigzag chains of alternating ZnO6 and NaO6 octahedra, sharing edges by way of O1···O5 and O4···O6 pairs. The chains propagate along [100]. The octahedral chains are crosslinked by the phosphite moieties: the P2-centred group links adjacent chains in the c direction, and the P3 group fuses the chains in the b direction. Various P—OH···O and OwH···O (w is water) hydrogen bonds also stabilize the structure, as described previously (Chmelikova et al., 1986).