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A new inorganic–organic hybrid zinc phosphite, [Zn(HPO3)(C6H11NO2)]n, has been synthesized hydro­thermally. Proton­ated piperidin-1-ium-4-carboxyl­ate (PDCA) was generated in situ by hydrolysis of the piperidine-4-carboxamide precursor. The P atom possesses a typical PO3H pseudo-pyramidal geom­etry. The crystal structure features an unusual (3,4)-connected two-dimensional inorganic zinc–phosphite layer, with organic PDCA ligands appended to the sheets and protruding into the inter­layer region. Helical chains of opposite chirality are involved in the construction of a puckered sheet structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614003118/fg3318sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614003118/fg3318Isup2.hkl
Contains datablock I

CCDC reference: 986313

Introduction top

Zeolites and related crystalline microporous materials have been extensively investigated for decades due to their rich structural chemistry and wide range of applications in catalysis, separation, ion-exchange etc (Cheetham et al., 1999; Davis, 2002; Parnham & Morris, 2007; Jiang et al., 2010). Of the many known open-framework compounds, metal phosphites have recently attracted special inter­est because they show structural diversity and versatility similar to that of the phosphates. Compared with the 4-connected PO4 unit, the presence of a 3-connected HPO32- group can reduce the M—O—P connectivity and thus favours the generation of open structures with larger pore sizes. Prominent examples include a trimetallic phosphite, Zn2Al0.57Cr0.10(HPO3)4(C6H11NH3)2(H2O)4 (Cr-NKU-24), a low density beryllium phosphite, (C4H12N)2[Be3(HPO3)4] (SCU-24), and six zinc phosphites with 24-ring channels, an aluminium-zinc bimetallic phosphite, (C4H9NH3)2[AlFZn2(HPO3)4] (NTHU-5), with 26R channels, and recently reported gallium zincophosphites (the NTHU-13 family) with 28R, 40R, 48R, 56R, 64R and 72R channels (Liang et al., 2006; Lai et al., 2007; Yang et al., 2007; Li et al., 2008; Luo et al., 2011; Wang et al., 2012; Lin et al., 2013) [Please associate the references with the examples above]. Metal–phosphite frameworks are usually synthesized hydro­thermally using various organic amines as templates. In most cases, such organic moieties are protonated and serve as charge-compensating and space-filling constituents. In a few cases, organic molecules are neutral and bonded directly to the metal atoms to form inorganic–organic hybrid architectures (Rodgers & Harrison, 2000; Shi et al., 2003; Kirkpatrick & Harrison, 2004). Herein, we prepared a new hybrid open-framework zinc phosphite, nanemy poly[(µ3-hydrogen phosphito-κ3O:O':O')(piperidin-1-ium-4-carboxyl­ate-κO)zinc(II)], (I), in which the unusual N-protonated piperidin-1-ium-4-carboxyl­ate (PDCA) was generated in situ from the piperidine-4-carboxamide precursor.

Experimental top

Synthesis and crystallization top

The title compound was synthesized under mild solvothermal conditions. In a typical synthesis, a mixture of Zn(CH3COO)2.2H2O (1 mmol, 0.22 g), H3PO3 (5 mmol, 0.41 g), piperidine-4-carboxamide (3 mmol, 0.39 g), ethanol (51 mmol, 3 ml) and H2O (56 mmol, 2 ml) was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 428 K for 7 d. Colourless prism-like crystals were recovered by filtration, washed with distilled water and dried in air.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bound to C atoms were positioned geometrically, with C—H distances of 0.97 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). H atoms bound to P, O and N atoms were located in a difference Fourier map and treated as riding, with Uiso(H) = 1.2Ueq(P,O,N).

Results and discussion top

As shown in Fig. 1, the asymmetric unit of (I) contains one Zn2+ ion, one [HPO3]2- (hydrogen phosphite) unit and one PDCA ligand. A review of the literature shows that most ligands introduced into the hybrid metal phosphites are of direct use, and mainly feature as rigid oxalate- and bi­pyridine-type molecules. By contrast, reports on in situ hydro­(solvo)thermal ligand (template) syntheses in this area are still limited. Thus, the in situ formation of the PDCA ligand in (I) is unique. The Zn1 atom is in a distorted tetra­hedral geometry formed by three O atoms from three neighboring [HPO3]2- groups and one O atom from the PDCA ligand. The Zn—O bond lengths range from 1.947 (2) to 1.999 (2) Å, and the O—Zn—O angles lie in the 91.47 (9)–117.82 (10)° range. Atom P1 makes three P—O—Zn linkages with adjacent Zn atoms, with the fourth vertex occupied by a terminal H atom. The P—O bond lengths are in the range of 1.515 (2)–1.528 (2) Å, and the O—P—O angles span from 110.29 (12) to 113.75 (13)°.

Each tetra­hedral [HPO3]2- group is alternately linked to three neighbouring tetra­hedral ZnO4 groups to form a two-dimensional wave-like (ZnHPO3)n layer with unique eight- and 16-membered rings (Fig. 2). The Zn···Zn distances in the eight-membered ring is 4.3712 (5) Å, while the separation of the inversion related Zn atoms [at (x, y, z) and (-x+1, -y, -z+1)] in the 16-membered ring is 7.6703 (5) Å. Inter­estingly, two types of helices with opposite chirality are involved in the construction of the inorganic layer. One-dimensional infinite helical chains of opposite chirality, co-existing in the structure consisting of –Zn1—O1—P1—O2– and –Zn1—O2i—P1i—O1i– chains [symmetry code: (i) -x+1, y-1/2, -z+1/2] couple with each other by sharing the common O3 atoms to generate the zinc–phosphite layer. The central axis of each helical chain is a twofold screw axis along the crystallographic b axis. It is worth noting that similar layer structures made up of chains of opposite chirality are particularly rare in microporous materials. One typical example is (C5H6N2)Zn(HPO3), which also crystallized in the space group P21/c and an aromatic cyclic amine (pyridin-2-amine) was introduced (Jiang et al., 2003). The monoprotonated zwitterionic PDCA ligand in (I), adopting a monodentate coordination mode, is bonded to the tetra­hedral Zn centre and protrude away from the inorganic layers as pendent groups. Fig. 3 shows the packing of the layers along the [100] direction. The cyclic hydro­phobic rings of the PDCA ligands protrude toward the inter­layer region. Strong hydrogen bonds exist between the –NH2 groups of the piperidine rings and the bridging phosphite O2 and carboxyl­ate O5 atoms within the layer [N···O = 2.787 (4)–2.837 (4) Å], which inter­connect adjacent zinc–phosphite sheets into a three-dimensional supra­molecular framework.

Related literature top

For related literature, see: Cheetham et al. (1999); Davis (2002); Jiang et al. (2003, 2010); Kirkpatrick & Harrison (2004); Lai et al. (2007); Li et al. (2008); Liang et al. (2006); Lin et al. (2013); Luo et al. (2011); Parnham & Morris (2007); Rodgers & Harrison (2000); Shi et al. (2003); Wang et al. (2012); Yang et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. See Table 2 for symmetry codes.
[Figure 2] Fig. 2. A view of the two-dimensional zinc phosphite layer in the bc plane. [Symmetry codes: (v) -x+1, -y+1, -z+1; (vi) -x+1, -y, -z+1.]
[Figure 3] Fig. 3. The packing of the wave-like layers of (I) along the [100] direction.
Poly[(µ3-hydrogen phosphito-κ3O:O':O')(piperidin-1-ium-4-carboxylate-κO)zinc(II)] top
Crystal data top
[Zn(HPO3)(C6H11NO2)]F(000) = 560
Mr = 274.51Dx = 1.858 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9838 reflections
a = 10.2729 (3) Åθ = 3.0–27.5°
b = 9.8483 (5) ŵ = 2.66 mm1
c = 10.6510 (3) ÅT = 295 K
β = 114.368 (4)°Prism, colourless
V = 981.57 (6) Å30.18 × 0.16 × 0.12 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer
2245 independent reflections
Radiation source: fine-focus sealed tube1948 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
φ and ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.646, Tmax = 0.741k = 1212
9838 measured reflectionsl = 1313
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0324P)2 + 0.3072P]
where P = (Fo2 + 2Fc2)/3
2245 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.83 e Å3
Crystal data top
[Zn(HPO3)(C6H11NO2)]V = 981.57 (6) Å3
Mr = 274.51Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.2729 (3) ŵ = 2.66 mm1
b = 9.8483 (5) ÅT = 295 K
c = 10.6510 (3) Å0.18 × 0.16 × 0.12 mm
β = 114.368 (4)°
Data collection top
Bruker APEXII area-detector
diffractometer
2245 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1948 reflections with I > 2σ(I)
Tmin = 0.646, Tmax = 0.741Rint = 0.086
9838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.09Δρmax = 0.51 e Å3
2245 reflectionsΔρmin = 0.83 e Å3
127 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
Zn10.59984 (4)0.09765 (3)0.20238 (3)0.02282 (15)
P10.56544 (9)0.32106 (8)0.40558 (8)0.0219 (2)
H10.69200.33520.46300.026*
O10.5465 (2)0.1791 (2)0.3426 (2)0.0275 (5)
O20.5000 (3)0.4281 (2)0.2952 (2)0.0381 (6)
O30.5101 (2)0.3250 (2)0.5181 (2)0.0305 (5)
O40.8064 (2)0.0573 (3)0.2548 (2)0.0388 (6)
O50.8103 (3)0.2806 (3)0.2693 (3)0.0553 (8)
C11.2002 (4)0.1373 (4)0.1882 (4)0.0416 (9)
H1A1.20930.11010.10470.050*
H1B1.23570.22950.21000.050*
C21.2730 (4)0.0739 (4)0.4343 (4)0.0375 (9)
H2A1.31270.16260.46870.045*
H2B1.32640.00680.50300.045*
C31.1170 (4)0.0700 (4)0.4119 (3)0.0329 (8)
H3A1.10930.09410.49690.039*
H3B1.08000.02130.38690.039*
C41.0443 (4)0.1332 (4)0.1641 (4)0.0394 (9)
H4A1.00600.04320.13340.047*
H4B0.99060.19750.09240.047*
C51.0278 (3)0.1687 (4)0.2979 (3)0.0318 (8)
H51.06620.26030.32610.038*
C60.8708 (4)0.1703 (4)0.2727 (3)0.0334 (8)
N11.2879 (3)0.0454 (3)0.3033 (3)0.0373 (7)
H1C1.38040.05390.31830.045*
H1D1.26170.04110.27800.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0280 (2)0.0227 (2)0.0242 (2)0.00042 (15)0.01722 (18)0.00089 (13)
P10.0270 (4)0.0213 (4)0.0231 (4)0.0013 (3)0.0161 (3)0.0020 (3)
O10.0382 (13)0.0209 (12)0.0334 (11)0.0017 (10)0.0248 (10)0.0041 (9)
O20.0621 (18)0.0270 (13)0.0383 (13)0.0166 (12)0.0338 (13)0.0090 (10)
O30.0410 (14)0.0325 (13)0.0275 (11)0.0077 (11)0.0237 (10)0.0069 (9)
O40.0264 (13)0.0436 (16)0.0504 (15)0.0007 (12)0.0200 (12)0.0056 (12)
O50.0499 (17)0.0443 (18)0.086 (2)0.0152 (14)0.0422 (16)0.0042 (15)
C10.036 (2)0.059 (3)0.039 (2)0.0049 (19)0.0246 (17)0.0136 (18)
C20.033 (2)0.043 (2)0.040 (2)0.0021 (17)0.0179 (17)0.0096 (16)
C30.0321 (19)0.041 (2)0.0294 (17)0.0012 (16)0.0163 (15)0.0056 (15)
C40.0278 (19)0.059 (3)0.0343 (18)0.0037 (18)0.0158 (16)0.0089 (17)
C50.0275 (18)0.033 (2)0.0391 (18)0.0020 (15)0.0184 (15)0.0013 (15)
C60.0283 (18)0.045 (2)0.0323 (17)0.0080 (17)0.0178 (15)0.0064 (15)
N10.0297 (16)0.0384 (18)0.0529 (18)0.0018 (14)0.0262 (15)0.0051 (14)
Geometric parameters (Å, º) top
Zn1—O11.9623 (19)C1—H1B0.9700
Zn1—O2i1.965 (2)C2—N11.492 (4)
Zn1—O3ii1.947 (2)C2—C31.521 (5)
Zn1—O41.999 (2)C2—H2A0.9700
P1—O11.528 (2)C2—H2B0.9700
P1—O21.515 (2)C3—C51.529 (5)
P1—O31.524 (2)C3—H3A0.9700
P1—H11.1950C3—H3B0.9700
O2—Zn1iii1.965 (2)C4—C51.544 (4)
O3—Zn1iv1.947 (2)C4—H4A0.9700
O4—C61.268 (4)C4—H4B0.9700
O5—C61.245 (4)C5—C61.522 (4)
C1—N11.490 (4)C5—H50.9800
C1—C41.514 (5)N1—H1C0.9000
C1—H1A0.9700N1—H1D0.9000
O3ii—Zn1—O1116.28 (9)C2—C3—C5110.9 (3)
O3ii—Zn1—O2i108.26 (10)C2—C3—H3A109.5
O1—Zn1—O2i91.47 (9)C5—C3—H3A109.5
O3ii—Zn1—O4111.45 (9)C2—C3—H3B109.5
O1—Zn1—O4117.82 (10)C5—C3—H3B109.5
O2i—Zn1—O4109.10 (11)H3A—C3—H3B108.1
O2—P1—O3113.75 (13)C1—C4—C5110.4 (3)
O2—P1—O1111.16 (13)C1—C4—H4A109.6
O3—P1—O1110.29 (12)C5—C4—H4A109.6
O2—P1—H1110.9C1—C4—H4B109.6
O3—P1—H1105.9C5—C4—H4B109.6
O1—P1—H1104.3H4A—C4—H4B108.1
P1—O1—Zn1133.06 (13)C6—C5—C3113.0 (3)
P1—O2—Zn1iii130.39 (14)C6—C5—C4110.6 (3)
P1—O3—Zn1iv128.88 (14)C3—C5—C4109.3 (3)
C6—O4—Zn1107.2 (2)C6—C5—H5107.9
N1—C1—C4111.2 (3)C3—C5—H5107.9
N1—C1—H1A109.4C4—C5—H5107.9
C4—C1—H1A109.4O5—C6—O4122.6 (3)
N1—C1—H1B109.4O5—C6—C5119.6 (3)
C4—C1—H1B109.4O4—C6—C5117.8 (3)
H1A—C1—H1B108.0C1—N1—C2113.2 (3)
N1—C2—C3110.9 (3)C1—N1—H1C108.9
N1—C2—H2A109.5C2—N1—H1C108.9
C3—C2—H2A109.5C1—N1—H1D108.9
N1—C2—H2B109.5C2—N1—H1D108.9
C3—C2—H2B109.5H1C—N1—H1D107.7
H2A—C2—H2B108.0
O2—P1—O1—Zn156.2 (2)N1—C1—C4—C556.1 (4)
O3—P1—O1—Zn1176.67 (16)C2—C3—C5—C6179.2 (3)
O3ii—Zn1—O1—P163.1 (2)C2—C3—C5—C457.2 (4)
O2i—Zn1—O1—P1174.33 (19)C1—C4—C5—C6177.7 (3)
O4—Zn1—O1—P173.1 (2)C1—C4—C5—C357.3 (4)
O3—P1—O2—Zn1iii19.0 (3)Zn1—O4—C6—O56.1 (4)
O1—P1—O2—Zn1iii144.26 (18)Zn1—O4—C6—C5173.3 (2)
O2—P1—O3—Zn1iv100.6 (2)C3—C5—C6—O5129.9 (3)
O1—P1—O3—Zn1iv133.71 (16)C4—C5—C6—O5107.3 (4)
O3ii—Zn1—O4—C670.4 (2)C3—C5—C6—O450.7 (4)
O1—Zn1—O4—C667.8 (2)C4—C5—C6—O472.2 (4)
O2i—Zn1—O4—C6170.15 (19)C4—C1—N1—C255.3 (4)
N1—C2—C3—C555.8 (4)C3—C2—N1—C154.8 (4)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1v0.902.032.837 (4)148
N1—H1D···O5vi0.901.892.787 (4)174
Symmetry codes: (v) x+1, y, z; (vi) x+2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(HPO3)(C6H11NO2)]
Mr274.51
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)10.2729 (3), 9.8483 (5), 10.6510 (3)
β (°) 114.368 (4)
V3)981.57 (6)
Z4
Radiation typeMo Kα
µ (mm1)2.66
Crystal size (mm)0.18 × 0.16 × 0.12
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.646, 0.741
No. of measured, independent and
observed [I > 2σ(I)] reflections
9838, 2245, 1948
Rint0.086
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.099, 1.09
No. of reflections2245
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.51, 0.83

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Zn1—O11.9623 (19)P1—O11.528 (2)
Zn1—O2i1.965 (2)P1—O21.515 (2)
Zn1—O3ii1.947 (2)P1—O31.524 (2)
Zn1—O41.999 (2)
O3ii—Zn1—O1116.28 (9)O2i—Zn1—O4109.10 (11)
O3ii—Zn1—O2i108.26 (10)O2—P1—O3113.75 (13)
O1—Zn1—O2i91.47 (9)O2—P1—O1111.16 (13)
O3ii—Zn1—O4111.45 (9)O3—P1—O1110.29 (12)
O1—Zn1—O4117.82 (10)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1iii0.902.032.837 (4)148.0
N1—H1D···O5iv0.901.892.787 (4)173.6
Symmetry codes: (iii) x+1, y, z; (iv) x+2, y1/2, z+1/2.
 

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