Coordination polymers are constructed from two basic components, namely metal ions, or metal-ion clusters, and bridging organic ligands. Their structures may also contain other auxiliary components, such as blocking ligands, counter-ions and nonbonding guest or template molecules. The choice or design of a suitable linker is essential. The new title zinc(II) coordination polymer, [Zn(C
5H
5NO
3P)Cl]
n, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction and vibrational spectroscopy (FT–IR and FT–Raman). Additionally, computational methods have been applied to derive quantitative information about interactions present in the solid state. The compound crystallizes in the monoclinic space group
C2/
c. The four-coordinated Zn
II cation is in a distorted tetrahedral environment, formed by three phosphonate O atoms from three different (pyridin-1-ium-3-yl)phosphonate ligands and one chloride anion. The Zn
II ions are extended by phosphonate ligands to generate a ladder chain along the [001] direction. Adjacent ladders are held together
via N—H
O hydrogen bonds and offset face-to-face π–π stacking interactions, forming a three-dimensional supramolecular network with channels. As calculated, the interaction energy between the neighbouring ladders is −115.2 kJ mol
−1. In turn, the cohesive energy evaluated per asymmetric unit-equivalent fragment of a polymeric chain in the crystal structure is −205.4 kJ mol
−1. This latter value reflects the numerous hydrogen bonds stabilizing the three-dimensional packing of the coordination chains.
Supporting information
CCDC reference: 1524251
Data collection: CrysAlis CCD (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis RED (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis RED (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
catena-Poly[chlorido[µ
3-(pyridin-1-ium-3-yl)phosphonato-
κ3O:
O':
O'']zinc(II)]
top
Crystal data top
| [Zn(C5H5NO3P)Cl] | F(000) = 1024 |
| Mr = 258.89 | Dx = 1.879 Mg m−3
Dm = 1.87 Mg m−3
Dm measured by floatation |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 15.260 (3) Å | Cell parameters from 1525 reflections |
| b = 11.750 (2) Å | θ = 3.1–28.0° |
| c = 10.334 (2) Å | µ = 3.12 mm−1 |
| β = 99.04 (3)° | T = 295 K |
| V = 1830.0 (7) Å3 | Parallelepiped, colourless |
| Z = 8 | 0.22 × 0.15 × 0.12 mm |
Data collection top
Kuma KM-4-CCD
diffractometer | 2323 independent reflections |
| Radiation source: fine-focus sealed tube | 1633 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.048 |
| Detector resolution: 10.6249 pixels mm-1 | θmax = 29.3°, θmin = 3.1° |
| ω–scan | h = −20→20 |
Absorption correction: multi-scan
CrysAlis PRO (Rigaku Oxford Diffraction, 2015) | k = −15→16 |
| Tmin = 0.832, Tmax = 1.000 | l = −14→12 |
| 11615 measured reflections | |
Refinement top
| 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)] = 0.035 | Hydrogen site location: mixed |
| wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0321P)2]
where P = (Fo2 + 2Fc2)/3 |
| 2323 reflections | (Δ/σ)max < 0.001 |
| 112 parameters | Δρmax = 0.87 e Å−3 |
| 0 restraints | Δρmin = −0.45 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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 | |
| Zn1 | 0.42687 (2) | 0.36427 (3) | 0.06577 (3) | 0.02247 (11) | |
| P3 | 0.62388 (4) | 0.45705 (6) | 0.16647 (7) | 0.02085 (17) | |
| Cl1 | 0.38814 (7) | 0.18155 (8) | 0.05663 (9) | 0.0508 (2) | |
| O31 | 0.55492 (13) | 0.37996 (17) | 0.0913 (2) | 0.0310 (5) | |
| O32 | 0.62312 (13) | 0.46205 (17) | 0.31321 (17) | 0.0282 (5) | |
| O33 | 0.62269 (12) | 0.57743 (17) | 0.11052 (17) | 0.0270 (5) | |
| N1 | 0.83978 (18) | 0.2531 (3) | 0.2128 (3) | 0.0389 (7) | |
| H1N | 0.855 (2) | 0.195 (3) | 0.269 (3) | 0.047* | |
| C2 | 0.7639 (2) | 0.3065 (3) | 0.2281 (3) | 0.0340 (7) | |
| H2 | 0.7337 | 0.2840 | 0.2952 | 0.041* | |
| C3 | 0.73016 (18) | 0.3943 (2) | 0.1455 (3) | 0.0240 (6) | |
| C4 | 0.7781 (2) | 0.4265 (3) | 0.0482 (3) | 0.0352 (7) | |
| H4 | 0.7576 | 0.4859 | −0.0081 | 0.042* | |
| C5 | 0.8562 (2) | 0.3711 (3) | 0.0338 (3) | 0.0455 (9) | |
| H5 | 0.8883 | 0.3925 | −0.0317 | 0.055* | |
| C6 | 0.8861 (2) | 0.2815 (3) | 0.1206 (4) | 0.0455 (9) | |
| H6 | 0.9381 | 0.2428 | 0.1126 | 0.055* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Zn1 | 0.02480 (18) | 0.02383 (19) | 0.01884 (17) | −0.00201 (15) | 0.00358 (12) | −0.00099 (15) |
| P3 | 0.0219 (4) | 0.0237 (4) | 0.0169 (4) | −0.0008 (3) | 0.0029 (3) | −0.0004 (3) |
| Cl1 | 0.0641 (6) | 0.0261 (5) | 0.0608 (6) | −0.0124 (4) | 0.0053 (5) | 0.0018 (4) |
| O31 | 0.0220 (10) | 0.0352 (13) | 0.0355 (12) | −0.0039 (9) | 0.0036 (9) | −0.0116 (10) |
| O32 | 0.0342 (11) | 0.0326 (12) | 0.0187 (10) | −0.0019 (9) | 0.0067 (8) | 0.0014 (9) |
| O33 | 0.0348 (11) | 0.0258 (11) | 0.0191 (10) | −0.0001 (9) | 0.0002 (9) | 0.0050 (9) |
| N1 | 0.0441 (17) | 0.0389 (18) | 0.0324 (16) | 0.0127 (14) | 0.0021 (13) | −0.0010 (13) |
| C2 | 0.0324 (17) | 0.0386 (19) | 0.0309 (17) | 0.0059 (15) | 0.0042 (14) | 0.0046 (15) |
| C3 | 0.0234 (14) | 0.0295 (17) | 0.0179 (13) | −0.0034 (12) | −0.0001 (11) | −0.0022 (12) |
| C4 | 0.0332 (17) | 0.039 (2) | 0.0344 (17) | −0.0022 (14) | 0.0076 (14) | 0.0026 (15) |
| C5 | 0.0397 (19) | 0.065 (3) | 0.0361 (19) | −0.0040 (18) | 0.0206 (16) | −0.0059 (18) |
| C6 | 0.0337 (19) | 0.055 (2) | 0.048 (2) | 0.0138 (17) | 0.0051 (17) | −0.0124 (19) |
Geometric parameters (Å, º) top
| Zn1—O31 | 1.9390 (19) | N1—C2 | 1.348 (4) |
| Zn1—O32i | 1.9406 (19) | N1—H1N | 0.91 (4) |
| Zn1—O33ii | 1.9817 (19) | C2—C3 | 1.386 (4) |
| Zn1—Cl1 | 2.2249 (10) | C2—H2 | 0.9300 |
| P3—O31 | 1.508 (2) | C3—C4 | 1.386 (4) |
| P3—O32 | 1.5195 (19) | C4—C5 | 1.387 (4) |
| P3—O33 | 1.527 (2) | C4—H4 | 0.9300 |
| P3—C3 | 1.825 (3) | C5—C6 | 1.411 (5) |
| O32—Zn1i | 1.9406 (19) | C5—H5 | 0.9300 |
| O33—Zn1ii | 1.9817 (19) | C6—H6 | 0.9300 |
| N1—C6 | 1.315 (4) | | |
| | | |
| O31—Zn1—O32i | 110.24 (8) | C2—N1—H1N | 115 (2) |
| O31—Zn1—O33ii | 108.85 (9) | N1—C2—C3 | 121.2 (3) |
| O32i—Zn1—O33ii | 104.83 (8) | N1—C2—H2 | 119.4 |
| O31—Zn1—Cl1 | 110.66 (7) | C3—C2—H2 | 119.4 |
| O32i—Zn1—Cl1 | 118.03 (7) | C2—C3—C4 | 117.6 (3) |
| O33ii—Zn1—Cl1 | 103.54 (6) | C2—C3—P3 | 118.6 (2) |
| O31—P3—O32 | 115.04 (12) | C4—C3—P3 | 123.8 (2) |
| O31—P3—O33 | 113.29 (12) | C3—C4—C5 | 120.7 (3) |
| O32—P3—O33 | 109.91 (12) | C3—C4—H4 | 119.7 |
| O31—P3—C3 | 104.92 (12) | C5—C4—H4 | 119.7 |
| O32—P3—C3 | 106.28 (12) | C4—C5—C6 | 118.6 (3) |
| O33—P3—C3 | 106.68 (12) | C4—C5—H5 | 120.7 |
| P3—O31—Zn1 | 137.21 (13) | C6—C5—H5 | 120.7 |
| P3—O32—Zn1i | 133.29 (13) | N1—C6—C5 | 119.6 (3) |
| P3—O33—Zn1ii | 130.42 (12) | N1—C6—H6 | 120.2 |
| C6—N1—C2 | 122.4 (3) | C5—C6—H6 | 120.2 |
| C6—N1—H1N | 123 (2) | | |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Cl1i | 0.93 | 2.85 | 3.756 (3) | 164 |
| N1—H1N···O33iii | 0.91 (4) | 1.85 (4) | 2.756 (4) | 175 (3) |
| C6—H6···O31iv | 0.93 | 2.57 | 3.134 (4) | 120 |
| Symmetry codes: (i) −x+1, y, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+3/2, −y+1/2, −z. |
The calculated cohesive and interaction energies for the crystal structure of
compound (1) top| Calculated energya | Energy per ASU (kJ mol-1) |
| Interaction energy of M1 | -115.4 |
| Interaction energy of M2 | 20.2 |
| Cohesive energy | -205.4 |
| Note: (a) the energy calculated per ASU-equivalent fragment of a
polymeric chain in the crystal structure of (1) |
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