Synthesis, structural characterization and computational studies of catena-poly[chlorido­[μ₃-(pyridin-1-ium-3-yl)phospho­nato-κ³O:O′:O′′]zinc(II)]

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(C₅H₅NO₃P)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.

Computing details

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[µ₃-(pyridin-1-ium-3-yl)phosphonato-κ³O:O':O'']zinc(II)]

Crystal data

[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) Å^3	Parallelepiped, colourless
Z = 8	0.22 × 0.15 × 0.12 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0321P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Zn1—O31	1.9390 (19)	N1—C2	1.348 (4)
Zn1—O32^i	1.9406 (19)	N1—H1N	0.91 (4)
Zn1—O33^ii	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—Zn1^i	1.9406 (19)	C5—H5	0.9300
O33—Zn1^ii	1.9817 (19)	C6—H6	0.9300
N1—C6	1.315 (4)
O31—Zn1—O32^i	110.24 (8)	C2—N1—H1N	115 (2)
O31—Zn1—O33^ii	108.85 (9)	N1—C2—C3	121.2 (3)
O32^i—Zn1—O33^ii	104.83 (8)	N1—C2—H2	119.4
O31—Zn1—Cl1	110.66 (7)	C3—C2—H2	119.4
O32^i—Zn1—Cl1	118.03 (7)	C2—C3—C4	117.6 (3)
O33^ii—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—Zn1^i	133.29 (13)	N1—C6—C5	119.6 (3)
P3—O33—Zn1^ii	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)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1^i	0.93	2.85	3.756 (3)	164
N1—H1N···O33^iii	0.91 (4)	1.85 (4)	2.756 (4)	175 (3)
C6—H6···O31^iv	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.