Poly[(μ4-phenyl­phospho­nato)zinc(II)]

Falvello, L.; Lotti, P.; Massera, C.; Tarantino, S.C.; Zema, M.; Puschmann, H.; Agbahoungbata, M.Y.; Andreo, J.; Sahadevan, S.A.; Bismuto, A.; Bonfant, G.; Bonou, S.A.S.; Carraro, C.; Zotti, M.D.; Biase, A. di; Fantini, R.; Ferraboschi, I.; Custodio, J.M.F.; Frigerio, M.; Gallo, G.; Gjyli, S.; Goudjil, M.; Igoa, F.; Kahveci, E.; Kalienko, M.; Lorenzon, S.; Macera, L.; Fajardo, J.J.M.; Nushi, E.; Ouaatta, S.; Parisi, E.; Pasqualetto, L.; Pesko, E.; Pierri, G.; Pinalli, R.; Poppe, R.; Santoro, A.; Smirnova, E.; Sorbara, S.; Tensi, L.; Tusha, G.

doi:10.1107/S2414314619012227

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191222

https://doi.org/10.1107/S2414314619012227

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Poly[(μ₄-phenylphosphonato)zinc(II)]

^aAIC School 2019 – Crystallographic Information Fiesta, Naples, Italy, ^bDepartment of Inorganic Chemistry, University of Zaragoza, Zaragoza, Spain, ^cDipartimento di Scienze della Terra, University of Milan, Milan, Italy, ^dDipartimento di Scienze Chimiche, della Vita e della Sostenibilit Ambientale, University of Parma, Parma, Italy, ^eDipartimento di Scienze della Terra e dell'Ambiente, University of Pavia, Italy, and ^fOlexSys Ltd, Durham University, Durham, DH1 3LE, UK
^*Correspondence e-mail: chiara.massera@unipr.it

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 September 2019; accepted 3 September 2019; online 6 September 2019)

The title two-dimensional coordination polymer, [Zn(C₆H₅PO₃)]_n, was synthesized serendipitously by reacting a tetraphosphonate cavitand Tiiii[C₃H₇, CH₃, C₆H₅] and Zn(CH₃COO)₂·2H₂O in a DMF/H₂O mixture. The basic conditions of the reaction cleaved the phosphonate bridges at the upper rim of the cavitand, making them available for reaction with the zinc ions. The coordination polymer can be described as an inorganic layer in which zinc coordinates the oxygen atoms of the phosphonate groups in a distorted tetrahedral environment, while the phenyl groups, which are statistically disordered over two orientations, point up and down with respect to the layer. The layers interact through van der Waals interactions. The crystal studied was refined as a two-component twin.

Keywords: crystal structure; zinc coordination polymer; phosphonate group; disorder.

CCDC reference: 1951130

Structure description

Resorcinarene-based cavitands (Cram, 1983 ; Cram & Cram, 1994 ) are synthetic organic compounds endowed with a rigid, pre-organized cavity which can be decorated both at the upper and lower rim with different functional groups. In particular, tetraphosphonate cavitands Tiiii have four P=O groups at the upper rim all pointing to the inside of the cavity; they are generally described as Tiiii[R, R₁, R₂], where R = lower rim substituents, R₁ = upper rim substituents and R₂ = substituents on the P atom (Pinalli & Dalcanale, 2013 ). These dipolar groups can act as hydrogen-bond acceptors and have been used as ligands for metal cations (Pinalli et al., 2016 ; Melegari et al., 2010 ). Within the framework of ongoing research on the interactions between cavitands and metal ions, a solvothermal reaction between the tetraphosphonate cavitand Tiiii[C₃H₇, CH₃, C₆H₅] and Zn(CH₃COO)₂·2H₂O was carried out in a DMF/H₂O mixture. The basicity of the solution resulting from the presence of the acetate anion hydrolysed the cavitands, cleaving the bridges at the upper rim, with a concomitant release of the phenylphosphonate groups. Their reaction with the zinc cations yielded the title compound, I, the crystal structure of which is reported here.

The asymmetric unit of I comprises a phenylphosphonate anion and a zinc(II) cation (Fig. 1); selected bond lengths are given in Table 1. The delocalization of the negative charge and the single/double-bond character within the phosphonate group are shown by the P—O distances, two of which are shorter than the third [P1—O1, P1—O2 and P1—O3 have values of 1.507 (4), 1.513 (4) and 1.561 (4) Å, respectively]. In particular, the longest P—O distance involves the O atom that bridges two metal cations, and it is therefore weakened by the double coordination. The coordination polymer is parallel to the (100) plane; each of the phosphonate groups connects four distinct zinc cations, with O1 and O2 monodentate and with O3 bridging two Zn cations. Overall, the structure can be seen as an inorganic zone, decorated on both sides by the phenyl groups (Fig. 2). Within the layer, the phenyl groups in one orientation form C—H⋯O hydrogen bonds with the oxygen atoms O1^iv of adjacent phosphate groups (see Table 2 and Fig. 3). Cohesion between layers is ensured by dispersion interactions.

Table 1
Selected bond lengths (Å)

Zn1—O1	1.914 (4)	P1—O1	1.507 (4)
Zn1—O2ⁱ	1.907 (4)	P1—O2	1.513 (4)
Zn1—O3ⁱⁱ	1.989 (4)	P1—O3	1.561 (4)
Zn1—O3ⁱⁱⁱ	1.988 (4)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2B—H2B⋯O1^iv	0.95	2.45	3.378 (13)	170
Symmetry code: (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
Asymmetric unit of I, plus the oxygen atoms needed to complete the tetrahedral coordination around Zn1. Symmetry codes: (i) −x + 1, −y + 2, −z + 1; (ii) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; (iii) −x + 1, −y + 1, −z + 1. Only one orientation of the disordered phenyl group is shown for clarity.

Figure 2
Side (A) and top (B) view of I highlighting its layered structure. H atoms have been omitted for clarity.

Figure 3
View along the b-axis direction of the intramolecular hydrogen bond (blue dotted line) in I. Symmetry code: (iv) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .

A search of the Cambridge Structural Database (Version 5.38, update May 2019; Groom et al., 2016 ) for phenylphosphonate in combination with zinc, yielded the structure of a catena-poly[[aquazinc(II)]-μ₄-phenylphosphonato] (refcode JAHGAA; Martin et al., 1989 ), closely related to the title compound. The main difference concerns the coordination sphere of the metal ion, which is a distorted octahedron comprising one oxygen atom of a coordinating water molecule and five oxygen atoms from the μ₄-phosphonate groups.

Synthesis and crystallization

The cavitand Tiiii[C₃H₇, CH₃, C₆H₅] was prepared following published procedures (Biavardi et al., 2008 ): 18.0 mg (0.015 mmol) of the Tiiii cavitand were dissolved in DMF (2 ml), while Zn(CH₃COO)₂·2H₂O (6.5 mg, 0.030 mmol) was dissolved in 1 ml of water. The two solutions were put in a Schlenk reactor with a volume of 10 ml, and left at room temperature overnight. The reaction mixture was then heated at 120°C in an oil bath for three days and allowed to cool to room temperature. Small, light-yellow crystals were formed; they were filtered, washed with DMF and dried.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. It was observed that F_obs was systematically greater than F_calc for the most discrepant reflections. A twin law was identified [−1 0 −0.768 0 −1 0 0 0 1] and for the final refinement, a two-component model was refined. The population of the second component refined to a value of 0.242 (6).

Table 3
Experimental details

Crystal data
Chemical formula	[Zn(C₆H₅O₃P)]
M_r	221.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	14.8549 (8), 5.1581 (3), 10.5471 (6)
β (°)	105.816 (2)
V (Å³)	777.56 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.98
Crystal size (mm)	0.10 × 0.08 × 0.07

Data collection
Diffractometer	Bruker D8 Venture PhotonII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.558, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	1897, 1544, 1498
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.121, 1.04
No. of reflections	1544
No. of parameters	138
No. of restraints	144
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −1.08
Computer programs: APEX2 and SAINT (Bruker, 2008), olex2.solve (Bourhis et al., 2015 ), olex2.refine (Bourhis et al., 2015), Mercury (Macrae et al., 2006 ) and OLEX2 (Dolomanov et al., 2009 ).

The phenyl ring of the phosphonate group was found to be disordered over two equally populated orientations, related by rotation about the P1—C1⋯C4 axis. The dihedral angle between the mean planes passing through the two orientations is 76.3 (6)°. Neighbouring disorder assemblies of this type must be populated by alternate disorder groups in order to avoid unreasonably short contacts. That is, for a given orientation of the half-occupied phenyl group, its neighbour must be the other congener. Examination of undistorted reciprocal-lattice plots revealed diffuse streaks, which we interpret as arising from stacking faults accompanying the disorder. We did not undertake more detailed analysis of the diffuse scattering.

Structural data

CCDC reference: 1951130

Crystal structure: contains datablock global. DOI: https://doi.org/10.1107/S2414314619012227/hb4317sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[(µ₄-phenylphosphonato)zinc(II)] top

Crystal data top

[Zn(C₆H₅O₃P)]	F(000) = 436.050
M_r = 221.47	D_x = 1.892 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 14.8549 (8) Å	Cell parameters from 1658 reflections
b = 5.1581 (3) Å	θ = 6.2–74.8°
c = 10.5471 (6) Å	µ = 5.98 mm⁻¹
β = 105.816 (2)°	T = 150 K
V = 777.56 (8) Å³	Prismatic, light yellow
Z = 4	0.10 × 0.08 × 0.07 mm

Data collection top

Bruker D8 Venture PhotonII diffractometer	1498 reflections with I > 2σ(I)
phi & ω scan	R_int = 0
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 72.7°, θ_min = 6.2°
T_min = 0.558, T_max = 0.754	h = −18→17
1897 measured reflections	k = −6→6
1544 independent reflections	l = 0→12

Refinement top

Refinement on F²	21 constraints
Least-squares matrix: full	Primary atom site location: iterative
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0246P)² + 7.9936P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.0004
1544 reflections	Δρ_max = 1.23 e Å⁻³
138 parameters	Δρ_min = −1.08 e Å⁻³
144 restraints

Special details top

Refinement. The H atoms bound to C atoms were placed in calculated positions and refined isotropically using a riding model C—H = 0.95 Å, and U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.49966 (5)	0.70559 (13)	0.64634 (6)	0.0168 (2)
P1	0.38324 (9)	0.7695 (3)	0.35527 (12)	0.0175 (3)
O3	0.4428 (2)	0.6262 (7)	0.2757 (3)	0.0212 (7)
O2	0.4026 (3)	1.0576 (8)	0.3577 (4)	0.0263 (8)
O1	0.4016 (2)	0.6435 (8)	0.4888 (3)	0.0233 (8)
c4	0.0722 (4)	0.6776 (16)	0.1495 (7)	0.0451 (16)
H4a	0.0075 (4)	0.6593 (16)	0.1062 (7)	0.054 (2)*	0.498 (9)
H4b	0.0074 (4)	0.6583 (16)	0.1066 (7)	0.054 (2)*	0.502 (9)
C1	0.2618 (3)	0.7270 (11)	0.2715 (5)	0.0215 (10)
C2A	0.2065 (8)	0.945 (3)	0.2247 (12)	0.036 (3)	0.498 (9)
H2A	0.2339 (8)	1.112 (3)	0.2334 (12)	0.043 (3)*	0.498 (9)
C5A	0.1266 (10)	0.459 (3)	0.1968 (17)	0.053 (4)	0.498 (9)
H5A	0.0988 (10)	0.292 (3)	0.1875 (17)	0.063 (4)*	0.498 (9)
C3B	0.1330 (9)	0.725 (3)	0.0761 (13)	0.045 (3)	0.502 (9)
H3B	0.1099 (9)	0.743 (3)	−0.0167 (13)	0.054 (4)*	0.502 (9)
C6B	0.1990 (8)	0.681 (3)	0.3468 (12)	0.037 (3)	0.502 (9)
H6B	0.2215 (8)	0.665 (3)	0.4398 (12)	0.044 (4)*	0.502 (9)
C3A	0.1118 (9)	0.914 (3)	0.1656 (15)	0.050 (4)	0.498 (9)
H3A	0.0741 (9)	1.062 (3)	0.1359 (15)	0.060 (4)*	0.498 (9)
C6A	0.2220 (9)	0.488 (3)	0.2578 (15)	0.041 (3)	0.498 (9)
H6A	0.2593 (9)	0.340 (3)	0.2899 (15)	0.049 (4)*	0.498 (9)
C2B	0.2298 (8)	0.746 (3)	0.1361 (11)	0.034 (3)	0.502 (9)
H2B	0.2722 (8)	0.772 (3)	0.0843 (11)	0.041 (3)*	0.502 (9)
C5B	0.1028 (9)	0.658 (3)	0.2850 (14)	0.047 (3)	0.502 (9)
H5B	0.0597 (9)	0.629 (3)	0.3355 (14)	0.056 (4)*	0.502 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0222 (3)	0.0162 (4)	0.0129 (3)	−0.0007 (3)	0.0061 (3)	0.0004 (2)
P1	0.0189 (6)	0.0221 (6)	0.0123 (5)	−0.0009 (5)	0.0056 (5)	−0.0003 (5)
O3	0.0247 (17)	0.0233 (18)	0.0164 (16)	0.0013 (14)	0.0069 (14)	0.0014 (14)
O2	0.0238 (17)	0.028 (2)	0.029 (2)	−0.0011 (15)	0.0114 (15)	−0.0033 (16)
O1	0.0227 (17)	0.033 (2)	0.0151 (16)	−0.0046 (15)	0.0059 (13)	0.0025 (15)
c4	0.022 (3)	0.059 (4)	0.048 (4)	−0.002 (3)	0.000 (2)	−0.006 (3)
C1	0.020 (2)	0.028 (3)	0.017 (2)	−0.0016 (18)	0.0051 (18)	−0.0021 (19)
C2A	0.031 (5)	0.040 (6)	0.034 (6)	0.003 (3)	0.002 (4)	0.004 (4)
C5A	0.031 (6)	0.050 (7)	0.071 (9)	−0.008 (4)	0.004 (4)	−0.006 (5)
C3B	0.030 (6)	0.069 (9)	0.028 (6)	−0.002 (4)	−0.005 (3)	−0.003 (4)
C6B	0.027 (5)	0.059 (8)	0.026 (5)	−0.004 (4)	0.010 (3)	0.001 (4)
C3A	0.029 (6)	0.060 (8)	0.054 (8)	0.003 (4)	0.000 (4)	−0.001 (4)
C6A	0.030 (6)	0.032 (6)	0.059 (8)	−0.004 (3)	0.008 (4)	−0.003 (4)
C2B	0.032 (5)	0.055 (7)	0.013 (4)	−0.003 (4)	0.003 (3)	0.001 (4)
C5B	0.022 (5)	0.069 (9)	0.048 (6)	−0.004 (4)	0.010 (4)	0.002 (4)

Geometric parameters (Å, º) top

Zn1—O1	1.914 (4)	C1—C6A	1.358 (14)
Zn1—O2ⁱ	1.907 (4)	C1—C2B	1.380 (12)
Zn1—O3ⁱⁱ	1.989 (4)	C2A—H2A	0.9500
Zn1—O3ⁱⁱⁱ	1.988 (4)	C2A—C3A	1.384 (18)
P1—O1	1.507 (4)	C5A—H5A	0.9500
P1—O2	1.513 (4)	C5A—C6A	1.396 (18)
P1—O3	1.561 (4)	C3B—H3B	0.9500
P1—C1	1.793 (5)	C3B—C2B	1.408 (16)
c4—C5A	1.397 (18)	C6B—H6B	0.9500
c4—C3B	1.362 (16)	C6B—C5B	1.404 (17)
c4—C3A	1.343 (18)	C3A—H3A	0.9500
c4—C5B	1.380 (16)	C6A—H6A	0.9500
C1—C2A	1.398 (14)	C2B—H2B	0.9500
C1—C6B	1.401 (13)	C5B—H5B	0.9500

O2ⁱ—Zn1—O3ⁱⁱⁱ	108.46 (16)	C3B—c4—H4b	119.4 (6)
O2ⁱ—Zn1—O3ⁱⁱ	101.79 (16)	C3A—c4—H4a	120.1 (7)
O1—Zn1—O3ⁱⁱⁱ	110.74 (16)	C3A—c4—C5A	119.7 (9)
O1—Zn1—O3ⁱⁱ	107.71 (15)	C5B—c4—H4b	119.4 (6)
O1—Zn1—O2ⁱ	119.43 (16)	C5B—c4—C3B	121.3 (8)
O2—P1—O3	110.0 (2)	C6A—C1—C2A	119.7 (8)
O1—P1—O3	108.2 (2)	C2B—C1—C6B	120.3 (8)
O1—P1—O2	115.0 (2)	C3A—C2A—H2A	120.2 (9)
C1—P1—O3	108.6 (2)	C6A—C5A—H5A	120.2 (9)
C1—P1—O2	106.8 (2)	C2B—C3B—H3B	119.6 (7)
C1—P1—O1	108.0 (2)	C5B—C6B—H6B	119.9 (8)
P1—O3—Zn1^iv	124.8 (2)	H3A—C3A—C2A	119.4 (9)
P1—O3—Zn1ⁱⁱⁱ	115.35 (19)	H6A—C6A—C5A	119.9 (9)
P1—O2—Zn1ⁱ	140.5 (2)	H2B—C2B—C3B	120.6 (7)
P1—O1—Zn1	129.8 (2)	H5B—C5B—C6B	120.6 (8)
C5A—c4—H4a	120.1 (7)

Zn1ⁱⁱⁱ—O3—P1—O2	138.3 (2)	Zn1ⁱ—O2—P1—O3	−29.8 (4)
Zn1^iv—O3—P1—O2	−19.8 (3)	Zn1ⁱ—O2—P1—O1	92.6 (4)
Zn1^iv—O3—P1—O1	−146.2 (2)	Zn1ⁱ—O2—P1—C1	−147.5 (4)
Zn1ⁱⁱⁱ—O3—P1—O1	12.0 (3)	Zn1—O1—P1—O3	85.0 (3)
Zn1ⁱⁱⁱ—O3—P1—C1	−105.1 (3)	Zn1—O1—P1—O2	−38.3 (4)
Zn1^iv—O3—P1—C1	96.7 (3)	Zn1—O1—P1—C1	−157.5 (3)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2B—H2B···O1^iv	0.95	2.45	3.378 (13)	170

Symmetry code: (iv) x, −y+3/2, z−1/2.

Acknowledgements

The "Laboratorio di Strutturistica Mario Nardelli" of the University of Parma and Chiesi Farmaceutici SpA are kindly acknowledged for support of the D8 Venture X-ray equipment. Data analysis, structure solution, refinement and validation were conducted as part of a tutorial session during the Crystallographic Information Fiesta held in Naples, Italy, from 29 August to 3 September 2019, and organized by the Italian Crystallographic Association in partnership with the IUCr.

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