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

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](P-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.045
• wR factor = 0.121
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found





Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT073_ALERT_1_G H-atoms ref, but _hydrogen_treatment Reported as     constr Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       7.99 Why ?
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        36% Note
PLAT793_ALERT_4_G Model has Chirality at P1          (Centro SPGR)          S Verify
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............        144 Note
PLAT881_ALERT_1_G No Datum for _diffrn_reflns_av_R_equivalents ...     Please Do !
PLAT882_ALERT_1_G No Datum for _diffrn_reflns_av_unetI/netI ......     Please Do !
PLAT982_ALERT_1_G The  C-f'=    0.0192 Deviates from  IT-value =       0.0181 Check
PLAT982_ALERT_1_G The  O-f'=    0.0524 Deviates from  IT-value =       0.0492 Check
PLAT982_ALERT_1_G The  P-f'=    0.3036 Deviates from  IT-value =       0.2955 Check
PLAT982_ALERT_1_G The Zn-f'=   -1.5564 Deviates from  IT-value =      -1.5491 Check
PLAT983_ALERT_1_G The  O-f"=    0.0338 Deviates from  IT-Value =       0.0322 Check
PLAT983_ALERT_1_G The  P-f"=    0.4370 Deviates from  IT-Value =       0.4335 Check
PLAT983_ALERT_1_G The Zn-f"=    0.7046 Deviates from  IT-Value =       0.6778 Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  17 ALERT level G = General information/check it is not something unexpected

  10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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Computing details

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)]

Crystal data

[Zn(C6H5O3P)]	F(000) = 436.050
Mr = 221.47	Dx = 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) Å^3	Prismatic, light yellow
Z = 4	0.10 × 0.08 × 0.07 mm

Data collection

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

Refinement

Refinement on F^2	21 constraints
Least-squares matrix: full	Primary atom site location: iterative
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0246P)^2 + 7.9936P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.0004
1544 reflections	Δρmax = 1.23 e Å^−3
138 parameters	Δρmin = −1.08 e Å^−3
144 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

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

Zn1—O1	1.914 (4)	C1—C6A	1.358 (14)
Zn1—O2^i	1.907 (4)	C1—C2B	1.380 (12)
Zn1—O3^ii	1.989 (4)	C2A—H2A	0.9500
Zn1—O3^iii	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
O2^i—Zn1—O3^iii	108.46 (16)	C3B—c4—H4b	119.4 (6)
O2^i—Zn1—O3^ii	101.79 (16)	C3A—c4—H4a	120.1 (7)
O1—Zn1—O3^iii	110.74 (16)	C3A—c4—C5A	119.7 (9)
O1—Zn1—O3^ii	107.71 (15)	C5B—c4—H4b	119.4 (6)
O1—Zn1—O2^i	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—Zn1^iii	115.35 (19)	H6A—C6A—C5A	119.9 (9)
P1—O2—Zn1^i	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)
Zn1^iii—O3—P1—O2	138.3 (2)	Zn1^i—O2—P1—O3	−29.8 (4)
Zn1^iv—O3—P1—O2	−19.8 (3)	Zn1^i—O2—P1—O1	92.6 (4)
Zn1^iv—O3—P1—O1	−146.2 (2)	Zn1^i—O2—P1—C1	−147.5 (4)
Zn1^iii—O3—P1—O1	12.0 (3)	Zn1—O1—P1—O3	85.0 (3)
Zn1^iii—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)

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.