Two-dimensional coordination polymeric structures in the sodium, potassium and rubidium complex salts with (4-fluoro­phen­oxy)acetic acid

The structures of the sodium, potassium and rubidium complex salts of (4-fluoro­phen­oxy)acetic acid (PFPA), namely poly[μ-aqua-aqua-μ-[2-(4-fluoro­phen­oxy)acetato]-κ³O¹,O²:O^1′-sodium], [Na(C₈H₆FO₃)(H₂O)₂]_n, (I), and iso­typic poly[μ₅-[2-(4-fluoro­phen­oxy)acetato]-κ⁵O¹,O²:O¹,O^1′:O^1′:O^1′:O^1′-potassium], [K(C₈H₆FO₃)]_n, (II), and poly[μ₅-[2-(4-fluoro­phen­oxy)acetato]-κ⁵O¹,O²:O¹,O^1′:O^1′:O^1′:O^1′-rubidium], [Rb(C₈H₆FO₃)]_n, (III), have been determined and their coordination polymeric structures described. In the structure of (I), the very distorted octa­hedral NaO₆ coordination polyhedron comprises two bidentate chelating O-atom donors (carboxyl­ate and phen­oxy) of the PFPA ligand and three O-atom donors from water mol­ecules, one mono­dentate and the other μ₂-bridging between inversion-related Na centres in a cyclic manner. A bridging carboxyl­ate donor generates two-dimensional polymer layers lying parallel to (001), in which intra­layer water O—H...O hydrogen-bonding associations are also present. Structures (II) and (III) are isotypic, each having an irregular MO₇ stereochemistry, with the primary metal–ligand bidentate chelate similar to that in (I) and extended into a two-dimensional polymeric layered structure, lying parallel to (100), through five additional bridging carboxyl­ate O atoms. Two of these bonds are from an O,O′-bidentate chelate inter­action and the other three are from μ₃-O-atom bridges, generating cyclic links with short M...M separations [3.9064 (17) Å for (II) and 4.1001 (8) for (III)], the shortest being a centrosymmetric four-membered cyclic link. In the crystals of (I)–(III), intra­layer C—H...F inter­actions are present, but no π–π ring inter­actions are found.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2014); cell refinement: CrysAlis PRO (Rigaku OD, 2014); data reduction: CrysAlis PRO (Rigaku OD, 2014). Program(s) used to solve structure: SIR92 (Altomare et al., 1993) for (I), (III); SHELXS97 (Sheldrick, 2008) for (II). For all structures, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Poly[µ-aqua-aqua-µ-[2-(4-fluorophenoxy)acetato]-κ³O¹,O²:O^1'-sodium] (I)

Crystal data

[Na(C8H6FO3)(H2O)2]	F(000) = 472
Mr = 228.15	Dx = 1.541 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 797 reflections
a = 5.4784 (5) Å	θ = 3.5–25.4°
b = 5.9139 (6) Å	µ = 0.17 mm^−1
c = 30.379 (3) Å	T = 200 K
β = 92.540 (7)°	Plate, colourless
V = 983.27 (17) Å^3	0.30 × 0.30 × 0.03 mm
Z = 4

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	1918 independent reflections
Radiation source: Enhance (Mo) X-ray source	1385 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.5°
ω scans	h = −3→6
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2014)	k = −5→7
Tmin = 0.883, Tmax = 0.990	l = −37→29
3173 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0577P)^2] where P = (Fo^2 + 2Fc^2)/3
1918 reflections	(Δ/σ)max < 0.001
138 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Na1	0.5911 (2)	0.5972 (2)	0.55378 (4)	0.0299 (4)
F4	−0.2056 (3)	0.5094 (4)	0.73896 (7)	0.0517 (8)
O1W	0.7177 (3)	0.6601 (4)	0.48056 (7)	0.0311 (7)
O2W	0.2745 (4)	0.8641 (4)	0.53340 (7)	0.0322 (7)
O11	0.4988 (4)	0.3523 (4)	0.62005 (7)	0.0321 (7)
O13	0.8176 (4)	0.2708 (4)	0.55680 (7)	0.0318 (7)
O14	0.8542 (4)	−0.0913 (4)	0.57744 (7)	0.0303 (7)
C1	0.3259 (5)	0.3815 (5)	0.65147 (10)	0.0274 (10)
C2	0.3028 (6)	0.2441 (6)	0.68762 (11)	0.0347 (11)
C3	0.1228 (6)	0.2868 (6)	0.71733 (11)	0.0364 (11)
C4	−0.0280 (5)	0.4681 (6)	0.70971 (11)	0.0358 (11)
C5	−0.0101 (6)	0.6078 (6)	0.67394 (12)	0.0423 (11)
C6	0.1697 (6)	0.5643 (6)	0.64466 (11)	0.0363 (11)
C12	0.6249 (6)	0.1416 (5)	0.62169 (10)	0.0304 (10)
C13	0.7776 (5)	0.1081 (6)	0.58167 (10)	0.0263 (10)
H2	0.41040	0.11960	0.69230	0.0420*
H3	0.10500	0.19250	0.74230	0.0440*
H5	−0.11890	0.73150	0.66940	0.0510*
H6	0.18660	0.65960	0.61980	0.0440*
H11W	0.69230	0.79650	0.47700	0.0470*
H12W	0.86350	0.62110	0.46890	0.0470*
H21W	0.15090	0.87260	0.54620	0.0480*
H22W	0.23830	0.82210	0.50520	0.0480*
H121	0.50470	0.01700	0.62320	0.0360*
H122	0.73250	0.13550	0.64870	0.0360*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0294 (6)	0.0191 (7)	0.0413 (8)	0.0015 (5)	0.0042 (5)	0.0018 (6)
F4	0.0406 (11)	0.0556 (15)	0.0608 (14)	0.0050 (10)	0.0226 (9)	−0.0113 (12)
O1W	0.0280 (11)	0.0222 (12)	0.0436 (14)	0.0004 (9)	0.0067 (9)	0.0016 (11)
O2W	0.0294 (11)	0.0287 (13)	0.0390 (13)	0.0022 (9)	0.0063 (9)	−0.0018 (11)
O11	0.0354 (12)	0.0245 (13)	0.0371 (13)	0.0102 (9)	0.0094 (9)	0.0056 (10)
O13	0.0289 (11)	0.0260 (13)	0.0410 (14)	0.0074 (9)	0.0073 (9)	0.0064 (11)
O14	0.0314 (11)	0.0205 (12)	0.0395 (13)	0.0050 (9)	0.0063 (9)	−0.0022 (10)
C1	0.0268 (15)	0.0261 (17)	0.0293 (18)	0.0045 (13)	0.0020 (12)	−0.0029 (15)
C2	0.0324 (17)	0.035 (2)	0.037 (2)	0.0101 (14)	0.0043 (13)	0.0030 (16)
C3	0.0363 (18)	0.038 (2)	0.035 (2)	0.0036 (15)	0.0044 (14)	0.0025 (16)
C4	0.0300 (18)	0.040 (2)	0.038 (2)	0.0004 (15)	0.0082 (14)	−0.0113 (17)
C5	0.0402 (19)	0.035 (2)	0.052 (2)	0.0123 (17)	0.0041 (16)	−0.0035 (19)
C6	0.0388 (18)	0.031 (2)	0.039 (2)	0.0081 (15)	0.0015 (14)	0.0063 (16)
C12	0.0349 (17)	0.0195 (17)	0.0370 (19)	0.0072 (13)	0.0049 (13)	0.0022 (14)
C13	0.0227 (15)	0.0236 (18)	0.0321 (18)	0.0019 (13)	−0.0028 (12)	0.0000 (14)

Geometric parameters (Å, º)

Na1—O1W	2.388 (2)	O2W—H22W	0.9100
Na1—O2W	2.406 (3)	C1—C2	1.377 (5)
Na1—O11	2.549 (3)	C1—C6	1.389 (4)
Na1—O13	2.294 (3)	C2—C3	1.389 (5)
Na1—O14^i	2.428 (3)	C3—C4	1.367 (5)
Na1—O1W^ii	2.472 (2)	C4—C5	1.372 (5)
F4—C4	1.368 (4)	C5—C6	1.380 (5)
O11—C1	1.385 (4)	C12—C13	1.519 (4)
O11—C12	1.425 (4)	C2—H2	0.9500
O13—C13	1.249 (4)	C3—H3	0.9500
O14—C13	1.260 (4)	C5—H5	0.9500
O1W—H11W	0.8200	C6—H6	0.9500
O1W—H12W	0.9200	C12—H121	0.9900
O2W—H21W	0.8000	C12—H122	0.9900
O1W—Na1—O2W	83.91 (8)	Na1—O2W—H21W	122.00
O1W—Na1—O11	154.17 (9)	O11—C1—C2	124.5 (3)
O1W—Na1—O13	89.39 (9)	O11—C1—C6	115.5 (3)
O1W—Na1—O14^i	87.96 (8)	C2—C1—C6	120.0 (3)
O1W—Na1—O1W^ii	85.66 (8)	C1—C2—C3	120.3 (3)
O2W—Na1—O11	114.21 (8)	C2—C3—C4	118.3 (3)
O2W—Na1—O13	160.86 (10)	F4—C4—C3	118.2 (3)
O2W—Na1—O14^i	89.44 (9)	C3—C4—C5	122.9 (3)
O1W^ii—Na1—O2W	79.81 (8)	F4—C4—C5	119.0 (3)
O11—Na1—O13	67.43 (8)	C4—C5—C6	118.4 (3)
O11—Na1—O14^i	109.47 (8)	C1—C6—C5	120.1 (3)
O1W^ii—Na1—O11	80.07 (8)	O11—C12—C13	111.7 (2)
O13—Na1—O14^i	108.27 (9)	O13—C13—C12	120.1 (3)
O1W^ii—Na1—O13	81.82 (8)	O14—C13—C12	113.7 (3)
O1W^ii—Na1—O14^i	168.02 (9)	O13—C13—O14	126.2 (3)
Na1—O1W—Na1^ii	94.34 (8)	C1—C2—H2	120.00
Na1—O11—C1	129.73 (18)	C3—C2—H2	120.00
Na1—O11—C12	114.32 (17)	C2—C3—H3	121.00
C1—O11—C12	115.5 (2)	C4—C3—H3	121.00
Na1—O13—C13	124.3 (2)	C4—C5—H5	121.00
Na1^iii—O14—C13	122.97 (19)	C6—C5—H5	121.00
Na1—O1W—H12W	128.00	C1—C6—H6	120.00
H11W—O1W—H12W	110.00	C5—C6—H6	120.00
Na1^ii—O1W—H11W	116.00	O11—C12—H121	109.00
Na1^ii—O1W—H12W	106.00	O11—C12—H122	109.00
Na1—O1W—H11W	103.00	C13—C12—H121	109.00
Na1—O2W—H22W	101.00	C13—C12—H122	109.00
H21W—O2W—H22W	109.00	H121—C12—H122	108.00
O2W—Na1—O1W—Na1^ii	−80.20 (8)	O11—Na1—O1W^ii—Na1^ii	−158.39 (9)
O11—Na1—O1W—Na1^ii	56.4 (2)	O13—Na1—O1W^ii—Na1^ii	−90.01 (9)
O13—Na1—O1W—Na1^ii	81.85 (9)	Na1—O11—C1—C2	−175.8 (2)
O14^i—Na1—O1W—Na1^ii	−169.85 (8)	Na1—O11—C1—C6	4.1 (4)
O1W^ii—Na1—O1W—Na1^ii	0.02 (12)	C12—O11—C1—C2	12.6 (4)
O1W—Na1—O11—C1	−147.6 (2)	C12—O11—C1—C6	−167.6 (3)
O1W—Na1—O11—C12	24.2 (3)	Na1—O11—C12—C13	−2.8 (3)
O2W—Na1—O11—C1	−16.1 (3)	C1—O11—C12—C13	170.2 (2)
O2W—Na1—O11—C12	155.62 (18)	Na1—O13—C13—O14	161.6 (2)
O13—Na1—O11—C1	−175.3 (2)	Na1—O13—C13—C12	−18.9 (4)
O13—Na1—O11—C12	−3.59 (18)	Na1^iii—O14—C13—O13	−107.3 (3)
O14^i—Na1—O11—C1	82.4 (2)	Na1^iii—O14—C13—C12	73.1 (3)
O14^i—Na1—O11—C12	−105.91 (19)	O11—C1—C2—C3	−179.8 (3)
O1W^ii—Na1—O11—C1	−90.1 (2)	C6—C1—C2—C3	0.3 (5)
O1W^ii—Na1—O11—C12	81.61 (19)	O11—C1—C6—C5	179.7 (3)
O1W—Na1—O13—C13	−156.1 (2)	C2—C1—C6—C5	−0.4 (5)
O11—Na1—O13—C13	12.2 (2)	C1—C2—C3—C4	−0.3 (5)
O14^i—Na1—O13—C13	116.2 (2)	C2—C3—C4—F4	179.8 (3)
O1W^ii—Na1—O13—C13	−70.4 (2)	C2—C3—C4—C5	0.5 (5)
O1W—Na1—O14^i—C13^i	95.5 (2)	F4—C4—C5—C6	−180.0 (3)
O2W—Na1—O14^i—C13^i	11.6 (2)	C3—C4—C5—C6	−0.7 (5)
O11—Na1—O14^i—C13^i	−104.0 (2)	C4—C5—C6—C1	0.6 (5)
O13—Na1—O14^i—C13^i	−175.8 (2)	O11—C12—C13—O13	13.2 (4)
O1W—Na1—O1W^ii—Na1^ii	0.00 (7)	O11—C12—C13—O14	−167.2 (2)
O2W—Na1—O1W^ii—Na1^ii	84.58 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2W^iv	0.82	2.04	2.846 (3)	165
O1W—H12W···O13^v	0.92	2.05	2.862 (3)	147
O2W—H21W···O14^vi	0.80	1.93	2.727 (3)	177
O2W—H22W···O13^ii	0.91	1.97	2.877 (3)	176
C3—H3···F4^vii	0.95	2.53	3.154 (4)	123

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iv) −x+1, −y+2, −z+1; (v) −x+2, −y+1, −z+1; (vi) x−1, y+1, z; (vii) −x−1/2, y−1/2, −z+3/2.

Poly[µ₅-[2-(4-fluorophenoxy)acetato]-κ⁵O¹,O²:O¹,O^1':O^1':O^1':O^1'-potassium] (II)

Crystal data

[K(C8H6FO3)]	F(000) = 424
Mr = 208.23	Dx = 1.647 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 802 reflections
a = 18.3542 (15) Å	θ = 4.4–27.8°
b = 6.9466 (8) Å	µ = 0.62 mm^−1
c = 6.5969 (5) Å	T = 200 K
β = 92.995 (7)°	Plate, colourless
V = 839.94 (13) Å^3	0.30 × 0.16 × 0.08 mm
Z = 4

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	1647 independent reflections
Radiation source: Enhance (Mo) X-ray source	1354 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −22→22
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2014)	k = −8→8
Tmin = 0.896, Tmax = 0.990	l = −7→8
1647 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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0535P)^2 + 3.5272P] where P = (Fo^2 + 2Fc^2)/3
1647 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
K1	0.56245 (6)	0.47997 (19)	0.24806 (18)	0.0289 (4)
F4	0.9737 (2)	0.4952 (7)	0.1957 (6)	0.0564 (14)
O11	0.7007 (2)	0.4839 (7)	0.4894 (6)	0.0339 (13)
O13	0.5763 (2)	0.3954 (6)	0.6505 (6)	0.0330 (14)
O14	0.5884 (2)	0.6318 (7)	0.8797 (6)	0.0340 (13)
C1	0.7706 (3)	0.4988 (9)	0.4222 (8)	0.0309 (19)
C2	0.8274 (3)	0.5930 (10)	0.5270 (9)	0.0340 (19)
C3	0.8966 (3)	0.5907 (11)	0.4485 (9)	0.0396 (19)
C4	0.9064 (3)	0.4968 (11)	0.2703 (10)	0.0406 (19)
C5	0.8507 (4)	0.4057 (10)	0.1637 (10)	0.040 (2)
C6	0.7815 (3)	0.4059 (10)	0.2397 (9)	0.0373 (19)
C12	0.6873 (3)	0.5768 (10)	0.6755 (8)	0.0310 (19)
C13	0.6105 (3)	0.5301 (9)	0.7406 (8)	0.0294 (19)
H2	0.81950	0.65830	0.65040	0.0410*
H3	0.93640	0.65370	0.51840	0.0480*
H5	0.85910	0.34310	0.03910	0.0490*
H6	0.74210	0.34310	0.16770	0.0450*
H121	0.69250	0.71770	0.65930	0.0370*
H122	0.72370	0.53360	0.78190	0.0370*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0266 (6)	0.0432 (8)	0.0167 (6)	0.0012 (6)	0.0008 (4)	−0.0015 (6)
F4	0.036 (2)	0.090 (3)	0.045 (2)	0.008 (2)	0.0202 (17)	0.004 (2)
O11	0.0231 (19)	0.058 (3)	0.0207 (19)	−0.0021 (19)	0.0022 (15)	−0.008 (2)
O13	0.031 (2)	0.046 (3)	0.022 (2)	−0.0031 (19)	0.0019 (16)	−0.002 (2)
O14	0.033 (2)	0.055 (3)	0.0146 (18)	0.002 (2)	0.0073 (16)	−0.004 (2)
C1	0.026 (3)	0.049 (4)	0.018 (3)	0.006 (3)	0.003 (2)	0.002 (3)
C2	0.026 (3)	0.052 (4)	0.024 (3)	0.001 (3)	0.002 (2)	−0.005 (3)
C3	0.029 (3)	0.065 (4)	0.025 (3)	0.002 (3)	0.003 (2)	0.003 (3)
C4	0.030 (3)	0.058 (4)	0.034 (3)	0.012 (3)	0.005 (3)	0.008 (3)
C5	0.045 (4)	0.053 (4)	0.024 (3)	0.010 (3)	0.009 (3)	−0.005 (3)
C6	0.030 (3)	0.054 (4)	0.027 (3)	0.000 (3)	−0.006 (2)	−0.010 (3)
C12	0.025 (3)	0.053 (4)	0.015 (3)	−0.001 (3)	0.001 (2)	−0.003 (3)
C13	0.025 (3)	0.046 (4)	0.017 (3)	0.002 (3)	−0.002 (2)	0.008 (3)

Geometric parameters (Å, º)

K1—O11	2.924 (4)	C1—C6	1.390 (8)
K1—O13	2.718 (4)	C2—C3	1.397 (8)
K1—O14^i	2.714 (4)	C3—C4	1.365 (9)
K1—O13^ii	2.804 (4)	C4—C5	1.366 (9)
K1—O14^ii	2.956 (4)	C5—C6	1.390 (9)
K1—O13^iii	2.701 (4)	C12—C13	1.530 (8)
K1—O14^iv	2.866 (5)	C2—H2	0.9500
F4—C4	1.353 (7)	C3—H3	0.9500
O11—C1	1.383 (7)	C5—H5	0.9500
O11—C12	1.420 (7)	C6—H6	0.9500
O13—C13	1.259 (7)	C12—H121	0.9900
O14—C13	1.243 (7)	C12—H122	0.9900
C1—C2	1.385 (8)
O11—K1—O13	55.67 (11)	K1^vii—O14—C13	111.5 (4)
O11—K1—O14^i	107.22 (12)	K1^vi—O14—K1^ii	87.00 (12)
O11—K1—O13^ii	129.81 (12)	K1^vi—O14—K1^vii	127.08 (16)
O11—K1—O14^ii	158.59 (13)	K1^ii—O14—K1^vii	91.29 (12)
O11—K1—O13^iii	92.81 (13)	O11—C1—C2	124.2 (5)
O11—K1—O14^iv	72.57 (13)	O11—C1—C6	114.9 (5)
O13—K1—O14^i	161.22 (13)	C2—C1—C6	120.9 (5)
O13—K1—O13^ii	82.73 (12)	C1—C2—C3	119.0 (6)
O13—K1—O14^ii	105.08 (12)	C2—C3—C4	119.2 (6)
O13—K1—O13^iii	91.08 (13)	F4—C4—C3	118.8 (5)
O13—K1—O14^iv	84.37 (12)	F4—C4—C5	118.8 (6)
O13^ii—K1—O14^i	107.33 (12)	C3—C4—C5	122.4 (6)
O14^i—K1—O14^ii	93.00 (12)	C4—C5—C6	119.2 (6)
O13^iii—K1—O14^i	97.97 (14)	C1—C6—C5	119.3 (6)
O14^i—K1—O14^iv	82.61 (13)	O11—C12—C13	110.5 (5)
O13^ii—K1—O14^ii	45.58 (12)	O13—C13—O14	126.7 (5)
O13^ii—K1—O13^iii	116.93 (12)	O13—C13—C12	118.0 (5)
O13^ii—K1—O14^iv	77.04 (12)	O14—C13—C12	115.3 (5)
O13^iii—K1—O14^ii	77.11 (12)	C1—C2—H2	121.00
O14^ii—K1—O14^iv	118.17 (13)	C3—C2—H2	120.00
O13^iii—K1—O14^iv	164.71 (12)	C2—C3—H3	120.00
K1—O11—C1	128.3 (3)	C4—C3—H3	120.00
K1—O11—C12	106.9 (3)	C4—C5—H5	120.00
C1—O11—C12	116.7 (4)	C6—C5—H5	120.00
K1—O13—C13	108.6 (3)	C1—C6—H6	120.00
K1—O13—K1^ii	97.28 (12)	C5—C6—H6	120.00
K1—O13—K1^v	115.87 (15)	O11—C12—H121	110.00
K1^ii—O13—C13	95.4 (3)	O11—C12—H122	110.00
K1^v—O13—C13	131.0 (4)	C13—C12—H121	110.00
K1^ii—O13—K1^v	98.24 (13)	C13—C12—H122	110.00
K1^vi—O14—C13	121.3 (4)	H121—C12—H122	108.00
K1^ii—O14—C13	88.7 (3)
O13—K1—O11—C1	169.5 (5)	O13^vii—K1^vii—O14—C13	−158.7 (4)
O14^i—K1—O11—C1	−19.1 (5)	O14^iii—K1^v—O13—C13	−133.5 (4)
O13^ii—K1—O11—C1	−150.8 (4)	O11^vi—K1^vi—O14—C13	86.2 (4)
O14^ii—K1—O11—C1	141.0 (5)	O13^v—K1^vi—O14—C13	−9.2 (4)
O13^iii—K1—O11—C1	80.1 (5)	O14^vii—K1^vi—O14—C13	155.3 (4)
O14^iv—K1—O11—C1	−95.4 (5)	O13—K1^ii—O14—C13	10.0 (3)
O13—K1—O11—C12	−43.7 (3)	O11^v—K1^v—O13—K1	127.46 (15)
O14^i—K1—O11—C12	127.6 (4)	O13^v—K1^v—O13—K1	−176.86 (15)
O13^ii—K1—O11—C12	−4.0 (4)	O11^vii—K1^vii—O14—C13	−103.0 (4)
O14^ii—K1—O11—C12	−72.3 (5)	O11^v—K1^v—O13—C13	−25.7 (5)
O13^iii—K1—O11—C12	−133.1 (4)	O13^v—K1^v—O13—C13	30.0 (5)
O14^iv—K1—O11—C12	51.4 (4)	O14^viii—K1^vii—O14—C13	97.2 (4)
O14—K1^ii—O13—C13	−9.9 (3)	O14^iv—K1^vii—O14—C13	7.7 (4)
O13^viii—K1^ii—O13—C13	22.1 (4)	K1—O11—C1—C6	−36.0 (7)
O11^ii—K1^ii—O13—C13	141.8 (3)	C12—O11—C1—C6	180.0 (5)
O13^ii—K1^ii—O13—C13	109.6 (3)	K1—O11—C1—C2	145.8 (5)
O14—K1^ii—O13—K1^v	122.9 (2)	K1—O11—C12—C13	34.7 (5)
O14^iii—K1^v—O13—K1	19.64 (16)	C12—O11—C1—C2	1.8 (9)
O11—K1—O13—C13	52.1 (3)	C1—O11—C12—C13	−174.1 (5)
O13^ii—K1—O13—C13	−98.3 (4)	K1^v—O13—C13—C12	95.5 (6)
O14^ii—K1—O13—C13	−138.3 (3)	K1^ii—O13—C13—O14	21.3 (6)
O13^iii—K1—O13—C13	144.7 (4)	K1—O13—C13—O14	120.9 (6)
O14^iv—K1—O13—C13	−20.7 (3)	K1—O13—C13—C12	−59.1 (5)
O11—K1—O13—K1^ii	150.32 (19)	K1^ii—O13—C13—C12	−158.7 (4)
O13^ii—K1—O13—K1^ii	0.00 (13)	K1^v—O13—C13—O14	−84.6 (7)
O14^ii—K1—O13—K1^ii	−40.08 (16)	K1^vii—O14—C13—C12	69.1 (5)
O13^iii—K1—O13—K1^ii	−117.02 (13)	K1^vi—O14—C13—O13	65.6 (7)
O14^iv—K1—O13—K1^ii	77.61 (13)	K1^vi—O14—C13—C12	−114.4 (5)
O11—K1—O13—K1^v	−106.83 (19)	K1^ii—O14—C13—O13	−20.1 (6)
O13^ii—K1—O13—K1^v	102.85 (16)	K1^ii—O14—C13—C12	159.9 (4)
O14^ii—K1—O13—K1^v	62.77 (17)	K1^vii—O14—C13—O13	−110.9 (6)
O13^iii—K1—O13—K1^v	−14.17 (15)	O11—C1—C2—C3	177.0 (6)
O14^iv—K1—O13—K1^v	−179.54 (16)	C6—C1—C2—C3	−1.1 (10)
O13^viii—K1^ii—O14—C13	−141.1 (4)	O11—C1—C6—C5	−177.3 (6)
O11^ii—K1^ii—O14—C13	−77.6 (5)	C2—C1—C6—C5	0.9 (10)
O13^ii—K1^ii—O14—C13	−53.5 (4)	C1—C2—C3—C4	0.4 (10)
O13—K1^ii—O14—K1^vi	−111.5 (2)	C2—C3—C4—F4	−179.9 (6)
O13—K1^ii—O14—K1^vii	121.46 (18)	C2—C3—C4—C5	0.6 (11)
O13^viii—K1^vii—O14—C13	117.5 (4)	F4—C4—C5—C6	179.7 (6)
O14—K1^ii—O13—K1	−119.5 (2)	C3—C4—C5—C6	−0.8 (11)
O13^viii—K1^ii—O13—K1	−87.51 (15)	C4—C5—C6—C1	0.0 (10)
O11^ii—K1^ii—O13—K1	32.2 (2)	O11—C12—C13—O13	13.0 (7)
O13^ii—K1^ii—O13—K1	0.00 (13)	O11—C12—C13—O14	−167.0 (5)

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

Poly[µ₅-[2-(4-fluorophenoxy)acetato]-κ⁵O¹,O²:O¹,O^1':O^1':O^1':O^1'-rubidium] (III)

Crystal data

[Rb(C8H6FO3)]	F(000) = 496
Mr = 254.60	Dx = 1.915 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1154 reflections
a = 18.0011 (16) Å	θ = 3.4–28.0°
b = 7.1625 (4) Å	µ = 5.59 mm^−1
c = 6.8548 (4) Å	T = 200 K
β = 91.995 (7)°	Plate, colourless
V = 883.27 (11) Å^3	0.35 × 0.30 × 0.03 mm
Z = 4

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	1735 independent reflections
Radiation source: Enhance (Mo) X-ray source	1315 reflections with I > 2]s(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 16.07 pixels mm^-1	θmax = 26.0°, θmin = 3.4°
ω scans	h = −22→15
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2014)	k = −8→8
Tmin = 0.42, Tmax = 0.98	l = −6→8
3411 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0365P)^2] where P = (Fo^2 + 2Fc^2)/3
1735 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 1.17 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Rb1	0.56818 (3)	0.47364 (7)	0.24428 (7)	0.0324 (2)
F4	0.9883 (2)	0.5090 (5)	0.1990 (5)	0.0584 (16)
O11	0.7111 (2)	0.4808 (5)	0.4986 (5)	0.0350 (12)
O13	0.5819 (2)	0.4066 (5)	0.6572 (5)	0.0389 (14)
O14	0.5951 (2)	0.6396 (5)	0.8734 (5)	0.0352 (14)
C1	0.7813 (3)	0.4990 (6)	0.4306 (7)	0.0304 (19)
C2	0.8368 (4)	0.6086 (7)	0.5143 (8)	0.0374 (19)
C3	0.9064 (4)	0.6096 (8)	0.4355 (8)	0.040 (2)
C4	0.9192 (3)	0.5044 (8)	0.2744 (8)	0.040 (2)
C5	0.8652 (4)	0.3972 (8)	0.1876 (8)	0.044 (2)
C6	0.7954 (4)	0.3956 (7)	0.2643 (8)	0.0384 (19)
C12	0.6952 (3)	0.5806 (7)	0.6728 (7)	0.0321 (19)
C13	0.6176 (4)	0.5380 (7)	0.7386 (8)	0.0323 (19)
H2	0.82720	0.68290	0.62550	0.0450*
H3	0.94520	0.68320	0.49330	0.0480*
H5	0.87540	0.32460	0.07570	0.0520*
H6	0.75690	0.32350	0.20330	0.0460*
H11	0.69980	0.71630	0.64880	0.0380*
H12	0.73180	0.54590	0.77750	0.0380*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0407 (4)	0.0287 (3)	0.0277 (3)	−0.0011 (2)	0.0006 (2)	0.0002 (2)
F4	0.044 (3)	0.086 (3)	0.046 (2)	0.009 (2)	0.0113 (18)	0.0016 (18)
O11	0.032 (2)	0.039 (2)	0.034 (2)	−0.0015 (18)	0.0004 (17)	−0.0097 (16)
O13	0.047 (3)	0.031 (2)	0.039 (2)	−0.0084 (18)	0.0066 (19)	−0.0007 (17)
O14	0.045 (3)	0.033 (2)	0.028 (2)	0.0004 (18)	0.0072 (18)	−0.0026 (16)
C1	0.036 (4)	0.030 (3)	0.025 (3)	0.004 (3)	0.000 (2)	0.001 (2)
C2	0.039 (4)	0.040 (3)	0.033 (3)	0.001 (3)	−0.001 (3)	−0.005 (2)
C3	0.034 (4)	0.051 (4)	0.035 (3)	−0.003 (3)	−0.001 (3)	−0.001 (3)
C4	0.035 (4)	0.048 (4)	0.038 (3)	0.010 (3)	0.004 (3)	0.008 (3)
C5	0.054 (5)	0.042 (3)	0.035 (3)	0.008 (3)	0.006 (3)	−0.008 (3)
C6	0.045 (4)	0.033 (3)	0.037 (3)	0.000 (3)	0.000 (3)	−0.005 (2)
C12	0.037 (4)	0.027 (3)	0.032 (3)	−0.001 (2)	−0.001 (3)	−0.009 (2)
C13	0.044 (4)	0.024 (3)	0.029 (3)	0.003 (3)	0.004 (2)	0.008 (2)

Geometric parameters (Å, º)

Rb1—O11	3.058 (4)	C1—C6	1.390 (7)
Rb1—O13	2.873 (3)	C2—C3	1.382 (10)
Rb1—O14^i	2.863 (4)	C3—C4	1.363 (8)
Rb1—O13^ii	2.936 (4)	C4—C5	1.360 (8)
Rb1—O14^ii	3.128 (4)	C5—C6	1.379 (10)
Rb1—O13^iii	2.801 (4)	C12—C13	1.514 (9)
Rb1—O14^iv	2.943 (4)	C2—H2	0.9500
F4—C4	1.364 (6)	C3—H3	0.9500
O11—C1	1.368 (6)	C5—H5	0.9500
O11—C12	1.429 (6)	C6—H6	0.9500
O13—C13	1.259 (7)	C12—H11	0.9900
O14—C13	1.254 (7)	C12—H12	0.9900
C1—C2	1.380 (8)
O11—Rb1—O13	53.08 (10)	Rb1^vii—O14—C13	112.2 (3)
O11—Rb1—O14^i	109.53 (10)	Rb1^vi—O14—Rb1^ii	86.26 (9)
O11—Rb1—O13^ii	128.81 (10)	Rb1^vi—O14—Rb1^vii	128.80 (13)
O11—Rb1—O14^ii	156.34 (9)	Rb1^ii—O14—Rb1^vii	91.32 (10)
O11—Rb1—O13^iii	93.39 (10)	O11—C1—C2	125.2 (5)
O11—Rb1—O14^iv	71.72 (10)	O11—C1—C6	115.2 (5)
O13—Rb1—O14^i	158.88 (10)	C2—C1—C6	119.6 (5)
O13—Rb1—O13^ii	82.56 (10)	C1—C2—C3	119.6 (5)
O13—Rb1—O14^ii	104.98 (10)	C2—C3—C4	119.7 (6)
O13—Rb1—O13^iii	92.42 (10)	F4—C4—C3	118.4 (5)
O13—Rb1—O14^iv	81.57 (10)	F4—C4—C5	119.7 (5)
O13^ii—Rb1—O14^i	105.58 (10)	C3—C4—C5	121.9 (6)
O14^i—Rb1—O14^ii	93.74 (10)	C4—C5—C6	119.0 (5)
O13^iii—Rb1—O14^i	101.28 (10)	C1—C6—C5	120.2 (6)
O14^i—Rb1—O14^iv	81.09 (10)	O11—C12—C13	111.2 (4)
O13^ii—Rb1—O14^ii	43.20 (9)	O13—C13—O14	126.0 (6)
O13^ii—Rb1—O13^iii	114.95 (10)	O13—C13—C12	118.7 (5)
O13^ii—Rb1—O14^iv	78.41 (10)	O14—C13—C12	115.3 (5)
O13^iii—Rb1—O14^ii	77.40 (10)	C1—C2—H2	120.00
O14^ii—Rb1—O14^iv	117.71 (10)	C3—C2—H2	120.00
O13^iii—Rb1—O14^iv	164.69 (10)	C2—C3—H3	120.00
Rb1—O11—C1	125.2 (3)	C4—C3—H3	120.00
Rb1—O11—C12	107.2 (3)	C4—C5—H5	120.00
C1—O11—C12	116.8 (4)	C6—C5—H5	121.00
Rb1—O13—C13	109.7 (3)	C1—C6—H6	120.00
Rb1—O13—Rb1^ii	97.45 (11)	C5—C6—H6	120.00
Rb1—O13—Rb1^v	111.55 (12)	O11—C12—H11	109.00
Rb1^ii—O13—C13	98.0 (4)	O11—C12—H12	109.00
Rb1^v—O13—C13	132.8 (3)	C13—C12—H11	109.00
Rb1^ii—O13—Rb1^v	98.42 (11)	C13—C12—H12	109.00
Rb1^vi—O14—C13	118.8 (3)	H11—C12—H12	108.00
Rb1^ii—O14—C13	89.1 (4)
O13—Rb1—O11—C1	173.2 (4)	O13—Rb1—O14^ii—C13^ii	51.2 (3)
O13—Rb1—O11—C12	−44.0 (3)	O11—Rb1—O13^iii—Rb1^iii	−129.02 (12)
O14^i—Rb1—O11—C1	−20.5 (3)	O11—Rb1—O13^iii—C13^iii	20.3 (5)
O14^i—Rb1—O11—C12	122.3 (3)	O13—Rb1—O13^iii—Rb1^iii	177.83 (13)
O13^ii—Rb1—O11—C1	−151.1 (3)	O13—Rb1—O13^iii—C13^iii	−32.9 (5)
O13^ii—Rb1—O11—C12	−8.4 (3)	O11—Rb1—O14^iv—C13^iv	106.0 (4)
O14^ii—Rb1—O11—C1	148.6 (3)	O11—Rb1—O14^iv—Rb1^vii	−78.18 (16)
O14^ii—Rb1—O11—C12	−68.7 (4)	O13—Rb1—O14^iv—C13^iv	159.8 (4)
O13^iii—Rb1—O11—C1	82.7 (3)	O13—Rb1—O14^iv—Rb1^vii	−24.38 (16)
O13^iii—Rb1—O11—C12	−134.5 (3)	Rb1—O11—C1—C2	138.1 (4)
O14^iv—Rb1—O11—C1	−93.6 (3)	Rb1—O11—C1—C6	−42.2 (5)
O14^iv—Rb1—O11—C12	49.1 (3)	C12—O11—C1—C2	−1.5 (7)
O11—Rb1—O13—C13	51.4 (4)	C12—O11—C1—C6	178.2 (4)
O11—Rb1—O13—Rb1^ii	152.73 (16)	Rb1—O11—C12—C13	37.4 (4)
O11—Rb1—O13—Rb1^v	−105.13 (16)	C1—O11—C12—C13	−176.3 (4)
O14^i—Rb1—O13—C13	13.1 (5)	Rb1—O13—C13—O14	122.7 (5)
O14^i—Rb1—O13—Rb1^ii	114.4 (3)	Rb1—O13—C13—C12	−57.8 (5)
O14^i—Rb1—O13—Rb1^v	−143.5 (2)	Rb1^ii—O13—C13—O14	21.8 (6)
O13^ii—Rb1—O13—C13	−101.3 (4)	Rb1^ii—O13—C13—C12	−158.7 (4)
O13^ii—Rb1—O13—Rb1^ii	0.00 (10)	Rb1^v—O13—C13—O14	−87.6 (7)
O13^ii—Rb1—O13—Rb1^v	102.14 (13)	Rb1^v—O13—C13—C12	91.9 (5)
O14^ii—Rb1—O13—C13	−138.5 (4)	Rb1^vi—O14—C13—O13	65.0 (7)
O14^ii—Rb1—O13—Rb1^ii	−37.25 (12)	Rb1^vi—O14—C13—C12	−114.5 (4)
O14^ii—Rb1—O13—Rb1^v	64.90 (14)	Rb1^ii—O14—C13—O13	−20.2 (6)
O13^iii—Rb1—O13—C13	143.9 (4)	Rb1^ii—O14—C13—C12	160.3 (4)
O13^iii—Rb1—O13—Rb1^ii	−114.85 (11)	Rb1^vii—O14—C13—O13	−111.3 (5)
O13^iii—Rb1—O13—Rb1^v	−12.71 (13)	Rb1^vii—O14—C13—C12	69.2 (5)
O14^iv—Rb1—O13—C13	−22.0 (4)	O11—C1—C2—C3	177.6 (5)
O14^iv—Rb1—O13—Rb1^ii	79.31 (11)	C6—C1—C2—C3	−2.1 (8)
O14^iv—Rb1—O13—Rb1^v	−178.55 (14)	O11—C1—C6—C5	−177.3 (5)
O11—Rb1—O14^i—C13^i	88.7 (4)	C2—C1—C6—C5	2.4 (8)
O11—Rb1—O14^i—Rb1^iv	−95.68 (16)	C1—C2—C3—C4	0.9 (8)
O13—Rb1—O14^i—C13^i	120.5 (5)	C2—C3—C4—F4	179.6 (5)
O13—Rb1—O14^i—Rb1^iv	−64.0 (4)	C2—C3—C4—C5	0.0 (9)
O11—Rb1—O13^ii—Rb1^ii	−28.05 (16)	F4—C4—C5—C6	−179.3 (5)
O11—Rb1—O13^ii—C13^ii	−139.2 (3)	C3—C4—C5—C6	0.3 (9)
O13—Rb1—O13^ii—Rb1^ii	0.00 (10)	C4—C5—C6—C1	−1.5 (8)
O13—Rb1—O13^ii—C13^ii	−111.2 (3)	O11—C12—C13—O13	10.4 (7)
O11—Rb1—O14^ii—C13^ii	71.3 (4)	O11—C12—C13—O14	−170.1 (4)

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