Two two-dimensional Mn^II and Na^I coordination polymers constructed by the flexible benzene-1,4-dioxy­acetate ligand

Two new two-dimensional coordination polymers, poly­[[[aqua(2,2′-bi­pyridine-κ²N,N′)manganese(II)]-μ₃-p-phenyl­enebis­(oxy­acet­ato)-κ³O:O′:O′′] dihydrate], {[Mn(C₁₀H₈O₆)(C₁₀H₈N₂)(H₂O)]·2H₂O}_n, (I), and poly­[[di-μ-aqua-bis­[aqua­sodium(I)]]-μ₄-p-phenyl­enebis­(oxy­acetato)-κO:O′,O′′:O′′′,O′′′′:O′′′′′], [Na₂(C₁₀H₈O₆)(H₂O)₄]_n, (II), have been synthesized and characterized by X-ray single-crystal diffraction. In (I), there are two 1,4-BDOA²⁻ [p-phenyl­enebis­(oxy­acetate) or, more commonly, benzene-1,4-dioxy­acetate] ligands, each lying about inversion centres, while in (II), there is one such ligand and it also has crystallographically imposed inversion symmetry. In (I), each Mn^II atom displays an octahedral MnN₂O₄ configuration, defined by three carboxyl O atoms of different 1,4-BDOA²⁻ groups, two N atoms of one 2,2′-bi­pyridine ligand and one water mol­ecule. In (II), each Na^I atom is octahedrally coordinated by one ether O atom, two carboxyl O atoms of different 1,4-BDOA²⁻ ligands and three water mol­ecules. The metal ions in complexes (I) and (II) are bridged by 1,4-BDOA²⁻ groups into two-dimensional layer structures. Furthermore, three-dimensional supramolecular networks are constructed via hydrogen bonds in (I) and (II), and by additional π–π stacking interactions in (I).

S1. Comment

Molecular self-assembly of coordination architectures has been a rapidly developing research area within supramolecular chemistry in recent years (Liu et al., 2003). Ligand design is an important factor which greatly influences the structure of the coordination architecture and the functionality of the complex formed. To date, a number of metal-organic polymers with one-, two- and three-dimensional infinite frameworks have been generated (Lee et al., 2003; Gutschke et al., 2001), in which the more rigid aromatic polycarboxylic acids, such as terephthalic acid or related species, are often chosen to fabricate these complexes (Gomez-Lor et al., 2002; Bian et al., 2003).

Previous studies by our group have shown that the flexible benzene-1,4-dioxydiacetic acid (1,4-BDOAH₂), an analogue of terephthalic acid, can exhibit versatile binding modes and forms a variety of topologies. In the case of the mononuclear [Mn(H₂O)₆](1,4-BDOA) complex, the 1,4-BDOA²⁻ dianion functions as counter-ion (Liu et al., 2004), while in the mononuclear [Co(1,4-BDOA)(2,2'-bipy)₂(H₂O)]·4H₂O complex (2,2'-bipy is 2,2'-bipyridine), only one of two oxyacetate groups of the 1,4-BDOA²⁻ ligand in the monodentate mode is coordinated to the metal centre (Gao Liu Huo & Zhao, 2004).

For one-dimensional coordination polymers, the 1,4-BDOA²⁻ dianion acts in a great variety of coordination modes, such as bidentate (Gao Liu Huo Zhao & Zhao, 2004c,d,f), tridentate (Gao Liu Huo Zhao & Zhao, 2004b,e) or tetradentate (Gao Liu Huo Zhao & Ng, 2004). In this paper, we report two novel two-dimensional coordination polymers, {[Mn(1,4-BDOA)(2,2'-bipy)(H₂O)]·2H₂O}_n, (I), and [Na₂(1,4-BDOA)(H₂O)₄]_n, (II), and describe their crystal structures. \sch

As shown in Fig.1, the asymmetric unit of (I) is composed of one Mn^II atom, one 2,2'-bipy ligand, two halves of independent 1,4-BDOA²⁻ groups lying about different inversion centres, one coordinated water molecule and two solvate water molecules. The carboxylate groups bind to each Mn^II atom in a monodentate fashion. Each Mn^II centre is coordinated by three carboxyl O atoms from different 1,4-BDOA²⁻ groups, two N atoms from one 2,2'-bipy ligand and one water molecule, resulting in a distorted octahedral environment. The Mn^II atom does not deviate significantly from the equatorial plane of atoms O1/O4ⁱ/N1/N2 [displacement 0.01 (2) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z]. The Mn1—O1 distance (Table 1) is slightly shorter than those of Mn1—O4 and Mn1—O4ⁱ. The 2,2'-bipy ligand connects the Mn^II atom to form a five-membered chelate ring, with a mean Mn—N distance of 2.28 (3) Å and an N1—Mn1—N2 bond angle of 72.14 (5)°.

It should be noted that the two C—O bond distances of the carboxyl group (O1—C11—O2) are almost equivalent, agreeing with its delocalized state, whereas the O4—C16 distance is longer than the O5—C16 distance, in accord with the formal double-bond character of the O5—C16 bond. This is also reflected by the fact that the two carboxyl groups are involved in coordination to Mn, exhibiting a monodentate-linked mode via atom O1 and a bidentate-bridged mode via atom O4. The bidentate-bridged oxyacetate group and aromatic ring are almost coplanar, with the C18—O6—C17—C16 torsion angle being 175.12 (13)°. In contrast, the monodentate-linked oxyacetate group is twisted out the aromatic ring plane, with the C13—O3—C2—C1 torsion angle being 80.0 (2)°. The 2,2'-bipy ligand is nearly perpendicular to the two phenyl rings, with dihedral angles of 88.6 (2) and 89.8 (2)°.

Fig. 2 shows the two-dimensional layer structure of (I). Two MnN₂O₄ octahedral units are linked by the carboxyl atoms O4 and O4ⁱ to form a binuclear unit [Mn1···Mn1ⁱ 3.588 (2) Å]. All the binuclear units are bridged by one 1,4-BDOA²⁻ group in tetradentate mode, to produce a one-dimensional chain, with Mn1···Mn1ⁱⁱ 14.537 (2), Mn1···Mn1ⁱⁱⁱ 13.428 (2) and Mn1ⁱ···Mn1ⁱⁱ 16.373 (2) Å [symmetry codes: (ii) 1 + x, y, z − 1; (iii) 2 − x, 1 − y, −z]. These infinite chains are further connected together by another 1,4-BDOA²⁻ group in bidentate mode [Mn1···Mn1^iv 11.401 (2) Å; symmetry code: (iv) 1 − x, 1 − y, −z], generating a two-dimensional architecture running in the crystallographic bc plane. In addition, the chains are connected through extensive hydrogen bonds involving the water molecules and 1,4-BDOA groups, with O···O distances in the range 2.655 (2)–2.822 (3) Å (Table 2).

There are partial face-to-face π–π stacking interactions between adjacent 2,2'-bipy ligands. The centroid···centroid separation between ring N1/C1—C5 and ring N2/C6—C10 at (2 − x, −y, 1 − z) is 3.898 (2) Å, and the shortest C···C separation is C2···C8(2 − x, −y, 1 − z) of 3.593 (3) Å. With the help of such interactions, the polymeric chains are assembled to form a three-dimensional supramolecular network.

As illustrated in Fig. 3, the asymmetric unit of (II) consists of one Na^I atom, half of a 1,4-BDOA²⁻ group lying about an inversion centre and two coordinated water molecules. The unique ether O atom of the 1,4-BDOA²⁻ group coordinates to the Na^I centre. The coordination sphere of the Na^I atom has distorted octahedral geometry, the basal plane consisting of carboxyl atom O1, ether atom O3 of the 1,4-BDOA²⁻ group and two water molecules (O1W and O2W) [r.m.s. deviation 0.04 (1) Å; deviation of Na1 from the basal plane −0.34 (2) Å], while the axial coordination sites are occupied by the carboxyl atom O2^vi atom and water molecule O2W^v (see Table 3 for symmetry codes). The Na1—O1W bond distance (terminal water) (Table 3) is somewhat longer than Na1—O2W and Na—O2W^v (bridging waters) and lies within the range of the corresponding bond distances [2.365 (2)–2.485 (2) Å] in the complex [Na(1,3-BDOA)₂(H₂O)₃][Cr(H₂O)₆]·(H₂O)₅, (III) (Gao Liu Huo Zhao & Zhao, 2004a).

The Na—O_ether and Na—O_carboxyl bond distances in (II) are shorter than the corresponding bond distances in complex (III) [Na—O_ether 2.966 (2) Å, and Na—O_carboxyl 2.381 (2) and 2.635 (2) Å]. In (III), each Na atom displays a distorted trigonal prism geometry, involving two carboxyl O atoms and one ether O atom of different oxyacetate groups and three water molecules. These differences are probably due to steric effects from the unusual coordination mode for the 1,4-BDOA²⁻ group in (II) compared with the 1,3-BDOA²⁻ group in (III).

In (II), the oxyacetate group combines with the Na^I centre through ether atom O3 and carboxyl atom O1 to give one five-membered chelate plane (O1—C1—C2—O3—Na), and the r.m.s. deviation for the five atoms is 0.01 (2) Å. The C—O bond distances of the unique carboxyl group do not differ, in accord with the electron delocalization. The oxyacetate group and the benzene ring are essentially coplanar, with a C3—O3—C2—C1 torsion angle of 175.08 (11)°.

The 1,4-BDOA²⁻ group in (II) serves as a rare hexadentate ligand, constructing a two-dimensional coordination polymer (Fig. 4). Two adjacent octahedral units are linked together by two H₂O bridges to form a four-membered ring with an Na₂O₂ core. The Na1···Na1^vi separation is 3.582 (2) Å [symmetry code: (vi) 1 − x, 1 − y, 1 − z]. Adjacent Na₂O₁₂ binuclear motifs are further joined by the oxyacetate groups of 1,4-BDOA²⁻ ligands through carboxyl atom O1 and ether atom O3, to produce a one-dimensional chain along the c axis, with an Na1···Na1^viii separation of 9.233 (2) Å [symmetry code: (viii) 2 − x, 1 − y, −z]; this is significantly longer than the corresponding Na···Na distance of 8.006 (3) Å in the three-dimensional Na-terephthalate polymer [Na₂(C₈H₄O₄)] (Kaduk, 2000). These chains are connected by the other carboxyl O atoms of the 1,4-BDOA ligands [Na1···Na1^vii 5.914 (2) Å and Na1···Na1^ix 10.301 (2) Å; symmetry codes: (vii) x, y − 1, z; (ix) 2 − x, 2 − y, z], generating a two-dimensional layer architecture in the crystallographic bc plane. These layers are stabilized by intermolecular hydrogen bonds, which are formed between the water molecules and carboxyl O atoms, with O···O distances in the range 2.757 (2)–2.938 (2) Å (Table 4), leading to the formation of a three-dimensional supramolecular network.

It is the conformational flexibility of the 1,4-BDOA²⁻ ligand, with bidentate and tridentate bridging modes in complex (I) and a hexadentate bridging mode in complex (II), which leads to the formation of two novel two-dimensional layer complexes, with octahedral geometries for the metal ions as well as different arrangements of the whole structures.

S2. Experimental

Benzene-1,4-dioxyacetic acid was prepared following the method described for the synthesis of benzene-1,2-dioxyacetic acid by Mirci (1990). Complex (I) was synthesized by the addition of MnCl₂·6H₂O (4.68 g, 20 mmol) and 2,2'-bipy (2.12 g, 20 mmol) to a hot aqueous solution of 1,4-BDOAH₂ (4.52 g, 20 mmol). The solution was allowed to evaporate at room temperature and yellow crystals of (I) were obtained after about 7 d. CHN analysis, calculated for C₂₀H₂₂N₂O₉Mn: C 49.09, H 4.53, N 5.72%; found: C 49.15, H 4.48, N 5.69%. Complex (II) was prepared by the addition of stoichiometric amounts of Ni(OAc)₂·4H₂O (4.96 g, 10 mmol), imidazole ((0.95 g, 10 mmol) and NaOH (0.80 g, 20 mmol) to a hot aqueous solution of 1,4-BDOAH₂ (2.26 g, 10 mmol), with subsequent filtration. Colourless crystals of (II) were obtained at room temperature over several days. CH analysis, calculated for C₁₀H₁₆O₁₀Na₂: C 35.10, H 4.71%; found: C 35.29, H 4.63%.

S3. Refinement

C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and U_iso(H) = 1.2U_eq(C), and were refined in the riding-model approximation. Water H atoms were located in a difference map and refined with O—H distance restraints of 0.85 (1) Å and with U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of complex (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 + x, y, z − 1; (iii) 2 − x, 1 − y, −z; (iv) 1 − x, 1 − y, −z].
	Fig. 2. The two-dimensional layer structure of (I), with the 2,2'-bipy ligand and water molecules omitted for clarity. Symmetry codes are as in Fig. 1.
	Fig. 3. A view of complex (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (v) x, 1 − y, 1 − z; (vi) 1 − x, 1 − y, 1 − z; (vii) x, y − 1, z; (viii) 2 − x, 1 − y, −z; (ix) 2 − x, 2 − y, z].
	Fig. 4. The two-dimensional layer structure of (II). Symmetry codes are as in Fig. 3.

(I) poly[[[aqua(2,2'-bipyridine-κ²N,N')manganese(II)]- µ₃-p-phenylenebis(oxyacetato)-κ³O:O':O''] dihydrate]

Crystal data

[Mn(C10H8O6)(C10H8N2)(H2O)]·2H2O	Z = 2
Mr = 489.34	F(000) = 506
Triclinic, P1	Dx = 1.500 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3142 (19) Å	Cell parameters from 5624 reflections
b = 10.315 (2) Å	θ = 3.0–27.5°
c = 12.169 (2) Å	µ = 0.66 mm^−1
α = 87.87 (3)°	T = 293 K
β = 84.04 (3)°	Prism, pale yellow
γ = 68.68 (3)°	0.41 × 0.32 × 0.21 mm
V = 1083.3 (4) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	4928 independent reflections
Radiation source: fine-focus sealed tube	4461 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→13
Tmin = 0.773, Tmax = 0.873	l = −15→15
10496 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.2938P] where P = (Fo^2 + 2Fc^2)/3
4928 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.41 e Å^−3
9 restraints	Δρmin = −0.17 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.61289 (2)	0.33086 (2)	0.444083 (17)	0.03233 (9)
N1	0.82625 (15)	0.29404 (15)	0.53092 (12)	0.0405 (3)
N2	0.82389 (16)	0.19612 (15)	0.33029 (11)	0.0401 (3)
O1	0.46484 (14)	0.35065 (13)	0.31732 (10)	0.0440 (3)
O2	0.42236 (19)	0.15119 (15)	0.32103 (12)	0.0575 (3)
O3	0.28052 (16)	0.45515 (15)	0.15279 (11)	0.0525 (3)
O4	0.56467 (12)	0.55628 (11)	0.41487 (8)	0.0345 (2)
O5	0.54889 (19)	0.74673 (14)	0.31933 (11)	0.0622 (4)
O6	0.76772 (14)	0.61715 (12)	0.16751 (9)	0.0407 (3)
O1W	0.59294 (14)	0.12852 (13)	0.49158 (10)	0.0444 (3)
O2W	0.7030 (3)	1.0068 (3)	0.00861 (19)	0.0955 (6)
O3W	0.4921 (3)	0.9463 (2)	0.16291 (15)	0.0959 (7)
C1	0.8236 (2)	0.3491 (2)	0.62901 (16)	0.0489 (4)
C2	0.9551 (2)	0.3220 (2)	0.68355 (18)	0.0583 (5)
C3	1.0945 (2)	0.2346 (3)	0.6346 (2)	0.0626 (5)
C4	1.1002 (2)	0.1775 (2)	0.53325 (19)	0.0566 (5)
C5	0.96390 (18)	0.20849 (17)	0.48245 (14)	0.0402 (3)
C6	0.96109 (18)	0.14972 (17)	0.37376 (14)	0.0403 (3)
C7	1.0920 (2)	0.0510 (2)	0.31974 (19)	0.0588 (5)
C8	1.0806 (3)	−0.0007 (2)	0.2198 (2)	0.0669 (6)
C9	0.9409 (3)	0.0455 (2)	0.17523 (17)	0.0595 (5)
C10	0.8158 (2)	0.1437 (2)	0.23322 (15)	0.0507 (4)
C11	0.4045 (2)	0.27009 (19)	0.28464 (14)	0.0426 (4)
C12	0.2966 (2)	0.3212 (2)	0.19308 (17)	0.0544 (5)
C13	0.3940 (2)	0.47122 (19)	0.07723 (14)	0.0453 (4)
C14	0.3788 (2)	0.6064 (2)	0.05119 (16)	0.0526 (4)
C15	0.5170 (2)	0.3634 (2)	0.02586 (16)	0.0532 (5)
C16	0.60170 (18)	0.62004 (16)	0.33130 (12)	0.0357 (3)
C17	0.71894 (19)	0.52999 (17)	0.24278 (12)	0.0383 (3)
C18	0.88372 (17)	0.55316 (16)	0.08559 (11)	0.0323 (3)
C19	0.93652 (18)	0.64205 (16)	0.01894 (12)	0.0347 (3)
C20	1.05291 (18)	0.58884 (16)	−0.06661 (12)	0.0350 (3)
H1W1	0.541 (2)	0.145 (3)	0.5540 (10)	0.067*
H1W2	0.537 (2)	0.122 (3)	0.4434 (13)	0.067*
H2W1	0.651 (4)	0.976 (4)	0.061 (2)	0.143*
H2W2	0.651 (4)	1.014 (5)	−0.0487 (19)	0.143*
H3W1	0.476 (5)	1.012 (2)	0.210 (2)	0.144*
H3W2	0.533 (5)	0.8689 (19)	0.197 (3)	0.144*
H1	0.7292	0.4083	0.6623	0.059*
H2	0.9489	0.3623	0.7518	0.070*
H3	1.1842	0.2141	0.6697	0.075*
H4	1.1941	0.1187	0.4988	0.068*
H7	1.1858	0.0204	0.3508	0.071*
H8	1.1670	−0.0667	0.1825	0.080*
H9	0.9310	0.0115	0.1078	0.071*
H10	0.7211	0.1749	0.2033	0.061*
H12A	0.3353	0.2558	0.1321	0.065*
H12B	0.1951	0.3214	0.2209	0.065*
H14	0.2968	0.6791	0.0860	0.063*
H15	0.5297	0.2715	0.0428	0.064*
H17A	0.8072	0.4651	0.2764	0.046*
H17B	0.6723	0.4770	0.2042	0.046*
H19	0.8939	0.7375	0.0316	0.042*
H20	1.0881	0.6486	−0.1110	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02757 (13)	0.03551 (14)	0.02905 (13)	−0.00632 (9)	0.00037 (8)	−0.00153 (9)
N1	0.0288 (6)	0.0424 (7)	0.0439 (7)	−0.0047 (5)	−0.0031 (5)	−0.0055 (6)
N2	0.0364 (7)	0.0425 (7)	0.0365 (7)	−0.0102 (6)	0.0048 (5)	−0.0034 (5)
O1	0.0461 (7)	0.0440 (6)	0.0426 (6)	−0.0144 (5)	−0.0149 (5)	0.0007 (5)
O2	0.0751 (10)	0.0545 (8)	0.0528 (8)	−0.0327 (7)	−0.0176 (7)	0.0078 (6)
O3	0.0505 (7)	0.0559 (8)	0.0460 (7)	−0.0116 (6)	−0.0127 (6)	0.0036 (6)
O4	0.0339 (5)	0.0370 (5)	0.0279 (5)	−0.0099 (4)	0.0070 (4)	−0.0010 (4)
O5	0.0787 (10)	0.0398 (7)	0.0449 (7)	−0.0034 (7)	0.0277 (7)	0.0046 (5)
O6	0.0438 (6)	0.0398 (6)	0.0328 (5)	−0.0134 (5)	0.0164 (5)	−0.0027 (4)
O1W	0.0464 (7)	0.0424 (6)	0.0369 (6)	−0.0092 (5)	0.0034 (5)	0.0004 (5)
O2W	0.1036 (16)	0.0904 (14)	0.0889 (14)	−0.0311 (13)	−0.0082 (12)	0.0017 (12)
O3W	0.161 (2)	0.0600 (10)	0.0558 (9)	−0.0270 (13)	−0.0161 (12)	0.0123 (8)
C1	0.0366 (8)	0.0530 (10)	0.0489 (9)	−0.0051 (8)	−0.0057 (7)	−0.0122 (8)
C2	0.0466 (10)	0.0673 (13)	0.0571 (11)	−0.0123 (9)	−0.0142 (9)	−0.0137 (9)
C3	0.0386 (10)	0.0749 (14)	0.0726 (14)	−0.0143 (9)	−0.0175 (9)	−0.0090 (11)
C4	0.0280 (8)	0.0620 (12)	0.0721 (13)	−0.0065 (8)	−0.0035 (8)	−0.0105 (10)
C5	0.0286 (7)	0.0387 (8)	0.0488 (9)	−0.0080 (6)	0.0015 (6)	−0.0029 (7)
C6	0.0306 (7)	0.0383 (8)	0.0477 (9)	−0.0097 (6)	0.0071 (6)	−0.0033 (7)
C7	0.0363 (9)	0.0583 (12)	0.0721 (13)	−0.0077 (8)	0.0098 (9)	−0.0196 (10)
C8	0.0514 (12)	0.0641 (13)	0.0740 (14)	−0.0126 (10)	0.0233 (10)	−0.0278 (11)
C9	0.0660 (13)	0.0629 (12)	0.0461 (10)	−0.0231 (10)	0.0153 (9)	−0.0186 (9)
C10	0.0498 (10)	0.0593 (11)	0.0381 (8)	−0.0156 (9)	0.0040 (7)	−0.0063 (8)
C11	0.0405 (8)	0.0499 (9)	0.0362 (8)	−0.0148 (7)	−0.0035 (6)	−0.0024 (7)
C12	0.0536 (11)	0.0631 (12)	0.0521 (10)	−0.0247 (10)	−0.0186 (9)	0.0051 (9)
C13	0.0476 (9)	0.0470 (9)	0.0371 (8)	−0.0088 (8)	−0.0157 (7)	−0.0023 (7)
C14	0.0534 (10)	0.0436 (9)	0.0502 (10)	−0.0033 (8)	−0.0076 (8)	−0.0075 (8)
C15	0.0611 (12)	0.0390 (9)	0.0532 (10)	−0.0087 (8)	−0.0122 (9)	−0.0030 (8)
C16	0.0324 (7)	0.0406 (8)	0.0296 (7)	−0.0100 (6)	0.0055 (6)	−0.0014 (6)
C17	0.0399 (8)	0.0392 (8)	0.0311 (7)	−0.0128 (7)	0.0113 (6)	−0.0008 (6)
C18	0.0303 (7)	0.0426 (8)	0.0230 (6)	−0.0133 (6)	0.0032 (5)	−0.0019 (5)
C19	0.0361 (7)	0.0358 (7)	0.0299 (7)	−0.0122 (6)	0.0043 (6)	−0.0025 (6)
C20	0.0367 (8)	0.0402 (8)	0.0282 (6)	−0.0167 (6)	0.0060 (6)	0.0010 (6)

Geometric parameters (Å, º)

Mn1—N1	2.2511 (15)	C3—H3	0.9300
Mn1—N2	2.3031 (17)	C4—C5	1.396 (2)
Mn1—O1	2.1298 (13)	C4—H4	0.9300
Mn1—O4	2.2241 (12)	C5—C6	1.482 (2)
Mn1—O4^i	2.2794 (14)	C6—C7	1.391 (2)
Mn1—O1W	2.2124 (14)	C7—C8	1.376 (3)
O1—C11	1.255 (2)	C7—H7	0.9300
O2—C11	1.247 (2)	C8—C9	1.375 (3)
O4—C16	1.2760 (18)	C8—H8	0.9300
O5—C16	1.227 (2)	C9—C10	1.381 (3)
N1—C1	1.335 (2)	C9—H9	0.9300
N1—C5	1.353 (2)	C10—H10	0.9300
N2—C6	1.349 (2)	C11—C12	1.528 (2)
N2—C10	1.338 (2)	C12—H12A	0.9700
O3—C12	1.409 (3)	C12—H12B	0.9700
O3—C13	1.380 (2)	C13—C14	1.378 (3)
O4—Mn1^i	2.2794 (14)	C13—C15	1.384 (3)
O6—C17	1.4153 (18)	C14—C15^ii	1.388 (3)
O6—C18	1.3798 (18)	C14—H14	0.9300
O1W—H1W1	0.843 (9)	C15—C14^ii	1.388 (3)
O1W—H1W1	0.84 (3)	C15—H15	0.9300
O1W—H1W2	0.85 (3)	C16—C17	1.519 (2)
O2W—H2W1	0.88 (3)	C17—H17A	0.9700
O2W—H2W2	0.88 (3)	C17—H17B	0.9700
O3W—H3W1	0.86 (3)	C18—C19	1.389 (2)
O3W—H3W2	0.86 (3)	C18—C20^iii	1.384 (2)
C1—C2	1.387 (3)	C19—C20	1.391 (2)
C1—H1	0.9300	C19—H19	0.9300
C2—C3	1.372 (3)	C20—C18^iii	1.384 (2)
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.374 (3)
N1—Mn1—N2	72.14 (5)	C3—C4—C5	119.40 (17)
N1—Mn1—O4^i	97.29 (5)	C3—C4—H4	120.3
O1—Mn1—N1	161.61 (5)	C4—C3—H3	120.3
O1—Mn1—N2	90.73 (5)	C4—C5—C6	122.37 (15)
O1—Mn1—O4	84.79 (5)	C5—N1—Mn1	118.18 (11)
O1—Mn1—O4^i	100.33 (5)	C5—C4—H4	120.3
O1—Mn1—O1W	89.49 (6)	C6—N2—Mn1	116.34 (11)
O4—Mn1—N1	94.99 (6)	C6—C7—H7	120.5
O4—Mn1—N2	111.09 (5)	C7—C6—C5	122.10 (17)
O4^i—Mn1—N2	168.19 (5)	C7—C8—H8	120.2
O4—Mn1—O4^i	74.38 (5)	C8—C7—C6	119.1 (2)
O1W—Mn1—N1	95.06 (6)	C8—C7—H7	120.5
O1W—Mn1—N2	83.69 (5)	C8—C9—C10	118.26 (19)
O1W—Mn1—O4	164.16 (4)	C8—C9—H9	120.9
O1W—Mn1—O4^i	92.21 (5)	C9—C8—C7	119.66 (18)
Mn1—O4—Mn1^i	105.62 (5)	C9—C8—H8	120.2
Mn1—O1W—H1W1	103.5 (17)	C9—C10—H10	118.4
Mn1—O1W—H1W2	100.0 (17)	C10—N2—Mn1	124.60 (12)
N1—C1—C2	123.06 (17)	C10—N2—C6	118.16 (15)
N1—C1—H1	118.5	C10—C9—H9	120.9
N1—C5—C4	121.28 (16)	C11—O1—Mn1	131.90 (12)
N1—C5—C6	116.35 (14)	C11—C12—H12A	108.6
N2—C6—C5	116.29 (14)	C11—C12—H12B	108.6
N2—C6—C7	121.61 (17)	C13—O3—C12	119.36 (16)
N2—C10—C9	123.26 (19)	C13—C14—C15^ii	121.49 (18)
N2—C10—H10	118.4	C13—C14—H14	119.3
O1—C11—C12	117.95 (16)	C13—C15—C14^ii	119.48 (19)
O2—C11—O1	126.10 (16)	C13—C15—H15	120.3
O2—C11—C12	115.94 (16)	C14—C13—O3	115.85 (17)
O3—C12—C11	114.53 (16)	C14—C13—C15	119.02 (19)
O3—C12—H12A	108.6	C14^ii—C15—H15	120.3
O3—C12—H12B	108.6	C15^ii—C14—H14	119.3
O3—C13—C15	125.12 (18)	C16—O4—Mn1	130.89 (10)
O4—C16—C17	116.37 (13)	C16—O4—Mn1^i	122.57 (10)
O5—C16—O4	124.12 (14)	C16—C17—H17A	109.9
O5—C16—C17	119.51 (14)	C16—C17—H17B	109.9
O6—C17—C16	108.78 (13)	C18—O6—C17	117.25 (12)
O6—C17—H17A	109.9	C18—C19—C20	120.26 (15)
O6—C17—H17B	109.9	C18—C19—H19	119.9
O6—C18—C19	115.36 (13)	C18^iii—C20—C19	119.93 (14)
O6—C18—C20^iii	124.84 (13)	C18^iii—C20—H20	120.0
C1—N1—Mn1	123.51 (11)	C19—C20—H20	120.0
C1—N1—C5	118.29 (15)	C20^iii—C18—C19	119.80 (13)
C1—C2—H2	120.7	C20—C19—H19	119.9
C2—C1—H1	118.5	H1W1—O1W—H1W2	109.8 (14)
C2—C3—C4	119.40 (18)	H2W1—O2W—H2W2	103.7 (15)
C2—C3—H3	120.3	H3W1—O3W—H3W2	106.3 (16)
C3—C2—C1	118.58 (19)	H12A—C12—H12B	107.6
C3—C2—H2	120.7	H17A—C17—H17B	108.3
Mn1—N1—C1—C2	177.77 (16)	O4^i—Mn1—N2—C10	149.0 (2)
Mn1—N1—C5—C4	−177.96 (15)	O4—Mn1—N2—C10	−95.25 (15)
Mn1—N1—C5—C6	1.7 (2)	O4^i—Mn1—O1—C11	−95.99 (16)
Mn1—N2—C6—C5	−9.14 (19)	O4—Mn1—O1—C11	−169.05 (16)
Mn1—N2—C6—C7	170.17 (15)	O4^i—Mn1—O4—Mn1^i	0.0
Mn1—N2—C10—C9	−169.20 (16)	O4^i—Mn1—O4—C16	−169.04 (16)
Mn1—O1—C11—O2	−1.5 (3)	O4—C16—C17—O6	−169.35 (14)
Mn1—O1—C11—C12	177.35 (12)	O5—C16—C17—O6	10.6 (2)
Mn1—O4—C16—O5	168.94 (14)	O6—C18—C19—C20	−179.75 (14)
Mn1^i—O4—C16—O5	1.5 (2)	O1W—Mn1—N1—C1	−101.06 (15)
Mn1—O4—C16—C17	−11.1 (2)	O1W—Mn1—N1—C5	77.04 (13)
Mn1^i—O4—C16—C17	−178.55 (10)	O1W—Mn1—N2—C6	−90.01 (12)
N1—Mn1—N2—C6	7.39 (12)	O1W—Mn1—N2—C10	78.86 (15)
N1—Mn1—N2—C10	176.26 (16)	O1W—Mn1—O1—C11	−3.84 (15)
N1—Mn1—O1—C11	100.8 (2)	O1W—Mn1—O4—Mn1^i	33.01 (17)
N1—Mn1—O4—Mn1^i	−96.20 (6)	O1W—Mn1—O4—C16	−136.03 (17)
N1—Mn1—O4—C16	94.76 (14)	C1—N1—C5—C4	0.2 (3)
N1—C1—C2—C3	0.0 (3)	C1—N1—C5—C6	179.90 (16)
N1—C5—C6—N2	5.1 (2)	C1—C2—C3—C4	0.5 (4)
N1—C5—C6—C7	−174.23 (18)	C2—C3—C4—C5	−0.6 (4)
N2—Mn1—N1—C1	177.24 (16)	C3—C4—C5—N1	0.2 (3)
N2—Mn1—N1—C5	−4.66 (12)	C3—C4—C5—C6	−179.42 (19)
N2—C6—C7—C8	−0.2 (3)	C4—C5—C6—N2	−175.27 (17)
N2—Mn1—O1—C11	79.84 (16)	C4—C5—C6—C7	5.4 (3)
N2—Mn1—O4—Mn1^i	−168.97 (5)	C5—N1—C1—C2	−0.3 (3)
N2—Mn1—O4—C16	21.99 (14)	C5—C6—C7—C8	179.03 (19)
O1—Mn1—N1—C1	155.17 (16)	C6—C7—C8—C9	−0.1 (4)
O1—Mn1—N1—C5	−26.7 (2)	C6—N2—C10—C9	−0.5 (3)
O1—Mn1—N2—C6	−179.41 (12)	C7—C8—C9—C10	0.2 (4)
O1—Mn1—N2—C10	−10.55 (15)	C8—C9—C10—N2	0.2 (3)
O1—Mn1—O4—Mn1^i	102.27 (5)	C10—N2—C6—C5	−178.76 (16)
O1—Mn1—O4—C16	−66.78 (14)	C10—N2—C6—C7	0.6 (3)
O1—C11—C12—O3	1.8 (3)	C12—O3—C13—C14	−173.02 (16)
O2—C11—C12—O3	−179.22 (17)	C12—O3—C13—C15	8.2 (2)
O3—C13—C14—C15^ii	−178.27 (16)	C13—O3—C12—C11	80.0 (2)
O3—C13—C15—C14^ii	178.17 (16)	C14—C13—C15—C14^ii	−0.5 (3)
O4—Mn1—N1—C1	66.67 (15)	C15—C13—C14—C15^ii	0.6 (3)
O4^i—Mn1—N1—C1	−8.18 (15)	C17—O6—C18—C19	−175.14 (14)
O4—Mn1—N1—C5	−115.23 (13)	C17—O6—C18—C20^iii	5.2 (2)
O4^i—Mn1—N1—C5	169.93 (12)	C18—O6—C17—C16	175.12 (13)
O4—Mn1—N2—C6	95.89 (12)	C18—C19—C20—C18^iii	0.1 (3)
O4^i—Mn1—N2—C6	−19.9 (3)	C20^iii—C18—C19—C20	−0.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O5^i	0.84 (3)	1.87 (3)	2.655 (2)	153 (2)
O1W—H1W2···O2	0.85 (3)	1.87 (3)	2.695 (2)	164 (2)
O3W—H3W1···O2^iv	0.86 (3)	1.90 (3)	2.763 (3)	174 (4)
O3W—H3W2···O5	0.86 (3)	1.89 (2)	2.695 (2)	154 (4)
O2W—H2W1···O3W	0.88 (3)	1.93 (3)	2.795 (4)	165 (4)
O2W—H2W2···O3W^v	0.88 (3)	1.96 (3)	2.822 (3)	171 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (iv) x, y+1, z; (v) −x+1, −y+2, −z.

(II) poly[[di-µ-aqua-bis[aquasodium(I)]]-µ₄-p-phenylenebis(oxyacetato)- κO:O',O'':O''',O'''':O''''']

Crystal data

[Na2(C10H8O6)(H2O)4]	Z = 1
Mr = 342.21	F(000) = 178
Triclinic, P1	Dx = 1.620 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3754 (11) Å	Cell parameters from 2648 reflections
b = 5.9136 (12) Å	θ = 3.9–27.5°
c = 11.236 (2) Å	µ = 0.19 mm^−1
α = 85.83 (3)°	T = 293 K
β = 82.01 (3)°	Prism, colourless
γ = 83.54 (3)°	0.38 × 0.24 × 0.17 mm
V = 350.87 (12) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	1588 independent reflections
Radiation source: fine-focus sealed tube	1415 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
ω scans	h = −6→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→7
Tmin = 0.930, Tmax = 0.968	l = −14→14
3380 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0604P)^2 + 0.0805P] where P = (Fo^2 + 2Fc^2)/3
1588 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 0.41 e Å^−3
6 restraints	Δρmin = −0.17 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.45322 (10)	0.60837 (9)	0.35083 (5)	0.03089 (18)
O1	0.23780 (18)	0.28698 (17)	0.34521 (9)	0.0331 (2)
O2	0.21557 (19)	−0.05454 (17)	0.27465 (9)	0.0330 (2)
O3	0.61125 (19)	0.37996 (17)	0.17376 (8)	0.0330 (3)
O1W	0.75382 (19)	0.86038 (19)	0.39989 (9)	0.0363 (3)
O2W	0.26331 (19)	0.66757 (18)	0.55011 (9)	0.0336 (2)
C1	0.2990 (2)	0.1358 (2)	0.27052 (11)	0.0252 (3)
C2	0.4912 (3)	0.1823 (2)	0.16067 (12)	0.0290 (3)
C3	0.8044 (2)	0.4319 (2)	0.08475 (11)	0.0263 (3)
C4	0.8590 (3)	0.3289 (2)	−0.02459 (12)	0.0304 (3)
C5	0.9457 (3)	0.6015 (2)	0.10882 (12)	0.0301 (3)
H1W2	0.896 (2)	0.888 (4)	0.3620 (14)	0.054*
H1W1	0.772 (4)	0.826 (4)	0.4732 (9)	0.054*
H2W1	0.304 (3)	0.797 (2)	0.5656 (18)	0.050*
H2W2	0.111 (2)	0.657 (3)	0.5835 (16)	0.050*
H2A	0.6174	0.0519	0.1507	0.035*
H2B	0.4067	0.2039	0.0892	0.035*
H4	0.7656	0.2145	−0.0412	0.036*
H5	0.9094	0.6695	0.1822	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0322 (3)	0.0277 (3)	0.0320 (3)	−0.0068 (2)	0.0025 (2)	−0.0036 (2)
O1	0.0316 (5)	0.0354 (5)	0.0317 (5)	−0.0127 (4)	0.0090 (4)	−0.0090 (4)
O2	0.0337 (5)	0.0297 (5)	0.0356 (5)	−0.0137 (4)	0.0036 (4)	−0.0019 (4)
O3	0.0357 (5)	0.0360 (5)	0.0272 (5)	−0.0184 (4)	0.0120 (4)	−0.0088 (4)
O1W	0.0320 (5)	0.0409 (6)	0.0360 (5)	−0.0115 (4)	0.0008 (4)	−0.0007 (4)
O2W	0.0288 (5)	0.0337 (5)	0.0368 (5)	−0.0043 (4)	0.0038 (4)	−0.0064 (4)
C1	0.0220 (6)	0.0286 (6)	0.0247 (6)	−0.0065 (5)	0.0006 (4)	−0.0001 (5)
C2	0.0313 (7)	0.0276 (6)	0.0274 (6)	−0.0107 (5)	0.0065 (5)	−0.0043 (5)
C3	0.0260 (6)	0.0291 (6)	0.0227 (6)	−0.0078 (5)	0.0053 (5)	−0.0016 (5)
C4	0.0326 (7)	0.0320 (7)	0.0276 (6)	−0.0144 (5)	0.0039 (5)	−0.0072 (5)
C5	0.0348 (7)	0.0328 (7)	0.0227 (6)	−0.0109 (5)	0.0049 (5)	−0.0075 (5)

Geometric parameters (Å, º)

Na1—Na1^i	3.582 (2)	O1W—H1W2	0.849 (13)
Na1—O1	2.343 (2)	O2W—H2W1	0.853 (13)
Na1—O2^ii	2.413 (2)	O2W—H2W2	0.860 (13)
Na1—O3	2.483 (2)	C1—C2	1.525 (2)
Na1—O1W	2.459 (2)	C2—H2A	0.9700
Na1—O2W	2.362 (2)	C2—H2B	0.9700
Na1—O2W^i	2.423 (2)	C3—C4	1.391 (2)
O1—C1	1.256 (2)	C3—C5	1.387 (2)
O2—C1	1.253 (2)	C4—C5^iii	1.390 (2)
O3—C2	1.423 (2)	C4—H4	0.9300
O3—C3	1.383 (2)	C5—C4^iii	1.390 (2)
O1W—H1W1	0.851 (12)	C5—H5	0.9300
O1—Na1—Na1^i	85.21 (4)	Na1^i—O2W—H2W2	109.2 (13)
O1—Na1—O2^ii	110.55 (4)	O1—C1—C2	118.80 (11)
O1—Na1—O3	66.75 (4)	O2—C1—O1	126.80 (12)
O1—Na1—O1W	161.53 (5)	O2—C1—C2	114.39 (11)
O1—Na1—O2W	91.18 (5)	O3—C2—C1	110.80 (11)
O1—Na1—O2W^i	81.75 (4)	O3—C2—H2A	109.5
O2^ii—Na1—Na1^i	132.69 (4)	O3—C2—H2B	109.5
O2^ii—Na1—O3	105.90 (5)	O3—C3—C4	124.31 (12)
O2^ii—Na1—O1W	87.29 (4)	O3—C3—C5	115.86 (11)
O2^ii—Na1—O2W^i	166.81 (4)	C1—O1—Na1	124.55 (8)
O3—Na1—Na1^i	121.12 (4)	C1—O2—Na1^iv	120.34 (9)
O1W—Na1—Na1^i	78.84 (4)	C1—C2—H2A	109.5
O1W—Na1—O3	114.08 (5)	C1—C2—H2B	109.5
O2W^i—Na1—Na1^i	40.87 (3)	C2—O3—Na1	117.90 (8)
O2W—Na1—Na1^i	42.18 (3)	C3—O3—Na1	125.16 (8)
O2W—Na1—O2^ii	91.69 (5)	C3—O3—C2	116.92 (10)
O2W—Na1—O3	155.35 (4)	C3—C4—H4	120.3
O2W^i—Na1—O3	83.00 (5)	C3—C5—C4^iii	120.78 (12)
O2W—Na1—O1W	83.28 (5)	C3—C5—H5	119.6
O2W^i—Na1—O1W	80.10 (4)	C4^iii—C5—H5	119.6
O2W—Na1—O2W^i	83.05 (5)	C5—C3—C4	119.82 (12)
Na1—O1W—H1W1	105.5 (14)	C5^iii—C4—C3	119.40 (12)
Na1—O1W—H1W2	129.4 (14)	C5^iii—C4—H4	120.3
Na1—O2W—Na1^i	96.95 (5)	H2W1—O2W—H2W2	107.5 (13)
Na1—O2W—H2W1	105.2 (13)	H1W2—O1W—H1W1	108.4 (13)
Na1^i—O2W—H2W1	104.6 (13)	H2A—C2—H2B	108.1
Na1—O2W—H2W2	130.6 (13)
Na1^i—Na1—O1—C1	−120.20 (11)	O3—Na1—O2W—Na1^i	55.95 (11)
Na1^i—Na1—O3—C2	69.38 (10)	O3—C3—C4—C5^iii	178.47 (12)
Na1^i—Na1—O3—C3	−112.05 (10)	O3—C3—C5—C4^iii	−178.56 (12)
Na1—O1—C1—O2	168.26 (10)	O1W—Na1—O1—C1	−89.93 (17)
Na1—O1—C1—C2	−12.86 (17)	O1W—Na1—O3—C2	160.65 (9)
Na1^iv—O2—C1—O1	−98.82 (14)	O1W—Na1—O3—C3	−20.78 (12)
Na1^iv—O2—C1—C2	82.26 (12)	O1W—Na1—O2W—Na1^i	−80.79 (4)
Na1—O3—C2—C1	−6.23 (14)	O2W—Na1—O1—C1	−161.99 (11)
Na1—O3—C3—C4	−167.21 (11)	O2W—Na1—O3—C2	28.85 (16)
Na1—O3—C3—C5	11.66 (17)	O2W^i—Na1—O3—C2	84.81 (10)
O1—Na1—O3—C2	0.81 (9)	O2W^i—Na1—O3—C3	−96.62 (11)
O1—Na1—O3—C3	179.38 (11)	O2W^i—Na1—O1—C1	−79.19 (11)
O1—Na1—O2W—Na1^i	81.54 (5)	O2W—Na1—O3—C3	−152.58 (11)
O1—C1—C2—O3	11.98 (17)	O2W^i—Na1—O2W—Na1^i	0.0
O2^ii—Na1—O1—C1	105.76 (11)	C2—O3—C3—C4	11.4 (2)
O2^ii—Na1—O3—C2	−105.13 (10)	C2—O3—C3—C5	−169.76 (12)
O2^ii—Na1—O3—C3	73.44 (11)	C3—O3—C2—C1	175.08 (11)
O2^ii—Na1—O2W—Na1^i	−167.86 (4)	C4—C3—C5—C4^iii	0.4 (2)
O2—C1—C2—O3	−169.00 (11)	C5—C3—C4—C5^iii	−0.4 (2)
O3—Na1—O1—C1	6.70 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1^i	0.85 (1)	2.10 (1)	2.938 (2)	170 (2)
O1W—H1W2···O2^v	0.85 (1)	1.91 (1)	2.757 (2)	179 (2)
O2W—H2W1···O1W^vi	0.85 (1)	2.07 (1)	2.876 (2)	157 (2)
O2W—H2W2···O1^vii	0.86 (1)	1.94 (1)	2.778 (2)	166 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (v) x+1, y+1, z; (vi) −x+1, −y+2, −z+1; (vii) −x, −y+1, −z+1.