Poly[aqua­(μ₃-benzene-1,2-dicarboxyl­ato)bis­(μ₃-hydroxido)­bis­(μ₂-isonicotinato)­dierbium(III) monohydrate] and the thulium analogue

The two isomorphous lanthanide coordination polymers, {[Ln₂(C₆H₄NO₂)₂(C₈H₄O₄)(OH)₂(H₂O)]·H₂O}_n (Ln = Er and Tm), contain two crystallographically independent Ln ions which are both eight-coordinated by O atoms, but with quite different coordination environments. In both crystal structures, adjacent Ln atoms are bridged by μ₃-OH groups and carboxyl­ate groups of isonicotinate and benzene-1,2-dicarboxyl­ate ligands, forming infinite chains in which the Er...Er and Tm...Tm distances are in the ranges 3.622 (3)–3.894 (4) and 3.599 (7)–3.873 (1) Å, respectively. Adjacent chains are further connected through hydrogen bonds and π–­π inter­actions into a three-dimensional supra­molecular framework.

S1. Comment

In recent years, the rational design and construction of metal coordination polymers has aroused great interest owing to their intriguing topological architectures and the potential application as functional materials (Meares & Wensel, 1984; Scott & Horrocks, 1992; Reineke et al., 1999; Eddaoudi et al., 2001). In constructing coordination polymers, multifunctional connectors such as a variety of carboxylate ligands are usually utilized as bridging groups, forming one-, two- and three-dimensional networks (Choi & Suh, 1998; MacGillivray et al., 1998; Evans et al., 1999; Chen et al., 2001; Suresh et al., 2001; Kumagai et al., 2002; Lu & Babb, 2003; Song et al., 2003; Zhang et al., 2004). So far, numerous architectures have been assembled from the particular combination of appropriate metal centers and versatile ligands. Our interest in the area is to explore the possible construction of coordination polymers involving two types of different ligands simultaneously in a system, and to understand the cooperativity of both ligands. To the best of our knowledge, this area still remains underdeveloped (Cheng et al., 2006). Selecting the acids HIN and H₂BDC as mixed ligands [where IN is the isonicotinate anion (C₆H₄NO₂) and BDC is the benzene-1,2-dicarboxylate anion (C₈H₄O₄)] and adopting the hydrothermal technique, we obtained the title compounds, (I) and (II), which display novel one-dimensional chain-like coordination features.

As shown in Fig. 1, the asymmetric unit contains two unique erbium(III) [or thulium(III)] atoms, two –OH⁻ ions, one BDC and two IN ligands, and one aqua ligand, as well as one uncoordinated water molecule. All the Ln^III ions are eight-coordinate, but with markedly different coordination enviroments. Atom Er1 (or Tm1) is surrounded by three –OH groups, two carboxylate O atoms from two IN ligands, two carboxylate O atoms from a BDC ligand and an aqua ligand. Atom Er2 (or Tm2), on the other hand, is coordinated by three –OH groups, two carboxylate O atoms from two IN ligands and three carboxylate O atoms from two BDC ligands. The Er—O and Tm—O distances span the ranges 2.278 (4)–2.499 (4) Å and 2.266 (3)–2.482 (3) Å, respectively.

The Ln^III centers are bridged by hydroxido and oxo groups to form an infinite wave-like chain with Er···Er distances in the range 3.622 (3)–3.894 (4) Å [Tm···Tm = 3.599 (7)–3.873 (1) Å]. The BDC and IN ligands, coordinating the metal centers through the carboxylate O atoms, protrude outside of the above chain (Fig. 2). Despite the abundant and versatile coordination modes often found in IN and BDC ligands, only a single bidentate (for IN) and a unique pentadentate bridging (for BDC) modes are adopted in the crystal structures of the title compounds (Fig. 3). This suggests a high cooperativity between the IN and BDC ligands in the formation of (I) and (II). Adjacent chains are further connected into a three-dimensional supramolecular framework through hydrogen bonds and π–π stacking interactions. The former, described in Tables 2 and 4, exhibit O/N···O distances in the ranges 2.716 (5)–3.170 (6) Å for (I) and 2.702 (4)–3.1723 (5) Å for (II); the latter, in turn, lead to interplanar distances between neighbouring IN ligands of 3.546 (1) Å for (I) and 3.540 (2) Å for (II) (Fig. 4).

Related literature

For related literature, see: Chen et al. (2001); Cheng et al. (2006); Choi & Suh (1998); Eddaoudi et al. (2001); Evans et al. (1999); Kumagai et al. (2002); Lu & Babb (2003); MacGillivray et al. (1998); Meares & Wensel (1984); Reineke et al. (1999); Scott & Horrocks (1992); Song et al. (2003); Suresh et al. (2001); Zhang et al. (2004).

S2. Experimental

The title compounds were synthesized under hydrothermal conditions. Typically, a mixture of Ln₂O₃ (0.5 mmol; Er 0.192 g, Tm 0.193 g), HIN (2.00 mmol, 0.247 g), H₂BDC (1.00 mmol, 0.167 g) and water (10 ml), in the ratio of 1:4:2:1112, was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 6 d. The prism-like crystals obtained were recovered by filtration, washed with distilled water and dried in air.

S3. Refinement

H atoms bound to C atoms were positioned geometrically, with C—H distances of 0.93 Å, and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)]. H atoms bound to O atoms were located in a difference Fourier map and refined as riding in the as-found positions [U_iso(H) = 1.2U_eq(O)].

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures

	Fig. 1. The molecular structure of (I) (as representative of both compounds), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z, (ii) 2 − x, 1 − y, 1 − z
	Fig. 2. Different views of the one-dimensional infinite chains in (I) and (II), (a) along b (aromatic rings have been omitted for clarity) and (b) along c.
	Fig. 3. Coordination modes of the IN and BDC ligands in (I) and (II).
	Fig. 4. The packing of (I) and (II), projected down the chain direction. Note the interdigitation of Ithe N groups.

(I) Poly[aqua(µ₃-benzene-1,2-dicarboxylato-κ⁴O,O':O':O'')bis(µ₃– hydroxido)bis(µ₂-isonicotinato-κ²O:O')dierbium(III) monohydrate

Crystal data

[Er2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O	F(000) = 1536
Mr = 812.88	Dx = 2.329 Mg m^−3
Monoclinic, p21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18413 reflections
a = 7.2706 (5) Å	θ = 1.8–26.5°
b = 24.2780 (4) Å	µ = 7.26 mm^−1
c = 13.3668 (2) Å	T = 295 K
β = 100.708 (4)°	Prism, red
V = 2318.36 (17) Å^3	0.45 × 0.10 × 0.09 mm
Z = 4

Data collection

Siemems SMART CCD diffractometer	4769 independent reflections
Radiation source: fine-focus sealed tube	4563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ and ω scans	θmax = 26.5°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.399, Tmax = 0.511	k = −30→29
18413 measured reflections	l = −16→16

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0263P)^2 + 4.9192P] where P = (Fo^2 + 2Fc^2)/3
4769 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 1.76 e Å^−3
0 restraints	Δρmin = −1.41 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
Er1	0.58951 (3)	0.454643 (8)	0.398835 (15)	0.01102 (7)
Er2	0.91911 (3)	0.492512 (8)	0.626252 (15)	0.01118 (7)
O1	0.1068 (5)	0.52598 (16)	0.1930 (3)	0.0240 (8)
O1W	0.9014 (7)	0.8486 (2)	1.0199 (4)	0.0569 (14)
H1W	0.9439	0.8167	0.9936	0.068*
H2W	0.7788	0.8481	1.0053	0.068*
O2	0.3687 (5)	0.51179 (15)	0.3019 (3)	0.0182 (7)
O3	0.6819 (6)	0.60570 (17)	0.3285 (4)	0.0423 (11)
O4	0.7641 (5)	0.51853 (14)	0.3102 (3)	0.0187 (7)
O5	0.6621 (4)	0.52711 (13)	0.5156 (2)	0.0120 (6)
H5	0.6796	0.5575	0.4866	0.014*
O6	0.9148 (4)	0.45157 (13)	0.4673 (2)	0.0128 (7)
H6	0.9509	0.4176	0.4651	0.015*
O7	0.7093 (5)	0.39610 (15)	0.2890 (3)	0.0236 (8)
H7W	0.6623	0.3652	0.2646	0.028*
H8W	0.8241	0.4002	0.2809	0.028*
O8	0.6144 (5)	0.38738 (16)	0.5195 (3)	0.0280 (9)
O9	0.8535 (6)	0.39941 (15)	0.6491 (3)	0.0289 (9)
O10	0.9275 (5)	0.57681 (14)	0.7090 (3)	0.0195 (7)
O11	0.6344 (5)	0.60890 (16)	0.6763 (3)	0.0288 (9)
C1	0.4039 (9)	0.5679 (3)	−0.0365 (4)	0.0430 (17)
H1A	0.3466	0.5686	−0.1048	0.052*
C2	0.5869 (10)	0.5846 (3)	−0.0078 (5)	0.0460 (19)
H2A	0.6521	0.5974	−0.0568	0.055*
C3	0.6754 (8)	0.5825 (3)	0.0935 (5)	0.0375 (15)
H3A	0.8000	0.5931	0.1117	0.045*
C4	0.5786 (7)	0.5645 (2)	0.1678 (4)	0.0197 (11)
C5	0.3910 (7)	0.5478 (2)	0.1389 (4)	0.0218 (11)
C6	0.3056 (9)	0.5502 (3)	0.0364 (4)	0.0327 (14)
H6A	0.1810	0.5398	0.0171	0.039*
C7	0.6792 (7)	0.5645 (2)	0.2771 (4)	0.0217 (11)
C8	0.2808 (7)	0.5273 (2)	0.2121 (4)	0.0192 (10)
C9	1.0018 (11)	0.6974 (4)	0.9441 (6)	0.056 (2)
H9A	1.0722	0.6917	1.0088	0.067*
C10	0.8399 (11)	0.7548 (3)	0.8268 (7)	0.055 (2)
H10A	0.7988	0.7902	0.8075	0.066*
C11	0.7928 (9)	0.7123 (3)	0.7569 (6)	0.0406 (16)
H11A	0.7191	0.7188	0.6934	0.049*
C12	0.9677 (9)	0.6535 (3)	0.8794 (5)	0.0414 (16)
H12A	1.0178	0.6191	0.8993	0.050*
C13	0.8585 (7)	0.6607 (2)	0.7846 (4)	0.0247 (12)
C14	0.8022 (7)	0.6119 (2)	0.7169 (4)	0.0185 (10)
C15	0.7356 (10)	0.2478 (3)	0.7691 (6)	0.0495 (19)
H15A	0.7844	0.2385	0.8363	0.059*
C16	0.5696 (10)	0.2249 (3)	0.6147 (6)	0.0439 (17)
H16A	0.5030	0.1987	0.5719	0.053*
C17	0.7622 (10)	0.3012 (3)	0.7372 (5)	0.0412 (16)
H17A	0.8299	0.3265	0.7816	0.049*
C18	0.5846 (9)	0.2772 (2)	0.5766 (5)	0.0362 (15)
H18A	0.5272	0.2861	0.5104	0.043*
C19	0.6869 (7)	0.3159 (2)	0.6391 (4)	0.0228 (11)
C20	0.7213 (8)	0.3727 (2)	0.6000 (4)	0.0229 (11)
N1	0.9394 (9)	0.7477 (3)	0.9189 (5)	0.0581 (19)
N2	0.6447 (8)	0.2097 (2)	0.7091 (5)	0.0459 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Er1	0.01092 (12)	0.00925 (12)	0.01294 (11)	−0.00006 (7)	0.00237 (8)	−0.00124 (7)
Er2	0.01085 (12)	0.01073 (12)	0.01217 (11)	−0.00049 (7)	0.00269 (8)	−0.00025 (7)
O1	0.0152 (19)	0.035 (2)	0.0209 (18)	0.0006 (16)	0.0021 (14)	0.0040 (16)
O1W	0.060 (3)	0.037 (3)	0.075 (4)	−0.011 (2)	0.015 (3)	−0.028 (3)
O2	0.0149 (18)	0.025 (2)	0.0147 (17)	0.0036 (14)	0.0030 (13)	0.0065 (14)
O3	0.045 (3)	0.020 (2)	0.058 (3)	0.0010 (19)	−0.001 (2)	−0.011 (2)
O4	0.0152 (18)	0.0196 (19)	0.0219 (18)	0.0026 (14)	0.0054 (14)	0.0051 (14)
O5	0.0137 (16)	0.0081 (16)	0.0144 (16)	−0.0006 (12)	0.0028 (12)	0.0015 (13)
O6	0.0161 (17)	0.0069 (16)	0.0158 (16)	0.0015 (12)	0.0044 (13)	−0.0004 (12)
O7	0.0198 (19)	0.020 (2)	0.034 (2)	−0.0063 (15)	0.0114 (15)	−0.0151 (16)
O8	0.025 (2)	0.022 (2)	0.037 (2)	0.0040 (16)	0.0066 (17)	0.0152 (17)
O9	0.044 (2)	0.017 (2)	0.027 (2)	−0.0068 (17)	0.0099 (18)	0.0035 (16)
O10	0.0165 (18)	0.0178 (19)	0.0257 (19)	−0.0010 (14)	0.0077 (14)	−0.0047 (15)
O11	0.0165 (19)	0.023 (2)	0.046 (2)	−0.0027 (15)	0.0025 (17)	−0.0163 (18)
C1	0.046 (4)	0.068 (5)	0.017 (3)	0.014 (3)	0.012 (3)	0.017 (3)
C2	0.047 (4)	0.059 (5)	0.038 (4)	0.019 (3)	0.026 (3)	0.033 (3)
C3	0.025 (3)	0.046 (4)	0.045 (4)	0.005 (3)	0.015 (3)	0.021 (3)
C4	0.020 (3)	0.019 (3)	0.022 (3)	0.007 (2)	0.009 (2)	0.008 (2)
C5	0.019 (3)	0.028 (3)	0.018 (3)	0.005 (2)	0.003 (2)	0.007 (2)
C6	0.029 (3)	0.049 (4)	0.019 (3)	0.010 (3)	0.002 (2)	0.008 (3)
C7	0.017 (3)	0.017 (3)	0.032 (3)	−0.003 (2)	0.007 (2)	0.006 (2)
C8	0.023 (3)	0.016 (3)	0.019 (3)	0.000 (2)	0.005 (2)	0.003 (2)
C9	0.056 (5)	0.062 (6)	0.049 (5)	−0.009 (4)	0.006 (4)	−0.034 (4)
C10	0.056 (5)	0.022 (4)	0.092 (6)	−0.009 (3)	0.023 (4)	−0.024 (4)
C11	0.035 (4)	0.029 (4)	0.058 (4)	−0.001 (3)	0.007 (3)	−0.014 (3)
C12	0.033 (4)	0.048 (4)	0.041 (4)	−0.006 (3)	0.002 (3)	−0.019 (3)
C13	0.014 (3)	0.026 (3)	0.037 (3)	−0.007 (2)	0.011 (2)	−0.016 (2)
C14	0.014 (2)	0.018 (3)	0.024 (3)	−0.0064 (19)	0.0079 (19)	−0.006 (2)
C15	0.057 (5)	0.036 (4)	0.056 (5)	0.009 (3)	0.012 (4)	0.030 (3)
C16	0.042 (4)	0.023 (3)	0.066 (5)	−0.007 (3)	0.008 (3)	0.005 (3)
C17	0.054 (4)	0.028 (4)	0.040 (4)	−0.008 (3)	0.004 (3)	0.012 (3)
C18	0.034 (3)	0.022 (3)	0.050 (4)	−0.001 (3)	0.000 (3)	0.009 (3)
C19	0.024 (3)	0.013 (3)	0.032 (3)	0.003 (2)	0.007 (2)	0.009 (2)
C20	0.033 (3)	0.012 (3)	0.027 (3)	0.003 (2)	0.014 (2)	0.004 (2)
N1	0.047 (4)	0.060 (5)	0.069 (5)	−0.018 (3)	0.014 (3)	−0.044 (4)
N2	0.041 (3)	0.022 (3)	0.079 (4)	0.006 (2)	0.023 (3)	0.025 (3)

Geometric parameters (Å, º)

Er1—O8	2.278 (4)	C1—C2	1.376 (10)
Er1—O2	2.325 (3)	C1—C6	1.380 (8)
Er1—O7	2.326 (3)	C1—H1A	0.9300
Er1—O11^i	2.331 (4)	C2—C3	1.388 (9)
Er1—O5	2.346 (3)	C2—H2A	0.9300
Er1—O5^i	2.372 (3)	C3—C4	1.390 (7)
Er1—O6	2.373 (3)	C3—H3A	0.9300
Er1—O4	2.445 (3)	C4—C5	1.406 (7)
Er1—Er2	3.6224 (3)	C4—C7	1.507 (7)
Er1—Er2^ii	3.8688 (4)	C5—C6	1.396 (7)
Er1—Er2^i	3.8694 (4)	C5—C8	1.463 (7)
Er1—Er1^i	3.8944 (4)	C6—H6A	0.9300
Er2—O5	2.315 (3)	C9—N1	1.325 (11)
Er2—O4^ii	2.318 (3)	C9—C12	1.365 (9)
Er2—O10	2.322 (3)	C9—H9A	0.9300
Er2—O6^ii	2.329 (3)	C10—N1	1.318 (11)
Er2—O6	2.341 (3)	C10—C11	1.391 (9)
Er2—O9	2.342 (4)	C10—H10A	0.9300
Er2—O2^i	2.461 (3)	C11—C13	1.367 (9)
Er2—O1^i	2.499 (4)	C11—H11A	0.9300
Er2—Er2^ii	3.7924 (4)	C12—C13	1.376 (8)
O1—C8	1.244 (6)	C12—H12A	0.9300
O1W—H1W	0.9268	C13—C14	1.501 (7)
O1W—H2W	0.8767	C15—N2	1.318 (10)
O2—C8	1.306 (6)	C15—C17	1.389 (9)
O3—C7	1.211 (7)	C15—H15A	0.9300
O4—C7	1.312 (6)	C16—N2	1.330 (9)
O5—H5	0.8539	C16—C18	1.380 (8)
O6—H6	0.8675	C16—H16A	0.9300
O7—H7W	0.8627	C17—C19	1.371 (8)
O7—H8W	0.8669	C17—H17A	0.9300
O8—C20	1.256 (6)	C18—C19	1.380 (8)
O9—C20	1.241 (7)	C18—H18A	0.9300
O10—C14	1.267 (6)	C19—C20	1.513 (7)
O11—C14	1.241 (6)
O8—Er1—O2	141.05 (12)	C2—C1—H1A	120.1
O8—Er1—O7	91.10 (14)	C6—C1—H1A	120.1
O2—Er1—O7	108.27 (13)	C1—C2—C3	120.7 (5)
O8—Er1—O11^i	77.76 (15)	C1—C2—H2A	119.7
O2—Er1—O11^i	78.47 (13)	C3—C2—H2A	119.7
O7—Er1—O11^i	68.72 (12)	C2—C3—C4	120.3 (6)
O8—Er1—O5	95.05 (13)	C2—C3—H3A	119.9
O2—Er1—O5	88.28 (11)	C4—C3—H3A	119.9
O7—Er1—O5	144.47 (11)	C3—C4—C5	119.2 (5)
O11^i—Er1—O5	146.72 (12)	C3—C4—C7	118.3 (5)
O8—Er1—O5^i	76.09 (12)	C5—C4—C7	122.5 (4)
O2—Er1—O5^i	69.07 (11)	C6—C5—C4	119.3 (5)
O7—Er1—O5^i	146.22 (12)	C6—C5—C8	118.1 (5)
O11^i—Er1—O5^i	77.99 (12)	C4—C5—C8	122.6 (5)
O5—Er1—O5^i	68.76 (12)	C1—C6—C5	120.8 (6)
O8—Er1—O6	76.26 (12)	C1—C6—H6A	119.6
O2—Er1—O6	140.25 (11)	C5—C6—H6A	119.6
O7—Er1—O6	76.16 (12)	O3—C7—O4	123.6 (5)
O11^i—Er1—O6	135.37 (12)	O3—C7—C4	120.2 (5)
O5—Er1—O6	71.47 (11)	O4—C7—C4	116.1 (5)
O5^i—Er1—O6	128.51 (11)	O1—C8—O2	119.1 (4)
O8—Er1—O4	144.83 (12)	O1—C8—C5	122.3 (4)
O2—Er1—O4	73.65 (11)	O2—C8—C5	118.5 (4)
O7—Er1—O4	78.03 (12)	O1—C8—Er2^i	60.7 (3)
O11^i—Er1—O4	126.51 (13)	O2—C8—Er2^i	59.2 (2)
O5—Er1—O4	76.93 (11)	C5—C8—Er2^i	168.9 (4)
O5^i—Er1—O4	129.15 (11)	N1—C9—C12	123.1 (8)
O6—Er1—O4	68.70 (11)	N1—C9—H9A	118.5
O5—Er2—O4^ii	154.89 (12)	C12—C9—H9A	118.5
O5—Er2—O10	86.05 (12)	N1—C10—C11	123.6 (7)
O4^ii—Er2—O10	89.48 (12)	N1—C10—H10A	118.2
O5—Er2—O6^ii	83.29 (11)	C11—C10—H10A	118.2
O4^ii—Er2—O6^ii	71.64 (12)	C13—C11—C10	117.9 (7)
O10—Er2—O6^ii	76.79 (11)	C13—C11—H11A	121.0
O5—Er2—O6	72.60 (11)	C10—C11—H11A	121.0
O4^ii—Er2—O6	97.38 (12)	C9—C12—C13	119.3 (7)
O10—Er2—O6	143.26 (12)	C9—C12—H12A	120.3
O6^ii—Er2—O6	71.40 (12)	C13—C12—H12A	120.3
O5—Er2—O9	105.88 (13)	C11—C13—C12	118.6 (6)
O4^ii—Er2—O9	93.06 (13)	C11—C13—C14	121.2 (5)
O10—Er2—O9	140.96 (13)	C12—C13—C14	120.1 (5)
O6^ii—Er2—O9	140.45 (12)	O11—C14—O10	126.0 (5)
O6—Er2—O9	74.92 (12)	O11—C14—C13	116.5 (4)
O5—Er2—O2^i	67.71 (11)	O10—C14—C13	117.5 (4)
O4^ii—Er2—O2^i	135.33 (11)	N2—C15—C17	123.4 (7)
O10—Er2—O2^i	78.50 (12)	N2—C15—H15A	118.3
O6^ii—Er2—O2^i	142.87 (11)	C17—C15—H15A	118.3
O6—Er2—O2^i	117.85 (11)	N2—C16—C18	124.0 (7)
O9—Er2—O2^i	72.52 (13)	N2—C16—H16A	118.0
O5—Er2—O1^i	119.08 (11)	C18—C16—H16A	118.0
O4^ii—Er2—O1^i	82.71 (11)	C19—C17—C15	118.9 (7)
O10—Er2—O1^i	72.41 (13)	C19—C17—H17A	120.6
O6^ii—Er2—O1^i	139.76 (12)	C15—C17—H17A	120.6
O6—Er2—O1^i	144.17 (12)	C19—C18—C16	118.2 (6)
O9—Er2—O1^i	69.32 (13)	C19—C18—H18A	120.9
O2^i—Er2—O1^i	52.62 (11)	C16—C18—H18A	120.9
O1W—O1W—H2W	107.5	C17—C19—C18	118.5 (5)
Er2^ii—O6—H6	110.2	C17—C19—C20	120.3 (5)
Er2—O6—H6	118.7	C18—C19—C20	121.1 (5)
Er1—O6—H6	107.7	O9—C20—O8	126.9 (5)
Er1—O7—H7W	126.9	O9—C20—C19	117.1 (5)
Er1—O7—H8W	119.4	O8—C20—C19	116.0 (5)
H7W—O7—H8W	112.1	C10—N1—C9	117.4 (6)
C2—C1—C6	119.7 (6)	C15—N2—C16	117.0 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N1	0.93	1.95	2.834 (8)	160
O5—H5···O3	0.85	2.42	3.170 (6)	147
O6—H6···O1W^iii	0.87	1.98	2.826 (6)	164
O7—H7W···N2^iv	0.86	1.96	2.788 (6)	161
O7—H8W···O10^ii	0.87	1.87	2.716 (5)	165

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

(II) Poly[aqua(µ₃-benzene-1,2-dicarboxylato-κ⁴O,O':O':O'')bis(µ₃-hydroxido)bis(µ₂-isonicotinato-κ²O:O')thulium(III) monohydrate

Crystal data

[Tm2(C6H4NO2)2(C8H4O4)(OH)2(H2O)]·H2O	F(000) = 1544
Mr = 816.22	Dx = 2.354 Mg m^−3
Monoclinic, p21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18502 reflections
a = 7.2434 (2) Å	θ = 1.7–26.5°
b = 24.2180 (6) Å	µ = 7.72 mm^−1
c = 13.3606 (4) Å	T = 295 K
β = 100.700 (3)°	Prism, brown
V = 2302.97 (11) Å^3	0.35 × 0.09 × 0.07 mm
Z = 4

Data collection

Siemems SMART CCD diffractometer	4754 independent reflections
Radiation source: fine-focus sealed tube	4602 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 26.5°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.373, Tmax = 0.577	k = −29→30
18502 measured reflections	l = −16→16

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 4.1831P] where P = (Fo^2 + 2Fc^2)/3
4754 reflections	(Δ/σ)max = 0.002
325 parameters	Δρmax = 1.11 e Å^−3
0 restraints	Δρmin = −1.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
Tm1	0.59003 (2)	0.454897 (7)	0.399404 (13)	0.01278 (6)
Tm2	0.91843 (2)	0.492537 (7)	0.625664 (13)	0.01309 (6)
O1	0.1057 (4)	0.52578 (15)	0.1945 (2)	0.0257 (7)
O1W	0.9011 (7)	0.84841 (18)	1.0193 (4)	0.0605 (13)
H1W	0.9435	0.8165	0.9930	0.073*
H2W	0.7784	0.8479	1.0047	0.073*
O2	0.3689 (4)	0.51172 (13)	0.3029 (2)	0.0212 (7)
O3	0.6818 (5)	0.60627 (16)	0.3283 (3)	0.0442 (10)
O4	0.7650 (4)	0.51876 (13)	0.3111 (2)	0.0193 (6)
O5	0.6622 (4)	0.52721 (12)	0.5154 (2)	0.0138 (6)
H5	0.6798	0.5576	0.4863	0.017*
O6	0.9153 (4)	0.45201 (11)	0.4675 (2)	0.0145 (6)
H6	0.9514	0.4181	0.4653	0.017*
O7	0.7094 (4)	0.39701 (14)	0.2895 (2)	0.0258 (7)
H7W	0.6624	0.3661	0.2651	0.031*
H8W	0.8242	0.4011	0.2814	0.031*
O8	0.6154 (5)	0.38747 (14)	0.5187 (3)	0.0315 (8)
O9	0.8544 (5)	0.39973 (14)	0.6484 (3)	0.0309 (8)
O10	0.9274 (4)	0.57651 (13)	0.7080 (2)	0.0222 (7)
O11	0.6328 (4)	0.60859 (14)	0.6750 (3)	0.0309 (8)
C1	0.4036 (9)	0.5674 (3)	−0.0361 (4)	0.0476 (16)
H1A	0.3465	0.5677	−0.1045	0.057*
C2	0.5870 (9)	0.5844 (3)	−0.0072 (5)	0.0515 (18)
H2A	0.6525	0.5970	−0.0564	0.062*
C3	0.6752 (8)	0.5829 (2)	0.0935 (4)	0.0410 (14)
H3A	0.7996	0.5942	0.1117	0.049*
C4	0.5787 (6)	0.5645 (2)	0.1685 (4)	0.0256 (10)
C5	0.3912 (6)	0.5475 (2)	0.1394 (4)	0.0247 (10)
C6	0.3051 (8)	0.5500 (2)	0.0368 (4)	0.0364 (13)
H6A	0.1798	0.5398	0.0176	0.044*
C7	0.6795 (6)	0.5645 (2)	0.2774 (4)	0.0245 (10)
C8	0.2815 (6)	0.52723 (19)	0.2139 (3)	0.0223 (9)
C9	1.0001 (10)	0.6968 (3)	0.9434 (6)	0.061 (2)
H9A	1.0706	0.6908	1.0081	0.073*
C10	0.8386 (10)	0.7551 (3)	0.8267 (7)	0.060 (2)
H10A	0.7982	0.7906	0.8075	0.072*
C11	0.7917 (8)	0.7124 (2)	0.7563 (5)	0.0439 (14)
H11A	0.7183	0.7189	0.6926	0.053*
C12	0.9665 (8)	0.6529 (3)	0.8785 (5)	0.0438 (14)
H12A	1.0172	0.6184	0.8980	0.053*
C13	0.8573 (6)	0.6603 (2)	0.7844 (4)	0.0287 (11)
C14	0.8011 (6)	0.61155 (19)	0.7157 (3)	0.0226 (10)
C15	0.7365 (9)	0.2477 (3)	0.7692 (5)	0.0526 (17)
H15A	0.7858	0.2383	0.8364	0.063*
C16	0.5699 (9)	0.2247 (2)	0.6158 (5)	0.0482 (16)
H16A	0.5015	0.1985	0.5734	0.058*
C17	0.7636 (9)	0.3011 (2)	0.7375 (5)	0.0441 (14)
H17A	0.8314	0.3265	0.7821	0.053*
C18	0.5864 (8)	0.2770 (2)	0.5766 (5)	0.0381 (13)
H18A	0.5304	0.2857	0.5101	0.046*
C19	0.6887 (6)	0.31574 (19)	0.6394 (4)	0.0252 (10)
C20	0.7218 (7)	0.37263 (19)	0.5994 (4)	0.0248 (10)
N1	0.9381 (8)	0.7474 (3)	0.9196 (5)	0.0615 (17)
N2	0.6451 (7)	0.2096 (2)	0.7099 (5)	0.0486 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tm1	0.01099 (10)	0.01237 (10)	0.01469 (10)	−0.00007 (6)	0.00161 (7)	−0.00139 (6)
Tm2	0.01116 (10)	0.01405 (10)	0.01391 (10)	−0.00044 (6)	0.00196 (7)	−0.00029 (6)
O1	0.0159 (16)	0.038 (2)	0.0219 (16)	−0.0004 (14)	0.0010 (13)	0.0046 (15)
O1W	0.068 (3)	0.042 (3)	0.075 (3)	−0.013 (2)	0.020 (3)	−0.030 (2)
O2	0.0161 (15)	0.0304 (18)	0.0172 (15)	0.0029 (12)	0.0032 (12)	0.0065 (13)
O3	0.042 (2)	0.027 (2)	0.059 (3)	0.0000 (17)	−0.0015 (19)	−0.0091 (19)
O4	0.0138 (14)	0.0223 (17)	0.0215 (16)	0.0019 (12)	0.0029 (12)	0.0066 (13)
O5	0.0146 (14)	0.0115 (14)	0.0145 (14)	0.0000 (11)	0.0011 (11)	0.0006 (11)
O6	0.0170 (14)	0.0094 (14)	0.0171 (15)	0.0014 (10)	0.0032 (12)	0.0000 (11)
O7	0.0171 (16)	0.0253 (18)	0.0371 (19)	−0.0067 (13)	0.0101 (14)	−0.0159 (15)
O8	0.0260 (18)	0.029 (2)	0.040 (2)	0.0027 (14)	0.0076 (15)	0.0163 (16)
O9	0.044 (2)	0.0177 (17)	0.0327 (19)	−0.0050 (15)	0.0101 (16)	0.0017 (14)
O10	0.0177 (15)	0.0207 (17)	0.0295 (17)	−0.0028 (12)	0.0077 (13)	−0.0065 (13)
O11	0.0167 (16)	0.0253 (18)	0.050 (2)	−0.0033 (13)	0.0043 (15)	−0.0151 (16)
C1	0.049 (4)	0.071 (4)	0.024 (3)	0.016 (3)	0.011 (3)	0.019 (3)
C2	0.054 (4)	0.071 (5)	0.038 (3)	0.018 (3)	0.028 (3)	0.033 (3)
C3	0.028 (3)	0.050 (4)	0.048 (3)	0.005 (2)	0.014 (2)	0.024 (3)
C4	0.023 (2)	0.026 (3)	0.028 (2)	0.0057 (19)	0.0071 (19)	0.011 (2)
C5	0.022 (2)	0.031 (3)	0.022 (2)	0.0074 (18)	0.0055 (19)	0.0078 (19)
C6	0.034 (3)	0.052 (4)	0.021 (3)	0.011 (2)	0.002 (2)	0.007 (2)
C7	0.016 (2)	0.023 (3)	0.034 (3)	−0.0018 (17)	0.0048 (19)	0.008 (2)
C8	0.021 (2)	0.021 (2)	0.025 (2)	0.0023 (18)	0.0050 (18)	0.0020 (19)
C9	0.051 (4)	0.070 (5)	0.057 (4)	−0.010 (4)	0.000 (3)	−0.035 (4)
C10	0.056 (4)	0.028 (3)	0.100 (6)	−0.006 (3)	0.025 (4)	−0.025 (4)
C11	0.039 (3)	0.035 (3)	0.058 (4)	−0.004 (2)	0.009 (3)	−0.014 (3)
C12	0.036 (3)	0.049 (4)	0.044 (3)	−0.003 (3)	0.003 (3)	−0.018 (3)
C13	0.018 (2)	0.031 (3)	0.040 (3)	−0.0063 (19)	0.011 (2)	−0.018 (2)
C14	0.019 (2)	0.023 (2)	0.028 (2)	−0.0069 (18)	0.0089 (18)	−0.0061 (19)
C15	0.058 (4)	0.045 (4)	0.055 (4)	0.001 (3)	0.011 (3)	0.032 (3)
C16	0.043 (3)	0.029 (3)	0.071 (5)	−0.006 (2)	0.007 (3)	0.004 (3)
C17	0.058 (4)	0.030 (3)	0.041 (3)	−0.007 (3)	0.001 (3)	0.012 (3)
C18	0.034 (3)	0.026 (3)	0.052 (3)	0.001 (2)	0.001 (3)	0.009 (2)
C19	0.023 (2)	0.016 (2)	0.037 (3)	0.0021 (18)	0.009 (2)	0.008 (2)
C20	0.032 (3)	0.019 (2)	0.028 (2)	0.0080 (19)	0.016 (2)	0.0050 (19)
N1	0.051 (3)	0.062 (4)	0.074 (4)	−0.017 (3)	0.018 (3)	−0.043 (3)
N2	0.039 (3)	0.028 (3)	0.082 (4)	0.004 (2)	0.019 (3)	0.023 (3)

Geometric parameters (Å, º)

Tm1—O8	2.266 (3)	C1—C2	1.376 (9)
Tm1—O7	2.311 (3)	C1—C6	1.376 (8)
Tm1—O2	2.314 (3)	C1—H1A	0.9300
Tm1—O11^i	2.315 (3)	C2—C3	1.379 (8)
Tm1—O5	2.332 (3)	C2—H2A	0.9300
Tm1—O6	2.364 (3)	C3—C4	1.396 (7)
Tm1—O5^i	2.366 (3)	C3—H3A	0.9300
Tm1—O4	2.439 (3)	C4—C5	1.404 (7)
Tm1—Tm2	3.5997 (3)	C4—C7	1.503 (7)
Tm1—Tm2^i	3.8521 (2)	C5—C6	1.398 (7)
Tm1—Tm2^ii	3.8539 (3)	C5—C8	1.469 (6)
Tm1—Tm1^i	3.8731 (4)	C6—H6A	0.9300
Tm2—O5	2.303 (3)	C9—N1	1.324 (10)
Tm2—O10	2.308 (3)	C9—C12	1.366 (8)
Tm2—O4^ii	2.308 (3)	C9—H9A	0.9300
Tm2—O6^ii	2.315 (3)	C10—N1	1.327 (10)
Tm2—O9	2.326 (3)	C10—C11	1.397 (9)
Tm2—O6	2.327 (3)	C10—H10A	0.9300
Tm2—O2^i	2.447 (3)	C11—C13	1.376 (8)
Tm2—O1^i	2.482 (3)	C11—H11A	0.9300
Tm2—Tm2^ii	3.7783 (4)	C12—C13	1.367 (8)
O1—C8	1.252 (5)	C12—H12A	0.9300
O1W—H1W	0.9247	C13—C14	1.503 (6)
O1W—H2W	0.8735	C15—N2	1.313 (9)
O2—C8	1.295 (5)	C15—C17	1.387 (8)
O3—C7	1.217 (6)	C15—H15A	0.9300
O4—C7	1.307 (5)	C16—N2	1.326 (8)
O5—H5	0.8521	C16—C18	1.384 (8)
O6—H6	0.8652	C16—H16A	0.9300
O7—H7W	0.8606	C17—C19	1.370 (7)
O7—H8W	0.8638	C17—H17A	0.9300
O8—C20	1.255 (6)	C18—C19	1.379 (7)
O9—C20	1.245 (6)	C18—H18A	0.9300
O10—C14	1.266 (5)	C19—C20	1.513 (6)
O11—C14	1.241 (5)
O8—Tm1—O7	91.08 (13)	Tm1—O7—H8W	119.5
O8—Tm1—O2	141.07 (11)	H7W—O7—H8W	112.0
O7—Tm1—O2	107.98 (11)	C2—C1—C6	119.5 (5)
O8—Tm1—O11^i	77.43 (13)	C2—C1—H1A	120.2
O7—Tm1—O11^i	68.76 (11)	C6—C1—H1A	120.2
O2—Tm1—O11^i	78.50 (12)	C1—C2—C3	120.9 (5)
O8—Tm1—O5	95.45 (12)	C1—C2—H2A	119.5
O7—Tm1—O5	144.43 (10)	C3—C2—H2A	119.5
O2—Tm1—O5	88.29 (10)	C2—C3—C4	120.4 (5)
O11^i—Tm1—O5	146.74 (11)	C2—C3—H3A	119.8
O8—Tm1—O6	76.29 (11)	C4—C3—H3A	119.8
O7—Tm1—O6	76.28 (10)	C3—C4—C5	118.9 (5)
O2—Tm1—O6	140.30 (10)	C3—C4—C7	118.5 (5)
O11^i—Tm1—O6	135.33 (10)	C5—C4—C7	122.6 (4)
O5—Tm1—O6	71.46 (9)	C6—C5—C4	119.4 (5)
O8—Tm1—O5^i	76.26 (11)	C6—C5—C8	118.7 (4)
O7—Tm1—O5^i	146.15 (10)	C4—C5—C8	121.9 (4)
O2—Tm1—O5^i	69.05 (10)	C1—C6—C5	120.8 (5)
O11^i—Tm1—O5^i	77.82 (11)	C1—C6—H6A	119.6
O5—Tm1—O5^i	68.94 (11)	C5—C6—H6A	119.6
O6—Tm1—O5^i	128.61 (9)	O3—C7—O4	123.8 (5)
O8—Tm1—O4	144.69 (11)	O3—C7—C4	119.7 (4)
O7—Tm1—O4	77.75 (11)	O4—C7—C4	116.6 (4)
O2—Tm1—O4	73.84 (10)	O1—C8—O2	119.2 (4)
O11^i—Tm1—O4	126.66 (12)	O1—C8—C5	121.7 (4)
O5—Tm1—O4	76.86 (10)	O2—C8—C5	119.0 (4)
O6—Tm1—O4	68.55 (10)	N1—C9—C12	123.7 (7)
O5^i—Tm1—O4	129.35 (10)	N1—C9—H9A	118.1
O5—Tm2—O10	86.09 (10)	C12—C9—H9A	118.1
O5—Tm2—O4^ii	154.84 (10)	N1—C10—C11	123.2 (7)
O10—Tm2—O4^ii	89.53 (11)	N1—C10—H10A	118.4
O5—Tm2—O6^ii	83.25 (10)	C11—C10—H10A	118.4
O10—Tm2—O6^ii	76.93 (10)	C13—C11—C10	117.9 (6)
O4^ii—Tm2—O6^ii	71.64 (10)	C13—C11—H11A	121.1
O5—Tm2—O9	106.22 (11)	C10—C11—H11A	121.1
O10—Tm2—O9	141.05 (12)	C9—C12—C13	119.1 (6)
O4^ii—Tm2—O9	92.65 (12)	C9—C12—H12A	120.4
O6^ii—Tm2—O9	140.08 (11)	C13—C12—H12A	120.4
O5—Tm2—O6	72.64 (10)	C12—C13—C11	118.8 (5)
O10—Tm2—O6	143.11 (11)	C12—C13—C14	120.2 (5)
O4^ii—Tm2—O6	97.13 (10)	C11—C13—C14	120.8 (5)
O6^ii—Tm2—O6	71.02 (11)	O11—C14—O10	126.3 (4)
O9—Tm2—O6	75.09 (11)	O11—C14—C13	116.5 (4)
O5—Tm2—O2^i	67.81 (10)	O10—C14—C13	117.2 (4)
O10—Tm2—O2^i	78.57 (11)	N2—C15—C17	123.8 (6)
O4^ii—Tm2—O2^i	135.33 (10)	N2—C15—H15A	118.1
O6^ii—Tm2—O2^i	143.03 (10)	C17—C15—H15A	118.1
O9—Tm2—O2^i	72.77 (12)	N2—C16—C18	124.3 (6)
O6—Tm2—O2^i	118.08 (10)	N2—C16—H16A	117.9
O5—Tm2—O1^i	119.44 (10)	C18—C16—H16A	117.9
O10—Tm2—O1^i	72.33 (11)	C19—C17—C15	118.7 (6)
O4^ii—Tm2—O1^i	82.42 (10)	C19—C17—H17A	120.6
O6^ii—Tm2—O1^i	139.60 (10)	C15—C17—H17A	120.6
O9—Tm2—O1^i	69.45 (12)	C19—C18—C16	117.8 (5)
O6—Tm2—O1^i	144.46 (11)	C19—C18—H18A	121.1
O2^i—Tm2—O1^i	52.92 (10)	C16—C18—H18A	121.1
H1W—O1W—H2W	107.5	C17—C19—C18	118.6 (5)
Tm2—O5—H5	115.8	C17—C19—C20	120.9 (5)
Tm1—O5—H5	112.3	C18—C19—C20	120.5 (5)
Tm1^i—O5—H5	104.7	O9—C20—O8	126.3 (4)
Tm2^ii—O6—H6	110.0	O9—C20—C19	116.8 (4)
Tm2—O6—H6	118.6	O8—C20—C19	116.9 (4)
Tm1—O6—H6	107.5	C9—N1—C10	117.1 (6)
Tm1—O7—H7W	126.8	C15—N2—C16	116.8 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N1	0.92	1.94	2.822 (7)	160
O5—H5···O3	0.85	2.42	3.172 (5)	148
O6—H6···O1W^iii	0.87	1.99	2.830 (5)	165
O7—H7W···N2^iv	0.86	1.97	2.798 (6)	161
O7—H8W···O10^ii	0.86	1.86	2.702 (4)	165

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