Poly[[triaqua­(μ3-4-oxidopyridine-2,6-dicarboxyl­ato)thulium(III)] monohydrate]

Gao, Z.-Q.; Lv, D.-Y.; Gu, J.-Z.; Li, H.-J.

doi:10.1107/S1600536811007628

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m409

doi:10.1107/S1600536811007628

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Poly[[triaqua(μ₃-4-oxidopyridine-2,6-dicarboxylato)thulium(III)] monohydrate]

Zhu-Qing Gao,^a ^* Dong-Yu Lv,^b Jin-Zhong Gu ^b and Hong-Jin Li ^a

^aSchool of Chemistry and Biology Engineering, Taiyuan University of Science and Technology, Taiyuan 030021, People's Republic of China, and ^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, People's Republic of China
^*Correspondence e-mail: zqgao2008@163.com

(Received 21 February 2011; accepted 28 February 2011; online 9 March 2011)

In the title coordination polymer, {[Tm(C₇H₂NO₅)(H₂O)₃]·H₂O}_n, the Tm^III atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxylate trianion, two monodentate anions and three water molecules, forming a distorted bicapped trigonal–prismatic TmNO₇ coordination geometry. The anions bridge adjacent Tm^III ions into double chains. Adjacent chains are further connected into sheets. O—H⋯O hydrogen bonds involving both coordinated and uncoordinated water molecules generate a three-dimensional supramolecular framework.

Related literature

For the structures and properties of lanthanide coordination compounds including the isotypic Dy and Eu analogues, see: Qin et al. (2011 ); Lv et al. (2010 ); Gao et al. (2006 ). For structures of complexes containing eight-coordinate Tm^III, see: Qin et al. (2011); Tian et al. (2009 ).

Experimental

Crystal data

[Tm(C₇H₂NO₅)(H₂O)₃]·H₂O
M_r = 421.09
Monoclinic, P 2₁ /n
a = 9.829 (3) Å
b = 7.559 (2) Å
c = 15.350 (5) Å
β = 105.589 (3)°
V = 1098.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 8.12 mm⁻¹
T = 296 K
0.28 × 0.26 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.118, T_max = 0.168
5810 measured reflections
2028 independent reflections
1721 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.082
S = 1.08
2028 reflections
176 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.45 e Å⁻³
Δρ_min = −1.83 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H8W⋯O2ⁱ	0.88	2.54	3.111 (6)	123
O9—H7W⋯O5ⁱⁱ	0.83	2.03	2.694 (6)	137
O8—H6W⋯O9ⁱⁱⁱ	0.95	1.73	2.679 (5)	179
O8—H5W⋯O9^iv	0.90	2.27	3.068 (6)	148
O7—H4W⋯O5^v	0.95	1.79	2.697 (5)	158
O7—H3W⋯O1ⁱ	0.90 (3)	1.85 (3)	2.672 (5)	151 (5)
O6—H2W⋯O4^vi	0.83 (4)	2.11 (5)	2.791 (5)	139 (5)
O6—H1W⋯O3^vii	0.91 (4)	1.84 (4)	2.706 (5)	156 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y+1, -z; (vi) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) -x+1, -y+2, -z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007628/pv2392sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007628/pv2392Isup2.hkl

checkCIF report

Comment top

The lanthanide coordination polymers have shown not only versatile architectures but also desirable properties, e.g., luminescent, magnetic, catalytic, and gas absorption and separation properties (Qin et al., 2011; Lv et al., 2010). In order to extend our investigations in this field, we have designed and synthesized a novel lanthanide coordination polymer, {[Tm(C₇H₂NO₅)(H₂O)₃].H₂O}_n, by choosing 4-oxidopyridine-2,6-dicarboxylicacid as a functional ligand, and report its crystal structure in this paper.

The title compound is isotypic with its Dy (Gao et al., 2006) and Eu (Lv et al., 2010) analogues. The asymmetrical unit of the the title complex contains a Tm(III) ion, a 4-oxidopyridine-2,6-dicarboxylate anion, three coordinated water molecules, and a molecule of water of crystallization (Fig. 1). The Tm atom is eight-coordinated by seven oxygen atoms from three anions and three coordinated water molecules and by a nitrogen atom from a tridentate anion (the other two anions are monodentate), forming a distorted bicapped trigonal-prismatic coordination environment. The Tm–O bond lengths [2.263 (3) - 2.385 (3) Å] are shorter than the Tm–N bond length [2.430 (4) Å], which is in agreement with the bond lengths observed in other Tm(III) complexes (Qin et al., 2011; Tian et al., 2009). The anion adopts a µ₃-pentadentate coordination mode. The anions bridge the adjacent Tm^III ions to form infinite double chains (Fig. 2). Adjacent chains are further connected by the coordination of the anions and Tm(III) ions into two-dimensional sheets (Fig. 3), which are further extended into a three-dimensional supramolecular framework through O–H···O hydrogen-bonding interactions including both coordinated and uncoordinated water molecules (Table 1).

Related literature top

For the structures and properties of lanthanide coordination compounds including the isotypic Dy and Eu analogues, see: Qin et al. (2011); Lv et al. (2010); Gao et al. (2006). For structures of complexes containing eight-coordinate Tm^III, see: Qin et al. (2011); Tian et al. (2009).

For related literature, see: .

Experimental top

To a solution of thulium(III)nitrate hexahydrate (0.139 g, 0.3 mmol) in water (5 ml) was added an aqueous solution (5 ml) of the ligand (0.060 g, 0.3 mmol) and a drop of triethylamine. The reactants were sealed in a 25-ml Teflon-lined, stainless-steel Parr bomb. The bomb was heated at 433 K for 3 days. On cooling the solution, single crystals (ca 70% yield) were obtained which were suitable for single crystal X-ray differaction studies.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Drawing of the asymmetric unit of the title complex, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the title structure along the b axis, showing the double chain.
	Fig. 3. A view of the unit cell along the a axis, showing the sheet structure of the title complex; H-atoms have been excluded for clarity.

Poly[[triaqua(µ₃-4-oxidopyridine-2,6-dicarboxylato)thulium(III)] monohydrate] top

Crystal data top

[Tm(C₇H₂NO₅)(H₂O)₃]·H₂O	F(000) = 800
M_r = 421.09	D_x = 2.546 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3206 reflections
a = 9.829 (3) Å	θ = 2.2–28.1°
b = 7.559 (2) Å	µ = 8.12 mm⁻¹
c = 15.350 (5) Å	T = 296 K
β = 105.589 (3)°	Block, colorless
V = 1098.6 (6) Å³	0.28 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2028 independent reflections
Radiation source: fine-focus sealed tube	1721 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.118, T_max = 0.168	k = −9→9
5810 measured reflections	l = −18→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.039P)² + 1.1506P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
2028 reflections	Δρ_max = 1.45 e Å⁻³
176 parameters	Δρ_min = −1.83 e Å⁻³
12 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0158 (6)

Crystal data top

[Tm(C₇H₂NO₅)(H₂O)₃]·H₂O	V = 1098.6 (6) Å³
M_r = 421.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.829 (3) Å	µ = 8.12 mm⁻¹
b = 7.559 (2) Å	T = 296 K
c = 15.350 (5) Å	0.28 × 0.26 × 0.22 mm
β = 105.589 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2028 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1721 reflections with I > 2σ(I)
T_min = 0.118, T_max = 0.168	R_int = 0.038
5810 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	12 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.45 e Å⁻³
2028 reflections	Δρ_min = −1.83 e Å⁻³
176 parameters

Special details top

Experimental. Anal. Calcd for C₇H₁₀TbNO₉: C, 19.97; H, 2.39; N, 3.33. Found: C, 20.31; H, 2.47; N, 3.12.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Tm1	0.498130 (19)	0.67912 (3)	0.252028 (12)	0.00947 (16)
C1	0.2175 (5)	0.9137 (7)	0.1631 (3)	0.0156 (11)
C2	0.2755 (5)	0.8881 (6)	0.0829 (3)	0.0127 (10)
C3	0.2046 (5)	0.9447 (6)	−0.0015 (3)	0.0155 (11)
H3	0.1204	1.0072	−0.0105	0.019*
C4	0.2614 (5)	0.9069 (6)	−0.0753 (3)	0.0121 (10)
C5	0.3907 (5)	0.8160 (6)	−0.0544 (3)	0.0132 (11)
H5	0.4336	0.7888	−0.0999	0.016*
C6	0.4537 (5)	0.7675 (6)	0.0335 (3)	0.0123 (10)
C7	0.5906 (5)	0.6682 (6)	0.0630 (4)	0.0132 (11)
N1	0.3961 (5)	0.8002 (5)	0.1020 (3)	0.0125 (9)
O1	0.2806 (4)	0.8294 (5)	0.2333 (3)	0.0242 (10)
O2	0.1121 (4)	1.0091 (5)	0.1562 (2)	0.0190 (8)
O3	0.1933 (4)	0.9514 (5)	−0.1587 (2)	0.0173 (8)
O4	0.6311 (4)	0.6267 (5)	0.1454 (2)	0.0168 (8)
O5	0.6587 (4)	0.6359 (5)	0.0068 (2)	0.0212 (9)
O6	0.6355 (4)	0.9322 (5)	0.2582 (3)	0.0251 (9)
O7	0.3975 (5)	0.4312 (5)	0.1720 (3)	0.0269 (10)
H4W	0.3923	0.3823	0.1140	0.032*
O8	0.5064 (5)	0.8348 (4)	0.3875 (3)	0.0232 (9)
H5W	0.4593	0.8051	0.4279	0.028*
H6W	0.5247	0.9565	0.4025	0.028*
O9	0.5599 (5)	0.1768 (5)	0.4284 (3)	0.0386 (12)
H7W	0.6306	0.1698	0.4728	0.046*
H8W	0.5610	0.2542	0.3853	0.046*
H1W	0.689 (5)	0.940 (7)	0.218 (3)	0.018 (14)*
H2W	0.689 (5)	0.964 (7)	0.307 (3)	0.017 (16)*
H3W	0.318 (5)	0.393 (6)	0.184 (3)	0.012 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tm1	0.0065 (2)	0.0139 (2)	0.0060 (2)	0.00015 (7)	−0.00175 (13)	0.00069 (7)
C1	0.010 (3)	0.020 (3)	0.014 (3)	0.002 (2)	−0.002 (2)	−0.001 (2)
C2	0.010 (3)	0.018 (2)	0.010 (3)	0.001 (2)	0.001 (2)	−0.001 (2)
C3	0.011 (3)	0.018 (3)	0.016 (3)	0.004 (2)	0.001 (2)	0.003 (2)
C4	0.008 (3)	0.016 (2)	0.011 (3)	−0.0047 (19)	−0.001 (2)	0.003 (2)
C5	0.010 (3)	0.019 (3)	0.010 (3)	−0.0025 (19)	0.001 (2)	−0.0009 (19)
C6	0.014 (3)	0.013 (2)	0.010 (3)	0.000 (2)	0.003 (2)	−0.001 (2)
C7	0.007 (3)	0.015 (2)	0.016 (3)	−0.0042 (19)	0.001 (2)	−0.004 (2)
N1	0.007 (2)	0.019 (2)	0.011 (2)	0.0006 (17)	0.0003 (19)	0.0006 (16)
O1	0.019 (2)	0.041 (2)	0.012 (2)	0.0165 (16)	0.0038 (18)	0.0091 (16)
O2	0.017 (2)	0.0239 (19)	0.015 (2)	0.0084 (16)	0.0027 (16)	0.0000 (15)
O3	0.015 (2)	0.025 (2)	0.008 (2)	−0.0046 (15)	−0.0036 (16)	0.0028 (14)
O4	0.013 (2)	0.0250 (19)	0.011 (2)	0.0046 (16)	0.0015 (15)	0.0032 (15)
O5	0.017 (2)	0.035 (2)	0.011 (2)	0.0074 (17)	0.0034 (16)	0.0002 (16)
O6	0.028 (3)	0.032 (2)	0.015 (2)	−0.0193 (18)	0.006 (2)	−0.0063 (18)
O7	0.037 (3)	0.030 (2)	0.018 (2)	−0.0158 (19)	0.013 (2)	−0.0105 (17)
O8	0.031 (3)	0.022 (2)	0.018 (2)	−0.0030 (16)	0.008 (2)	−0.0017 (15)
O9	0.027 (3)	0.027 (2)	0.055 (3)	−0.0055 (17)	−0.001 (2)	−0.0030 (19)

Geometric parameters (Å, º) top

Tm1—O3ⁱ	2.263 (3)	C5—C6	1.374 (7)
Tm1—O7	2.312 (4)	C5—H5	0.9300
Tm1—O6	2.329 (4)	C6—N1	1.345 (6)
Tm1—O1	2.369 (4)	C6—C7	1.501 (7)
Tm1—O8	2.372 (4)	C7—O5	1.250 (6)
Tm1—O2ⁱⁱ	2.372 (3)	C7—O4	1.260 (6)
Tm1—O4	2.385 (3)	O2—Tm1ⁱⁱⁱ	2.372 (3)
Tm1—N1	2.430 (4)	O3—Tm1^iv	2.263 (3)
C1—O2	1.243 (6)	O6—H1W	0.91 (4)
C1—O1	1.262 (6)	O6—H2W	0.83 (4)
C1—C2	1.502 (7)	O7—H4W	0.9517
C2—N1	1.321 (6)	O7—H3W	0.90 (3)
C2—C3	1.364 (7)	O8—H5W	0.8963
C3—C4	1.421 (7)	O8—H6W	0.9533
C3—H3	0.9300	O9—H7W	0.8345
C4—O3	1.318 (6)	O9—H8W	0.8850
C4—C5	1.404 (7)

O3ⁱ—Tm1—O7	98.07 (13)	C3—C2—C1	121.9 (5)
O3ⁱ—Tm1—O6	86.88 (14)	C2—C3—C4	119.0 (5)
O7—Tm1—O6	147.98 (14)	C2—C3—H3	120.5
O3ⁱ—Tm1—O1	150.82 (12)	C4—C3—H3	120.5
O7—Tm1—O1	94.66 (15)	O3—C4—C5	122.6 (4)
O6—Tm1—O1	96.05 (14)	O3—C4—C3	121.2 (5)
O3ⁱ—Tm1—O8	82.05 (13)	C5—C4—C3	116.2 (4)
O7—Tm1—O8	141.00 (13)	C6—C5—C4	119.8 (5)
O6—Tm1—O8	70.96 (13)	C6—C5—H5	120.1
O1—Tm1—O8	71.66 (14)	C4—C5—H5	120.1
O3ⁱ—Tm1—O2ⁱⁱ	81.52 (13)	N1—C6—C5	123.1 (5)
O7—Tm1—O2ⁱⁱ	71.23 (12)	N1—C6—C7	112.8 (4)
O6—Tm1—O2ⁱⁱ	140.63 (13)	C5—C6—C7	124.1 (4)
O1—Tm1—O2ⁱⁱ	77.90 (13)	O5—C7—O4	124.2 (5)
O8—Tm1—O2ⁱⁱ	70.24 (12)	O5—C7—C6	119.5 (5)
O3ⁱ—Tm1—O4	79.12 (12)	O4—C7—C6	116.3 (4)
O7—Tm1—O4	74.67 (13)	C2—N1—C6	117.4 (4)
O6—Tm1—O4	75.29 (13)	C2—N1—Tm1	121.1 (3)
O1—Tm1—O4	129.75 (12)	C6—N1—Tm1	121.3 (3)
O8—Tm1—O4	141.98 (13)	C1—O1—Tm1	124.5 (3)
O2ⁱⁱ—Tm1—O4	137.63 (11)	C1—O2—Tm1ⁱⁱⁱ	140.1 (3)
O3ⁱ—Tm1—N1	143.61 (13)	C4—O3—Tm1^iv	127.1 (3)
O7—Tm1—N1	78.04 (14)	C7—O4—Tm1	124.4 (3)
O6—Tm1—N1	79.41 (14)	Tm1—O6—H1W	117 (3)
O1—Tm1—N1	64.89 (13)	Tm1—O6—H2W	120 (4)
O8—Tm1—N1	123.52 (13)	H1W—O6—H2W	104 (4)
O2ⁱⁱ—Tm1—N1	128.94 (14)	Tm1—O7—H4W	136.0
O4—Tm1—N1	64.86 (13)	Tm1—O7—H3W	115 (3)
O2—C1—O1	124.9 (5)	H4W—O7—H3W	103.9
O2—C1—C2	119.8 (4)	Tm1—O8—H5W	125.4
O1—C1—C2	115.3 (4)	Tm1—O8—H6W	130.5
N1—C2—C3	124.6 (5)	H5W—O8—H6W	100.0
N1—C2—C1	113.5 (4)	H7W—O9—H8W	118.5

O2—C1—C2—N1	172.9 (5)	O4—Tm1—N1—C2	180.0 (4)
O1—C1—C2—N1	−8.8 (6)	O3ⁱ—Tm1—N1—C6	14.6 (5)
O2—C1—C2—C3	−9.9 (7)	O7—Tm1—N1—C6	−72.8 (4)
O1—C1—C2—C3	168.4 (5)	O6—Tm1—N1—C6	84.3 (4)
N1—C2—C3—C4	0.6 (7)	O1—Tm1—N1—C6	−173.8 (4)
C1—C2—C3—C4	−176.2 (4)	O8—Tm1—N1—C6	142.8 (3)
C2—C3—C4—O3	176.7 (4)	O2ⁱⁱ—Tm1—N1—C6	−126.4 (4)
C2—C3—C4—C5	−1.6 (7)	O4—Tm1—N1—C6	5.7 (3)
O3—C4—C5—C6	−177.6 (4)	O2—C1—O1—Tm1	−171.5 (4)
C3—C4—C5—C6	0.7 (7)	C2—C1—O1—Tm1	10.3 (6)
C4—C5—C6—N1	1.2 (7)	O3ⁱ—Tm1—O1—C1	163.5 (4)
C4—C5—C6—C7	179.2 (4)	O7—Tm1—O1—C1	−80.7 (4)
N1—C6—C7—O5	−176.9 (4)	O6—Tm1—O1—C1	69.1 (4)
C5—C6—C7—O5	5.0 (7)	O8—Tm1—O1—C1	136.7 (4)
N1—C6—C7—O4	1.3 (6)	O2ⁱⁱ—Tm1—O1—C1	−150.3 (4)
C5—C6—C7—O4	−176.9 (4)	O4—Tm1—O1—C1	−6.8 (5)
C3—C2—N1—C6	1.3 (7)	N1—Tm1—O1—C1	−6.2 (4)
C1—C2—N1—C6	178.4 (4)	O1—C1—O2—Tm1ⁱⁱⁱ	25.6 (9)
C3—C2—N1—Tm1	−173.2 (4)	C2—C1—O2—Tm1ⁱⁱⁱ	−156.3 (4)
C1—C2—N1—Tm1	3.9 (6)	C5—C4—O3—Tm1^iv	104.5 (5)
C5—C6—N1—C2	−2.2 (7)	C3—C4—O3—Tm1^iv	−73.7 (5)
C7—C6—N1—C2	179.6 (4)	O5—C7—O4—Tm1	−177.8 (3)
C5—C6—N1—Tm1	172.3 (4)	C6—C7—O4—Tm1	4.1 (6)
C7—C6—N1—Tm1	−5.9 (5)	O3ⁱ—Tm1—O4—C7	−179.8 (4)
O3ⁱ—Tm1—N1—C2	−171.1 (3)	O7—Tm1—O4—C7	78.6 (4)
O7—Tm1—N1—C2	101.5 (4)	O6—Tm1—O4—C7	−90.2 (4)
O6—Tm1—N1—C2	−101.4 (4)	O1—Tm1—O4—C7	−4.6 (4)
O1—Tm1—N1—C2	0.5 (4)	O8—Tm1—O4—C7	−118.1 (4)
O8—Tm1—N1—C2	−42.9 (4)	O2ⁱⁱ—Tm1—O4—C7	115.9 (4)
O2ⁱⁱ—Tm1—N1—C2	47.9 (4)	N1—Tm1—O4—C7	−5.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H8W···O2ⁱⁱ	0.88	2.54	3.111 (6)	123
O9—H7W···O5^v	0.83	2.03	2.694 (6)	137
O8—H6W···O9^vi	0.95	1.73	2.679 (5)	179
O8—H5W···O9^vii	0.90	2.27	3.068 (6)	148
O7—H4W···O5^viii	0.95	1.79	2.697 (5)	158
O7—H3W···O1ⁱⁱ	0.90 (3)	1.85 (3)	2.672 (5)	151 (5)
O6—H2W···O4^ix	0.83 (4)	2.11 (5)	2.791 (5)	139 (5)
O6—H1W···O3^x	0.91 (4)	1.84 (4)	2.706 (5)	156 (4)

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

Experimental details

Crystal data
Chemical formula	[Tm(C₇H₂NO₅)(H₂O)₃]·H₂O
M_r	421.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.829 (3), 7.559 (2), 15.350 (5)
β (°)	105.589 (3)
V (Å³)	1098.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.12
Crystal size (mm)	0.28 × 0.26 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.118, 0.168
No. of measured, independent and observed [I > 2σ(I)] reflections	5810, 2028, 1721
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.08
No. of reflections	2028
No. of parameters	176
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.45, −1.83

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H8W···O2ⁱ	0.88	2.54	3.111 (6)	123
O9—H7W···O5ⁱⁱ	0.83	2.03	2.694 (6)	137
O8—H6W···O9ⁱⁱⁱ	0.95	1.73	2.679 (5)	179
O8—H5W···O9^iv	0.90	2.27	3.068 (6)	148
O7—H4W···O5^v	0.95	1.79	2.697 (5)	158
O7—H3W···O1ⁱ	0.90 (3)	1.85 (3)	2.672 (5)	151 (5)
O6—H2W···O4^vi	0.83 (4)	2.11 (5)	2.791 (5)	139 (5)
O6—H1W···O3^vii	0.91 (4)	1.84 (4)	2.706 (5)	156 (4)

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

References

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