Poly[[triaqua-(μ(3)-4-oxidopyridine-2,6-dicarboxyl-ato)thulium(III)] monohydrate].

In the title coordination polymer, {[Tm(C(7)H(2)NO(5))(H(2)O)(3)]·H(2)O}(n), the Tm(III) atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxyl-ate trianion, two monodentate anions and three water mol-ecules, forming a distorted bicapped trigonal-prismatic TmNO(7) 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 mol-ecules generate a three-dimensional supra-molecular 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 TmIII, see: Qin et al. (2011 ▶); Tian et al. (2009 ▶).

Experimental

Crystal data

[Tm(C7H2NO5)(H2O)3]·H2O

M = 421.09

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.082

S = 1.08

2028 reflections

176 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.45 e Å−3

Δρmin = −1.83 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Tm(C7H2NO5)(H2O)3]·H2O	F(000) = 800
Mr = 421.09	Dx = 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

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

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(Fo2) + (0.039P)2 + 1.1506P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.002
2028 reflections	Δρmax = 1.45 e Å−3
176 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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—Tm1iv	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—Tm1iv	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—Tm1iv	104.5 (5)
C5—C6—N1—C2	−2.2 (7)	C3—C4—O3—Tm1iv	−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)

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···O5v	0.83	2.03	2.694 (6)	137
O8—H6W···O9vi	0.95	1.73	2.679 (5)	179
O8—H5W···O9vii	0.90	2.27	3.068 (6)	148
O7—H4W···O5viii	0.95	1.79	2.697 (5)	158
O7—H3W···O1ii	0.90 (3)	1.85 (3)	2.672 (5)	151 (5)
O6—H2W···O4ix	0.83 (4)	2.11 (5)	2.791 (5)	139 (5)
O6—H1W···O3x	0.91 (4)	1.84 (4)	2.706 (5)	156 (4)

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⋯O9iv	0.90	2.27	3.068 (6)	148
O7—H4W⋯O5v	0.95	1.79	2.697 (5)	158
O7—H3W⋯O1i	0.90 (3)	1.85 (3)	2.672 (5)	151 (5)
O6—H2W⋯O4vi	0.83 (4)	2.11 (5)	2.791 (5)	139 (5)
O6—H1W⋯O3vii	0.91 (4)	1.84 (4)	2.706 (5)	156 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .