Tris(6-carb-oxy-pyridine-2-carboxyl-ato)terbium(III) 2.75-hydrate.

In the title compound, [Tb(C(7)H(4)NO(4))(3)]·2.75H(2)O, the Tb(3+) atom is coordinated by three tridentate 6-carb-oxy-pyridine-2-carboxyl-ate ligands and lies on a crystallographic threefold rotation axis. The coordination polyhedron around Tb(III) adopts a distorted tricapped trigonal-prismatic geometry. Disordered water mol-ecules with partial occupancy are also present in the crystal, one of which is associated with each of the carboxyl-ate O atoms of the complex unit.

Related literature

For details of the synthesis, see: Zebret et al. (2009 ▶). For related structures, see: D’Aléo, et al. (2007 ▶, 2008 ▶); Borthwick (1980 ▶); Albertsson (1970 ▶); Hamacek et al. (2009 ▶). For isotypic structures, see: Brayshaw et al. (2005 ▶); Chen et al. (2002 ▶); Iwamura et al. (2007 ▶); Lunstroot et al. (2009 ▶); Pompidor et al. (2008 ▶); Shengzhi et al. (1989 ▶); Van Meervelt et al. (1997 ▶). For the Squeeze/bypass procedure, see: van der Sluis & Spek (1990 ▶). For a description of the Cambridge Structural Database, see: Allen (2002) ▶.

Experimental

Crystal data

[Tb(C7H4NO4)3]·2.75H2O

M = 706.79

Trigonal,

a = 13.0115 (15) Å

c = 9.4142 (13) Å

V = 1380.3 (5) Å3

Z = 2

Mo Kα radiation

μ = 2.63 mm−1

T = 200 K

0.15 × 0.10 × 0.05 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: Gaussian (Busing & Levy, 1957 ▶) T min = 0.72, T max = 0.88

3830 measured reflections

1569 independent reflections

1464 reflections with I > 2.0σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.082

S = 1.00

1566 reflections

122 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −1.01 e Å−3

Absolute structure: Flack (1983 ▶), 679 Friedel pairs

Flack parameter: −0.05 (2)

Data collection: IPDS (Stoe & Cie, 1996 ▶); cell refinement: IPDS; data reduction: X-RED (Stoe & Cie 1996 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996) ▶; software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811024135/zs2104sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024135/zs2104Isup2.hkl

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

[Tb(C7H4NO4)3]·2.75H2O	Dx = 1.701 Mg m−3
Mr = 706.79	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 4000 reflections
Hall symbol: P 3 -2c	θ = 2.8–32.1°
a = 13.0115 (15) Å	µ = 2.63 mm−1
c = 9.4142 (13) Å	T = 200 K
V = 1380.3 (5) Å3	Prism, colourless
Z = 2	0.15 × 0.10 × 0.05 mm
F(000) = 694.85

Stoe IPDS diffractometer	1464 reflections with I > 2.0σ(I)
graphite	Rint = 0.035
ω scans	θmax = 25.8°, θmin = 2.8°
Absorption correction: gaussian (Busing & Levy, 1957)	h = −13→15
Tmin = 0.72, Tmax = 0.88	k = −12→15
3830 measured reflections	l = −10→11
1569 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.03P)2 + 8.38P] where P = (max(Fo2,0) + 2Fc2)/3
wR(F2) = 0.082	(Δ/σ)max = 0.009
S = 1.00	Δρmax = 0.57 e Å−3
1566 reflections	Δρmin = −1.01 e Å−3
122 parameters	Absolute structure: Flack (1983), 679 Friedel pairs: the crystal is achiral.
1 restraint	Flack parameter: −0.05 (2)
Primary atom site location: structure-invariant direct methods

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105 107.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Tb1	0.3333	0.6667	0.38705 (17)	0.0281
O2	0.4896 (5)	0.7887 (6)	0.2190 (6)	0.0368
C3	0.5468 (8)	0.9002 (8)	0.2214 (10)	0.0390
O4	0.6394 (7)	0.9631 (7)	0.1429 (9)	0.0940
C5	0.5045 (7)	0.9629 (7)	0.3171 (8)	0.0342
N6	0.4104 (5)	0.8890 (6)	0.3959 (7)	0.0284
C7	0.3641 (7)	0.9320 (8)	0.4896 (9)	0.0310
C8	0.2606 (7)	0.8377 (8)	0.5728 (8)	0.0345
O9	0.2404 (5)	0.7332 (5)	0.5607 (6)	0.0366
O10	0.2028 (7)	0.8686 (6)	0.6551 (8)	0.0659
C11	0.4116 (7)	1.0542 (7)	0.5101 (9)	0.0392
C12	0.5099 (9)	1.1317 (8)	0.4296 (10)	0.0450
C13	0.5560 (8)	1.0869 (8)	0.3313 (9)	0.0412
H111	0.3784	1.0822	0.5748	0.0471*
H121	0.5442	1.2128	0.4413	0.0541*
H131	0.6209	1.1381	0.2763	0.0490*
O17	0.2402 (15)	0.1736 (16)	0.4073 (16)	0.0795	0.5000

	U11	U22	U33	U12	U13	U23
Tb1	0.02359 (17)	0.02359 (17)	0.0372 (3)	0.01180 (8)	0.0000	0.0000
O2	0.032 (3)	0.034 (4)	0.045 (3)	0.017 (3)	0.008 (2)	−0.002 (3)
C3	0.031 (5)	0.032 (5)	0.040 (5)	0.006 (4)	0.009 (4)	−0.002 (4)
O4	0.066 (6)	0.060 (5)	0.119 (7)	0.003 (4)	0.049 (5)	−0.016 (5)
C5	0.032 (4)	0.028 (4)	0.035 (4)	0.009 (3)	0.002 (3)	0.001 (3)
N6	0.025 (3)	0.032 (3)	0.028 (3)	0.015 (3)	0.005 (3)	0.000 (3)
C7	0.027 (5)	0.028 (4)	0.037 (5)	0.012 (4)	−0.001 (3)	0.003 (3)
C8	0.025 (4)	0.037 (5)	0.043 (5)	0.017 (4)	0.004 (3)	0.000 (3)
O9	0.031 (3)	0.026 (3)	0.048 (3)	0.011 (3)	0.013 (3)	0.007 (3)
O10	0.064 (5)	0.053 (4)	0.087 (5)	0.034 (4)	0.035 (4)	0.011 (4)
C11	0.041 (5)	0.030 (4)	0.048 (5)	0.019 (4)	0.001 (3)	−0.005 (3)
C12	0.047 (5)	0.026 (5)	0.052 (6)	0.011 (4)	0.003 (4)	−0.009 (4)
C13	0.034 (5)	0.024 (4)	0.055 (5)	0.007 (4)	0.008 (4)	0.004 (4)
O17	0.071 (11)	0.098 (13)	0.071 (10)	0.043 (10)	−0.007 (8)	−0.044 (9)

Tb1—N6i	2.545 (6)	C5—N6	1.340 (9)
Tb1—N6ii	2.545 (6)	C5—C13	1.410 (12)
Tb1—O9ii	2.436 (6)	N6—C7	1.338 (11)
Tb1—O9i	2.436 (6)	C7—C8	1.510 (11)
Tb1—O2i	2.435 (6)	C7—C11	1.402 (11)
Tb1—O2ii	2.435 (6)	C8—O9	1.253 (10)
Tb1—O2	2.435 (6)	C8—O10	1.277 (10)
Tb1—N6	2.545 (6)	C11—C12	1.392 (12)
Tb1—O9	2.436 (6)	C11—H111	0.921
O2—C3	1.257 (11)	C12—C13	1.381 (12)
C3—O4	1.297 (11)	C12—H121	0.924
C3—C5	1.494 (12)	C13—H131	0.929
N6i—Tb1—N6ii	119.893 (19)	O2ii—Tb1—N6	74.7 (2)
N6i—Tb1—O9ii	70.1 (2)	O2—Tb1—N6	63.52 (19)
N6ii—Tb1—O9ii	63.73 (19)	O2ii—Tb1—O9	83.45 (18)
N6i—Tb1—O9i	63.73 (19)	O2—Tb1—O9	127.2 (2)
N6ii—Tb1—O9i	135.8 (2)	N6—Tb1—O9	63.73 (19)
O9ii—Tb1—O9i	79.9 (2)	Tb1—O2—C3	124.1 (5)
N6i—Tb1—O2i	63.52 (19)	O2—C3—O4	123.1 (8)
N6ii—Tb1—O2i	74.7 (2)	O2—C3—C5	118.3 (7)
O9ii—Tb1—O2i	83.45 (18)	O4—C3—C5	118.6 (8)
O9i—Tb1—O2i	127.2 (2)	C3—C5—N6	113.3 (7)
N6i—Tb1—O2ii	140.7 (2)	C3—C5—C13	126.0 (7)
N6ii—Tb1—O2ii	63.52 (19)	N6—C5—C13	120.7 (8)
O9ii—Tb1—O2ii	127.2 (2)	Tb1—N6—C5	119.8 (5)
O9i—Tb1—O2ii	144.8 (2)	Tb1—N6—C7	119.5 (5)
O2i—Tb1—O2ii	82.3 (2)	C5—N6—C7	120.3 (7)
N6i—Tb1—O2	74.7 (2)	N6—C7—C8	114.0 (7)
N6ii—Tb1—O2	140.7 (2)	N6—C7—C11	122.0 (8)
O9ii—Tb1—O2	144.8 (2)	C8—C7—C11	123.9 (8)
O9i—Tb1—O2	83.45 (18)	C7—C8—O9	116.9 (7)
O2i—Tb1—O2	82.3 (2)	C7—C8—O10	119.0 (8)
N6i—Tb1—N6	119.893 (19)	O9—C8—O10	124.0 (7)
N6ii—Tb1—N6	119.893 (18)	Tb1—O9—C8	125.0 (5)
O9ii—Tb1—N6	135.8 (2)	C7—C11—C12	118.1 (8)
O9i—Tb1—N6	70.1 (2)	C7—C11—H111	120.8
O2i—Tb1—N6	140.7 (2)	C12—C11—H111	121.0
N6i—Tb1—O9	135.8 (2)	C11—C12—C13	119.6 (8)
N6ii—Tb1—O9	70.1 (2)	C11—C12—H121	120.4
O9ii—Tb1—O9	79.9 (2)	C13—C12—H121	119.9
O9i—Tb1—O9	79.9 (2)	C5—C13—C12	119.2 (7)
O2i—Tb1—O9	144.8 (2)	C5—C13—H131	120.7
O2ii—Tb1—O2	82.3 (2)	C12—C13—H131	120.1

D—H···A	D—H	H···A	D···A	D—H···A
C13—H131···O9iii	0.93	2.47	3.345 (13)	158

Space group	Counter-ion	d(Tb-N)	d(Tb-O1)	d(Tb-O2)
P-1	[Co(NH3)6]3+a	2.509	2.416	2.446
		2.495	2.428	2.428
		2.492	2.408	2.419
P-1	[N(CH2CH2NH3)]3+b	2.492	2.398	2.431
		2.509	2.393	2.448
		2.499	2.428	2.435
P-1	[(NH2)2CNHCH2CH3)]+c	2.500	2.403	2.410
		2.491	2.402	2.429
		2.544	2.383	2.453
P21	[Co(NH2CH2CH2NH2)3]3+d	2.533	2.412	2.418
		2.505	2.413	2.440
		2.508	2.417	2.431
		2.505	2.418	2.432
		2.512	2.432	2.441
		2.486	2.402	2.423
P21/c	Na+e	2.504	2.406	2.415
		2.509	2.424	2.429
		2.505	2.410	2.439
C2/c	[Co(NH2CH2CH2NH2)3]3+d	2.486	2.400	2.423
		2.509	2.419	2.429
		2.518	2.407	2.416
P31c	H+f	2.548	2.426	2.436
		2.547	2.426	2.435
		2.546	2.425	2.435
R-3c	[(CH3)3NCH2CH2OH)]+g	2.497	2.401	2.405
		2.496	2.401	2.404
		2.497	2.402	2.405
P-62c	Na+, ClO4-h	2.489	2.400	2.400

Table 1

Selected bond lengths (Å)

Tb1—O2	2.435 (6)
Tb1—N6	2.545 (6)
Tb1—O9	2.436 (6)

Symmetry codes: (i) ; (ii) .