Poly[ethyl­enediaminium [di-μ-aqua-(μ6-benzene-1,2,4,5-tetra­carboxyl­ato-κ10O1,O1′:O2,O2′:O2′:O4,O4′:O5:O5,O5′)dithallium(I)]]

Rafizadeh, M.; Manteghi, F.

doi:10.1107/S1600536808040282

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m17-m18

doi:10.1107/S1600536808040282

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Poly[ethylenediaminium [di-μ-aqua-(μ₆-benzene-1,2,4,5-tetracarboxylato-κ¹⁰O¹,O^1′:O²,O^2′:O^2′:O⁴,O^4′:O⁵:O⁵,O^5′)dithallium(I)]]

Masoud Rafizadeh ^a ^* and Faranak Manteghi ^a

^aFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
^*Correspondence e-mail: m_rafizadeh6@yahoo.com

(Received 18 November 2008; accepted 30 November 2008; online 6 December 2008)

The title compound, {(C₂H₁₀N₂)[Tl₂(C₁₀H₂O₈)(H₂O)₂)]}_n, was prepared using (enH₂)₂(btc)·2H₂O and thallium(I) nitrate (en = ethylenediamine and btcH₄ = benzene-1,2,4,5-tetracarboxylic acid). The enH₂ cation and btc ligand are each located on an inversion centre. The Tl^I atom is seven-coordinated by three btc ligands and two water molecules in an irregular geometry due to the stereochemically active lone pair on the Tl centre. The water molecule and btc ligand are bonded to the Tl atoms in μ- and μ₆-forms, respectively, leading to a three-dimensional structure. The crystal structure involves O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, and also a Tl⋯π interaction of 3.537 (1) Å.

Related literature

For general background, see: Akhbari & Morsali (2008 ); Day & Luehrs (1988 ); Fabelo et al. (2005 ); Murugavel et al. (2000 ); Shimoni-Livny et al. (1998 ). For related structures, see: Li et al. (2008 ); Rafizadeh et al. (2005 , 2007a ,b ). For the ligand synthesis, see: Rafizadeh et al. (2006 ).

Experimental

Crystal data

(C₂H₁₀N₂)[Tl₂(C₁₀H₂O₈)(H₂O)₂)]
M_r = 757.01
Monoclinic, P 2₁ /n
a = 9.925 (5) Å
b = 7.073 (4) Å
c = 11.325 (6) Å
β = 98.397 (10)°
V = 786.5 (7) Å³
Z = 2
Mo Kα radiation
μ = 20.53 mm⁻¹
T = 100 (2) K
0.16 × 0.12 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.064, T_max = 0.201
5272 measured reflections
1787 independent reflections
1487 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.070
S = 1.00
1787 reflections
107 parameters
H-atom parameters constrained
Δρ_max = 2.02 e Å⁻³
Δρ_min = −1.80 e Å⁻³

Table 1
Selected bond lengths (Å)

Tl1—O3ⁱ	2.702 (5)
Tl1—O2	2.763 (5)
Tl1—O1W	2.882 (5)
Tl1—O4ⁱⁱ	2.952 (5)
Tl1—O1	3.135 (5)
Tl1—O1Wⁱⁱⁱ	3.209 (5)
Tl1—O3ⁱⁱ	3.350 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z; (iii) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H4⋯O2^iv	0.91	1.90	2.791 (8)	166
N1—H5⋯O3	0.91	1.85	2.741 (8)	166
N1—H6⋯O1^v	0.91	2.11	2.828 (8)	136
N1—H6⋯O4^vi	0.91	2.20	2.942 (8)	138
O1W—H7⋯O2ⁱ	0.85	2.06	2.909 (8)	172
O1W—H8⋯O1^v	0.85	2.00	2.846 (8)	177
C3—H1⋯O1^v	0.95	2.45	3.353 (9)	159
C6—H3⋯O3^vii	0.99	2.59	3.523 (9)	157
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040282/hy2169sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040282/hy2169Isup2.hkl

checkCIF report

Comment top

Thallium reagents, despite their inherent toxicity and cost, have played a conspicuous role in the development of modern inorganic and organometallic chemistry. Thallium(I) chemistry is very interesting due to a variety of reasons. (a) Thallium salts and complexes are often anhydrous. (b) The lone pair on thallium may or may not be stereochemically active. (c) High coordination number presents because of large size of Tl^I ion. (d) Thallium(I) complexes have potential ability to form metal–metal bonds and thallium(I) also forms complexes with aromatic hydrocarbons (Akhbari & Morsali, 2008).

The deprotonated forms of benzene-1,2,4,5-tetracarboxylic acid (btcH₄) can act not only as hydrogen bond acceptors but also as hydrogen bond donors, depending on the deprotonated carboxylate groups, to give different supramolecular adducts (Fabelo et al., 2005). There is an instance of benzene-1,2,4,5-tetracarboxylate coordinated to thallium in a mixed ligand system (Day & Luehrs, 1988). However, there are some coordination polymers reported that contain an anionic coordination polymer together with a cationic part, such as metal–organic framework-based hydrogen-bonded porous solids, [(pipzH₂)M(btc)(H₂O)₄.4H₂O]_n (M = Co^II, Ni^II, Zn^II; pipz = piperazine) (Murugavel et al., 2000). As the recent examples of this category, Cu^II and Zn^II anionic coordination polymers with ethylenediaminium and propane-1,2-diaminium (pn) as counter ions, {(enH₂)[Cu(btc)].2.5H₂O}_n (Rafizadeh et al., 2007a) and {(pnH₂)[Zn(btc)].4H₂O]}_n (Rafizadeh et al., 2007b), have been synthesized.

In the title compound (Fig. 1), the coordination behavior of carboxylate groups of btc are different. Compared with another Tl^I complex, [Tl(pydcH)]_n (pydcH₂ = pyridine-2,6-dicarboxylic acid), with the bond lengths of Tl—O being 2.853 (6) and 3.019 (6) Å (Rafizadeh et al., 2005), the Tl—O bond lengths of the title compound are in a more extended range [2.702 (5) to 3.350 (5) Å] (Table 1). In the crystal structure, O—H···O, N—H···O and C—H···O hydrogen bonds are present. Moreover, an interesting Tl···π interaction is found that is classified as cation···π interaction at a Tl–centroid distance of 3.537 (1) Å, as shown in Fig. 2. These interactions make all components assemble together in a packing arrangement.

As illustrated in Fig. 1, coordination number of the Tl^I atom is seven, with all coordinated atoms forced into one side of Tl^I and other side is left empty. This can be caused by the stereochemically active lone pair on Tl^I center. Based on crystal data available in the Cambridge Structural Database, stereochemistry of Pb^II complexes has been reviewed (Shimoni-Livny et al., 1998). Evidently, in the case of Pb^II complexes when the lone pair appears to have no steric effects, the bonds with ligand donor atoms are arranged throughout the surface of encompassing sphere (holodirected coordination) and there are no marked differences in the Pb—L bond lengths. But the Pb^II complexes, in which the lone pair is stereochemically active, have hemidirected coordination and the Pb—L bonds are directed only to a part of the coordination sphere, leaving a gap in the distribution of bonds to the ligands. There are shorter Pb—L bonds away from the proposed site of the lone pair and longer Pb—L bonds adjacent to this site of the lone pair (Li et al., 2008). Here also, the Tl^I atom shows the same behavior. In effect, the Tl1—O3ⁱⁱ and Tl1—O1Wⁱⁱⁱ (symmetry codes: (ii) -1+x, y, z; (iii) -x, -y, 1-z), that are apparently longer than other bonds (see Fig. 1 and Table 1), lie on the side of the putative lone pair and the shorter bonds lie away from the site of the lone pair.

Related literature top

For general background, see: Akhbari & Morsali (2008); Day & Luehrs (1988); Fabelo et al. (2005); Murugavel et al. (2000); Shimoni-Livny et al. (1998). For related structures, see: Li et al. (2008); Rafizadeh et al. (2005, 2007a,b). For the ligand synthesis, see: Rafizadeh et al. (2006).

Experimental top

An aqueous solution of (enH₂)₂(btc).2H₂O (0.34 g, 0.82 mmol), synthesized according to the literature (Rafizadeh et al., 2006), was added dropwise to a solution of TlNO₃ (0.061 g, 0.23 mmol) in water. The mixture was slightly heated and stirred for 5 h. The obtained clear solution with a volume of 40 ml was left at room temperature for 40 d. Then the lustrous pale yellow crystals were obtained (decomposing temperature > 673 K).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination environment around the Tl atom in the title compound, showing an empty space on one side of the atom Tl1. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1/2-x, -1/2+y, 3/2-z; (ii) -1+x, y, z; (iii) -x, -y, 1-z.]
	Fig. 2. Tl···π interactions with a Tl–centroid distance of 3.537 (1) Å. [Symmetry codes: (i) 1/2-x, -1/2+y, 3/2-z; (viii) 1/2+x, 1/2-y, 1/2+z.]

Poly[ethylenediaminium [di-µ-aqua-(µ₆-benzene-1,2,4,5-tetracarboxylato-κ¹⁰O¹,O^1':O²,O^2':O^2':O⁴,O^4':O⁵:O⁵,O^5')dithallium(I)]] top

Crystal data top

(C₂H₁₀N₂)[Tl₂(C₁₀H₂O₈)(H₂O)₂)]	F(000) = 688
M_r = 757.01	D_x = 3.197 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1231 reflections
a = 9.925 (5) Å	θ = 3.4–32.7°
b = 7.073 (4) Å	µ = 20.53 mm⁻¹
c = 11.325 (6) Å	T = 100 K
β = 98.397 (10)°	Prism, colourless
V = 786.5 (7) Å³	0.16 × 0.12 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1787 independent reflections
Radiation source: fine-focus sealed tube	1487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→12
T_min = 0.064, T_max = 0.201	k = −9→9
5272 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: mixed
wR(F²) = 0.070	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.031P)²] where P = (F_o² + 2F_c²)/3
1787 reflections	(Δ/σ)_max = 0.001
107 parameters	Δρ_max = 2.02 e Å⁻³
0 restraints	Δρ_min = −1.80 e Å⁻³

Crystal data top

(C₂H₁₀N₂)[Tl₂(C₁₀H₂O₈)(H₂O)₂)]	V = 786.5 (7) Å³
M_r = 757.01	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.925 (5) Å	µ = 20.53 mm⁻¹
b = 7.073 (4) Å	T = 100 K
c = 11.325 (6) Å	0.16 × 0.12 × 0.08 mm
β = 98.397 (10)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1787 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1487 reflections with I > 2σ(I)
T_min = 0.064, T_max = 0.201	R_int = 0.061
5272 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.00	Δρ_max = 2.02 e Å⁻³
1787 reflections	Δρ_min = −1.80 e Å⁻³
107 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tl1	−0.05121 (3)	0.10847 (4)	0.68253 (2)	0.01266 (11)
O1	0.1709 (5)	−0.1391 (7)	0.8360 (4)	0.0122 (11)
O2	0.1667 (5)	0.1726 (8)	0.8595 (4)	0.0128 (10)
O3	0.6799 (5)	0.2759 (7)	0.7972 (4)	0.0130 (11)
O4	0.8315 (5)	0.0925 (8)	0.9073 (5)	0.0136 (11)
C1	0.2231 (7)	0.0140 (11)	0.8761 (6)	0.0105 (14)
C2	0.3648 (8)	0.0083 (10)	0.9445 (6)	0.0098 (14)
C3	0.4680 (7)	0.0882 (10)	0.8919 (6)	0.0085 (8)
H1	0.4463	0.1491	0.8168	0.010*
C4	0.6041 (7)	0.0817 (10)	0.9465 (6)	0.0085 (8)
C5	0.7143 (7)	0.1550 (10)	0.8785 (6)	0.0085 (8)
C6	0.5359 (8)	0.0285 (11)	0.5608 (6)	0.0122 (15)
H2	0.4801	−0.0087	0.6226	0.015*
H3	0.6244	−0.0381	0.5775	0.015*
N1	0.5585 (6)	0.2319 (8)	0.5655 (5)	0.0086 (12)
H4	0.6070	0.2664	0.5067	0.010*
H5	0.6058	0.2636	0.6378	0.010*
H6	0.4768	0.2927	0.5550	0.010*
O1W	0.1899 (5)	0.0253 (8)	0.5778 (5)	0.0167 (12)
H7	0.2389	−0.0717	0.5965	0.025*
H8	0.2341	0.1244	0.6018	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.01330 (15)	0.01092 (15)	0.01267 (14)	−0.00149 (13)	−0.00175 (9)	0.00115 (12)
O1	0.011 (2)	0.010 (3)	0.014 (2)	−0.001 (2)	−0.0051 (19)	−0.002 (2)
O2	0.013 (3)	0.015 (3)	0.010 (2)	0.004 (2)	−0.001 (2)	0.002 (2)
O3	0.014 (3)	0.012 (3)	0.012 (2)	−0.001 (2)	0.000 (2)	0.006 (2)
O4	0.014 (3)	0.013 (3)	0.015 (2)	0.000 (2)	0.003 (2)	0.003 (2)
C1	0.010 (3)	0.017 (4)	0.005 (3)	0.001 (3)	0.000 (3)	0.001 (3)
C2	0.015 (4)	0.004 (3)	0.010 (3)	0.003 (3)	0.000 (3)	−0.002 (3)
C3	0.011 (2)	0.005 (2)	0.0092 (17)	−0.0004 (15)	0.0007 (15)	−0.0011 (15)
C4	0.011 (2)	0.005 (2)	0.0092 (17)	−0.0004 (15)	0.0007 (15)	−0.0011 (15)
C5	0.011 (2)	0.005 (2)	0.0092 (17)	−0.0004 (15)	0.0007 (15)	−0.0011 (15)
C6	0.014 (4)	0.007 (3)	0.014 (4)	0.001 (3)	−0.002 (3)	0.001 (3)
N1	0.008 (3)	0.008 (3)	0.009 (3)	0.001 (2)	−0.002 (2)	0.003 (2)
O1W	0.019 (3)	0.013 (3)	0.018 (3)	0.002 (2)	−0.001 (2)	0.001 (2)

Geometric parameters (Å, º) top

Tl1—O3ⁱ	2.702 (5)	C3—C4	1.402 (10)
Tl1—O2	2.763 (5)	C3—H1	0.9500
Tl1—O1W	2.882 (5)	C4—C2^iv	1.384 (10)
Tl1—O4ⁱⁱ	2.952 (5)	C4—C5	1.518 (10)
Tl1—O1	3.135 (5)	C6—N1	1.456 (10)
Tl1—O1Wⁱⁱⁱ	3.209 (5)	C6—C6^v	1.510 (14)
Tl1—O3ⁱⁱ	3.350 (5)	C6—H2	0.9900
O1—C1	1.257 (9)	C6—H3	0.9900
O2—C1	1.256 (9)	N1—H4	0.9100
O3—C5	1.266 (8)	N1—H5	0.9100
O4—C5	1.242 (9)	N1—H6	0.9100
C1—C2	1.503 (10)	O1W—H7	0.8500
C2—C3	1.378 (10)	O1W—H8	0.8500
C2—C4^iv	1.384 (10)

O3ⁱ—Tl1—O2	114.26 (16)	C4—C3—H1	119.2
O3ⁱ—Tl1—O1W	106.77 (16)	C2^iv—C4—C3	118.9 (6)
O2—Tl1—O1W	73.92 (15)	C2^iv—C4—C5	121.8 (6)
O3ⁱ—Tl1—O4ⁱⁱ	69.06 (15)	C3—C4—C5	119.0 (6)
O2—Tl1—O4ⁱⁱ	75.31 (15)	O4—C5—O3	125.0 (6)
O1W—Tl1—O4ⁱⁱ	143.40 (15)	O4—C5—C4	117.5 (6)
O3ⁱ—Tl1—O1	76.67 (15)	O3—C5—C4	117.5 (6)
O2—Tl1—O1	43.70 (14)	N1—C6—C6^v	110.3 (8)
O1W—Tl1—O1	63.61 (15)	N1—C6—H2	109.6
O4ⁱⁱ—Tl1—O1	80.47 (14)	C6^v—C6—H2	109.6
C1—O1—Tl1	86.5 (4)	N1—C6—H3	109.6
C1—O2—Tl1	104.3 (4)	C6^v—C6—H3	109.6
C5—O3—Tl1^vi	127.4 (4)	H2—C6—H3	108.1
C5—O4—Tl1^vii	103.4 (4)	C6—N1—H4	109.5
O2—C1—O1	124.3 (6)	C6—N1—H5	109.5
O2—C1—C2	117.7 (7)	H4—N1—H5	109.5
O1—C1—C2	118.0 (7)	C6—N1—H6	109.5
C3—C2—C4^iv	119.4 (7)	H4—N1—H6	109.5
C3—C2—C1	117.7 (6)	H5—N1—H6	109.5
C4^iv—C2—C1	122.8 (6)	Tl1—O1W—H7	122.8
C2—C3—C4	121.6 (7)	Tl1—O1W—H8	96.9
C2—C3—H1	119.2	H7—O1W—H8	109.6

O3ⁱ—Tl1—O1—C1	−155.0 (4)	O2—C1—C2—C4^iv	116.3 (8)
O2—Tl1—O1—C1	−5.8 (4)	O1—C1—C2—C4^iv	−66.1 (9)
O1W—Tl1—O1—C1	88.3 (4)	C4^iv—C2—C3—C4	−0.4 (11)
O4ⁱⁱ—Tl1—O1—C1	−84.5 (4)	C1—C2—C3—C4	−177.0 (6)
O3ⁱ—Tl1—O2—C1	39.1 (4)	C2—C3—C4—C2^iv	0.4 (11)
O1W—Tl1—O2—C1	−62.4 (4)	C2—C3—C4—C5	174.0 (6)
O4ⁱⁱ—Tl1—O2—C1	97.5 (4)	Tl1^vii—O4—C5—O3	−30.4 (8)
O1—Tl1—O2—C1	6.0 (4)	Tl1^vii—O4—C5—C4	150.1 (5)
Tl1—O2—C1—O1	−12.6 (8)	Tl1^vi—O3—C5—O4	−125.2 (6)
Tl1—O2—C1—C2	164.9 (5)	Tl1^vi—O3—C5—C4	54.4 (8)
Tl1—O1—C1—O2	10.7 (6)	C2^iv—C4—C5—O4	17.5 (10)
Tl1—O1—C1—C2	−166.7 (6)	C3—C4—C5—O4	−156.0 (6)
O2—C1—C2—C3	−67.2 (8)	C2^iv—C4—C5—O3	−162.1 (7)
O1—C1—C2—C3	110.4 (8)	C3—C4—C5—O3	24.5 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O2^viii	0.91	1.90	2.791 (8)	166
N1—H5···O3	0.91	1.85	2.741 (8)	166
N1—H6···O1^vi	0.91	2.11	2.828 (8)	136
N1—H6···O4^ix	0.91	2.20	2.942 (8)	138
O1W—H7···O2ⁱ	0.85	2.06	2.909 (8)	172
O1W—H8···O1^vi	0.85	2.00	2.846 (8)	177
C3—H1···O1^vi	0.95	2.45	3.353 (9)	159
C6—H3···O3^x	0.99	2.59	3.523 (9)	157

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

Experimental details

Crystal data
Chemical formula	(C₂H₁₀N₂)[Tl₂(C₁₀H₂O₈)(H₂O)₂)]
M_r	757.01
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.925 (5), 7.073 (4), 11.325 (6)
β (°)	98.397 (10)
V (Å³)	786.5 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	20.53
Crystal size (mm)	0.16 × 0.12 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.064, 0.201
No. of measured, independent and observed [I > 2σ(I)] reflections	5272, 1787, 1487
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.070, 1.00
No. of reflections	1787
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.02, −1.80

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Selected bond lengths (Å) top

Tl1—O3ⁱ	2.702 (5)	Tl1—O1	3.135 (5)
Tl1—O2	2.763 (5)	Tl1—O1Wⁱⁱⁱ	3.209 (5)
Tl1—O1W	2.882 (5)	Tl1—O3ⁱⁱ	3.350 (5)
Tl1—O4ⁱⁱ	2.952 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O2^iv	0.91	1.900	2.791 (8)	166
N1—H5···O3	0.91	1.850	2.741 (8)	166
N1—H6···O1^v	0.91	2.105	2.828 (8)	136
N1—H6···O4^vi	0.91	2.199	2.942 (8)	138
O1W—H7···O2ⁱ	0.85	2.064	2.909 (8)	172
O1W—H8···O1^v	0.85	1.997	2.846 (8)	177
C3—H1···O1^v	0.95	2.4500	3.353 (9)	159
C6—H3···O3^vii	0.99	2.5900	3.523 (9)	157

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

References

Akhbari, K. & Morsali, A. (2008). J. Mol. Struct. 878, 65–70. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Day, C. S. & Luehrs, D. C. (1988). Inorg. Chim. Acta, 142, 201–202. CSD CrossRef CAS Web of Science Google Scholar
Fabelo, O., Cañadillas-Delgado, L., Delgado, F. S., Lorenzo-Luis, P., Laz, M. M., Julve, M. & Ruiz-Pérez, C. (2005). Cryst. Growth Des. 5, 1163–1167. Web of Science CSD CrossRef CAS Google Scholar
Li, D.-Q., Liu, X. & Zhou, J. (2008). Inorg. Chem. Commun. 11, 367–371. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Murugavel, R., Anantharaman, G., Krishnamurthy, D., Sathiyendiran, M. & Walawalkar, M. G. (2000). J. Chem. Sci. 112, 273–290. CrossRef CAS Google Scholar
Rafizadeh, M., Aghayan, H. & Amani, V. (2006). Acta Cryst. E62, o5034–o5035. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rafizadeh, M., Amani, V., Dehghan, L., Azadbakht, F. & Sahlolbei, E. (2007a). Acta Cryst. E63, m1841–m1842. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rafizadeh, M., Amani, V. & Neumüller, B. (2005). Z. Anorg. Allg. Chem. 631, 1753–1755. Web of Science CSD CrossRef CAS Google Scholar
Rafizadeh, M., Amani, V. & Zahiri, S. (2007b). Acta Cryst. E63, m1938–m1939. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shimoni-Livny, L., Glusker, J. P. & Bock, C. W. (1998). Inorg. Chem. 37, 1853–1867. Web of Science CrossRef CAS Google Scholar

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