Poly[{μ10-[(phosphono­meth­yl)imino­dimethyl­ene]diphospho­nato}dithallium(I)]

Gholivand, K.; Farrokhi, A.R.

doi:10.1107/S1600536809031006

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m873

https://doi.org/10.1107/S1600536809031006

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Poly[{μ₁₀-[(phosphonomethyl)iminodimethylene]diphosphonato}dithallium(I)]

Khodayar Gholivand ^a ^* and Ali Reza Farrokhi ^a ^*

^aDepartment of Chemistry, Tarbiat Modares University, PO Box 14115-175 Tehran, Iran
^*Correspondence e-mail: gholi_kh@modares.ac.ir, arfmhf@yahoo.com

(Received 9 July 2009; accepted 4 August 2009; online 3 July 2010)

The title compound, [Tl₂(C₃H₁₀NO₉P₃)]_n, a Tl^I organic–inorganic hybrid complex, was synthesized by the reaction of nitrilotris(methylenephosphonic acid) with thallium(I) nitrate. There are two types of Tl⁺ ions in the complex, with coordination numbers of eight and seven and with stereochemically active and inactive lone-pair electrons, respectively. In the crystal, the doubly deprotonated ligands form two-dimensional hydrogen-bonded layers through O—H⋯O hydrogen bonds. The NH group is involved in a trifurcated intramolecular hydrogen bond. Coordination of the phosphonate ligands to the Tl⁺ ions creates a three-dimensional structure.

Related literature

For related metal phosphonate complexes of the same ligand, see: Sharma et al. (2001 ).

Experimental

Crystal data

[Tl₂(C₃H₁₀NO₉P₃)]
M_r = 705.77
Triclinic, $[P \overline 1]$
a = 7.9236 (6) Å
b = 8.0932 (6) Å
c = 10.9136 (8) Å
α = 81.422 (1)°
β = 79.023 (1)°
γ = 68.085 (1)°
V = 635.06 (8) Å³
Z = 2
Mo Kα radiation
μ = 25.76 mm⁻¹
T = 100 K
0.16 × 0.14 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: numerical (XPREP; Bruker, 2007 ) T_min = 0.104, T_max = 0.183
6627 measured reflections
2744 independent reflections
2437 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.055
S = 1.05
2744 reflections
163 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 1.72 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
N1—H1N⋯O3	0.87	2.39	2.882 (5)	116
N1—H1N⋯O5	0.87	2.53	2.957 (6)	111
N1—H1N⋯O8	0.87	2.19	2.837 (7)	131
O1—H1O⋯O1ⁱ	0.82	1.78	2.504 (8)	147
O2—H2O⋯O2ⁱⁱ	0.82	1.68	2.497 (7)	171
O6—H6O⋯O9ⁱⁱⁱ	0.82	1.67	2.484 (6)	171
O7—H7O⋯O4^iv	0.82	1.70	2.521 (6)	180
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) x+1, y-1, z; (iv) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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: https://doi.org/10.1107/S1600536809031006/su2128sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809031006/su2128Isup2.hkl

checkCIF report

Comment top

Metal phosphonate complexes of the ligand nitrilotris(methylenephosphonic acid (H6L), giving two different types of 1:1 (M/L) metal phosphonate complexes, M[NH(CH₂PO₃H)₃(H₂O)₃](M = Mn, Co, Ni, Cu, Zn, Cd), with two-dimensional hydrogen-bonded layered structures, have been prepared previously by (Sharma et al., 2001).

In the structure of the title compound, synthesized by the reaction of the same ligand with thallium(I) nitrate, the nitrilotris(methylenephosphonate) (H4L^2-) group is doublely deprotonated and two different environments for the Thallium atoms are observed, as shown in Figs. 1 and 2. Eight O-atoms of five H4L^2- phosphonate ligands are coordinated to the Tl1 ion (Fig. 1), while seven oxygen atoms of five H4L^2- phosphonate ligands are coordinated to the Tl2 ion (Fig. 2).

The conformation of the doublely deprotonated nitrilotris(methylenephosphonate) ligand is illustrated in Fig. 3. The hydrogen atoms on atoms O1 and O2 are positionally disordered with relative occupancies of 0.5:0.5. Each H4L^2- dianion links to five Tl1 and five Tl2 ions (Fig. 4).

The doublely deprotonated H4L^2- ligand forms two-dimensional hydrogen bonded layers via O—H···O hydrogen bonds involving hydroxyl groups O1, O2, O6 and O7 (Table 1 and Fig. 5). Atoms O3, O5 and O8 do not contribute in this type of hydrogen bond, rather they coordinate only to the Tl⁺ions. The NH group is involved in a 4-centre trifurcated intramolecular hydrogen bond with O-atoms O3, O5 and O8 (Table 1). Coordination of the ligand to the metal ions in the interlayer space creates a three-dimensional structure (Fig. 6).

Related literature top

For related metal phosphonate complexes of the same ligand, see: Sharma et al. (2001).

Experimental top

Thallium(I)nitrate (0.133 g, 0.5 mmol) was added in several portions to a solution of nitrilotris(methylenephosphonicacid) (H6L) (0.104 g, 0.35 mmol) in 12 ml of a deionized water-ethanol mixture (3:5). The solution was stirred for seven days and a white precipitate was obtained. This was filtered off and recrystallized from deionized water at rt. Colorless prism-like crystals of the title compound were obtained in 68% yield (based on the Tl atom). Elemental analysis for Tl₂(H₄L), C₃H₁₀NO₉P₃Tl₂:C, 5.06; H, 1.36; N, 2.03%. Calc.: C, 5.10; H, 1.41; N, 1.98%.

Structure description top

For related metal phosphonate complexes of the same ligand, see: Sharma et al. (2001).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Environment of the Tl1 atom.
	Fig. 2. Environment of the Tl2 atom.
	Fig. 3. The conformation of the doubly deprotonated nitrilotris(methylenephosphonate) ligand.
	Fig. 4. Each H4L^2- dianion links to five Tl1 and five Tl2 ions.
	Fig. 5. Two-dimensional hydrogen-bonded layers formed via O—H···O hydrogen bonds involving hydroxyl groups.
	Fig. 6. The three-dimensional structure resulting from the coordination of the ligand to the metal ions in the interlayer space.
	Fig. 7. Reaction scheme.

Poly[{µ-[(phosphonomethyl)iminodimethylene]diphosphonato}dithallium(I)] top

Crystal data top

[Tl₂(C₃H₁₀NO₉P₃)]	Z = 2
M_r = 705.77	F(000) = 628
Triclinic, P1	D_x = 3.691 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9236 (6) Å	Cell parameters from 266 reflections
b = 8.0932 (6) Å	θ = 3–26°
c = 10.9136 (8) Å	µ = 25.76 mm⁻¹
α = 81.422 (1)°	T = 100 K
β = 79.023 (1)°	Prism, colorless
γ = 68.085 (1)°	0.16 × 0.14 × 0.10 mm
V = 635.06 (8) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	2744 independent reflections
Radiation source: fine-focus sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: numerical (XPREP; Bruker, 2007)	h = −10→10
T_min = 0.104, T_max = 0.183	k = −10→10
6627 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0225P)² + 1.104P] where P = (F_o² + 2F_c²)/3
2744 reflections	(Δ/σ)_max = 0.003
163 parameters	Δρ_max = 1.72 e Å⁻³
12 restraints	Δρ_min = −1.83 e Å⁻³

Crystal data top

[Tl₂(C₃H₁₀NO₉P₃)]	γ = 68.085 (1)°
M_r = 705.77	V = 635.06 (8) Å³
Triclinic, P1	Z = 2
a = 7.9236 (6) Å	Mo Kα radiation
b = 8.0932 (6) Å	µ = 25.76 mm⁻¹
c = 10.9136 (8) Å	T = 100 K
α = 81.422 (1)°	0.16 × 0.14 × 0.10 mm
β = 79.023 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2744 independent reflections
Absorption correction: numerical (XPREP; Bruker, 2007)	2437 reflections with I > 2σ(I)
T_min = 0.104, T_max = 0.183	R_int = 0.029
6627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	12 restraints
wR(F²) = 0.055	H-atom parameters constrained
S = 1.05	Δρ_max = 1.72 e Å⁻³
2744 reflections	Δρ_min = −1.83 e Å⁻³
163 parameters

Special details top

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	Occ. (<1)
Tl1	0.29076 (3)	−0.05875 (3)	0.25484 (2)	0.01064 (7)
Tl2	0.23248 (3)	0.24843 (3)	0.54672 (2)	0.01703 (8)
P1	0.7521 (3)	0.2462 (3)	0.42352 (16)	0.0201 (4)
P2	0.7554 (2)	−0.0669 (2)	0.10302 (14)	0.0090 (3)
P3	0.2557 (2)	0.4329 (2)	0.20298 (14)	0.0091 (3)
O1	0.6684 (8)	0.4387 (7)	0.4597 (5)	0.0331 (13)
H1O	0.5753	0.4894	0.5072	0.040*	0.50
O2	0.9424 (7)	0.1622 (8)	0.4631 (5)	0.0311 (12)
H2O	0.9828	0.0586	0.4936	0.037*	0.50
O3	0.6291 (6)	0.1391 (5)	0.4655 (4)	0.0119 (9)
O4	0.7469 (6)	−0.1263 (6)	−0.0199 (4)	0.0148 (9)
O5	0.6365 (6)	−0.1126 (6)	0.2173 (4)	0.0151 (9)
O6	0.9564 (6)	−0.1194 (5)	0.1274 (4)	0.0129 (9)
H6O	1.0047	−0.2157	0.1660	0.015*
O7	0.2360 (6)	0.4303 (6)	0.0624 (4)	0.0145 (9)
H7O	0.2418	0.3313	0.0485	0.017*
O8	0.2641 (6)	0.2594 (5)	0.2794 (4)	0.0108 (8)
O9	0.1203 (6)	0.6039 (6)	0.2530 (4)	0.0141 (9)
N1	0.6274 (7)	0.2583 (6)	0.2032 (4)	0.0086 (10)
H1N	0.5590	0.2094	0.2560	0.010*
C1	0.7944 (8)	0.2553 (8)	0.2523 (6)	0.0116 (12)
H1A	0.8225	0.3638	0.2177	0.014*
H1B	0.9018	0.1497	0.2251	0.014*
C2	0.6768 (8)	0.1763 (8)	0.0791 (5)	0.0089 (11)
H2A	0.7749	0.2130	0.0257	0.011*
H2B	0.5677	0.2209	0.0351	0.011*
C3	0.4836 (8)	0.4433 (8)	0.1986 (6)	0.0111 (12)
H3A	0.5140	0.5133	0.1209	0.013*
H3B	0.4828	0.5047	0.2708	0.013*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.00946 (12)	0.01138 (12)	0.01117 (12)	−0.00463 (9)	−0.00049 (9)	−0.00006 (9)
Tl2	0.01643 (14)	0.01862 (14)	0.00967 (13)	−0.00101 (10)	0.00066 (10)	0.00088 (10)
P1	0.0291 (10)	0.0340 (10)	0.0090 (8)	−0.0260 (9)	−0.0018 (7)	0.0005 (7)
P2	0.0088 (7)	0.0092 (7)	0.0072 (7)	−0.0023 (6)	0.0003 (6)	0.0001 (6)
P3	0.0081 (7)	0.0095 (7)	0.0080 (7)	−0.0021 (6)	0.0001 (6)	0.0003 (6)
O1	0.048 (3)	0.031 (2)	0.028 (2)	−0.026 (2)	0.006 (2)	−0.0084 (19)
O2	0.023 (2)	0.051 (3)	0.027 (2)	−0.0233 (19)	−0.0095 (18)	0.0074 (19)
O3	0.011 (2)	0.012 (2)	0.013 (2)	−0.0062 (17)	−0.0001 (18)	0.0018 (17)
O4	0.023 (2)	0.010 (2)	0.011 (2)	−0.0034 (18)	−0.0045 (19)	−0.0010 (17)
O5	0.010 (2)	0.020 (2)	0.011 (2)	−0.0038 (18)	0.0011 (18)	0.0028 (18)
O6	0.010 (2)	0.010 (2)	0.015 (2)	−0.0028 (17)	−0.0031 (18)	0.0090 (17)
O7	0.020 (2)	0.012 (2)	0.011 (2)	−0.0045 (19)	−0.0062 (19)	0.0013 (17)
O8	0.010 (2)	0.009 (2)	0.012 (2)	−0.0033 (17)	0.0013 (17)	−0.0001 (16)
O9	0.011 (2)	0.013 (2)	0.014 (2)	0.0010 (18)	−0.0017 (18)	−0.0027 (18)
N1	0.009 (2)	0.011 (2)	0.007 (2)	−0.005 (2)	0.0031 (19)	−0.0031 (19)
C1	0.009 (3)	0.016 (3)	0.014 (3)	−0.007 (2)	−0.001 (2)	−0.004 (2)
C2	0.006 (3)	0.011 (3)	0.007 (3)	−0.001 (2)	0.002 (2)	−0.001 (2)
C3	0.010 (3)	0.012 (3)	0.009 (3)	−0.003 (2)	0.004 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Tl1—O8	2.555 (4)	P3—C3	1.830 (6)
Tl1—O5	2.569 (4)	O1—Tl2ⁱⁱⁱ	2.906 (5)
Tl1—O4ⁱ	2.778 (4)	O1—H1O	0.8200
Tl1—O3ⁱⁱ	3.159 (4)	O2—Tl2^vi	2.965 (5)
Tl2—O5ⁱⁱ	2.870 (4)	O2—H2O	0.8201
Tl2—O8	2.871 (4)	O3—Tl2ⁱⁱ	2.926 (4)
Tl2—O1ⁱⁱⁱ	2.906 (5)	O3—Tl1ⁱⁱ	3.159 (4)
Tl2—O3	2.922 (4)	O4—Tl1ⁱ	2.778 (4)
Tl2—O3ⁱⁱ	2.926 (4)	O5—Tl2ⁱⁱ	2.870 (4)
Tl2—O2^iv	2.965 (5)	O6—H6O	0.8200
Tl2—O9^v	3.159 (4)	O7—H7O	0.8201
P1—O3	1.501 (4)	O9—Tl2^v	3.159 (4)
P1—O2	1.522 (5)	N1—C3	1.506 (7)
P1—O1	1.529 (6)	N1—C1	1.510 (7)
P1—C1	1.829 (6)	N1—C2	1.517 (7)
P2—O5	1.502 (5)	N1—H1N	0.8699
P2—O4	1.512 (4)	C1—H1A	0.9900
P2—O6	1.552 (4)	C1—H1B	0.9900
P2—C2	1.823 (6)	C2—H2A	0.9900
P3—O9	1.503 (4)	C2—H2B	0.9900
P3—O8	1.507 (4)	C3—H3A	0.9900
P3—O7	1.576 (4)	C3—H3B	0.9900

O8—Tl1—O5	82.65 (14)	O9—P3—O7	109.6 (2)
O8—Tl1—O4ⁱ	73.72 (13)	O8—P3—O7	112.4 (2)
O5—Tl1—O4ⁱ	90.64 (13)	O9—P3—C3	105.9 (3)
O8—Tl1—O3ⁱⁱ	84.83 (12)	O8—P3—C3	104.2 (3)
O5—Tl1—O3ⁱⁱ	80.14 (12)	O7—P3—C3	105.6 (3)
O4ⁱ—Tl1—O3ⁱⁱ	157.62 (11)	P1—O1—Tl2ⁱⁱⁱ	140.5 (3)
O8—Tl1—Tl2	42.43 (9)	P1—O1—H1O	131.2
O5—Tl1—Tl2	88.38 (10)	Tl2ⁱⁱⁱ—O1—H1O	87.0
O4ⁱ—Tl1—Tl2	115.70 (8)	P1—O2—Tl2^vi	142.9 (3)
O3ⁱⁱ—Tl1—Tl2	44.31 (7)	P1—O2—H2O	122.8
O5ⁱⁱ—Tl2—O8	153.26 (12)	Tl2^vi—O2—H2O	91.4
O5ⁱⁱ—Tl2—O1ⁱⁱⁱ	90.93 (14)	P1—O3—Tl2	131.5 (2)
O8—Tl2—O1ⁱⁱⁱ	94.48 (13)	P1—O3—Tl2ⁱⁱ	121.5 (2)
O5ⁱⁱ—Tl2—O3	79.76 (12)	Tl2—O3—Tl2ⁱⁱ	106.77 (13)
O8—Tl2—O3	76.90 (12)	P1—O3—Tl1ⁱⁱ	95.14 (19)
O1ⁱⁱⁱ—Tl2—O3	72.87 (14)	Tl2—O3—Tl1ⁱⁱ	91.85 (11)
O5ⁱⁱ—Tl2—O3ⁱⁱ	76.88 (12)	Tl2ⁱⁱ—O3—Tl1ⁱⁱ	86.74 (11)
O8—Tl2—O3ⁱⁱ	84.01 (11)	P2—O4—Tl1ⁱ	130.9 (2)
O1ⁱⁱⁱ—Tl2—O3ⁱⁱ	145.49 (14)	P2—O5—Tl1	130.2 (2)
O3—Tl2—O3ⁱⁱ	73.23 (13)	P2—O5—Tl2ⁱⁱ	122.6 (2)
O5ⁱⁱ—Tl2—O2^iv	123.69 (14)	Tl1—O5—Tl2ⁱⁱ	106.85 (15)
O8—Tl2—O2^iv	66.41 (13)	P2—O6—H6O	119.1
O1ⁱⁱⁱ—Tl2—O2^iv	137.28 (16)	P3—O7—H7O	111.0
O3—Tl2—O2^iv	132.04 (14)	P3—O8—Tl1	141.1 (2)
O3ⁱⁱ—Tl2—O2^iv	73.22 (14)	P3—O8—Tl2	118.2 (2)
O5ⁱⁱ—Tl2—O9^v	76.06 (12)	Tl1—O8—Tl2	100.67 (13)
O8—Tl2—O9^v	129.64 (11)	P3—O9—Tl2^v	141.9 (3)
O1ⁱⁱⁱ—Tl2—O9^v	92.73 (14)	C3—N1—C1	111.4 (4)
O3—Tl2—O9^v	151.59 (11)	C3—N1—C2	112.6 (4)
O3ⁱⁱ—Tl2—O9^v	114.72 (11)	C1—N1—C2	112.4 (4)
O2^iv—Tl2—O9^v	74.91 (13)	C3—N1—H1N	95.5
O5ⁱⁱ—Tl2—Tl1	125.55 (9)	C1—N1—H1N	113.9
O8—Tl2—Tl1	36.90 (8)	C2—N1—H1N	109.9
O1ⁱⁱⁱ—Tl2—Tl1	129.09 (10)	N1—C1—P1	110.2 (4)
O3—Tl2—Tl1	79.78 (8)	N1—C1—H1A	109.6
O3ⁱⁱ—Tl2—Tl1	48.95 (8)	P1—C1—H1A	109.6
O2^iv—Tl2—Tl1	52.33 (11)	N1—C1—H1B	109.6
O9^v—Tl2—Tl1	126.82 (8)	P1—C1—H1B	109.6
O3—P1—O2	115.2 (3)	H1A—C1—H1B	108.1
O3—P1—O1	114.5 (3)	N1—C2—P2	110.9 (4)
O2—P1—O1	108.2 (3)	N1—C2—H2A	109.5
O3—P1—C1	106.0 (3)	P2—C2—H2A	109.5
O2—P1—C1	104.8 (3)	N1—C2—H2B	109.5
O1—P1—C1	107.4 (3)	P2—C2—H2B	109.5
O5—P2—O4	117.4 (3)	H2A—C2—H2B	108.1
O5—P2—O6	111.2 (2)	N1—C3—P3	110.7 (4)
O4—P2—O6	112.0 (3)	N1—C3—H3A	109.5
O5—P2—C2	106.8 (3)	P3—C3—H3A	109.5
O4—P2—C2	104.8 (3)	N1—C3—H3B	109.5
O6—P2—C2	103.2 (3)	P3—C3—H3B	109.5
O9—P3—O8	118.1 (3)	H3A—C3—H3B	108.1

O8—Tl1—Tl2—O5ⁱⁱ	−151.22 (18)	O5—P2—O4—Tl1ⁱ	132.5 (3)
O5—Tl1—Tl2—O5ⁱⁱ	−70.36 (17)	O6—P2—O4—Tl1ⁱ	−97.0 (3)
O4ⁱ—Tl1—Tl2—O5ⁱⁱ	−160.29 (15)	C2—P2—O4—Tl1ⁱ	14.2 (4)
O3ⁱⁱ—Tl1—Tl2—O5ⁱⁱ	7.15 (15)	O4—P2—O5—Tl1	−51.5 (4)
O5—Tl1—Tl2—O8	80.86 (17)	O6—P2—O5—Tl1	177.6 (3)
O4ⁱ—Tl1—Tl2—O8	−9.07 (17)	C2—P2—O5—Tl1	65.7 (4)
O3ⁱⁱ—Tl1—Tl2—O8	158.37 (18)	O4—P2—O5—Tl2ⁱⁱ	136.2 (3)
O8—Tl1—Tl2—O1ⁱⁱⁱ	−23.9 (2)	O6—P2—O5—Tl2ⁱⁱ	5.3 (3)
O5—Tl1—Tl2—O1ⁱⁱⁱ	56.95 (18)	C2—P2—O5—Tl2ⁱⁱ	−106.6 (3)
O4ⁱ—Tl1—Tl2—O1ⁱⁱⁱ	−32.99 (19)	O8—Tl1—O5—P2	−77.8 (3)
O3ⁱⁱ—Tl1—Tl2—O1ⁱⁱⁱ	134.46 (19)	O4ⁱ—Tl1—O5—P2	−4.3 (3)
O8—Tl1—Tl2—O3	−81.77 (16)	O3ⁱⁱ—Tl1—O5—P2	−163.8 (3)
O5—Tl1—Tl2—O3	−0.90 (12)	Tl2—Tl1—O5—P2	−120.0 (3)
O4ⁱ—Tl1—Tl2—O3	−90.84 (13)	O8—Tl1—O5—Tl2ⁱⁱ	95.39 (16)
O3ⁱⁱ—Tl1—Tl2—O3	76.60 (15)	O4ⁱ—Tl1—O5—Tl2ⁱⁱ	168.88 (15)
O8—Tl1—Tl2—O3ⁱⁱ	−158.37 (18)	O3ⁱⁱ—Tl1—O5—Tl2ⁱⁱ	9.39 (13)
O5—Tl1—Tl2—O3ⁱⁱ	−77.51 (15)	Tl2—Tl1—O5—Tl2ⁱⁱ	53.19 (12)
O4ⁱ—Tl1—Tl2—O3ⁱⁱ	−167.44 (15)	O9—P3—O8—Tl1	137.8 (3)
O8—Tl1—Tl2—O2^iv	100.75 (19)	O7—P3—O8—Tl1	8.7 (5)
O5—Tl1—Tl2—O2^iv	−178.39 (16)	C3—P3—O8—Tl1	−105.1 (4)
O4ⁱ—Tl1—Tl2—O2^iv	91.67 (17)	O9—P3—O8—Tl2	−39.7 (3)
O3ⁱⁱ—Tl1—Tl2—O2^iv	−100.88 (17)	O7—P3—O8—Tl2	−168.8 (2)
O8—Tl1—Tl2—O9^v	109.29 (17)	C3—P3—O8—Tl2	77.3 (3)
O5—Tl1—Tl2—O9^v	−169.85 (14)	O5—Tl1—O8—P3	86.5 (4)
O4ⁱ—Tl1—Tl2—O9^v	100.22 (15)	O4ⁱ—Tl1—O8—P3	−6.3 (4)
O3ⁱⁱ—Tl1—Tl2—O9^v	−92.34 (15)	O3ⁱⁱ—Tl1—O8—P3	167.2 (4)
O3—P1—O1—Tl2ⁱⁱⁱ	173.5 (4)	Tl2—Tl1—O8—P3	−177.8 (5)
O2—P1—O1—Tl2ⁱⁱⁱ	43.6 (5)	O5—Tl1—O8—Tl2	−95.68 (14)
C1—P1—O1—Tl2ⁱⁱⁱ	−69.0 (5)	O4ⁱ—Tl1—O8—Tl2	171.49 (16)
O3—P1—O2—Tl2^vi	−143.4 (4)	O3ⁱⁱ—Tl1—O8—Tl2	−14.98 (12)
O1—P1—O2—Tl2^vi	−13.9 (6)	O5ⁱⁱ—Tl2—O8—P3	−121.0 (3)
C1—P1—O2—Tl2^vi	100.4 (5)	O1ⁱⁱⁱ—Tl2—O8—P3	−20.0 (3)
O2—P1—O3—Tl2	144.1 (3)	O3—Tl2—O8—P3	−91.2 (2)
O1—P1—O3—Tl2	17.7 (4)	O3ⁱⁱ—Tl2—O8—P3	−165.3 (3)
C1—P1—O3—Tl2	−100.5 (3)	O2^iv—Tl2—O8—P3	120.4 (3)
O2—P1—O3—Tl2ⁱⁱ	−42.3 (4)	O9^v—Tl2—O8—P3	77.3 (3)
O1—P1—O3—Tl2ⁱⁱ	−168.6 (3)	Tl1—Tl2—O8—P3	178.4 (3)
C1—P1—O3—Tl2ⁱⁱ	73.1 (3)	O5ⁱⁱ—Tl2—O8—Tl1	60.5 (3)
O2—P1—O3—Tl1ⁱⁱ	47.0 (3)	O1ⁱⁱⁱ—Tl2—O8—Tl1	161.60 (16)
O1—P1—O3—Tl1ⁱⁱ	−79.3 (3)	O3—Tl2—O8—Tl1	90.36 (14)
C1—P1—O3—Tl1ⁱⁱ	162.5 (2)	O3ⁱⁱ—Tl2—O8—Tl1	16.23 (13)
O5ⁱⁱ—Tl2—O3—P1	−106.4 (3)	O2^iv—Tl2—O8—Tl1	−58.05 (16)
O8—Tl2—O3—P1	86.7 (3)	O9^v—Tl2—O8—Tl1	−101.10 (16)
O1ⁱⁱⁱ—Tl2—O3—P1	−12.2 (3)	O8—P3—O9—Tl2^v	−15.8 (5)
O3ⁱⁱ—Tl2—O3—P1	174.3 (4)	O7—P3—O9—Tl2^v	114.7 (4)
O2^iv—Tl2—O3—P1	127.0 (3)	C3—P3—O9—Tl2^v	−131.9 (4)
O9^v—Tl2—O3—P1	−74.5 (4)	C3—N1—C1—P1	80.8 (5)
Tl1—Tl2—O3—P1	124.3 (3)	C2—N1—C1—P1	−151.7 (4)
O5ⁱⁱ—Tl2—O3—Tl2ⁱⁱ	79.25 (14)	O3—P1—C1—N1	33.2 (5)
O8—Tl2—O3—Tl2ⁱⁱ	−87.61 (13)	O2—P1—C1—N1	155.5 (4)
O1ⁱⁱⁱ—Tl2—O3—Tl2ⁱⁱ	173.44 (17)	O1—P1—C1—N1	−89.7 (5)
O3ⁱⁱ—Tl2—O3—Tl2ⁱⁱ	0.0	C3—N1—C2—P2	−152.4 (4)
O2^iv—Tl2—O3—Tl2ⁱⁱ	−47.3 (2)	C1—N1—C2—P2	80.8 (5)
O9^v—Tl2—O3—Tl2ⁱⁱ	111.2 (2)	O5—P2—C2—N1	39.1 (4)
Tl1—Tl2—O3—Tl2ⁱⁱ	−50.01 (10)	O4—P2—C2—N1	164.3 (4)
O5ⁱⁱ—Tl2—O3—Tl1ⁱⁱ	−7.90 (11)	O6—P2—C2—N1	−78.3 (4)
O8—Tl2—O3—Tl1ⁱⁱ	−174.76 (12)	C1—N1—C3—P3	−156.6 (4)
O1ⁱⁱⁱ—Tl2—O3—Tl1ⁱⁱ	86.28 (14)	C2—N1—C3—P3	76.0 (5)
O3ⁱⁱ—Tl2—O3—Tl1ⁱⁱ	−87.15 (13)	O9—P3—C3—N1	156.2 (4)
O2^iv—Tl2—O3—Tl1ⁱⁱ	−134.49 (15)	O8—P3—C3—N1	31.0 (4)
O9^v—Tl2—O3—Tl1ⁱⁱ	24.0 (3)	O7—P3—C3—N1	−87.6 (4)
Tl1—Tl2—O3—Tl1ⁱⁱ	−137.17 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3	0.87	2.39	2.882 (5)	116
N1—H1N···O5	0.87	2.53	2.957 (6)	111
N1—H1N···O8	0.87	2.19	2.837 (7)	131
O1—H1O···O1ⁱⁱⁱ	0.82	1.78	2.504 (8)	147
O2—H2O···O2^vii	0.82	1.68	2.497 (7)	171
O6—H6O···O9^viii	0.82	1.67	2.484 (6)	171
O7—H7O···O4ⁱ	0.82	1.70	2.521 (6)	180

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

Experimental details

Crystal data
Chemical formula	[Tl₂(C₃H₁₀NO₉P₃)]
M_r	705.77
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.9236 (6), 8.0932 (6), 10.9136 (8)
α, β, γ (°)	81.422 (1), 79.023 (1), 68.085 (1)
V (Å³)	635.06 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	25.76
Crystal size (mm)	0.16 × 0.14 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Numerical (XPREP; Bruker, 2007)
T_min, T_max	0.104, 0.183
No. of measured, independent and observed [I > 2σ(I)] reflections	6627, 2744, 2437
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.055, 1.05
No. of reflections	2744
No. of parameters	163
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.72, −1.83

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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
N1—H1N···O3	0.87	2.39	2.882 (5)	116
N1—H1N···O5	0.87	2.53	2.957 (6)	111
N1—H1N···O8	0.87	2.19	2.837 (7)	131
O1—H1O···O1ⁱ	0.82	1.78	2.504 (8)	147
O2—H2O···O2ⁱⁱ	0.82	1.68	2.497 (7)	171
O6—H6O···O9ⁱⁱⁱ	0.82	1.67	2.484 (6)	171
O7—H7O···O4^iv	0.82	1.70	2.521 (6)	180

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

Acknowledgements

Support of this investigation by Tarbiat Modares University Research Council is gratefully acknowledged.

References

Bruker (2007). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sharma, C. V. K., Clearfield, A., Cabeza, A., Aranda, M. A. G. & Bruque, S. (2001). J. Am. Chem. Soc. 123, 2885–2886. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef IUCr Journals Google Scholar

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