TlHP₂O₇: structure determination from X-ray powder diffraction data

The crystal structure of monoclinic thallium(III) hydrogendiphosphate, TlHP₂O₇, has been solved from laboratory X-ray powder diffraction data and refined by the Rietveld method. All atoms occupy general positions. The Tl^III ions have a distorted octa­hedral coordination environment of O atoms from four diphosphate groups. Adjacent TlO₆ octa­hedra form edge-shared Tl₂O₁₀ dimers which share corners with PO₄ tetra­hedra to build a three-dimensional polymeric structure.

Key indicators

• Powder X-ray study
• T = 295 K
• Mean [sigma](P-O) = 0.015 Å
• R factor = 0.076
• wR factor = 0.106
• Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level C
REFI023_ALERT_1_C  _refine_diff_density_max is missing
            Maximum value of final difference map (e A-3).
            The following tests will not be performed
            DIFMN_01,DIFMX_01,DIFMX_02
REFI024_ALERT_1_C  _refine_diff_density_min is missing
            Minimum value of final difference map (e A-3).
            The following tests will not be performed
            DIFMN_01,DIFMN_02,DIFMN_03

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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Computing details

Data collection: local program; cell refinement: FULLPROF (Rodríguez-Carvajal, 2001); data reduction: local program; program(s) used to solve structure: EXPO (Altomare et al., 1999); program(s) used to refine structure: FULLPROF; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: FULLPROF and PLATON (Spek, 2003).

thallium(III) hydrogen diphosphate

Crystal data

TlHP2O7	Z = 4
Mr = 379.33	F(000) = 672
Monoclinic, P21/n	Dx = 4.527 Mg m^−3
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54180 Å
a = 8.78516 (15) Å	T = 295 K
b = 9.09283 (17) Å	Particle morphology: plate-like
c = 7.24420 (12) Å	colourless
β = 105.8725 (9)°	flat sheet, 30 × 30 mm
V = 556.62 (2) Å^3	Specimen preparation: Prepared at 295 K

Data collection

HZG-4A (Carl Zeiss, Jena) diffractometer	Data collection mode: reflection
Radiation source: fine-focus sealed X-ray tube, BSV-29	Scan method: step
Specimen mounting: packed powder pellet	2θmin = 12.0°, 2θmax = 137.0°, 2θstep = 0.02°

Refinement

Refinement on Inet	Profile function: A pseudo-Voigt profile function was used. The value of the η-parameter is 0.62.
Least-squares matrix: full with fixed elements per cycle	52 parameters
Rp = 0.076	8 restraints
Rwp = 0.106	0 constraints
Rexp = 0.135	H-atom parameters constrained
RBragg = 0.055	Weighting scheme based on measured s.u.'s
R(F^2) = 0.035	(Δ/σ)max = 0.03
6251 data points	Background function: A polynomial background function was used. Five polynomial coefficients were refined.
Excluded region(s): none	Preferred orientation correction: A Marsh–Dollase correction of intensities (Marsh, 1932; Dollase, 1986) for the (101) preferred orientation of plate-like grains was applied. The refined values of coefficients are G1 = 0.668(6), G2 = 0.316(19).

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tl	0.4945 (2)	0.29669 (18)	0.5376 (2)	0.0060 (4)*
P1	0.7278 (8)	−0.0021 (9)	0.6794 (10)	0.0047 (19)*
P2	0.7351 (9)	0.1374 (8)	0.3049 (10)	0.0047 (19)*
O1	0.5857 (18)	0.084 (2)	0.664 (3)	0.0060 (19)*
O2	0.692 (2)	−0.1578 (13)	0.662 (3)	0.0060 (19)*
O3	0.8646 (15)	0.011 (3)	0.8528 (18)	0.0060 (19)*
O4	0.8009 (19)	0.042 (2)	0.4989 (18)	0.0060 (19)*
O5	0.662 (2)	0.2699 (15)	0.354 (3)	0.0060 (19)*
O6	0.626 (2)	0.038 (2)	0.142 (2)	0.0060 (19)*
H6	0.67616	−0.03768	0.12077	0.050*
O7	0.8863 (17)	0.187 (2)	0.271 (3)	0.0060 (19)*

Geometric parameters (Å, º)

Tl—O1	2.195 (19)	P1—O3	1.487 (15)
Tl—O5	2.250 (19)	P1—O4	1.656 (16)
Tl—O3^i	2.33 (2)	P2—O4	1.618 (16)
Tl—O2^ii	2.253 (18)	P2—O5	1.455 (17)
Tl—O3^iii	2.31 (2)	P2—O6	1.584 (18)
Tl—O7^iv	2.160 (19)	P2—O7	1.486 (18)
P1—O1	1.452 (19)	O6—H6	0.8500
P1—O2	1.448 (15)
O1—Tl—O5	85.9 (6)	O2—P1—O3	105.0 (14)
O1—Tl—O3^i	119.7 (7)	O2—P1—O4	106.9 (11)
O1—Tl—O2^ii	83.8 (6)	O3—P1—O4	104.4 (9)
O1—Tl—O3^iii	167.6 (7)	O4—P2—O5	108.0 (11)
O1—Tl—O7^iv	85.6 (7)	O4—P2—O6	109.9 (10)
O3^i—Tl—O5	85.4 (5)	O4—P2—O7	100.6 (11)
O2^ii—Tl—O5	92.2 (7)	O5—P2—O6	115.9 (11)
O3^iii—Tl—O5	92.2 (5)	O5—P2—O7	105.3 (11)
O5—Tl—O7^iv	165.7 (7)	O6—P2—O7	115.9 (11)
O2^ii—Tl—O3^i	156.0 (6)	Tl—O1—P1	135.7 (12)
O3^i—Tl—O3^iii	72.3 (7)	Tl^ii—O2—P1	135.0 (12)
O3^i—Tl—O7^iv	89.0 (6)	Tl^v—O3—P1	116.9 (14)
O2^ii—Tl—O3^iii	84.0 (6)	Tl^vi—O3—P1	135.1 (15)
O2^ii—Tl—O7^iv	98.2 (7)	Tl^v—O3—Tl^vi	107.7 (5)
O3^iii—Tl—O7^iv	98.5 (6)	P1—O4—P2	133.8 (12)
O1—P1—O2	111.0 (11)	Tl—O5—P2	129.7 (10)
O1—P1—O3	120.1 (12)	Tl^vii—O7—P2	139.1 (13)
O1—P1—O4	108.7 (11)	P2—O6—H6	111.00
O5—Tl—O1—P1	21.4 (18)	O4—P1—O2—Tl^ii	−72.4 (17)
O3^i—Tl—O1—P1	−60.9 (19)	O1—P1—O3—Tl^v	143.0 (10)
O2^ii—Tl—O1—P1	114.1 (18)	O1—P1—O3—Tl^vi	−43.8 (17)
O7^iv—Tl—O1—P1	−147.2 (18)	O2—P1—O3—Tl^v	17.3 (12)
O1—Tl—O5—P2	21.0 (16)	O2—P1—O3—Tl^vi	−169.5 (12)
O3^i—Tl—O5—P2	141.3 (16)	O4—P1—O3—Tl^v	−94.9 (11)
O2^ii—Tl—O5—P2	−62.7 (16)	O4—P1—O3—Tl^vi	78.3 (13)
O3^iii—Tl—O5—P2	−146.7 (16)	O1—P1—O4—P2	−10.4 (19)
O1—Tl—O3^i—P1^i	−8.6 (12)	O2—P1—O4—P2	109.5 (17)
O5—Tl—O3^i—P1^i	−91.2 (10)	O3—P1—O4—P2	−139.6 (17)
O1—Tl—O2^ii—P1^ii	2.5 (17)	O5—P2—O4—P1	43.4 (19)
O5—Tl—O2^ii—P1^ii	88.2 (17)	O6—P2—O4—P1	−83.9 (17)
O5—Tl—O3^iii—P1^iii	89.2 (12)	O7—P2—O4—P1	153.5 (16)
O1—Tl—O7^iv—P2^iv	−139.6 (18)	O4—P2—O5—Tl	−45.2 (17)
O2—P1—O1—Tl	−143.2 (16)	O6—P2—O5—Tl	78.6 (17)
O3—P1—O1—Tl	94 (2)	O7—P2—O5—Tl	−152.0 (14)
O4—P1—O1—Tl	−26 (2)	O4—P2—O7—Tl^vii	134.2 (16)
O1—P1—O2—Tl^ii	46 (2)	O5—P2—O7—Tl^vii	−113.7 (17)
O3—P1—O2—Tl^ii	177.1 (14)	O6—P2—O7—Tl^vii	16 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O5^viii	0.8500	2.2300	3.06 (2)	165.00

Symmetry code: (viii) −x+3/2, y−1/2, −z+1/2.