The layered monodiphosphate Li₉Ga₃(P₂O₇)₃(PO₄)₂ refined from X-ray powder data

Nona­lithium trigallium(III) tris­[pyro­phosphate(V)] diphos­phate(V), Li₉Ga₃(P₂O₇)₃(PO₄)₂, has been synthesized by a hydro­thermal method and its crystal structure solved from X-ray powder diffraction data using Rietveld analysis. The structure is based on separate layers parallel to (001), consisting of GaO₆ octa­hedra that share corners with PO₄ tetra­hedra and P₂O₇ groups. The lithium ions are located in the inter­stitial space.

Key indicators

• Powder X-ray study
• T = 295 K
• Mean [sigma](P-O) = 0.010 Å
• R factor = 0.000
• wR factor = 0.000
• Data-to-parameter ratio = 11.8

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
RADNW01_ALERT_1_C  The radiation wavelength lies outside the expected range
            for the supplied radiation type. Expected range 1.54175-1.54180
            Wavelength given =    1.54439
PLAT799_ALERT_4_C Numeric Label on Displacement Par. Record ......          ?

Alert level G
RADNT01_ALERT_1_G  Extra text has been found in the _diffrn_radiation_type field.
            Radiation given as Cu K\a~1~ Cu K\a~2~
            Radiation identified as Cu K\a

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   4 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: X'pert Data collector (PANalytical, 2003); cell refinement: GSAS (Larson & Von Dreele, 2000) and EXPGUI (Toby, 2001); program(s) used to refine structure: GSAS and EXPGUI; molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Nonalithium trigallium(III) tris[pyrophosphate(V)] diphosphate(V)

Crystal data

Li9Ga3(P2O7)3(PO4)2	F(000) = 944.0
Mr = 983.39	Dx = 2.933 Mg m^−3
Trigonal, P3c1	Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å
a = 9.72879 (13) Å	T = 295 K
c = 13.5827 (3) Å	Particle morphology: laminar
V = 1113.36 (3) Å^3	white
Z = 2	flat_sheet, 10 × 10 mm

Data collection

PANalytical X'pert PRO Diffractometer	Data collection mode: reflection
Radiation source: fine-focus sealed tube, PANalytical X'pert	Scan method: continuous
Graphite monochromator	2θmin = 4.963°, 2θmax = 99.939°, 2θstep = 0.008°
Specimen mounting: packed powder sample container

Refinement

Least-squares matrix: full	65 parameters
Rp = 0.047	1 restraint
Rwp = 0.061	0 constraints
Rexp = 0.049	(Δ/σ)max = 0.02
R(F^2) = 0.11835	Background function: GSAS Background function number 1 with 30 terms. Shifted Chebyshev function of 1st kind 1: 396.391 2: -390.915 3: 175.085 4: -60.8638 5: 14.8885 6: 5.54921 7: -4.37525 8: 10.8573 9: -19.0968 10: 22.4582 11: -14.0394 12: 2.52708 13: 6.09238 14: -7.46171 15: 3.80752 16: 0.299572 17: 0.855120 18: -3.83141 19: 4.92177 20: -2.26483 21: -0.804778 22: 1.92868 23: -0.408054 24: 0.276157 25: -1.69598 26: 2.24824 27: -3.06344 28: 2.95966 29: -1.95750 30: 1.10098
11873 data points	Preferred orientation correction: March-Dollase (March (1932) and Dollase (1986)) AXIS 1 Ratio= 0.73101 h= 1.000 k= 0.000 l= 1.000 Prefered orientation correction range: Min= 0.82553, Max= 1.27264
Profile function: CW Profile function number 3 with 19 terms Pseudovoigt profile coefficients as parameterized in Thompson et al. (1987). Asymmetry correction of Finger et al. (1994). #1(GU) = 480.794 #2(GV) = -436.187 #3(GW) = 81.492 #4(GP) = 47.258 #5(LX) = 1.896 #6(LY) = 0.574 #7(S/L) = 0.0005 #8(H/L) = 0.0005 #9(trns) = -4.77 #10(shft)= -3.4119 #11(stec)= 0.15 #12(ptec)= 0.93 #13(sfec)= 0.00 #14(L11) = 0.019 #15(L22) = 0.089 #16(L33) = -0.029 #17(L12) = 0.034 #18(L13) = 0.030 #19(L23) = -0.058 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0

Special details

Refinement. Chemical restraint is set. Chemical restraint χ² contribution: 0.00

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

	x	y	z	Uiso*/Ueq
P1	0.6667	0.3333	0.6255 (5)	0.010 (2)*
P2	0.3192 (4)	0.0886 (6)	0.8416 (3)	0.0071 (11)*
Ga1	0.5705 (3)	0.0	0.75	0.0055 (6)*
Li1	0.0	0.0	0.0	0.04 (2)*
Li2	0.6667	0.3333	0.868 (5)	0.09 (3)*
Li3	0.328 (3)	0.106 (4)	0.0589 (18)	0.021 (8)*
O1	0.6667	0.3333	0.5125 (12)	0.011 (5)*
O2	0.2145 (10)	0.0	0.75	0.009 (3)*
O3	0.6764 (9)	0.1896 (9)	0.6630 (7)	0.008 (3)*
O4	0.4820 (9)	0.1094 (8)	0.8310 (6)	0.012 (3)*
O5	0.3228 (10)	0.2437 (10)	0.8431 (6)	0.029 (2)*
O6	0.2367 (8)	0.9963 (12)	0.9331 (5)	0.007 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Geometric parameters (Å, º)

P1—Li3^i	3.05 (3)	Li2—P2^iv	3.028 (8)
P1—Li3^ii	3.05 (3)	Li2—P2^v	3.029 (8)
P1—Li3^iii	3.05 (3)	Li2—Ga1	3.30 (3)
P1—O1	1.535 (17)	Li2—Ga1^iv	3.30 (3)
P1—O3	1.535 (7)	Li2—Ga1^v	3.31 (3)
P1—O3^iv	1.536 (7)	Li2—O1^i	1.97 (6)
P1—O3^v	1.536 (7)	Li2—O4	2.076 (15)
P2—P2^vi	2.902 (8)	Li2—O4^iv	2.075 (15)
P2—Li2	3.029 (8)	Li2—O4^v	2.077 (15)
P2—Li3^vii	2.96 (2)	Li3—P1^xxiv	3.05 (3)
P2—Li3^viii	3.00 (3)	Li3—P2^xxv	2.96 (2)
P2—Li3^ix	3.22 (3)	Li3—P2^viii	3.22 (3)
P2—O2	1.565 (5)	Li3—P2^ix	3.00 (3)
P2—O4	1.500 (8)	Li3—Ga1^xxiv	3.13 (3)
P2—O5	1.492 (9)	Li3—Li1	2.93 (3)
P2—O6^x	1.509 (9)	Li3—Li3^xvi	3.24 (3)
Ga1—Li2	3.30 (3)	Li3—Li3^xvii	3.24 (3)
Ga1—Li2^vi	3.30 (3)	Li3—O3^xxiv	2.11 (3)
Ga1—Li3^i	3.13 (3)	Li3—O5^viii	2.05 (3)
Ga1—Li3^xi	3.13 (3)	Li3—O6^xviii	1.97 (2)
Ga1—O3	1.990 (8)	Li3—O6^xxiii	1.86 (3)
Ga1—O3^vi	1.990 (8)	O1—P1	1.535 (17)
Ga1—O4	2.001 (7)	O1—Li2^xxiv	1.97 (6)
Ga1—O4^vi	2.001 (7)	O2—P2	1.565 (5)
Ga1—O5^iv	2.016 (8)	O2—P2^vi	1.565 (5)
Ga1—O5^xii	2.016 (8)	O3—P1	1.535 (7)
Li1—Li3	2.93 (3)	O3—Ga1	1.990 (8)
Li1—Li3^xiii	2.93 (3)	O3—Li3^i	2.11 (3)
Li1—Li3^xiv	2.93 (3)	O4—P2	1.500 (8)
Li1—Li3^xv	2.93 (3)	O4—Ga1	2.001 (7)
Li1—Li3^xvi	2.93 (3)	O4—Li2	2.076 (15)
Li1—Li3^xvii	2.93 (3)	O5—P2	1.492 (9)
Li1—O6^xviii	2.492 (6)	O5—Ga1^v	2.016 (8)
Li1—O6^xix	2.492 (6)	O5—Li3^ix	2.05 (3)
Li1—O6^xx	2.492 (6)	O6—P2^xxvi	1.509 (9)
Li1—O6^xxi	2.492 (6)	O6—Li1^xxvii	2.492 (6)
Li1—O6^xxii	2.492 (6)	O6—Li3^xxvii	1.97 (2)
Li1—O6^xxiii	2.492 (6)	O6—Li3^xxviii	1.86 (3)
Li2—P2	3.029 (8)
O1—P1—O3	109.4 (5)	Li3^xiv—Li1—Li3^xv	67.1 (4)
O1—P1—O3^iv	109.4 (5)	Li3^xiv—Li1—Li3^xvi	67.1 (4)
O1—P1—O3^v	109.4 (5)	Li3^xiv—Li1—Li3^xvii	180.0
O3—P1—O3^iv	109.6 (5)	Li3^xv—Li1—Li3^xvi	112.9 (4)
O3—P1—O3^v	109.6 (5)	Li3^xv—Li1—Li3^xvii	112.9 (4)
O3^iv—P1—O3^v	109.5 (5)	Li3^xvi—Li1—Li3^xvii	112.9 (4)
O2—P2—O4	110.5 (6)	O1^i—Li2—O4	103.9 (17)
O2—P2—O5	104.4 (5)	O1^i—Li2—O4^iv	103.9 (17)
O2—P2—O6^x	108.7 (4)	O1^i—Li2—O4^v	103.9 (17)
O4—P2—O5	112.1 (5)	O4—Li2—O4^iv	114.4 (13)
O4—P2—O6^x	111.7 (5)	O4—Li2—O4^v	114.4 (13)
O5—P2—O6^x	109.1 (5)	O4^iv—Li2—O4^v	114.4 (13)
O3—Ga1—O3^xxix	173.8 (5)	Li1—Li3—O3^xxiv	152.7 (11)
O3—Ga1—O4	89.7 (3)	Li1—Li3—O5^viii	88.9 (10)
O3—Ga1—O4^xxix	94.6 (3)	Li1—Li3—O6^xviii	57.1 (7)
O3—Ga1—O5^iv	94.0 (3)	Li1—Li3—O6^xxiii	57.6 (7)
O3—Ga1—O5^xxx	81.6 (3)	O3^xxiv—Li3—O5^viii	78.1 (10)
O3^xxix—Ga1—O4	94.6 (3)	O3^xxiv—Li3—O6^xviii	149.0 (13)
O3^xxix—Ga1—O4^xxix	89.7 (3)	O3^xxiv—Li3—O6^xxiii	107.0 (13)
O3^xxix—Ga1—O5^iv	81.6 (3)	O5^viii—Li3—O6^xviii	102.3 (13)
O3^xxix—Ga1—O5^xxx	94.0 (3)	O5^viii—Li3—O6^xxiii	116.3 (14)
O4—Ga1—O4^xxix	91.7 (4)	O6^xviii—Li3—O6^xxiii	100.5 (13)
O4—Ga1—O5^iv	89.7 (3)	P1—O1—Li2^xxiv	179.9802
O4—Ga1—O5^xxx	171.3 (3)	P2—O2—P2^vi	136.0 (8)
O4^xxix—Ga1—O5^iv	171.3 (3)	P1—O3—Ga1	143.4 (5)
O4^xxix—Ga1—O5^xxx	89.7 (3)	P1—O3—Li3^i	112.5 (10)
O5^iv—Ga1—O5^xxx	90.3 (5)	Ga1—O3—Li3^i	99.5 (9)
Li3—Li1—Li3^xiii	112.9 (4)	P2—O4—Ga1	133.4 (4)
Li3—Li1—Li3^xiv	112.9 (4)	P2—O4—Li2	114.8 (5)
Li3—Li1—Li3^xv	180.0	Ga1—O4—Li2	108.3 (10)
Li3—Li1—Li3^xvi	67.1 (4)	P2—O5—Ga1^v	129.7 (5)
Li3—Li1—Li3^xvii	67.1 (4)	P2—O5—Li3^ix	129.7 (9)
Li3^xiii—Li1—Li3^xiv	112.9 (4)	Ga1^v—O5—Li3^ix	100.5 (8)
Li3^xiii—Li1—Li3^xv	67.1 (4)	P2^xxvi—O6—Li3^xxvii	115.5 (9)
Li3^xiii—Li1—Li3^xvi	180.0	P2^xxvi—O6—Li3^xxviii	125.9 (10)
Li3^xiii—Li1—Li3^xvii	67.1 (4)	Li3^xxvii—O6—Li3^xxviii	115.7 (7)

Symmetry codes: (i) y−x+1, y, z+1/2; (ii) −y+1, −x+1, z+1/2; (iii) x, x−y, z+1/2; (iv) −y+1, x−y, z; (v) y−x+1, −x+1, z; (vi) x−y, −y, −z+3/2; (vii) x, y, z+1; (viii) y, y−x, −z+1; (ix) x−y, x, −z+1; (x) x, y−1, z; (xi) −x+1, −y, −z+1; (xii) −x+1, y−x, −z+3/2; (xiii) −y, x−y, z; (xiv) y−x, −x, z; (xv) −x, −y, −z; (xvi) y, y−x, −z; (xvii) x−y, x, −z; (xviii) x, y−1, z−1; (xix) −y+1, x−y+1, z−1; (xx) y−x−1, −x, z−1; (xxi) −x, −y+1, −z+1; (xxii) y−1, y−x−1, −z+1; (xxiii) x−y+1, x, −z+1; (xxiv) y−x+1, y, z−1/2; (xxv) x, y, z−1; (xxvi) x, y+1, z; (xxvii) x, y+1, z+1; (xxviii) y, y−x+1, −z+1; (xxix) x−y, −y, −z+5/2; (xxx) −x+1, y−x, −z+5/2.