LiNi_0.66Fe_0.34PO₄

Lithium nickel(II) iron(II) phosphate, LiNi_0.66Fe_0.34PO₄, was crystallized from an LiCl melt. The structure is closely related to the known phase LiFePO₄ but with mixed occupancy at the metal atom site of approximately 66% nickel and 34% iron. The Ni/Fe atom is octa­hedrally coordinated by six O atoms. The P atoms are tetra­hedrally coordinated by four O atoms.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](P-O) = 0.002 Å
• Disorder in main residue
• R factor = 0.020
• wR factor = 0.043
• Data-to-parameter ratio = 8.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.568     0.692
            Tmin and Tmax expected:      0.281     0.376
            RR =      1.101
            Please check that your absorption correction is appropriate.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.12
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.54
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       8.02
PLAT301_ALERT_3_C Main Residue  Disorder .........................      12.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              FE1  -O1   -NI1     1.556   1.555   1.556
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              FE1  -O3   -NI1     2.545   1.555   2.545

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.544
            Tmax scaled      0.376 Tmin scaled      0.309

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  12 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SCXmini Benchtop Crystallography System Software; software used to prepare material for publication: CrystalStructure.

Lithium ferrous nickel phosphate

Crystal data

LiNi0.66Fe0.34PO4	F(000) = 416
Mr = 159.63	Dx = 3.815 Mg m^−3 Dm = 3.749 Mg m^−3 Dm measured by floatation
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ac 2n	Cell parameters from 50 reflections
a = 10.0871 (16) Å	θ = 1.0–27.5°
b = 5.8845 (10) Å	µ = 6.84 mm^−1
c = 4.6820 (8) Å	T = 150 K
V = 277.91 (8) Å^3	Block, dark amber-brown
Z = 4	0.19 × 0.18 × 0.14 mm

Data collection

Rigaku SCXmini diffractometer	345 independent reflections
Radiation source: fine-focus sealed tube	328 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 4900 pixels mm^-1	θmax = 27.5°, θmin = 4.0°
data collected from ω scans	h = −13→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→7
Tmin = 0.568, Tmax = 0.692	l = −6→5
2026 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0162P)^2 + 0.3281P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.044	(Δ/σ)max < 0.001
S = 1.18	Δρmax = 0.37 e Å^−3
345 reflections	Δρmin = −0.47 e Å^−3
43 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.055 (4)

Special details

Experimental. high-temperature flux

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.27649 (4)	0.2500	−0.01877 (8)	0.0034 (2)	0.66
Fe1	0.27649 (4)	0.2500	−0.01877 (8)	0.0034 (2)	0.34
P1	0.09411 (8)	0.2500	0.41781 (17)	0.0041 (2)
O1	0.0988 (2)	0.2500	0.7429 (5)	0.0058 (5)
O2	0.4521 (2)	0.2500	0.2019 (5)	0.0051 (5)
O3	0.16550 (14)	0.0433 (3)	0.2782 (3)	0.0058 (4)
Li1	0.0000	0.0000	0.0000	0.0050 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0031 (3)	0.0022 (3)	0.0048 (3)	0.000	−0.00022 (14)	0.000
Fe1	0.0031 (3)	0.0022 (3)	0.0048 (3)	0.000	−0.00022 (14)	0.000
P1	0.0040 (4)	0.0033 (4)	0.0049 (4)	0.000	0.0003 (3)	0.000
O1	0.0061 (11)	0.0050 (10)	0.0063 (11)	0.000	−0.0006 (9)	0.000
O2	0.0043 (11)	0.0043 (10)	0.0067 (11)	0.000	0.0005 (9)	0.000
O3	0.0070 (8)	0.0044 (7)	0.0060 (7)	0.0007 (6)	0.0014 (6)	0.0001 (5)
Li1	0.006 (3)	0.005 (2)	0.004 (3)	−0.004 (2)	−0.0009 (18)	−0.0013 (18)

Geometric parameters (Å, º)

Ni1—O2	2.051 (2)	O1—Li1^vi	2.1464 (16)
Ni1—O3^i	2.0557 (15)	O2—P1^vii	1.538 (2)
Ni1—O3^ii	2.0557 (15)	O2—Li1^viii	2.0844 (15)
Ni1—O1^iii	2.111 (2)	O2—Li1^ix	2.0844 (15)
Ni1—O3^iv	2.1599 (15)	O3—Fe1^x	2.0557 (15)
Ni1—O3	2.1600 (15)	O3—Ni1^x	2.0557 (15)
Ni1—P1	2.7501 (10)	O3—Li1	2.1327 (15)
Ni1—Li1	3.1544 (5)	Li1—O2^v	2.0844 (15)
Ni1—Li1^iv	3.1544 (5)	Li1—O2^xi	2.0844 (15)
P1—O1	1.523 (2)	Li1—O3^xii	2.1327 (15)
P1—O2^v	1.538 (2)	Li1—O1^xiii	2.1464 (16)
P1—O3^iv	1.5572 (16)	Li1—O1^iii	2.1464 (16)
P1—O3	1.5572 (16)	Li1—P1^xii	2.6253 (7)
P1—Li1	2.6253 (7)	Li1—Li1^iv	2.9423 (5)
P1—Li1^iv	2.6253 (7)	Li1—Li1^xiv	2.9423 (5)
O1—Fe1^vi	2.111 (2)	Li1—Ni1^xii	3.1544 (5)
O1—Ni1^vi	2.111 (2)	Li1—Fe1^xii	3.1544 (5)
O2—Ni1—O3^i	89.26 (5)	Fe1^x—O3—Ni1^x	0.000 (19)
O2—Ni1—O3^ii	89.26 (5)	P1—O3—Li1	89.30 (7)
O3^i—Ni1—O3^ii	114.22 (9)	Fe1^x—O3—Li1	113.88 (7)
O2—Ni1—O1^iii	178.34 (8)	Ni1^x—O3—Li1	113.88 (7)
O3^i—Ni1—O1^iii	89.84 (5)	P1—O3—Ni1	94.03 (7)
O3^ii—Ni1—O1^iii	89.84 (5)	Fe1^x—O3—Ni1	128.53 (7)
O2—Ni1—O3^iv	97.09 (6)	Ni1^x—O3—Ni1	128.53 (7)
O3^i—Ni1—O3^iv	156.63 (7)	Li1—O3—Ni1	94.59 (6)
O3^ii—Ni1—O3^iv	88.42 (4)	O2^v—Li1—O2^xi	180.00 (9)
O1^iii—Ni1—O3^iv	84.28 (6)	O2^v—Li1—O3	71.82 (7)
O2—Ni1—O3	97.09 (6)	O2^xi—Li1—O3	108.18 (7)
O3^i—Ni1—O3	88.42 (4)	O2^v—Li1—O3^xii	108.18 (7)
O3^ii—Ni1—O3	156.63 (7)	O2^xi—Li1—O3^xii	71.82 (7)
O1^iii—Ni1—O3	84.28 (6)	O3—Li1—O3^xii	180.0
O3^iv—Ni1—O3	68.53 (8)	O2^v—Li1—O1^xiii	90.04 (6)
O2—Ni1—P1	101.74 (6)	O2^xi—Li1—O1^xiii	89.96 (6)
O3^i—Ni1—P1	122.29 (4)	O3—Li1—O1^xiii	95.91 (7)
O3^ii—Ni1—P1	122.29 (4)	O3^xii—Li1—O1^xiii	84.09 (7)
O1^iii—Ni1—P1	79.92 (6)	O2^v—Li1—O1^iii	89.96 (6)
O3^iv—Ni1—P1	34.39 (4)	O2^xi—Li1—O1^iii	90.04 (6)
O3—Ni1—P1	34.39 (4)	O3—Li1—O1^iii	84.09 (7)
O2—Ni1—Li1	138.57 (4)	O3^xii—Li1—O1^iii	95.91 (7)
O3^i—Ni1—Li1	82.70 (4)	O1^xiii—Li1—O1^iii	180.00 (10)
O3^ii—Ni1—Li1	131.01 (4)	O2^v—Li1—P1	35.84 (6)
O1^iii—Ni1—Li1	42.62 (4)	O2^xi—Li1—P1	144.16 (6)
O3^iv—Ni1—Li1	77.66 (4)	O3—Li1—P1	36.38 (4)
O3—Ni1—Li1	42.37 (4)	O3^xii—Li1—P1	143.62 (4)
P1—Ni1—Li1	52.252 (16)	O1^xiii—Li1—P1	97.70 (5)
O2—Ni1—Li1^iv	138.57 (4)	O1^iii—Li1—P1	82.30 (5)
O3^i—Ni1—Li1^iv	131.01 (4)	O2^v—Li1—P1^xii	144.16 (6)
O3^ii—Ni1—Li1^iv	82.70 (4)	O2^xi—Li1—P1^xii	35.84 (6)
O1^iii—Ni1—Li1^iv	42.62 (4)	O3—Li1—P1^xii	143.62 (4)
O3^iv—Ni1—Li1^iv	42.37 (4)	O3^xii—Li1—P1^xii	36.38 (4)
O3—Ni1—Li1^iv	77.66 (4)	O1^xiii—Li1—P1^xii	82.30 (5)
P1—Ni1—Li1^iv	52.252 (16)	O1^iii—Li1—P1^xii	97.70 (5)
Li1—Ni1—Li1^iv	55.597 (13)	P1—Li1—P1^xii	180.0
O1—P1—O2^v	113.17 (13)	O2^v—Li1—Li1^iv	45.11 (4)
O1—P1—O3^iv	113.90 (8)	O2^xi—Li1—Li1^iv	134.89 (4)
O2^v—P1—O3^iv	106.12 (8)	O3—Li1—Li1^iv	83.13 (4)
O1—P1—O3	113.90 (8)	O3^xii—Li1—Li1^iv	96.87 (4)
O2^v—P1—O3	106.12 (8)	O1^xiii—Li1—Li1^iv	133.27 (4)
O3^iv—P1—O3	102.69 (12)	O1^iii—Li1—Li1^iv	46.73 (4)
O1—P1—Li1	139.12 (5)	P1—Li1—Li1^iv	55.919 (11)
O2^v—P1—Li1	52.53 (6)	P1^xii—Li1—Li1^iv	124.081 (12)
O3^iv—P1—Li1	106.98 (7)	O2^v—Li1—Li1^xiv	134.89 (4)
O3—P1—Li1	54.32 (6)	O2^xi—Li1—Li1^xiv	45.11 (4)
O1—P1—Li1^iv	139.12 (5)	O3—Li1—Li1^xiv	96.87 (4)
O2^v—P1—Li1^iv	52.53 (6)	O3^xii—Li1—Li1^xiv	83.13 (4)
O3^iv—P1—Li1^iv	54.32 (6)	O1^xiii—Li1—Li1^xiv	46.73 (4)
O3—P1—Li1^iv	106.98 (7)	O1^iii—Li1—Li1^xiv	133.27 (4)
Li1—P1—Li1^iv	68.16 (2)	P1—Li1—Li1^xiv	124.082 (11)
O1—P1—Ni1	136.23 (9)	P1^xii—Li1—Li1^xiv	55.918 (11)
O2^v—P1—Ni1	110.61 (9)	Li1^iv—Li1—Li1^xiv	180.0
O3^iv—P1—Ni1	51.58 (6)	O2^v—Li1—Ni1^xii	96.07 (5)
O3—P1—Ni1	51.58 (6)	O2^xi—Li1—Ni1^xii	83.93 (5)
Li1—P1—Ni1	71.82 (2)	O3—Li1—Ni1^xii	136.96 (4)
Li1^iv—P1—Ni1	71.82 (2)	O3^xii—Li1—Ni1^xii	43.04 (4)
P1—O1—Fe1^vi	123.70 (13)	O1^xiii—Li1—Ni1^xii	41.77 (6)
P1—O1—Ni1^vi	123.70 (13)	O1^iii—Li1—Ni1^xii	138.23 (6)
Fe1^vi—O1—Ni1^vi	0.000 (18)	P1—Li1—Ni1^xii	124.08 (2)
P1—O1—Li1^xv	123.10 (8)	P1^xii—Li1—Ni1^xii	55.92 (2)
Fe1^vi—O1—Li1^xv	95.61 (8)	Li1^iv—Li1—Ni1^xii	117.799 (7)
Ni1^vi—O1—Li1^xv	95.61 (8)	Li1^xiv—Li1—Ni1^xii	62.201 (7)
P1—O1—Li1^vi	123.10 (8)	O2^v—Li1—Fe1^xii	96.07 (5)
Fe1^vi—O1—Li1^vi	95.61 (8)	O2^xi—Li1—Fe1^xii	83.93 (5)
Ni1^vi—O1—Li1^vi	95.61 (8)	O3—Li1—Fe1^xii	136.96 (4)
Li1^xv—O1—Li1^vi	86.53 (8)	O3^xii—Li1—Fe1^xii	43.04 (4)
P1^vii—O2—Ni1	128.37 (13)	O1^xiii—Li1—Fe1^xii	41.77 (6)
P1^vii—O2—Li1^viii	91.63 (8)	O1^iii—Li1—Fe1^xii	138.23 (6)
Ni1—O2—Li1^viii	122.50 (7)	P1—Li1—Fe1^xii	124.08 (2)
P1^vii—O2—Li1^ix	91.63 (8)	P1^xii—Li1—Fe1^xii	55.92 (2)
Ni1—O2—Li1^ix	122.50 (7)	Li1^iv—Li1—Fe1^xii	117.799 (7)
Li1^viii—O2—Li1^ix	89.79 (8)	Li1^xiv—Li1—Fe1^xii	62.201 (7)
P1—O3—Fe1^x	126.39 (9)	Ni1^xii—Li1—Fe1^xii	0.000 (16)
P1—O3—Ni1^x	126.39 (9)

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1/2, y+1/2, z−1/2; (iii) x, y, z−1; (iv) x, −y+1/2, z; (v) x−1/2, −y+1/2, −z+1/2; (vi) x, y, z+1; (vii) x+1/2, −y+1/2, −z+1/2; (viii) −x+1/2, y+1/2, z+1/2; (ix) −x+1/2, −y, z+1/2; (x) −x+1/2, y−1/2, z+1/2; (xi) −x+1/2, y−1/2, z−1/2; (xii) −x, −y, −z; (xiii) −x, −y, −z+1; (xiv) x, −y−1/2, z; (xv) x, −y+1/2, z+1.