Synthesis and crystal structure of a new alluaudite-like iron phosphate Na₂CaMnFe(PO₄)₃

Disodium calcium manganese iron tris­(phosphate), Na₂CaMnFe(PO₄)₃, crystallizes in the monoclinic space group C2/c. The structure belongs to the alluaudite structural type and thus, it obeys the X(2)X(1)M(1)M(2)₂(PO₄)₃ general formula. Both the X(2) and X(1) sites are fully occupied by sodium, while M(1) is occupied by calcium and M(2) exhibits a statistical distribution of iron and manganese.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](P-O) = 0.003 Å
• Disorder in main residue
• R factor = 0.028
• wR factor = 0.081
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7 Report

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT128_ALERT_4_G Alternate Setting for Input Space Group     C2/c       I2/a Note
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe     --  O22     ..       13.6 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe     --  O11_a   ..        5.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe     --  O23_e   ..        9.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe     --  O24_g   ..        9.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe     --  O12_h   ..        7.6 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn     --  O22     ..       13.6 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn     --  O11_a   ..        5.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn     --  O23_e   ..        9.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn     --  O24_g   ..        9.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn     --  O12_h   ..        7.6 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =          7 Note
PLAT793_ALERT_4_G The Model has Chirality at P2      (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  21 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Disodium calcium manganese iron tris(phosphate)

Crystal data

Na2CaMnFe(PO4)3	F(000) = 936
Mr = 481.76	Dx = 3.469 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.283 (1) Å	Cell parameters from 25 reflections
b = 12.736 (1) Å	θ = 8.0–14.7°
c = 6.494 (5) Å	µ = 4.19 mm^−1
β = 114.76 (3)°	T = 293 K
V = 922.5 (7) Å^3	Prism, brown
Z = 4	0.22 × 0.14 × 0.07 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.4°
non–profiled ω/2τ scans	h = −17→16
Absorption correction: ψ scan (North et al., 1968)	k = −1→17
Tmin = 0.514, Tmax = 0.689	l = −1→9
1780 measured reflections	2 standard reflections every 60 min
1333 independent reflections	intensity decay: none
1139 reflections with I > 2σ(I)

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0351P)^2 + 3.0677P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.028	(Δ/σ)max < 0.001
wR(F^2) = 0.081	Δρmax = 0.63 e Å^−3
S = 1.07	Δρmin = −0.90 e Å^−3
1333 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
97 parameters	Extinction coefficient: 0.0026 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Na1	0.5000	0.0000	0.0000	0.0223 (4)
Na2	0.0000	0.0217 (2)	0.7500	0.0464 (7)
Ca	0.0000	0.26845 (6)	0.2500	0.01178 (18)
Mn	0.22734 (3)	0.15466 (3)	0.14341 (7)	0.01013 (14)	0.4999 (3)
Fe	0.22734 (3)	0.15466 (3)	0.14341 (7)	0.01013 (14)	0.5001 (2)
P1	0.0000	0.27735 (8)	0.7500	0.0081 (2)
O11	0.05225 (18)	0.20662 (17)	0.9616 (3)	0.0139 (4)
O12	0.0910 (2)	0.35033 (18)	0.7174 (4)	0.0204 (5)
P2	0.23941 (6)	−0.10428 (6)	0.13282 (11)	0.00951 (17)
O21	0.37036 (19)	−0.08841 (17)	0.1794 (4)	0.0160 (4)
O22	0.1756 (2)	0.00101 (19)	0.1190 (4)	0.0228 (5)
O23	0.1718 (2)	−0.16191 (17)	−0.0952 (4)	0.0165 (4)
O24	0.23187 (19)	−0.17266 (18)	0.3233 (4)	0.0164 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0296 (10)	0.0080 (8)	0.0110 (8)	−0.0041 (7)	−0.0095 (7)	0.0027 (6)
Na2	0.0339 (13)	0.0492 (16)	0.0406 (15)	0.000	0.0004 (11)	0.000
Ca	0.0109 (3)	0.0092 (4)	0.0175 (4)	0.000	0.0082 (3)	0.000
Mn	0.0079 (2)	0.0119 (2)	0.0101 (2)	−0.00091 (14)	0.00324 (16)	−0.00062 (14)
Fe	0.0079 (2)	0.0119 (2)	0.0101 (2)	−0.00091 (14)	0.00324 (16)	−0.00062 (14)
P1	0.0079 (4)	0.0090 (4)	0.0060 (4)	0.000	0.0016 (3)	0.000
O11	0.0132 (9)	0.0180 (10)	0.0082 (8)	−0.0031 (8)	0.0023 (7)	0.0036 (8)
O12	0.0163 (10)	0.0184 (11)	0.0255 (12)	−0.0014 (8)	0.0076 (9)	0.0111 (9)
P2	0.0116 (3)	0.0087 (3)	0.0062 (3)	0.0015 (2)	0.0017 (2)	0.0004 (2)
O21	0.0143 (9)	0.0160 (10)	0.0160 (10)	−0.0034 (8)	0.0049 (8)	−0.0015 (8)
O22	0.0291 (12)	0.0189 (11)	0.0173 (11)	0.0124 (9)	0.0064 (10)	−0.0018 (9)
O23	0.0211 (10)	0.0138 (10)	0.0094 (9)	−0.0034 (8)	0.0012 (8)	−0.0015 (8)
O24	0.0159 (9)	0.0212 (11)	0.0114 (10)	−0.0005 (9)	0.0052 (8)	0.0028 (8)

Geometric parameters (Å, º)

Na1—O21^i	2.315 (2)	Ca—O11^x	2.355 (3)
Na1—O21^ii	2.315 (2)	Ca—O12^vi	2.951 (3)
Na1—O12^iii	2.357 (2)	Ca—O12	2.951 (3)
Na1—O12^iv	2.357 (2)	Mn—O12^xv	2.027 (2)
Na1—O21^v	2.591 (2)	Mn—O22	2.043 (3)
Na1—O21	2.591 (2)	Mn—O23^ix	2.080 (3)
Na2—O22^vi	2.477 (3)	Mn—O11^xiv	2.081 (2)
Na2—O22^vii	2.477 (3)	Mn—O24^i	2.115 (3)
Na2—O22^viii	2.645 (3)	Mn—O24^xi	2.246 (2)
Na2—O22^ix	2.645 (3)	P1—O12^x	1.535 (2)
Na2—O11^x	2.667 (3)	P1—O12	1.535 (2)
Na2—O11	2.667 (3)	P1—O11	1.541 (2)
Ca—O21^xi	2.336 (2)	P1—O11^x	1.541 (2)
Ca—O21^xii	2.336 (2)	P2—O21	1.521 (2)
Ca—O23^xiii	2.351 (2)	P2—O22	1.537 (2)
Ca—O23^ix	2.351 (2)	P2—O23	1.546 (2)
Ca—O11^xiv	2.355 (3)	P2—O24	1.547 (2)
O21^i—Na1—O21^ii	180.00 (13)	O23^ix—Ca—O11^x	87.80 (8)
O21^i—Na1—O12^iii	96.91 (9)	O11^xiv—Ca—O11^x	140.93 (11)
O21^ii—Na1—O12^iii	83.09 (9)	O21^xi—Ca—O12^vi	81.93 (8)
O21^i—Na1—O12^iv	83.09 (9)	O21^xii—Ca—O12^vi	65.72 (7)
O21^ii—Na1—O12^iv	96.91 (9)	O23^xiii—Ca—O12^vi	83.03 (8)
O12^iii—Na1—O12^iv	180.00 (13)	O23^ix—Ca—O12^vi	121.96 (7)
O21^i—Na1—O21^v	72.85 (9)	O11^xiv—Ca—O12^vi	54.00 (8)
O21^ii—Na1—O21^v	107.15 (9)	O11^x—Ca—O12^vi	145.50 (7)
O12^iii—Na1—O21^v	72.01 (9)	O21^xi—Ca—O12	65.72 (7)
O12^iv—Na1—O21^v	107.99 (9)	O21^xii—Ca—O12	81.93 (8)
O21^i—Na1—O21	107.15 (9)	O23^xiii—Ca—O12	121.96 (7)
O21^ii—Na1—O21	72.85 (9)	O23^ix—Ca—O12	83.03 (8)
O12^iii—Na1—O21	107.99 (9)	O11^xiv—Ca—O12	145.50 (7)
O12^iv—Na1—O21	72.01 (9)	O11^x—Ca—O12	54.00 (8)
O21^v—Na1—O21	180.0	O12^vi—Ca—O12	138.61 (10)
O22^vi—Na2—O22^vii	167.80 (17)	O12^xv—Mn—O22	104.67 (10)
O22^vi—Na2—O22^viii	78.62 (9)	O12^xv—Mn—O23^ix	108.27 (10)
O22^vii—Na2—O22^viii	100.03 (9)	O22—Mn—O23^ix	84.73 (9)
O22^vi—Na2—O22^ix	100.03 (9)	O12^xv—Mn—O11^xiv	161.07 (9)
O22^vii—Na2—O22^ix	78.62 (9)	O22—Mn—O11^xiv	92.66 (9)
O22^viii—Na2—O22^ix	167.47 (16)	O23^ix—Mn—O11^xiv	80.46 (9)
O22^vi—Na2—O11^x	70.80 (8)	O12^xv—Mn—O24^i	87.98 (10)
O22^vii—Na2—O11^x	121.10 (12)	O22—Mn—O24^i	99.38 (10)
O22^viii—Na2—O11^x	102.10 (9)	O23^ix—Mn—O24^i	161.79 (9)
O22^ix—Na2—O11^x	89.04 (9)	O11^xiv—Mn—O24^i	81.62 (9)
O22^vi—Na2—O11	121.10 (12)	O12^xv—Mn—O24^xi	80.11 (9)
O22^vii—Na2—O11	70.80 (8)	O22—Mn—O24^xi	174.29 (9)
O22^viii—Na2—O11	89.04 (9)	O23^ix—Mn—O24^xi	90.82 (8)
O22^ix—Na2—O11	102.10 (9)	O11^xiv—Mn—O24^xi	83.06 (8)
O11^x—Na2—O11	55.90 (11)	O24^i—Mn—O24^xi	83.79 (9)
O21^xi—Ca—O21^xii	77.41 (11)	O12^x—P1—O12	105.48 (19)
O21^xi—Ca—O23^xiii	161.85 (8)	O12^x—P1—O11	106.63 (13)
O21^xii—Ca—O23^xiii	87.17 (8)	O12—P1—O11	114.95 (12)
O21^xi—Ca—O23^ix	87.17 (8)	O12^x—P1—O11^x	114.95 (12)
O21^xii—Ca—O23^ix	161.85 (8)	O12—P1—O11^x	106.63 (13)
O23^xiii—Ca—O23^ix	109.49 (11)	O11—P1—O11^x	108.44 (18)
O21^xi—Ca—O11^xiv	91.53 (8)	O21—P2—O22	111.53 (14)
O21^xii—Ca—O11^xiv	119.68 (8)	O21—P2—O23	110.66 (13)
O23^xiii—Ca—O11^xiv	87.80 (8)	O22—P2—O23	107.57 (13)
O23^ix—Ca—O11^xiv	69.66 (8)	O21—P2—O24	109.17 (13)
O21^xi—Ca—O11^x	119.68 (8)	O22—P2—O24	109.76 (14)
O21^xii—Ca—O11^x	91.53 (8)	O23—P2—O24	108.08 (13)
O23^xiii—Ca—O11^x	69.66 (8)

Symmetry codes: (i) x, −y, z−1/2; (ii) −x+1, y, −z+1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x+1, −y, −z; (vi) −x, y, −z+1/2; (vii) x, y, z+1; (viii) −x, −y, −z+1; (ix) x, −y, z+1/2; (x) −x, y, −z+3/2; (xi) −x+1/2, y+1/2, −z+1/2; (xii) x−1/2, y+1/2, z; (xiii) −x, −y, −z; (xiv) x, y, z−1; (xv) −x+1/2, −y+1/2, −z+1.