Synthesis and crystal structure of calcium dizinc iron(III) tris­(orthophosphate), CaZn₂Fe(PO₄)₃

The orthophosphate CaZn₂Fe(PO₄)₃ crystallizes in the monoclinic system. The structure of this phosphate is built up from edge-sharing [ZnO₅] polyhedra linked together by FeO₆ octa­hedra and PO₄ tetra­hedra.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](P-O) = 0.001 Å
• R factor = 0.017
• wR factor = 0.041
• Data-to-parameter ratio = 29.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2 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
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn2    --  O9      ..       12.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn2    --  O11     ..        8.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn2    --  O8_g    ..       14.0 s.u.
PLAT793_ALERT_4_G The Model has Chirality at P1      (Centro SPGR)          S Verify
PLAT793_ALERT_4_G The Model has Chirality at P2      (Centro SPGR)          R Verify
PLAT793_ALERT_4_G The Model has Chirality at P3      (Centro SPGR)          R Verify
PLAT933_ALERT_2_G Number of OMIT records in Embedded RES .........          2 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
   9 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Calcium dizinc iron(III) tris(orthophosphate)

Crystal data

CaZn2Fe(PO4)3	F(000) = 988
Mr = 511.58	Dx = 3.618 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5619 (3) Å	Cell parameters from 4985 reflections
b = 15.2699 (5) Å	θ = 2.7–37.6°
c = 8.1190 (3) Å	µ = 7.72 mm^−1
β = 117.788 (2)°	T = 296 K
V = 939.06 (6) Å^3	Block, black
Z = 4	0.30 × 0.26 × 0.18 mm

Data collection

Bruker X8 APEX diffractometer	4985 independent reflections
Radiation source: fine-focus sealed tube	4493 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 37.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −14→14
Tmin = 0.600, Tmax = 0.747	k = −26→26
54053 measured reflections	l = −10→13

Refinement

Refinement on F^2	172 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.017	w = 1/[σ^2(Fo^2) + (0.0174P)^2 + 0.7655P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.041	(Δ/σ)max = 0.003
S = 1.04	Δρmax = 1.07 e Å^−3
4985 reflections	Δρmin = −0.78 e Å^−3

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
Zn1	0.81685 (2)	0.73588 (2)	0.30142 (2)	0.00740 (3)
Zn2	0.88412 (2)	0.52265 (2)	0.59417 (2)	0.01026 (3)
Fe1	0.67075 (2)	0.49009 (2)	0.83003 (2)	0.00500 (3)
Ca1	0.27619 (3)	0.75762 (2)	0.47919 (3)	0.01070 (4)
P1	0.29665 (3)	0.58370 (2)	0.77261 (4)	0.00503 (4)
P2	0.96807 (3)	0.62244 (2)	0.09438 (4)	0.00499 (4)
P3	0.60325 (3)	0.64096 (2)	0.49014 (4)	0.00491 (4)
O1	0.29942 (13)	0.67932 (6)	0.72349 (13)	0.01271 (15)
O2	0.30273 (12)	0.58596 (6)	0.96463 (12)	0.01006 (14)
O3	0.12207 (10)	0.54161 (6)	0.62684 (12)	0.01114 (15)
O4	0.43948 (11)	0.52893 (6)	0.76475 (14)	0.01312 (16)
O5	0.77926 (10)	0.58832 (5)	0.00379 (12)	0.00895 (13)
O6	1.00136 (11)	0.67493 (6)	−0.04745 (13)	0.01045 (14)
O7	1.00262 (11)	0.68143 (6)	0.26134 (13)	0.01055 (14)
O8	1.09932 (10)	0.54481 (5)	0.17408 (12)	0.00724 (13)
O9	0.75426 (11)	0.65280 (6)	0.43941 (13)	0.01160 (15)
O10	0.59377 (10)	0.71947 (6)	0.60355 (12)	0.00974 (14)
O11	0.66602 (11)	0.55677 (5)	0.61102 (12)	0.00822 (13)
O12	0.41993 (10)	0.62799 (6)	0.32620 (12)	0.01012 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00645 (5)	0.00817 (5)	0.00801 (6)	0.00013 (4)	0.00374 (4)	0.00104 (4)
Zn2	0.00760 (5)	0.01471 (6)	0.01073 (6)	0.00042 (4)	0.00616 (4)	−0.00080 (5)
Fe1	0.00454 (5)	0.00602 (6)	0.00488 (6)	0.00044 (4)	0.00256 (4)	0.00061 (4)
Ca1	0.01029 (8)	0.01095 (9)	0.01178 (10)	0.00175 (6)	0.00591 (7)	0.00601 (7)
P1	0.00467 (9)	0.00607 (10)	0.00452 (10)	0.00011 (7)	0.00229 (8)	−0.00022 (8)
P2	0.00441 (9)	0.00482 (10)	0.00581 (11)	0.00038 (7)	0.00243 (8)	−0.00009 (8)
P3	0.00448 (9)	0.00500 (10)	0.00483 (10)	0.00004 (7)	0.00182 (8)	0.00031 (8)
O1	0.0222 (4)	0.0076 (3)	0.0109 (4)	−0.0001 (3)	0.0098 (3)	0.0019 (3)
O2	0.0169 (3)	0.0093 (3)	0.0063 (3)	0.0009 (3)	0.0073 (3)	0.0011 (3)
O3	0.0051 (3)	0.0176 (4)	0.0102 (4)	−0.0030 (3)	0.0030 (3)	−0.0063 (3)
O4	0.0065 (3)	0.0172 (4)	0.0157 (4)	0.0026 (3)	0.0052 (3)	−0.0045 (3)
O5	0.0056 (3)	0.0100 (3)	0.0101 (3)	−0.0016 (2)	0.0028 (2)	−0.0034 (3)
O6	0.0097 (3)	0.0107 (3)	0.0132 (4)	0.0029 (3)	0.0072 (3)	0.0061 (3)
O7	0.0079 (3)	0.0122 (3)	0.0115 (4)	−0.0005 (2)	0.0045 (3)	−0.0062 (3)
O8	0.0065 (3)	0.0073 (3)	0.0088 (3)	0.0026 (2)	0.0043 (2)	0.0020 (2)
O9	0.0111 (3)	0.0118 (3)	0.0161 (4)	0.0008 (3)	0.0098 (3)	0.0042 (3)
O10	0.0076 (3)	0.0091 (3)	0.0103 (3)	0.0006 (2)	0.0024 (3)	−0.0040 (3)
O11	0.0100 (3)	0.0080 (3)	0.0082 (3)	0.0028 (2)	0.0055 (3)	0.0039 (3)
O12	0.0068 (3)	0.0086 (3)	0.0097 (3)	−0.0002 (2)	−0.0006 (3)	−0.0020 (3)

Geometric parameters (Å, º)

Zn1—O9	1.9266 (9)	Ca1—O2^i	2.4075 (9)
Zn1—O7	1.9518 (8)	Ca1—O7^viii	2.4709 (9)
Zn1—O10^i	1.9578 (8)	Ca1—O6^ix	2.4840 (9)
Zn1—O6^ii	2.0120 (8)	Ca1—O10	2.4885 (8)
Zn2—O3^iii	1.9496 (8)	Ca1—O12	2.8984 (9)
Zn2—O11	2.0038 (8)	P1—O4	1.5073 (9)
Zn2—O3^iv	2.0241 (9)	P1—O1	1.5166 (9)
Zn2—O8^v	2.0911 (8)	P1—O2	1.5358 (9)
Zn2—O9	2.3371 (9)	P1—O3	1.5487 (8)
Fe1—O4	1.8908 (8)	P2—O5	1.5222 (8)
Fe1—O2^vi	1.9561 (9)	P2—O6	1.5348 (9)
Fe1—O5^vii	1.9700 (8)	P2—O7	1.5371 (9)
Fe1—O11	2.0330 (8)	P2—O8	1.5519 (8)
Fe1—O8^v	2.0547 (8)	P3—O12	1.5253 (8)
Fe1—O12^iv	2.1318 (8)	P3—O10	1.5365 (9)
Ca1—O1	2.2439 (9)	P3—O9	1.5396 (9)
Ca1—O1^i	2.3795 (10)	P3—O11	1.5534 (8)
O9—Zn1—O7	106.60 (4)	O2^i—Ca1—O6^ix	72.04 (3)
O9—Zn1—O10^i	106.09 (4)	O7^viii—Ca1—O6^ix	65.76 (3)
O7—Zn1—O10^i	124.80 (4)	O1—Ca1—O10	83.50 (3)
O9—Zn1—O6^ii	116.31 (4)	O1^i—Ca1—O10	85.92 (3)
O7—Zn1—O6^ii	85.46 (3)	O2^i—Ca1—O10	98.16 (3)
O10^i—Zn1—O6^ii	116.93 (4)	O7^viii—Ca1—O10	132.22 (3)
O3^iii—Zn2—O11	154.16 (4)	O6^ix—Ca1—O10	160.73 (3)
O3^iii—Zn2—O3^iv	77.67 (4)	O1—Ca1—O12	97.73 (3)
O11—Zn2—O3^iv	123.13 (3)	O1^i—Ca1—O12	71.19 (3)
O3^iii—Zn2—O8^v	108.82 (4)	O2^i—Ca1—O12	126.00 (3)
O11—Zn2—O8^v	75.00 (3)	O7^viii—Ca1—O12	79.74 (3)
O3^iv—Zn2—O8^v	121.44 (4)	O6^ix—Ca1—O12	145.10 (3)
O3^iii—Zn2—O9	98.73 (4)	O10—Ca1—O12	53.99 (3)
O11—Zn2—O9	65.84 (3)	O1—Ca1—O12^ii	69.93 (3)
O3^iv—Zn2—O9	97.26 (4)	O1^i—Ca1—O12^ii	114.39 (3)
O8^v—Zn2—O9	135.92 (3)	O2^i—Ca1—O12^ii	57.96 (3)
O4—Fe1—O2^vi	96.63 (4)	O7^viii—Ca1—O12^ii	140.52 (3)
O4—Fe1—O5^vii	92.55 (4)	O6^ix—Ca1—O12^ii	78.49 (3)
O2^vi—Fe1—O5^vii	90.75 (4)	O10—Ca1—O12^ii	82.24 (3)
O4—Fe1—O11	90.37 (4)	O12—Ca1—O12^ii	135.98 (3)
O2^vi—Fe1—O11	171.82 (3)	O4—P1—O1	114.24 (6)
O5^vii—Fe1—O11	93.18 (4)	O4—P1—O2	114.28 (5)
O4—Fe1—O8^v	164.34 (4)	O1—P1—O2	104.36 (5)
O2^vi—Fe1—O8^v	97.38 (3)	O4—P1—O3	104.50 (5)
O5^vii—Fe1—O8^v	94.22 (3)	O1—P1—O3	109.05 (5)
O11—Fe1—O8^v	75.18 (3)	O2—P1—O3	110.42 (5)
O4—Fe1—O12^iv	93.16 (4)	O5—P2—O6	110.07 (5)
O2^vi—Fe1—O12^iv	82.55 (4)	O5—P2—O7	110.55 (5)
O5^vii—Fe1—O12^iv	171.65 (3)	O6—P2—O7	109.20 (5)
O11—Fe1—O12^iv	92.86 (4)	O5—P2—O8	109.84 (5)
O8^v—Fe1—O12^iv	81.77 (3)	O6—P2—O8	111.11 (5)
O1—Ca1—O1^i	167.91 (4)	O7—P2—O8	106.00 (5)
O1—Ca1—O2^i	126.91 (3)	O12—P3—O10	107.69 (5)
O1^i—Ca1—O2^i	60.49 (3)	O12—P3—O9	115.63 (5)
O1—Ca1—O7^viii	92.62 (3)	O10—P3—O9	110.75 (5)
O1^i—Ca1—O7^viii	90.17 (3)	O12—P3—O11	110.86 (5)
O2^i—Ca1—O7^viii	120.77 (3)	O10—P3—O11	111.50 (5)
O1—Ca1—O6^ix	89.31 (3)	O9—P3—O11	100.36 (5)
O1^i—Ca1—O6^ix	102.55 (3)

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