Crystal structure of BaMn₂(AsO₄)₂ containing discrete [Mn₄O₁₈]²⁸⁻ units

BaMn₂(AsO₄)₂ was isolated from a high-temperature halide flux. Its crystal structure is characterized by infinite sheets made up of AsO₄ units and distorted MnO₆ octa­hedra while barium cations inter­leave successive sheets. The layered framework comprises weakly inter­acting [Mn₄O₁₈]²⁸⁻ tetra­meric units. These units in the neighboring layer are separated from each other by 6.614 (2) Å (Mn...Mn distance).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](As-O) = 0.005 Å
• R factor = 0.039
• wR factor = 0.097
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT971_ALERT_2_B Check Calcd Residual Density  1.03A From     Ba1       3.17 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT971_ALERT_2_B Check Calcd Residual Density  0.74A From     Ba1       2.94 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_B Check Calcd Residual Density  0.97A From     Ba1      -2.72 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_B Check Calcd Residual Density  0.84A From     Ba1      -2.54 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

Alert level C
PLAT213_ALERT_2_C Atom O8              has ADP max/min Ratio .....        3.1 prolat
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         17 Report
PLAT971_ALERT_2_C Check Calcd Residual Density  0.93A From     As1       1.91 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT971_ALERT_2_C Check Calcd Residual Density  0.88A From     As2       1.88 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT971_ALERT_2_C Check Calcd Residual Density  0.86A From     As2       1.62 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT971_ALERT_2_C Check Calcd Residual Density  0.76A From     As1       1.58 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.83A From     As1      -2.10 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.82A From     Ba1      -2.03 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.76A From     As2      -1.85 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.76A From     As1      -1.69 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.89A From     As2      -1.68 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT972_ALERT_2_C Check Calcd Residual Density  0.71A From     Ba1      -1.68 eA-3

Author Response: This appears to be noise associated with the heavy Ba or As atoms, as the electron density does not exhibit suitable coordination to be resolved as a disordered metal site in the structure.

PLAT975_ALERT_2_C Check Calcd Residual Density  0.92A From      O4       0.99 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.69A From      O5       0.98 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.72A From      O6       0.92 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.91A From      O7       0.74 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.84A From      O6      -0.90 eA-3

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)       0.03 Degree
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT804_ALERT_5_G Number of ARU-Code Packing Problem(s) in PLATON           1 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  20 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: CrystalClear (Rigaku, 2006); cell refinement: CrystalClear (Rigaku, 2006); data reduction: CrystalClear (Rigaku, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Barium dimanganese(II) bis(arsenate)

Crystal data

BaMn2(AsO4)2	Z = 2
Mr = 525.06	F(000) = 472
Triclinic, P1	Dx = 4.787 Mg m^−3
a = 5.7981 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.0938 (14) Å	Cell parameters from 3100 reflections
c = 9.817 (2) Å	θ = 2.3–25.2°
α = 109.75 (3)°	µ = 17.78 mm^−1
β = 100.42 (3)°	T = 293 K
γ = 98.40 (3)°	Column, light pink
V = 364.26 (15) Å^3	0.20 × 0.10 × 0.06 mm

Data collection

Rigaku AFC8S diffractometer	1254 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
φ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −6→7
Tmin = 0.808, Tmax = 1.000	k = −8→8
3149 measured reflections	l = −11→11
1330 independent reflections	1 standard reflections every 1 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)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0674P)^2 + 0.2802P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max = 0.001
S = 1.14	Δρmax = 3.25 e Å^−3
1330 reflections	Δρmin = −2.93 e Å^−3
119 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.076 (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
Ba1	0.24355 (7)	0.79849 (6)	0.05371 (4)	0.0100 (2)
Mn1	0.36901 (17)	1.15237 (15)	0.44407 (11)	0.0091 (3)
Mn2	0.00727 (18)	0.59526 (15)	0.35472 (12)	0.0105 (3)
As1	−0.15775 (11)	1.02502 (10)	0.30239 (7)	0.0061 (3)
As2	0.40017 (11)	0.42782 (10)	0.24010 (7)	0.0062 (3)
O1	−0.3934 (8)	0.9502 (7)	0.3669 (5)	0.0092 (10)
O2	0.3546 (8)	0.1879 (7)	0.2382 (5)	0.0124 (10)
O3	0.0571 (8)	0.8910 (7)	0.3296 (5)	0.0105 (10)
O4	0.3801 (8)	0.5917 (7)	0.4075 (5)	0.0099 (10)
O5	−0.0125 (8)	1.2729 (7)	0.4122 (5)	0.0125 (10)
O6	−0.2437 (9)	0.9808 (7)	0.1213 (5)	0.0139 (11)
O7	0.1684 (8)	0.4587 (7)	0.1276 (6)	0.0133 (11)
O8	0.6676 (8)	0.4888 (7)	0.2047 (5)	0.0127 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.0116 (3)	0.0073 (3)	0.0072 (3)	−0.00194 (18)	0.00103 (18)	0.0003 (2)
Mn1	0.0061 (5)	0.0097 (5)	0.0073 (5)	−0.0021 (4)	0.0006 (4)	0.0000 (4)
Mn2	0.0053 (5)	0.0125 (6)	0.0087 (6)	0.0006 (4)	0.0003 (4)	−0.0009 (4)
As1	0.0043 (4)	0.0072 (4)	0.0043 (4)	−0.0005 (3)	0.0007 (3)	−0.0001 (3)
As2	0.0036 (4)	0.0060 (4)	0.0069 (4)	−0.0002 (3)	0.0007 (3)	0.0007 (3)
O1	0.006 (2)	0.011 (2)	0.010 (2)	0.0021 (17)	0.0015 (17)	0.0034 (19)
O2	0.017 (2)	0.006 (2)	0.012 (3)	0.0009 (18)	0.0022 (19)	0.0023 (19)
O3	0.006 (2)	0.009 (2)	0.016 (3)	0.0021 (17)	0.0009 (18)	0.005 (2)
O4	0.009 (2)	0.009 (2)	0.008 (2)	0.0015 (18)	0.0040 (17)	−0.0008 (18)
O5	0.013 (2)	0.013 (2)	0.006 (2)	−0.0032 (18)	0.0037 (18)	−0.001 (2)
O6	0.017 (3)	0.018 (3)	0.004 (2)	0.002 (2)	−0.0009 (19)	0.004 (2)
O7	0.008 (2)	0.013 (2)	0.016 (3)	−0.0008 (18)	−0.0042 (19)	0.007 (2)
O8	0.006 (2)	0.018 (2)	0.011 (2)	−0.0018 (18)	0.0055 (18)	0.002 (2)

Geometric parameters (Å, º)

Ba1—O2^i	2.647 (4)	Mn2—O8^viii	2.094 (5)
Ba1—O7^ii	2.682 (5)	Mn2—O4	2.136 (5)
Ba1—O6^iii	2.687 (5)	Mn2—O5^vii	2.152 (5)
Ba1—O7	2.741 (5)	Mn2—O3	2.178 (5)
Ba1—O8^iv	2.853 (5)	Mn2—O7	2.518 (5)
Ba1—O6^v	2.921 (5)	Mn2—O5^ix	2.526 (5)
Ba1—O3	3.000 (5)	As1—O6	1.663 (5)
Ba1—O1^v	3.131 (5)	As1—O1	1.697 (5)
Mn1—O4^vi	2.052 (5)	As1—O5	1.709 (5)
Mn1—O2^i	2.108 (5)	As1—O3	1.710 (4)
Mn1—O1^v	2.179 (4)	As2—O7	1.669 (5)
Mn1—O1^vii	2.200 (5)	As2—O2	1.677 (5)
Mn1—O3	2.202 (5)	As2—O8	1.677 (4)
Mn1—O5	2.491 (5)	As2—O4	1.698 (5)
Mn1—Mn1^vi	3.185 (2)
O2^i—Ba1—O7^ii	133.63 (15)	O8^viii—Mn2—O5^ix	94.05 (18)
O2^i—Ba1—O6^iii	74.41 (15)	O4—Mn2—O5^ix	79.10 (17)
O7^ii—Ba1—O6^iii	90.91 (15)	O5^vii—Mn2—O5^ix	81.45 (17)
O2^i—Ba1—O7	127.00 (15)	O3—Mn2—O5^ix	173.25 (17)
O7^ii—Ba1—O7	71.27 (16)	O7—Mn2—O5^ix	94.82 (16)
O6^iii—Ba1—O7	158.19 (14)	O6—As1—O1	111.1 (2)
O2^i—Ba1—O8^iv	144.78 (15)	O6—As1—O5	114.6 (2)
O7^ii—Ba1—O8^iv	69.26 (14)	O1—As1—O5	110.1 (2)
O6^iii—Ba1—O8^iv	79.72 (15)	O6—As1—O3	109.1 (2)
O7—Ba1—O8^iv	82.17 (15)	O1—As1—O3	109.0 (2)
O2^i—Ba1—O6^v	67.93 (15)	O5—As1—O3	102.5 (2)
O7^ii—Ba1—O6^v	152.74 (15)	O7—As2—O2	111.2 (2)
O6^iii—Ba1—O6^v	78.74 (16)	O7—As2—O8	114.4 (3)
O7—Ba1—O6^v	111.37 (14)	O2—As2—O8	109.7 (2)
O8^iv—Ba1—O6^v	84.02 (14)	O7—As2—O4	99.8 (2)
O2^i—Ba1—O3	63.79 (14)	O2—As2—O4	109.1 (2)
O7^ii—Ba1—O3	94.34 (15)	O8—As2—O4	112.2 (2)
O6^iii—Ba1—O3	126.26 (14)	As1—O1—Mn1^viii	121.9 (2)
O7—Ba1—O3	69.23 (14)	As1—O1—Mn1^vii	125.5 (2)
O8^iv—Ba1—O3	150.59 (13)	Mn1^viii—O1—Mn1^vii	93.34 (18)
O6^v—Ba1—O3	112.17 (13)	As1—O1—Ba1^viii	93.03 (18)
O2^i—Ba1—O1^v	58.18 (14)	Mn1^viii—O1—Ba1^viii	85.45 (14)
O7^ii—Ba1—O1^v	146.18 (14)	Mn1^vii—O1—Ba1^viii	133.22 (19)
O6^iii—Ba1—O1^v	121.73 (13)	As2—O2—Mn1^ix	117.6 (2)
O7—Ba1—O1^v	78.33 (13)	As2—O2—Ba1^ix	141.9 (3)
O8^iv—Ba1—O1^v	121.31 (13)	Mn1^ix—O2—Ba1^ix	100.46 (18)
O6^v—Ba1—O1^v	54.34 (13)	As1—O3—Mn2	127.5 (2)
O3—Ba1—O1^v	60.47 (12)	As1—O3—Mn1	98.5 (2)
O4^vi—Mn1—O2^i	102.96 (19)	Mn2—O3—Mn1	127.0 (2)
O4^vi—Mn1—O1^v	99.75 (17)	As1—O3—Ba1	104.3 (2)
O2^i—Mn1—O1^v	82.98 (19)	Mn2—O3—Ba1	101.98 (16)
O4^vi—Mn1—O1^vii	84.93 (19)	Mn1—O3—Ba1	88.38 (16)
O2^i—Mn1—O1^vii	167.89 (17)	As2—O4—Mn1^vi	127.8 (3)
O1^v—Mn1—O1^vii	86.66 (18)	As2—O4—Mn2	99.8 (2)
O4^vi—Mn1—O3	166.2 (2)	Mn1^vi—O4—Mn2	121.3 (2)
O2^i—Mn1—O3	88.15 (19)	As1—O5—Mn2^vii	122.2 (3)
O1^v—Mn1—O3	89.68 (17)	As1—O5—Mn1	88.39 (19)
O1^vii—Mn1—O3	85.54 (18)	Mn2^vii—O5—Mn1	97.19 (19)
O4^vi—Mn1—O5	104.50 (16)	As1—O5—Mn2^i	129.8 (3)
O2^i—Mn1—O5	79.89 (17)	Mn2^vii—O5—Mn2^i	98.55 (17)
O1^v—Mn1—O5	152.85 (16)	Mn1—O5—Mn2^i	116.29 (18)
O1^vii—Mn1—O5	107.30 (17)	As1—O6—Ba1^iii	137.3 (3)
O3—Mn1—O5	68.96 (16)	As1—O6—Ba1^viii	101.6 (2)
O8^viii—Mn2—O4	150.46 (18)	Ba1^iii—O6—Ba1^viii	101.26 (16)
O8^viii—Mn2—O5^vii	116.23 (18)	As2—O7—Mn2	87.0 (2)
O4—Mn2—O5^vii	91.36 (18)	As2—O7—Ba1^ii	132.7 (2)
O8^viii—Mn2—O3	92.31 (19)	Mn2—O7—Ba1^ii	96.77 (16)
O4—Mn2—O3	96.40 (18)	As2—O7—Ba1	116.9 (2)
O5^vii—Mn2—O3	93.72 (19)	Mn2—O7—Ba1	100.85 (16)
O8^viii—Mn2—O7	85.61 (17)	Ba1^ii—O7—Ba1	108.73 (16)
O4—Mn2—O7	66.64 (17)	As2—O8—Mn2^v	127.9 (3)
O5^vii—Mn2—O7	157.97 (16)	As2—O8—Ba1^iv	116.1 (2)
O3—Mn2—O7	87.90 (17)	Mn2^v—O8—Ba1^iv	102.60 (17)

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