Synthesis, crystal structure and charge-distribution validation of β-Na₄Cu(MoO₄)₃ adopting the alluadite structure-type

A new variety of tetra­sodium copper(II) tris­[molybdate(VI)] is characterized by the presence of infinite layers of composition (Cu1/Na1)₂Mo₃O₁₄ parallel to the (100) plane, which are linked by MoO₄ tetra­hedra, forming a three-dimensional framework containing two types of hexa­gonal tunnels in which Na⁺ cations reside.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](Mo-O) = 0.003 Å
• Disorder in main residue
• R factor = 0.023
• wR factor = 0.058
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF019_ALERT_1_A  _diffrn_standards_number is missing
            Number of standards used in measurement.
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.
DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Alert level C
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O6 Check

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       5.22 Why ?
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          2 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  O6      ..        6.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo1    --  O2_a    ..        6.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  O3      ..        7.4 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mo2    --  O3_c    ..        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O2      ..       23.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O6      ..       22.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O5_e    ..        6.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O6_f    ..       10.6 s.u.
PLAT300_ALERT_4_G Atom Site Occupancy of *Mo2    is Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *Cu1    is Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *Na1    is Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O4     is Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O41    is Constrained at        0.5 Check
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         26 Note

   3 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

   6 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
   1 ALERT type 3 Indicator that the structure quality may be low
   7 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 (Duisenberg, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Tetrasodium copper(II) tris[molybdate(VI)]

Crystal data

Na4Cu(MoO4)3	F(000) = 1180
Mr = 635.32	Dx = 3.692 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.5318 (9) Å	Cell parameters from 25 reflections
b = 13.8181 (9) Å	θ = 10–15°
c = 7.1159 (7) Å	µ = 5.26 mm^−1
β = 111.95 (2)°	T = 298 K
V = 1142.9 (2) Å^3	Prism, green
Z = 4	0.28 × 0.22 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1208 reflections with I > 2σ(I)
ω/2θ scans	Rint = 0.030
Absorption correction: ψ scan (North et al., 1968)	θmax = 27.0°, θmin = 2.3°
Tmin = 0.224, Tmax = 0.387	h = −15→15
2678 measured reflections	k = −1→17
1238 independent reflections	l = −9→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0173P)^2 + 5.2182P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.023	(Δ/σ)max = 0.001
wR(F^2) = 0.058	Δρmax = 0.80 e Å^−3
S = 1.17	Δρmin = −0.72 e Å^−3
1238 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
104 parameters	Extinction coefficient: 0.00081 (11)

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)
Mo1	0.72812 (2)	0.10879 (2)	0.11920 (4)	0.01991 (12)
Mo2	0.48085 (7)	0.28610 (4)	0.2400 (3)	0.0133 (3)	0.5
Cu1	0.70643 (5)	0.16100 (5)	0.61691 (9)	0.01741 (16)	0.5
Na1	0.70643 (5)	0.16100 (5)	0.61691 (9)	0.01741 (16)	0.5
Na2	0.5000	0.0169 (3)	0.2500	0.0482 (8)
Na3	0.0000	0.0000	0.0000	0.0299 (5)
Na4	0.5000	0.26934 (16)	0.7500	0.0219 (4)
O1	0.8745 (2)	0.0849 (2)	0.1859 (4)	0.0292 (6)
O2	0.6715 (2)	0.1702 (2)	0.8852 (4)	0.0337 (6)
O3	0.5390 (2)	0.2147 (2)	0.4714 (4)	0.0247 (6)
O4	0.3657 (5)	0.3629 (6)	0.2376 (11)	0.0239 (10)	0.5
O41	0.4153 (5)	0.3707 (6)	0.2551 (11)	0.0239 (10)	0.5
O5	0.6504 (3)	−0.0001 (2)	0.0904 (5)	0.0346 (7)
O6	0.7095 (3)	0.1754 (2)	0.3178 (5)	0.0373 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01593 (17)	0.02069 (18)	0.01973 (18)	0.00034 (10)	0.00275 (11)	−0.00104 (11)
Mo2	0.0147 (8)	0.0162 (2)	0.0079 (4)	0.0004 (2)	0.0032 (6)	0.0000 (3)
Cu1	0.0227 (3)	0.0219 (3)	0.0093 (3)	−0.0007 (3)	0.0079 (2)	0.0006 (2)
Na1	0.0227 (3)	0.0219 (3)	0.0093 (3)	−0.0007 (3)	0.0079 (2)	0.0006 (2)
Na2	0.0217 (11)	0.098 (3)	0.0203 (11)	0.000	0.0031 (9)	0.000
Na3	0.0397 (12)	0.0224 (10)	0.0179 (9)	−0.0013 (10)	−0.0004 (9)	−0.0006 (9)
Na4	0.0225 (9)	0.0270 (11)	0.0189 (9)	0.000	0.0110 (7)	0.000
O1	0.0187 (12)	0.0341 (15)	0.0307 (14)	0.0037 (11)	0.0044 (10)	0.0072 (12)
O2	0.0268 (14)	0.0330 (16)	0.0327 (15)	0.0083 (12)	0.0011 (12)	0.0017 (13)
O3	0.0275 (13)	0.0335 (15)	0.0160 (12)	−0.0003 (12)	0.0113 (10)	0.0011 (11)
O4	0.017 (3)	0.0250 (18)	0.0238 (18)	0.005 (3)	0.001 (3)	−0.0039 (16)
O41	0.017 (3)	0.0250 (18)	0.0238 (18)	0.005 (3)	0.001 (3)	−0.0039 (16)
O5	0.0357 (15)	0.0279 (14)	0.0410 (17)	−0.0059 (13)	0.0152 (13)	0.0005 (13)
O6	0.0305 (14)	0.0398 (17)	0.0385 (17)	0.0010 (14)	0.0095 (13)	−0.0084 (14)

Geometric parameters (Å, º)

Mo1—O1	1.746 (3)	Na2—O5^iv	2.462 (3)
Mo1—O5	1.762 (3)	Na2—O5	2.549 (3)
Mo1—O2^i	1.764 (3)	Na2—O5^ii	2.549 (3)
Mo1—O6	1.774 (3)	Na3—O41^vii	2.443 (7)
Mo2—Mo2^ii	0.447 (2)	Na3—O41^viii	2.443 (7)
Mo2—O41	1.456 (7)	Na3—O1^ix	2.493 (3)
Mo2—O3^ii	1.738 (3)	Na3—O1^ii	2.493 (3)
Mo2—O41^ii	1.740 (7)	Na3—O1^vi	2.675 (3)
Mo2—O4	1.787 (7)	Na3—O1^x	2.675 (3)
Mo2—O3	1.822 (3)	Na3—O4^vii	2.749 (7)
Mo2—O4^ii	2.150 (6)	Na3—O4^viii	2.749 (7)
Cu1—O4^iii	1.884 (6)	Na3—O41^xi	3.008 (7)
Cu1—O3	2.098 (3)	Na3—O41^xii	3.008 (7)
Cu1—O2	2.116 (3)	Na4—O3	2.337 (2)
Cu1—O6	2.152 (3)	Na4—O3^xiii	2.337 (2)
Cu1—O5^iv	2.317 (3)	Na4—O2	2.424 (3)
Cu1—O6^v	2.464 (4)	Na4—O2^xiii	2.424 (3)
Cu1—O41^iii	2.467 (4)	Na4—O1^v	2.490 (4)
Na2—O5^vi	2.462 (3)	Na4—O1^xiv	2.490 (4)
O1—Mo1—O5	110.42 (15)	O3—Cu1—O2	85.28 (10)
O1—Mo1—O2^i	111.01 (14)	O4^iii—Cu1—O6	93.4 (2)
O5—Mo1—O2^i	106.95 (15)	O3—Cu1—O6	82.16 (11)
O1—Mo1—O6	108.63 (14)	O2—Cu1—O6	166.61 (12)
O5—Mo1—O6	107.69 (15)	O4^iii—Cu1—O5^iv	96.1 (2)
O2^i—Mo1—O6	112.08 (15)	O3—Cu1—O5^iv	94.73 (11)
O3^ii—Mo2—O4	118.4 (2)	O2—Cu1—O5^iv	88.43 (12)
O3^ii—Mo2—O3	110.75 (17)	O6—Cu1—O5^iv	97.18 (12)
O4—Mo2—O3	112.3 (3)	O6^v—Cu1—O2	89.55 (14)
O3^ii—Mo2—O4^ii	100.3 (2)	O6^v—Cu1—O4^iii	76.78 (15)
O4—Mo2—O4^ii	113.9 (4)	O6^v—Cu1—O5^iv	172.13 (15)
O3—Mo2—O4^ii	99.0 (2)	O6^v—Cu1—O6	86.42 (14)
O4^iii—Cu1—O3	168.8 (2)	O6^v—Cu1—O3	92.66 (12)
O4^iii—Cu1—O2	98.1 (2)

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