Modulated crystal structure of InMo₄O₆

The (3 + 1)-dimensional modulated crystal structure of the metal-rich cluster compound InMo₄O₆ was solved and refined from single-crystal data in the superspace group P4/mbm(00γ)00ss [q = 0, 0, 0.1536 (4); a = 9.6664 (9), c = 2.8645 (3) Å; R1(all) = 0.046, wR(all) = 0.076]. The crystal structure is closely related to the NaMo₄O₆ structure type. It is built from rods of Mo₆ clusters condensed via trans edges. These form channels parallel to [001], in which In₆ and In₇ oligomers alternate. Weak diffuse planes parallel to (001)* interconnect the satellite reflections; they occur due to two-dimensional rod disorder of the In oligomer chains.

Computing details

Data collection: IPDS Software package (Stoe, 2002); cell refinement: IPDS Software package (Stoe, 2002); data reduction: X-AREA (Stoe, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: JANA2006 (Petricek, Dusek & Palatinus, 2006); molecular graphics: Diamond 3.1.

indium tetramolybdenum hexoxide

Crystal data

InMo4O6	Dx = 7.38 Mg m^−3
Mr = 594.55	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, P4/mbm(00γ)00ss†	Cell parameters from 15099 reflections
q = 0.153600c*	θ = 4.2–34.1°
a = 9.6664 (9) Å	µ = 13.32 mm^−1
c = 2.8645 (3) Å	T = 293 K
V = 267.66 (6) Å^3	Black needle, black
Z = 2	0.30 × 0.07 × 0.05 mm
F(000) = 530

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, −x₂, x₃, x₄; (3) −x₂, x₁, x₃, x₄; (4) x₂, −x₁, x₃, x₄; (5) −x₁+1/2, x₂+1/2, −x₃, −x₄+1/2; (6) x₁+1/2, −x₂+1/2, −x₃, −x₄+1/2; (7) x₂+1/2, x₁+1/2, −x₃, −x₄+1/2; (8) −x₂+1/2, −x₁+1/2, −x₃, −x₄+1/2; (9) −x₁, −x₂, −x₃, −x₄; (10) x₁, x₂, −x₃, −x₄; (11) x₂, −x₁, −x₃, −x₄; (12) −x₂, x₁, −x₃, −x₄; (13) x₁+1/2, −x₂+1/2, x₃, x₄+1/2; (14) −x₁+1/2, x₂+1/2, x₃, x₄+1/2; (15) −x₂+1/2, −x₁+1/2, x₃, x₄+1/2; (16) x₂+1/2, x₁+1/2, x₃, x₄+1/2.

Data collection

Stoe IPDS-II diffractometer	800 independent reflections
Radiation source: X-ray tube	686 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.044
oscillation scans	θmax = 33.4°, θmin = 3.7°
Absorption correction: numerical Jana2006 (Petricek, Dusek & Palatinus, 2000)	h = −13→14
Tmin = 0.287, Tmax = 0.532	k = −14→14
14543 measured reflections	l = −3→4

Refinement

Refinement on F	0 restraints
R[F > 3σ(F)] = 0.039	0 constraints
wR(F) = 0.076	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.000225F^2)
S = 3.66	(Δ/σ)max = 0.001
800 reflections	Δρmax = 2.77 e Å^−3
30 parameters	Δρmin = −2.65 e Å^−3

Special details

Refinement. The following entries contain R values for all reflection, the table in this comment specifies them for individual classes of reflections.

————————————————————————– |R factors : [800=686+114/30], Damping factor: 1.0000 | |GOF(obs)= 3.85 GOF(all)= 3.66 | |R(obs)= 3.89 wR(obs)= 7.39 R(all)= 4.56 wR(all)= 7.60 | |R factors for main reflections : [312=312+0] | |R(obs)= 2.52 wR(obs)= 5.44 R(all)= 2.52 wR(all)= 5.44 | |R factors for satellites of order 1 : [488=374+114] | |R(obs)= 9.43 wR(obs)= 10.48 R(all)= 12.35 wR(all)= 10.95 | |Last wR(all): 7.60 7.60 | |Maximum change/s.u. : 0.0005 for x[Mo2] | ————————————————————————–

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

	x	y	z	Uiso*/Ueq
In1	0	0	0	0.0146 (3)
Mo1	0.60152 (4)	0.10152 (4)	0	0.00569 (17)
Mo2	0.35697 (4)	0.14303 (4)	0.5	0.00926 (18)
O1	0.4558 (4)	0.2579 (4)	0	0.0089 (7)
O2	0.7059 (3)	0.2059 (3)	0.5	0.0066 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
In1	0.0159 (3)	0.0159 (3)	0.0119 (8)	0	0	0
Mo1	0.0060 (3)	0.0060 (3)	0.0051 (3)	−0.00044 (14)	0	0
Mo2	0.0052 (3)	0.0052 (3)	0.0173 (4)	−0.00049 (14)	0	0
O1	0.0124 (13)	0.0085 (13)	0.0057 (11)	0.0040 (12)	0	0
O2	0.0081 (11)	0.0081 (11)	0.0036 (16)	−0.0063 (16)	0	0

Geometric parameters (Å, º)

Mo1—O2	2.025 (7)	Mo2—Mo1^iv	2.7941 (11)
Mo1—O2^i	2.025 (7)	Mo2—Mo1^iii	2.7941 (11)
Mo1—O1^ii	2.064 (8)	Mo2—Mo1^v	2.7941 (11)
Mo1—O1	2.064 (8)	Mo2—Mo2^i	2.8645 (3)
Mo1—Mo1^iii	2.777 (2)	Mo2—Mo2^v	2.8645 (3)
Mo1—Mo2	2.7941 (11)	In1—O1^vi	2.379 (8)
Mo1—Mo2^iv	2.7942 (11)	In1—O1^ix	2.379 (8)
Mo1—Mo2^iii	2.7942 (11)	In1—O1^x	2.379 (8)
Mo1—Mo2^i	2.7942 (11)	In1—O1^xi	2.379 (8)
Mo1—Mo1^v	2.8645 (3)	In1—In1^v	2.8645 (3)
Mo1—Mo1^i	2.8645 (3)	In1—In1^i	2.8645 (3)
Mo2—O1	2.049 (6)	O1—Mo2^i	2.049 (6)
Mo2—O1^vi	2.049 (6)	O1—In1^xii	2.379 (8)
Mo2—O1^vii	2.049 (6)	O2—Mo1^v	2.025 (7)
Mo2—O1^v	2.049 (6)	O2—Mo2^xiii	2.059 (10)
Mo2—O2^viii	2.059 (10)
O2—Mo1—O2^i	90.0 (4)	O1^vii—Mo2—Mo1^iv	92.3 (2)
O2—Mo1—O1^ii	88.55 (17)	O1^v—Mo2—Mo1^iv	91.85 (19)
O2^i—Mo1—O1^ii	88.55 (17)	O2^viii—Mo2—Mo1^iv	134.45 (2)
O2—Mo1—O1	88.55 (17)	O1—Mo2—Mo1^iii	91.85 (19)
O2^i—Mo1—O1	88.55 (17)	O1^vi—Mo2—Mo1^iii	92.3 (2)
O1^ii—Mo1—O1	175.9 (5)	O1^vii—Mo2—Mo1^iii	47.4 (2)
O2—Mo1—Mo1^iii	135.0 (2)	O1^v—Mo2—Mo1^iii	138.5 (2)
O2^i—Mo1—Mo1^iii	135.0 (2)	O2^viii—Mo2—Mo1^iii	134.45 (2)
O1^ii—Mo1—Mo1^iii	92.0 (2)	Mo1^iv—Mo2—Mo1^iii	61.67 (3)
O1—Mo1—Mo1^iii	92.0 (2)	O1—Mo2—Mo1^v	92.3 (2)
O2—Mo1—Mo2	89.35 (15)	O1^vi—Mo2—Mo1^v	91.85 (19)
O2^i—Mo1—Mo2	135.55 (2)	O1^vii—Mo2—Mo1^v	138.5 (2)
O1^ii—Mo1—Mo2	135.85 (17)	O1^v—Mo2—Mo1^v	47.4 (2)
O1—Mo1—Mo2	47.00 (17)	O2^viii—Mo2—Mo1^v	134.45 (2)
Mo1^iii—Mo1—Mo2	60.21 (2)	Mo1^iv—Mo2—Mo1^v	59.59 (5)
O2—Mo1—Mo2^iv	89.35 (15)	Mo1^iii—Mo2—Mo1^v	91.10 (4)
O2^i—Mo1—Mo2^iv	135.55 (2)	O1—Mo2—Mo1	47.4 (2)
O1^ii—Mo1—Mo2^iv	47.00 (17)	O1^vi—Mo2—Mo1	138.5 (2)
O1—Mo1—Mo2^iv	135.85 (17)	O1^vii—Mo2—Mo1	91.85 (19)
Mo1^iii—Mo1—Mo2^iv	60.21 (2)	O1^v—Mo2—Mo1	92.3 (2)
Mo2—Mo1—Mo2^iv	88.90 (4)	O2^viii—Mo2—Mo1	134.45 (2)
O2—Mo1—Mo2^iii	135.55 (2)	Mo1^iv—Mo2—Mo1	91.10 (4)
O2^i—Mo1—Mo2^iii	89.35 (15)	Mo1^iii—Mo2—Mo1	59.59 (5)
O1^ii—Mo1—Mo2^iii	47.00 (17)	Mo1^v—Mo2—Mo1	61.67 (3)
O1—Mo1—Mo2^iii	135.85 (17)	O1—Mo2—Mo2^i	45.67 (17)
Mo1^iii—Mo1—Mo2^iii	60.21 (2)	O1^vi—Mo2—Mo2^i	134.33 (17)
Mo2—Mo1—Mo2^iii	120.41 (5)	O1^vii—Mo2—Mo2^i	45.67 (17)
Mo2^iv—Mo1—Mo2^iii	61.67 (3)	O1^v—Mo2—Mo2^i	134.33 (17)
O2—Mo1—Mo2^i	135.55 (2)	O2^viii—Mo2—Mo2^i	90.0
O2^i—Mo1—Mo2^i	89.35 (15)	Mo1^iv—Mo2—Mo2^i	120.837 (13)
O1^ii—Mo1—Mo2^i	135.86 (17)	Mo1^iii—Mo2—Mo2^i	59.164 (13)
O1—Mo1—Mo2^i	47.00 (17)	Mo1^v—Mo2—Mo2^i	120.837 (13)
Mo1^iii—Mo1—Mo2^i	60.21 (2)	Mo1—Mo2—Mo2^i	59.164 (13)
Mo2—Mo1—Mo2^i	61.67 (3)	O1—Mo2—Mo2^v	134.33 (17)
Mo2^iv—Mo1—Mo2^i	120.41 (5)	O1^vi—Mo2—Mo2^v	45.67 (17)
Mo2^iii—Mo1—Mo2^i	88.90 (4)	O1^vii—Mo2—Mo2^v	134.33 (17)
O2—Mo1—Mo1^v	45.0 (2)	O1^v—Mo2—Mo2^v	45.67 (17)
O2^i—Mo1—Mo1^v	135.0 (2)	O2^viii—Mo2—Mo2^v	90.0
O1^ii—Mo1—Mo1^v	90.0	Mo1^iv—Mo2—Mo2^v	59.164 (13)
O1—Mo1—Mo1^v	90.0	Mo1^iii—Mo2—Mo2^v	120.837 (14)
Mo1^iii—Mo1—Mo1^v	90.0	Mo1^v—Mo2—Mo2^v	59.164 (13)
Mo2—Mo1—Mo1^v	59.163 (13)	Mo1—Mo2—Mo2^v	120.837 (13)
Mo2^iv—Mo1—Mo1^v	59.163 (13)	Mo2^i—Mo2—Mo2^v	180.0
Mo2^iii—Mo1—Mo1^v	120.836 (13)	O1^vi—In1—O1^ix	180.0
Mo2^i—Mo1—Mo1^v	120.836 (13)	O1^vi—In1—O1^x	90.0
O2—Mo1—Mo1^i	135.0 (2)	O1^ix—In1—O1^x	90.0
O2^i—Mo1—Mo1^i	45.0 (2)	O1^vi—In1—O1^xi	90.0
O1^ii—Mo1—Mo1^i	90.0	O1^ix—In1—O1^xi	90.000 (1)
O1—Mo1—Mo1^i	90.0	O1^x—In1—O1^xi	180.0 (4)
Mo1^iii—Mo1—Mo1^i	90.0	O1^vi—In1—In1^v	90.0
Mo2—Mo1—Mo1^i	120.836 (13)	O1^ix—In1—In1^v	90.0
Mo2^iv—Mo1—Mo1^i	120.836 (13)	O1^x—In1—In1^v	90.0
Mo2^iii—Mo1—Mo1^i	59.163 (13)	O1^xi—In1—In1^v	90.0
Mo2^i—Mo1—Mo1^i	59.163 (14)	O1^vi—In1—In1^i	90.0
Mo1^v—Mo1—Mo1^i	180.0	O1^ix—In1—In1^i	90.0
O1—Mo2—O1^vi	174.1 (4)	O1^x—In1—In1^i	90.0
O1—Mo2—O1^vii	91.0 (3)	O1^xi—In1—In1^i	90.0
O1^vi—Mo2—O1^vii	88.7 (3)	In1^v—In1—In1^i	180.0
O1—Mo2—O1^v	88.7 (3)	Mo2^i—O1—Mo2	88.7 (3)
O1^vi—Mo2—O1^v	91.0 (3)	Mo2^i—O1—Mo1	85.6 (3)
O1^vii—Mo2—O1^v	174.1 (4)	Mo2—O1—Mo1	85.6 (3)
O1—Mo2—O2^viii	87.0 (2)	Mo2^i—O1—In1^xii	128.0 (2)
O1^vi—Mo2—O2^viii	87.0 (2)	Mo2—O1—In1^xii	128.0 (2)
O1^vii—Mo2—O2^viii	87.0 (2)	Mo1—O1—In1^xii	126.8 (4)
O1^v—Mo2—O2^viii	87.0 (2)	Mo1—O2—Mo1^v	90.0 (4)
O1—Mo2—Mo1^iv	138.5 (2)	Mo1—O2—Mo2^xiii	135.0 (2)
O1^vi—Mo2—Mo1^iv	47.4 (2)	Mo1^v—O2—Mo2^xiii	135.0 (2)

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