Dihydro-nium tetra-chromate(VI), (H(3)O)(2)Cr(4)O(13).

The crystal structure of (H(3)O)(2)Cr(4)O(13) is isotypic with K(2)Cr(4)O(13). The finite tetra-chromate anion in the title structure consists of four vertex-sharing CrO(4) tetra-hedra and exhibits a typical zigzag arrangement. The crystal packing is stabilized by hydrogen bonds between these anions and hydro-nium cations. The two different hydro-nium cations are surrounded by nine O atoms of tetra-chromate anions, with O⋯O distances ranging between 2.866 (8) and 3.282 (7) Å.

Related literature

The title chromate is isotypic with its potassium analogue (Casari & Langer, 2005 ▶). Löfgren (1973 ▶) and Kolitsch (2004 ▶) determined the structures of the corresponding Rb and Cs salts, respectively. For industrial applications of tetra­chromates, see: Cainelli & Cardillo (1984 ▶); Çengeloğlu et al. (2003 ▶). For related bond-length data, see: Casari et al. (2007 ▶). For cell parameters of further isolated compounds stated in the experimental procedure, see: Durif & Averbuch-Pouchot (1978 ▶) and Rahman et al. (2003 ▶).

Experimental

Crystal data

(H3O)2Cr4O13

M = 454.05

Monoclinic,

a = 8.9765 (13) Å

b = 7.6431 (8) Å

c = 9.3451 (14) Å

β = 91.888 (18)°

V = 640.80 (15) Å3

Z = 2

Mo Kα radiation

μ = 3.37 mm−1

T = 293 K

1.0 × 0.4 × 0.2 mm

Data collection

Stoe IPDS I diffractometer

Absorption correction: numerical [X-RED (Stoe & Cie, 2001 ▶) and X-SHAPE (Stoe & Cie, 1999 ▶)] T min = 0.121, T max = 0.314

5900 measured reflections

2696 independent reflections

2497 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.110

S = 1.06

2696 reflections

174 parameters

2 restraints

Δρmax = 0.69 e Å−3

Δρmin = −0.58 e Å−3

Absolute structure: Flack (1983 ▶), 1212 Friedel pairs

Flack parameter: 0.53 (4)

Data collection: IPDS (Stoe & Cie, 1997 ▶); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2012 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813001608/wm2714sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813001608/wm2714Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(H3O)2Cr4O13	F(000) = 444
Mr = 454.05	Dx = 2.353 Mg m−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 1754 reflections
a = 8.9765 (13) Å	θ = 1.9–28.2°
b = 7.6431 (8) Å	µ = 3.37 mm−1
c = 9.3451 (14) Å	T = 293 K
β = 91.888 (18)°	Block, orange-red
V = 640.80 (15) Å3	1.0 × 0.4 × 0.2 mm
Z = 2

Stoe IPDS I diffractometer	2696 independent reflections
Radiation source: fine-focus sealed tube	2497 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ scans	θmax = 28.1°, θmin = 2.3°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −11→11
Tmin = 0.121, Tmax = 0.314	k = −9→9
5900 measured reflections	l = −12→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0842P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.040	(Δ/σ)max < 0.001
wR(F2) = 0.110	Δρmax = 0.69 e Å−3
S = 1.06	Δρmin = −0.58 e Å−3
2696 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
174 parameters	Extinction coefficient: 0.083 (5)
2 restraints	Absolute structure: Flack (1983), 1212 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.53 (4)

Experimental. A suitable single-crystal was carefully selected under a microscope and mounted in a glass capillary. The scattering intensities were collected on an imaging plate diffractometer (IPDS I, Stoe & Cie) equipped with a fine focus sealed tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 40 mA. Intensity data for the title compound were collected at room temperature by φ-scans in 100 frames (0 < φ < 200°, Δφ = 2°, exposure time of 7 min) in the 2 Θ range 3.8 to 56.3°. Structure solution and refinement were carried out using the programs SIR92 (Altomare et al., 1993) and SHELXL97 (Sheldrick, 1997) embedded into WinGX program package (Farrugia, 1999). A numerical absorption correction (X-RED (Stoe & Cie, 2001) was applied after optimization of the crystal shape (X-SHAPE (Stoe & Cie, 1999)). The last cycles of refinement included atomic positions and anisotropic parameters for all non-hydrogen atoms. Positions of hydrogen atoms were not determined. The final difference maps were free of any chemically significant features. The refinement was based on F2 for ALL reflections.

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Cr2	0.44108 (9)	1.10692 (11)	1.05710 (8)	0.0219 (2)
Cr1	0.12169 (8)	0.92974 (12)	1.17627 (8)	0.0242 (2)
Cr3	0.44219 (9)	1.44260 (12)	0.83187 (8)	0.0263 (2)
Cr4	0.78483 (9)	1.42919 (12)	0.79827 (9)	0.0283 (2)
O21	0.4560 (6)	0.9751 (8)	0.9295 (4)	0.0437 (12)
O31	0.4312 (7)	1.3165 (9)	0.7003 (5)	0.0542 (13)
O14	0.2882 (5)	1.0642 (5)	1.1542 (4)	0.0324 (9)
O33	0.6117 (5)	1.5476 (5)	0.8324 (4)	0.0296 (8)
O12	0.1024 (6)	0.7916 (8)	1.0473 (6)	0.0497 (12)
O22	0.5891 (5)	1.0957 (7)	1.1545 (4)	0.0401 (11)
O23	0.4224 (5)	1.3239 (6)	0.9907 (4)	0.0334 (9)
O43	0.9211 (5)	1.5638 (6)	0.8196 (5)	0.0360 (10)
O11	−0.0193 (5)	1.0612 (6)	1.1705 (5)	0.0395 (11)
O13	0.1342 (5)	0.8307 (8)	1.3278 (6)	0.0522 (14)
O42	0.7792 (7)	1.3587 (12)	0.6374 (7)	0.074 (2)
O32	0.3119 (5)	1.5822 (7)	0.8197 (6)	0.0477 (13)
O41	0.8015 (6)	1.2744 (8)	0.9121 (7)	0.0595 (16)
O1W	0.0967 (6)	0.4158 (8)	1.0652 (6)	0.0469 (12)
O2W	0.7959 (6)	0.9005 (7)	0.9169 (5)	0.0456 (12)

	U11	U22	U33	U12	U13	U23
Cr2	0.0205 (3)	0.0256 (4)	0.0197 (3)	−0.0006 (3)	0.0010 (2)	0.0020 (3)
Cr1	0.0221 (4)	0.0208 (5)	0.0296 (4)	−0.0019 (3)	0.0017 (3)	0.0052 (3)
Cr3	0.0235 (4)	0.0274 (5)	0.0278 (4)	−0.0021 (3)	0.0004 (3)	0.0068 (3)
Cr4	0.0255 (4)	0.0222 (5)	0.0374 (4)	−0.0005 (3)	0.0057 (3)	−0.0052 (3)
O21	0.047 (3)	0.060 (4)	0.0242 (18)	0.010 (2)	0.0025 (17)	−0.0114 (18)
O31	0.063 (3)	0.062 (4)	0.038 (2)	−0.024 (3)	0.0033 (19)	−0.008 (2)
O14	0.034 (2)	0.029 (3)	0.0349 (19)	−0.0062 (15)	0.0083 (16)	0.0006 (13)
O33	0.0289 (19)	0.024 (2)	0.036 (2)	−0.0003 (16)	0.0045 (15)	0.0024 (14)
O12	0.048 (3)	0.035 (3)	0.065 (3)	−0.003 (2)	−0.004 (2)	−0.017 (2)
O22	0.027 (2)	0.058 (3)	0.035 (2)	−0.0030 (18)	−0.0041 (16)	0.0082 (17)
O23	0.038 (2)	0.028 (2)	0.0344 (19)	−0.0032 (18)	0.0057 (15)	0.0107 (14)
O43	0.026 (2)	0.036 (3)	0.046 (2)	−0.0044 (15)	0.0092 (17)	0.0016 (16)
O11	0.030 (2)	0.040 (3)	0.049 (2)	0.0044 (16)	0.0039 (18)	0.0018 (17)
O13	0.038 (2)	0.061 (4)	0.057 (3)	−0.010 (2)	0.002 (2)	0.034 (3)
O42	0.059 (4)	0.092 (5)	0.071 (4)	0.006 (3)	0.007 (3)	−0.047 (4)
O32	0.029 (3)	0.057 (4)	0.057 (3)	0.006 (2)	−0.0039 (19)	0.022 (2)
O41	0.048 (3)	0.034 (3)	0.097 (4)	0.002 (2)	0.010 (3)	0.026 (3)
O1W	0.044 (3)	0.051 (3)	0.046 (2)	0.007 (2)	0.0014 (19)	−0.0030 (19)
O2W	0.043 (3)	0.049 (4)	0.044 (2)	0.009 (2)	−0.0039 (19)	0.0003 (19)

Cr2—O21	1.570 (4)	Cr3—O31	1.563 (6)
Cr2—O22	1.588 (4)	Cr3—O32	1.584 (5)
Cr2—O14	1.701 (4)	Cr3—O33	1.720 (5)
Cr2—O23	1.776 (4)	Cr3—O23	1.754 (4)
Cr1—O13	1.606 (4)	Cr4—O41	1.595 (5)
Cr1—O12	1.607 (5)	Cr4—O42	1.596 (6)
Cr1—O11	1.615 (5)	Cr4—O43	1.606 (5)
Cr1—O14	1.831 (4)	Cr4—O33	1.836 (5)
O21—Cr2—O22	108.1 (3)	O32—Cr3—O33	109.7 (3)
O21—Cr2—O14	111.9 (2)	O31—Cr3—O23	110.0 (3)
O22—Cr2—O14	111.0 (2)	O32—Cr3—O23	108.3 (2)
O21—Cr2—O23	110.1 (3)	O33—Cr3—O23	110.7 (2)
O22—Cr2—O23	108.5 (2)	O41—Cr4—O42	112.2 (4)
O14—Cr2—O23	107.3 (2)	O41—Cr4—O43	109.7 (3)
O13—Cr1—O12	110.7 (3)	O42—Cr4—O43	109.5 (4)
O13—Cr1—O11	110.8 (3)	O41—Cr4—O33	108.1 (2)
O12—Cr1—O11	108.6 (3)	O42—Cr4—O33	109.3 (3)
O13—Cr1—O14	109.3 (2)	O43—Cr4—O33	108.0 (2)
O12—Cr1—O14	110.6 (2)	Cr2—O14—Cr1	147.5 (3)
O11—Cr1—O14	106.8 (2)	Cr3—O33—Cr4	121.6 (2)
O31—Cr3—O32	109.3 (3)	Cr3—O23—Cr2	140.1 (3)
O31—Cr3—O33	108.9 (3)