Tris(morpholinium) hexa-μ3-hydroxido-hexa-μ2-oxido-dodeca­oxidohexa­molybdenum(VI)chromate(III) tetra­hydrate

Yang, Y.-Y.; Song, Y.; Liu, L.-Y.; Qu, X.-S.

doi:10.1107/S1600536811018149

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m776

doi:10.1107/S1600536811018149

Open

access

Tris(morpholinium) hexa-μ₃-hydroxido-hexa-μ₂-oxido-dodecaoxidohexamolybdenum(VI)chromate(III) tetrahydrate

Yan-Yan Yang,^a Yu Song,^b Li-Ye Liu ^a and Xiao-Shu Qu ^a ^*

^aDepartment of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, People's Republic of China, and ^bDepartment of Animal Science, Jilin Agricultural Science and Technology College, Jilin 132101, People's Republic of China
^*Correspondence e-mail: xiaoshuqu@yahoo.com.cn

(Received 3 May 2011; accepted 13 May 2011; online 20 May 2011)

In the title organic–inorganic hybrid compound, (C₄H₁₀NO)₃[H₆CrMo₆O₂₄]·4H₂O, the Anderson-type [H₆CrMo₆O₂₄]³⁻ polyoxoanion is centrosymmetric, with the Cr^III ion lying on an inversion center. One of the two crystallographiclly independent morpholinium cations is half-occupied. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the cations, polyoxoanions and uncoordinated water molecules.

Related literature

For general background to the properties and applications of polyoxometalates, see: Hill (1998 ). For related compounds with Anderson-type polyoxometalate anions and organic cations, see: An et al. (2004 ); Wang et al. (2010 ). For synthetic details, see: Perloff (1970 ).

Experimental

Crystal data

(C₄H₁₀NO)₃[H₆CrMo₆O₂₄]·4H₂O
M_r = 1354.14
Triclinic, $[P \overline 1]$
a = 7.9474 (4) Å
b = 9.9654 (5) Å
c = 13.7404 (7) Å
α = 110.392 (1)°
β = 102.921 (1)°
γ = 90.635 (1)°
V = 989.47 (9) Å³
Z = 1
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 296 K
0.53 × 0.50 × 0.44 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.324, T_max = 0.380
5458 measured reflections
3855 independent reflections
3562 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.082
S = 1.09
3855 reflections
297 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O6ⁱ	0.90	1.86	2.755 (4)	172
N1—H1B⋯O5	0.90	1.94	2.783 (4)	155
N2—H2C⋯O13ⁱⁱ	0.90	2.19	2.976 (8)	145
N2—H2D⋯O2Wⁱⁱⁱ	0.90	2.53	3.294 (9)	144
O1—H1⋯O1W^iv	0.84 (1)	1.87 (1)	2.709 (4)	173 (5)
O2—H2⋯O2Wⁱⁱⁱ	0.85 (1)	1.80 (1)	2.640 (4)	172 (4)
O3—H3⋯O9^v	0.84 (1)	2.02 (1)	2.853 (4)	171 (5)
O1W—H7⋯O8^vi	0.84 (1)	2.08 (3)	2.837 (4)	148 (5)
O1W—H8⋯O10^vi	0.85 (1)	2.01 (2)	2.807 (5)	157 (5)
O2W—H4⋯O7	0.85 (1)	2.03 (2)	2.851 (4)	165 (5)
O2W—H5⋯O1W^vii	0.85 (1)	2.00 (2)	2.801 (5)	157 (4)
Symmetry codes: (i) x+1, y, z; (ii) x-1, y-1, z-1; (iii) x-1, y, z; (iv) x-1, y, z-1; (v) -x+1, -y, -z; (vi) -x+1, -y+1, -z+1; (vii) x, y, z-1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018149/hy2428sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018149/hy2428Isup2.hkl

checkCIF report

Comment top

It is known that the compounds containing molybdenum atoms, especially containing polyoxometalates and organic molecules, are good catalysts for oxidation reactions, because they can be applied as models for the interactions between organic substrates and catalytic metal oxide surfaces in heterogeneous catalysis employing solid molybdenum oxides (Hill, 1998). Herein, we report the structure of the title compound containning Anderson-type [H₆CrMo₆O₂₄]^3- polyoxoanion, morpholinium cations and water molecules.

The title compound consists of one Anderson-type [H₆CrMo₆O₂₄]^3- polyoxoanion (An et al., 2004; Wang et al., 2010), three morpholinium cations and four uncoordinated water molecules. The [H₆CrMo₆O₂₄]^3- cluster with four different types of O atoms shows a classical B-type Anderson structure (Fig. 1), which made up of seven edge-sharing octahedra. Six [MoO₆] octahedra are arranged hexagonally around one central [Cr(OH)₆] octahedron. The Cr—O and Mo—O distances are normal. The molecules are linked into a three-dimensional network by a combination of intermolecular N—H···O and O—H···O hydrogen bonds (Table 1).

Related literature top

For general background to the properties and applications of polyoxometalates, see: Hill (1998). For related compounds with Anderson-type polyoxometalate anions and organic cations, see: An et al. (2004); Wang et al. (2010). For synthetic details, see: Perloff (1970).

Experimental top

The title compound was synthesized by mixing CrCl₃.6H₂O (0.266 g, 1 mmol), Na₂MoO₄.2H₂O (1.464 g, 6 mmol) and morpholine (1.80 g, 1.2 mmol) in H₂O (50 ml) and boiling the mixture (Perloff, 1970). The pH value of the solution was adjusted to 1.0 by addition of 1 M hydrochloric acid. The mixture was refluxed for 2 h, and then the solution was cooled to room temperature. After two days, pink block crystals were formed by evaporation of the filtrate at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. The morpholinium cation containing N2 is half-occupied. H atoms have been omitted for clarity. [Symmetry code: (i) -x, -y, -z.]

Tris(morpholinium) hexa-µ₃-hydroxido-hexa-µ₂-oxido- dodecaoxidohexamolybdenum(VI)chromate(III) tetrahydrate top

Crystal data top

(C₄H₁₀NO)₃[H₆CrMo₆O₂₄]·4H₂O	Z = 1
M_r = 1354.14	F(000) = 661
Triclinic, P1	D_x = 2.273 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9474 (4) Å	Cell parameters from 3855 reflections
b = 9.9654 (5) Å	θ = 2.8–26.1°
c = 13.7404 (7) Å	µ = 2.20 mm⁻¹
α = 110.392 (1)°	T = 296 K
β = 102.921 (1)°	Block, pink
γ = 90.635 (1)°	0.53 × 0.50 × 0.44 mm
V = 989.47 (9) Å³

Data collection top

Bruker APEX CCD diffractometer	3855 independent reflections
Radiation source: sealed tube	3562 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ϕ and ω scans	θ_max = 26.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.324, T_max = 0.380	k = −10→12
5458 measured reflections	l = −16→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0428P)² + 2.0824P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3855 reflections	Δρ_max = 1.18 e Å⁻³
297 parameters	Δρ_min = −0.55 e Å⁻³
10 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0147 (6)

Crystal data top

(C₄H₁₀NO)₃[H₆CrMo₆O₂₄]·4H₂O	γ = 90.635 (1)°
M_r = 1354.14	V = 989.47 (9) Å³
Triclinic, P1	Z = 1
a = 7.9474 (4) Å	Mo Kα radiation
b = 9.9654 (5) Å	µ = 2.20 mm⁻¹
c = 13.7404 (7) Å	T = 296 K
α = 110.392 (1)°	0.53 × 0.50 × 0.44 mm
β = 102.921 (1)°

Data collection top

Bruker APEX CCD diffractometer	3855 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3562 reflections with I > 2σ(I)
T_min = 0.324, T_max = 0.380	R_int = 0.014
5458 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	10 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.18 e Å⁻³
3855 reflections	Δρ_min = −0.55 e Å⁻³
297 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.0340 (3)	0.2032 (3)	0.0153 (2)	0.0204 (5)
O13	0.7910 (5)	0.7096 (3)	0.3943 (3)	0.0447 (8)
O2	−0.0919 (3)	−0.0753 (3)	−0.1564 (2)	0.0205 (5)
O1W	0.8003 (5)	0.3343 (3)	0.9120 (3)	0.0412 (7)
O3	0.2284 (3)	−0.0122 (3)	−0.0349 (2)	0.0198 (5)
O2W	0.6478 (4)	0.0583 (4)	−0.2236 (3)	0.0446 (8)
O4	0.1684 (3)	0.1183 (3)	−0.1629 (2)	0.0248 (6)
O5	0.3302 (3)	0.2637 (3)	0.1333 (2)	0.0243 (5)
O6	−0.0971 (3)	0.2717 (3)	0.2074 (2)	0.0252 (6)
O7	0.3543 (4)	−0.1184 (3)	−0.2346 (3)	0.0344 (7)
O8	0.2897 (4)	0.3888 (3)	−0.0229 (2)	0.0336 (7)
O9	0.5077 (4)	0.1801 (3)	−0.0249 (2)	0.0328 (6)
O10	0.1025 (4)	0.4800 (3)	0.1838 (3)	0.0393 (7)
O11	0.0268 (4)	−0.1150 (3)	−0.3466 (2)	0.0366 (7)
O12	0.2504 (4)	0.3553 (4)	0.3249 (2)	0.0416 (8)
N1	0.6350 (4)	0.4279 (3)	0.2668 (3)	0.0283 (7)
H1A	0.7251	0.3830	0.2453	0.034*
H1B	0.5404	0.3637	0.2389	0.034*
C1	0.6718 (7)	0.4811 (5)	0.3856 (4)	0.0393 (10)
H1C	0.6971	0.4019	0.4105	0.047*
H1D	0.5712	0.5222	0.4090	0.047*
C2	0.8249 (7)	0.5935 (5)	0.4315 (4)	0.0448 (11)
H2A	0.8490	0.6295	0.5090	0.054*
H2B	0.9264	0.5506	0.4106	0.054*
C3	0.7596 (7)	0.6595 (5)	0.2798 (4)	0.0411 (11)
H3A	0.8614	0.6180	0.2583	0.049*
H3B	0.7394	0.7402	0.2561	0.049*
C4	0.6052 (6)	0.5484 (5)	0.2269 (4)	0.0389 (10)
H4A	0.5012	0.5912	0.2435	0.047*
H4B	0.5895	0.5130	0.1499	0.047*
C5	−0.2731 (15)	0.2565 (11)	−0.3890 (8)	0.054 (3)	0.50
H5A	−0.3428	0.2530	−0.3402	0.064*	0.50
H5B	−0.1983	0.3460	−0.3567	0.064*	0.50
C6	−0.1584 (11)	0.1245 (9)	−0.4092 (8)	0.040 (2)	0.50
H6A	−0.0830	0.1297	−0.4547	0.048*	0.50
H6B	−0.0875	0.1239	−0.3421	0.048*	0.50
C7	−0.468 (2)	0.1422 (11)	−0.5420 (8)	0.080 (5)	0.50
H7A	−0.5141	0.1491	−0.6114	0.095*	0.50
H7B	−0.5667	0.1395	−0.5115	0.095*	0.50
C8	−0.4008 (15)	−0.0005 (11)	−0.5624 (8)	0.048 (2)	0.50
H8A	−0.3368	−0.0183	−0.6174	0.057*	0.50
H8B	−0.4971	−0.0746	−0.5883	0.057*	0.50
N2	−0.2850 (10)	−0.0078 (8)	−0.4633 (6)	0.0391 (17)	0.50
H2C	−0.2270	−0.0865	−0.4799	0.047*	0.50
H2D	−0.3490	−0.0146	−0.4185	0.047*	0.50
O14	−0.3839 (10)	0.2508 (8)	−0.4885 (6)	0.0518 (19)	0.50
H5	0.671 (5)	0.141 (2)	−0.174 (3)	0.059 (18)*
H4	0.563 (5)	0.015 (5)	−0.215 (4)	0.07 (2)*
H8	0.853 (7)	0.376 (5)	0.881 (4)	0.054 (17)*
H7	0.759 (8)	0.397 (4)	0.957 (4)	0.08 (2)*
H1	−0.035 (5)	0.242 (5)	−0.021 (4)	0.045 (15)*
H2	−0.173 (4)	−0.035 (4)	−0.183 (3)	0.031 (12)*
H3	0.308 (5)	−0.055 (5)	−0.010 (4)	0.039 (14)*
Cr1	0.0000	0.0000	0.0000	0.01611 (17)
Mo1	0.30066 (4)	0.22031 (3)	−0.01793 (2)	0.02057 (11)
Mo2	0.14776 (4)	−0.08727 (3)	−0.22125 (2)	0.02130 (11)
Mo3	0.13429 (4)	0.31724 (3)	0.19717 (3)	0.02276 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0201 (12)	0.0182 (12)	0.0251 (13)	0.0049 (10)	0.0060 (10)	0.0102 (11)
O13	0.065 (2)	0.0260 (15)	0.0362 (17)	−0.0043 (15)	0.0085 (16)	0.0054 (13)
O2	0.0194 (12)	0.0202 (12)	0.0214 (13)	0.0032 (10)	0.0029 (10)	0.0079 (10)
O1W	0.051 (2)	0.0317 (16)	0.049 (2)	0.0146 (15)	0.0166 (16)	0.0209 (16)
O3	0.0171 (12)	0.0195 (12)	0.0259 (13)	0.0052 (10)	0.0059 (10)	0.0114 (10)
O2W	0.0327 (17)	0.043 (2)	0.061 (2)	0.0049 (15)	0.0136 (16)	0.0219 (19)
O4	0.0311 (14)	0.0210 (13)	0.0245 (13)	0.0018 (11)	0.0070 (11)	0.0107 (11)
O5	0.0199 (12)	0.0282 (14)	0.0225 (13)	−0.0010 (10)	0.0049 (10)	0.0065 (11)
O6	0.0253 (13)	0.0177 (12)	0.0335 (14)	0.0020 (10)	0.0123 (11)	0.0071 (11)
O7	0.0316 (15)	0.0301 (15)	0.0453 (17)	0.0041 (12)	0.0194 (13)	0.0121 (13)
O8	0.0441 (17)	0.0230 (14)	0.0371 (16)	0.0033 (12)	0.0132 (14)	0.0127 (12)
O9	0.0245 (14)	0.0360 (16)	0.0393 (16)	0.0023 (12)	0.0114 (12)	0.0129 (13)
O10	0.0471 (19)	0.0217 (14)	0.054 (2)	0.0064 (13)	0.0241 (16)	0.0113 (14)
O11	0.0443 (18)	0.0374 (17)	0.0263 (15)	0.0009 (14)	0.0069 (13)	0.0104 (13)
O12	0.0386 (17)	0.052 (2)	0.0251 (15)	−0.0105 (15)	0.0043 (13)	0.0051 (14)
N1	0.0234 (16)	0.0205 (16)	0.0365 (18)	0.0029 (12)	0.0053 (14)	0.0060 (14)
C1	0.052 (3)	0.034 (2)	0.038 (2)	0.003 (2)	0.015 (2)	0.017 (2)
C2	0.059 (3)	0.039 (3)	0.029 (2)	−0.003 (2)	0.001 (2)	0.010 (2)
C3	0.057 (3)	0.030 (2)	0.038 (2)	0.000 (2)	0.011 (2)	0.0153 (19)
C4	0.040 (2)	0.035 (2)	0.038 (2)	0.0034 (19)	0.0001 (19)	0.014 (2)
C5	0.058 (7)	0.037 (5)	0.040 (5)	−0.007 (5)	−0.005 (5)	−0.008 (4)
C6	0.029 (4)	0.025 (4)	0.060 (6)	−0.010 (3)	−0.023 (4)	0.029 (4)
C7	0.123 (11)	0.030 (5)	0.030 (5)	0.040 (6)	−0.042 (6)	−0.020 (4)
C8	0.062 (7)	0.040 (5)	0.031 (5)	0.007 (5)	0.003 (4)	0.005 (4)
N2	0.045 (4)	0.030 (4)	0.042 (4)	0.009 (3)	0.011 (3)	0.011 (3)
O14	0.060 (4)	0.048 (4)	0.072 (5)	0.026 (4)	0.021 (4)	0.048 (4)
Cr1	0.0156 (4)	0.0152 (4)	0.0185 (4)	0.0027 (3)	0.0045 (3)	0.0070 (3)
Mo1	0.02050 (17)	0.01772 (17)	0.02474 (18)	0.00128 (12)	0.00787 (12)	0.00772 (13)
Mo2	0.02274 (18)	0.02019 (18)	0.02183 (18)	0.00160 (12)	0.00814 (12)	0.00695 (13)
Mo3	0.02303 (18)	0.01904 (18)	0.02415 (18)	−0.00106 (12)	0.00799 (13)	0.00396 (13)

Geometric parameters (Å, º) top

O1—Cr1	1.971 (2)	N1—H1B	0.9000
O1—Mo1	2.282 (2)	C1—C2	1.506 (7)
O1—Mo3	2.298 (3)	C1—H1C	0.9700
O1—H1	0.84 (1)	C1—H1D	0.9700
O13—C2	1.425 (6)	C2—H2A	0.9700
O13—C3	1.435 (5)	C2—H2B	0.9700
O2—Cr1	1.969 (2)	C3—C4	1.506 (6)
O2—Mo2	2.264 (3)	C3—H3A	0.9700
O2—Mo3ⁱ	2.280 (3)	C3—H3B	0.9700
O2—H2	0.85 (1)	C4—H4A	0.9700
O1W—H8	0.85 (1)	C4—H4B	0.9700
O1W—H7	0.84 (1)	C5—O14	1.432 (12)
O3—Cr1	1.973 (2)	C5—C6	1.589 (14)
O3—Mo1	2.300 (2)	C5—H5A	0.9700
O3—Mo2	2.334 (3)	C5—H5B	0.9700
O3—H3	0.84 (1)	C6—N2	1.502 (10)
O2W—H5	0.85 (1)	C6—H6A	0.9700
O2W—H4	0.85 (1)	C6—H6B	0.9700
O4—Mo2	1.912 (3)	C7—O14	1.171 (13)
O4—Mo1	1.932 (3)	C7—C8	1.481 (13)
O5—Mo1	1.927 (3)	C7—H7A	0.9700
O5—Mo3	1.944 (3)	C7—H7B	0.9700
O6—Mo3	1.936 (3)	C8—N2	1.489 (12)
O6—Mo2ⁱ	1.959 (3)	C8—H8A	0.9700
O7—Mo2	1.712 (3)	C8—H8B	0.9700
O8—Mo1	1.707 (3)	N2—H2C	0.9000
O9—Mo1	1.713 (3)	N2—H2D	0.9000
O10—Mo3	1.710 (3)	Cr1—O2ⁱ	1.969 (2)
O11—Mo2	1.700 (3)	Cr1—O1ⁱ	1.971 (2)
O12—Mo3	1.697 (3)	Cr1—O3ⁱ	1.973 (2)
N1—C4	1.486 (5)	Mo2—O6ⁱ	1.959 (3)
N1—C1	1.486 (5)	Mo3—O2ⁱ	2.280 (3)
N1—H1A	0.9000

Cr1—O1—Mo1	102.97 (10)	C7—C8—H8A	109.4
Cr1—O1—Mo3	102.58 (11)	N2—C8—H8A	109.4
Mo1—O1—Mo3	93.90 (9)	C7—C8—H8B	109.4
Cr1—O1—H1	123 (4)	N2—C8—H8B	109.4
Mo1—O1—H1	108 (4)	H8A—C8—H8B	108.0
Mo3—O1—H1	121 (4)	C8—N2—C6	109.9 (7)
C2—O13—C3	110.5 (3)	C8—N2—H2C	109.7
Cr1—O2—Mo2	103.98 (11)	C6—N2—H2C	109.7
Cr1—O2—Mo3ⁱ	103.28 (11)	C8—N2—H2D	109.7
Mo2—O2—Mo3ⁱ	94.50 (9)	C6—N2—H2D	109.7
Cr1—O2—H2	118 (3)	H2C—N2—H2D	108.2
Mo2—O2—H2	115 (3)	C7—O14—C5	117.2 (8)
Mo3ⁱ—O2—H2	118 (3)	O2—Cr1—O2ⁱ	180.00 (8)
H8—O1W—H7	109 (3)	O2—Cr1—O1	96.14 (11)
Cr1—O3—Mo1	102.31 (10)	O2ⁱ—Cr1—O1	83.86 (11)
Cr1—O3—Mo2	101.36 (10)	O2—Cr1—O1ⁱ	83.86 (11)
Mo1—O3—Mo2	91.99 (9)	O2ⁱ—Cr1—O1ⁱ	96.14 (11)
Cr1—O3—H3	123 (3)	O1—Cr1—O1ⁱ	180.0 (2)
Mo1—O3—H3	117 (3)	O2—Cr1—O3ⁱ	95.74 (11)
Mo2—O3—H3	115 (3)	O2ⁱ—Cr1—O3ⁱ	84.26 (11)
H5—O2W—H4	108 (2)	O1—Cr1—O3ⁱ	95.80 (10)
Mo2—O4—Mo1	120.21 (13)	O1ⁱ—Cr1—O3ⁱ	84.20 (10)
Mo1—O5—Mo3	119.65 (13)	O2—Cr1—O3	84.26 (11)
Mo3—O6—Mo2ⁱ	117.85 (13)	O2ⁱ—Cr1—O3	95.74 (11)
C4—N1—C1	110.9 (3)	O1—Cr1—O3	84.20 (10)
C4—N1—H1A	109.4	O1ⁱ—Cr1—O3	95.80 (10)
C1—N1—H1A	109.4	O3ⁱ—Cr1—O3	180.00 (14)
C4—N1—H1B	109.4	O8—Mo1—O9	105.30 (14)
C1—N1—H1B	109.4	O8—Mo1—O5	100.53 (13)
H1A—N1—H1B	108.0	O9—Mo1—O5	97.80 (13)
N1—C1—C2	109.0 (4)	O8—Mo1—O4	96.53 (13)
N1—C1—H1C	109.9	O9—Mo1—O4	102.55 (13)
C2—C1—H1C	109.9	O5—Mo1—O4	148.89 (11)
N1—C1—H1D	109.9	O8—Mo1—O1	95.70 (12)
C2—C1—H1D	109.9	O9—Mo1—O1	157.96 (12)
H1C—C1—H1D	108.3	O5—Mo1—O1	71.37 (10)
O13—C2—C1	110.6 (4)	O4—Mo1—O1	81.24 (10)
O13—C2—H2A	109.5	O8—Mo1—O3	162.78 (12)
C1—C2—H2A	109.5	O9—Mo1—O3	89.88 (12)
O13—C2—H2B	109.5	O5—Mo1—O3	85.08 (10)
C1—C2—H2B	109.5	O4—Mo1—O3	71.79 (10)
H2A—C2—H2B	108.1	O1—Mo1—O3	70.48 (9)
O13—C3—C4	111.3 (4)	O11—Mo2—O7	105.69 (15)
O13—C3—H3A	109.4	O11—Mo2—O4	99.59 (13)
C4—C3—H3A	109.4	O7—Mo2—O4	100.91 (13)
O13—C3—H3B	109.4	O11—Mo2—O6ⁱ	101.27 (13)
C4—C3—H3B	109.4	O7—Mo2—O6ⁱ	94.73 (12)
H3A—C3—H3B	108.0	O4—Mo2—O6ⁱ	149.40 (11)
N1—C4—C3	108.9 (4)	O11—Mo2—O2	91.86 (13)
N1—C4—H4A	109.9	O7—Mo2—O2	159.77 (12)
C3—C4—H4A	109.9	O4—Mo2—O2	85.64 (10)
N1—C4—H4B	109.9	O6ⁱ—Mo2—O2	71.57 (10)
C3—C4—H4B	109.9	O11—Mo2—O3	160.09 (12)
H4A—C4—H4B	108.3	O7—Mo2—O3	93.59 (12)
O14—C5—C6	109.7 (8)	O4—Mo2—O3	71.32 (10)
O14—C5—H5A	109.7	O6ⁱ—Mo2—O3	81.66 (10)
C6—C5—H5A	109.7	O2—Mo2—O3	70.19 (9)
O14—C5—H5B	109.7	O12—Mo3—O10	105.71 (17)
C6—C5—H5B	109.7	O12—Mo3—O6	101.54 (14)
H5A—C5—H5B	108.2	O10—Mo3—O6	97.65 (13)
N2—C6—C5	105.6 (7)	O12—Mo3—O5	95.12 (13)
N2—C6—H6A	110.6	O10—Mo3—O5	101.30 (13)
C5—C6—H6A	110.6	O6—Mo3—O5	150.28 (11)
N2—C6—H6B	110.6	O12—Mo3—O2ⁱ	95.74 (14)
C5—C6—H6B	110.6	O10—Mo3—O2ⁱ	157.68 (13)
H6A—C6—H6B	108.7	O6—Mo3—O2ⁱ	71.59 (10)
O14—C7—C8	123.5 (11)	O5—Mo3—O2ⁱ	82.47 (10)
O14—C7—H7A	106.5	O12—Mo3—O1	160.85 (13)
C8—C7—H7A	106.5	O10—Mo3—O1	90.09 (13)
O14—C7—H7B	106.5	O6—Mo3—O1	86.65 (10)
C8—C7—H7B	106.5	O5—Mo3—O1	70.75 (10)
H7A—C7—H7B	106.5	O2ⁱ—Mo3—O1	70.22 (9)
C7—C8—N2	111.0 (7)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6ⁱⁱ	0.90	1.86	2.755 (4)	172
N1—H1B···O5	0.90	1.94	2.783 (4)	155
N2—H2C···O13ⁱⁱⁱ	0.90	2.19	2.976 (8)	145
N2—H2D···O2W^iv	0.90	2.53	3.294 (9)	144
O1—H1···O1W^v	0.84 (1)	1.87 (1)	2.709 (4)	173 (5)
O2—H2···O2W^iv	0.85 (1)	1.80 (1)	2.640 (4)	172 (4)
O3—H3···O9^vi	0.84 (1)	2.02 (1)	2.853 (4)	171 (5)
O1W—H7···O8^vii	0.84 (1)	2.08 (3)	2.837 (4)	148 (5)
O1W—H8···O10^vii	0.85 (1)	2.01 (2)	2.807 (5)	157 (5)
O2W—H4···O7	0.85 (1)	2.03 (2)	2.851 (4)	165 (5)
O2W—H5···O1W^viii	0.85 (1)	2.00 (2)	2.801 (5)	157 (4)

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₀NO)₃[H₆CrMo₆O₂₄]·4H₂O
M_r	1354.14
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.9474 (4), 9.9654 (5), 13.7404 (7)
α, β, γ (°)	110.392 (1), 102.921 (1), 90.635 (1)
V (Å³)	989.47 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.53 × 0.50 × 0.44

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.324, 0.380
No. of measured, independent and observed [I > 2σ(I)] reflections	5458, 3855, 3562
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.082, 1.09
No. of reflections	3855
No. of parameters	297
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.18, −0.55

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6ⁱ	0.90	1.86	2.755 (4)	172
N1—H1B···O5	0.90	1.94	2.783 (4)	155
N2—H2C···O13ⁱⁱ	0.90	2.19	2.976 (8)	145
N2—H2D···O2Wⁱⁱⁱ	0.90	2.53	3.294 (9)	144
O1—H1···O1W^iv	0.84 (1)	1.87 (1)	2.709 (4)	173 (5)
O2—H2···O2Wⁱⁱⁱ	0.85 (1)	1.80 (1)	2.640 (4)	172 (4)
O3—H3···O9^v	0.84 (1)	2.02 (1)	2.853 (4)	171 (5)
O1W—H7···O8^vi	0.84 (1)	2.08 (3)	2.837 (4)	148 (5)
O1W—H8···O10^vi	0.85 (1)	2.01 (2)	2.807 (5)	157 (5)
O2W—H4···O7	0.85 (1)	2.03 (2)	2.851 (4)	165 (5)
O2W—H5···O1W^vii	0.85 (1)	2.00 (2)	2.801 (5)	157 (4)

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

References

An, H.-Y., Lan, Y., Li, Y.-G., Hao, N., Xiao, D.-R., Duan, L.-Y. & Xu, X. (2004). Inorg. Chem. Commun. 7, 356–358. CrossRef CAS Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hill, C. L. (1998). Chem. Rev. 98, 1–2. CSD CrossRef PubMed CAS Web of Science Google Scholar
Perloff, A. (1970). Inorg. Chem. 9, 2228–2239. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, S.-M., Chen, W.-L. & Wang, E.-B. (2010). J. Clust. Sci. 21, 133–145. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.