Tris(morpholinium) hexa-μ(3)-hydroxido-hexa-μ(2)-oxido-dodeca-oxidohexa-molybdenum(VI)chromate(III) tetra-hydrate.

In the title organic-inorganic hybrid compound, (C(4)H(10)NO)(3)[H(6)CrMo(6)O(24)]·4H(2)O, the Anderson-type [H(6)CrMo(6)O(24)](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. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds link the cations, polyoxoanions and uncoordinated water mol-ecules.

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 = 1354.14

Triclinic,

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[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.082

S = 1.09

3855 reflections

297 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.18 e Å−3

Δρmin = −0.55 e Å−3

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.

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

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

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

(C4H10NO)3[H6CrMo6O24]·4H2O	Z = 1
Mr = 1354.14	F(000) = 661
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0428P)2 + 2.0824P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
3855 reflections	Δρmax = 1.18 e Å−3
297 parameters	Δρmin = −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)

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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···O2Wiv	0.90	2.53	3.294 (9)	144
O1—H1···O1Wv	0.84 (1)	1.87 (1)	2.709 (4)	173 (5)
O2—H2···O2Wiv	0.85 (1)	1.80 (1)	2.640 (4)	172 (4)
O3—H3···O9vi	0.84 (1)	2.02 (1)	2.853 (4)	171 (5)
O1W—H7···O8vii	0.84 (1)	2.08 (3)	2.837 (4)	148 (5)
O1W—H8···O10vii	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···O1Wviii	0.85 (1)	2.00 (2)	2.801 (5)	157 (4)

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⋯O1Wiv	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⋯O9v	0.84 (1)	2.02 (1)	2.853 (4)	171 (5)
O1W—H7⋯O8vi	0.84 (1)	2.08 (3)	2.837 (4)	148 (5)
O1W—H8⋯O10vi	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⋯O1Wvii	0.85 (1)	2.00 (2)	2.801 (5)	157 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .