CsMoO₂(HO₃P-CH₂-PO₃): a new metallodiphosphonate with a hybrid framework

Crystals of caesium molybdeno­methyl­enedi­phospho­nate, [CsMoO₂(CH₃O₆P₂)], were hydro­thermally synthesized at 473 K. The monoclinic structure, as determined from single-crystal X-ray diffraction, is two-dimensional and consists of stacked mixed layers of corner-sharing tetrahedral di­phosphon­ate groups and MoO₆ octahedra, between which Cs⁺ cations are intercalated.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL.

Caesium molybdenomethylendiphosphonate

Crystal data

[CsMoO2(CH3O6P2)]	F(000) = 800
Mr = 434	Dx = 3.552 Mg m^−3 Dm = 3.423 (8) Mg m^−3 Dm measured by pycnometry
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.0859 (5) Å	Cell parameters from 5728 reflections
b = 11.8567 (7) Å	θ = 2.8–29.9°
c = 9.2347 (5) Å	µ = 6.44 mm^−1
β = 113.512 (1)°	T = 296 K
V = 811.84 (8) Å^3	Parallelepiped, blue
Z = 4	0.20 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2142 independent reflections
Radiation source: fine-focus sealed tube	1646 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 29.9°, θmin = 2.8°
Absorption correction: semi-empirical (using intensity measurements) (SADABS; Blessing, 1995)	h = −10→6
Tmin = 0.390, Tmax = 0.597	k = −15→16
5609 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0487P)^2 + 0.4123P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2142 reflections	Δρmax = 1.62 e Å^−3
119 parameters	Δρmin = −1.58 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (3)

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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.

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

	x	y	z	Uiso*/Ueq
Cs	0.68614 (4)	0.12463 (3)	0.98461 (4)	0.02315 (13)
Mo	0.98806 (5)	0.12786 (3)	0.74580 (4)	0.01204 (12)
P1	0.2533 (2)	0.24800 (9)	1.07243 (12)	0.0121 (2)
P2	0.7315 (2)	0.00573 (9)	1.40591 (12)	0.0119 (2)
O1	0.4390 (5)	0.2234 (3)	1.2024 (4)	0.0214 (7)
O2	0.2154 (5)	0.1576 (3)	0.9430 (4)	0.0157 (6)
O3	0.8023 (4)	0.1033 (3)	1.5250 (4)	0.0159 (7)
O4	0.5394 (5)	0.0321 (3)	1.2937 (4)	0.0222 (7)
O5	0.8509 (5)	−0.0134 (3)	1.3170 (4)	0.0184 (7)
O6	0.1041 (5)	0.2547 (3)	1.1318 (4)	0.0162 (6)
O7	0.8717 (5)	0.2374 (3)	0.7776 (4)	0.0190 (7)
O8	0.9228 (5)	0.0189 (3)	0.8290 (4)	0.0196 (7)
C	0.2711 (7)	0.3802 (3)	0.9863 (6)	0.0148 (9)
HA	0.1725	0.3851	0.8831	0.018*
HB	0.3823	0.3797	0.9698	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.0286 (2)	0.0256 (2)	0.0145 (2)	−0.00188 (13)	0.00780 (14)	−0.00111 (11)
Mo	0.0163 (2)	0.0129 (2)	0.0073 (2)	−0.00014 (14)	0.0052 (2)	−0.00119 (12)
P1	0.0161 (6)	0.0117 (5)	0.0081 (5)	0.0007 (4)	0.0044 (4)	−0.0006 (4)
P2	0.0148 (6)	0.0119 (5)	0.0084 (5)	0.0011 (4)	0.0041 (4)	−0.0010 (4)
O1	0.020 (2)	0.020 (2)	0.017 (2)	0.0004 (14)	−0.0003 (15)	−0.0026 (13)
O2	0.019 (2)	0.0162 (14)	0.0111 (15)	0.0016 (14)	0.0053 (13)	−0.0020 (12)
O3	0.021 (2)	0.0145 (14)	0.010 (2)	−0.0013 (13)	0.0038 (14)	−0.0019 (12)
O4	0.018 (2)	0.017 (2)	0.022 (2)	0.0012 (14)	−0.0011 (15)	−0.0014 (14)
O5	0.029 (2)	0.0154 (15)	0.016 (2)	0.0053 (14)	0.0137 (15)	0.0008 (13)
O6	0.022 (2)	0.0158 (15)	0.013 (2)	−0.0004 (14)	0.0102 (13)	−0.0012 (12)
O7	0.024 (2)	0.021 (2)	0.013 (2)	0.0033 (15)	0.0082 (14)	−0.0011 (13)
O8	0.027 (2)	0.021 (2)	0.011 (2)	−0.0031 (15)	0.0089 (14)	0.0011 (13)
C	0.026 (2)	0.009 (2)	0.017 (2)	−0.001 (2)	0.017 (2)	−0.002 (2)

Geometric parameters (Å, º)

Cs—O7^i	3.001 (3)	P1—O2	1.543 (3)
Cs—O8	3.081 (3)	P1—C	1.790 (4)
Cs—O4^ii	3.106 (3)	P2—O5	1.514 (3)
Cs—O1^iii	3.143 (3)	P2—O4	1.516 (4)
Cs—O7	3.159 (3)	P2—O3	1.540 (3)
Cs—O5	3.257 (3)	P2—C^viii	1.795 (4)
Cs—O3^iii	3.339 (3)	P2—Cs^ii	4.1329 (12)
Cs—O8^iv	3.394 (4)	O1—Cs^i	3.143 (3)
Cs—O2^ii	3.443 (3)	O2—Mo^ix	2.037 (3)
Cs—O6^v	3.461 (3)	O2—Cs^ii	3.443 (3)
Cs—O1	3.552 (3)	O3—Mo^x	2.014 (3)
Cs—O4	3.669 (4)	O3—Cs^i	3.339 (3)
Mo—O8	1.692 (3)	O4—Cs^ii	3.105 (3)
Mo—O7	1.697 (3)	O5—Mo^iv	2.115 (3)
Mo—O3^vi	2.014 (3)	O6—Mo^xi	2.172 (3)
Mo—O2^v	2.037 (3)	O6—Cs^ix	3.461 (3)
Mo—O5^iv	2.115 (3)	O7—Cs^iii	3.001 (3)
Mo—O6^vii	2.172 (3)	O8—Cs^iv	3.394 (4)
Mo—Cs^iii	3.9612 (5)	C—P2^xii	1.795 (4)
Mo—Cs^iv	4.1070 (5)	C—HA	0.97
P1—O6	1.513 (3)	C—HB	0.97
P1—O1	1.530 (4)
O7^i—Cs—O8	117.53 (9)	O5^iv—Mo—O6^vii	81.17 (12)
O7^i—Cs—O4^ii	171.67 (9)	O8—Mo—Cs	49.81 (11)
O8—Cs—O4^ii	68.86 (9)	O7—Mo—Cs	52.58 (11)
O7^i—Cs—O1^iii	111.04 (9)	O3^vi—Mo—Cs	100.92 (9)
O8—Cs—O1^iii	98.87 (9)	O2^v—Mo—Cs	92.39 (9)
O4^ii—Cs—O1^iii	71.79 (9)	O5^iv—Mo—Cs	138.01 (9)
O7^i—Cs—O7	97.33 (7)	O6^vii—Mo—Cs	140.51 (8)
O8—Cs—O7	49.97 (9)	O8—Mo—Cs^iii	127.89 (12)
O4^ii—Cs—O7	90.94 (9)	O7—Mo—Cs^iii	44.66 (10)
O1^iii—Cs—O7	63.51 (9)	O3^vi—Mo—Cs^iii	57.39 (9)
O7^i—Cs—O5	63.57 (8)	O2^v—Mo—Cs^iii	122.23 (9)
O8—Cs—O5	97.96 (8)	O5^iv—Mo—Cs^iii	127.27 (8)
O4^ii—Cs—O5	111.33 (9)	O6^vii—Mo—Cs^iii	60.68 (9)
O1^iii—Cs—O5	162.78 (8)	Cs—Mo—Cs^iii	88.783 (11)
O7—Cs—O5	131.93 (9)	O8—Mo—Cs^iv	53.77 (12)
O7^i—Cs—O3^iii	49.88 (8)	O7—Mo—Cs^iv	135.96 (10)
O8—Cs—O3^iii	104.23 (8)	O3^vi—Mo—Cs^iv	123.19 (9)
O4^ii—Cs—O3^iii	135.78 (8)	O2^v—Mo—Cs^iv	56.80 (9)
O1^iii—Cs—O3^iii	66.19 (8)	O5^iv—Mo—Cs^iv	51.86 (8)
O7—Cs—O3^iii	58.55 (8)	O6^vii—Mo—Cs^iv	117.69 (9)
O5—Cs—O3^iii	112.89 (8)	Cs—Mo—Cs^iv	92.581 (10)
O7^i—Cs—O8^iv	77.67 (9)	Cs^iii—Mo—Cs^iv	178.344 (11)
O8—Cs—O8^iv	53.57 (10)	O6—P1—O1	113.6 (2)
O4^ii—Cs—O8^iv	103.92 (8)	O6—P1—O2	112.1 (2)
O1^iii—Cs—O8^iv	149.74 (8)	O1—P1—O2	107.7 (2)
O7—Cs—O8^iv	87.01 (8)	O6—P1—C	109.4 (2)
O5—Cs—O8^iv	47.31 (7)	O1—P1—C	106.7 (2)
O3^iii—Cs—O8^iv	105.32 (8)	O2—P1—C	106.9 (2)
O7^i—Cs—O2^ii	111.15 (8)	O6—P1—Cs	160.59 (13)
O8—Cs—O2^ii	63.69 (8)	O1—P1—Cs	56.45 (13)
O4^ii—Cs—O2^ii	66.00 (8)	O2—P1—Cs	61.76 (13)
O1^iii—Cs—O2^ii	137.69 (8)	C—P1—Cs	89.88 (15)
O7—Cs—O2^ii	113.59 (8)	O5—P2—O4	111.2 (2)
O5—Cs—O2^ii	49.66 (7)	O5—P2—O3	111.3 (2)
O3^iii—Cs—O2^ii	152.18 (8)	O4—P2—O3	108.7 (2)
O8^iv—Cs—O2^ii	46.97 (8)	O5—P2—C^viii	109.1 (2)
O7^i—Cs—O6^v	49.06 (8)	O4—P2—C^viii	108.3 (2)
O8—Cs—O6^v	70.95 (8)	O3—P2—C^viii	108.1 (2)
O4^ii—Cs—O6^v	138.63 (8)	O5—P2—Cs	50.08 (12)
O1^iii—Cs—O6^v	105.57 (8)	O4—P2—Cs	65.97 (14)
O7—Cs—O6^v	54.83 (8)	O3—P2—Cs	107.00 (12)
O5—Cs—O6^v	83.43 (8)	C^viii—P2—Cs	144.3 (2)
O3^iii—Cs—O6^v	48.60 (8)	O5—P2—Cs^ii	86.94 (14)
O8^iv—Cs—O6^v	57.17 (8)	O4—P2—Cs^ii	39.03 (13)
O2^ii—Cs—O6^v	104.05 (8)	O3—P2—Cs^ii	147.72 (13)
O7^i—Cs—O1	60.11 (8)	C^viii—P2—Cs^ii	89.3 (2)
O8—Cs—O1	173.06 (8)	Cs—P2—Cs^ii	63.82 (2)
O4^ii—Cs—O1	112.86 (9)	P1—O1—Cs^i	129.9 (2)
O1^iii—Cs—O1	88.00 (7)	P1—O1—Cs	102.50 (15)
O7—Cs—O1	135.50 (8)	Cs^i—O1—Cs	110.07 (10)
O5—Cs—O1	75.12 (8)	P1—O2—Mo^ix	130.0 (2)
O3^iii—Cs—O1	79.33 (8)	P1—O2—Cs^ii	124.4 (2)
O8^iv—Cs—O1	119.94 (7)	Mo^ix—O2—Cs^ii	93.54 (11)
O2^ii—Cs—O1	110.44 (8)	P1—O2—Cs	96.63 (15)
O6^v—Cs—O1	108.22 (7)	Mo^ix—O2—Cs	126.90 (12)
O7^i—Cs—O4	70.25 (8)	Cs^ii—O2—Cs	74.21 (6)
O8—Cs—O4	134.03 (8)	P2—O3—Mo^x	138.3 (2)
O4^ii—Cs—O4	101.51 (8)	P2—O3—Cs^i	129.6 (2)
O1^iii—Cs—O4	121.37 (8)	Mo^x—O3—Cs^i	92.08 (10)
O7—Cs—O4	167.50 (8)	P2—O4—Cs^ii	123.1 (2)
O5—Cs—O4	41.79 (8)	P2—O4—Cs	91.86 (15)
O3^iii—Cs—O4	111.46 (7)	Cs^ii—O4—Cs	78.49 (8)
O8^iv—Cs—O4	88.88 (7)	P2—O5—Mo^iv	147.2 (2)
O2^ii—Cs—O4	71.31 (7)	P2—O5—Cs	109.0 (2)
O6^v—Cs—O4	113.33 (7)	Mo^iv—O5—Cs	97.43 (10)
O1—Cs—O4	39.52 (8)	P1—O6—Mo^xi	140.4 (2)
O8—Mo—O7	102.2 (2)	P1—O6—Cs^ix	129.0 (2)
O8—Mo—O3^vi	96.16 (14)	Mo^xi—O6—Cs^ix	86.15 (10)
O7—Mo—O3^vi	92.57 (14)	Mo—O7—Cs^iii	111.92 (13)
O8—Mo—O2^v	93.46 (15)	Mo—O7—Cs	102.17 (13)
O7—Mo—O2^v	94.47 (14)	Cs^iii—O7—Cs	126.08 (12)
O3^vi—Mo—O2^v	166.62 (13)	Mo—O8—Cs	105.39 (14)
O8—Mo—O5^iv	88.39 (14)	Mo—O8—Cs^iv	102.53 (15)
O7—Mo—O5^iv	169.40 (13)	Cs—O8—Cs^iv	126.42 (9)
O3^vi—Mo—O5^iv	85.51 (13)	P1—C—P2^xii	117.3 (2)
O2^v—Mo—O5^iv	85.49 (13)	P1—C—HA	108.0
O8—Mo—O6^vii	169.53 (14)	P2^xii—C—HA	108.0
O7—Mo—O6^vii	88.27 (14)	P1—C—HB	108.0
O3^vi—Mo—O6^vii	83.91 (12)	P2^xii—C—HB	108.0
O2^v—Mo—O6^vii	84.95 (13)	HA—C—HB	107.2

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+2; (iii) x, −y+1/2, z−1/2; (iv) −x+2, −y, −z+2; (v) x+1, y, z; (vi) x, y, z−1; (vii) x+1, −y+1/2, z−1/2; (viii) −x+1, y−1/2, −z+5/2; (ix) x−1, y, z; (x) x, y, z+1; (xi) x−1, −y+1/2, z+1/2; (xii) −x+1, y+1/2, −z+5/2.