supplementary materials
An open-framework borophosphate, LiCu2BP2O8(OH)2
The open-framework alkaline-earth metal borophosphate, lithium dicopper(II) borophosphate dihydroxide, LiCu2BP2O8(OH)2, was synthesized hydrothermally. Its structure may be regarded as a layer formed via BO4 and PO4 tetrahedra bonding together with distorted CuO6 and LiO6 octahedral units. Each P atom is connected to B, Li and Cu atoms through a bridging O atom. The B atom lies on a crystallographic twofold axis and the Li atom lies on a center of symmetry. The two metal centers are connected to each other by Cu-O-Li bonds.
Blue block crystals were synthesized hydrothermally from a mixture of
Cu(NO3)2, Li2B4O7,water and H3PO4. In a typical synthesis, 0.725 g Cu(NO3)2 were dissolved in a mixture of 5 mL water, 1.691 g Li2B4O7
and 2 ml (85%) H3PO4 with constant stirring. Finally,the mixture was kept
in a 30 ml Teflon–lined steel autoclave at 443 K for 6days.The autoclave was
slowly cooled to room temperature. Blue block crystals of thetitle compound
were obtained.
The H atoms of the coordinated water molecule were refined with
Uiso(H)=2.4Ueq(O)and distance restraints d(O-H)of 0.86 (1)Å. The highest peak
in the difference map is 0.63e/Å, and 0.77Å from O2, and the minimum
peak is -0.53e/Å, and 0.70Å from Cu1.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
lithium dicopper borophosphate dihydroxide
top
Crystal data top
| LiCu2BP2O8(OH)2 | F(000) = 712 |
| Mr = 368.79 | Dx = 3.528 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 3236 reflections |
| a = 15.0974 (19) Å | θ = 2.7–29.3° |
| b = 4.7617 (6) Å | µ = 6.64 mm−1 |
| c = 9.6585 (12) Å | T = 296 K |
| β = 91.019 (1)° | Block, blue |
| V = 694.23 (15) Å3 | 0.20 × 0.18 × 0.17 mm |
| Z = 4 | |
Data collection top
Bruker APEXII CCD
diffractometer | 925 independent reflections |
| Radiation source: fine-focus sealed tube | 897 reflections with I > 2σ(I) |
| graphite | Rint = 0.032 |
| φ and ω scans | θmax = 29.3°, θmin = 2.7° |
Absorption correction: multi-scan
(SADABS; Bruker, 2007) | h = −20→20 |
| Tmin = 0.350, Tmax = 0.398 | k = −6→6 |
| 4076 measured reflections | l = −12→12 |
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)] = 0.019 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0258P)2 + 1.3109P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.18 | (Δ/σ)max = 0.001 |
| 925 reflections | Δρmax = 0.63 e Å−3 |
| 79 parameters | Δρmin = −0.52 e Å−3 |
| 1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0350 (13) |
Crystal data top
| LiCu2BP2O8(OH)2 | V = 694.23 (15) Å3 |
| Mr = 368.79 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 15.0974 (19) Å | µ = 6.64 mm−1 |
| b = 4.7617 (6) Å | T = 296 K |
| c = 9.6585 (12) Å | 0.20 × 0.18 × 0.17 mm |
| β = 91.019 (1)° | |
Data collection top
Bruker APEXII CCD
diffractometer | 925 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2007) | 897 reflections with I > 2σ(I) |
| Tmin = 0.350, Tmax = 0.398 | Rint = 0.032 |
| 4076 measured reflections | θmax = 29.3° |
Refinement top
| R[F2 > 2σ(F2)] = 0.019 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.054 | Δρmax = 0.63 e Å−3 |
| S = 1.18 | Δρmin = −0.52 e Å−3 |
| 925 reflections | Absolute structure: ? |
| 79 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
Special details top
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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Cu1 | 0.350210 (15) | 1.20604 (5) | 0.77155 (2) | 0.00731 (13) | |
| P2 | 0.35630 (3) | 0.67849 (9) | 0.58833 (5) | 0.00503 (14) | |
| O3 | 0.44649 (9) | 0.5916 (3) | 0.65917 (14) | 0.0085 (3) | |
| O2 | 0.34451 (9) | 0.9972 (3) | 0.59584 (13) | 0.0080 (3) | |
| O1 | 0.28531 (9) | 0.5146 (3) | 0.66790 (13) | 0.0074 (3) | |
| O5 | 0.35401 (9) | 0.5717 (3) | 0.44007 (13) | 0.0085 (3) | |
| O4 | 0.44543 (9) | 0.9550 (3) | 0.83773 (13) | 0.0101 (3) | |
| B | 0.5000 | 0.7756 (6) | 0.7500 | 0.0069 (5) | |
| Li | 0.2500 | 1.2500 | 0.5000 | 0.0201 (11) | |
| H4 | 0.425 (2) | 0.852 (6) | 0.901 (2) | 0.024* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.01075 (17) | 0.00604 (17) | 0.00510 (16) | 0.00214 (8) | −0.00107 (9) | −0.00075 (7) |
| P2 | 0.0066 (2) | 0.0042 (2) | 0.0042 (2) | −0.00019 (15) | −0.00068 (16) | 0.00003 (15) |
| O3 | 0.0084 (6) | 0.0069 (6) | 0.0100 (6) | 0.0005 (5) | −0.0034 (5) | −0.0008 (5) |
| O2 | 0.0118 (6) | 0.0048 (6) | 0.0072 (6) | 0.0011 (5) | −0.0018 (5) | −0.0006 (5) |
| O1 | 0.0082 (6) | 0.0068 (6) | 0.0073 (6) | 0.0005 (5) | 0.0014 (4) | 0.0022 (5) |
| O5 | 0.0130 (7) | 0.0076 (6) | 0.0049 (6) | 0.0003 (5) | −0.0001 (5) | −0.0001 (5) |
| O4 | 0.0119 (6) | 0.0116 (7) | 0.0067 (6) | 0.0041 (5) | 0.0004 (5) | 0.0000 (5) |
| B | 0.0079 (13) | 0.0056 (12) | 0.0073 (13) | 0.000 | −0.0006 (10) | 0.000 |
| Li | 0.021 (3) | 0.017 (2) | 0.022 (3) | 0.006 (2) | −0.012 (2) | −0.006 (2) |
Geometric parameters (Å, °) top
| Cu1—O5i | 1.9415 (13) | P2—O1 | 1.5420 (14) |
| Cu1—O2 | 1.9674 (14) | P2—O3 | 1.5686 (14) |
| Cu1—O4 | 1.9676 (14) | B—O4iv | 1.467 (2) |
| Cu1—O1ii | 2.0213 (13) | B—O3iv | 1.471 (2) |
| Cu1—O1iii | 2.3242 (13) | Li—O2v | 2.0723 (14) |
| P2—O5 | 1.5195 (13) | Li—O1ii | 2.1143 (13) |
| P2—O2 | 1.5300 (15) | Li—O5ii | 2.2758 (14) |
| | | |
| O5i—Cu1—O2 | 177.21 (6) | P2—O5—Cu1viii | 127.40 (8) |
| O5i—Cu1—O4 | 92.77 (6) | P2—O5—Livi | 89.42 (6) |
| O2—Cu1—O4 | 89.64 (6) | Cu1viii—O5—Livi | 124.75 (6) |
| O5i—Cu1—O1ii | 91.48 (6) | B—O4—Cu1 | 125.51 (9) |
| O2—Cu1—O1ii | 85.80 (6) | O4iv—B—O4 | 108.8 (2) |
| O4—Cu1—O1ii | 161.34 (6) | O4iv—B—O3 | 108.09 (7) |
| O5i—Cu1—O1iii | 90.91 (5) | O4—B—O3 | 112.53 (8) |
| O2—Cu1—O1iii | 89.63 (5) | O4iv—B—O3iv | 112.53 (8) |
| O4—Cu1—O1iii | 108.74 (6) | O4—B—O3iv | 108.09 (7) |
| O1ii—Cu1—O1iii | 89.35 (3) | O3—B—O3iv | 106.9 (2) |
| O5—P2—O2 | 112.09 (8) | O2—Li—O2v | 180.0 |
| O5—P2—O1 | 107.21 (8) | O2—Li—O1ii | 80.86 (5) |
| O2—P2—O1 | 113.33 (8) | O2v—Li—O1ii | 99.14 (5) |
| O5—P2—O3 | 109.13 (8) | O2—Li—O1ix | 99.14 (5) |
| O2—P2—O3 | 109.99 (8) | O2v—Li—O1ix | 80.86 (5) |
| O1—P2—O3 | 104.75 (7) | O1ii—Li—O1ix | 180.0 |
| B—O3—P2 | 124.48 (13) | O2—Li—O5ii | 91.82 (5) |
| P2—O2—Cu1 | 122.61 (8) | O2v—Li—O5ii | 88.18 (5) |
| P2—O2—Li | 129.39 (8) | O1ii—Li—O5ii | 68.18 (5) |
| Cu1—O2—Li | 96.37 (6) | O1ix—Li—O5ii | 111.82 (5) |
| P2—O1—Cu1vi | 106.24 (7) | O2—Li—O5ix | 88.18 (5) |
| P2—O1—Livi | 95.01 (6) | O2v—Li—O5ix | 91.82 (5) |
| Cu1vi—O1—Livi | 93.45 (6) | O1ii—Li—O5ix | 111.82 (5) |
| P2—O1—Cu1vii | 123.34 (8) | O1ix—Li—O5ix | 68.18 (5) |
| Cu1vi—O1—Cu1vii | 125.56 (6) | O5ii—Li—O5ix | 180.0 |
| Livi—O1—Cu1vii | 102.45 (5) | | |
| Symmetry codes: (i) x, −y+2, z+1/2; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, y, −z+3/2; (v) −x+1/2, −y+5/2, −z+1; (vi) x, y−1, z; (vii) −x+1/2, y−1/2, −z+3/2; (viii) x, −y+2, z−1/2; (ix) −x+1/2, −y+3/2, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O2i | 0.85 (1) | 2.37 (3) | 2.9535 (19) | 126 (3) |
| O4—H4···O5x | 0.85 (1) | 2.32 (2) | 3.036 (2) | 143 (3) |
| Symmetry codes: (i) x, −y+2, z+1/2; (x) x, −y+1, z+1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O2i | 0.85 (1) | 2.37 (3) | 2.9535 (19) | 126 (3) |
| O4—H4···O5ii | 0.85 (1) | 2.32 (2) | 3.036 (2) | 143 (3) |
| Symmetry codes: (i) x, −y+2, z+1/2; (ii) x, −y+1, z+1/2. |
This work was supported by the Main Teacher Project of Henan Province (Reference
649082) and the Foundation of Graduate Produce (Reference 2008-M-17).
Boy, I. & Kniep, R. J. (2001). Z. Kristallogr. New Cryst. Struct. 216, 9–10.
Bruker (2007). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Ewald, B., Huang, Y.-X. & Kniep, R. (2007). Z. Anorg. Allg. Chem. 633, 1517–1540.
Kniep, R., Will, H. G., Boy, I. & Röhr, C. (1997). Angew. Chem. Int. Ed. 36, 1013–1014.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Yang, T., Sun, J.-L., Li, G.-B., Eriksson, L., Zou, X.-D., Liao, F.-H. & Ling, J.-H. (2008). Chem. Eur. J. 14, 7212–7217.
![[Figure 1]](./br2104fig1thm.gif)
![[Figure 2]](./br2104fig2thm.gif)
In the last decade, much attention has been paid to the large family of borophosphates with the general formula AM(H2O)2[BP2O8].yH2O (A=Li, Na, K, NH4+; M=Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) (y = 0.5–1) due to their chiral structure property and potential applications for catalysts (Kniep et al., 1997; Ewald et al., 2007).
The crystal structure of LiCu2BP2O8(OH)2 contains one unique Li atom, two Cu atoms, one boron atom, two phosphor atoms, and eight oxygen atoms and two –OH groups in the asymmetric unit of the framework. The borophosphate units are isolated anions linked by the bonds them form to Cu, Li and H. (Fig.1) Each BO4 tetrahedron belongs to the adjacent CuO6 octahedra. The phosphorous atoms are allocated in regular tetrahedral environments with four types of oxygen atoms. Bond lengths and angles within the anionic partial structure are consistent with related borophosphates (Boy et al., 2001; Yang et al. 2008),. Li+ is coordinated by the oxygen functions groups of PO4 groups. Cu2+ is adjacent to six oxygen atoms, five from PO4 groups and one BO4 groups, but one of the five PO4 links (O3) is also bonded to BO4 (Fig.2)