The structure of copper(II) hydrogenphosphite dihydrate, CuHPO3·2H2O, has been redetermined on the basis of area-detector data. The results confirm the literature data of Handlovic [Acta Cryst. (1969), B25, 227-231] but with s.u. values about ten times lower and with all H-atom positions located. The microporous framework topology of the structure is discussed.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (P-O) = 0.001 Å
- R factor = 0.022
- wR factor = 0.047
- Data-to-parameter ratio = 21.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
ABSTM_02 Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
Tmin and Tmax reported: 0.406 0.710
Tmin' and Tmax expected: 0.653 0.771
RR' = 0.675
Please check that your absorption correction is appropriate.
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor P - H(1) ?
General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced
by the scaled T values. Since the ratio of scaled T's is
identical to the ratio of reported T values, the scaling does
not imply a change to the absorption corrections used in the
study.
Ratio of Tmax expected/reported 1.085
Tmax scaled 0.771 Tmin scaled 0.441
REFLT_03
From the CIF: _diffrn_reflns_theta_max 33.98
From the CIF: _reflns_number_total 1798
Count of symmetry unique reflns 1063
Completeness (_total/calc) 169.14%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 735
Fraction of Friedel pairs measured 0.691
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999).
Crystal data top
CuHPO3·2H2O | Dx = 2.700 Mg m−3 |
Mr = 179.55 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8000 reflections |
a = 6.6906 (5) Å | θ = 3.6–32.8° |
b = 7.3727 (5) Å | µ = 5.21 mm−1 |
c = 8.9552 (5) Å | T = 193 K |
V = 441.74 (5) Å3 | Block, light blue |
Z = 4 | 0.08 × 0.06 × 0.05 mm |
F(000) = 356 | |
Data collection top
Stoe IPDS-II image-plate diffractometer | 1798 independent reflections |
Radiation source: fine-focus sealed tube | 1765 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
D=90 mm, Δω = 1°, 5 min/rec scans | θmax = 34.0°, θmin = 3.6° |
Absorption correction: multi-scan (SHELXTL; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.406, Tmax = 0.710 | k = −11→11 |
11632 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.022 | w = 1/[σ2(Fo2) + (0.02P)2 + 0.05P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.66 e Å−3 |
1798 reflections | Δρmin = −0.62 e Å−3 |
84 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.019 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.010 (8) |
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 >
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.26767 (2) | 0.02867 (2) | 0.095756 (17) | 0.00937 (6) | |
P | 0.01075 (5) | −0.31863 (5) | 0.14769 (4) | 0.00821 (7) | |
O1 | −0.02312 (17) | −0.38942 (15) | 0.30688 (11) | 0.01191 (18) | |
O2 | 0.21498 (17) | −0.22526 (14) | 0.14162 (12) | 0.01153 (17) | |
O3 | −0.00358 (16) | −0.47100 (16) | 0.03114 (11) | 0.01178 (16) | |
O4 | 0.29938 (18) | 0.28458 (16) | 0.03218 (12) | 0.0144 (2) | |
H41 | 0.184 (5) | 0.350 (5) | 0.033 (4) | 0.031 (6)* | |
H42 | 0.353 (5) | 0.304 (5) | −0.054 (4) | 0.031 (6)* | |
O5 | 0.45467 (19) | 0.05250 (18) | 0.31261 (14) | 0.0181 (2) | |
H51 | 0.512 (5) | −0.042 (5) | 0.324 (3) | 0.021 (4)* | |
H52 | 0.549 (5) | 0.123 (4) | 0.325 (3) | 0.021 (4)* | |
H1 | −0.113 (4) | −0.208 (3) | 0.119 (3) | 0.008 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.01033 (8) | 0.00762 (8) | 0.01016 (8) | 0.00021 (5) | 0.00246 (5) | −0.00008 (5) |
P | 0.00875 (14) | 0.00723 (13) | 0.00863 (13) | −0.0002 (1) | 0.0000 (1) | −0.0002 (2) |
O1 | 0.0116 (4) | 0.0139 (4) | 0.0102 (4) | −0.0028 (4) | 0.0016 (3) | 0.0008 (3) |
O2 | 0.0114 (4) | 0.0094 (4) | 0.0137 (4) | −0.0020 (4) | 0.0002 (3) | 0.0007 (3) |
O3 | 0.0123 (4) | 0.0106 (3) | 0.0124 (4) | 0.0006 (4) | −0.0028 (3) | −0.0027 (4) |
O4 | 0.0162 (5) | 0.0105 (4) | 0.0166 (4) | 0.0023 (4) | 0.0051 (4) | 0.0023 (4) |
O5 | 0.0161 (5) | 0.0167 (5) | 0.0217 (5) | −0.0009 (4) | −0.0053 (4) | −0.0010 (4) |
Geometric parameters (Å, º) top
Cu—O2 | 1.9488 (10) | P—O3 | 1.5364 (11) |
Cu—O1i | 1.9499 (11) | P—H1 | 1.19 (2) |
Cu—O3ii | 1.9531 (10) | O1—Cuiv | 1.9499 (11) |
Cu—O4 | 1.9822 (12) | O3—Cuv | 1.9531 (10) |
Cu—O5 | 2.3168 (12) | O4—H41 | 0.91 (3) |
Cu—O5iii | 3.0001 (13) | O4—H42 | 0.86 (4) |
P—O2 | 1.5310 (12) | O5—H51 | 0.80 (3) |
P—O1 | 1.5349 (11) | O5—H52 | 0.82 (3) |
| | | |
O2—Cu—O1i | 92.95 (5) | O2—P—O1 | 108.52 (6) |
O2—Cu—O3ii | 93.17 (5) | O2—P—O3 | 111.12 (6) |
O1i—Cu—O3ii | 170.12 (4) | O1—P—O3 | 111.91 (6) |
O2—Cu—O4 | 173.88 (5) | O2—P—H1 | 107.8 (12) |
O1i—Cu—O4 | 85.61 (5) | O1—P—H1 | 109.1 (12) |
O3ii—Cu—O4 | 87.49 (5) | O3—P—H1 | 108.3 (12) |
O2—Cu—O5 | 89.65 (5) | P—O1—Cuiv | 130.13 (7) |
O1i—Cu—O5 | 93.14 (5) | P—O2—Cu | 126.93 (7) |
O3ii—Cu—O5 | 94.65 (5) | P—O3—Cuv | 127.11 (7) |
O4—Cu—O5 | 96.36 (5) | Cu—O4—H41 | 114 (2) |
O2—Cu—O5iii | 84.08 (4) | Cu—O4—H42 | 117 (2) |
O1i—Cu—O5iii | 91.36 (4) | H41—O4—H42 | 106 (3) |
O3ii—Cu—O5iii | 81.57 (4) | Cu—O5—H51 | 108 (2) |
O4—Cu—O5iii | 90.01 (4) | Cu—O5—H52 | 125 (2) |
O5—Cu—O5iii | 172.461 (11) | H51—O5—H52 | 100 (3) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1/2, −y−1/2, −z; (iii) −x+1/2, −y, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) x−1/2, −y−1/2, −z. |