Buy article online - an online subscription or single-article purchase is required to access this article.
The title compound, [Ca(C3H3O4)2]n, has a polymeric structure, built up from noncentrosymmetric Ca2O12 face-sharing bipolyhedra, linked through the spacers of the ligands and forming a complex three-dimensional framework containing empty channels parallel to the [001] direction. The calcium ion lies on a 2 axis and is coordinated by eight O atoms from six hydrogen malonate ligands in a distorted bicapped dodecahedron. The tridentate ligand displays an η5-chelating coordination mode and forms both μ1,1 and μ1,3 bridges. In the extended network, the protonated O atom is involved in a strong hydrogen bond with a deprotonated O atom, forming an infinite array of the ligands. An M—O—M infinite linkage characteristic of metal–organic frameworks is prevented here by cage assembly around the metal.
Supporting information
CCDC reference: 654720
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.070
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 87 PerFi
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.03
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.33 Ratio
Alert level G
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 29.98
From the CIF: _reflns_number_total 1215
Count of symmetry unique reflns 712
Completeness (_total/calc) 170.65%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 503
Fraction of Friedel pairs measured 0.706
Are heavy atom types Z>Si present yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
2 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-MSN (Otwinowski & Minor, 1997); data reduction: DENZO-MSN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Poly[bis(µ
3-dihydrogen malonato)calcium(II)]
top
Crystal data top
[Ca(C3H3O4)2] | Dx = 1.965 Mg m−3 |
Mr = 246.19 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P421c | Cell parameters from 17857 reflections |
Hall symbol: P-42n | θ = 3.0–32.7° |
a = 7.8705 (1) Å | µ = 0.78 mm−1 |
c = 13.4367 (7) Å | T = 100 K |
V = 832.33 (5) Å3 | Prism, colourless |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
F(000) = 504 | |
Data collection top
Nonius KappaCCD diffractometer | 1215 independent reflections |
Radiation source: fine-focus sealed tube | 1183 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 30.0°, θmin = 3.0° |
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) | h = −10→11 |
Tmin = 0.804, Tmax = 0.830 | k = −11→11 |
16443 measured reflections | l = −18→18 |
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0477P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1215 reflections | Δρmax = 0.39 e Å−3 |
72 parameters | Δρmin = −0.25 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 504 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (6) |
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 | |
Ca | 0.5000 | 0.5000 | 0.13496 (3) | 0.01000 (11) | |
O1 | 0.69334 (15) | 0.63476 (16) | 0.02648 (8) | 0.0139 (2) | |
O2 | 0.94509 (15) | 0.69424 (17) | −0.03949 (8) | 0.0158 (3) | |
C1 | 0.84141 (19) | 0.68269 (19) | 0.03595 (10) | 0.0112 (3) | |
C2 | 0.9185 (2) | 0.7426 (2) | 0.13265 (11) | 0.0133 (3) | |
H21 | 0.9017 | 0.8671 | 0.1372 | 0.016* | |
H22 | 1.0425 | 0.7221 | 0.1295 | 0.016* | |
C3 | 0.8517 (2) | 0.6630 (2) | 0.22875 (11) | 0.0115 (3) | |
O3 | 0.74402 (17) | 0.54852 (15) | 0.22770 (8) | 0.0160 (3) | |
O4 | 0.91839 (15) | 0.72053 (15) | 0.30858 (8) | 0.0138 (3) | |
H2 | 0.895 (3) | 0.651 (3) | −0.0995 (12) | 0.021* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ca | 0.01005 (19) | 0.0113 (2) | 0.00867 (18) | −0.0009 (2) | 0.000 | 0.000 |
O1 | 0.0133 (5) | 0.0175 (6) | 0.0110 (5) | −0.0032 (4) | 0.0005 (4) | 0.0003 (4) |
O2 | 0.0154 (5) | 0.0241 (6) | 0.0080 (5) | −0.0042 (5) | 0.0012 (4) | −0.0012 (5) |
C1 | 0.0137 (7) | 0.0112 (6) | 0.0087 (6) | −0.0003 (6) | 0.0010 (5) | 0.0010 (5) |
C2 | 0.0163 (7) | 0.0155 (7) | 0.0081 (6) | −0.0044 (6) | −0.0003 (6) | −0.0005 (6) |
C3 | 0.0118 (7) | 0.0113 (7) | 0.0113 (6) | 0.0023 (5) | 0.0000 (5) | 0.0002 (5) |
O3 | 0.0161 (6) | 0.0200 (6) | 0.0118 (5) | −0.0047 (4) | −0.0038 (5) | 0.0025 (4) |
O4 | 0.0188 (6) | 0.0141 (6) | 0.0086 (5) | −0.0018 (5) | −0.0010 (4) | −0.0005 (4) |
Geometric parameters (Å, º) top
Ca—O3 | 2.3210 (12) | O1—Cav | 2.8541 (12) |
Ca—O3i | 2.3210 (12) | O2—H2 | 0.962 (14) |
Ca—O1i | 2.3591 (12) | C1—C2 | 1.509 (2) |
Ca—O1 | 2.3591 (12) | C2—C3 | 1.528 (3) |
Ca—O4ii | 2.4137 (12) | C2—H21 | 0.990 |
Ca—O4iii | 2.4137 (12) | C2—H22 | 0.990 |
Ca—O1iv | 2.8541 (12) | C3—O3 | 1.236 (3) |
Ca—O1v | 2.8541 (12) | C3—O4 | 1.278 (2) |
Ca—Cav | 3.6268 (8) | O4—Cavi | 2.4134 (15) |
O1—C1 | 1.231 (2) | | |
| | | |
O3—Ca—O3i | 115.06 (6) | O1—Ca—O1iv | 61.99 (2) |
O3—Ca—O1i | 159.96 (4) | O4ii—Ca—O1iv | 145.45 (4) |
O3i—Ca—O1i | 73.98 (4) | O4iii—Ca—O1iv | 69.76 (4) |
O3—Ca—O1 | 73.98 (4) | O3—Ca—O1v | 128.89 (4) |
O3i—Ca—O1 | 159.96 (4) | O3i—Ca—O1v | 100.85 (4) |
O1i—Ca—O1 | 103.68 (6) | O1i—Ca—O1v | 61.99 (2) |
O3—Ca—O4ii | 84.35 (4) | O1—Ca—O1v | 61.99 (2) |
O3i—Ca—O4ii | 76.17 (4) | O4ii—Ca—O1v | 69.76 (4) |
O1i—Ca—O4ii | 115.61 (4) | O4iii—Ca—O1v | 145.45 (4) |
O1—Ca—O4ii | 87.49 (4) | O1iv—Ca—O1v | 81.07 (5) |
O3—Ca—O4iii | 76.17 (4) | C1—O2—H2 | 112.6 (16) |
O3i—Ca—O4iii | 84.35 (4) | O1—C1—O2 | 122.13 (18) |
O1i—Ca—O4iii | 87.49 (4) | O1—C1—C2 | 124.43 (17) |
O1—Ca—O4iii | 115.61 (4) | O2—C1—C2 | 113.36 (17) |
O4ii—Ca—O4iii | 143.36 (6) | C1—C2—C3 | 117.45 (17) |
O3—Ca—O1iv | 100.85 (4) | O3—C3—O4 | 123.32 (18) |
O3i—Ca—O1iv | 128.89 (4) | O3—C3—C2 | 121.68 (17) |
O1i—Ca—O1iv | 61.99 (2) | O4—C3—C2 | 114.98 (18) |
| | | |
O4iii—Ca—O1—Cav | 93.82 (4) | C2—C3—O3—Ca | −40.7 (2) |
O1iv—Ca—O1—Cav | 47.40 (3) | O3i—Ca—O3—C3 | −126.36 (16) |
O1v—Ca—O1—Cav | −47.40 (3) | O1i—Ca—O3—C3 | 120.52 (16) |
Ca—O1—C1—O2 | 153.10 (11) | O1—Ca—O3—C3 | 34.50 (15) |
Cav—O1—C1—O2 | 6.7 (2) | O4ii—Ca—O3—C3 | −54.50 (15) |
Ca—O1—C1—C2 | −30.5 (2) | O4iii—Ca—O3—C3 | 156.76 (16) |
Cav—O1—C1—C2 | −176.83 (10) | O1iv—Ca—O3—C3 | 90.96 (15) |
O1—C1—C2—C3 | 31.6 (2) | O1v—Ca—O3—C3 | 3.74 (17) |
O2—C1—C2—C3 | −151.72 (14) | Cav—Ca—O3—C3 | 53.64 (16) |
C1—C2—C3—O3 | 3.1 (2) | O3—C3—O4—Cavi | −141.14 (13) |
C1—C2—C3—O4 | −178.56 (14) | C2—C3—O4—Cavi | 40.5 (2) |
O4—C3—O3—Ca | 141.05 (13) | | |
Symmetry codes: (i) −x+1, −y+1, z; (ii) x−1/2, −y+3/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) y, −x+1, −z; (v) −y+1, x, −z; (vi) x+1/2, −y+3/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4vii | 0.96 (2) | 1.63 (2) | 2.5800 (17) | 168 (1) |
O2—H2···O3vii | 0.96 (2) | 2.50 (2) | 3.1660 (18) | 126 (1) |
Symmetry code: (vii) −y+3/2, −x+3/2, z−1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.