Crystal structure of a polymeric calcium levulinate dihydrate: catena-poly[[di­aqua­calcium]-bis­(μ₂-4-oxo­butano­ato)]

The crystal structure of calcium levulinate dihydrate forms a one-dimensional coordination polymer based on a CaO₈ complex unit which lies on a twofold rotation axis. This unit comprises two monodentate water O-atom donors and six carboxyl­ate O-atom donors, two of which are also bridging, from the two bidentate chelate levulinate ligands. The complex chains are stabilized by intra- and inter­molecular water O—H...O hydrogen bonds, forming an overall three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.083
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.94 mm
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....         C5 Check
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

catena-Poly[[diaquacalcium]-bis(µ₂-4-oxobutanoato)]

Crystal data

[Ca(C5H7O3)2(H2O)2]	F(000) = 648
Mr = 306.32	Dx = 1.481 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 8589 reflections
a = 17.644 (3) Å	θ = 2.3–30.5°
b = 9.9627 (19) Å	µ = 0.49 mm^−1
c = 7.8160 (15) Å	T = 100 K
V = 1373.9 (5) Å^3	Needle, colourless
Z = 4	0.94 × 0.11 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1664 independent reflections
Radiation source: fine-focus sealed tube	1571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 28.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −23→23
Tmin = 0.656, Tmax = 0.963	k = −13→13
11806 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0384P)^2 + 1.0525P] where P = (Fo^2 + 2Fc^2)/3
1664 reflections	(Δ/σ)max < 0.001
88 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−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 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 (Ų)

	x	y	z	Uiso*/Ueq
Ca1	0.5000	0.04993 (4)	0.2500	0.00808 (12)
O4	0.40994 (5)	0.20740 (10)	0.12520 (12)	0.0141 (2)
H4A	0.3629	0.1929	0.1655	0.021*
H4B	0.4086	0.1988	0.0107	0.021*
O2	0.58523 (5)	−0.14668 (10)	0.21809 (12)	0.0123 (2)
C4	0.71782 (8)	−0.37537 (14)	0.25360 (16)	0.0120 (3)
O1	0.55856 (5)	−0.10067 (9)	0.48715 (12)	0.0115 (2)
C1	0.58068 (7)	−0.18090 (13)	0.37294 (16)	0.0094 (2)
C2	0.59849 (8)	−0.32410 (14)	0.42594 (18)	0.0149 (3)
H2A	0.5507	−0.3682	0.4616	0.018*
H2B	0.6324	−0.3215	0.5269	0.018*
C3	0.63568 (8)	−0.40979 (13)	0.28835 (19)	0.0140 (3)
H3A	0.6326	−0.5052	0.3232	0.017*
H3B	0.6066	−0.3997	0.1807	0.017*
O3	0.74945 (6)	−0.28329 (10)	0.32774 (13)	0.0166 (2)
C5	0.75831 (8)	−0.46004 (14)	0.12409 (18)	0.0155 (3)
H5A	0.8107	−0.4287	0.1123	0.023*
H5B	0.7325	−0.4530	0.0135	0.023*
H5C	0.7583	−0.5539	0.1618	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.00891 (19)	0.00906 (19)	0.00626 (18)	0.000	0.00041 (11)	0.000
O4	0.0144 (5)	0.0187 (5)	0.0092 (4)	0.0031 (4)	0.0010 (3)	0.0003 (4)
O2	0.0133 (4)	0.0152 (5)	0.0084 (4)	0.0034 (4)	0.0011 (3)	0.0007 (4)
C4	0.0140 (6)	0.0107 (6)	0.0113 (6)	0.0030 (5)	−0.0017 (4)	0.0023 (5)
O1	0.0111 (4)	0.0140 (5)	0.0093 (4)	0.0021 (3)	0.0009 (3)	−0.0016 (4)
C1	0.0058 (5)	0.0125 (6)	0.0099 (6)	0.0001 (4)	−0.0001 (4)	0.0001 (5)
C2	0.0168 (6)	0.0136 (6)	0.0142 (6)	0.0041 (5)	0.0044 (5)	0.0032 (5)
C3	0.0136 (6)	0.0114 (6)	0.0172 (6)	0.0020 (5)	0.0007 (5)	−0.0009 (5)
O3	0.0163 (5)	0.0148 (5)	0.0187 (5)	0.0005 (4)	−0.0029 (4)	−0.0037 (4)
C5	0.0154 (6)	0.0153 (6)	0.0160 (6)	0.0011 (5)	0.0024 (5)	−0.0026 (5)

Geometric parameters (Å, º)

Ca1—O1^i	2.3546 (10)	C4—C3	1.5138 (19)
Ca1—O1^ii	2.3546 (10)	O1—C1	1.2602 (16)
Ca1—O4^iii	2.4367 (10)	O1—Ca1^i	2.3546 (10)
Ca1—O4	2.4367 (10)	C1—C2	1.5185 (18)
Ca1—O2^iii	2.4820 (10)	C2—C3	1.5218 (19)
Ca1—O2	2.4820 (11)	C2—H2A	0.9900
Ca1—O1	2.5989 (10)	C2—H2B	0.9900
Ca1—O1^iii	2.5990 (10)	C3—H3A	0.9900
O4—H4A	0.8999	C3—H3B	0.9900
O4—H4B	0.8994	C5—H5A	0.9800
O2—C1	1.2599 (16)	C5—H5B	0.9800
C4—O3	1.2203 (17)	C5—H5C	0.9800
C4—C5	1.4988 (18)
O1^i—Ca1—O1^ii	155.21 (5)	O2—Ca1—Ca1^iv	73.02 (2)
O1^i—Ca1—O4^iii	78.38 (3)	O1—Ca1—Ca1^iv	123.28 (3)
O1^ii—Ca1—O4^iii	85.69 (3)	O1^iii—Ca1—Ca1^iv	33.53 (2)
O1^i—Ca1—O4	85.69 (3)	C1—Ca1—Ca1^iv	97.28 (3)
O1^ii—Ca1—O4	78.39 (3)	C1^iii—Ca1—Ca1^iv	58.53 (3)
O4^iii—Ca1—O4	99.84 (5)	O1^i—Ca1—Ca1^i	37.57 (2)
O1^i—Ca1—O2^iii	79.39 (3)	O1^ii—Ca1—Ca1^i	153.97 (2)
O1^ii—Ca1—O2^iii	121.53 (3)	O4^iii—Ca1—Ca1^i	76.76 (2)
O4^iii—Ca1—O2^iii	149.65 (3)	O4—Ca1—Ca1^i	123.15 (2)
O4—Ca1—O2^iii	98.81 (4)	O2^iii—Ca1—Ca1^i	73.02 (2)
O1^i—Ca1—O2	121.53 (3)	O2—Ca1—Ca1^i	84.41 (2)
O1^ii—Ca1—O2	79.39 (3)	O1—Ca1—Ca1^i	33.53 (2)
O4^iii—Ca1—O2	98.81 (4)	O1^iii—Ca1—Ca1^i	123.28 (3)
O4—Ca1—O2	149.65 (3)	C1—Ca1—Ca1^i	58.53 (3)
O2^iii—Ca1—O2	75.78 (5)	C1^iii—Ca1—Ca1^i	97.28 (3)
O1^i—Ca1—O1	71.10 (4)	Ca1—O4—H4A	111.0
O1^ii—Ca1—O1	124.87 (4)	Ca1—O4—H4B	110.8
O4^iii—Ca1—O1	80.03 (3)	H4A—O4—H4B	108.0
O4—Ca1—O1	156.41 (3)	C1—O2—Ca1	94.50 (8)
O2^iii—Ca1—O1	73.36 (3)	O3—C4—C5	121.72 (13)
O2—Ca1—O1	51.33 (3)	O3—C4—C3	121.53 (12)
O1^i—Ca1—O1^iii	124.87 (4)	C5—C4—C3	116.75 (12)
O1^ii—Ca1—O1^iii	71.10 (4)	C1—O1—Ca1^i	152.89 (9)
O4^iii—Ca1—O1^iii	156.41 (3)	C1—O1—Ca1	89.09 (8)
O4—Ca1—O1^iii	80.03 (3)	Ca1^i—O1—Ca1	108.90 (4)
O2^iii—Ca1—O1^iii	51.33 (3)	O2—C1—O1	121.91 (12)
O2—Ca1—O1^iii	73.36 (3)	O2—C1—C2	120.21 (12)
O1—Ca1—O1^iii	109.48 (5)	O1—C1—C2	117.82 (11)
O1^i—Ca1—C1	95.60 (4)	O2—C1—Ca1	59.55 (7)
O1^ii—Ca1—C1	104.27 (4)	O1—C1—Ca1	64.87 (7)
O4^iii—Ca1—C1	93.35 (4)	C2—C1—Ca1	161.22 (9)
O4—Ca1—C1	166.72 (4)	C1—C2—C3	115.05 (11)
O2^iii—Ca1—C1	68.56 (4)	C1—C2—H2A	108.5
O2—Ca1—C1	25.95 (3)	C3—C2—H2A	108.5
O1—Ca1—C1	26.04 (3)	C1—C2—H2B	108.5
O1^iii—Ca1—C1	88.47 (4)	C3—C2—H2B	108.5
O1^i—Ca1—C1^iii	104.27 (4)	H2A—C2—H2B	107.5
O1^ii—Ca1—C1^iii	95.60 (4)	C4—C3—C2	114.37 (11)
O4^iii—Ca1—C1^iii	166.72 (4)	C4—C3—H3A	108.7
O4—Ca1—C1^iii	93.35 (4)	C2—C3—H3A	108.7
O2^iii—Ca1—C1^iii	25.95 (3)	C4—C3—H3B	108.7
O2—Ca1—C1^iii	68.56 (4)	C2—C3—H3B	108.7
O1—Ca1—C1^iii	88.47 (4)	H3A—C3—H3B	107.6
O1^iii—Ca1—C1^iii	26.04 (3)	C4—C5—H5A	109.5
C1—Ca1—C1^iii	73.51 (5)	C4—C5—H5B	109.5
O1^i—Ca1—Ca1^iv	153.97 (2)	H5A—C5—H5B	109.5
O1^ii—Ca1—Ca1^iv	37.57 (2)	C4—C5—H5C	109.5
O4^iii—Ca1—Ca1^iv	123.15 (2)	H5A—C5—H5C	109.5
O4—Ca1—Ca1^iv	76.76 (2)	H5B—C5—H5C	109.5
O2^iii—Ca1—Ca1^iv	84.41 (2)
O1^i—Ca1—O2—C1	−2.30 (9)	O1^i—Ca1—C1—O2	178.03 (8)
O1^ii—Ca1—O2—C1	163.32 (8)	O1^ii—Ca1—C1—O2	−16.92 (8)
O4^iii—Ca1—O2—C1	79.43 (8)	O4^iii—Ca1—C1—O2	−103.32 (8)
O4—Ca1—O2—C1	−153.18 (8)	O4—Ca1—C1—O2	83.05 (17)
O2^iii—Ca1—O2—C1	−70.07 (7)	O2^iii—Ca1—C1—O2	101.76 (8)
O1—Ca1—O2—C1	9.82 (7)	O1—Ca1—C1—O2	−162.35 (12)
O1^iii—Ca1—O2—C1	−123.41 (8)	O1^iii—Ca1—C1—O2	53.14 (8)
C1^iii—Ca1—O2—C1	−96.30 (8)	C1^iii—Ca1—C1—O2	74.78 (8)
Ca1^iv—Ca1—O2—C1	−158.49 (8)	Ca1^iv—Ca1—C1—O2	20.71 (8)
Ca1^i—Ca1—O2—C1	3.79 (7)	Ca1^i—Ca1—C1—O2	−175.57 (9)
O1^i—Ca1—O1—C1	159.32 (9)	O1^i—Ca1—C1—O1	−19.62 (9)
O1^ii—Ca1—O1—C1	−42.09 (8)	O1^ii—Ca1—C1—O1	145.43 (7)
O4^iii—Ca1—O1—C1	−119.65 (7)	O4^iii—Ca1—C1—O1	59.02 (7)
O4—Ca1—O1—C1	148.55 (9)	O4—Ca1—C1—O1	−114.60 (15)
O2^iii—Ca1—O1—C1	75.10 (7)	O2^iii—Ca1—C1—O1	−95.90 (7)
O2—Ca1—O1—C1	−9.79 (7)	O2—Ca1—C1—O1	162.35 (12)
O1^iii—Ca1—O1—C1	37.99 (6)	O1^iii—Ca1—C1—O1	−144.52 (6)
C1^iii—Ca1—O1—C1	53.67 (9)	C1^iii—Ca1—C1—O1	−122.87 (9)
Ca1^iv—Ca1—O1—C1	3.63 (8)	Ca1^iv—Ca1—C1—O1	−176.95 (7)
Ca1^i—Ca1—O1—C1	159.32 (9)	Ca1^i—Ca1—C1—O1	−13.22 (6)
O1^i—Ca1—O1—Ca1^i	0.0	O1^i—Ca1—C1—C2	83.2 (3)
O1^ii—Ca1—O1—Ca1^i	158.59 (4)	O1^ii—Ca1—C1—C2	−111.8 (3)
O4^iii—Ca1—O1—Ca1^i	81.03 (4)	O4^iii—Ca1—C1—C2	161.8 (3)
O4—Ca1—O1—Ca1^i	−10.77 (10)	O4—Ca1—C1—C2	−11.8 (4)
O2^iii—Ca1—O1—Ca1^i	−84.22 (4)	O2^iii—Ca1—C1—C2	6.9 (3)
O2—Ca1—O1—Ca1^i	−169.10 (6)	O2—Ca1—C1—C2	−94.8 (3)
O1^iii—Ca1—O1—Ca1^i	−121.33 (4)	O1—Ca1—C1—C2	102.8 (3)
C1—Ca1—O1—Ca1^i	−159.32 (9)	O1^iii—Ca1—C1—C2	−41.7 (3)
C1^iii—Ca1—O1—Ca1^i	−105.65 (4)	C1^iii—Ca1—C1—C2	−20.0 (3)
Ca1^iv—Ca1—O1—Ca1^i	−155.69 (2)	Ca1^iv—Ca1—C1—C2	−74.1 (3)
Ca1—O2—C1—O1	−18.87 (13)	Ca1^i—Ca1—C1—C2	89.6 (3)
Ca1—O2—C1—C2	158.21 (10)	O2—C1—C2—C3	11.36 (18)
Ca1^i—O1—C1—O2	150.77 (13)	O1—C1—C2—C3	−171.45 (11)
Ca1—O1—C1—O2	17.93 (12)	Ca1—C1—C2—C3	95.1 (3)
Ca1^i—O1—C1—C2	−26.4 (2)	O3—C4—C3—C2	−2.20 (18)
Ca1—O1—C1—C2	−159.21 (10)	C5—C4—C3—C2	177.69 (12)
Ca1^i—O1—C1—Ca1	132.83 (18)	C1—C2—C3—C4	73.21 (15)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y, z−1/2; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3^v	0.90	2.02	2.8568 (15)	155
O4—H4B···O2^iv	0.90	1.87	2.7519 (14)	168

Symmetry codes: (iv) −x+1, −y, −z; (v) x−1/2, y+1/2, −z+1/2.