Acta Cryst. (2009). E65, o835 [ doi:10.1107/S1600536809009970 ]
The asymmetric unit of the title compound, C8H10O8·2H2O, contains one half-molecule of butane-1,2,3,4-tetracarboxylic acid and a water molecule, with the complete tetra-acid generated by crystallographic inversion symmetry. Intermolecular O-H
O hydrogen bonds form an extensive three-dimensional network, which consolidates the crystal packing.
Zn(NO3)2.6H2O (0.1461 g, 1.0 mmol) was added to a stirred aqueous solution of butane-1,2,3,4-tetracarboxylic acid (0.1176 g, 0.50 mmol) in 15 ml H2O, the resulting mixture was stirred for 20 min and then was filtered out. Colorless crystals were obtained from the filtrate (pH=2.80) after standing at room temperature for three months.
H atoms bonded to C atoms were palced in geometrically calculated position and were refined using a riding model, with Uiso(H) = 1.2 Ueq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O—H distances fixed as initially found and with Uiso(H) values set at 1.5 Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv2528fig1thm.gif)
| Fig. 1. View of the title compound showing the atomic numbering and 45% probability dispalcement ellipsoids [symmetry code: (i) -x + 1, -y + 1, -z]. H atoms omitted for clarity. |
| C8H10O8·2H2O | F(000) = 284 |
| Mr = 270.19 | Dx = 1.545 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5478 reflections |
| a = 7.4668 (15) Å | θ = 3.3–27.4° |
| b = 9.3385 (19) Å | µ = 0.15 mm−1 |
| c = 8.8406 (18) Å | T = 293 K |
| β = 109.60 (3)° | Platelet, colorless |
| V = 580.7 (2) Å3 | 0.55 × 0.46 × 0.26 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID diffractometer | 1327 independent reflections |
| Radiation source: fine-focus sealed tube | 960 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| Detector resolution: 0 pixels mm-1 | θmax = 27.4°, θmin = 3.3° |
| ω scans | h = −9→9 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −12→12 |
| Tmin = 0.921, Tmax = 0.965 | l = −11→11 |
| 5478 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.116 | H-atom parameters constrained |
| S = 1.17 | w = 1/[σ2(Fo2) + (0.0345P)2 + 0.3695P] where P = (Fo2 + 2Fc2)/3 |
| 1327 reflections | (Δ/σ)max < 0.001 |
| 82 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.23 e Å−3 |
| C8H10O8·2H2O | V = 580.7 (2) Å3 |
| Mr = 270.19 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.4668 (15) Å | µ = 0.15 mm−1 |
| b = 9.3385 (19) Å | T = 293 K |
| c = 8.8406 (18) Å | 0.55 × 0.46 × 0.26 mm |
| β = 109.60 (3)° |
| Rigaku R-AXIS RAPID diffractometer | 1327 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 960 reflections with I > 2σ(I) |
| Tmin = 0.921, Tmax = 0.965 | Rint = 0.027 |
| 5478 measured reflections | θmax = 27.4° |
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.116 | Δρmax = 0.26 e Å−3 |
| S = 1.17 | Δρmin = −0.23 e Å−3 |
| 1327 reflections | Absolute structure: ? |
| 82 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.1296 (3) | 0.38628 (19) | 0.1509 (2) | 0.0561 (5) | |
| O2 | 0.0636 (2) | 0.20225 (18) | −0.0167 (2) | 0.0494 (5) | |
| H2C | −0.0132 | 0.1808 | 0.0327 | 0.074* | |
| C1 | 0.1546 (3) | 0.3207 (2) | 0.0422 (2) | 0.0319 (5) | |
| C2 | 0.2916 (3) | 0.3636 (2) | −0.0416 (2) | 0.0371 (5) | |
| H2A | 0.2201 | 0.3991 | −0.1479 | 0.044* | |
| H2B | 0.3613 | 0.2795 | −0.0547 | 0.044* | |
| C3 | 0.4336 (3) | 0.4784 (2) | 0.0479 (2) | 0.0294 (4) | |
| H3A | 0.3640 | 0.5630 | 0.0633 | 0.035* | |
| C4 | 0.5554 (3) | 0.4210 (2) | 0.2107 (2) | 0.0299 (4) | |
| O3 | 0.6322 (3) | 0.30568 (17) | 0.23027 (19) | 0.0510 (5) | |
| O4 | 0.5724 (2) | 0.50976 (17) | 0.33017 (16) | 0.0454 (4) | |
| H4A | 0.6470 | 0.4737 | 0.4186 | 0.068* | |
| O5 | 0.8064 (2) | 0.09678 (15) | 0.10900 (16) | 0.0369 (4) | |
| H5A | 0.7639 | 0.1616 | 0.1518 | 0.055* | |
| H5B | 0.8321 | 0.0309 | 0.1725 | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0693 (12) | 0.0600 (11) | 0.0536 (10) | −0.0267 (9) | 0.0398 (9) | −0.0219 (8) |
| O2 | 0.0483 (9) | 0.0517 (10) | 0.0578 (10) | −0.0243 (8) | 0.0303 (8) | −0.0182 (8) |
| C1 | 0.0289 (10) | 0.0377 (11) | 0.0272 (9) | −0.0048 (8) | 0.0069 (8) | 0.0003 (8) |
| C2 | 0.0337 (10) | 0.0477 (13) | 0.0309 (10) | −0.0117 (9) | 0.0124 (8) | −0.0073 (9) |
| C3 | 0.0267 (9) | 0.0347 (11) | 0.0286 (9) | −0.0025 (8) | 0.0116 (8) | −0.0012 (8) |
| C4 | 0.0275 (9) | 0.0348 (11) | 0.0294 (9) | −0.0040 (8) | 0.0122 (8) | −0.0023 (8) |
| O3 | 0.0669 (11) | 0.0366 (9) | 0.0451 (9) | 0.0151 (8) | 0.0126 (8) | −0.0019 (7) |
| O4 | 0.0549 (10) | 0.0470 (9) | 0.0278 (7) | 0.0170 (7) | 0.0054 (7) | −0.0057 (6) |
| O5 | 0.0434 (8) | 0.0352 (8) | 0.0358 (7) | −0.0005 (6) | 0.0182 (6) | 0.0018 (6) |
| O1—C1 | 1.206 (2) | C3—C3i | 1.559 (3) |
| O2—C1 | 1.311 (2) | C3—H3A | 0.9800 |
| O2—H2C | 0.8523 | C4—O3 | 1.205 (2) |
| C1—C2 | 1.505 (3) | C4—O4 | 1.315 (2) |
| C2—C3 | 1.528 (3) | O4—H4A | 0.8618 |
| C2—H2A | 0.9700 | O5—H5A | 0.8314 |
| C2—H2B | 0.9700 | O5—H5B | 0.8111 |
| C3—C4 | 1.518 (3) | ||
| C1—O2—H2C | 110.1 | C4—C3—C3i | 108.55 (18) |
| O1—C1—O2 | 123.13 (18) | C2—C3—C3i | 110.94 (19) |
| O1—C1—C2 | 124.71 (18) | C4—C3—H3A | 109.3 |
| O2—C1—C2 | 112.15 (17) | C2—C3—H3A | 109.3 |
| C1—C2—C3 | 113.57 (16) | C3i—C3—H3A | 109.3 |
| C1—C2—H2A | 108.9 | O3—C4—O4 | 122.30 (18) |
| C3—C2—H2A | 108.9 | O3—C4—C3 | 123.80 (18) |
| C1—C2—H2B | 108.9 | O4—C4—C3 | 113.89 (17) |
| C3—C2—H2B | 108.9 | C4—O4—H4A | 110.0 |
| H2A—C2—H2B | 107.7 | H5A—O5—H5B | 105.9 |
| C4—C3—C2 | 109.54 (16) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2C···O5ii | 0.85 | 1.87 | 2.707 (2) | 167 |
| O4—H4A···O5iii | 0.86 | 1.83 | 2.689 (2) | 178 |
| O5—H5A···O3 | 0.83 | 1.93 | 2.754 (2) | 172 |
| O5—H5B···O1iv | 0.81 | 2.01 | 2.814 (2) | 170 |
| Symmetry codes: (ii) x−1, y, z; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2C···O5i | 0.85 | 1.87 | 2.707 (2) | 167 |
| O4—H4A···O5ii | 0.86 | 1.83 | 2.689 (2) | 178 |
| O5—H5A···O3 | 0.83 | 1.93 | 2.754 (2) | 172 |
| O5—H5B···O1iii | 0.81 | 2.01 | 2.814 (2) | 170 |
| Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2. |
This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project fo Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).
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A search of the Cambridge Structural Database (Version 5.30, February 2009) showed that most of literature dealing with butane-1,2,3,4-tetracarboxylic acid mainly concentrated in the metal organic coordination polymers (Delgado et al., 2007; Liu et al., 2008). In this paper, we report the crystal structure of butane–1,2,3,4–tetracarboxylic acid dihydrate (Fig. 1).
The asymmetric unit of the title compound contains a half of the butane-1,2,3,4-tetracarboxylic acid molecule and one water molecule. The carboxylic acid group with C1 and C4 atoms are gauche with the C1—C2—C3—C4 torsion angle being 62.13 (1)°, which match well with that in the reported structures (McKee et al., 2007; Najafpour et al., 2008). Intermolecular O—H···O hydrogen bonds (Table 1) form an extensive three-dimensional hydrogen-bonding network, which consolidate the crystal packing.