Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030619/xu2280sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030619/xu2280Isup2.hkl |
CCDC reference: 654828
DL-Malic acid (27 mg, 0.2 mmol) was mixed with potassium hydroxide (12 mg, 0.2 mmol) in water (10 ml) to give a blue solution. Slow evaporation of the solution gave colorless prismatic crystals.
Carbon- and oxygen-bound H atoms were positioned geometrically (C–H 0.97 – 0.97, O–H 0.82 Å), and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 or 1.5Ueq(C,O).
The Flack parameter was refined from 82 Friedel pairs.
In the previous C-centered monoclinic modification of racemic potassium hydrogen malate hydrate (Geize et al., 1983), the potassium atom is in an octahedron of oxygen atoms, and for the carboxylate anion the ionized and un-ionized groups cannot be distinguished. In the present C-centered monoclinic modification, the potassium atom exists in an irregular, eight-coordinate environment (Table 1). The anion features unambiguous ionized and un-ionized groups; interestingly, the double-bond oxygen atom of the ionized group is the oxygen atom that is closest to potassium despite being involved in another briding interaction.
For the first C-centered monoclinic modification, see: Geize et al. (1983).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
[K(C4H5O5)(H2O)] | F(000) = 392 |
Mr = 190.20 | Dx = 1.759 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 1338 reflections |
a = 10.534 (1) Å | θ = 3.0–27.0° |
b = 10.494 (1) Å | µ = 0.72 mm−1 |
c = 7.5640 (8) Å | T = 291 K |
β = 120.801 (1)° | Prism, colorless |
V = 718.19 (13) Å3 | 0.42 × 0.21 × 0.15 mm |
Z = 4 |
Bruker APEX area-detector diffractometer | 876 independent reflections |
Radiation source: fine-focus sealed tube | 839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 27.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→10 |
Tmin = 0.717, Tmax = 0.900 | k = −13→11 |
1561 measured reflections | l = −3→9 |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0732P)2 + 2.0212P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.001 |
876 reflections | Δρmax = 0.41 e Å−3 |
100 parameters | Δρmin = −0.28 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 82 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.1 (1) |
[K(C4H5O5)(H2O)] | V = 718.19 (13) Å3 |
Mr = 190.20 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.534 (1) Å | µ = 0.72 mm−1 |
b = 10.494 (1) Å | T = 291 K |
c = 7.5640 (8) Å | 0.42 × 0.21 × 0.15 mm |
β = 120.801 (1)° |
Bruker APEX area-detector diffractometer | 876 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 839 reflections with I > 2σ(I) |
Tmin = 0.717, Tmax = 0.900 | Rint = 0.014 |
1561 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.41 e Å−3 |
S = 1.19 | Δρmin = −0.28 e Å−3 |
876 reflections | Absolute structure: Flack (1983), 82 Friedel pairs |
100 parameters | Absolute structure parameter: −0.1 (1) |
2 restraints |
x | y | z | Uiso*/Ueq | ||
K1 | 0.50000 (12) | 0.56252 (10) | 0.50000 (14) | 0.0192 (3) | |
O1 | 0.6110 (4) | 0.8267 (4) | 0.5299 (6) | 0.0203 (8) | |
O2 | 0.8346 (4) | 0.8883 (4) | 0.5947 (6) | 0.0203 (8) | |
O3 | 0.7334 (4) | 0.6285 (3) | 0.3048 (6) | 0.0202 (8) | |
H3 | 0.8143 | 0.5933 | 0.3621 | 0.030* | |
O4 | 0.6024 (4) | 0.6425 (4) | −0.1149 (6) | 0.0214 (8) | |
O5 | 0.7244 (4) | 0.8251 (3) | −0.0892 (6) | 0.0212 (8) | |
H5 | 0.6844 | 0.8079 | −0.2120 | 0.032* | |
O6 | 0.8351 (5) | 0.5749 (4) | 0.7211 (7) | 0.0273 (9) | |
H61 | 0.8632 | 0.6450 | 0.7751 | 0.041* | |
H62 | 0.8621 | 0.5636 | 0.6381 | 0.041* | |
C1 | 0.7049 (6) | 0.8543 (5) | 0.4753 (8) | 0.0158 (10) | |
C2 | 0.6503 (6) | 0.8418 (5) | 0.2466 (8) | 0.0163 (10) | |
H2A | 0.6570 | 0.9236 | 0.1921 | 0.020* | |
H2B | 0.5477 | 0.8151 | 0.1729 | 0.020* | |
C3 | 0.7450 (6) | 0.7435 (5) | 0.2164 (7) | 0.0163 (11) | |
H3A | 0.8482 | 0.7717 | 0.2860 | 0.020* | |
C4 | 0.6835 (6) | 0.7304 (5) | −0.0148 (8) | 0.0153 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.0231 (5) | 0.0221 (5) | 0.0108 (5) | 0.0012 (5) | 0.0076 (4) | −0.0016 (5) |
O1 | 0.0222 (18) | 0.0286 (19) | 0.0117 (18) | 0.0017 (16) | 0.0098 (16) | 0.0009 (15) |
O2 | 0.0234 (19) | 0.0249 (18) | 0.0124 (18) | −0.0062 (16) | 0.0092 (16) | −0.0031 (16) |
O3 | 0.027 (2) | 0.0168 (16) | 0.017 (2) | 0.0058 (15) | 0.0117 (17) | 0.0033 (14) |
O4 | 0.0211 (19) | 0.0282 (19) | 0.0129 (18) | −0.0082 (16) | 0.0072 (16) | −0.0055 (15) |
O5 | 0.026 (2) | 0.0260 (19) | 0.0121 (17) | −0.0078 (16) | 0.0097 (16) | −0.0032 (15) |
O6 | 0.030 (2) | 0.032 (2) | 0.022 (2) | −0.0099 (19) | 0.0149 (18) | −0.0025 (18) |
C1 | 0.024 (3) | 0.009 (2) | 0.014 (3) | 0.0053 (18) | 0.009 (2) | 0.0013 (17) |
C2 | 0.017 (2) | 0.020 (2) | 0.010 (2) | 0.003 (2) | 0.006 (2) | 0.0007 (19) |
C3 | 0.015 (2) | 0.025 (2) | 0.009 (3) | −0.0009 (19) | 0.007 (2) | 0.000 (2) |
C4 | 0.019 (2) | 0.017 (2) | 0.014 (2) | 0.0032 (19) | 0.011 (2) | 0.0000 (18) |
K1—O1 | 2.972 (4) | O4—C4 | 1.222 (6) |
K1—O2i | 2.858 (4) | O4—K1ix | 2.671 (4) |
K1—O2ii | 2.689 (4) | O4—K1viii | 2.740 (4) |
K1—O3iii | 3.094 (4) | O5—C4 | 1.318 (6) |
K1—O4iv | 2.671 (4) | O5—K1x | 2.876 (4) |
K1—O4iii | 2.740 (4) | O5—H5 | 0.8200 |
K1—O5v | 2.876 (4) | O6—H61 | 0.8200 |
K1—O6 | 3.038 (5) | O6—H62 | 0.8200 |
O1—C1 | 1.285 (7) | C1—C2 | 1.524 (7) |
O2—C1 | 1.243 (6) | C2—C3 | 1.531 (7) |
O2—K1vi | 2.689 (4) | C2—H2A | 0.9700 |
O2—K1vii | 2.858 (4) | C2—H2B | 0.9700 |
O3—C3 | 1.415 (7) | C3—C4 | 1.529 (6) |
O3—K1viii | 3.094 (4) | C3—H3A | 0.9800 |
O3—H3 | 0.8200 | ||
O4iv—K1—O2ii | 147.89 (13) | K1vi—O2—K1vii | 92.34 (12) |
O4iv—K1—O4iii | 126.01 (15) | C3—O3—K1viii | 115.4 (3) |
O2ii—K1—O4iii | 85.38 (12) | C3—O3—H3 | 108.4 |
O4iv—K1—O2i | 83.42 (12) | K1viii—O3—H3 | 108.4 |
O2ii—K1—O2i | 106.65 (14) | C4—O4—K1ix | 132.6 (3) |
O4iii—K1—O2i | 88.08 (13) | C4—O4—K1viii | 131.3 (4) |
O4iv—K1—O5v | 85.55 (12) | K1ix—O4—K1viii | 95.41 (12) |
O2ii—K1—O5v | 70.55 (11) | C4—O5—K1x | 136.1 (3) |
O4iii—K1—O5v | 139.62 (12) | C4—O5—H5 | 103.1 |
O2i—K1—O5v | 69.48 (12) | K1x—O5—H5 | 103.1 |
O4iv—K1—O1 | 72.57 (11) | K1—O6—H61 | 109.5 |
O2ii—K1—O1 | 84.69 (12) | K1—O6—H62 | 109.5 |
O4iii—K1—O1 | 123.58 (12) | H61—O6—H62 | 109.5 |
O2i—K1—O1 | 147.59 (12) | O2—C1—O1 | 124.9 (5) |
O5v—K1—O1 | 86.90 (11) | O2—C1—C2 | 119.0 (5) |
O4iv—K1—O6 | 71.32 (12) | O1—C1—C2 | 116.1 (5) |
O2ii—K1—O6 | 120.74 (12) | C1—C2—C3 | 109.3 (4) |
O4iii—K1—O6 | 70.91 (12) | C1—C2—H2A | 109.8 |
O2i—K1—O6 | 125.09 (12) | C3—C2—H2A | 109.8 |
O5v—K1—O6 | 149.39 (12) | C1—C2—H2B | 109.8 |
O1—K1—O6 | 67.50 (11) | C3—C2—H2B | 109.8 |
O4iv—K1—O3iii | 70.60 (11) | H2A—C2—H2B | 108.3 |
O2ii—K1—O3iii | 141.05 (12) | O3—C3—C4 | 112.1 (4) |
O4iii—K1—O3iii | 55.67 (11) | O3—C3—C2 | 106.5 (4) |
O2i—K1—O3iii | 75.66 (11) | C4—C3—C2 | 107.7 (4) |
O5v—K1—O3iii | 139.64 (12) | O3—C3—H3A | 110.1 |
O1—K1—O3iii | 114.59 (11) | C4—C3—H3A | 110.1 |
O6—K1—O3iii | 50.32 (11) | C2—C3—H3A | 110.1 |
C1—O1—K1 | 121.6 (3) | O4—C4—O5 | 125.6 (5) |
C1—O2—K1vi | 135.4 (3) | O4—C4—C3 | 121.9 (5) |
C1—O2—K1vii | 125.8 (3) | O5—C4—C3 | 112.4 (4) |
O4iv—K1—O1—C1 | 127.0 (4) | O1—C1—C2—C3 | −119.5 (5) |
O2ii—K1—O1—C1 | −76.0 (4) | K1viii—O3—C3—C4 | −21.2 (5) |
O4iii—K1—O1—C1 | 4.9 (4) | K1viii—O3—C3—C2 | 96.4 (4) |
O2i—K1—O1—C1 | 171.0 (3) | C1—C2—C3—O3 | 57.7 (5) |
O5v—K1—O1—C1 | −146.7 (4) | C1—C2—C3—C4 | 178.1 (4) |
O6—K1—O1—C1 | 50.5 (4) | K1ix—O4—C4—O5 | 12.0 (8) |
O3iii—K1—O1—C1 | 68.7 (4) | K1viii—O4—C4—O5 | −179.5 (3) |
K1viii—K1—O1—C1 | −33.2 (4) | K1ix—O4—C4—C3 | −170.3 (3) |
K1vi—O2—C1—O1 | −3.5 (8) | K1viii—O4—C4—C3 | −1.8 (7) |
K1vii—O2—C1—O1 | −147.1 (4) | K1x—O5—C4—O4 | −126.8 (5) |
K1vi—O2—C1—C2 | 177.4 (3) | K1x—O5—C4—C3 | 55.3 (6) |
K1vii—O2—C1—C2 | 33.8 (6) | O3—C3—C4—O4 | 17.0 (7) |
K1—O1—C1—O2 | −112.4 (5) | C2—C3—C4—O4 | −99.9 (6) |
K1—O1—C1—C2 | 66.7 (5) | O3—C3—C4—O5 | −165.0 (4) |
O2—C1—C2—C3 | 59.7 (6) | C2—C3—C4—O5 | 78.1 (5) |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x, −y+1, z+1/2; (iv) x, y, z+1; (v) x−1/2, −y+3/2, z+1/2; (vi) x+1/2, −y+3/2, z+1/2; (vii) x+1/2, y+1/2, z; (viii) x, −y+1, z−1/2; (ix) x, y, z−1; (x) x+1/2, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6viii | 0.82 | 2.13 | 2.607 (5) | 117 |
O5—H5···O1ix | 0.82 | 1.70 | 2.491 (5) | 160 |
O6—H61···O1vi | 0.82 | 2.34 | 2.831 (6) | 119 |
O6—H62···O3 | 0.82 | 2.27 | 2.815 (6) | 124 |
Symmetry codes: (vi) x+1/2, −y+3/2, z+1/2; (viii) x, −y+1, z−1/2; (ix) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [K(C4H5O5)(H2O)] |
Mr | 190.20 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 291 |
a, b, c (Å) | 10.534 (1), 10.494 (1), 7.5640 (8) |
β (°) | 120.801 (1) |
V (Å3) | 718.19 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.42 × 0.21 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.717, 0.900 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1561, 876, 839 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.124, 1.19 |
No. of reflections | 876 |
No. of parameters | 100 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.28 |
Absolute structure | Flack (1983), 82 Friedel pairs |
Absolute structure parameter | −0.1 (1) |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
K1—O1 | 2.972 (4) | K1—O4iv | 2.671 (4) |
K1—O2i | 2.858 (4) | K1—O4iii | 2.740 (4) |
K1—O2ii | 2.689 (4) | K1—O5v | 2.876 (4) |
K1—O3iii | 3.094 (4) | K1—O6 | 3.038 (5) |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x, −y+1, z+1/2; (iv) x, y, z+1; (v) x−1/2, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6vi | 0.82 | 2.13 | 2.607 (5) | 117 |
O5—H5···O1vii | 0.82 | 1.70 | 2.491 (5) | 160 |
O6—H61···O1viii | 0.82 | 2.34 | 2.831 (6) | 119 |
O6—H62···O3 | 0.82 | 2.27 | 2.815 (6) | 124 |
Symmetry codes: (vi) x, −y+1, z−1/2; (vii) x, y, z−1; (viii) x+1/2, −y+3/2, z+1/2. |
In the previous C-centered monoclinic modification of racemic potassium hydrogen malate hydrate (Geize et al., 1983), the potassium atom is in an octahedron of oxygen atoms, and for the carboxylate anion the ionized and un-ionized groups cannot be distinguished. In the present C-centered monoclinic modification, the potassium atom exists in an irregular, eight-coordinate environment (Table 1). The anion features unambiguous ionized and un-ionized groups; interestingly, the double-bond oxygen atom of the ionized group is the oxygen atom that is closest to potassium despite being involved in another briding interaction.