The crystal structure of lithium benzilate hemihydrate (C
14H
11O
Li
+·0.5H
2O) was solved from synchrotron powder diffraction data. This compound crystallizes in the monoclinic space group
P2
1/
a. The structure was solved
via the direct space search for two benzilate fragments using the simulated-annealing program
DASH, localization of the lithium ions and water molecule from a difference Fourier map, and a restrained Rietveld refinement (
Rwp = 0.0687). The structure is a coordination polymer of [Li
2(C
14H
11O
3)
2·H
2O]
2 tetramers building helical fourfold one-dimensional channels parallel to [010]. Inside the channels the tetrahedral coordination spheres of the lithium ions contain hydroxyl and carbonyl groups, and water molecules. The water molecule functions as the cohesive entity forming extended hydrogen-bonded chains running along [010], and bifurcated donor hydrogen bonds with the two nearest carboxylates. At the outer edge of the channels, weaker intermolecular C—H
Ph hydrogen bonds along [100] and [001] contribute to the supramolecular aggregation of the structure.
Supporting information
CCDC reference: 219247
Cell refinement: GSAS; program(s) used to solve structure: DASH; program(s) used to refine structure: GSAS; software used to prepare material for publication: ?.
Crystal data top
C14H13LiO4·C14H11LiO3 | Z = 4 |
Mr = 486.35 | F(000) = 1016 |
Monoclinic, P21/a | Dx = 1.332 Mg m−3 |
a = 34.1916 (2) Å | Synchrotron radiation |
b = 5.5346 (1) Å | T = 295 K |
c = 14.0289 (1) Å | Particle morphology: thin powder |
β = 113.998 (1)° | yellow |
V = 2425.31 (5) Å3 | cylinder, 40 mm × 1.5 mm mm |
Data collection top
High Resolution Diffractometer BM16 | Data collection mode: transmission |
Double crystal Si <111> monochromator | 2θmin = 1.0°, 2θmax = 35.998°, 2θstep = 0.003° |
Specimen mounting: borosilicate glass capillary | |
Refinement top
Refinement on Inet | 221 parameters |
Rp = 0.056 | 60 restraints |
Rwp = 0.068 | Secondary atom site location: difference Fourier map |
Rexp = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
11667 data points | (Δ/σ)max < 0.001 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1w | 0.74906 (3) | 0.4359 (2) | 0.0447 (3) | 0.0347 (1)* | |
O30 | 0.8337 (1) | 1.1310 (7) | 0.1894 (3) | 0.0275 (1)* | |
O32 | 0.8351 (1) | 0.7450 (8) | 0.1525 (3) | 0.0275 (1)* | |
O33 | 0.80786 (5) | 0.6085 (2) | 0.28944 (9) | 0.0275 (1)* | |
C35 | 0.82575 (2) | 0.8465 (2) | 0.30844 (7) | 0.0275 (1)* | |
C36 | 0.83045 (6) | 0.9196 (5) | 0.20911 (8) | 0.0275 (1)* | |
C37 | 0.79416 (3) | 1.0077 (3) | 0.32985 (6) | 0.0275 (1)* | |
C38 | 0.80328 (3) | 1.1065 (3) | 0.42734 (7) | 0.0275 (1)* | |
C40 | 0.77476 (3) | 1.2603 (3) | 0.44405 (7) | 0.0275 (1)* | |
C42 | 0.73513 (3) | 1.3053 (3) | 0.36415 (7) | 0.0275 (1)* | |
C44 | 0.72540 (3) | 1.2034 (3) | 0.26675 (7) | 0.0275 (1)* | |
C46 | 0.75416 (3) | 1.0497 (3) | 0.25095 (7) | 0.0275 (1)* | |
C48 | 0.87036 (3) | 0.8441 (2) | 0.3964 (1) | 0.0275 (1)* | |
C49 | 0.88480 (3) | 0.6474 (2) | 0.4625 (1) | 0.0275 (1)* | |
C51 | 0.92567 (3) | 0.6384 (2) | 0.5411 (1) | 0.0275 (1)* | |
C53 | 0.95501 (3) | 0.8184 (2) | 0.5498 (1) | 0.0275 (1)* | |
C55 | 0.94115 (3) | 1.0135 (2) | 0.4826 (1) | 0.0275 (1)* | |
C57 | 0.89984 (3) | 1.0243 (2) | 0.4060 (1) | 0.0275 (1)* | |
Li59 | 0.8084 (5) | 0.459 (4) | 0.158 (1) | 0.0656 (1)* | |
Li60 | 0.8459 (5) | 0.773 (3) | 0.025 (1) | 0.0600 (1)* | |
O1 | 0.67582 (5) | 0.5529 (3) | 0.0451 (3) | 0.0275 (1)* | |
C6 | 0.60462 (3) | 0.6609 (2) | −0.00457 (6) | 0.0275 (1)* | |
C7 | 0.65130 (3) | 0.7152 (2) | 0.0197 (3) | 0.0275 (1)* | |
C8 | 0.57352 (3) | 0.8322 (2) | −0.08431 (6) | 0.0275 (1)* | |
C9 | 0.53740 (3) | 0.9248 (2) | −0.07600 (7) | 0.0275 (1)* | |
C11 | 0.51061 (3) | 1.0831 (2) | −0.15034 (6) | 0.0275 (1)* | |
C13 | 0.51800 (3) | 1.1370 (3) | −0.23793 (6) | 0.0275 (1)* | |
C15 | 0.55288 (3) | 1.0362 (3) | −0.24944 (7) | 0.0275 (1)* | |
C17 | 0.58032 (3) | 0.8847 (3) | −0.17291 (6) | 0.0275 (1)* | |
C19 | 0.59955 (4) | 0.6579 (2) | 0.09824 (6) | 0.0275 (1)* | |
C20 | 0.61744 (4) | 0.8350 (2) | 0.17322 (6) | 0.0275 (1)* | |
C22 | 0.61503 (4) | 0.8210 (2) | 0.26918 (6) | 0.0275 (1)* | |
C24 | 0.59525 (4) | 0.6244 (2) | 0.29165 (6) | 0.0275 (1)* | |
C26 | 0.57769 (4) | 0.4450 (2) | 0.21776 (6) | 0.0275 (1)* | |
C28 | 0.57943 (4) | 0.4634 (2) | 0.12119 (6) | 0.0275 (1)* | |
O4 | 0.59672 (9) | 0.4261 (2) | −0.05123 (8) | 0.0275 (1)* | |
O3 | 0.66466 (1) | 0.9420 (8) | 0.0230 (3) | 0.0275 (1)* | |
H1W | 0.71714 (4) | 0.4518 (9) | 0.011 (3) | 0.4738 (1)* | |
H2W | 0.75700 (10) | 0.2609 (2) | 0.0558 (9) | 0.0521 (1)* | |
H34 | 0.80501 (7) | 0.5471 (6) | 0.35320 (9) | 0.0275 (1)* | |
H39 | 0.83178 (5) | 1.0780 (10) | 0.4860 (2) | 0.0275 (1)* | |
H41 | 0.7820 (2) | 1.3315 (5) | 0.51473 (9) | 0.0275 (1)* | |
H43 | 0.71396 (4) | 1.4100 (4) | 0.3763 (2) | 0.0275 (1)* | |
H45 | 0.69669 (5) | 1.2330 (10) | 0.20990 (2) | 0.0275 (1)* | |
H47 | 0.7468 (2) | 0.9796 (5) | 0.18004 (9) | 0.0275 (1)* | |
H50 | 0.86436 (5) | 0.5135 (3) | 0.4570 (3) | 0.0275 (1)* | |
H52 | 0.9347 (2) | 0.4965 (3) | 0.58930 (10) | 0.0275 (1)* | |
H54 | 0.98424 (5) | 0.8150 (10) | 0.6079 (2) | 0.0275 (1)* | |
H56 | 0.9614 (5) | 1.1488 (3) | 0.4890 (3) | 0.0275 (1)* | |
H58 | 0.8911 (2) | 1.1643 (3) | 0.3567 (2) | 0.0275 (1)* | |
H10 | 0.53220 (1) | 0.8888 (8) | −0.01260 (8) | 0.0275 (1)* | |
H12 | 0.48520 (4) | 1.1535 (5) | −0.1423 (2) | 0.0275 (1)* | |
H14 | 0.49843 (8) | 1.2491 (3) | −0.2924 (2) | 0.0275 (1)* | |
H16 | 0.55880 (6) | 1.0774 (8) | −0.31172 (8) | 0.0275 (1)* | |
H18 | 0.60575 (4) | 0.8154 (5) | −0.1813 (2) | 0.0275 (1)* | |
H21 | 0.63241 (6) | 0.9756 (4) | 0.1582 (2) | 0.0275 (1)* | |
H23 | 0.6276 (2) | 0.9517 (3) | 0.32210 (10) | 0.0275 (1)* | |
H25 | 0.59230 (6) | 0.6160 (10) | 0.35963 (8) | 0.0275 (1)* | |
H27 | 0.56240 (5) | 0.3059 (3) | 0.2328 (2) | 0.0275 (1)* | |
H29 | 0.5673 (2) | 0.3306 (3) | 0.06910 (10) | 0.0275 (1)* | |
H5 | 0.5915 (1) | 0.440 (1) | −0.12641 (8) | 0.0275 (1)* | |
Geometric parameters (Å, º) top
O1W—Li59 | 2.009 (16) | C8—C17 | 1.3851 (13) |
O30—C36 | 1.218 (5) | C35—C36 | 1.5210 (18) |
O30—Li59i | 1.98 (2) | C9—C11 | 1.3846 (14) |
O32—C36 | 1.301 (5) | C37—C38 | 1.3856 (14) |
O32—Li59 | 1.84 (2) | C11—C13 | 1.3840 (13) |
O32—Li60 | 1.974 (15) | C37—C46 | 1.3850 (14) |
O33—Li59 | 2.028 (16) | C13—C15 | 1.3843 (17) |
O1W—H1W | 1.00 (2) | C38—C40 | 1.3843 (19) |
O1W—H2W | 1.001 (3) | C15—C17 | 1.3844 (17) |
O3—C7 | 1.330 (4) | C40—C42 | 1.3853 (14) |
O33—H34 | 0.998 (2) | C19—C28 | 1.3842 (17) |
O1—C7 | 1.181 (3) | C42—C44 | 1.3878 (15) |
O4—C6 | 1.4305 (15) | C19—C20 | 1.3849 (14) |
O4—H5 | 0.9985 (19) | C44—C46 | 1.3846 (19) |
O33—C35 | 1.4310 (16) | C20—C22 | 1.3839 (13) |
C53—C55 | 1.3842 (17) | C48—C57 | 1.3851 (16) |
C55—C57 | 1.3852 (17) | C22—C24 | 1.3835 (17) |
C38—H39 | 1.000 (3) | C48—C49 | 1.3844 (17) |
C40—H41 | 1.000 (2) | C24—C26 | 1.3837 (14) |
C42—H43 | 0.995 (2) | C49—C51 | 1.3848 (17) |
C44—H45 | 0.9948 (18) | C26—C28 | 1.3838 (13) |
C46—H47 | 1.000 (2) | C51—C53 | 1.3835 (16) |
C49—H50 | 1.000 (2) | C9—H10 | 0.9955 (16) |
C51—H52 | 0.9998 (19) | C11—H12 | 1.000 (2) |
C53—H54 | 1.000 (3) | C22—H23 | 1.000 (2) |
C55—H56 | 0.999 (11) | C13—H14 | 1.000 (3) |
C57—H58 | 1.000 (2) | C24—H25 | 1.0000 (17) |
C6—C8 | 1.5210 (14) | C15—H16 | 1.000 (2) |
C6—C19 | 1.5212 (13) | C26—H27 | 1.000 (2) |
C6—C7 | 1.520 (2) | C17—H18 | 1.000 (2) |
C35—C37 | 1.5221 (16) | C28—H29 | 0.9999 (19) |
C8—C9 | 1.3851 (15) | C20—H21 | 1.000 (3) |
C35—C48 | 1.5226 (15) | | |
| | | |
O1W···O1Wii | 3.050 (3) | O1···O32ii | 3.144 (5) |
O1W···O32 | 3.201 (5) | O1···Li60ii | 1.823 (16) |
O1W···O1Wiii | 3.050 (3) | O1···O1W | 2.589 (3) |
O1W···O1 | 2.589 (3) | O3···Li60iii | 1.934 (17) |
O1W···Li60ii | 3.119 (18) | O4···Li60ii | 2.029 (18) |
O1···O4 | 2.581 (4) | Li59···O30iv | 1.98 (2) |
O1···O30ii | 3.201 (5) | | |
| | | |
C36—O30—Li59i | 149.2 (6) | C57—C55—H56 | 119.2 (5) |
C36—O32—Li59 | 115.2 (6) | C53—C55—H56 | 119.4 (5) |
C36—O32—Li60 | 127.5 (6) | C48—C57—H58 | 119.3 (3) |
Li59—O32—Li60 | 112.5 (7) | C55—C57—H58 | 119.6 (3) |
C35—O33—Li59 | 112.6 (6) | C7—C6—C8 | 113.44 (13) |
H1W—O1W—H2W | 109.5 (5) | C7—C6—C19 | 107.69 (16) |
Li59—O1W—H2W | 79.4 (8) | O4—C6—C7 | 105.53 (16) |
Li59—O1W—H1W | 158 (2) | O4—C6—C19 | 110.54 (11) |
C35—O33—H34 | 109.7 (2) | C8—C6—C19 | 112.89 (9) |
Li59—O33—H34 | 135.8 (6) | O4—C6—C8 | 106.52 (9) |
C6—O4—H5 | 109.4 (3) | O1—C7—C6 | 117.98 (15) |
C36—C35—C37 | 111.88 (12) | O3—C7—C6 | 120.58 (16) |
C37—C35—C48 | 113.74 (8) | O1—C7—O3 | 121.1 (2) |
O33—C35—C37 | 107.00 (10) | C9—C8—C17 | 118.60 (9) |
C36—C35—C48 | 107.49 (10) | C6—C8—C17 | 117.94 (10) |
O33—C35—C48 | 110.75 (10) | C6—C8—C9 | 123.32 (8) |
O33—C35—C36 | 105.70 (12) | C8—C9—H10 | 119.37 (17) |
O30—C36—C35 | 121.1 (2) | C11—C9—H10 | 119.72 (19) |
O32—C36—C35 | 116.5 (3) | C8—C9—C11 | 120.67 (9) |
O30—C36—O32 | 122.0 (3) | C9—C11—C13 | 120.09 (10) |
C38—C37—C46 | 118.38 (11) | C9—C11—H12 | 120.05 (17) |
C35—C37—C46 | 119.34 (9) | C13—C11—H12 | 119.81 (18) |
C35—C37—C38 | 122.22 (9) | C11—C13—C15 | 119.59 (11) |
C37—C38—C40 | 121.24 (10) | C11—C13—H14 | 120.3 (2) |
C38—C40—C42 | 119.87 (10) | C15—C13—H14 | 120.08 (19) |
C40—C42—C44 | 119.18 (12) | C17—C15—H16 | 120.1 (2) |
C42—C44—C46 | 120.39 (10) | C13—C15—H16 | 120.0 (2) |
C37—C46—C44 | 120.66 (10) | C13—C15—C17 | 119.86 (9) |
C49—C48—C57 | 117.00 (11) | C8—C17—C15 | 120.99 (11) |
C35—C48—C49 | 121.10 (10) | C8—C17—H18 | 119.76 (19) |
C35—C48—C57 | 121.47 (10) | C15—C17—H18 | 119.24 (18) |
C48—C49—C51 | 122.08 (11) | C22—C20—H21 | 119.12 (17) |
C49—C51—C53 | 120.33 (11) | C19—C20—H21 | 119.78 (17) |
C51—C53—C55 | 117.81 (11) | C19—C20—C22 | 121.10 (11) |
C53—C55—C57 | 121.38 (11) | C20—C22—C24 | 119.58 (9) |
C48—C57—C55 | 121.10 (11) | C20—C22—H23 | 120.3 (3) |
C40—C38—H39 | 118.4 (2) | C24—C22—H23 | 120.1 (3) |
C37—C38—H39 | 120.2 (2) | C22—C24—H25 | 120.1 (3) |
C38—C40—H41 | 120.2 (3) | C26—C24—H25 | 120.0 (3) |
C42—C40—H41 | 119.8 (4) | C22—C24—C26 | 119.80 (9) |
C40—C42—H43 | 120.44 (18) | C28—C26—H27 | 119.83 (17) |
C44—C42—H43 | 120.38 (17) | C24—C26—C28 | 120.15 (11) |
C46—C44—H45 | 120.4 (2) | C24—C26—H27 | 119.94 (17) |
C42—C44—H45 | 119.1 (2) | C19—C28—C26 | 120.55 (9) |
C44—C46—H47 | 119.3 (3) | C19—C28—H29 | 120.0 (3) |
C37—C46—H47 | 119.8 (4) | C26—C28—H29 | 119.4 (3) |
C51—C49—H50 | 118.8 (2) | C20—C19—C28 | 118.79 (9) |
C48—C49—H50 | 118.9 (2) | C6—C19—C28 | 119.22 (9) |
C49—C51—H52 | 120.1 (3) | C6—C19—C20 | 121.80 (11) |
C53—C51—H52 | 119.5 (3) | O1W—Li59—O33 | 111.4 (9) |
C55—C53—H54 | 121.4 (3) | O32—Li59—O33 | 82.9 (8) |
C51—C53—H54 | 120.4 (3) | O1W—Li59—O32 | 112.3 (9) |
| | | |
Li59i—O30—C36—O32 | 123.6 (9) | C35—C48—C57—C55 | −176.22 (11) |
Li59i—O30—C36—C35 | −63.5 (10) | C49—C48—C57—C55 | −3.70 (18) |
C36—O30—Li59i—O1Wi | −49.0 (12) | C35—C48—C49—C51 | 178.11 (11) |
C36—O30—Li59i—O32i | 169.7 (6) | C57—C48—C49—C51 | 5.56 (18) |
C36—O30—Li59i—O33i | 73.3 (13) | C48—C49—C51—C53 | −6.13 (19) |
Li59—O32—C36—O30 | −156.0 (6) | C49—C51—C53—C55 | 4.51 (18) |
Li59—O32—C36—C35 | 30.8 (6) | C51—C53—C55—C57 | −2.76 (18) |
Li60—O32—C36—O30 | −2.2 (8) | C53—C55—C57—C48 | 2.46 (19) |
Li60—O32—C36—C35 | −175.5 (6) | O4—C6—C7—O1 | −34.7 (4) |
C36—O32—Li59—O1W | 92.3 (7) | O4—C6—C7—O3 | 152.4 (3) |
C36—O32—Li59—O33 | −18.0 (7) | C8—C6—C7—O1 | −150.9 (3) |
Li60—O32—Li59—O1W | −65.4 (11) | O4—C6—C8—C9 | 105.17 (16) |
Li60—O32—Li59—O33 | −175.6 (6) | O4—C6—C8—C17 | −70.42 (17) |
Li59—O33—C35—C36 | 11.3 (5) | C7—C6—C8—C9 | −139.19 (15) |
Li59—O33—C35—C37 | 130.7 (5) | C7—C6—C8—C17 | 45.23 (17) |
Li59—O33—C35—C48 | −104.8 (5) | C19—C6—C8—C9 | −16.33 (14) |
C35—O33—Li59—O1W | −109.2 (8) | C19—C6—C8—C17 | 168.09 (11) |
C35—O33—Li59—O32 | 1.9 (7) | O4—C6—C19—C20 | 160.13 (15) |
O33—C35—C48—C49 | −15.07 (15) | O4—C6—C19—C28 | −14.71 (18) |
O33—C35—C48—C57 | 157.15 (12) | C7—C6—C19—C20 | 45.32 (15) |
O33—C35—C36—O30 | 159.9 (3) | C7—C6—C19—C28 | −129.52 (12) |
O33—C35—C36—O32 | −26.8 (3) | C8—C6—C19—C20 | −80.68 (14) |
C37—C35—C36—O30 | 43.8 (3) | C8—C6—C19—C28 | 104.48 (12) |
C37—C35—C48—C57 | −82.30 (14) | C19—C6—C7—O3 | −89.5 (3) |
C37—C35—C36—O32 | −142.9 (2) | C8—C6—C7—O3 | 36.2 (4) |
C48—C35—C36—O30 | −81.8 (3) | C19—C6—C7—O1 | 83.4 (4) |
C48—C35—C36—O32 | 91.6 (2) | C6—C8—C9—C11 | 179.00 (10) |
O33—C35—C37—C38 | 111.67 (14) | C9—C8—C17—C15 | 3.19 (19) |
O33—C35—C37—C46 | −65.48 (15) | C17—C8—C9—C11 | −5.44 (16) |
C36—C35—C37—C46 | 49.85 (18) | C6—C8—C17—C15 | 178.99 (12) |
C48—C35—C37—C38 | −10.96 (18) | C8—C9—C11—C13 | 4.66 (16) |
C48—C35—C37—C46 | 171.89 (12) | C9—C11—C13—C15 | −1.52 (19) |
C36—C35—C48—C57 | 42.14 (17) | C11—C13—C15—C17 | −0.7 (2) |
C37—C35—C48—C49 | 105.48 (13) | C13—C15—C17—C8 | −0.1 (2) |
C35—C37—C38—C40 | 177.43 (13) | C6—C19—C20—C22 | −175.56 (11) |
C35—C37—C46—C44 | −177.32 (12) | C20—C19—C28—C26 | −0.76 (19) |
C38—C37—C46—C44 | 5.4 (2) | C28—C19—C20—C22 | −0.70 (19) |
C46—C37—C38—C40 | −5.4 (2) | C6—C19—C28—C26 | 174.24 (11) |
C37—C38—C40—C42 | 4.2 (2) | C19—C20—C22—C24 | 1.41 (19) |
C38—C40—C42—C44 | −2.9 (2) | C20—C22—C24—C26 | −0.66 (19) |
C40—C42—C44—C46 | 3.0 (2) | C22—C24—C26—C28 | −0.78 (19) |
C42—C44—C46—C37 | −4.3 (2) | C24—C26—C28—C19 | 1.50 (19) |
Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z; (iii) −x+3/2, y+1/2, −z; (iv) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1W···O1 | 1.00 (2) | 1.757 (18) | 2.589 (3) | 138 (3) |
O1w—H1W···O32ii | 1.00 (2) | 2.54 (3) | 3.252 (5) | 128.2 (18) |
O1w—H2W···O1wii | 1.001 (3) | 2.242 (7) | 3.050 (3) | 136.8 (9) |
Symmetry code: (ii) −x+3/2, y−1/2, −z. |