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The crystal structure of lithium benzilate hemihydrate (C14H11O_3^-Li+·0.5H2O) was solved from synchrotron powder diffraction data. This compound crystallizes in the monoclinic space group P21/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 [Li2(C14H11O3)2·H2O]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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103004634/ws0002sup1.cif
Contains datablocks LIBENZIL2003, I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768103004634/ws0002Isup2.rtv
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103004634/ws0002Isup3.hkl
Contains datablock I

CCDC reference: 219247

Computing details top

Cell refinement: GSAS; program(s) used to solve structure: DASH; program(s) used to refine structure: GSAS; software used to prepare material for publication: ?.

(I) top
Crystal data top
C14H13LiO4·C14H11LiO3Z = 4
Mr = 486.35F(000) = 1016
Monoclinic, P21/aDx = 1.332 Mg m3
a = 34.1916 (2) ÅSynchrotron radiation
b = 5.5346 (1) ÅT = 295 K
c = 14.0289 (1) ÅParticle morphology: thin powder
β = 113.998 (1)°yellow
V = 2425.31 (5) Å3cylinder, 40 mm × 1.5 mm mm
Data collection top
High Resolution Diffractometer BM16Data collection mode: transmission
Double crystal Si <111> monochromator2θmin = 1.0°, 2θmax = 35.998°, 2θstep = 0.003°
Specimen mounting: borosilicate glass capillary
Refinement top
Refinement on Inet221 parameters
Rp = 0.05660 restraints
Rwp = 0.068Secondary atom site location: difference Fourier map
Rexp = 0.030H 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
xyzUiso*/Ueq
O1w0.74906 (3)0.4359 (2)0.0447 (3)0.0347 (1)*
O300.8337 (1)1.1310 (7)0.1894 (3)0.0275 (1)*
O320.8351 (1)0.7450 (8)0.1525 (3)0.0275 (1)*
O330.80786 (5)0.6085 (2)0.28944 (9)0.0275 (1)*
C350.82575 (2)0.8465 (2)0.30844 (7)0.0275 (1)*
C360.83045 (6)0.9196 (5)0.20911 (8)0.0275 (1)*
C370.79416 (3)1.0077 (3)0.32985 (6)0.0275 (1)*
C380.80328 (3)1.1065 (3)0.42734 (7)0.0275 (1)*
C400.77476 (3)1.2603 (3)0.44405 (7)0.0275 (1)*
C420.73513 (3)1.3053 (3)0.36415 (7)0.0275 (1)*
C440.72540 (3)1.2034 (3)0.26675 (7)0.0275 (1)*
C460.75416 (3)1.0497 (3)0.25095 (7)0.0275 (1)*
C480.87036 (3)0.8441 (2)0.3964 (1)0.0275 (1)*
C490.88480 (3)0.6474 (2)0.4625 (1)0.0275 (1)*
C510.92567 (3)0.6384 (2)0.5411 (1)0.0275 (1)*
C530.95501 (3)0.8184 (2)0.5498 (1)0.0275 (1)*
C550.94115 (3)1.0135 (2)0.4826 (1)0.0275 (1)*
C570.89984 (3)1.0243 (2)0.4060 (1)0.0275 (1)*
Li590.8084 (5)0.459 (4)0.158 (1)0.0656 (1)*
Li600.8459 (5)0.773 (3)0.025 (1)0.0600 (1)*
O10.67582 (5)0.5529 (3)0.0451 (3)0.0275 (1)*
C60.60462 (3)0.6609 (2)0.00457 (6)0.0275 (1)*
C70.65130 (3)0.7152 (2)0.0197 (3)0.0275 (1)*
C80.57352 (3)0.8322 (2)0.08431 (6)0.0275 (1)*
C90.53740 (3)0.9248 (2)0.07600 (7)0.0275 (1)*
C110.51061 (3)1.0831 (2)0.15034 (6)0.0275 (1)*
C130.51800 (3)1.1370 (3)0.23793 (6)0.0275 (1)*
C150.55288 (3)1.0362 (3)0.24944 (7)0.0275 (1)*
C170.58032 (3)0.8847 (3)0.17291 (6)0.0275 (1)*
C190.59955 (4)0.6579 (2)0.09824 (6)0.0275 (1)*
C200.61744 (4)0.8350 (2)0.17322 (6)0.0275 (1)*
C220.61503 (4)0.8210 (2)0.26918 (6)0.0275 (1)*
C240.59525 (4)0.6244 (2)0.29165 (6)0.0275 (1)*
C260.57769 (4)0.4450 (2)0.21776 (6)0.0275 (1)*
C280.57943 (4)0.4634 (2)0.12119 (6)0.0275 (1)*
O40.59672 (9)0.4261 (2)0.05123 (8)0.0275 (1)*
O30.66466 (1)0.9420 (8)0.0230 (3)0.0275 (1)*
H1W0.71714 (4)0.4518 (9)0.011 (3)0.4738 (1)*
H2W0.75700 (10)0.2609 (2)0.0558 (9)0.0521 (1)*
H340.80501 (7)0.5471 (6)0.35320 (9)0.0275 (1)*
H390.83178 (5)1.0780 (10)0.4860 (2)0.0275 (1)*
H410.7820 (2)1.3315 (5)0.51473 (9)0.0275 (1)*
H430.71396 (4)1.4100 (4)0.3763 (2)0.0275 (1)*
H450.69669 (5)1.2330 (10)0.20990 (2)0.0275 (1)*
H470.7468 (2)0.9796 (5)0.18004 (9)0.0275 (1)*
H500.86436 (5)0.5135 (3)0.4570 (3)0.0275 (1)*
H520.9347 (2)0.4965 (3)0.58930 (10)0.0275 (1)*
H540.98424 (5)0.8150 (10)0.6079 (2)0.0275 (1)*
H560.9614 (5)1.1488 (3)0.4890 (3)0.0275 (1)*
H580.8911 (2)1.1643 (3)0.3567 (2)0.0275 (1)*
H100.53220 (1)0.8888 (8)0.01260 (8)0.0275 (1)*
H120.48520 (4)1.1535 (5)0.1423 (2)0.0275 (1)*
H140.49843 (8)1.2491 (3)0.2924 (2)0.0275 (1)*
H160.55880 (6)1.0774 (8)0.31172 (8)0.0275 (1)*
H180.60575 (4)0.8154 (5)0.1813 (2)0.0275 (1)*
H210.63241 (6)0.9756 (4)0.1582 (2)0.0275 (1)*
H230.6276 (2)0.9517 (3)0.32210 (10)0.0275 (1)*
H250.59230 (6)0.6160 (10)0.35963 (8)0.0275 (1)*
H270.56240 (5)0.3059 (3)0.2328 (2)0.0275 (1)*
H290.5673 (2)0.3306 (3)0.06910 (10)0.0275 (1)*
H50.5915 (1)0.440 (1)0.12641 (8)0.0275 (1)*
Geometric parameters (Å, º) top
O1W—Li592.009 (16)C8—C171.3851 (13)
O30—C361.218 (5)C35—C361.5210 (18)
O30—Li59i1.98 (2)C9—C111.3846 (14)
O32—C361.301 (5)C37—C381.3856 (14)
O32—Li591.84 (2)C11—C131.3840 (13)
O32—Li601.974 (15)C37—C461.3850 (14)
O33—Li592.028 (16)C13—C151.3843 (17)
O1W—H1W1.00 (2)C38—C401.3843 (19)
O1W—H2W1.001 (3)C15—C171.3844 (17)
O3—C71.330 (4)C40—C421.3853 (14)
O33—H340.998 (2)C19—C281.3842 (17)
O1—C71.181 (3)C42—C441.3878 (15)
O4—C61.4305 (15)C19—C201.3849 (14)
O4—H50.9985 (19)C44—C461.3846 (19)
O33—C351.4310 (16)C20—C221.3839 (13)
C53—C551.3842 (17)C48—C571.3851 (16)
C55—C571.3852 (17)C22—C241.3835 (17)
C38—H391.000 (3)C48—C491.3844 (17)
C40—H411.000 (2)C24—C261.3837 (14)
C42—H430.995 (2)C49—C511.3848 (17)
C44—H450.9948 (18)C26—C281.3838 (13)
C46—H471.000 (2)C51—C531.3835 (16)
C49—H501.000 (2)C9—H100.9955 (16)
C51—H520.9998 (19)C11—H121.000 (2)
C53—H541.000 (3)C22—H231.000 (2)
C55—H560.999 (11)C13—H141.000 (3)
C57—H581.000 (2)C24—H251.0000 (17)
C6—C81.5210 (14)C15—H161.000 (2)
C6—C191.5212 (13)C26—H271.000 (2)
C6—C71.520 (2)C17—H181.000 (2)
C35—C371.5221 (16)C28—H290.9999 (19)
C8—C91.3851 (15)C20—H211.000 (3)
C35—C481.5226 (15)
O1W···O1Wii3.050 (3)O1···O32ii3.144 (5)
O1W···O323.201 (5)O1···Li60ii1.823 (16)
O1W···O1Wiii3.050 (3)O1···O1W2.589 (3)
O1W···O12.589 (3)O3···Li60iii1.934 (17)
O1W···Li60ii3.119 (18)O4···Li60ii2.029 (18)
O1···O42.581 (4)Li59···O30iv1.98 (2)
O1···O30ii3.201 (5)
C36—O30—Li59i149.2 (6)C57—C55—H56119.2 (5)
C36—O32—Li59115.2 (6)C53—C55—H56119.4 (5)
C36—O32—Li60127.5 (6)C48—C57—H58119.3 (3)
Li59—O32—Li60112.5 (7)C55—C57—H58119.6 (3)
C35—O33—Li59112.6 (6)C7—C6—C8113.44 (13)
H1W—O1W—H2W109.5 (5)C7—C6—C19107.69 (16)
Li59—O1W—H2W79.4 (8)O4—C6—C7105.53 (16)
Li59—O1W—H1W158 (2)O4—C6—C19110.54 (11)
C35—O33—H34109.7 (2)C8—C6—C19112.89 (9)
Li59—O33—H34135.8 (6)O4—C6—C8106.52 (9)
C6—O4—H5109.4 (3)O1—C7—C6117.98 (15)
C36—C35—C37111.88 (12)O3—C7—C6120.58 (16)
C37—C35—C48113.74 (8)O1—C7—O3121.1 (2)
O33—C35—C37107.00 (10)C9—C8—C17118.60 (9)
C36—C35—C48107.49 (10)C6—C8—C17117.94 (10)
O33—C35—C48110.75 (10)C6—C8—C9123.32 (8)
O33—C35—C36105.70 (12)C8—C9—H10119.37 (17)
O30—C36—C35121.1 (2)C11—C9—H10119.72 (19)
O32—C36—C35116.5 (3)C8—C9—C11120.67 (9)
O30—C36—O32122.0 (3)C9—C11—C13120.09 (10)
C38—C37—C46118.38 (11)C9—C11—H12120.05 (17)
C35—C37—C46119.34 (9)C13—C11—H12119.81 (18)
C35—C37—C38122.22 (9)C11—C13—C15119.59 (11)
C37—C38—C40121.24 (10)C11—C13—H14120.3 (2)
C38—C40—C42119.87 (10)C15—C13—H14120.08 (19)
C40—C42—C44119.18 (12)C17—C15—H16120.1 (2)
C42—C44—C46120.39 (10)C13—C15—H16120.0 (2)
C37—C46—C44120.66 (10)C13—C15—C17119.86 (9)
C49—C48—C57117.00 (11)C8—C17—C15120.99 (11)
C35—C48—C49121.10 (10)C8—C17—H18119.76 (19)
C35—C48—C57121.47 (10)C15—C17—H18119.24 (18)
C48—C49—C51122.08 (11)C22—C20—H21119.12 (17)
C49—C51—C53120.33 (11)C19—C20—H21119.78 (17)
C51—C53—C55117.81 (11)C19—C20—C22121.10 (11)
C53—C55—C57121.38 (11)C20—C22—C24119.58 (9)
C48—C57—C55121.10 (11)C20—C22—H23120.3 (3)
C40—C38—H39118.4 (2)C24—C22—H23120.1 (3)
C37—C38—H39120.2 (2)C22—C24—H25120.1 (3)
C38—C40—H41120.2 (3)C26—C24—H25120.0 (3)
C42—C40—H41119.8 (4)C22—C24—C26119.80 (9)
C40—C42—H43120.44 (18)C28—C26—H27119.83 (17)
C44—C42—H43120.38 (17)C24—C26—C28120.15 (11)
C46—C44—H45120.4 (2)C24—C26—H27119.94 (17)
C42—C44—H45119.1 (2)C19—C28—C26120.55 (9)
C44—C46—H47119.3 (3)C19—C28—H29120.0 (3)
C37—C46—H47119.8 (4)C26—C28—H29119.4 (3)
C51—C49—H50118.8 (2)C20—C19—C28118.79 (9)
C48—C49—H50118.9 (2)C6—C19—C28119.22 (9)
C49—C51—H52120.1 (3)C6—C19—C20121.80 (11)
C53—C51—H52119.5 (3)O1W—Li59—O33111.4 (9)
C55—C53—H54121.4 (3)O32—Li59—O3382.9 (8)
C51—C53—H54120.4 (3)O1W—Li59—O32112.3 (9)
Li59i—O30—C36—O32123.6 (9)C35—C48—C57—C55176.22 (11)
Li59i—O30—C36—C3563.5 (10)C49—C48—C57—C553.70 (18)
C36—O30—Li59i—O1Wi49.0 (12)C35—C48—C49—C51178.11 (11)
C36—O30—Li59i—O32i169.7 (6)C57—C48—C49—C515.56 (18)
C36—O30—Li59i—O33i73.3 (13)C48—C49—C51—C536.13 (19)
Li59—O32—C36—O30156.0 (6)C49—C51—C53—C554.51 (18)
Li59—O32—C36—C3530.8 (6)C51—C53—C55—C572.76 (18)
Li60—O32—C36—O302.2 (8)C53—C55—C57—C482.46 (19)
Li60—O32—C36—C35175.5 (6)O4—C6—C7—O134.7 (4)
C36—O32—Li59—O1W92.3 (7)O4—C6—C7—O3152.4 (3)
C36—O32—Li59—O3318.0 (7)C8—C6—C7—O1150.9 (3)
Li60—O32—Li59—O1W65.4 (11)O4—C6—C8—C9105.17 (16)
Li60—O32—Li59—O33175.6 (6)O4—C6—C8—C1770.42 (17)
Li59—O33—C35—C3611.3 (5)C7—C6—C8—C9139.19 (15)
Li59—O33—C35—C37130.7 (5)C7—C6—C8—C1745.23 (17)
Li59—O33—C35—C48104.8 (5)C19—C6—C8—C916.33 (14)
C35—O33—Li59—O1W109.2 (8)C19—C6—C8—C17168.09 (11)
C35—O33—Li59—O321.9 (7)O4—C6—C19—C20160.13 (15)
O33—C35—C48—C4915.07 (15)O4—C6—C19—C2814.71 (18)
O33—C35—C48—C57157.15 (12)C7—C6—C19—C2045.32 (15)
O33—C35—C36—O30159.9 (3)C7—C6—C19—C28129.52 (12)
O33—C35—C36—O3226.8 (3)C8—C6—C19—C2080.68 (14)
C37—C35—C36—O3043.8 (3)C8—C6—C19—C28104.48 (12)
C37—C35—C48—C5782.30 (14)C19—C6—C7—O389.5 (3)
C37—C35—C36—O32142.9 (2)C8—C6—C7—O336.2 (4)
C48—C35—C36—O3081.8 (3)C19—C6—C7—O183.4 (4)
C48—C35—C36—O3291.6 (2)C6—C8—C9—C11179.00 (10)
O33—C35—C37—C38111.67 (14)C9—C8—C17—C153.19 (19)
O33—C35—C37—C4665.48 (15)C17—C8—C9—C115.44 (16)
C36—C35—C37—C4649.85 (18)C6—C8—C17—C15178.99 (12)
C48—C35—C37—C3810.96 (18)C8—C9—C11—C134.66 (16)
C48—C35—C37—C46171.89 (12)C9—C11—C13—C151.52 (19)
C36—C35—C48—C5742.14 (17)C11—C13—C15—C170.7 (2)
C37—C35—C48—C49105.48 (13)C13—C15—C17—C80.1 (2)
C35—C37—C38—C40177.43 (13)C6—C19—C20—C22175.56 (11)
C35—C37—C46—C44177.32 (12)C20—C19—C28—C260.76 (19)
C38—C37—C46—C445.4 (2)C28—C19—C20—C220.70 (19)
C46—C37—C38—C405.4 (2)C6—C19—C28—C26174.24 (11)
C37—C38—C40—C424.2 (2)C19—C20—C22—C241.41 (19)
C38—C40—C42—C442.9 (2)C20—C22—C24—C260.66 (19)
C40—C42—C44—C463.0 (2)C22—C24—C26—C280.78 (19)
C42—C44—C46—C374.3 (2)C24—C26—C28—C191.50 (19)
Symmetry codes: (i) x, y+1, z; (ii) x+3/2, y1/2, z; (iii) x+3/2, y+1/2, z; (iv) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H1W···O11.00 (2)1.757 (18)2.589 (3)138 (3)
O1w—H1W···O32ii1.00 (2)2.54 (3)3.252 (5)128.2 (18)
O1w—H2W···O1wii1.001 (3)2.242 (7)3.050 (3)136.8 (9)
Symmetry code: (ii) x+3/2, y1/2, z.
 

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