Structure of lithium benzilate hemihydrate solved by simulated annealing and difference Fourier synthesis from powder data

The crystal structure of lithium benzilate hemihydrate (C₁₄H₁₁OLi⁺·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 (R_wp = 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.

Computing details

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)

Crystal data

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) Å^3	cylinder, 40 mm × 1.5 mm mm

Data collection

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

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

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 (Ų)

	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)

O1W—Li59	2.009 (16)	C8—C17	1.3851 (13)
O30—C36	1.218 (5)	C35—C36	1.5210 (18)
O30—Li59^i	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···O1W^ii	3.050 (3)	O1···O32^ii	3.144 (5)
O1W···O32	3.201 (5)	O1···Li60^ii	1.823 (16)
O1W···O1W^iii	3.050 (3)	O1···O1W	2.589 (3)
O1W···O1	2.589 (3)	O3···Li60^iii	1.934 (17)
O1W···Li60^ii	3.119 (18)	O4···Li60^ii	2.029 (18)
O1···O4	2.581 (4)	Li59···O30^iv	1.98 (2)
O1···O30^ii	3.201 (5)
C36—O30—Li59^i	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)
Li59^i—O30—C36—O32	123.6 (9)	C35—C48—C57—C55	−176.22 (11)
Li59^i—O30—C36—C35	−63.5 (10)	C49—C48—C57—C55	−3.70 (18)
C36—O30—Li59^i—O1W^i	−49.0 (12)	C35—C48—C49—C51	178.11 (11)
C36—O30—Li59^i—O32^i	169.7 (6)	C57—C48—C49—C51	5.56 (18)
C36—O30—Li59^i—O33^i	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)

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···O32^ii	1.00 (2)	2.54 (3)	3.252 (5)	128.2 (18)
O1w—H2W···O1w^ii	1.001 (3)	2.242 (7)	3.050 (3)	136.8 (9)

Symmetry code: (ii) −x+3/2, y−1/2, −z.