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In bis­(glycine) lithium chromate monohydrate {systematic name: poly[aquadi-μ-glycinato-μ-tetra­oxochromato(VI)-dilithium(I)]}, [CrLi2(C2H5NO2)2O4(H2O)]n, (I) (space group P212121), and bis­(glycine) lithium molybdate {systematic name: poly[di-μ-glycinato-μ-tetra­oxomolybdato(VI)-dilithium(I)]}, [Li2Mo(C2H5NO2)2O4]n, (II) (space group P21), all atoms are located on general positions. The crystal structure of (I) is characterized by infinite chains of corner-sharing [LiO4] tetra­hedra, which are connected by glycine mol­ecules to form layers. [CrO4] tetra­hedra are attached to the [LiO4] tetra­hedra. Compound (II) contains dimers of [LiO4] tetra­hedra which are connected by [MoO4] tetra­hedra to form chains, which are in turn connected by glycine mol­ecules to form double layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106003477/em1005sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003477/em1005Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003477/em1005IIsup3.hkl
Contains datablock II

CCDC references: 605656; 605657

Comment top

Compounds of glycine and inorganic lithium salts are rare; to date, only four such structures have been published (if lithium glycinate is included), namely glycine lithium nitrate (Baran et al., 2003), glycine lithium sulfate (Fleck & Bohatý, 2004), and glycine lithium chloride monohydrate and lithium glycinate (both Müller et al., 1994). During our studies of compounds of glycine and inorganic salts, we have found two new examples, namely bis(glycine) dilithium chromate monohydrate, [(Li(C2H5NO2))2(CrO4)(H2O)]n, (I), and bis(glycine) dilithium molybdate, [(Li(C2H5NO2))2(MoO4)]n, (II).

Although stoichiometrically similar, the title compounds differ greatly in terms of their crystal structures. Both can be considered as layer structures if only strong bonds are considered. (Weak hydrogen bonds connect all units into three-dimensional frameworks in both structures). However, the connectivities are rather different in the two structures.

In compound (I), both crystallographically different Li atoms are four-coordinate. The coordination polyhedra can be described as distorted tetrahedra [Li1—O distances range from 1.980 (3) to 2.080 (2) Å and Li2—O distances range from 1.936 (3) to 2.104 (3) Å]. However, there is an additional long contact between atoms Li2 and O1A [2.395 (3) Å]. Bond-valence calculations [using the bond-valence parameters from Brese & O'Keeffe (1991) and the ionic radii from Shannon (1976)] have shown that the contribution of this `bond' can be neglected. The [LiO4] tetrahedra are connected by shared corners into infinite chains parallel to [100], which are in turn connected to form layers parallel to (001) by the glycine molecules in the interstices between the chains. Tetrahedral chromate groups [Cr—O 1.6339 (10)–1.6666 (9) Å] are connected to these chains, but are not otherwise attached to the chains. Each [CrO4] tetrahedron shares one common corner with an [Li1O4] tetrahedron (namely atom O4). The amino acids provide additional connections: glycine molecules A and B act as bridging ligands between adjacent tetrahedral chains (Fig. 3). (If the long Li2—O1A contact is taken into account, molecule A can be further considered as a bidentate ligand to atom Li2.) Hydrogen bonds connect these units to form a three-dimensional framework (Table 1).

In compound (II), there are also two crystallographically different four-coordinate Li atoms. As in the structure of (I), the [LiO4] polyhedra are slightly distorted tetrahedra [Li1—O distances range from 1.904 (6) to 1.959 (7) Å and Li2—O distances range from 1.906 (6) to 1.967 (7) Å]. Two neighbouring tetrahedra form dimers through shared corners, which are actually O3 atoms from the molybdate tetrahedra [Mo—O 1.751 (3)–1.7657 (13) Å]. As a result, these three tetrahedra are connected to [Li2MoO10] clusters, the central O3 atoms being more or less centres of nearly planar triangles of the three different cations, Li1, Li2 and Mo. The molybdate groups are also attached to two symmetry-equivalent LiO4 tetrahedra via atoms O2 and O4, thus forming infinite chains parallel to [100]. In Fig. 4, these [Li2MoO10] clusters are seen side on, and in Fig 5 from above (as part of the chains). The two crystallographically different glycine molecules play different roles in the connectivity of these chains, although both act as bridging ligands. Glycine moiety A connects two adjacent chains into layers parallel to (001), while glycine moiety B lies between two such layers and provides connection to form double layers (Fig. 4). Hydrogen bonds provide further interlayer connections, as well as linkage between the double layers, to form a three-dimensional structure (Table 2).

In both compounds, the glycine molecules exist as zwitterions, NH3+CH2COO, as is usually the case in compounds of amino acids with inorganic salts. The glycine molecules are more or less planar and their backbones have extended conformations. The O1—C1—C2—N torsion angles are 168.9 (1) and −173.6 (1)° for the molecules in (I), and −173.2 (2) and −176.3 (2)° for the molecules in (II). Perfectly planar glycine molecules (torsion angle 180°) are very rare, the only example being glycine magnesium dichloride tetrahydrate (Fleck & Bohatý, 2005). All covalent bond lengths in the organic molecules of (I) and (II) are unremarkable and in good agreement with the values given by Allen et al. (1987).

All six known structures of compounds of glycine with lithium or inorganic lithium salts are rather different (Table 3). In most cases, however, building units of [LiO4] tetrahedra and linkage by the organic ligands occurs. Lithium glycinate (Müller et al., 1994) is the only member of this group that contains [LiO3N] tetrahedra. The connectivity of the tetrahedra varies throughout this group: corner-sharing dimers [compound (II)], edge-sharing dimers (glycine lithium nitrate; Baran et al., 2003), tetrahedral chains [compound (I), and lithium glycinate and glycine lithium chloride monohydrate (both Müller et al., 1994)], and tetrahedral layers (glycine lithium sulfate; Fleck & Bohatý, 2004). The carboxylate groups always assume the role of bridging ligands. In one case, namely lithium glycinate (Müller et al., 1994), the organic molecule acts as a triply bridging ligand, i.e. both O atoms, as well as the N atoms of the molecule, are part of coordination tetrahedra. Fig. 5 shows the connectivities of these compounds.

It is striking that four out of these six compounds are non-centrosymmetric, including both title compounds. Although the atomic arrangement of compound (II) is close to being centrosymmetric [i.e. P21/m, for which the program PLATON (Spek, 2003) indicated an 82% probability], a refinement in this space group does not give any sensible results.

Experimental top

Radiating aggregates of yellow transparent acicular to bladed crystals of (I) were grown by slow evaporation of an aqueous solution containing dissolved Li2CO3, CrO3 and glycine at about 295 K and pH 7. [Quantities or molar ratio?] Aggregates of colourless tabular crystals of (II) were grown by slow evaporation of an aqueous solution of Li2MoO4 and glycine at about 295 K and pH 8. [Quantities or molar ratio?]

Refinement top

For (I), the positions of the water H atoms were refined but their Uiso(H) values were constrained [Please give details of constraints]. All other H atoms of (I), and all those of (II), were refined freely.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 2003); cell refinement: HKL SCALEPACK (Otwinowski et al., 2003); data reduction: HKL DENZO (Otwinowski et al., 2003) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Version 3.0; Bergerhoff et al., 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The connectivity in compound (I), shown with displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) 2 − x, 1/2 + y, 1/2 − z; (ii) 1 − x, 1/2 + y, 1/2 − z.]
[Figure 2] Fig. 2. The connectivity in compound (II), shown with displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) −x, −1/2 + y, −z; (ii) 1 + x, y, z; (iii) x, 1 + y, z.]
[Figure 3] Fig. 3. A packing diagram for compound (I), viewed perpendicular to the chains. The layers are oriented vertically.
[Figure 4] Fig. 4. A packing diagram for compound (II). The double layers are oriented vertically. Note that two double layers are interlocked, but are not connected by any strong bonds (only by hydrogen bonds, which are not shown).
[Figure 5] Fig. 5. Connectivities and building units in compounds of glycine with lithium and inorganic lithium salts. From top to bottom: Glycine lithium chloride monohydrate (Müller et al., 1994), compound (I), glycine lithium nitrate (Baran et al., 2003), compound (II), glycine lithium sulfate (Fleck & Bohatý, 2004) and lithium glycinate (Müller et al., 1994).
(I) poly[aquadi-µ-glycinato-µ-tetraoxo-chromato(VI)lithium(I)]} top
Crystal data top
[CrLi2(C2H5NO2)2O4(H2O)]Dx = 1.800 Mg m3
Mr = 298.04Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 1654 reflections
a = 6.202 (1) Åθ = 3.9–28.7°
b = 9.192 (2) ŵ = 1.08 mm1
c = 19.294 (4) ÅT = 293 K
V = 1099.9 (4) Å3Plate, yellow
Z = 40.20 × 0.20 × 0.05 mm
F(000) = 608
Data collection top
Nonius Kappa CCD area-detector
diffractometer
4010 independent reflections
Radiation source: fine-focus sealed tube3872 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
Detector resolution: 9 pixels mm-1θmax = 32.6°, θmin = 2.5°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(Otwinowski et al., 2003)
k = 1313
Tmin = 0.813, Tmax = 0.948l = 2829
4010 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.022 w = 1/[σ2(Fo2) + (0.0363P)2 + 0.171P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.061(Δ/σ)max = 0.001
S = 1.10Δρmax = 0.32 e Å3
4010 reflectionsΔρmin = 0.38 e Å3
210 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0168 (14)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with how many Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.003 (11)
Crystal data top
[CrLi2(C2H5NO2)2O4(H2O)]V = 1099.9 (4) Å3
Mr = 298.04Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.202 (1) ŵ = 1.08 mm1
b = 9.192 (2) ÅT = 293 K
c = 19.294 (4) Å0.20 × 0.20 × 0.05 mm
Data collection top
Nonius Kappa CCD area-detector
diffractometer
4010 independent reflections
Absorption correction: multi-scan
(Otwinowski et al., 2003)
3872 reflections with I > 2σ(I)
Tmin = 0.813, Tmax = 0.948Rint = 0.000
4010 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061Δρmax = 0.32 e Å3
S = 1.10Δρmin = 0.38 e Å3
4010 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs
210 parametersAbsolute structure parameter: 0.003 (11)
0 restraints
Special details top

Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD-area detector, using 758 frames with phi- and omega-increments of 1.5 degrees and a counting time of 100 s per frame. The crystal-to-detector-distance was 40 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by Direct methods (SHELXS97, Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97, Sheldrick, 1997). All hydrogen atoms were refined freely. Using anisotropic treatment of the non-H atoms and unrestrained isotropic treatment of the H atoms (except for the H atoms of the water molecule, of which the displacement parameters were fixed), the refinement converged at the R-values of 0.022.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Li10.7598 (4)0.4913 (3)0.20004 (12)0.0267 (4)
Li20.7456 (4)0.8129 (3)0.28800 (12)0.0274 (4)
Cr10.82181 (3)0.478399 (19)0.015061 (8)0.01745 (5)
O10.58884 (15)0.53915 (12)0.01188 (6)0.0326 (2)
O20.88265 (18)0.32478 (10)0.02400 (5)0.02998 (19)
O31.01152 (17)0.59704 (10)0.00582 (5)0.0298 (2)
O40.82147 (19)0.44745 (11)0.10017 (4)0.0317 (2)
O1A0.40657 (18)0.17559 (12)0.30549 (6)0.0354 (2)
O2A0.57709 (17)0.33964 (13)0.24312 (5)0.0323 (2)
C1A0.56064 (18)0.25867 (12)0.29507 (5)0.02012 (19)
C2A0.7396 (2)0.26633 (15)0.34885 (6)0.0240 (2)
H21A0.881 (3)0.239 (2)0.3326 (9)0.028 (4)*
H22A0.781 (3)0.361 (2)0.3567 (10)0.035 (5)*
N3A0.6793 (2)0.18825 (12)0.41262 (5)0.0277 (2)
H31A0.800 (4)0.169 (3)0.4358 (12)0.050 (6)*
H32A0.639 (4)0.115 (3)0.3945 (12)0.049 (6)*
H33A0.587 (4)0.250 (2)0.4425 (11)0.046 (6)*
O1B1.06007 (15)0.46934 (12)0.24697 (5)0.02859 (18)
O2B0.9291 (2)0.64924 (14)0.31051 (6)0.0414 (3)
C1B1.06213 (19)0.55296 (12)0.29842 (6)0.0208 (2)
C2B1.24332 (19)0.53153 (15)0.35059 (6)0.0225 (2)
H21B1.367 (4)0.557 (2)0.3288 (11)0.039 (5)*
H22B1.233 (4)0.433 (2)0.3654 (11)0.039 (5)*
N3B1.21268 (19)0.62506 (13)0.41199 (6)0.0255 (2)
H31B1.181 (4)0.713 (2)0.3982 (10)0.038 (5)*
H32B1.323 (4)0.624 (3)0.4381 (12)0.043 (6)*
H33B1.115 (4)0.593 (3)0.4333 (12)0.040 (6)*
O1W0.7216 (2)0.88723 (13)0.38296 (6)0.0340 (2)
H1W0.616 (4)0.872 (2)0.3785 (11)0.026*
H2W0.689 (4)0.827 (2)0.4184 (10)0.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.0263 (9)0.0282 (11)0.0255 (9)0.0032 (8)0.0005 (8)0.0042 (8)
Li20.0264 (10)0.0299 (10)0.0260 (10)0.0032 (8)0.0011 (8)0.0036 (8)
Cr10.01830 (7)0.01935 (8)0.01470 (7)0.00010 (6)0.00060 (6)0.00023 (6)
O10.0223 (4)0.0427 (5)0.0328 (4)0.0050 (4)0.0042 (4)0.0038 (5)
O20.0393 (5)0.0238 (4)0.0268 (4)0.0016 (4)0.0058 (4)0.0060 (3)
O30.0288 (4)0.0283 (4)0.0325 (5)0.0092 (3)0.0056 (4)0.0050 (4)
O40.0404 (5)0.0399 (5)0.0148 (3)0.0054 (5)0.0019 (4)0.0004 (3)
O1A0.0339 (5)0.0369 (5)0.0354 (5)0.0155 (4)0.0077 (4)0.0023 (4)
O2A0.0333 (5)0.0395 (5)0.0239 (4)0.0009 (4)0.0035 (4)0.0125 (4)
C1A0.0214 (5)0.0206 (4)0.0184 (4)0.0022 (4)0.0026 (4)0.0012 (4)
C2A0.0222 (5)0.0311 (6)0.0187 (4)0.0010 (4)0.0027 (4)0.0006 (4)
N3A0.0398 (6)0.0241 (5)0.0192 (4)0.0003 (5)0.0075 (5)0.0030 (3)
O1B0.0293 (4)0.0363 (5)0.0203 (3)0.0004 (4)0.0047 (3)0.0081 (4)
O2B0.0447 (6)0.0431 (6)0.0364 (5)0.0240 (5)0.0156 (5)0.0074 (5)
C1B0.0215 (5)0.0239 (5)0.0171 (4)0.0003 (4)0.0030 (3)0.0014 (3)
C2B0.0222 (4)0.0251 (5)0.0203 (4)0.0039 (4)0.0038 (4)0.0044 (4)
N3B0.0290 (5)0.0272 (5)0.0203 (4)0.0039 (4)0.0063 (4)0.0054 (4)
O1W0.0478 (7)0.0273 (4)0.0268 (4)0.0023 (4)0.0029 (4)0.0020 (4)
Geometric parameters (Å, º) top
Li1—O2A1.980 (3)O2A—Li2iv2.104 (3)
Li1—O1Ai1.987 (2)C1A—C2A1.5212 (16)
Li1—O42.005 (2)C1A—Li2iv2.535 (3)
Li1—O1B2.080 (2)C2A—N3A1.4729 (16)
Li1—C1B2.728 (3)C2A—H21A0.963 (19)
Li1—Li23.410 (3)C2A—H22A0.92 (2)
Li1—Li2ii3.486 (3)N3A—H31A0.89 (2)
Li2—O2B1.936 (3)N3A—H32A0.80 (3)
Li2—O1W1.961 (3)N3A—H33A0.99 (2)
Li2—O1Biii1.994 (3)O1B—C1B1.2555 (14)
Li2—O2Ai2.104 (3)O2B—C1B1.2322 (16)
Li2—O1Ai2.395 (3)C1B—C2B1.5214 (16)
Li2—C1Ai2.535 (3)C2B—N3B1.4761 (16)
Cr1—O11.6339 (10)C2B—H21B0.90 (2)
Cr1—O21.6445 (10)C2B—H22B0.95 (2)
Cr1—O31.6541 (10)N3B—H31B0.88 (2)
Cr1—O41.6666 (9)N3B—H32B0.85 (2)
O1A—C1A1.2396 (15)N3B—H33B0.79 (2)
O1A—Li1iv1.987 (3)O1W—H1W0.68 (2)
O1A—Li2iv2.395 (3)O1W—H2W0.90 (2)
O2A—C1A1.2526 (14)
O2A—Li1—O1Ai109.00 (12)O1—Cr1—O2110.52 (6)
O2A—Li1—O4111.78 (12)O1—Cr1—O3109.04 (6)
O1Ai—Li1—O4102.64 (11)O2—Cr1—O3106.94 (5)
O2A—Li1—O1B105.15 (11)O1—Cr1—O4111.76 (6)
O1Ai—Li1—O1B124.82 (13)O2—Cr1—O4107.77 (5)
O4—Li1—O1B103.19 (11)O3—Cr1—O4110.70 (5)
O2A—Li1—C1B104.34 (10)Cr1—O4—Li1155.88 (9)
O1Ai—Li1—C1B102.55 (10)C1A—O1A—Li1iv156.50 (12)
O4—Li1—C1B125.41 (11)C1A—O1A—Li2iv81.77 (9)
O1B—Li1—C1B26.10 (5)Li1iv—O1A—Li2iv101.79 (10)
O2A—Li1—Li2112.74 (10)C1A—O2A—Li1143.23 (11)
O1Ai—Li1—Li243.44 (7)C1A—O2A—Li2iv94.68 (11)
O4—Li1—Li2131.10 (11)Li1—O2A—Li2iv120.46 (11)
O1B—Li1—Li283.72 (9)O1A—C1A—O2A123.96 (11)
C1B—Li1—Li259.42 (6)O1A—C1A—C2A118.71 (11)
O2A—Li1—Li2ii98.33 (9)O2A—C1A—C2A117.32 (11)
O1Ai—Li1—Li2ii149.52 (12)O1A—C1A—Li2iv69.28 (9)
O4—Li1—Li2ii78.54 (9)O2A—C1A—Li2iv55.81 (9)
O1B—Li1—Li2ii30.45 (6)C2A—C1A—Li2iv165.71 (10)
C1B—Li1—Li2ii56.41 (6)N3A—C2A—C1A111.21 (11)
Li2—Li1—Li2ii113.43 (7)N3A—C2A—H21A111.9 (11)
O2B—Li2—O1W96.07 (11)C1A—C2A—H21A115.4 (11)
O2B—Li2—O1Biii106.31 (12)N3A—C2A—H22A113.2 (12)
O1W—Li2—O1Biii96.36 (12)C1A—C2A—H22A111.2 (13)
O2B—Li2—O2Ai135.57 (15)H21A—C2A—H22A92.8 (17)
O1W—Li2—O2Ai98.85 (11)C2A—N3A—H31A107.8 (15)
O1Biii—Li2—O2Ai113.22 (12)C2A—N3A—H32A97.2 (17)
O2B—Li2—O1Ai89.49 (10)H31A—N3A—H32A108 (2)
O1W—Li2—O1Ai149.01 (13)C2A—N3A—H33A110.7 (13)
O1Biii—Li2—O1Ai111.30 (11)H31A—N3A—H33A108 (2)
O2Ai—Li2—O1Ai58.12 (7)H32A—N3A—H33A124 (2)
O2B—Li2—C1Ai115.44 (12)C1B—O1B—Li2ii134.66 (11)
O1W—Li2—C1Ai127.05 (12)C1B—O1B—Li1107.09 (10)
O1Biii—Li2—C1Ai112.38 (11)Li2ii—O1B—Li1117.63 (10)
O2Ai—Li2—C1Ai29.51 (5)C1B—O2B—Li2155.43 (13)
O1Ai—Li2—C1Ai28.95 (4)O2B—C1B—O1B125.63 (11)
O2B—Li2—Li154.74 (8)O2B—C1B—C2B117.54 (10)
O1W—Li2—Li1140.26 (11)O1B—C1B—C2B116.82 (10)
O1Biii—Li2—Li1116.17 (11)O2B—C1B—Li179.68 (9)
O2Ai—Li2—Li189.07 (9)O1B—C1B—Li146.81 (8)
O1Ai—Li2—Li134.77 (6)C2B—C1B—Li1160.25 (9)
C1Ai—Li2—Li162.23 (7)N3B—C2B—C1B111.13 (10)
O2B—Li2—Li1iii80.40 (10)N3B—C2B—H21B109.3 (14)
O1W—Li2—Li1iii80.85 (10)C1B—C2B—H21B106.4 (14)
O1Biii—Li2—Li1iii31.92 (6)N3B—C2B—H22B107.8 (13)
O2Ai—Li2—Li1iii143.23 (11)C1B—C2B—H22B105.7 (13)
O1Ai—Li2—Li1iii130.12 (10)H21B—C2B—H22B116.5 (19)
C1Ai—Li2—Li1iii142.54 (10)C2B—N3B—H31B108.9 (13)
Li1—Li2—Li1iii114.70 (7)C2B—N3B—H32B111.6 (15)
O2B—Li2—H1W104.5 (7)H31B—N3B—H32B112 (2)
O1W—Li2—H1W19.7 (6)C2B—N3B—H33B107.6 (17)
O1Biii—Li2—H1W110.2 (7)H31B—N3B—H33B109 (2)
O2Ai—Li2—H1W80.5 (6)H32B—N3B—H33B108 (2)
O1Ai—Li2—H1W129.9 (6)Li2—O1W—H1W83.2 (18)
C1Ai—Li2—H1W107.7 (6)Li2—O1W—H2W121.0 (12)
Li1—Li2—H1W132.9 (7)H1W—O1W—H2W76 (2)
Li1iii—Li2—H1W99.8 (6)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+2, y1/2, z+1/2; (iii) x+2, y+1/2, z+1/2; (iv) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H31A···O3ii0.89 (2)1.90 (2)2.7592 (15)161 (2)
N3A—H32A···O1Wv0.80 (3)2.16 (3)2.8377 (17)142 (2)
N3A—H33A···O3vi0.99 (2)1.83 (2)2.7877 (16)162 (2)
N3B—H31B···O4iii0.88 (2)2.15 (2)2.9801 (17)157.5 (19)
N3B—H32B···O2vii0.85 (2)2.02 (2)2.8349 (15)160 (2)
N3B—H33B···O1vi0.79 (2)2.05 (2)2.8166 (17)164 (2)
O1W—H1W···O2Ai0.68 (2)2.65 (2)3.0887 (17)125 (2)
O1W—H2W···O2vi0.90 (2)1.84 (2)2.7273 (15)167.5 (18)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+2, y1/2, z+1/2; (iii) x+2, y+1/2, z+1/2; (v) x, y1, z; (vi) x+3/2, y+1, z+1/2; (vii) x+5/2, y+1, z+1/2.
(II) poly[aquadi-µ-glycinato-µ-tetraoxo-chromato(VI)lithium(I)]} top
Crystal data top
[Li2Mo(C2H5NO2)2O4]F(000) = 320
Mr = 323.96Dx = 2.151 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 5.1924 (10) ÅCell parameters from 1222 reflections
b = 7.7339 (15) Åθ = 4.1–27.5°
c = 12.492 (3) ŵ = 1.34 mm1
β = 94.28 (3)°T = 293 K
V = 500.27 (17) Å3Block, colourless
Z = 20.10 × 0.06 × 0.06 mm
Data collection top
Nonius Kappa CCD area-detector
diffractometer
2257 independent reflections
Radiation source: fine-focus sealed tube2233 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 4.2°
ϕ and ω scansh = 66
Absorption correction: multi-scan
(Otwinowski et al., 2003)
k = 109
Tmin = 0.878, Tmax = 0.924l = 1616
2257 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.016 w = 1/[σ2(Fo2) + (0.0187P)2 + 0.143P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.040(Δ/σ)max = 0.001
S = 1.11Δρmax = 0.47 e Å3
2257 reflectionsΔρmin = 0.38 e Å3
195 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0209 (14)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with how many Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.01 (3)
Crystal data top
[Li2Mo(C2H5NO2)2O4]V = 500.27 (17) Å3
Mr = 323.96Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.1924 (10) ŵ = 1.34 mm1
b = 7.7339 (15) ÅT = 293 K
c = 12.492 (3) Å0.10 × 0.06 × 0.06 mm
β = 94.28 (3)°
Data collection top
Nonius Kappa CCD area-detector
diffractometer
2257 independent reflections
Absorption correction: multi-scan
(Otwinowski et al., 2003)
2233 reflections with I > 2σ(I)
Tmin = 0.878, Tmax = 0.924Rint = 0.000
2257 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.016All H-atom parameters refined
wR(F2) = 0.040Δρmax = 0.47 e Å3
S = 1.11Δρmin = 0.38 e Å3
2257 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs
195 parametersAbsolute structure parameter: 0.01 (3)
1 restraint
Special details top

Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD-area detector, using 310 frames with phi- and omega-increments of 2 degrees and a counting time of 120 s per frame. The crystal-to-detector-distance was 30 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by Direct methods (SHELXS97, Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97, Sheldrick, 1997). All hydrogen atoms were refined freely. Using anisotropic treatment of the non-H atoms and unrestrained isotropic treatment of the H atoms, the refinement converged at the R-values of 0.016.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Li10.2248 (11)0.4819 (8)0.2351 (4)0.0190 (11)
Li20.1996 (13)0.0303 (8)0.2086 (4)0.0235 (11)
Mo10.26350 (2)0.25000 (4)0.279775 (10)0.01523 (7)
O10.2782 (3)0.2313 (5)0.41942 (12)0.0379 (6)
O20.4266 (4)0.0753 (3)0.21502 (18)0.0221 (5)
O30.0624 (2)0.2551 (4)0.24841 (11)0.0219 (3)
O40.4118 (5)0.4456 (3)0.2405 (2)0.0313 (6)
O1A0.0975 (6)0.1084 (4)0.3242 (2)0.0437 (8)
O2A0.0962 (5)0.3926 (3)0.3516 (2)0.0312 (5)
C1A0.0134 (4)0.2449 (6)0.36305 (14)0.0231 (4)
C2A0.2191 (5)0.2190 (3)0.4296 (2)0.0246 (7)
H21A0.213 (7)0.134 (5)0.485 (3)0.031 (11)*
H22A0.357 (7)0.182 (4)0.380 (3)0.043 (9)*
N3A0.2916 (6)0.3781 (3)0.4838 (3)0.0332 (6)
H31A0.429 (7)0.365 (5)0.517 (3)0.042 (9)*
H32A0.155 (9)0.402 (5)0.528 (3)0.054 (12)*
H33A0.313 (9)0.462 (7)0.438 (4)0.082 (15)*
O1B0.0579 (3)0.4900 (3)0.06416 (16)0.0245 (4)
O2B0.1442 (4)0.5715 (3)0.09222 (14)0.0272 (4)
C1B0.1241 (4)0.4824 (3)0.00685 (19)0.0184 (4)
C2B0.3421 (4)0.3549 (3)0.00547 (18)0.0200 (5)
H21B0.494 (6)0.417 (4)0.002 (2)0.024 (7)*
H22B0.336 (4)0.236 (6)0.0501 (18)0.022 (6)*
N3B0.3096 (4)0.2663 (5)0.10997 (16)0.0211 (5)
H31B0.445 (8)0.201 (6)0.117 (3)0.064 (14)*
H32B0.307 (6)0.340 (4)0.156 (3)0.026 (8)*
H33B0.171 (6)0.216 (5)0.111 (2)0.035 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.016 (2)0.019 (2)0.022 (2)0.0009 (17)0.0009 (17)0.0001 (19)
Li20.020 (2)0.023 (3)0.028 (2)0.003 (2)0.0016 (19)0.000 (2)
Mo10.01119 (9)0.01734 (10)0.01734 (9)0.00024 (12)0.00229 (5)0.00259 (10)
O10.0335 (8)0.0620 (17)0.0186 (7)0.0098 (14)0.0039 (6)0.0027 (12)
O20.0164 (9)0.0200 (10)0.0305 (10)0.0023 (8)0.0054 (7)0.0071 (8)
O30.0141 (5)0.0158 (7)0.0365 (7)0.0005 (12)0.0061 (5)0.0028 (12)
O40.0165 (9)0.0175 (11)0.0598 (16)0.0035 (8)0.0021 (10)0.0016 (9)
O1A0.0409 (15)0.0451 (17)0.0471 (16)0.0019 (13)0.0157 (12)0.0225 (12)
O2A0.0326 (12)0.0304 (13)0.0319 (11)0.0018 (10)0.0120 (9)0.0132 (9)
C1A0.0203 (8)0.0323 (12)0.0165 (8)0.0005 (19)0.0003 (7)0.0042 (18)
C2A0.0219 (10)0.019 (2)0.0332 (11)0.0041 (10)0.0060 (9)0.0072 (11)
N3A0.0361 (15)0.0227 (13)0.0435 (15)0.0016 (11)0.0218 (13)0.0003 (11)
O1B0.0183 (8)0.0286 (11)0.0261 (10)0.0052 (8)0.0018 (7)0.0034 (8)
O2B0.0373 (11)0.0250 (10)0.0192 (8)0.0089 (8)0.0016 (7)0.0022 (7)
C1B0.0192 (11)0.0170 (11)0.0197 (11)0.0015 (9)0.0055 (9)0.0039 (9)
C2B0.0184 (11)0.0197 (12)0.0220 (11)0.0023 (9)0.0021 (8)0.0007 (9)
N3B0.0261 (10)0.0157 (14)0.0221 (8)0.0011 (11)0.0059 (7)0.0018 (12)
Geometric parameters (Å, º) top
Li1—O4i1.904 (6)O2A—C1A1.232 (5)
Li1—O2Aii1.911 (6)C1A—C2A1.529 (3)
Li1—O2B1.931 (5)C2A—N3A1.467 (4)
Li1—O31.959 (7)C2A—H21A0.95 (4)
Li1—Mo13.189 (6)C2A—H22A0.95 (3)
Li1—Mo1i3.220 (6)N3A—H31A0.86 (4)
Li1—Li23.510 (6)N3A—H32A0.88 (4)
Li2—O1A1.906 (6)N3A—H33A0.87 (6)
Li2—O1Biii1.923 (6)O1B—C1B1.248 (3)
Li2—O31.957 (7)O2B—C1B1.267 (3)
Li2—O2i1.967 (7)C1B—C2B1.517 (3)
Li2—Mo13.127 (6)C2B—N3B1.473 (3)
Li2—Mo1i3.328 (7)C2B—H21B0.92 (3)
Mo1—O41.751 (3)C2B—H22B1.15 (4)
Mo1—O11.7577 (16)N3B—H31B0.87 (5)
Mo1—O21.760 (2)N3B—H32B0.81 (4)
Mo1—O31.7657 (13)N3B—H33B0.82 (3)
O1A—C1A1.254 (5)
O4i—Li1—O2Aii116.7 (3)Li2—O3—Li1127.36 (17)
O4i—Li1—O2B103.4 (3)Mo1—O4—Li1iv123.5 (2)
O2Aii—Li1—O2B117.3 (3)C1A—O1A—Li2153.1 (3)
O4i—Li1—O3107.3 (3)C1A—O2A—Li1v134.7 (3)
O2Aii—Li1—O3102.3 (3)O2A—C1A—O1A127.0 (2)
O2B—Li1—O3109.6 (2)O2A—C1A—C2A118.7 (3)
O4i—Li1—Mo1135.2 (3)O1A—C1A—C2A114.3 (4)
O2Aii—Li1—Mo179.9 (2)N3A—C2A—C1A112.4 (3)
O2B—Li1—Mo1104.1 (2)N3A—C2A—H21A104 (2)
O3—Li1—Mo129.36 (11)C1A—C2A—H21A120 (2)
O4i—Li1—Mo1i26.99 (13)N3A—C2A—H22A110 (2)
O2Aii—Li1—Mo1i118.8 (2)C1A—C2A—H22A105 (2)
O2B—Li1—Mo1i118.6 (3)H21A—C2A—H22A105 (3)
O3—Li1—Mo1i80.9 (2)C2A—N3A—H31A112 (2)
Mo1—Li1—Mo1i108.24 (19)C2A—N3A—H32A104 (3)
O4i—Li1—Li283.5 (3)H31A—N3A—H32A112 (3)
O2Aii—Li1—Li2124.4 (3)C2A—N3A—H33A110 (3)
O2B—Li1—Li2105.4 (2)H31A—N3A—H33A110 (4)
O3—Li1—Li226.31 (12)H32A—N3A—H33A108 (4)
Mo1—Li1—Li255.41 (16)C1B—O1B—Li2vi153.0 (3)
Mo1i—Li1—Li259.10 (18)C1B—O2B—Li1125.5 (2)
O1A—Li2—O1Biii120.8 (4)O1B—C1B—O2B125.6 (3)
O1A—Li2—O3100.4 (3)O1B—C1B—C2B119.3 (2)
O1Biii—Li2—O3105.2 (3)O2B—C1B—C2B115.05 (19)
O1A—Li2—O2i113.4 (3)N3B—C2B—C1B110.8 (2)
O1Biii—Li2—O2i112.0 (3)N3B—C2B—H21B108.7 (18)
O3—Li2—O2i102.1 (3)C1B—C2B—H21B107.7 (17)
O4—Mo1—O1107.36 (16)N3B—C2B—H22B99.1 (17)
O4—Mo1—O2110.38 (10)C1B—C2B—H22B113.8 (13)
O1—Mo1—O2109.76 (15)H21B—C2B—H22B116 (2)
O4—Mo1—O3109.11 (13)C2B—N3B—H31B108 (3)
O1—Mo1—O3109.59 (8)C2B—N3B—H32B108 (2)
O2—Mo1—O3110.59 (11)H31B—N3B—H32B108 (3)
Mo1—O2—Li2iv126.4 (2)C2B—N3B—H33B106 (2)
Mo1—O3—Li2114.2 (2)H31B—N3B—H33B116 (4)
Mo1—O3—Li1117.7 (2)H32B—N3B—H33B111 (3)
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) x, y1/2, z; (iv) x1, y, z; (v) x, y1, z; (vi) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H31A···O1vii0.86 (4)1.92 (4)2.752 (3)164 (4)
N3A—H32A···O1Aviii0.88 (4)2.45 (4)3.095 (4)131 (4)
N3A—H32A···O1viii0.88 (4)2.52 (4)3.225 (4)138 (4)
N3A—H33A···O1v0.87 (6)2.39 (6)3.128 (5)143 (4)
N3B—H31B···O2Bix0.87 (5)2.36 (5)3.204 (4)164 (4)
N3B—H32B···O2vi0.81 (4)2.07 (4)2.814 (4)151 (3)
N3B—H33B···O2Biii0.82 (3)2.01 (4)2.820 (3)171 (3)
Symmetry codes: (iii) x, y1/2, z; (v) x, y1, z; (vi) x, y+1/2, z; (vii) x1, y1/2, z+1; (viii) x, y1/2, z+1; (ix) x+1, y1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[CrLi2(C2H5NO2)2O4(H2O)][Li2Mo(C2H5NO2)2O4]
Mr298.04323.96
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21
Temperature (K)293293
a, b, c (Å)6.202 (1), 9.192 (2), 19.294 (4)5.1924 (10), 7.7339 (15), 12.492 (3)
α, β, γ (°)90, 90, 9090, 94.28 (3), 90
V3)1099.9 (4)500.27 (17)
Z42
Radiation typeMo KαMo Kα
µ (mm1)1.081.34
Crystal size (mm)0.20 × 0.20 × 0.050.10 × 0.06 × 0.06
Data collection
DiffractometerNonius Kappa CCD area-detector
diffractometer
Nonius Kappa CCD area-detector
diffractometer
Absorption correctionMulti-scan
(Otwinowski et al., 2003)
Multi-scan
(Otwinowski et al., 2003)
Tmin, Tmax0.813, 0.9480.878, 0.924
No. of measured, independent and
observed [I > 2σ(I)] reflections
4010, 4010, 3872 2257, 2257, 2233
Rint0.0000.000
(sin θ/λ)max1)0.7580.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.061, 1.10 0.016, 0.040, 1.11
No. of reflections40102257
No. of parameters210195
No. of restraints01
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.32, 0.380.47, 0.38
Absolute structureFlack (1983), with how many Friedel pairsFlack (1983), with how many Friedel pairs
Absolute structure parameter0.003 (11)0.01 (3)

Computer programs: COLLECT (Nonius, 2003), HKL SCALEPACK (Otwinowski et al., 2003), HKL DENZO (Otwinowski et al., 2003) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Version 3.0; Bergerhoff et al., 1996), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N3A—H31A···O3i0.89 (2)1.90 (2)2.7592 (15)161 (2)
N3A—H32A···O1Wii0.80 (3)2.16 (3)2.8377 (17)142 (2)
N3A—H33A···O3iii0.99 (2)1.83 (2)2.7877 (16)162 (2)
N3B—H31B···O4iv0.88 (2)2.15 (2)2.9801 (17)157.5 (19)
N3B—H32B···O2v0.85 (2)2.02 (2)2.8349 (15)160 (2)
N3B—H33B···O1iii0.79 (2)2.05 (2)2.8166 (17)164 (2)
O1W—H1W···O2Avi0.68 (2)2.65 (2)3.0887 (17)125 (2)
O1W—H2W···O2iii0.90 (2)1.84 (2)2.7273 (15)167.5 (18)
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x, y1, z; (iii) x+3/2, y+1, z+1/2; (iv) x+2, y+1/2, z+1/2; (v) x+5/2, y+1, z+1/2; (vi) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3A—H31A···O1i0.86 (4)1.92 (4)2.752 (3)164 (4)
N3A—H32A···O1Aii0.88 (4)2.45 (4)3.095 (4)131 (4)
N3A—H32A···O1ii0.88 (4)2.52 (4)3.225 (4)138 (4)
N3A—H33A···O1iii0.87 (6)2.39 (6)3.128 (5)143 (4)
N3B—H31B···O2Biv0.87 (5)2.36 (5)3.204 (4)164 (4)
N3B—H32B···O2v0.81 (4)2.07 (4)2.814 (4)151 (3)
N3B—H33B···O2Bvi0.82 (3)2.01 (4)2.820 (3)171 (3)
Symmetry codes: (i) x1, y1/2, z+1; (ii) x, y1/2, z+1; (iii) x, y1, z; (iv) x+1, y1/2, z; (v) x, y+1/2, z; (vi) x, y1/2, z.
Compounds of glycine with lithium and inorganic lithium salts: overview of stoichiometries, space groups and connectivities. If connectivities are described with two words, the first word refers to the connection of the tetrahedra via shared corners or edges and the second to the connection of the tetrahedral units via glycine molecules. top
CompoundSpace groupConnectivityReference
Lithium glycinateP212121chains/framework(a)
Glycine LiCl·H2OP21/cchains(a)
Glycine Li2SO4Pna21layer(b)
Glycine LiNO3P1dimers/chains(c)
Glycine2 Li2CrO4·H2OP212121chains/layers(d)
Glycine2 Li2MoO4P21dimers/layers(d)
References: (a) Müller et al. (1994); (b) Fleck & Bohatý (2004); (c) Baran et al. (2003); (d) this work.
 

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