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The title compound, catena-poly­[[(1,2-di­methoxy­ethane)­lithium(I)]-μ-nitrato-O:O′], [Li(NO3)(C4H10O2)]n, is a one-dimensional polymer. In the asymmetric unit, there are two Li+ cations and two monoglyme mol­ecules located on crystallographic twofold axes and one NO3 anion on a general position. Both cations are coordinated by two ether O atoms from a single monoglyme. In addition, one cation is coordinated by two bidentate anions, making a six-coordinate Li+, and the other by two monodentate anions, making a four-coordinate Li+. Each NO3 anion is coordinated to two Li+ cations, to one in a monodentate fashion and to the other in a bidentate fashion. The one-dimensional Li(monoglyme)NO3 chains are propagated by the 31 screw axis along the c axis, with alternating four- and six-coordinate Li+ cations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201499X/bt6184sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680201499X/bt6184Isup2.hkl
Contains datablock I

CCDC reference: 197456

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.025
  • wR factor = 0.060
  • Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.716 0.846 Tmin' and Tmax expected: 0.947 0.981 RR' = 0.876 Please check that your absorption correction is appropriate. STRVAL_01 From the CIF: _refine_ls_abs_structure_Flack -0.200 From the CIF: _refine_ls_abs_structure_Flack_su 1.100 Alert C Flack test results are meaningless. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.159 Tmax scaled 0.981 Tmin scaled 0.830 REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.02 From the CIF: _reflns_number_total 1367 Count of symmetry unique reflns 849 Completeness (_total/calc) 161.01% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 518 Fraction of Friedel pairs measured 0.610 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

Structural characterization of the title compound, (I), was performed as part of a comprehensive study of lithium salt phase behavior with glyme ligands (Henderson, 2002). LiNO3 tends to be highly associated into contact ion pair or aggregate solvate structures with ether solvents. During the course of preparing a phase diagram of the monoglyme–LiNO3 system, it was found that addition of excess monoglyme to the salt resulted in the rapid formation of long needle-like single crystals of (I). These crystals were structurally characterized to determine the stoichiometry of the crystalline phase formed.

Experimental top

Preparations were carried out in a dry room (<1% relative humidity). LiNO3 (Aldrich) was dried at 393 K under high vacuum for 24 h. Anhydrous monoglyme (1,2-dimethoxyethane; 99.5%, Aldrich) was used as received. The title compound was formed by the addition of excess monoglyme to the salt. Single crystals grew rapidly at room temperature. A phase diagram of the monoglyme–LiNO3 system could not be prepared as heating the mixtures does not result in homogeneous liquids. Rather, the title compound melts and the salt, LiNO3, precipitates out of the mixture.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 1998); software used to prepare material for publication: SHELXTL/PC (Bruker, 1998) and PLATON (Spek, 2001).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the Li coordination environment and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x, −x + y, 1/3 − z; (ii) y, x, −z.]
[Figure 2] Fig. 2. A view of the polymeric structure of the title compound. Key: C shaded, H open, Li dotted, O cross-hatched, and N hatched.
(I) top
Crystal data top
[Li(NO3)(C4H10O2)]Dx = 1.359 Mg m3
Mr = 159.07Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121Cell parameters from 2682 reflections
a = 7.4925 (5) Åθ = 3.1–23.8°
c = 23.989 (3) ŵ = 0.12 mm1
V = 1166.3 (2) Å3T = 173 K
Z = 6Block, colourless
F(000) = 5040.44 × 0.16 × 0.16 mm
Data collection top
Siemens CCD area-detector
diffractometer
1367 independent reflections
Radiation source: fine-focus sealed tube1255 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Blessing, 1995; Sheldrick, 2000)
h = 88
Tmin = 0.716, Tmax = 0.846k = 88
5711 measured reflectionsl = 2825
Refinement top
Refinement on F2Hydrogen site location: placed geometrically
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025 w = 1/[σ2(Fo2) + (0.0312P)2 + 0.0933P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.060(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.10 e Å3
1367 reflectionsΔρmin = 0.11 e Å3
104 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0059 (15)
Primary atom site location: direct methodsAbsolute structure: Flack (1983), 0000 Friedel pairs
Secondary atom site location: difference Fourier synthesisAbsolute structure parameter: 0.2 (11)
Crystal data top
[Li(NO3)(C4H10O2)]Z = 6
Mr = 159.07Mo Kα radiation
Trigonal, P3121µ = 0.12 mm1
a = 7.4925 (5) ÅT = 173 K
c = 23.989 (3) Å0.44 × 0.16 × 0.16 mm
V = 1166.3 (2) Å3
Data collection top
Siemens CCD area-detector
diffractometer
1367 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995; Sheldrick, 2000)
1255 reflections with I > 2σ(I)
Tmin = 0.716, Tmax = 0.846Rint = 0.025
5711 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.060Δρmax = 0.10 e Å3
S = 1.06Δρmin = 0.11 e Å3
1367 reflectionsAbsolute structure: Flack (1983), 0000 Friedel pairs
104 parametersAbsolute structure parameter: 0.2 (11)
0 restraints
Special details top

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
Li10.00000.1863 (4)0.16670.0319 (7)
Li20.2464 (5)0.2464 (5)0.00000.0370 (8)
O10.19362 (13)0.48621 (14)0.14834 (4)0.0294 (2)
C10.4097 (2)0.5737 (2)0.15760 (7)0.0369 (4)
H1A0.43720.58540.19780.055*
H1B0.48370.71080.14050.055*
H1C0.45660.48500.14080.055*
C20.1143 (2)0.6077 (2)0.17184 (7)0.0336 (4)
H2A0.17910.74510.15400.040*
H2B0.14300.62650.21230.040*
O20.53970 (15)0.35352 (14)0.02001 (4)0.0353 (3)
C30.6403 (3)0.2348 (3)0.02289 (7)0.0453 (4)
H3A0.76320.30610.04640.068*
H3B0.68080.21750.01470.068*
H3C0.54600.09930.03890.068*
C40.6692 (2)0.5533 (2)0.00218 (7)0.0374 (4)
H4A0.70270.54380.04160.045*
H4B0.79950.62500.01920.045*
N10.00426 (18)0.02720 (17)0.08617 (5)0.0275 (3)
O30.14202 (16)0.02032 (16)0.08818 (4)0.0370 (3)
O40.14688 (15)0.05930 (15)0.11836 (4)0.0347 (3)
O50.01781 (18)0.16051 (17)0.05232 (4)0.0420 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.0334 (19)0.0281 (13)0.0361 (19)0.0167 (9)0.0013 (15)0.0007 (8)
Li20.0314 (13)0.0314 (13)0.046 (2)0.0139 (16)0.0026 (8)0.0026 (8)
O10.0260 (5)0.0254 (5)0.0373 (6)0.0132 (4)0.0005 (4)0.0010 (4)
C10.0284 (8)0.0364 (8)0.0439 (9)0.0148 (7)0.0011 (7)0.0013 (7)
C20.0338 (9)0.0240 (8)0.0442 (9)0.0153 (7)0.0001 (7)0.0016 (6)
O20.0325 (6)0.0327 (6)0.0436 (6)0.0183 (5)0.0010 (5)0.0031 (5)
C30.0518 (10)0.0477 (10)0.0510 (10)0.0358 (9)0.0008 (8)0.0009 (8)
C40.0290 (8)0.0338 (8)0.0483 (10)0.0148 (7)0.0006 (7)0.0002 (7)
N10.0280 (6)0.0265 (6)0.0288 (6)0.0143 (5)0.0009 (5)0.0013 (5)
O30.0338 (6)0.0436 (6)0.0412 (6)0.0250 (5)0.0008 (4)0.0010 (5)
O40.0295 (6)0.0364 (6)0.0363 (6)0.0151 (5)0.0080 (5)0.0064 (4)
O50.0503 (7)0.0450 (7)0.0407 (7)0.0313 (6)0.0100 (5)0.0170 (5)
Geometric parameters (Å, º) top
Li1—O1i2.021 (2)Li2—N1ii2.699 (2)
Li1—O12.021 (2)Li2—N12.699 (2)
Li1—O4i2.123 (2)O1—C11.4281 (16)
Li1—O42.123 (2)O1—C21.4285 (16)
Li1—O3i2.2138 (14)C2—C2i1.504 (3)
Li1—O32.2138 (14)O2—C41.4187 (18)
Li1—N1i2.498 (2)O2—C31.4260 (18)
Li1—N12.498 (2)C4—C4ii1.509 (3)
Li2—O5ii1.955 (2)N1—O31.2498 (15)
Li2—O51.955 (2)N1—O41.2510 (15)
Li2—O21.985 (3)N1—O51.2514 (14)
Li2—O2ii1.985 (3)
O1i—Li1—O182.37 (12)O5—Li2—O2ii108.81 (5)
O1i—Li1—O4i97.75 (4)O2—Li2—O2ii81.83 (15)
O1—Li1—O4i158.47 (4)O5ii—Li2—N1ii25.31 (5)
O1i—Li1—O4158.47 (4)O5—Li2—N1ii97.58 (13)
O1—Li1—O497.75 (4)O2—Li2—N1ii129.47 (4)
O4i—Li1—O489.93 (13)O2ii—Li2—N1ii109.41 (4)
O1i—Li1—O3i108.41 (6)O5ii—Li2—N197.58 (13)
O1—Li1—O3i99.69 (6)O5—Li2—N125.31 (5)
O4i—Li1—O3i59.68 (6)O2—Li2—N1109.41 (4)
O4—Li1—O3i92.85 (10)O2ii—Li2—N1129.47 (4)
O1i—Li1—O399.69 (6)N1ii—Li2—N1100.34 (12)
O1—Li1—O3108.41 (6)C1—O1—C2112.55 (10)
O4i—Li1—O392.85 (10)C1—O1—Li1119.69 (9)
O4—Li1—O359.68 (6)C2—O1—Li1109.05 (9)
O3i—Li1—O3142.48 (16)O1—C2—C2i106.87 (9)
O1i—Li1—N1i108.42 (4)C4—O2—C3112.33 (11)
O1—Li1—N1i129.68 (4)C4—O2—Li2111.77 (10)
O4i—Li1—N1i30.04 (4)C3—O2—Li2125.66 (11)
O4—Li1—N1i88.18 (11)O2—C4—C4ii107.11 (9)
O3i—Li1—N1i30.00 (5)O3—N1—O4119.42 (11)
O3—Li1—N1i117.27 (12)O3—N1—O5120.24 (12)
O1i—Li1—N1129.68 (4)O4—N1—O5120.35 (11)
O1—Li1—N1108.42 (4)O3—N1—Li162.32 (8)
O4i—Li1—N188.18 (11)O4—N1—Li158.17 (7)
O4—Li1—N130.04 (4)O5—N1—Li1169.39 (10)
O3i—Li1—N1117.27 (12)O3—N1—Li278.66 (7)
O3—Li1—N130.00 (5)O4—N1—Li2161.29 (9)
N1i—Li1—N1101.29 (12)O5—N1—Li241.89 (6)
O5ii—Li2—O5105.86 (17)Li1—N1—Li2140.48 (6)
O5ii—Li2—O2108.81 (5)N1—O3—Li187.69 (10)
O5—Li2—O2126.05 (5)N1—O4—Li191.79 (7)
O5ii—Li2—O2ii126.05 (5)N1—O5—Li2112.80 (9)
Symmetry codes: (i) x, x+y, z+1/3; (ii) y, x, z.

Experimental details

Crystal data
Chemical formula[Li(NO3)(C4H10O2)]
Mr159.07
Crystal system, space groupTrigonal, P3121
Temperature (K)173
a, c (Å)7.4925 (5), 23.989 (3)
V3)1166.3 (2)
Z6
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.44 × 0.16 × 0.16
Data collection
DiffractometerSiemens CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Blessing, 1995; Sheldrick, 2000)
Tmin, Tmax0.716, 0.846
No. of measured, independent and
observed [I > 2σ(I)] reflections
5711, 1367, 1255
Rint0.025
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.060, 1.06
No. of reflections1367
No. of parameters104
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.10, 0.11
Absolute structureFlack (1983), 0000 Friedel pairs
Absolute structure parameter0.2 (11)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Bruker, 1998) and PLATON (Spek, 2001).

Selected bond lengths (Å) top
Li1—O12.021 (2)Li2—O51.955 (2)
Li1—O42.123 (2)Li2—O21.985 (3)
Li1—O32.2138 (14)
 

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