A redetermination of lithium chloride dioxane

The crystal structure of the title compound, poly­[μ₂-chloro-μ₂-dioxane-κ²O:O′-lithium(I)], [LiCl(C₄H₈O₂)]_n, displays a three-dimensional diamondoid network composed of Li—Cl and Li—O interactions. Each metal centre is similarly surrounded by two dioxane mol­ecules and two chlorine atoms. The Li—O coordination is propagated along the c axis, forming a one-dimensional chain, and the three-dimensional structure is completed by Li—Cl interactions parallel to the ab plane. Principal dimensions include Li—Cl distances of 2.3115 (10) and 2.3270 (11) Å and Li—O distances of 1.9574 (10) and 1.9981 (11) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.017
• wR factor = 0.045
• Data-to-parameter ratio = 41.0

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C There is an ordering error in _exptl_crystal_colour.
            It should be (QUALIFIER) (INTENSITY) (BASE_COLOUR).
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.09
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.50 Ratio

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           36.32
           From the CIF: _reflns_number_total               3031
           Count of symmetry unique reflns         1748
           Completeness (_total/calc)            173.40%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1283
           Fraction of Friedel pairs measured     0.734
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Sheldrick, 2003); program(s) used to solve structure: XS (Sheldrick, 2001); program(s) used to refine structure: XL (Sheldrick, 2001); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XCIF (Sheldrick, 2001).

poly[µ₂-chloro-µ₂-dioxane-κ²O:O'-lithium(I)]

Crystal data

[LiCl(C4H8O2)]	F(000) = 272
Mr = 130.49	Dx = 1.380 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7757 reflections
a = 7.1227 (1) Å	θ = 3.2–38.3°
b = 7.7284 (1) Å	µ = 0.51 mm^−1
c = 11.4138 (1) Å	T = 100 K
V = 628.30 (1) Å^3	Needle, clear colourless
Z = 4	0.35 × 0.21 × 0.16 mm

Data collection

Bruker SMART APEX diffractometer	3031 independent reflections
Radiation source: fine-focus sealed tube, Siemens KFFMO2K-90	2941 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.33 pixels mm^-1	θmax = 36.3°, θmin = 3.2°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −12→12
Tmin = 0.841, Tmax = 0.922	l = −19→18
30357 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.017	H-atom parameters constrained
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 0.007P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3031 reflections	Δρmax = 0.38 e Å^−3
74 parameters	Δρmin = −0.12 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1285 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Special details

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. Three-dimensional diamondoid network formed by lithium-chloride and lithium- dioxane interactions. H atoms were placed on at calculated positions and allowed to ride on parent atom. Hydrogen thermal parameters were set to 1.2 × the equivalent isotropic U of the parent atom.

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 (Ų)

	x	y	z	Uiso*/Ueq
Li1	0.86206 (14)	0.12734 (14)	0.03626 (8)	0.01514 (16)
Cl1	0.685733 (16)	0.365608 (15)	−0.022286 (11)	0.01480 (3)
O1	0.80639 (6)	0.09282 (5)	0.20256 (3)	0.01520 (7)
O2	0.72100 (5)	0.07984 (5)	0.44527 (3)	0.01363 (7)
C1	0.93006 (8)	0.00899 (7)	0.28467 (5)	0.01644 (9)
H1A	1.0614	0.0192	0.2571	0.020*
H1B	0.8984	−0.1155	0.2897	0.020*
C2	0.91189 (7)	0.09083 (7)	0.40439 (4)	0.01515 (8)
H2A	0.9960	0.0309	0.4603	0.018*
H2B	0.9506	0.2137	0.4003	0.018*
C3	0.60039 (7)	0.16809 (7)	0.36373 (4)	0.01485 (8)
H3A	0.6368	0.2915	0.3588	0.018*
H3B	0.4688	0.1620	0.3913	0.018*
C4	0.61601 (7)	0.08537 (8)	0.24411 (5)	0.01611 (9)
H4A	0.5749	−0.0368	0.2486	0.019*
H4B	0.5327	0.1464	0.1884	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.0160 (4)	0.0177 (4)	0.0118 (4)	0.0001 (3)	0.0003 (3)	−0.0011 (3)
Cl1	0.01154 (5)	0.01466 (5)	0.01820 (5)	0.00052 (4)	−0.00224 (4)	0.00037 (4)
O1	0.01494 (15)	0.02127 (16)	0.00938 (13)	0.00168 (14)	0.00048 (12)	0.00138 (12)
O2	0.01435 (16)	0.01624 (15)	0.01031 (13)	0.00198 (12)	0.00079 (11)	0.00285 (12)
C1	0.0157 (2)	0.0201 (2)	0.01351 (18)	0.00490 (18)	0.00200 (15)	0.00266 (16)
C2	0.01311 (19)	0.0200 (2)	0.01233 (17)	−0.00085 (16)	−0.00196 (15)	0.00277 (16)
C3	0.0150 (2)	0.0175 (2)	0.01207 (17)	0.00399 (16)	0.00072 (15)	0.00307 (15)
C4	0.01371 (19)	0.0224 (2)	0.01217 (18)	−0.00213 (17)	−0.00183 (15)	0.00026 (17)

Geometric parameters (Å, º)

Li1—O1	1.9574 (10)	C1—C2	1.5112 (8)
Li1—O2^i	1.9981 (11)	C1—H1A	0.9900
Li1—Cl1^ii	2.3115 (10)	C1—H1B	0.9900
Li1—Cl1	2.3270 (11)	C2—H2A	0.9900
Cl1—Li1^iii	2.3116 (10)	C2—H2B	0.9900
O1—C4	1.4377 (7)	C3—C4	1.5117 (8)
O1—C1	1.4401 (7)	C3—H3A	0.9900
O2—C3	1.4385 (6)	C3—H3B	0.9900
O2—C2	1.4400 (6)	C4—H4A	0.9900
O2—Li1^iv	1.9981 (11)	C4—H4B	0.9900
O1—Li1—O2^i	109.56 (5)	O2—C2—C1	110.43 (4)
O1—Li1—Cl1^ii	105.79 (4)	O2—C2—H2A	109.6
O2^i—Li1—Cl1^ii	106.16 (4)	C1—C2—H2A	109.6
O1—Li1—Cl1	106.08 (4)	O2—C2—H2B	109.6
O2^i—Li1—Cl1	108.97 (4)	C1—C2—H2B	109.6
Cl1^ii—Li1—Cl1	119.99 (4)	H2A—C2—H2B	108.1
Li1^iii—Cl1—Li1	125.22 (3)	O2—C3—C4	109.87 (4)
C4—O1—C1	110.14 (4)	O2—C3—H3A	109.7
C4—O1—Li1	121.09 (4)	C4—C3—H3A	109.7
C1—O1—Li1	124.64 (4)	O2—C3—H3B	109.7
C3—O2—C2	109.04 (4)	C4—C3—H3B	109.7
C3—O2—Li1^iv	122.64 (4)	H3A—C3—H3B	108.2
C2—O2—Li1^iv	119.69 (4)	O1—C4—C3	110.51 (4)
O1—C1—C2	110.35 (4)	O1—C4—H4A	109.5
O1—C1—H1A	109.6	C3—C4—H4A	109.5
C2—C1—H1A	109.6	O1—C4—H4B	109.5
O1—C1—H1B	109.6	C3—C4—H4B	109.5
C2—C1—H1B	109.6	H4A—C4—H4B	108.1
H1A—C1—H1B	108.1

Symmetry codes: (i) −x+3/2, −y, z−1/2; (ii) x+1/2, −y+1/2, −z; (iii) x−1/2, −y+1/2, −z; (iv) −x+3/2, −y, z+1/2.