Lithium hydrogen iodo­fumarate monohydrate

Yellow crystals of the title compound, poly[[aqua­lithium(I)]-μ₃-iodo­fumarato], [Li(HOOC—CH=CI—COO)(H₂O)]_n, crystallized unexpectedly from an aqueous solution containing acetyl­ene­dicarboxylic acid and LiI. The lithium cation is coordinated tetra­hedrally by four O atoms of three iodo­fumarate anions and one water mol­ecule. These tetra­hedra are connected such that a layered coordination polymer is formed.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.091
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.93

Author Response: This is probably due to the diffractometer we used (Stoe IPDS I) and the orientation of the plate-like crystal.

Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O3     -   H32    ...          ?

Author Response: Surprinsingly, there is just an acceptor for H31, but no acceptor for H32 was found. This is a rare, but not a completely unusual feature. It was found for water molecules in some compounds we synthesized within the last years.

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           28.00
           From the CIF: _diffrn_reflns_theta_full          28.00
           From the CIF: _reflns_number_total               1740
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         1869
           Completeness (_total/calc)             93.10%
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.41
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.53 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.82(7), Rep     0.81(2) ......       3.50 su-Rat
              O3   -H31     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(6), Rep     0.81(2) ......       3.00 su-Rat
              O3   -H32     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(7), Rep     0.81(2) ......       3.50 su-Rat
              O3   -H31     1.555   1.555

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

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

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Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.

poly[[aqualithium(I)]-µ₃-iodofumarato]

Crystal data

[Li(C4H2IO4)(H2O)]	F(000) = 496
Mr = 265.91	Dx = 2.270 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1058 reflections
a = 7.5649 (15) Å	θ = 1.9–28.2°
b = 6.7833 (8) Å	µ = 4.08 mm^−1
c = 15.502 (3) Å	T = 295 K
β = 101.98 (2)°	Plate, yellow
V = 778.2 (2) Å^3	0.50 × 0.20 × 0.05 mm
Z = 4

Data collection

Stoe IPDS-I diffractometer	1740 independent reflections
Radiation source: fine-focus sealed tube	1523 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ scans	θmax = 28.0°, θmin = 2.8°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001); the crystal shape was optimized by X-SHAPE (Stoe & Cie, 1999)]	h = −9→10
Tmin = 0.202, Tmax = 0.608	k = −8→8
10677 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0429P)^2 + 1.7418P] where P = (Fo^2 + 2Fc^2)/3
1740 reflections	(Δ/σ)max = 0.001
113 parameters	Δρmax = 1.12 e Å^−3
3 restraints	Δρmin = −1.52 e Å^−3

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. 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
I1	0.89974 (5)	0.13664 (5)	0.215616 (18)	0.05235 (15)
Li1	1.3194 (11)	0.0323 (12)	0.4625 (4)	0.0434 (17)
C1	0.8871 (5)	−0.1968 (7)	0.0797 (2)	0.0344 (8)
O11	0.7601 (6)	−0.0952 (6)	0.0387 (2)	0.0582 (10)
O12	0.9537 (5)	−0.3443 (5)	0.04943 (19)	0.0451 (8)
C2	0.9665 (5)	−0.1432 (6)	0.1755 (2)	0.0312 (8)
C3	1.0607 (5)	−0.2770 (6)	0.2298 (2)	0.0344 (8)
H3	1.0800	−0.3979	0.2051	0.044 (14)*
C4	1.1374 (5)	−0.2523 (7)	0.3253 (2)	0.0360 (8)
O41	1.1491 (5)	−0.4200 (6)	0.36729 (19)	0.0515 (8)
H41	1.177 (9)	−0.393 (9)	0.4199 (16)	0.064 (18)*
O42	1.1868 (5)	−0.0963 (5)	0.35916 (19)	0.0506 (8)
O3	1.1407 (6)	0.1933 (7)	0.4997 (3)	0.0631 (10)
H31	1.184 (11)	0.291 (8)	0.527 (5)	0.09 (3)*
H32	1.051 (8)	0.204 (16)	0.460 (4)	0.12 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0598 (2)	0.0508 (2)	0.04005 (18)	0.01789 (14)	−0.00440 (13)	−0.01448 (12)
Li1	0.052 (4)	0.044 (5)	0.030 (3)	−0.010 (3)	−0.002 (3)	0.002 (3)
C1	0.0391 (19)	0.041 (2)	0.0199 (14)	0.0015 (16)	−0.0002 (13)	−0.0029 (14)
O11	0.073 (2)	0.064 (2)	0.0283 (14)	0.0276 (19)	−0.0121 (14)	−0.0098 (14)
O12	0.0569 (19)	0.046 (2)	0.0277 (13)	0.0096 (14)	−0.0019 (12)	−0.0111 (11)
C2	0.0353 (18)	0.035 (2)	0.0223 (14)	0.0001 (14)	0.0032 (12)	−0.0062 (12)
C3	0.041 (2)	0.037 (2)	0.0220 (14)	−0.0018 (16)	−0.0006 (13)	−0.0051 (13)
C4	0.0345 (19)	0.045 (3)	0.0258 (16)	0.0005 (16)	−0.0012 (13)	−0.0017 (15)
O41	0.072 (2)	0.050 (2)	0.0258 (13)	−0.0070 (16)	−0.0052 (13)	0.0028 (13)
O42	0.067 (2)	0.047 (2)	0.0288 (13)	−0.0040 (16)	−0.0105 (13)	−0.0066 (12)
O3	0.056 (2)	0.066 (3)	0.063 (2)	−0.0078 (19)	0.0021 (18)	−0.016 (2)

Geometric parameters (Å, º)

Li1—O42	1.915 (7)	C2—I1	2.092 (4)
Li1—O3	1.917 (10)	C3—C4	1.484 (5)
Li1—O12^i	1.952 (8)	C3—H3	0.9300
Li1—O12^ii	1.977 (8)	C4—O42	1.206 (5)
Li1—Li1^iii	2.773 (15)	C4—O41	1.304 (6)
C1—O11	1.244 (5)	O41—H41	0.82 (2)
C1—O12	1.255 (5)	O3—H31	0.81 (2)
C1—C2	1.526 (5)	O3—H32	0.81 (2)
C2—C3	1.338 (5)
O42—Li1—O3	103.4 (4)	C1—O12—Li1^iv	143.8 (4)
O42—Li1—O12^i	115.8 (4)	C1—O12—Li1^v	125.5 (4)
O3—Li1—O12^i	118.2 (4)	Li1^iv—O12—Li1^v	89.8 (3)
O42—Li1—O12^ii	112.5 (4)	C3—C2—C1	120.1 (3)
O3—Li1—O12^ii	117.2 (4)	C3—C2—I1	123.9 (3)
O12^i—Li1—O12^ii	90.2 (3)	C1—C2—I1	115.8 (3)
O42—Li1—Li1^iii	125.4 (6)	C2—C3—C4	126.8 (4)
O3—Li1—Li1^iii	131.2 (5)	C2—C3—H3	116.6
O12^i—Li1—Li1^iii	45.5 (2)	C4—C3—H3	116.6
O12^ii—Li1—Li1^iii	44.7 (2)	O42—C4—O41	124.5 (3)
O42—Li1—H32	85.0 (18)	O42—C4—C3	123.7 (4)
O3—Li1—H32	19.1 (16)	O41—C4—C3	111.8 (3)
O12^i—Li1—H32	124 (3)	C4—O41—H41	106 (4)
O12^ii—Li1—H32	131 (2)	C4—O42—Li1	145.6 (4)
Li1^iii—Li1—H32	149.6 (19)	Li1—O3—H31	113 (6)
O11—C1—O12	125.3 (3)	Li1—O3—H32	111 (7)
O11—C1—C2	118.1 (4)	H31—O3—H32	120 (9)
O12—C1—C2	116.5 (3)

Symmetry codes: (i) −x+5/2, y+1/2, −z+1/2; (ii) x+1/2, −y−1/2, z+1/2; (iii) −x+3, −y, −z+1; (iv) −x+5/2, y−1/2, −z+1/2; (v) x−1/2, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O41—H41···O11^ii	0.82 (2)	1.82 (3)	2.618 (4)	164 (6)
O3—H31···O11^vi	0.81 (2)	2.14 (4)	2.896 (6)	154 (8)

Symmetry codes: (ii) x+1/2, −y−1/2, z+1/2; (vi) x+1/2, −y+1/2, z+1/2.