Blue crystals of the title compound, poly[[[diaquacopper(II)]-μ3-chlorofumarato] monohydrate], {[Cu(OOC–CH=CCl–COO)(H2O)2]·H2O}n, crystallized unexpectedly from an aqueous solution containing acetylenedicarboxylic acid and CuCl2. Each copper cation is coordinated by five O atoms – three from three fumarate anions and two from two water molecules – in the form of a distorted square pyramid. All atoms of the asymmetric unit, except a carboxylate oxygen and the coordinated water molecule, lie on a mirror plane. These units are connected by the bifunctional anions to form ribbons along [001]. These ribbons are held together by hydrogen bonds, which also involve the third water molecule.
Supporting information
CCDC reference: 605134
Key indicators
- Single-crystal X-ray study
- T = 170 K
- Mean (C-C) = 0.006 Å
- H-atom completeness 86%
- Disorder in main residue
- R factor = 0.031
- wR factor = 0.079
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 3.84
PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc.
PLAT731_ALERT_1_C Bond Calc 0.84(4), Rep 0.844(10) ...... 4.00 su-Rat
O3 -H31 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.848(10) ...... 4.00 su-Rat
O3 -H32 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.84(4), Rep 0.844(10) ...... 4.00 su-Rat
O4 -H41 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.84(4), Rep 0.844(10) ...... 4.00 su-Rat
O3 -H31 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.848(10) ...... 4.00 su-Rat
O3 -H32 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.84(4), Rep 0.844(10) ...... 4.00 su-Rat
O4 -H41 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.84(4), Rep 0.844(10) ...... 4.00 su-Rat
O4 -H41 1.555 1.555
PLAT736_ALERT_1_C H...A Calc 1.97(5), Rep 1.98(2) ...... 2.50 su-Rat
H32 -O4 1.555 7.667
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C4 H7 Cl1 Cu1 O7
Atom count from the _atom_site data: C4 H6 Cl1 Cu1 O7
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C4 H7 Cl Cu O7
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 16.00 16.00 0.00
H 28.00 24.00 4.00
Cl 4.00 4.00 0.00
Cu 4.00 4.00 0.00
O 28.00 28.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
15 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
14 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
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; 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.
catena-poly[[[diaquacopper(II)]-µ-chlorofumarato-
κO,
O']
hydrate]
top
Crystal data top
[Cu(C4HClO4)(H2O)2]·H2O | F(000) = 532 |
Mr = 266.09 | Dx = 2.087 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 6215 reflections |
a = 14.849 (3) Å | θ = 1.5–32.4° |
b = 7.1407 (6) Å | µ = 2.90 mm−1 |
c = 8.7237 (15) Å | T = 170 K |
β = 113.751 (13)° | Plate, blue |
V = 846.7 (2) Å3 | 0.2 × 0.2 × 0.05 mm |
Z = 4 | |
Data collection top
Stoe IPDS-II diffractometer | 1109 independent reflections |
Radiation source: fine-focus sealed tube | 1019 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: not measured pixels mm-1 | θmax = 28.0°, θmin = 2.6° |
ω and φ scans | h = −19→19 |
Absorption correction: numerical The absorption correction (X-RED; Stoe & Cie, 2001)
was performed after optimizing the crystal shape
using X-SHAPE (Stoe & Cie, 1999). | k = −9→8 |
Tmin = 0.531, Tmax = 0.847 | l = −11→11 |
7365 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0435P)2 + 2.1723P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
1109 reflections | Δρmax = 0.74 e Å−3 |
92 parameters | Δρmin = −0.66 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0054 (11) |
Special details top
Experimental. A suitable single-crystal was carefully selected under a polarizing microscope
and mounted in a glass capillary. The scattering intensities were collected on
an imaging plate diffractometer (IPDS II, Stoe & Cie) equipped with a
fine focus sealed tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 40 mA. Intensity data for the title compound were collected at 170 K by
ω-scans in 180 frames (0 < ω < 180°; φ = O°, 0 < ω < 180°; φ = 90°,
Δω = 2°, exposure time of 4 min) in the 2 Θ range 2.9 to 64.8°. Structure
solution and refinement were carried out using the programs SIR92
(Altomare et al., 1993) and SHELXL97 (Sheldrick, 1997). The
methylene H atom was placed in idealized position and constrained to ride on
their parent atom, with C—H distances of 0.930 Å and Uiso(H)
values of 0.042 Å2. The remaining H atoms were located in a difference
Fourier map and refined, with O—H2 distances restrained to 0.82 (2) Å. A
numerical absorption correction (X-RED (Stoe & Cie, 2001b) was
applied after optimization of the crystal shape (X-SHAPE (Stoe & Cie,
1999)). The last cycles of refinement included atomic positions for all atoms,
anisotropic parameters for all non-hydrogen atoms and isotropic thermal
parameters for all hydrogen atoms. The final difference maps were free of any
chemically significant features. The refinement was based on F2 for ALL
reflections. |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.91085 (3) | 0.5000 | 1.06457 (5) | 0.01759 (16) | |
C1 | 0.8398 (3) | 0.5000 | 0.7198 (5) | 0.0448 (12) | |
O11 | 0.92114 (18) | 0.5000 | 0.8482 (3) | 0.0251 (5) | |
O12 | 0.7617 (3) | 0.5506 (8) | 0.7315 (5) | 0.046 (2) | 0.50 |
C2 | 0.8529 (3) | 0.5000 | 0.5582 (5) | 0.0451 (13) | |
H2 | 0.9174 | 0.5000 | 0.5672 | 0.043 (15)* | |
C3 | 0.7835 (3) | 0.5000 | 0.4043 (5) | 0.0390 (11) | |
Cl1 | 0.65892 (7) | 0.5000 | 0.35671 (12) | 0.0496 (4) | |
C4 | 0.8088 (3) | 0.5000 | 0.2530 (5) | 0.0341 (9) | |
O41 | 0.8999 (2) | 0.5000 | 0.2814 (3) | 0.0330 (7) | |
O42 | 0.7420 (2) | 0.5000 | 0.1107 (4) | 0.0445 (9) | |
O3 | 0.91202 (18) | 0.7759 (3) | 1.0631 (3) | 0.0416 (6) | |
H31 | 0.863 (2) | 0.825 (7) | 0.986 (4) | 0.072 (15)* | |
H32 | 0.913 (5) | 0.822 (8) | 1.154 (4) | 0.10 (2)* | |
O4 | 0.5695 (2) | 0.5000 | 0.6635 (4) | 0.0307 (6) | |
H41 | 0.624 (2) | 0.5000 | 0.655 (8) | 0.062 (19)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0169 (2) | 0.0227 (2) | 0.0134 (2) | 0.000 | 0.00624 (15) | 0.000 |
C1 | 0.0227 (19) | 0.095 (4) | 0.0162 (16) | 0.000 | 0.0078 (14) | 0.000 |
O11 | 0.0200 (12) | 0.0402 (14) | 0.0148 (11) | 0.000 | 0.0066 (9) | 0.000 |
O12 | 0.0176 (15) | 0.099 (7) | 0.0190 (14) | 0.002 (2) | 0.0039 (12) | 0.000 (2) |
C2 | 0.0159 (17) | 0.098 (4) | 0.0204 (18) | 0.000 | 0.0066 (14) | 0.000 |
C3 | 0.0189 (18) | 0.079 (3) | 0.0193 (17) | 0.000 | 0.0080 (14) | 0.000 |
Cl1 | 0.0149 (4) | 0.1080 (11) | 0.0247 (5) | 0.000 | 0.0070 (3) | 0.000 |
C4 | 0.0227 (17) | 0.063 (3) | 0.0196 (16) | 0.000 | 0.0114 (14) | 0.000 |
O41 | 0.0195 (12) | 0.063 (2) | 0.0159 (11) | 0.000 | 0.0063 (10) | 0.000 |
O42 | 0.0208 (13) | 0.091 (3) | 0.0201 (13) | 0.000 | 0.0062 (11) | 0.000 |
O3 | 0.0557 (14) | 0.0240 (9) | 0.0261 (10) | 0.0057 (9) | −0.0034 (10) | −0.0028 (8) |
O4 | 0.0248 (13) | 0.0386 (15) | 0.0298 (14) | 0.000 | 0.0121 (11) | 0.000 |
Geometric parameters (Å, º) top
Cu1—O11 | 1.954 (2) | C2—C3 | 1.322 (6) |
Cu1—O41i | 1.962 (3) | C2—H2 | 0.9300 |
Cu1—O3ii | 1.970 (2) | C3—C4 | 1.511 (5) |
Cu1—O3 | 1.970 (2) | C3—Cl1 | 1.726 (4) |
Cu1—O11iii | 2.297 (3) | C4—O42 | 1.239 (5) |
C1—O12ii | 1.257 (6) | C4—O41 | 1.273 (5) |
C1—O12 | 1.257 (6) | O41—Cu1iv | 1.962 (3) |
C1—O11 | 1.274 (5) | O3—H31 | 0.844 (10) |
C1—C2 | 1.498 (5) | O3—H32 | 0.848 (10) |
O11—Cu1iii | 2.297 (3) | O4—H41 | 0.844 (10) |
O12—O12ii | 0.722 (12) | | |
| | | |
O11—Cu1—O41i | 179.76 (11) | C1—O11—Cu1iii | 144.1 (2) |
O11—Cu1—O3ii | 89.41 (7) | Cu1—O11—Cu1iii | 100.21 (10) |
O41i—Cu1—O3ii | 90.60 (7) | O12ii—O12—C1 | 73.3 (3) |
O11—Cu1—O3 | 89.41 (7) | C3—C2—C1 | 127.8 (4) |
O41i—Cu1—O3 | 90.60 (7) | C3—C2—H2 | 116.1 |
O3ii—Cu1—O3 | 178.54 (16) | C1—C2—H2 | 116.1 |
O11—Cu1—O11iii | 79.79 (10) | C2—C3—C4 | 121.4 (4) |
O41i—Cu1—O11iii | 100.44 (10) | C2—C3—Cl1 | 124.4 (3) |
O3ii—Cu1—O11iii | 89.48 (8) | C4—C3—Cl1 | 114.2 (3) |
O3—Cu1—O11iii | 89.48 (8) | O42—C4—O41 | 123.6 (3) |
O12ii—C1—O11 | 120.5 (4) | O42—C4—C3 | 119.7 (4) |
O12—C1—O11 | 120.5 (4) | O41—C4—C3 | 116.7 (3) |
O12ii—C1—C2 | 123.3 (4) | C4—O41—Cu1iv | 107.8 (2) |
O12—C1—C2 | 123.3 (4) | Cu1—O3—H31 | 115 (4) |
O11—C1—C2 | 113.1 (3) | Cu1—O3—H32 | 112 (4) |
C1—O11—Cu1 | 115.7 (2) | H31—O3—H32 | 106 (5) |
| | | |
O12ii—C1—O11—Cu1 | −19.5 (3) | C2—C1—O12—O12ii | 101.4 (2) |
O12—C1—O11—Cu1 | 19.5 (3) | O12ii—C1—C2—C3 | 20.1 (3) |
C2—C1—O11—Cu1 | 180.0 | O12—C1—C2—C3 | −20.1 (3) |
O12ii—C1—O11—Cu1iii | 160.5 (3) | O11—C1—C2—C3 | 180.000 (1) |
O12—C1—O11—Cu1iii | −160.5 (3) | C1—C2—C3—C4 | 180.0 |
C2—C1—O11—Cu1iii | 0.0 | C1—C2—C3—Cl1 | 0.000 (1) |
O3ii—Cu1—O11—C1 | 90.42 (7) | C2—C3—C4—O42 | 180.0 |
O3—Cu1—O11—C1 | −90.42 (7) | Cl1—C3—C4—O42 | 0.0 |
O11iii—Cu1—O11—C1 | 180.000 (1) | C2—C3—C4—O41 | 0.0 |
O3ii—Cu1—O11—Cu1iii | −89.58 (7) | Cl1—C3—C4—O41 | 180.0 |
O3—Cu1—O11—Cu1iii | 89.58 (7) | O42—C4—O41—Cu1iv | 0.0 |
O11iii—Cu1—O11—Cu1iii | 0.0 | C3—C4—O41—Cu1iv | 180.0 |
O11—C1—O12—O12ii | −100.2 (2) | | |
Symmetry codes: (i) x, y, z+1; (ii) x, −y+1, z; (iii) −x+2, −y+1, −z+2; (iv) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···O42v | 0.84 (1) | 1.91 (2) | 2.702 (3) | 156 (5) |
O3—H32···O4vi | 0.85 (1) | 1.98 (2) | 2.792 (3) | 161 (6) |
O4—H41···O12 | 0.84 (1) | 1.91 (3) | 2.696 (5) | 154 (6) |
O4—H41···O12ii | 0.84 (1) | 1.91 (3) | 2.696 (5) | 154 (6) |
Symmetry codes: (ii) x, −y+1, z; (v) −x+3/2, −y+3/2, −z+1; (vi) −x+3/2, −y+3/2, −z+2. |