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In the polymeric title compound, {[Cu(C10H7NO5)(H2O)]·H2O}n, the Cu atom adopts a square-based pyramidal coordination involving a N,O,O′-tridentate glycine dianionic ligand, a water O atom and an apical bridging carboxyl­ate O atom from an adjacent ligand. The title compound also adopts a carboxyl­ate-bridged chain structure. The mol­ecular chain propagates in a helical fashion along the b axis of the monoclinic unit cell. Neighbouring chains are linked together to form a three-dimensional network via hydrogen-bonding inter­actions between coordinated and uncoordinated water mol­ecules and O atoms of the bridging carboxyl­ate groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107019312/av3081sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107019312/av3081Isup2.hkl
Contains datablock I

CCDC reference: 652497

Comment top

Metal–organic frameworks (MOF), which consist of metal ions and organic molecules, have attracted considerable attention in recent decades due to their rich structural chemistry and potential applications. To date, a large number of architectures with MOFs have been reported, including helical, zigzag chain, honeycomb, square grid, ladder, brick wall and diamondoid (Peng et al., 2003; Wang et al., 2007). Among these architectures, helical structures have received extraordinary attention, because helicity is an essential feature of living systems and is also important in ligand exchange, asymmetric catalysis, chiral synthesis, nonlinear optical devices and magnetic materials (Cui et al., 2003). Many single-, double- and higher-order stranded helical complexes have been synthesized by self-assembly processes (Chen & Liu, 2002; Qi et al., 2003), in particular metal ion-directed polynuclear helical complexes of well designed ligands. These facts have provided an important impetus for the creation of artifical helical structures.

Aminophenol-containing Schiff base ligands are a unique type of ligand showing flexible coordination modes and are well known as excellent building blocks for hydrogen-bonded networks. Some helical complexes with Schiff base ligands derived from amino acids have been reported (Ranford et al., 1999; Erxleben, 2001). We therefore expected them to be good chiral building blocks for supramolecular assembly. Glycine Schiff base ligand is particularly fascinating, due to its extra β-carboxylic group possessing bridging capability. It can connect metal ions in different directions, so it is an excellent candidate for the design and construction of chiral coordination polymers. We focused our attention on the assembly of transition metal ions with this flexible ligand. One helical structure of the ligand 3-carboxysalicylideneglycinate has been reported recently (Cai et al., 2006). As an extension of our work on these complexes, we report here the preparation and crystal structure characterization of the title helical coordination polymer, (I).

In the crystal structure of complex (I), there is one CuIIatom, one 3-carboxysalicylideneglycinate anion, one coordinated water molecule and one solvent water molecule in the asymmetric unit. Each CuII atom adopts a square-based pyramidal geometry. The four basal coordination sites are filled by the imine N atom, the phenolate O atom, one carboxyl O atom of the Schiff base ligand and one O atom of the coordinated water molecule, while the apical site is occupied by one carboxylate O atom from an adjacent ligand. Due to the Jahn–Teller effect, the pendant carboxy O atoms have weak bonding interactions with the CuII atom: Cu1—O4i = 2.253 (4) Å [symmetry code: (i) -x + 1, y - 1/2, -z + 1/2], which is longer than other bonds. However, this bond is somewhat shorter than that in the unsubstituted compound [2.420 (2) Å; Butcher et al., 2003]. The Cu—N and other Cu—O bond lengths (Table 1) are comparable with the corresponding values observed in other Schiff base CuII complexes (Marsh & Spek, 2001 [This reference does not discuss Schiff base complexes. Has the correct citation been given?]; Valent et al., 2002). It is worthy of mention that the remaining protonated carboxylate group does not participate in coordination, but is involved in hydrogen bonding.

In complex (I), each pair of adjacent CuII atoms is bridged by a carboxy group of the ligand to form a chiral helical chain running along a crystallographic 21 axis in the b direction, with a pitch of 6.968 Å and decorated with the ligands alternately on two sides, while the phenyl rings of the ligands on each side of the helix are arranged in a parallel fashion.

There are some intra- and intermolecular hydrogen bonds in (I). The acidic H atom forms a strong intramolecular O—H···O hydrogen bond to the phenoxy O atom [O···O = 2.465 (5) Å]. Intermolecular hydrogen bonds are formed between the carboxylate O atoms (O1 and O4) of the ligand and the coordinated and uncoordinated O atoms of the water molecules, with distance of approximately 2.619 (7)–2.842 (7) Å (Table 2). The chains are connected via these bonds to form a three-dimensional network.

Related literature top

For related literature, see: Butcher et al. (2003); Cai et al. (2006); Chen & Liu (2002); Cui et al. (2003); Erxleben (2001); Marsh & Spek (2001); Peng et al. (2003); Qi et al. (2003); Ranford et al. (1999); Valent et al. (2002); Wang et al. (2007).

Experimental top

3-Carboxysalicylaldehyde (2 mmol, 0.336 g), glycine (2 mmol, 0.150 g) and potassium hydroxide (2 mmol, 0.112 g) were dissolved in 80% aqueous methanol (30 ml). To this clear yellow solution was added an aqueous solution (10 ml) of copper(II) sulfate pentahydrate (2 mmol, 0.50 g). The solution was kept at 323 K for 7 h and then filtered. Green crystals of (I) were separated from the solution after two weeks in ca 46% yield. CHN elemental analysis, found: C 37.46, H 3.47, N 4.36%; calculated for C10H11CuNO7: C 37.45, H 3.46, N 4.37%.

Refinement top

Water H atoms were located in a difference Fourier map and refined with O—H distance restraints of 0.85 (1) Å, and with Uiso(H) = 1.5Ueq(O). The carboxylic H atom was placed in a calculated position, with O—H = 0.82 Å, and refined as riding, with Uiso(H) = 1.5Ueq(O). All other H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, Year?); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the intramolecular hydrogen bond. [Symmetry code: (i) -x + 1, y - 1/2, -z + 1/2.]
[Figure 2] Fig. 2. The crystal packing of the one-dimensional helical chains in (I). H atoms and cyclic fragments have been omitted for clarity. Hydrogen bonds are shown as dotted lines.
catena-poly[[[aquacopper(II)]-µ-N-(3-carboxy-2- oxidobenzylidene-κO2)glycinato-κ3N,O':O'] monohydrate] top
Crystal data top
[Cu(C10H7NO5)(H2O)]·H2OF(000) = 652
Mr = 320.75Dx = 1.890 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 947 reflections
a = 8.314 (2) Åθ = 3.1–26.9°
b = 6.968 (2) ŵ = 1.97 mm1
c = 19.460 (2) ÅT = 293 K
β = 90.645 (5)°Plate, green
V = 1127.3 (4) Å30.40 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2414 independent reflections
Radiation source: fine-focus sealed tube2057 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 0 pixels mm-1θmax = 27.0°, θmin = 3.1°
ϕ and ω scansh = 109
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 88
Tmin = 0.630, Tmax = 0.744l = 1924
5984 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0775P)2 + 2.7627P]
where P = (Fo2 + 2Fc2)/3
1981 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.68 e Å3
6 restraintsΔρmin = 0.53 e Å3
Crystal data top
[Cu(C10H7NO5)(H2O)]·H2OV = 1127.3 (4) Å3
Mr = 320.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.314 (2) ŵ = 1.97 mm1
b = 6.968 (2) ÅT = 293 K
c = 19.460 (2) Å0.40 × 0.20 × 0.15 mm
β = 90.645 (5)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2414 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2057 reflections with I > 2σ(I)
Tmin = 0.630, Tmax = 0.744Rint = 0.035
5984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0536 restraints
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.68 e Å3
1981 reflectionsΔρmin = 0.53 e Å3
184 parameters
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
Cu10.63472 (7)0.91538 (9)0.83887 (3)0.0294 (3)
N10.4172 (5)0.8689 (6)0.8674 (2)0.0299 (9)
O10.9907 (5)0.7112 (7)1.0935 (2)0.0522 (11)
O20.9823 (4)0.7693 (8)0.9830 (2)0.0547 (12)
H20.91440.79130.95310.082*
O30.7217 (4)0.8154 (6)0.92365 (17)0.0370 (9)
O40.2953 (4)1.1602 (6)0.72553 (18)0.0394 (9)
O50.5334 (4)1.0628 (6)0.76454 (18)0.0370 (9)
O60.8465 (5)1.0281 (8)0.8209 (2)0.0497 (11)
H6A0.876 (8)1.102 (9)0.853 (3)0.075*
H6B0.919 (6)1.033 (12)0.791 (3)0.075*
O70.0222 (5)1.0674 (8)0.7000 (2)0.0595 (13)
H7A0.074 (4)1.107 (12)0.702 (4)0.089*
H7B0.038 (9)1.037 (13)0.6580 (14)0.089*
C10.9110 (6)0.7307 (8)1.0407 (3)0.0388 (12)
C20.7336 (6)0.7180 (7)1.0399 (3)0.0309 (11)
C30.6554 (6)0.6598 (8)1.0980 (2)0.0337 (11)
H3A0.71550.62451.13660.040*
C40.4910 (7)0.6523 (8)1.1006 (3)0.0364 (12)
H4A0.43980.61321.14040.044*
C50.4020 (6)0.7042 (7)1.0426 (2)0.0314 (11)
H5A0.29030.69931.04400.038*
C60.4763 (6)0.7630 (7)0.9829 (3)0.0309 (11)
C70.6449 (6)0.7680 (7)0.9795 (2)0.0270 (10)
C80.3719 (6)0.8157 (7)0.9256 (2)0.0296 (10)
H8A0.26160.80950.93280.036*
C90.3002 (6)0.9275 (8)0.8146 (3)0.0339 (12)
H9A0.21000.99180.83580.041*
H9B0.25990.81550.79030.041*
C100.3812 (6)1.0618 (7)0.7647 (2)0.0291 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0239 (4)0.0443 (4)0.0202 (4)0.0011 (2)0.0011 (2)0.0020 (2)
N10.025 (2)0.035 (2)0.030 (2)0.0011 (17)0.0019 (17)0.0056 (18)
O10.043 (2)0.075 (3)0.039 (2)0.009 (2)0.0153 (18)0.008 (2)
O20.0272 (18)0.098 (4)0.039 (2)0.001 (2)0.0025 (16)0.012 (2)
O30.0250 (16)0.057 (2)0.0287 (19)0.0007 (16)0.0020 (14)0.0074 (17)
O40.0332 (18)0.050 (2)0.034 (2)0.0018 (17)0.0085 (16)0.0124 (18)
O50.0290 (19)0.056 (2)0.0256 (19)0.0032 (16)0.0039 (14)0.0050 (16)
O60.034 (2)0.079 (3)0.036 (2)0.024 (2)0.0045 (17)0.006 (2)
O70.041 (2)0.089 (4)0.049 (3)0.016 (2)0.001 (2)0.012 (2)
C10.036 (3)0.044 (3)0.036 (3)0.003 (2)0.009 (2)0.000 (2)
C20.034 (3)0.031 (3)0.027 (3)0.000 (2)0.004 (2)0.004 (2)
C30.047 (3)0.034 (3)0.021 (2)0.000 (2)0.004 (2)0.004 (2)
C40.047 (3)0.037 (3)0.025 (3)0.002 (2)0.003 (2)0.003 (2)
C50.032 (2)0.037 (3)0.026 (2)0.001 (2)0.0080 (19)0.001 (2)
C60.031 (2)0.032 (3)0.030 (3)0.000 (2)0.001 (2)0.001 (2)
C70.034 (2)0.031 (2)0.016 (2)0.001 (2)0.0014 (18)0.0036 (19)
C80.028 (2)0.034 (3)0.027 (3)0.000 (2)0.0029 (19)0.001 (2)
C90.027 (2)0.045 (3)0.029 (3)0.001 (2)0.004 (2)0.004 (2)
C100.032 (3)0.040 (3)0.015 (2)0.003 (2)0.0005 (18)0.003 (2)
Geometric parameters (Å, º) top
Cu1—O31.924 (4)O7—H7B0.85 (3)
Cu1—N11.926 (5)C1—C21.477 (7)
Cu1—O51.957 (4)C2—C31.372 (7)
Cu1—O61.963 (4)C2—C71.425 (7)
Cu1—O4i2.256 (4)C3—C41.370 (8)
N1—C81.254 (6)C3—H3A0.9300
N1—C91.466 (6)C4—C51.390 (7)
O1—C11.224 (6)C4—H4A0.9300
O2—C11.304 (7)C5—C61.384 (7)
O2—H20.8200C5—H5A0.9300
O3—C71.309 (6)C6—C71.405 (7)
O4—C101.245 (6)C6—C81.453 (7)
O4—Cu1ii2.256 (4)C8—H8A0.9300
O5—C101.265 (6)C9—C101.511 (7)
O6—H6A0.84 (6)C9—H9A0.9700
O6—H6B0.84 (5)C9—H9B0.9700
O7—H7A0.85 (4)
N1—Cu1—O4i106.06 (17)C4—C3—C2121.6 (5)
N1—Cu1—O584.47 (17)C4—C3—H3A119.2
N1—Cu1—O6165.0 (2)C2—C3—H3A119.2
O3—Cu1—N192.11 (17)C3—C4—C5118.9 (5)
O3—Cu1—O4i95.42 (17)C3—C4—H4A120.6
O3—Cu1—O5168.00 (17)C5—C4—H4A120.6
O3—Cu1—O688.22 (18)C6—C5—C4121.3 (5)
O5—Cu1—O4i96.58 (17)C6—C5—H5A119.3
O5—Cu1—O692.15 (19)C4—C5—H5A119.3
O6—Cu1—O4i88.78 (19)C5—C6—C7120.2 (4)
C8—N1—C9120.9 (4)C5—C6—C8116.8 (4)
C8—N1—Cu1127.1 (3)C7—C6—C8123.0 (5)
C9—N1—Cu1111.6 (3)O3—C7—C6122.8 (4)
C1—O2—H2109.5O3—C7—C2119.7 (4)
C7—O3—Cu1128.4 (3)C6—C7—C2117.5 (4)
C10—O4—Cu1ii128.7 (3)N1—C8—C6125.8 (5)
C10—O5—Cu1114.7 (3)N1—C8—H8A117.1
Cu1—O6—H6A112 (5)C6—C8—H8A117.1
Cu1—O6—H6B142 (4)N1—C9—C10109.1 (4)
H6A—O6—H6B106 (6)N1—C9—H9A109.9
H7A—O7—H7B105 (7)C10—C9—H9A109.9
O1—C1—O2120.0 (5)N1—C9—H9B109.9
O1—C1—C2122.2 (5)C10—C9—H9B109.9
O2—C1—C2117.8 (4)H9A—C9—H9B108.3
C3—C2—C7120.5 (5)O4—C10—O5124.2 (5)
C3—C2—C1119.5 (4)O4—C10—C9118.5 (4)
C7—C2—C1120.1 (5)O5—C10—C9117.2 (4)
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x+1, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O30.821.702.465 (5)153
O6—H6A···O1iii0.84 (6)1.99 (3)2.803 (6)160 (6)
O6—H6B···O7iv0.84 (5)1.86 (4)2.619 (7)150 (7)
O7—H7A···O40.85 (4)1.92 (2)2.758 (6)167 (8)
O7—H7B···O1v0.85 (3)2.15 (7)2.842 (7)138 (9)
Symmetry codes: (iii) x+2, y+2, z+2; (iv) x+1, y, z; (v) x1, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[Cu(C10H7NO5)(H2O)]·H2O
Mr320.75
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.314 (2), 6.968 (2), 19.460 (2)
β (°) 90.645 (5)
V3)1127.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.97
Crystal size (mm)0.40 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.630, 0.744
No. of measured, independent and
observed [I > 2σ(I)] reflections
5984, 2414, 2057
Rint0.035
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.150, 1.11
No. of reflections1981
No. of parameters184
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.68, 0.53

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, Year?), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—O31.924 (4)Cu1—O61.963 (4)
Cu1—N11.926 (5)Cu1—O4i2.256 (4)
Cu1—O51.957 (4)
N1—Cu1—O4i106.06 (17)O3—Cu1—O5168.00 (17)
N1—Cu1—O584.47 (17)O3—Cu1—O688.22 (18)
N1—Cu1—O6165.0 (2)O5—Cu1—O4i96.58 (17)
O3—Cu1—N192.11 (17)O5—Cu1—O692.15 (19)
O3—Cu1—O4i95.42 (17)O6—Cu1—O4i88.78 (19)
Symmetry code: (i) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O30.821.702.465 (5)153.4
O6—H6A···O1ii0.84 (6)1.99 (3)2.803 (6)160 (6)
O6—H6B···O7iii0.84 (5)1.86 (4)2.619 (7)150 (7)
O7—H7A···O40.85 (4)1.92 (2)2.758 (6)167 (8)
O7—H7B···O1iv0.85 (3)2.15 (7)2.842 (7)138 (9)
Symmetry codes: (ii) x+2, y+2, z+2; (iii) x+1, y, z; (iv) x1, y+3/2, z1/2.
 

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