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
CCDC reference: 652497
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%.
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).
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.
catena-poly[[[aquacopper(II)]-µ-
N-(3-carboxy-2-
oxidobenzylidene-
κO2)glycinato-
κ3N,
O':
O']
monohydrate]
top
Crystal data top
[Cu(C10H7NO5)(H2O)]·H2O | F(000) = 652 |
Mr = 320.75 | Dx = 1.890 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 947 reflections |
a = 8.314 (2) Å | θ = 3.1–26.9° |
b = 6.968 (2) Å | µ = 1.97 mm−1 |
c = 19.460 (2) Å | T = 293 K |
β = 90.645 (5)° | Plate, green |
V = 1127.3 (4) Å3 | 0.40 × 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 tube | 2057 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 0 pixels mm-1 | θmax = 27.0°, θmin = 3.1° |
ϕ and ω scans | h = −10→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→8 |
Tmin = 0.630, Tmax = 0.744 | l = −19→24 |
5984 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H 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 parameters | Δρmax = 0.68 e Å−3 |
6 restraints | Δρmin = −0.53 e Å−3 |
Crystal data top
[Cu(C10H7NO5)(H2O)]·H2O | V = 1127.3 (4) Å3 |
Mr = 320.75 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.314 (2) Å | µ = 1.97 mm−1 |
b = 6.968 (2) Å | T = 293 K |
c = 19.460 (2) Å | 0.40 × 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 = 0.744 | Rint = 0.035 |
5984 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 6 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.68 e Å−3 |
1981 reflections | Δρmin = −0.53 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.63472 (7) | 0.91538 (9) | 0.83887 (3) | 0.0294 (3) | |
N1 | 0.4172 (5) | 0.8689 (6) | 0.8674 (2) | 0.0299 (9) | |
O1 | 0.9907 (5) | 0.7112 (7) | 1.0935 (2) | 0.0522 (11) | |
O2 | 0.9823 (4) | 0.7693 (8) | 0.9830 (2) | 0.0547 (12) | |
H2 | 0.9144 | 0.7913 | 0.9531 | 0.082* | |
O3 | 0.7217 (4) | 0.8154 (6) | 0.92365 (17) | 0.0370 (9) | |
O4 | 0.2953 (4) | 1.1602 (6) | 0.72553 (18) | 0.0394 (9) | |
O5 | 0.5334 (4) | 1.0628 (6) | 0.76454 (18) | 0.0370 (9) | |
O6 | 0.8465 (5) | 1.0281 (8) | 0.8209 (2) | 0.0497 (11) | |
H6A | 0.876 (8) | 1.102 (9) | 0.853 (3) | 0.075* | |
H6B | 0.919 (6) | 1.033 (12) | 0.791 (3) | 0.075* | |
O7 | −0.0222 (5) | 1.0674 (8) | 0.7000 (2) | 0.0595 (13) | |
H7A | 0.074 (4) | 1.107 (12) | 0.702 (4) | 0.089* | |
H7B | −0.038 (9) | 1.037 (13) | 0.6580 (14) | 0.089* | |
C1 | 0.9110 (6) | 0.7307 (8) | 1.0407 (3) | 0.0388 (12) | |
C2 | 0.7336 (6) | 0.7180 (7) | 1.0399 (3) | 0.0309 (11) | |
C3 | 0.6554 (6) | 0.6598 (8) | 1.0980 (2) | 0.0337 (11) | |
H3A | 0.7155 | 0.6245 | 1.1366 | 0.040* | |
C4 | 0.4910 (7) | 0.6523 (8) | 1.1006 (3) | 0.0364 (12) | |
H4A | 0.4398 | 0.6132 | 1.1404 | 0.044* | |
C5 | 0.4020 (6) | 0.7042 (7) | 1.0426 (2) | 0.0314 (11) | |
H5A | 0.2903 | 0.6993 | 1.0440 | 0.038* | |
C6 | 0.4763 (6) | 0.7630 (7) | 0.9829 (3) | 0.0309 (11) | |
C7 | 0.6449 (6) | 0.7680 (7) | 0.9795 (2) | 0.0270 (10) | |
C8 | 0.3719 (6) | 0.8157 (7) | 0.9256 (2) | 0.0296 (10) | |
H8A | 0.2616 | 0.8095 | 0.9328 | 0.036* | |
C9 | 0.3002 (6) | 0.9275 (8) | 0.8146 (3) | 0.0339 (12) | |
H9A | 0.2100 | 0.9918 | 0.8358 | 0.041* | |
H9B | 0.2599 | 0.8155 | 0.7903 | 0.041* | |
C10 | 0.3812 (6) | 1.0618 (7) | 0.7647 (2) | 0.0291 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0239 (4) | 0.0443 (4) | 0.0202 (4) | −0.0011 (2) | 0.0011 (2) | 0.0020 (2) |
N1 | 0.025 (2) | 0.035 (2) | 0.030 (2) | −0.0011 (17) | −0.0019 (17) | 0.0056 (18) |
O1 | 0.043 (2) | 0.075 (3) | 0.039 (2) | −0.009 (2) | −0.0153 (18) | 0.008 (2) |
O2 | 0.0272 (18) | 0.098 (4) | 0.039 (2) | −0.001 (2) | −0.0025 (16) | 0.012 (2) |
O3 | 0.0250 (16) | 0.057 (2) | 0.0287 (19) | 0.0007 (16) | 0.0020 (14) | 0.0074 (17) |
O4 | 0.0332 (18) | 0.050 (2) | 0.034 (2) | −0.0018 (17) | −0.0085 (16) | 0.0124 (18) |
O5 | 0.0290 (19) | 0.056 (2) | 0.0256 (19) | −0.0032 (16) | 0.0039 (14) | 0.0050 (16) |
O6 | 0.034 (2) | 0.079 (3) | 0.036 (2) | −0.024 (2) | 0.0045 (17) | −0.006 (2) |
O7 | 0.041 (2) | 0.089 (4) | 0.049 (3) | −0.016 (2) | 0.001 (2) | −0.012 (2) |
C1 | 0.036 (3) | 0.044 (3) | 0.036 (3) | −0.003 (2) | −0.009 (2) | 0.000 (2) |
C2 | 0.034 (3) | 0.031 (3) | 0.027 (3) | 0.000 (2) | −0.004 (2) | −0.004 (2) |
C3 | 0.047 (3) | 0.034 (3) | 0.021 (2) | 0.000 (2) | −0.004 (2) | −0.004 (2) |
C4 | 0.047 (3) | 0.037 (3) | 0.025 (3) | −0.002 (2) | 0.003 (2) | 0.003 (2) |
C5 | 0.032 (2) | 0.037 (3) | 0.026 (2) | −0.001 (2) | 0.0080 (19) | 0.001 (2) |
C6 | 0.031 (2) | 0.032 (3) | 0.030 (3) | 0.000 (2) | −0.001 (2) | −0.001 (2) |
C7 | 0.034 (2) | 0.031 (2) | 0.016 (2) | 0.001 (2) | 0.0014 (18) | −0.0036 (19) |
C8 | 0.028 (2) | 0.034 (3) | 0.027 (3) | 0.000 (2) | 0.0029 (19) | 0.001 (2) |
C9 | 0.027 (2) | 0.045 (3) | 0.029 (3) | −0.001 (2) | −0.004 (2) | 0.004 (2) |
C10 | 0.032 (3) | 0.040 (3) | 0.015 (2) | −0.003 (2) | 0.0005 (18) | −0.003 (2) |
Geometric parameters (Å, º) top
Cu1—O3 | 1.924 (4) | O7—H7B | 0.85 (3) |
Cu1—N1 | 1.926 (5) | C1—C2 | 1.477 (7) |
Cu1—O5 | 1.957 (4) | C2—C3 | 1.372 (7) |
Cu1—O6 | 1.963 (4) | C2—C7 | 1.425 (7) |
Cu1—O4i | 2.256 (4) | C3—C4 | 1.370 (8) |
N1—C8 | 1.254 (6) | C3—H3A | 0.9300 |
N1—C9 | 1.466 (6) | C4—C5 | 1.390 (7) |
O1—C1 | 1.224 (6) | C4—H4A | 0.9300 |
O2—C1 | 1.304 (7) | C5—C6 | 1.384 (7) |
O2—H2 | 0.8200 | C5—H5A | 0.9300 |
O3—C7 | 1.309 (6) | C6—C7 | 1.405 (7) |
O4—C10 | 1.245 (6) | C6—C8 | 1.453 (7) |
O4—Cu1ii | 2.256 (4) | C8—H8A | 0.9300 |
O5—C10 | 1.265 (6) | C9—C10 | 1.511 (7) |
O6—H6A | 0.84 (6) | C9—H9A | 0.9700 |
O6—H6B | 0.84 (5) | C9—H9B | 0.9700 |
O7—H7A | 0.85 (4) | | |
| | | |
N1—Cu1—O4i | 106.06 (17) | C4—C3—C2 | 121.6 (5) |
N1—Cu1—O5 | 84.47 (17) | C4—C3—H3A | 119.2 |
N1—Cu1—O6 | 165.0 (2) | C2—C3—H3A | 119.2 |
O3—Cu1—N1 | 92.11 (17) | C3—C4—C5 | 118.9 (5) |
O3—Cu1—O4i | 95.42 (17) | C3—C4—H4A | 120.6 |
O3—Cu1—O5 | 168.00 (17) | C5—C4—H4A | 120.6 |
O3—Cu1—O6 | 88.22 (18) | C6—C5—C4 | 121.3 (5) |
O5—Cu1—O4i | 96.58 (17) | C6—C5—H5A | 119.3 |
O5—Cu1—O6 | 92.15 (19) | C4—C5—H5A | 119.3 |
O6—Cu1—O4i | 88.78 (19) | C5—C6—C7 | 120.2 (4) |
C8—N1—C9 | 120.9 (4) | C5—C6—C8 | 116.8 (4) |
C8—N1—Cu1 | 127.1 (3) | C7—C6—C8 | 123.0 (5) |
C9—N1—Cu1 | 111.6 (3) | O3—C7—C6 | 122.8 (4) |
C1—O2—H2 | 109.5 | O3—C7—C2 | 119.7 (4) |
C7—O3—Cu1 | 128.4 (3) | C6—C7—C2 | 117.5 (4) |
C10—O4—Cu1ii | 128.7 (3) | N1—C8—C6 | 125.8 (5) |
C10—O5—Cu1 | 114.7 (3) | N1—C8—H8A | 117.1 |
Cu1—O6—H6A | 112 (5) | C6—C8—H8A | 117.1 |
Cu1—O6—H6B | 142 (4) | N1—C9—C10 | 109.1 (4) |
H6A—O6—H6B | 106 (6) | N1—C9—H9A | 109.9 |
H7A—O7—H7B | 105 (7) | C10—C9—H9A | 109.9 |
O1—C1—O2 | 120.0 (5) | N1—C9—H9B | 109.9 |
O1—C1—C2 | 122.2 (5) | C10—C9—H9B | 109.9 |
O2—C1—C2 | 117.8 (4) | H9A—C9—H9B | 108.3 |
C3—C2—C7 | 120.5 (5) | O4—C10—O5 | 124.2 (5) |
C3—C2—C1 | 119.5 (4) | O4—C10—C9 | 118.5 (4) |
C7—C2—C1 | 120.1 (5) | O5—C10—C9 | 117.2 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.82 | 1.70 | 2.465 (5) | 153 |
O6—H6A···O1iii | 0.84 (6) | 1.99 (3) | 2.803 (6) | 160 (6) |
O6—H6B···O7iv | 0.84 (5) | 1.86 (4) | 2.619 (7) | 150 (7) |
O7—H7A···O4 | 0.85 (4) | 1.92 (2) | 2.758 (6) | 167 (8) |
O7—H7B···O1v | 0.85 (3) | 2.15 (7) | 2.842 (7) | 138 (9) |
Symmetry codes: (iii) −x+2, −y+2, −z+2; (iv) x+1, y, z; (v) x−1, −y+3/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H7NO5)(H2O)]·H2O |
Mr | 320.75 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.314 (2), 6.968 (2), 19.460 (2) |
β (°) | 90.645 (5) |
V (Å3) | 1127.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.97 |
Crystal size (mm) | 0.40 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.630, 0.744 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5984, 2414, 2057 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.150, 1.11 |
No. of reflections | 1981 |
No. of parameters | 184 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.53 |
Selected geometric parameters (Å, º) topCu1—O3 | 1.924 (4) | Cu1—O6 | 1.963 (4) |
Cu1—N1 | 1.926 (5) | Cu1—O4i | 2.256 (4) |
Cu1—O5 | 1.957 (4) | | |
| | | |
N1—Cu1—O4i | 106.06 (17) | O3—Cu1—O5 | 168.00 (17) |
N1—Cu1—O5 | 84.47 (17) | O3—Cu1—O6 | 88.22 (18) |
N1—Cu1—O6 | 165.0 (2) | O5—Cu1—O4i | 96.58 (17) |
O3—Cu1—N1 | 92.11 (17) | O5—Cu1—O6 | 92.15 (19) |
O3—Cu1—O4i | 95.42 (17) | O6—Cu1—O4i | 88.78 (19) |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.82 | 1.70 | 2.465 (5) | 153.4 |
O6—H6A···O1ii | 0.84 (6) | 1.99 (3) | 2.803 (6) | 160 (6) |
O6—H6B···O7iii | 0.84 (5) | 1.86 (4) | 2.619 (7) | 150 (7) |
O7—H7A···O4 | 0.85 (4) | 1.92 (2) | 2.758 (6) | 167 (8) |
O7—H7B···O1iv | 0.85 (3) | 2.15 (7) | 2.842 (7) | 138 (9) |
Symmetry codes: (ii) −x+2, −y+2, −z+2; (iii) x+1, y, z; (iv) x−1, −y+3/2, z−1/2. |
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.