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In the title coordination polymer, [Cu(C11H7O2)(OH)(H2O)]n, the CuII center is five-coordinated by two O atoms from two different naphthalene-1-carboxyl­ate (L) ligands, one O atom from one coordinated water mol­ecule and two O atoms from two hydroxide anions. L ligands and hydroxide anions jointly bridge adjacent CuII centers to generate a one-dimensional chain along the b-axis direction. The results reveal that the steric bulk of the naphthalene ring system in L may play an important role in the formation of the title complex.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107054650/gd3161sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107054650/gd3161Isup2.hkl
Contains datablock I

CCDC reference: 672408

Comment top

Metallosupramolecular species assembled from transition metal and organic ligands have attracted great interest because of not only their intriguing structural diversities but also their potential uses as functional materials (Leininger et al., 2000; Robin & Fromm, 2006; Steel, 2005). The effective and facile approach for the synthesis of such complexes is still the appropriate choice of well designed organic ligands as bridges or terminal groups (building blocks) with metal ions or metal clusters as nodes; this method, so far, has been at an evolutionary stage, with the current focus mainly on understanding the factors that determine the crystal packing as well as exploring relevant potential properties (Ye et al., 2005). Among various ligands, the versatile carboxylic acid ligands exhibiting diverse coordination modes, especially for benzene-based carboxylic acids, have been used and well documented in the preparation of various carboxylate-containing CuII metal-organic complexes, such as benzoic acid (HBA, see Scheme II) (Bkouche-Waksman et al., 1980; Kawata et al., 1992; Koizumi et al., 1963; Gavrilenko et al., 2005) and 1,4-benzenedicarboxylic acid (Du et al., 2005; Hu et al., 2006).

In comparison with the aforementioned benzene-based carboxylic acid ligands, however, far less common has been the investigation of naphthalene- and anthracene-based carboxylic acids, such as naphthalene-1-carboxylic acid (HL) and anthracene-9-carboxylic acid (HACA) (see Scheme II). In general, such bulky aromatic carboxylic acid ligands have larger conjugated π-systems, and the steric hindrance of the bulky naphthalene and anthracene ring systems may affect the coordination abilities and modes of related carboxylate groups, leading to the formation of supramolecular structures that differ from those of related benzene-based carboxylic acid ligands. In our recent work, HL and HACA have been used successfully to construct a series of novel CuII, CoII, NiII, MnII and CdII complexes having mononuclear, dinuclear, tetranuclear, one-dimensional and two-dimensional structures, and exhibiting interesting magnetic and luminescence properties (Liu et al., 2006, 2007; Zou et al., 2005).

To further explore the coordination architectures of the L ligand bearing the bulky skeleton of the naphthalene ring system, in this research, a new CuII complex, (I), with HL was synthesized by taking advantage of the carboxylate bridging coordination abilities and the steric bulk of the naphthalene ring system. We report here the crystal structure of (I) and further compare it with the structurally related benzene- and anthracene-based CuII–carboxylate complexes whose crystal structures have been reported in the literature (Bkouche-Waksman et al., 1980; Kawata et al., 1992; Koizumi et al., 1963; Liu et al., 2007) .

Complex (I) consists of one-dimensional polymeric coordination chains containing only one kind of CuII coordination environment (Fig. 1). The asymmetric unit of (I) is composed of one CuII ion, one L ligand, one OH anion and one coordinated water molecule. Each CuII center is five-coordinated to two O atoms of carboxylate groups from two distinct L ligands and two O atoms from two OH- anions in the equatorial plane, as well as one O atom from one coordinated water molecule located at the axial position [Cu1—O4 = 2.3879 (19) Å; see Table 1]. In general, several parameters are often used to define the coordination geometry of the five-coordinated metal center, and one of the most common parameters is the τ factor defined by Addison et al. (1984) (τ = 0 for regular square pyramidal and τ = 1 for regular bpt geometry). The calculated τ value of (I) is 0.0432 for the CuII center, i.e. close to zero, indicating an almost ideal square-pyramidal coordination environment, and the CuII center deviates from the mean equatorial plane of the square pyramid [O1/O3/O1A/O3A; symmetry code: (A) 1 - x, 1/2 + y, 3/2 - z] towards the apical O4 atom of the coordinated water molecule by ca 0.0718 Å. Moreover, L in (I) adopts a bidentate syn–syn bridging coordination mode using two O atoms of the carboxylate group, which further bridge adjacent CuII centers to generate a one-dimensional chain along the [010] direction (Fig. 1).

In the crystal structure of (I), adjacent one-dimensional [Cu(L)(OH)(H2O)]nchains are arranged into a two-dimensional network running parallel to the (100) plane by inter-chain O—H···O hydrogen-bonding interactions between the coordinated water molecules and the carboxylate O atoms of the L ligands (see Fig. 2 and Table 2).

As typical aromatic carboxylic acid ligands, benzene-based carboxylic acids have been widely used to construct metal-organic coordination architectures, such as benzoic acid (HBA, see Scheme II) (Bkouche-Waksman et al., 1980; Kawata et al., 1992; Koizumi et al., 1963; Gavrilenko et al., 2005) and 1,4-benzenedicarboxylic acid (Du et al., 2005; Hu et al., 2006). So far, a one-dimensional CuII–benzoate complex [Cu(BA)](BA)(H2O)3]n (Koizumi et al., 1963; BA is benzoate, C6H5CO2) and two dinuclear CuII–benzoate complexes, [Cu2(BA)4(CH3OH)2](CH3OH) (Bkouche-Waksman et al., 1980) and [Cu2(BA)4(HBA)2] (Kawata et al., 1992), have been reported. However, in this work, where we use HL instead of HBA to react with Cu(NO3)2 under certain conditions, only one one-dimensional polymer, (I), was produced. When we futher used HACA, with a larger bulky skeleton of aromatic rings, instead of HL to react with Cu(NO3)2 under the same conditions, one dinuclear discrete structure analogous to that of copper acetate, [Cu2(ACA)4(CH3OH)2](CH3OH), was obtained (Liu et al., 2007). Thus, although the carboxylic acid coordination sites of HL, HACA and HBA are very similar, their coordination chemistry is obviously different, presumably as a result of the different skeletal bulk of the naphthalene, anthracene and benzene ring systems.

Our results, therefore, reveal that the steric bulk of different aromatic ring systems (naphthalene, anthracene or benzene) may play an important role in the formation of related metal-organic complexes. From the viewpoint of ligand design, this fact may offer the means to construct unique coordination architectures with specific potential properties just by means of the steric bulk of different aromatic skeleton. Bulky carboxylate ligands containing naphthalene or anthracene ring systems might be generally used with different d10 transition metal ions, such as Ag, Zn and Cd, for constructing other metal-organic complexes with luminescence properties; research into this possiblity is underway in our laboratory.

Related literature top

For related literature, see: Bkouche-Waksman, Bois, Popovitch & L'Haridon (1980); Du et al. (2005); Gavrilenko et al. (2005); Hu et al. (2006); Kawata et al. (1992); Koizumi et al. (1963); Leininger et al. (2000); Liu et al. (2006, 2007); Robin & Fromm (2006); Steel (2005); Ye et al. (2005); Zou et al. (2005).

Experimental top

A solution of HL (0.05 mmol) in CH3OH (10 ml) in the presence of excess 2,6-dimethylpyridine (ca 0.05 ml for adjusting the pH value of reaction system to basic condition) was carefully layered on top of an aqueous solution (15 ml) of Cu(NO3)2 (0.1 mmol) in a test tube. Blue single crystals suitable for X-ray analysis appeared at the boundary between CH3OH and H2O after ca one month at room temperature (yield ~30% based on HL). Analysis calculated for C11H10CuO4: C 48.98, H 3.74%; found: C 49.09, H 3.67%.

Refinement top

H atoms of the water molecules and hydroxy anions were located in difference maps and were allowed to ride on the parent atoms for refinement [with Uiso(H) = 1.2Ueq(O)]. The remaining H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The one-dimensional molecular structure of the title compound, viewed along the b axis. Displacement ellipsoids are drawn at the 30% probability level and atoms labelled with the suffix A are generated by the symmetry operation (1 - x, 1/2 + y, 3/2 - z).
[Figure 2] Fig. 2. Part of the crystal packing showing, the two-dimensional network in the title compound formed by interchain O—H···O hydrogen-bonded interactions (dashed lines). For the sake of clarity, only H atoms of water molecules and OH ligands involved in the interactions are shown.
catena-Poly[[aquacopper(II)]-µ-hydroxido-µ-naphthalene-1-carboxylato- κ2O:O'] top
Crystal data top
[Cu(C11H7O2)(OH)(H2O)]F(000) = 548
Mr = 269.73Dx = 1.732 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2348 reflections
a = 15.9395 (7) Åθ = 3.5–25.3°
b = 6.2397 (2) ŵ = 2.11 mm1
c = 10.6094 (6) ÅT = 294 K
β = 101.383 (3)°Block, blue
V = 1034.43 (8) Å30.16 × 0.14 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2545 independent reflections
Radiation source: fine-focus sealed tube2010 reflections with i > 2σ(I)
Graphite monochromatorRint = 0.042
phi and ω scansθmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker,1998)
h = 2120
Tmin = 0.729, Tmax = 0.786k = 88
10552 measured reflectionsl = 1114
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0378P)2 + 0.4928P]
where P = (Fo2 + 2Fc2)/3
2545 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Cu(C11H7O2)(OH)(H2O)]V = 1034.43 (8) Å3
Mr = 269.73Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.9395 (7) ŵ = 2.11 mm1
b = 6.2397 (2) ÅT = 294 K
c = 10.6094 (6) Å0.16 × 0.14 × 0.12 mm
β = 101.383 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2545 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker,1998)
2010 reflections with i > 2σ(I)
Tmin = 0.729, Tmax = 0.786Rint = 0.042
10552 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.03Δρmax = 0.43 e Å3
2545 reflectionsΔρmin = 0.42 e Å3
145 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
Cu10.503028 (18)0.55314 (4)0.74841 (3)0.02082 (11)
C10.34611 (16)0.3047 (4)0.6379 (2)0.0237 (5)
C20.25356 (16)0.3156 (4)0.5722 (2)0.0245 (5)
C30.20007 (17)0.1589 (4)0.6014 (3)0.0339 (6)
H30.22250.04890.65720.041*
C40.11182 (19)0.1620 (5)0.5485 (3)0.0410 (7)
H40.07630.05660.57110.049*
C50.07856 (18)0.3184 (5)0.4646 (3)0.0382 (7)
H50.02030.31850.42970.046*
C60.13114 (17)0.4815 (4)0.4294 (3)0.0300 (6)
C70.22005 (16)0.4844 (4)0.4841 (3)0.0258 (5)
C80.0962 (2)0.6442 (5)0.3396 (3)0.0402 (7)
H80.03800.64380.30440.048*
C90.1467 (2)0.7995 (5)0.3048 (3)0.0456 (8)
H90.12320.90320.24530.055*
C100.2344 (2)0.8031 (5)0.3590 (3)0.0438 (8)
H100.26860.91060.33520.053*
C110.27066 (18)0.6512 (5)0.4463 (3)0.0343 (6)
H110.32890.65720.48110.041*
O10.37940 (11)0.1210 (3)0.65603 (19)0.0311 (4)
O20.38330 (11)0.4794 (3)0.6721 (2)0.0317 (4)
O30.54490 (11)0.2984 (2)0.67951 (17)0.0224 (4)
H310.59870.29600.70740.027*
O40.52295 (14)0.7749 (3)0.57325 (19)0.0376 (5)
H410.49950.73710.49750.045*
H420.57140.82050.56310.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01926 (17)0.01780 (17)0.02369 (18)0.00016 (11)0.00010 (11)0.00240 (12)
C10.0211 (13)0.0285 (13)0.0214 (13)0.0004 (10)0.0041 (10)0.0020 (10)
C20.0195 (12)0.0277 (13)0.0251 (13)0.0001 (10)0.0018 (10)0.0029 (10)
C30.0272 (15)0.0303 (14)0.0404 (17)0.0003 (11)0.0023 (12)0.0066 (12)
C40.0260 (15)0.0414 (17)0.054 (2)0.0088 (13)0.0044 (14)0.0036 (14)
C50.0176 (13)0.0500 (18)0.0432 (18)0.0030 (12)0.0034 (12)0.0019 (14)
C60.0237 (13)0.0380 (15)0.0266 (14)0.0046 (11)0.0008 (11)0.0026 (11)
C70.0226 (13)0.0300 (13)0.0238 (14)0.0039 (10)0.0023 (10)0.0004 (10)
C80.0290 (15)0.0521 (18)0.0353 (17)0.0091 (14)0.0035 (13)0.0011 (14)
C90.048 (2)0.0486 (19)0.0379 (18)0.0151 (15)0.0026 (15)0.0140 (15)
C100.0461 (19)0.0450 (18)0.0414 (18)0.0001 (14)0.0109 (15)0.0127 (14)
C110.0252 (14)0.0413 (16)0.0358 (16)0.0006 (12)0.0046 (12)0.0071 (13)
O10.0226 (9)0.0238 (9)0.0425 (12)0.0002 (7)0.0046 (8)0.0015 (8)
O20.0217 (9)0.0239 (9)0.0442 (12)0.0009 (7)0.0064 (8)0.0057 (8)
O30.0212 (9)0.0208 (8)0.0251 (9)0.0008 (7)0.0041 (7)0.0013 (7)
O40.0474 (13)0.0439 (11)0.0214 (10)0.0047 (10)0.0066 (9)0.0015 (9)
Geometric parameters (Å, º) top
Cu1—O31.9232 (16)C6—C71.422 (4)
Cu1—O3i1.9342 (16)C6—C81.428 (4)
Cu1—O21.9747 (18)C7—C111.422 (4)
Cu1—O1i1.9923 (18)C8—C91.356 (4)
Cu1—O42.3879 (19)C8—H80.9300
C1—O21.260 (3)C9—C101.403 (5)
C1—O11.262 (3)C9—H90.9300
C1—C21.504 (3)C10—C111.370 (4)
C2—C31.372 (4)C10—H100.9300
C2—C71.439 (4)C11—H110.9300
C3—C41.408 (4)O1—Cu1ii1.9923 (18)
C3—H30.9300O4—H410.8500
C4—C51.356 (4)O4—H420.8500
C4—H40.9300O3—Cu1ii1.9342 (16)
C5—C61.414 (4)O3—H310.8500
C5—H50.9300
O3—Cu1—O3i176.35 (5)C5—C6—C8121.0 (3)
O3—Cu1—O291.80 (8)C7—C6—C8119.3 (3)
O3i—Cu1—O285.48 (7)C6—C7—C11118.0 (2)
O3—Cu1—O1i90.40 (8)C6—C7—C2117.9 (2)
O3i—Cu1—O1i92.06 (8)C11—C7—C2124.1 (2)
O2—Cu1—O1i173.75 (8)C9—C8—C6121.0 (3)
O3—Cu1—O494.23 (7)C9—C8—H8119.5
O3i—Cu1—O488.44 (7)C6—C8—H8119.5
O2—Cu1—O494.71 (8)C8—C9—C10119.8 (3)
O1i—Cu1—O490.95 (8)C8—C9—H9120.1
O2—C1—O1125.6 (2)C10—C9—H9120.1
O2—C1—C2117.2 (2)C11—C10—C9121.2 (3)
O1—C1—C2117.1 (2)C11—C10—H10119.4
C3—C2—C7120.1 (2)C9—C10—H10119.4
C3—C2—C1117.4 (2)C10—C11—C7120.7 (3)
C7—C2—C1122.6 (2)C10—C11—H11119.7
C2—C3—C4121.1 (3)C7—C11—H11119.7
C2—C3—H3119.5C1—O1—Cu1ii126.57 (17)
C4—C3—H3119.5Cu1—O4—H41118.2
C5—C4—C3120.1 (3)Cu1—O4—H42123.8
C5—C4—H4119.9H41—O4—H42102.5
C3—C4—H4119.9C1—O2—Cu1132.96 (17)
C4—C5—C6121.0 (3)Cu1—O3—Cu1ii108.05 (8)
C4—C5—H5119.5Cu1—O3—H31106.5
C6—C5—H5119.5Cu1ii—O3—H31107.4
C5—C6—C7119.8 (3)
O2—C1—C2—C3141.6 (3)C5—C6—C8—C9179.4 (3)
O1—C1—C2—C337.2 (4)C7—C6—C8—C90.7 (4)
O2—C1—C2—C736.8 (4)C6—C8—C9—C101.0 (5)
O1—C1—C2—C7144.4 (3)C8—C9—C10—C110.5 (5)
C7—C2—C3—C41.2 (4)C9—C10—C11—C70.2 (5)
C1—C2—C3—C4177.3 (3)C6—C7—C11—C100.4 (4)
C2—C3—C4—C51.6 (5)C2—C7—C11—C10178.1 (3)
C3—C4—C5—C60.5 (5)O2—C1—O1—Cu1ii3.7 (4)
C4—C5—C6—C71.1 (4)C2—C1—O1—Cu1ii174.98 (16)
C4—C5—C6—C8179.0 (3)O1—C1—O2—Cu16.4 (4)
C5—C6—C7—C11179.9 (3)C2—C1—O2—Cu1174.93 (17)
C8—C6—C7—C110.1 (4)O3—Cu1—O2—C124.1 (3)
C5—C6—C7—C21.4 (4)O3i—Cu1—O2—C1153.4 (3)
C8—C6—C7—C2178.7 (2)O4—Cu1—O2—C1118.5 (3)
C3—C2—C7—C60.3 (4)O2—Cu1—O3—Cu1ii61.24 (9)
C1—C2—C7—C6178.7 (2)O1i—Cu1—O3—Cu1ii112.91 (9)
C3—C2—C7—C11178.8 (3)O4—Cu1—O3—Cu1ii156.11 (9)
C1—C2—C7—C112.8 (4)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H41···O3iii0.851.882.725 (3)169
O3—H31···O1i0.852.482.779 (2)102
O3—H31···O2ii0.852.342.653 (2)102
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C11H7O2)(OH)(H2O)]
Mr269.73
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)15.9395 (7), 6.2397 (2), 10.6094 (6)
β (°) 101.383 (3)
V3)1034.43 (8)
Z4
Radiation typeMo Kα
µ (mm1)2.11
Crystal size (mm)0.16 × 0.14 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker,1998)
Tmin, Tmax0.729, 0.786
No. of measured, independent and
observed [i > 2σ(I)] reflections
10552, 2545, 2010
Rint0.042
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.084, 1.03
No. of reflections2545
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.42

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Cu1—O31.9232 (16)Cu1—O42.3879 (19)
Cu1—O3i1.9342 (16)O1—Cu1ii1.9923 (18)
Cu1—O21.9747 (18)O3—Cu1ii1.9342 (16)
Cu1—O1i1.9923 (18)
O3—Cu1—O3i176.35 (5)O2—Cu1—O1i173.75 (8)
O3—Cu1—O291.80 (8)O3—Cu1—O494.23 (7)
O3i—Cu1—O285.48 (7)O3i—Cu1—O488.44 (7)
O3—Cu1—O1i90.40 (8)O2—Cu1—O494.71 (8)
O3i—Cu1—O1i92.06 (8)O1i—Cu1—O490.95 (8)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H41···O3iii0.851.882.725 (3)169
O3—H31···O1i0.852.482.779 (2)102
O3—H31···O2ii0.852.342.653 (2)102
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1.
 

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