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Acta Cryst. (2007). E63, m2559-m2560    [ doi:10.1107/S1600536807044650 ]

catena-Poly[[[(4,7-dimethyl-1,10-phenanthroline-[kappa]2N,N')(formato-[kappa]O)copper(II)]-[mu]-formato-[kappa]2O:O'] monohydrate]

J.-L. Lin, X.-K. Qiu and Y.-Q. Zheng

Abstract top

The title compound, [Cu(CHO2)2(C14H12N2)]·H2O, consists of solvent water molecules and one-dimensional [Cu(dmph)(HCOO)([mu]-HCOO)2/2]n polymeric chains (dmph = 4,7-dimethyl-1,10-phenanthroline). The polymeric chains are generated from the [Cu(dmph)(HCOO)]+ units bridged by formate anions. The Cu atom is coordinated in a square-pyramidal environment. Interdigitation of the polymeric chains results in two-dimensional layers, which are stabilized by interchain [pi]-[pi] stacking interactions (mean 3.53 Å). The supramolecular assembly of the resulting layers is accomplished by interlayer C-H...O hydrogen-bonding interactions.

Comment top

Metal–organic coordination complexes containing the aliphatic carboxylic acid ligand has been studied extensively due to their wide range of applications (Maruoka et al., 1993; Chen & Suslick, 1993; Hoskins & Robson, 1990; Kondo et al., 1997). Here, we report the crystal structure of one such complex, the title compound, (I).

The molecular structure of (I) is illustrated in Fig. 1. The asymmetric unit of (I) contains a Cu2+ ion, a 4,7-dimethyl-1,10-phenanthroline (dmph) molecule, two formate ions and a H2O molecule. As depicted in Fig.1, two crystallographically distinct formate ions are bonded to Cu atoms in different coordination modes, one being a monodentate ligand in an syn fashion and the other bidentate one bridging two Cu atoms in an anti-anti fashion with the one end axially bonded to one Cu atom and the other end equatorially approaching the other metal atom. The Cu atoms are coordinated by two N atoms of one dmph ligand and three O atoms of different formate anions to complete square pyramidal CuN2O5 chromophore with one oxygen atom of one bidentate formate anion at the apex. The Cu atom is found to be displaced by 0.237 Å from the basal plane towards the apical O4 atom. Through the bidentate formate anions, the [Cu(dmph)(HCO2)]+ units are bridged to generate infinite chains formulated as [Cu(dmph)(HCO2)(µ-HCO2)2/2]n. The resulting chains extend along the crystallographic b axis with the dmph ligands pendent on both sides and the lattice water molecules are attached to the chains by forming hydrogen bonds to the uncoordinating formate oxygen atom as well as to the axially coordinated formate oxygen atom. The dmph ligands of one polymeric chain are each sandwiched by two aromatic neighbors of adjacent chains and such interdigitation of the chains give two-dimensional layers parallel to (100) as shown in Fig. 2. The mean interplanar distance between interdigitating dmph ligands is 3.53 Å, indicating the resulting two-dimensional layers are stabilized by the interchain π-π stacking interactions. The layers are stacked along the [100] and between them are present weak C—H···O hydrogen bonds, which result from the —CH groups on the aromatic ring donating hydrogen atoms to the uncoordinating formate oxygen atoms as well as to the water oxygen atoms. According to the above description, the interlayer C—H···O hydrogen bonding interactions are responsible for supramolecular assembly of the two-dimensional layers.

Related literature top

For related literature, see: Chen & Suslick (1993); Hoskins & Robson (1990); Kondo et al. (1997); Maruoka et al. (1993); Sheldrick (1990).

Experimental top

1.0 ml (1 M) Na2CO3 was dropwise added to a stirring aqueous solution of 0.110 g (0.442 mmol) CuSO4.5H2O in 5.0 ml H2O, yielding pale blue precipitate, which was separated by centrifugalization and washed with de-ionized H2O unit no detectable SO42− ions in supernatant. The fresh precipitate was then added to a stirred methanolic aqueous solution of 0.100 g (0.442 mmol) 4,7-dimethyl-1,10-phenanthroline (dmph) in 20 ml CH3OH/H2O (v/v = 1:1). Under continuous stirring, 1.0 ml formic acid was added and the dark green suspension was filtered off. Slow evaporation of the dark green filtrate (pH = 3.55) at room temperature afforded a small amount of dark green prismatic crystals.

Refinement top

The H5A and H5B atoms of the aqua molecules were located from difference Fourier synthesis, with O—H distances refined. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 and 0.96 Å.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. (I: 0.5-X, 0.5+Y, 0.5-Z)
[Figure 2] Fig. 2. A view of a single layer of (I). H atoms, solvent water molecules and hydrogen bonds have been omitted.
catena-Poly[[[(4,7-dimethyl-1,10-phenanthroline- κ2N,N')(formato-κO)copper(II)]- µ-formato-κ2O:O'] monohydrate] top
Crystal data top
[Cu(CHO2)2(C14H12N2)]·H2OF000 = 1560
Mr = 379.85Dx = 1.609 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 21.260 (4) Åθ = 5.0–12.5º
b = 7.5010 (15) ŵ = 1.42 mm−1
c = 20.819 (4) ÅT = 295 (2) K
β = 109.17 (3)ºBlock, blue
V = 3135.9 (11) Å30.49 × 0.42 × 0.20 mm
Z = 8
Data collection top
Bruker P4
diffractometer		Rint = 0.026
Radiation source: fine-focus sealed tubeθmax = 27.5º
Monochromator: graphiteθmin = 2.0º
T = 295(2) Kh = −27→1
θ/2θ scansk = −1→9
Absorption correction: empirical (using intensity measurements)
XSCANS (Siemens, 1996)		l = −25→27
Tmin = 0.514, Tmax = 0.7583 standard reflections
4506 measured reflections every 97 reflections
3610 independent reflections intensity decay: none
2545 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.043P)2 + 3.5441P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
3610 reflectionsΔρmax = 0.29 e Å−3
220 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(CHO2)2(C14H12N2)]·H2OV = 3135.9 (11) Å3
Mr = 379.85Z = 8
Monoclinic, C2/cMo Kα
a = 21.260 (4) ŵ = 1.42 mm−1
b = 7.5010 (15) ÅT = 295 (2) K
c = 20.819 (4) Å0.49 × 0.42 × 0.20 mm
β = 109.17 (3)º
Data collection top
Bruker P4
diffractometer		2545 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
XSCANS (Siemens, 1996)		Rint = 0.026
Tmin = 0.514, Tmax = 0.7583 standard reflections
4506 measured reflections every 97 reflections
3610 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.042220 parameters
wR(F2) = 0.104H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.29 e Å−3
3610 reflectionsΔρmin = −0.37 e Å−3
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
Cu0.210963 (17)0.14358 (5)0.138649 (17)0.03511 (13)
N10.28595 (12)0.0478 (3)0.10998 (11)0.0343 (5)
N20.16109 (12)0.1064 (3)0.03976 (12)0.0382 (6)
C10.34873 (15)0.0172 (5)0.14787 (16)0.0430 (8)
H10.36160.03840.19440.066 (4)*
C20.39574 (17)−0.0458 (5)0.12009 (19)0.0532 (9)
H20.4390−0.06740.14850.066 (4)*
C30.37948 (18)−0.0761 (5)0.05218 (19)0.0503 (9)
C40.31229 (17)−0.0472 (4)0.01027 (16)0.0434 (8)
C50.2868 (2)−0.0771 (5)−0.06134 (18)0.0563 (10)
H50.3152−0.1194−0.08370.066 (4)*
C60.2223 (2)−0.0452 (5)−0.09741 (16)0.0556 (10)
H60.2076−0.0655−0.14410.066 (4)*
C70.17582 (18)0.0183 (4)−0.06652 (15)0.0447 (8)
C80.10791 (19)0.0569 (5)−0.10138 (16)0.0541 (9)
C90.07013 (19)0.1179 (5)−0.06408 (17)0.0596 (10)
H90.02540.1439−0.08580.066 (4)*
C100.09741 (17)0.1416 (5)0.00558 (16)0.0496 (8)
H100.07030.18370.02940.066 (4)*
C110.19947 (15)0.0465 (4)0.00405 (14)0.0359 (7)
C120.26794 (15)0.0136 (4)0.04252 (14)0.0352 (7)
C130.4312 (2)−0.1361 (6)0.0215 (2)0.0773 (13)
H13A0.4743−0.13610.05590.116*
H13B0.4314−0.0561−0.01440.116*
H13C0.4207−0.25430.00350.116*
C140.0778 (2)0.0341 (7)−0.17721 (17)0.0812 (14)
H14A0.03400.0855−0.19250.122*
H14B0.0749−0.0906−0.18820.122*
H14C0.10530.0927−0.19930.122*
O10.13880 (11)0.2811 (3)0.14987 (11)0.0510 (6)
O20.05869 (16)0.3299 (5)0.19201 (18)0.0922 (11)
C150.23199 (16)−0.1615 (5)0.23724 (16)0.0450 (8)
H150.2727−0.10260.25120.066 (4)*
O30.22397 (11)−0.2789 (3)0.27525 (11)0.0495 (6)
O40.19140 (11)−0.1144 (3)0.18250 (10)0.0484 (6)
C160.09874 (19)0.2349 (6)0.1778 (2)0.0637 (11)
H160.09900.11500.18930.066 (4)*
O50.06640 (15)0.6969 (5)0.1560 (2)0.1152 (14)
H5A0.06350.58500.15550.120*
H5B0.10330.74090.16350.120*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0352 (2)0.0401 (2)0.02959 (18)0.00407 (18)0.01001 (14)−0.00091 (17)
N10.0356 (13)0.0347 (14)0.0332 (12)0.0012 (12)0.0119 (10)0.0004 (11)
N20.0397 (14)0.0402 (15)0.0320 (12)0.0043 (12)0.0081 (11)0.0027 (11)
C10.0354 (17)0.0459 (19)0.0461 (17)0.0012 (15)0.0114 (14)0.0007 (15)
C20.0358 (18)0.053 (2)0.072 (2)0.0016 (17)0.0201 (17)0.000 (2)
C30.053 (2)0.0385 (18)0.073 (2)0.0006 (16)0.0396 (19)−0.0017 (18)
C40.057 (2)0.0319 (18)0.0519 (18)−0.0009 (16)0.0329 (16)−0.0004 (15)
C50.084 (3)0.047 (2)0.053 (2)−0.006 (2)0.044 (2)−0.0059 (18)
C60.092 (3)0.048 (2)0.0343 (16)−0.006 (2)0.0303 (19)−0.0022 (16)
C70.064 (2)0.0357 (17)0.0315 (14)−0.0048 (16)0.0117 (15)0.0005 (14)
C80.071 (2)0.046 (2)0.0334 (16)−0.0072 (19)0.0008 (16)0.0048 (16)
C90.052 (2)0.061 (3)0.0476 (19)0.0043 (19)−0.0076 (17)0.0050 (18)
C100.0460 (18)0.051 (2)0.0441 (17)0.0126 (17)0.0046 (14)0.0039 (17)
C110.0476 (17)0.0303 (16)0.0294 (13)−0.0031 (14)0.0122 (13)0.0018 (13)
C120.0420 (17)0.0322 (16)0.0327 (14)−0.0027 (14)0.0142 (13)0.0023 (13)
C130.072 (3)0.075 (3)0.110 (3)0.007 (2)0.063 (3)−0.001 (3)
C140.102 (3)0.087 (3)0.0343 (17)−0.004 (3)−0.006 (2)−0.002 (2)
O10.0474 (13)0.0567 (15)0.0531 (13)0.0103 (12)0.0222 (11)0.0009 (12)
O20.071 (2)0.110 (3)0.114 (3)0.0250 (19)0.057 (2)0.007 (2)
C150.0428 (18)0.0456 (19)0.0448 (17)0.0007 (15)0.0119 (15)0.0096 (16)
O30.0497 (13)0.0542 (14)0.0396 (11)−0.0064 (12)0.0077 (10)0.0149 (11)
O40.0510 (13)0.0515 (15)0.0383 (11)−0.0002 (11)0.0088 (10)0.0147 (10)
C160.052 (2)0.073 (3)0.074 (3)0.012 (2)0.032 (2)0.009 (2)
O50.0537 (19)0.093 (3)0.167 (4)0.0016 (19)−0.006 (2)0.014 (3)
Geometric parameters (Å, °) top
Cu—O11.925 (2)C7—C81.417 (5)
Cu—O3i1.959 (2)C8—C91.367 (5)
Cu—N22.002 (2)C8—C141.506 (4)
Cu—N12.010 (2)C9—C101.385 (5)
Cu—O42.236 (2)C9—H90.9300
N1—C11.329 (4)C10—H100.9300
N1—C121.353 (3)C11—C121.434 (4)
N2—C101.333 (4)C13—H13A0.9600
N2—C111.349 (4)C13—H13B0.9600
C1—C21.391 (4)C13—H13C0.9600
C1—H10.9300C14—H14A0.9600
C2—C31.360 (5)C14—H14B0.9600
C2—H20.9300C14—H14C0.9600
C3—C41.425 (5)O1—C161.228 (4)
C3—C131.510 (5)O2—C161.219 (5)
C4—C121.401 (4)C15—O31.232 (4)
C4—C51.427 (5)C15—O41.234 (4)
C5—C61.351 (5)C15—H150.9300
C5—H50.9300O3—Cuii1.959 (2)
C6—C71.426 (5)C16—H160.9300
C6—H60.9300O5—H5A0.8414
C7—C111.404 (4)O5—H5B0.8169
O1—Cu—O3i94.67 (10)C9—C8—C7117.9 (3)
O1—Cu—N291.45 (10)C9—C8—C14120.5 (4)
O3i—Cu—N2163.53 (10)C7—C8—C14121.6 (4)
O1—Cu—N1165.67 (10)C8—C9—C10121.1 (3)
O3i—Cu—N189.27 (10)C8—C9—H9119.5
N2—Cu—N181.30 (10)C10—C9—H9119.5
O1—Cu—O498.72 (10)N2—C10—C9122.4 (3)
O3i—Cu—O493.07 (9)N2—C10—H10118.8
N2—Cu—O4101.11 (9)C9—C10—H10118.8
N1—Cu—O494.82 (9)N2—C11—C7123.6 (3)
C1—N1—C12118.0 (3)N2—C11—C12115.9 (2)
C1—N1—Cu128.7 (2)C7—C11—C12120.5 (3)
C12—N1—Cu113.22 (19)N1—C12—C4123.6 (3)
C10—N2—C11117.6 (3)N1—C12—C11115.9 (2)
C10—N2—Cu128.6 (2)C4—C12—C11120.5 (3)
C11—N2—Cu113.7 (2)C3—C13—H13A109.5
N1—C1—C2122.1 (3)C3—C13—H13B109.5
N1—C1—H1119.0H13A—C13—H13B109.5
C2—C1—H1119.0C3—C13—H13C109.5
C3—C2—C1121.1 (3)H13A—C13—H13C109.5
C3—C2—H2119.4H13B—C13—H13C109.5
C1—C2—H2119.4C8—C14—H14A109.5
C2—C3—C4118.2 (3)C8—C14—H14B109.5
C2—C3—C13121.2 (4)H14A—C14—H14B109.5
C4—C3—C13120.6 (3)C8—C14—H14C109.5
C12—C4—C3117.0 (3)H14A—C14—H14C109.5
C12—C4—C5117.9 (3)H14B—C14—H14C109.5
C3—C4—C5125.2 (3)C16—O1—Cu127.6 (3)
C6—C5—C4121.4 (3)O3—C15—O4126.5 (3)
C6—C5—H5119.3O3—C15—H15116.7
C4—C5—H5119.3O4—C15—H15116.7
C5—C6—C7122.4 (3)C15—O3—Cuii126.5 (2)
C5—C6—H6118.8C15—O4—Cu117.2 (2)
C7—C6—H6118.8O2—C16—O1126.8 (4)
C11—C7—C8117.4 (3)O2—C16—H16116.6
C11—C7—C6117.3 (3)O1—C16—H16116.6
C8—C7—C6125.3 (3)H5A—O5—H5B117.9
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.8412.0702.872 (5)158
O5—H5B···O4iii0.8172.0902.899 (6)172
C1—H1···O3iv0.932.522.986 (2)111
C2—H2···O2v0.932.523.422 (4)162
C9—H9···O5vi0.932.343.220 (5)157
C10—H10···O10.932.563.026 (3)111
C15—H15···O1ii0.932.453.002 (3)118
C15—H15···O3iv0.932.503.057 (5)119
Symmetry codes: (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) x+1/2, y−1/2, z; (vi) −x, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu—O11.925 (2)Cu—N12.010 (2)
Cu—O3i1.959 (2)Cu—O42.236 (2)
Cu—N22.002 (2)
O1—Cu—O3i94.67 (10)N2—Cu—N181.30 (10)
O1—Cu—N291.45 (10)O1—Cu—O498.72 (10)
O3i—Cu—N2163.53 (10)O3i—Cu—O493.07 (9)
O1—Cu—N1165.67 (10)N2—Cu—O4101.11 (9)
O3i—Cu—N189.27 (10)N1—Cu—O494.82 (9)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.8412.0702.872 (5)158
O5—H5B···O4ii0.8172.0902.899 (6)172
C1—H1···O3iii0.932.522.986 (2)111
C2—H2···O2iv0.932.523.422 (4)162
C9—H9···O5v0.932.343.220 (5)157
C10—H10···O10.932.563.026 (3)111
C15—H15···O1vi0.932.453.002 (3)118
C15—H15···O3iii0.932.503.057 (5)119
Symmetry codes: (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, y−1/2, z; (v) −x, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2.
Acknowledgements top

This project was supported by the Zhejiang Provincial Fund for Analysis and Measurements (grant No. 04058), the Scientific Research Fund of Ningbo University (grant No. XK200457), the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067), and the Ningbo Municipal Natural Science Foundation (grant No. 2003 A62026).

references
References top

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