Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044650/bq2034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044650/bq2034Isup2.hkl |
CCDC reference: 663616
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.042
- wR factor = 0.104
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level G PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero. 0.01 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu (2) 2.21
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Chen & Suslick (1993); Hoskins & Robson (1990); Kondo et al. (1997); Maruoka et al. (1993); Sheldrick (1990).
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.
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.
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.
For related literature, see: Chen & Suslick (1993); Hoskins & Robson (1990); Kondo et al. (1997); Maruoka et al. (1993); Sheldrick (1990).
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).
[Cu(CHO2)2(C14H12N2)]·H2O | F(000) = 1560 |
Mr = 379.85 | Dx = 1.609 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 21.260 (4) Å | θ = 5.0–12.5° |
b = 7.5010 (15) Å | µ = 1.42 mm−1 |
c = 20.819 (4) Å | T = 295 K |
β = 109.17 (3)° | Block, blue |
V = 3135.9 (11) Å3 | 0.49 × 0.42 × 0.20 mm |
Z = 8 |
Bruker P4 diffractometer | 2545 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
θ/2θ scans | h = −27→1 |
Absorption correction: empirical (using intensity measurements) XSCANS (Siemens, 1996) | k = −1→9 |
Tmin = 0.514, Tmax = 0.758 | l = −25→27 |
4506 measured reflections | 3 standard reflections every 97 reflections |
3610 independent reflections | intensity decay: none |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.043P)2 + 3.5441P] where P = (Fo2 + 2Fc2)/3 |
3610 reflections | (Δ/σ)max = 0.001 |
220 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Cu(CHO2)2(C14H12N2)]·H2O | V = 3135.9 (11) Å3 |
Mr = 379.85 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.260 (4) Å | µ = 1.42 mm−1 |
b = 7.5010 (15) Å | T = 295 K |
c = 20.819 (4) Å | 0.49 × 0.42 × 0.20 mm |
β = 109.17 (3)° |
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 = 0.758 | 3 standard reflections every 97 reflections |
4506 measured reflections | intensity decay: none |
3610 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.29 e Å−3 |
3610 reflections | Δρmin = −0.37 e Å−3 |
220 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.210963 (17) | 0.14358 (5) | 0.138649 (17) | 0.03511 (13) | |
N1 | 0.28595 (12) | 0.0478 (3) | 0.10998 (11) | 0.0343 (5) | |
N2 | 0.16109 (12) | 0.1064 (3) | 0.03976 (12) | 0.0382 (6) | |
C1 | 0.34873 (15) | 0.0172 (5) | 0.14787 (16) | 0.0430 (8) | |
H1 | 0.3616 | 0.0384 | 0.1944 | 0.066 (4)* | |
C2 | 0.39574 (17) | −0.0458 (5) | 0.12009 (19) | 0.0532 (9) | |
H2 | 0.4390 | −0.0674 | 0.1485 | 0.066 (4)* | |
C3 | 0.37948 (18) | −0.0761 (5) | 0.05218 (19) | 0.0503 (9) | |
C4 | 0.31229 (17) | −0.0472 (4) | 0.01027 (16) | 0.0434 (8) | |
C5 | 0.2868 (2) | −0.0771 (5) | −0.06134 (18) | 0.0563 (10) | |
H5 | 0.3152 | −0.1194 | −0.0837 | 0.066 (4)* | |
C6 | 0.2223 (2) | −0.0452 (5) | −0.09741 (16) | 0.0556 (10) | |
H6 | 0.2076 | −0.0655 | −0.1441 | 0.066 (4)* | |
C7 | 0.17582 (18) | 0.0183 (4) | −0.06652 (15) | 0.0447 (8) | |
C8 | 0.10791 (19) | 0.0569 (5) | −0.10138 (16) | 0.0541 (9) | |
C9 | 0.07013 (19) | 0.1179 (5) | −0.06408 (17) | 0.0596 (10) | |
H9 | 0.0254 | 0.1439 | −0.0858 | 0.066 (4)* | |
C10 | 0.09741 (17) | 0.1416 (5) | 0.00558 (16) | 0.0496 (8) | |
H10 | 0.0703 | 0.1837 | 0.0294 | 0.066 (4)* | |
C11 | 0.19947 (15) | 0.0465 (4) | 0.00405 (14) | 0.0359 (7) | |
C12 | 0.26794 (15) | 0.0136 (4) | 0.04252 (14) | 0.0352 (7) | |
C13 | 0.4312 (2) | −0.1361 (6) | 0.0215 (2) | 0.0773 (13) | |
H13A | 0.4743 | −0.1361 | 0.0559 | 0.116* | |
H13B | 0.4314 | −0.0561 | −0.0144 | 0.116* | |
H13C | 0.4207 | −0.2543 | 0.0035 | 0.116* | |
C14 | 0.0778 (2) | 0.0341 (7) | −0.17721 (17) | 0.0812 (14) | |
H14A | 0.0340 | 0.0855 | −0.1925 | 0.122* | |
H14B | 0.0749 | −0.0906 | −0.1882 | 0.122* | |
H14C | 0.1053 | 0.0927 | −0.1993 | 0.122* | |
O1 | 0.13880 (11) | 0.2811 (3) | 0.14987 (11) | 0.0510 (6) | |
O2 | 0.05869 (16) | 0.3299 (5) | 0.19201 (18) | 0.0922 (11) | |
C15 | 0.23199 (16) | −0.1615 (5) | 0.23724 (16) | 0.0450 (8) | |
H15 | 0.2727 | −0.1026 | 0.2512 | 0.066 (4)* | |
O3 | 0.22397 (11) | −0.2789 (3) | 0.27525 (11) | 0.0495 (6) | |
O4 | 0.19140 (11) | −0.1144 (3) | 0.18250 (10) | 0.0484 (6) | |
C16 | 0.09874 (19) | 0.2349 (6) | 0.1778 (2) | 0.0637 (11) | |
H16 | 0.0990 | 0.1150 | 0.1893 | 0.066 (4)* | |
O5 | 0.06640 (15) | 0.6969 (5) | 0.1560 (2) | 0.1152 (14) | |
H5A | 0.0635 | 0.5850 | 0.1555 | 0.120* | |
H5B | 0.1033 | 0.7409 | 0.1635 | 0.120* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0352 (2) | 0.0401 (2) | 0.02959 (18) | 0.00407 (18) | 0.01001 (14) | −0.00091 (17) |
N1 | 0.0356 (13) | 0.0347 (14) | 0.0332 (12) | 0.0012 (12) | 0.0119 (10) | 0.0004 (11) |
N2 | 0.0397 (14) | 0.0402 (15) | 0.0320 (12) | 0.0043 (12) | 0.0081 (11) | 0.0027 (11) |
C1 | 0.0354 (17) | 0.0459 (19) | 0.0461 (17) | 0.0012 (15) | 0.0114 (14) | 0.0007 (15) |
C2 | 0.0358 (18) | 0.053 (2) | 0.072 (2) | 0.0016 (17) | 0.0201 (17) | 0.000 (2) |
C3 | 0.053 (2) | 0.0385 (18) | 0.073 (2) | 0.0006 (16) | 0.0396 (19) | −0.0017 (18) |
C4 | 0.057 (2) | 0.0319 (18) | 0.0519 (18) | −0.0009 (16) | 0.0329 (16) | −0.0004 (15) |
C5 | 0.084 (3) | 0.047 (2) | 0.053 (2) | −0.006 (2) | 0.044 (2) | −0.0059 (18) |
C6 | 0.092 (3) | 0.048 (2) | 0.0343 (16) | −0.006 (2) | 0.0303 (19) | −0.0022 (16) |
C7 | 0.064 (2) | 0.0357 (17) | 0.0315 (14) | −0.0048 (16) | 0.0117 (15) | 0.0005 (14) |
C8 | 0.071 (2) | 0.046 (2) | 0.0334 (16) | −0.0072 (19) | 0.0008 (16) | 0.0048 (16) |
C9 | 0.052 (2) | 0.061 (3) | 0.0476 (19) | 0.0043 (19) | −0.0076 (17) | 0.0050 (18) |
C10 | 0.0460 (18) | 0.051 (2) | 0.0441 (17) | 0.0126 (17) | 0.0046 (14) | 0.0039 (17) |
C11 | 0.0476 (17) | 0.0303 (16) | 0.0294 (13) | −0.0031 (14) | 0.0122 (13) | 0.0018 (13) |
C12 | 0.0420 (17) | 0.0322 (16) | 0.0327 (14) | −0.0027 (14) | 0.0142 (13) | 0.0023 (13) |
C13 | 0.072 (3) | 0.075 (3) | 0.110 (3) | 0.007 (2) | 0.063 (3) | −0.001 (3) |
C14 | 0.102 (3) | 0.087 (3) | 0.0343 (17) | −0.004 (3) | −0.006 (2) | −0.002 (2) |
O1 | 0.0474 (13) | 0.0567 (15) | 0.0531 (13) | 0.0103 (12) | 0.0222 (11) | 0.0009 (12) |
O2 | 0.071 (2) | 0.110 (3) | 0.114 (3) | 0.0250 (19) | 0.057 (2) | 0.007 (2) |
C15 | 0.0428 (18) | 0.0456 (19) | 0.0448 (17) | 0.0007 (15) | 0.0119 (15) | 0.0096 (16) |
O3 | 0.0497 (13) | 0.0542 (14) | 0.0396 (11) | −0.0064 (12) | 0.0077 (10) | 0.0149 (11) |
O4 | 0.0510 (13) | 0.0515 (15) | 0.0383 (11) | −0.0002 (11) | 0.0088 (10) | 0.0147 (10) |
C16 | 0.052 (2) | 0.073 (3) | 0.074 (3) | 0.012 (2) | 0.032 (2) | 0.009 (2) |
O5 | 0.0537 (19) | 0.093 (3) | 0.167 (4) | 0.0016 (19) | −0.006 (2) | 0.014 (3) |
Cu—O1 | 1.925 (2) | C7—C8 | 1.417 (5) |
Cu—O3i | 1.959 (2) | C8—C9 | 1.367 (5) |
Cu—N2 | 2.002 (2) | C8—C14 | 1.506 (4) |
Cu—N1 | 2.010 (2) | C9—C10 | 1.385 (5) |
Cu—O4 | 2.236 (2) | C9—H9 | 0.9300 |
N1—C1 | 1.329 (4) | C10—H10 | 0.9300 |
N1—C12 | 1.353 (3) | C11—C12 | 1.434 (4) |
N2—C10 | 1.333 (4) | C13—H13A | 0.9600 |
N2—C11 | 1.349 (4) | C13—H13B | 0.9600 |
C1—C2 | 1.391 (4) | C13—H13C | 0.9600 |
C1—H1 | 0.9300 | C14—H14A | 0.9600 |
C2—C3 | 1.360 (5) | C14—H14B | 0.9600 |
C2—H2 | 0.9300 | C14—H14C | 0.9600 |
C3—C4 | 1.425 (5) | O1—C16 | 1.228 (4) |
C3—C13 | 1.510 (5) | O2—C16 | 1.219 (5) |
C4—C12 | 1.401 (4) | C15—O3 | 1.232 (4) |
C4—C5 | 1.427 (5) | C15—O4 | 1.234 (4) |
C5—C6 | 1.351 (5) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | O3—Cuii | 1.959 (2) |
C6—C7 | 1.426 (5) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | O5—H5A | 0.8414 |
C7—C11 | 1.404 (4) | O5—H5B | 0.8169 |
O1—Cu—O3i | 94.67 (10) | C9—C8—C7 | 117.9 (3) |
O1—Cu—N2 | 91.45 (10) | C9—C8—C14 | 120.5 (4) |
O3i—Cu—N2 | 163.53 (10) | C7—C8—C14 | 121.6 (4) |
O1—Cu—N1 | 165.67 (10) | C8—C9—C10 | 121.1 (3) |
O3i—Cu—N1 | 89.27 (10) | C8—C9—H9 | 119.5 |
N2—Cu—N1 | 81.30 (10) | C10—C9—H9 | 119.5 |
O1—Cu—O4 | 98.72 (10) | N2—C10—C9 | 122.4 (3) |
O3i—Cu—O4 | 93.07 (9) | N2—C10—H10 | 118.8 |
N2—Cu—O4 | 101.11 (9) | C9—C10—H10 | 118.8 |
N1—Cu—O4 | 94.82 (9) | N2—C11—C7 | 123.6 (3) |
C1—N1—C12 | 118.0 (3) | N2—C11—C12 | 115.9 (2) |
C1—N1—Cu | 128.7 (2) | C7—C11—C12 | 120.5 (3) |
C12—N1—Cu | 113.22 (19) | N1—C12—C4 | 123.6 (3) |
C10—N2—C11 | 117.6 (3) | N1—C12—C11 | 115.9 (2) |
C10—N2—Cu | 128.6 (2) | C4—C12—C11 | 120.5 (3) |
C11—N2—Cu | 113.7 (2) | C3—C13—H13A | 109.5 |
N1—C1—C2 | 122.1 (3) | C3—C13—H13B | 109.5 |
N1—C1—H1 | 119.0 | H13A—C13—H13B | 109.5 |
C2—C1—H1 | 119.0 | C3—C13—H13C | 109.5 |
C3—C2—C1 | 121.1 (3) | H13A—C13—H13C | 109.5 |
C3—C2—H2 | 119.4 | H13B—C13—H13C | 109.5 |
C1—C2—H2 | 119.4 | C8—C14—H14A | 109.5 |
C2—C3—C4 | 118.2 (3) | C8—C14—H14B | 109.5 |
C2—C3—C13 | 121.2 (4) | H14A—C14—H14B | 109.5 |
C4—C3—C13 | 120.6 (3) | C8—C14—H14C | 109.5 |
C12—C4—C3 | 117.0 (3) | H14A—C14—H14C | 109.5 |
C12—C4—C5 | 117.9 (3) | H14B—C14—H14C | 109.5 |
C3—C4—C5 | 125.2 (3) | C16—O1—Cu | 127.6 (3) |
C6—C5—C4 | 121.4 (3) | O3—C15—O4 | 126.5 (3) |
C6—C5—H5 | 119.3 | O3—C15—H15 | 116.7 |
C4—C5—H5 | 119.3 | O4—C15—H15 | 116.7 |
C5—C6—C7 | 122.4 (3) | C15—O3—Cuii | 126.5 (2) |
C5—C6—H6 | 118.8 | C15—O4—Cu | 117.2 (2) |
C7—C6—H6 | 118.8 | O2—C16—O1 | 126.8 (4) |
C11—C7—C8 | 117.4 (3) | O2—C16—H16 | 116.6 |
C11—C7—C6 | 117.3 (3) | O1—C16—H16 | 116.6 |
C8—C7—C6 | 125.3 (3) | H5A—O5—H5B | 117.9 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.841 | 2.070 | 2.872 (5) | 158 |
O5—H5B···O4iii | 0.817 | 2.090 | 2.899 (6) | 172 |
C1—H1···O3i | 0.93 | 2.52 | 2.986 (2) | 111 |
C2—H2···O2iv | 0.93 | 2.52 | 3.422 (4) | 162 |
C9—H9···O5v | 0.93 | 2.34 | 3.220 (5) | 157 |
C10—H10···O1 | 0.93 | 2.56 | 3.026 (3) | 111 |
C15—H15···O1ii | 0.93 | 2.45 | 3.002 (3) | 118 |
C15—H15···O3i | 0.93 | 2.50 | 3.057 (5) | 119 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y+1, z; (iv) x+1/2, y−1/2, z; (v) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(CHO2)2(C14H12N2)]·H2O |
Mr | 379.85 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 21.260 (4), 7.5010 (15), 20.819 (4) |
β (°) | 109.17 (3) |
V (Å3) | 3135.9 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.42 |
Crystal size (mm) | 0.49 × 0.42 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Empirical (using intensity measurements) XSCANS (Siemens, 1996) |
Tmin, Tmax | 0.514, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4506, 3610, 2545 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.104, 1.01 |
No. of reflections | 3610 |
No. of parameters | 220 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.37 |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Cu—O1 | 1.925 (2) | Cu—N1 | 2.010 (2) |
Cu—O3i | 1.959 (2) | Cu—O4 | 2.236 (2) |
Cu—N2 | 2.002 (2) | ||
O1—Cu—O3i | 94.67 (10) | N2—Cu—N1 | 81.30 (10) |
O1—Cu—N2 | 91.45 (10) | O1—Cu—O4 | 98.72 (10) |
O3i—Cu—N2 | 163.53 (10) | O3i—Cu—O4 | 93.07 (9) |
O1—Cu—N1 | 165.67 (10) | N2—Cu—O4 | 101.11 (9) |
O3i—Cu—N1 | 89.27 (10) | N1—Cu—O4 | 94.82 (9) |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.841 | 2.070 | 2.872 (5) | 158 |
O5—H5B···O4ii | 0.817 | 2.090 | 2.899 (6) | 172 |
C1—H1···O3i | 0.930 | 2.520 | 2.986 (2) | 111 |
C2—H2···O2iii | 0.930 | 2.520 | 3.422 (4) | 162 |
C9—H9···O5iv | 0.930 | 2.340 | 3.220 (5) | 157 |
C10—H10···O1 | 0.930 | 2.560 | 3.026 (3) | 111 |
C15—H15···O1v | 0.930 | 2.450 | 3.002 (3) | 118 |
C15—H15···O3i | 0.930 | 2.500 | 3.057 (5) | 119 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) x+1/2, y−1/2, z; (iv) −x, −y+1, −z; (v) −x+1/2, y−1/2, −z+1/2. |
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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.