Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043449/xu2313sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043449/xu2313Isup2.hkl |
CCDC reference: 663592
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.004 Å
- R factor = 0.038
- wR factor = 0.105
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O2 .. 5.99 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.20 PLAT411_ALERT_2_C Short Inter H...H Contact H6 .. H6 .. 2.13 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C12 .. 3.01 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.27
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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: Wang et al. (1996); Wall et al. (1999); Naing et al. (1995).
An aqueous solution (10 ml) of 3-hydroxybenzoic acid (0.0698 g, 0.5 mmol), NaOH (0.0198 g, 0.5 mmol) and Cu(NO3)2.3H2O (0.1212 g, 0.5 mmol) was mixed with an ethanol solution (10 ml) of 2,9-dimethyl-1,10-phenanthroline hemihydrate (0.1088 g, 0.5 mmol). The mixture was refluxed for 4 h. After cooling to room temperature the solution was filtered. The single crystals of the title compound were obtained after 3 weeks at room temperature.
Methyl H and hydroxy H atoms were placed in calculated positions with C—H = 0.96 and O—H = 0.82 Å, and refined with free torsion angles to fit the electron density, Uiso(H) = 1.5Ueq(carrier). Other H atoms were placed in calculated positions with C—H = 0.93 Å and refined in the riding model approximation with Uiso(H) = 1.2Ueq(C).
Metal-phenanthroline complexes and its derivatives have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Recently, we obtained the title mononuclear copper(II) complex (I), by reaction of 2,9-dimethyl-1,10-phenanthroline, m-hydroxybenzoic acid and Cu(NO3)2 in an ethanol/water mixture. Here we report its crystal structure.
Each CuII ion is four-coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, and two O atoms from two m-hydroxybenzoic anions. The CuII ion locates on a twofold rotation axis, and CuO2N2 unit forms a distorted tetrahedral geometry (Fig. 1). The Cu1–N1 bond length is slightly longer than Cu1—O1 bond length (Table 1).
In the crystal structure, molecules are linked into a two dimensional framework by intermolecular O—H···O hydrogen bonds (Fig. 2). The crystal further stabilized by π-π interactions between the dmphen ring systems (Fig. 3). These intermolecular interactions occur between the parallel rings within offset face-to-face packing. The face-to-face distance of the parallel ring planes between the neighboring molecules related by 1 - x,2 - y,1 - z is 3.385 (18) Å.
For related literature, see: Wang et al. (1996); Wall et al. (1999); Naing et al. (1995).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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(C7H5O3)2(C14H12N2)] | F(000) = 1124 |
Mr = 546.02 | Dx = 1.450 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1908 reflections |
a = 17.623 (3) Å | θ = 2.3–24.8° |
b = 14.587 (2) Å | µ = 0.92 mm−1 |
c = 9.7581 (15) Å | T = 291 K |
β = 94.199 (2)° | Block, yellow |
V = 2501.8 (7) Å3 | 0.44 × 0.33 × 0.24 mm |
Z = 4 |
Bruker SMART CCD area detector diffractometer | 2275 independent reflections |
Radiation source: fine-focus sealed tube | 1766 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 25.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −21→21 |
Tmin = 0.690, Tmax = 0.809 | k = −12→17 |
7268 measured reflections | l = −8→11 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0535P)2 + 1.4781P] where P = (Fo2 + 2Fc2)/3 |
2275 reflections | (Δ/σ)max = 0.001 |
170 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Cu(C7H5O3)2(C14H12N2)] | V = 2501.8 (7) Å3 |
Mr = 546.02 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.623 (3) Å | µ = 0.92 mm−1 |
b = 14.587 (2) Å | T = 291 K |
c = 9.7581 (15) Å | 0.44 × 0.33 × 0.24 mm |
β = 94.199 (2)° |
Bruker SMART CCD area detector diffractometer | 2275 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1766 reflections with I > 2σ(I) |
Tmin = 0.690, Tmax = 0.809 | Rint = 0.030 |
7268 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.28 e Å−3 |
2275 reflections | Δρmin = −0.33 e Å−3 |
170 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 | ||
Cu1 | 0.5000 | 0.76339 (3) | 0.7500 | 0.0548 (2) | |
O1 | 0.48033 (10) | 0.67482 (13) | 0.89294 (19) | 0.0591 (5) | |
O2 | 0.37612 (12) | 0.75613 (14) | 0.8785 (2) | 0.0708 (6) | |
O3 | 0.22168 (12) | 0.6282 (2) | 1.2567 (3) | 0.0946 (9) | |
H3 | 0.2009 | 0.6713 | 1.2151 | 0.142* | |
N1 | 0.44985 (11) | 0.86705 (14) | 0.6396 (2) | 0.0475 (5) | |
C1 | 0.28890 (14) | 0.6092 (2) | 1.2022 (3) | 0.0569 (7) | |
C2 | 0.32881 (17) | 0.5350 (2) | 1.2543 (3) | 0.0758 (9) | |
H2 | 0.3098 | 0.4999 | 1.3236 | 0.091* | |
C3 | 0.3970 (2) | 0.5128 (2) | 1.2036 (4) | 0.0938 (13) | |
H3A | 0.4242 | 0.4623 | 1.2389 | 0.113* | |
C4 | 0.42579 (18) | 0.5645 (2) | 1.1005 (3) | 0.0761 (10) | |
H4 | 0.4725 | 0.5494 | 1.0680 | 0.091* | |
C5 | 0.38563 (14) | 0.63782 (16) | 1.0463 (2) | 0.0443 (6) | |
C6 | 0.31729 (14) | 0.66047 (19) | 1.0984 (3) | 0.0515 (6) | |
H6 | 0.2900 | 0.7109 | 1.0632 | 0.062* | |
C7 | 0.41479 (14) | 0.69351 (17) | 0.9321 (2) | 0.0455 (6) | |
C8 | 0.47227 (14) | 0.95027 (18) | 0.6924 (2) | 0.0480 (6) | |
C9 | 0.44369 (17) | 1.0339 (2) | 0.6395 (3) | 0.0588 (7) | |
C10 | 0.38814 (19) | 1.0287 (2) | 0.5295 (3) | 0.0714 (9) | |
H10 | 0.3674 | 1.0822 | 0.4908 | 0.086* | |
C11 | 0.36452 (17) | 0.9460 (3) | 0.4793 (3) | 0.0687 (9) | |
H11 | 0.3272 | 0.9432 | 0.4069 | 0.082* | |
C12 | 0.39594 (15) | 0.8639 (2) | 0.5356 (3) | 0.0560 (7) | |
C13 | 0.36969 (19) | 0.7725 (2) | 0.4826 (3) | 0.0752 (9) | |
H13A | 0.4130 | 0.7357 | 0.4642 | 0.113* | |
H13B | 0.3378 | 0.7804 | 0.3994 | 0.113* | |
H13C | 0.3414 | 0.7424 | 0.5501 | 0.113* | |
C14 | 0.47253 (19) | 1.1177 (2) | 0.6983 (3) | 0.0738 (9) | |
H14 | 0.4530 | 1.1732 | 0.6646 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0702 (3) | 0.0494 (3) | 0.0457 (3) | 0.000 | 0.0106 (2) | 0.000 |
O1 | 0.0571 (11) | 0.0621 (12) | 0.0615 (12) | 0.0067 (9) | 0.0269 (9) | 0.0056 (9) |
O2 | 0.0672 (13) | 0.0720 (14) | 0.0761 (14) | 0.0143 (10) | 0.0260 (11) | 0.0323 (11) |
O3 | 0.0623 (13) | 0.139 (2) | 0.0871 (16) | 0.0299 (13) | 0.0399 (12) | 0.0534 (15) |
N1 | 0.0468 (11) | 0.0572 (14) | 0.0403 (11) | −0.0009 (10) | 0.0155 (9) | 0.0027 (10) |
C1 | 0.0466 (14) | 0.0730 (19) | 0.0524 (16) | 0.0042 (13) | 0.0124 (12) | 0.0153 (14) |
C2 | 0.070 (2) | 0.086 (2) | 0.074 (2) | 0.0079 (17) | 0.0206 (17) | 0.0384 (18) |
C3 | 0.096 (3) | 0.082 (2) | 0.108 (3) | 0.037 (2) | 0.040 (2) | 0.055 (2) |
C4 | 0.078 (2) | 0.073 (2) | 0.083 (2) | 0.0322 (17) | 0.0380 (18) | 0.0270 (17) |
C5 | 0.0506 (14) | 0.0424 (14) | 0.0413 (13) | 0.0013 (11) | 0.0121 (11) | −0.0004 (11) |
C6 | 0.0513 (14) | 0.0554 (16) | 0.0489 (15) | 0.0092 (12) | 0.0111 (12) | 0.0128 (12) |
C7 | 0.0508 (14) | 0.0440 (15) | 0.0429 (13) | −0.0012 (12) | 0.0110 (11) | −0.0038 (11) |
C8 | 0.0549 (15) | 0.0510 (16) | 0.0410 (13) | 0.0027 (12) | 0.0239 (11) | 0.0029 (11) |
C9 | 0.0705 (18) | 0.0584 (18) | 0.0513 (16) | 0.0077 (14) | 0.0311 (15) | 0.0102 (14) |
C10 | 0.081 (2) | 0.077 (2) | 0.0592 (19) | 0.0209 (18) | 0.0271 (17) | 0.0202 (17) |
C11 | 0.0601 (18) | 0.096 (3) | 0.0507 (17) | 0.0072 (17) | 0.0110 (14) | 0.0189 (17) |
C12 | 0.0492 (14) | 0.073 (2) | 0.0478 (15) | −0.0022 (13) | 0.0183 (12) | 0.0058 (14) |
C13 | 0.0652 (19) | 0.096 (3) | 0.064 (2) | −0.0180 (17) | −0.0016 (16) | −0.0019 (17) |
C14 | 0.106 (3) | 0.0518 (18) | 0.069 (2) | 0.0085 (16) | 0.0412 (17) | 0.0083 (14) |
Cu1—O1 | 1.9509 (18) | C5—C6 | 1.381 (3) |
Cu1—O1i | 1.9509 (18) | C5—C7 | 1.500 (3) |
Cu1—N1 | 2.022 (2) | C6—H6 | 0.9300 |
Cu1—N1i | 2.022 (2) | C8—C9 | 1.403 (4) |
O1—C7 | 1.272 (3) | C8—C8i | 1.434 (5) |
O2—C7 | 1.233 (3) | C9—C10 | 1.400 (4) |
O3—C1 | 1.362 (3) | C9—C14 | 1.428 (4) |
O3—H3 | 0.8200 | C10—C11 | 1.356 (4) |
N1—C12 | 1.339 (3) | C10—H10 | 0.9300 |
N1—C8 | 1.366 (3) | C11—C12 | 1.413 (4) |
C1—C2 | 1.367 (4) | C11—H11 | 0.9300 |
C1—C6 | 1.382 (4) | C12—C13 | 1.492 (4) |
C2—C3 | 1.372 (4) | C13—H13A | 0.9600 |
C2—H2 | 0.9300 | C13—H13B | 0.9600 |
C3—C4 | 1.383 (4) | C13—H13C | 0.9600 |
C3—H3A | 0.9300 | C14—C14i | 1.346 (7) |
C4—C5 | 1.367 (4) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | ||
O1—Cu1—O1i | 97.05 (11) | C1—C6—H6 | 119.6 |
O1—Cu1—N1 | 141.50 (8) | O2—C7—O1 | 121.2 (2) |
O1i—Cu1—N1 | 102.00 (8) | O2—C7—C5 | 120.5 (2) |
O1—Cu1—N1i | 102.00 (8) | O1—C7—C5 | 118.3 (2) |
O1i—Cu1—N1i | 141.50 (8) | N1—C8—C9 | 123.2 (2) |
N1—Cu1—N1i | 83.20 (12) | N1—C8—C8i | 117.22 (14) |
C7—O1—Cu1 | 106.58 (16) | C9—C8—C8i | 119.62 (17) |
C1—O3—H3 | 109.5 | C10—C9—C8 | 116.6 (3) |
C12—N1—C8 | 119.1 (2) | C10—C9—C14 | 124.2 (3) |
C12—N1—Cu1 | 129.51 (19) | C8—C9—C14 | 119.2 (3) |
C8—N1—Cu1 | 111.12 (16) | C11—C10—C9 | 120.2 (3) |
O3—C1—C2 | 117.1 (2) | C11—C10—H10 | 119.9 |
O3—C1—C6 | 123.2 (2) | C9—C10—H10 | 119.9 |
C2—C1—C6 | 119.8 (2) | C10—C11—C12 | 120.8 (3) |
C1—C2—C3 | 119.6 (3) | C10—C11—H11 | 119.6 |
C1—C2—H2 | 120.2 | C12—C11—H11 | 119.6 |
C3—C2—H2 | 120.2 | N1—C12—C11 | 120.1 (3) |
C2—C3—C4 | 120.7 (3) | N1—C12—C13 | 118.6 (3) |
C2—C3—H3A | 119.6 | C11—C12—C13 | 121.3 (3) |
C4—C3—H3A | 119.6 | C12—C13—H13A | 109.5 |
C5—C4—C3 | 120.1 (3) | C12—C13—H13B | 109.5 |
C5—C4—H4 | 120.0 | H13A—C13—H13B | 109.5 |
C3—C4—H4 | 120.0 | C12—C13—H13C | 109.5 |
C4—C5—C6 | 119.0 (2) | H13A—C13—H13C | 109.5 |
C4—C5—C7 | 121.0 (2) | H13B—C13—H13C | 109.5 |
C6—C5—C7 | 120.0 (2) | C14i—C14—C9 | 121.10 (18) |
C5—C6—C1 | 120.8 (2) | C14i—C14—H14 | 119.4 |
C5—C6—H6 | 119.6 | C9—C14—H14 | 119.4 |
O1i—Cu1—O1—C7 | −124.17 (18) | C6—C5—C7—O2 | −4.3 (4) |
N1—Cu1—O1—C7 | −4.7 (2) | C4—C5—C7—O1 | −4.7 (4) |
N1i—Cu1—O1—C7 | 89.48 (17) | C6—C5—C7—O1 | 175.2 (2) |
O1—Cu1—N1—C12 | −74.0 (2) | C12—N1—C8—C9 | −2.6 (3) |
O1i—Cu1—N1—C12 | 43.9 (2) | Cu1—N1—C8—C9 | −177.13 (18) |
N1i—Cu1—N1—C12 | −174.8 (2) | C12—N1—C8—C8i | 177.4 (2) |
O1—Cu1—N1—C8 | 99.75 (19) | Cu1—N1—C8—C8i | 2.8 (3) |
O1i—Cu1—N1—C8 | −142.29 (15) | N1—C8—C9—C10 | 1.7 (4) |
N1i—Cu1—N1—C8 | −1.00 (11) | C8i—C8—C9—C10 | −178.3 (3) |
O3—C1—C2—C3 | −179.8 (4) | N1—C8—C9—C14 | −177.8 (2) |
C6—C1—C2—C3 | 0.5 (5) | C8i—C8—C9—C14 | 2.3 (4) |
C1—C2—C3—C4 | 0.0 (6) | C8—C9—C10—C11 | 0.0 (4) |
C2—C3—C4—C5 | −1.1 (6) | C14—C9—C10—C11 | 179.4 (3) |
C3—C4—C5—C6 | 1.6 (5) | C9—C10—C11—C12 | −0.7 (4) |
C3—C4—C5—C7 | −178.5 (3) | C8—N1—C12—C11 | 1.8 (3) |
C4—C5—C6—C1 | −1.1 (4) | Cu1—N1—C12—C11 | 175.13 (17) |
C7—C5—C6—C1 | 179.0 (2) | C8—N1—C12—C13 | −177.5 (2) |
O3—C1—C6—C5 | −179.6 (3) | Cu1—N1—C12—C13 | −4.2 (3) |
C2—C1—C6—C5 | 0.0 (5) | C10—C11—C12—N1 | −0.2 (4) |
Cu1—O1—C7—O2 | 1.7 (3) | C10—C11—C12—C13 | 179.1 (3) |
Cu1—O1—C7—C5 | −177.83 (17) | C10—C9—C14—C14i | −178.2 (3) |
C4—C5—C7—O2 | 175.8 (3) | C8—C9—C14—C14i | 1.2 (5) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2ii | 0.82 | 1.90 | 2.688 (3) | 160 |
Symmetry code: (ii) −x+1/2, −y+3/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H5O3)2(C14H12N2)] |
Mr | 546.02 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 291 |
a, b, c (Å) | 17.623 (3), 14.587 (2), 9.7581 (15) |
β (°) | 94.199 (2) |
V (Å3) | 2501.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.44 × 0.33 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART CCD area detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.690, 0.809 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7268, 2275, 1766 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.01 |
No. of reflections | 2275 |
No. of parameters | 170 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.33 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Cu1—O1 | 1.9509 (18) | Cu1—N1 | 2.022 (2) |
O1—Cu1—O1i | 97.05 (11) | O1i—Cu1—N1 | 102.00 (8) |
O1—Cu1—N1 | 141.50 (8) | N1—Cu1—N1i | 83.20 (12) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2ii | 0.82 | 1.90 | 2.688 (3) | 160 |
Symmetry code: (ii) −x+1/2, −y+3/2, −z+2. |
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Metal-phenanthroline complexes and its derivatives have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Recently, we obtained the title mononuclear copper(II) complex (I), by reaction of 2,9-dimethyl-1,10-phenanthroline, m-hydroxybenzoic acid and Cu(NO3)2 in an ethanol/water mixture. Here we report its crystal structure.
Each CuII ion is four-coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, and two O atoms from two m-hydroxybenzoic anions. The CuII ion locates on a twofold rotation axis, and CuO2N2 unit forms a distorted tetrahedral geometry (Fig. 1). The Cu1–N1 bond length is slightly longer than Cu1—O1 bond length (Table 1).
In the crystal structure, molecules are linked into a two dimensional framework by intermolecular O—H···O hydrogen bonds (Fig. 2). The crystal further stabilized by π-π interactions between the dmphen ring systems (Fig. 3). These intermolecular interactions occur between the parallel rings within offset face-to-face packing. The face-to-face distance of the parallel ring planes between the neighboring molecules related by 1 - x,2 - y,1 - z is 3.385 (18) Å.