(2,9-Dimethyl-1,10-phenanthroline-κ²N,N′)bis­(3-hydroxy­benzoato-κO) copper(II)

In the title compound, [Cu(C₇H₅O₃)₂(C₁₄H₁₂N₂)], the Cu^II ion is located on a twofold rotation axis and is coordinated by a 2,9-dimethyl-1,10-phenanthroline (dmphen) mol­ecule and two 3-hydroxy­benzoate anions in a distorted tetra­hedral geometry. Mol­ecules are linked into a one-dimensional framework by O—H...O hydrogen bonding. The packing is further stabilized by π–π stacking between parallel dmphen rings of neighboring mol­ecules, with a face-to-face distance of 3.385 (18) Å.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](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

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S1. Comment

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 Cu^II 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 Cu^II 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.

Related literature

For related literature, see: Wang et al. (1996); Wall et al. (1999); Naing et al. (1995).

S2. Experimental

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.

S3. Refinement

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, U_iso(H) = 1.5U_eq(carrier). Other H atoms were placed in calculated positions with C—H = 0.93 Å and refined in the riding model approximation with U_iso(H) = 1.2U_eq(C).

Computing details

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).

Figures

	Fig. 1. The molecular structure of the title complex(I),with atom labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry code for the symbol 'A': -x + 1, y, -z + 3/2
	Fig. 2. The hydrogen-bonding motifs in the crystal structure of (I). Dashed lines indicate the hydrogen.
	Fig. 3. The π-π interaction between the dmphen rings of neighboring molecules in the crystal structure of (I). Symmetry code: -x + 1, y, -z + 3/2

(2,9-Dimethyl-1,10-phenanthroline-κ²N,N')bis(3-hydroxybenzoato-κO) copper(II)

Crystal data

[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) Å^3	0.44 × 0.33 × 0.24 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0535P)^2 + 1.4781P] where P = (Fo^2 + 2Fc^2)/3
2275 reflections	(Δ/σ)max = 0.001
170 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—O1	1.9509 (18)	C5—C6	1.381 (3)
Cu1—O1^i	1.9509 (18)	C5—C7	1.500 (3)
Cu1—N1	2.022 (2)	C6—H6	0.9300
Cu1—N1^i	2.022 (2)	C8—C9	1.403 (4)
O1—C7	1.272 (3)	C8—C8^i	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—C14^i	1.346 (7)
C4—C5	1.367 (4)	C14—H14	0.9300
C4—H4	0.9300
O1—Cu1—O1^i	97.05 (11)	C1—C6—H6	119.6
O1—Cu1—N1	141.50 (8)	O2—C7—O1	121.2 (2)
O1^i—Cu1—N1	102.00 (8)	O2—C7—C5	120.5 (2)
O1—Cu1—N1^i	102.00 (8)	O1—C7—C5	118.3 (2)
O1^i—Cu1—N1^i	141.50 (8)	N1—C8—C9	123.2 (2)
N1—Cu1—N1^i	83.20 (12)	N1—C8—C8^i	117.22 (14)
C7—O1—Cu1	106.58 (16)	C9—C8—C8^i	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)	C14^i—C14—C9	121.10 (18)
C5—C6—C1	120.8 (2)	C14^i—C14—H14	119.4
C5—C6—H6	119.6	C9—C14—H14	119.4
O1^i—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)
N1^i—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)
O1^i—Cu1—N1—C12	43.9 (2)	Cu1—N1—C8—C9	−177.13 (18)
N1^i—Cu1—N1—C12	−174.8 (2)	C12—N1—C8—C8^i	177.4 (2)
O1—Cu1—N1—C8	99.75 (19)	Cu1—N1—C8—C8^i	2.8 (3)
O1^i—Cu1—N1—C8	−142.29 (15)	N1—C8—C9—C10	1.7 (4)
N1^i—Cu1—N1—C8	−1.00 (11)	C8^i—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)	C8^i—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—C14^i	−178.2 (3)
C4—C5—C7—O2	175.8 (3)	C8—C9—C14—C14^i	1.2 (5)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^ii	0.82	1.90	2.688 (3)	160

Symmetry code: (ii) −x+1/2, −y+3/2, −z+2.