Bis(3,4-dimethoxy­benzoato-κ2O,O′)(1,10-phenanthroline-κ2N,N′)copper(II)

Liu, Y.; Sun, J.; Niu, X.

doi:10.1107/S1600536809052234

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m34

doi:10.1107/S1600536809052234

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Bis(3,4-dimethoxybenzoato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)copper(II)

Yaru Liu,^a ^* Junshan Sun ^b and Xiaoli Niu ^c

^aSchool of Science, North University of China, 030051 Taiyuan, Shanxi, People's Republic of China, ^bDepartment of Materials and Chemical Engineering, Taishan University, 271021 Tai'an, Shandong, People's Republic of China, and ^cCollege of Foreign Languages, Shandong Agricultural University, 271000 Tai'an, Shandong, People's Republic of China
^*Correspondence e-mail: klsz79@163.com

(Received 24 November 2009; accepted 4 December 2009; online 9 December 2009)

The asymmetric unit of the title compound, [Cu(C₉H₉O₄)₂(C₁₂H₈N₂)], contains one half-molecule, the complete molecule being generated by a twofold rotation axis. The Cu^II atom exhibits a six-coordinated distorted octahedral geometry with two N atoms from the phenanthroline ligand [Cu—N 2.007 (2) Å] and four O atoms from two 3,4-dimethoxybenzoate ligands [Cu—O 1.950 (1) and 2.524 (1) Å]. The difference in Cu—O bond distances indicates a strong Jahn–Teller effect. In the crystal, C—H⋯π interactions result in chains of molecules along the c axis.

Related literature

For metal–1,10-phenanthroline complexes with unusual features, see: Ma et al. (2004 ); Bi et al. (2004 ).

Experimental

Crystal data

[Cu(C₉H₉O₄)₂(C₁₂H₈N₂)]
M_r = 606.07
Monoclinic, C 2/c
a = 12.1639 (10) Å
b = 11.4296 (9) Å
c = 19.7470 (16) Å
β = 104.027 (1)°
V = 2663.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 273 K
0.23 × 0.21 × 0.19 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.824, T_max = 0.851
6857 measured reflections
2351 independent reflections
2136 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.086
S = 1.01
2351 reflections
187 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg1	0.96	2.98	3.642 (3)	127
C1 is the centroid of the C22,C23,C29,C22′,C23′,C29′ ring.

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052234/ez2194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052234/ez2194Isup2.hkl

checkCIF report

Comment top

Metal complexes with carboxylate ligands are among the most investigated complexes in the field of coordination chemistry. In addition, metal–1,10-phenanthroline complexes and their derivatives have attracted much attention during recent decades because of their unusual features (Ma et al., 2004; Bi et al., 2004). In this work, the title compound was obtained from the reaction of 3,4-dimethoxybenzoic acid and cupric acetate in the presence of 1,10-phenanthroline.

The molecular structure of the title complex is shown in Fig. 1. The Cu(II) atom exhibits a six-coordinated distorted octahedral geometry with two N atoms [Cu—N 2.007 (2) Å] from the phenanthroline ligand and four O atoms from the two 3,4-dimethoxybenzoate ligands [Cu—O 1.950 (1), 2.524 (1) Å]. The difference in Cu—O bond distances [Cu—O 1.950 (1), 2.524 (1) Å] indicates a strong Jahn-Teller effect. Two O atoms and two N atoms occupy the equatorial planar position with a slight deviation from the ideal plane of 0.0263 (2)Å, while two O atoms lie in the apical positions with an axis angle of 127.6 (2)° showing a large deviation from the normal 180°. A C8—H8b···π interaction results in chains of molecules along the c-axis [H8b···CG1 2.979 (3) Å, where CG1 is the centroid of the C22, C23, C29, C22ⁱ, C23ⁱ, C29ⁱ ring; symmetry operator, i: -x, y, 0.5 - z].

Related literature top

For metal–1,10-phenanthroline complexes with unusual features, see: Ma et al. (2004); Bi et al. (2004).

Experimental top

The reaction was carried out by the solvothermal method. 3,4-dimythoxybenzoic acid (0.121 g, 2 mmol), cupric acetate (0.199 g, 1 mmol) and 1,10-phenanthroline (0.180 g, 1 mmol) were added to the airtight vessel with a 1:2 ratio of ethanol to water. The resulting blue solution was filtered. The filtrate was left for several days at room temperature to yield blue, block-shaped crystals.

The yield was 78% and elemental analysis: calc. for C₃₀H₂₆CuN₂O₈: C 59.45, H 4.32, N 4.62; found: C 59.31, H 4.49, N 4.53. The elemental analyses were performed with a PERKIN ELMER MODEL 2400 SERIES II.

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms. (Symmetry code: -x, y, 0.5 - z)

Bis(3,4-dimethoxybenzoato-κ²O,O')(1,10-phenanthroline- κ²N,N')copper(II) top

Crystal data top

[Cu(C₉H₉O₄)₂(C₁₂H₈N₂)]	F(000) = 1252
M_r = 606.07	D_x = 1.511 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1639 (10) Å	Cell parameters from 4483 reflections
b = 11.4296 (9) Å	θ = 2.5–28.3°
c = 19.7470 (16) Å	µ = 0.88 mm⁻¹
β = 104.027 (1)°	T = 273 K
V = 2663.5 (4) Å³	Block, blue
Z = 4	0.23 × 0.21 × 0.19 mm

Data collection top

Bruker SMART APEX diffractometer	2351 independent reflections
Radiation source: fine-focus sealed tube	2136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
T_min = 0.824, T_max = 0.851	k = −10→13
6857 measured reflections	l = −23→22

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.045P)² + 1.2527P] where P = (F_o² + 2F_c²)/3
2351 reflections	(Δ/σ)_max = 0.001
187 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cu(C₉H₉O₄)₂(C₁₂H₈N₂)]	V = 2663.5 (4) Å³
M_r = 606.07	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.1639 (10) Å	µ = 0.88 mm⁻¹
b = 11.4296 (9) Å	T = 273 K
c = 19.7470 (16) Å	0.23 × 0.21 × 0.19 mm
β = 104.027 (1)°

Data collection top

Bruker SMART APEX diffractometer	2351 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2136 reflections with I > 2σ(I)
T_min = 0.824, T_max = 0.851	R_int = 0.059
6857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.01	Δρ_max = 0.30 e Å⁻³
2351 reflections	Δρ_min = −0.38 e Å⁻³
187 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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.96118 (3)	0.2500	0.03588 (14)
O1	0.00052 (11)	0.87873 (12)	0.36863 (7)	0.0437 (3)
O2	0.10961 (12)	0.84452 (12)	0.29637 (7)	0.0445 (3)
O5	0.11674 (13)	0.56453 (14)	0.55593 (8)	0.0539 (4)
O6	0.27611 (14)	0.44980 (13)	0.52542 (9)	0.0592 (4)
N1	−0.10829 (13)	1.09400 (15)	0.21869 (8)	0.0389 (4)
C1	0.07772 (15)	0.82281 (16)	0.35206 (9)	0.0364 (4)
C2	0.13570 (15)	0.72454 (16)	0.39696 (9)	0.0341 (4)
C3	0.09898 (15)	0.69411 (16)	0.45613 (10)	0.0365 (4)
H3	0.0407	0.7364	0.4676	0.044*
C4	0.14771 (16)	0.60242 (17)	0.49769 (10)	0.0385 (4)
C5	0.23698 (17)	0.53957 (16)	0.48098 (11)	0.0406 (5)
C6	0.27502 (16)	0.57054 (18)	0.42332 (11)	0.0418 (5)
H6	0.3349	0.5300	0.4126	0.050*
C7	0.22402 (16)	0.66243 (17)	0.38092 (10)	0.0389 (4)
H7	0.2493	0.6823	0.3416	0.047*
C8	0.0266 (2)	0.6253 (2)	0.57448 (12)	0.0583 (6)
H8A	0.0494	0.7045	0.5868	0.087*
H8B	0.0079	0.5872	0.6135	0.087*
H8C	−0.0385	0.6255	0.5356	0.087*
C9	0.3730 (2)	0.3888 (3)	0.51835 (16)	0.0801 (9)
H9A	0.3578	0.3514	0.4735	0.120*
H9B	0.3926	0.3307	0.5544	0.120*
H9C	0.4349	0.4426	0.5223	0.120*
C19	−0.21817 (17)	1.0896 (2)	0.18725 (11)	0.0482 (5)
H19	−0.2525	1.0172	0.1756	0.058*
C20	−0.28296 (19)	1.1910 (2)	0.17132 (12)	0.0588 (6)
H20	−0.3597	1.1854	0.1497	0.071*
C21	−0.23515 (19)	1.2974 (2)	0.18712 (11)	0.0547 (6)
H21	−0.2793	1.3646	0.1774	0.066*
C22	−0.11811 (18)	1.30632 (18)	0.21845 (10)	0.0454 (5)
C23	−0.05979 (16)	1.20062 (17)	0.23347 (9)	0.0375 (4)
C29	−0.0562 (2)	1.41293 (19)	0.23526 (11)	0.0541 (6)
H29	−0.0942	1.4839	0.2257	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0365 (2)	0.0395 (2)	0.0311 (2)	0.000	0.00731 (14)	0.000
O1	0.0448 (7)	0.0459 (8)	0.0407 (7)	0.0081 (6)	0.0110 (6)	0.0047 (6)
O2	0.0497 (8)	0.0496 (8)	0.0357 (7)	0.0074 (6)	0.0134 (6)	0.0075 (6)
O5	0.0605 (9)	0.0624 (9)	0.0452 (8)	0.0236 (7)	0.0253 (7)	0.0197 (7)
O6	0.0618 (10)	0.0582 (10)	0.0624 (10)	0.0301 (8)	0.0244 (8)	0.0214 (8)
N1	0.0365 (8)	0.0467 (9)	0.0323 (8)	0.0016 (7)	0.0060 (7)	−0.0015 (7)
C1	0.0377 (9)	0.0363 (10)	0.0330 (9)	−0.0037 (8)	0.0044 (8)	−0.0019 (8)
C2	0.0369 (9)	0.0339 (9)	0.0304 (9)	−0.0024 (8)	0.0062 (7)	−0.0038 (8)
C3	0.0359 (9)	0.0377 (10)	0.0362 (10)	0.0059 (8)	0.0093 (8)	−0.0022 (8)
C4	0.0400 (10)	0.0423 (11)	0.0345 (10)	0.0049 (8)	0.0115 (8)	0.0023 (8)
C5	0.0415 (10)	0.0381 (11)	0.0410 (11)	0.0074 (8)	0.0077 (9)	0.0009 (8)
C6	0.0391 (10)	0.0430 (10)	0.0449 (11)	0.0061 (8)	0.0133 (9)	−0.0075 (9)
C7	0.0426 (10)	0.0421 (10)	0.0336 (9)	−0.0013 (8)	0.0125 (8)	−0.0040 (8)
C8	0.0647 (14)	0.0700 (15)	0.0497 (12)	0.0195 (12)	0.0321 (11)	0.0105 (11)
C9	0.0833 (19)	0.0836 (19)	0.0792 (18)	0.0514 (16)	0.0313 (15)	0.0234 (15)
C19	0.0376 (10)	0.0640 (13)	0.0404 (11)	0.0020 (10)	0.0042 (9)	−0.0029 (10)
C20	0.0405 (11)	0.0834 (18)	0.0493 (13)	0.0151 (12)	0.0046 (10)	0.0050 (12)
C21	0.0580 (13)	0.0639 (15)	0.0431 (12)	0.0226 (12)	0.0139 (10)	0.0087 (11)
C22	0.0599 (12)	0.0508 (12)	0.0290 (9)	0.0124 (10)	0.0173 (9)	0.0053 (9)
C23	0.0435 (10)	0.0451 (11)	0.0255 (9)	0.0019 (8)	0.0116 (8)	0.0001 (8)
C29	0.0834 (15)	0.0426 (11)	0.0415 (12)	0.0092 (11)	0.0251 (11)	0.0036 (10)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.950 (1)	C6—C7	1.392 (3)
Cu1—O2	1.950 (1)	C6—H6	0.9300
Cu1—N1ⁱ	2.007 (2)	C7—H7	0.9300
Cu1—N1	2.007 (2)	C8—H8A	0.9600
Cu1—O1	2.524 (1)	C8—H8B	0.9600
O1—C1	1.244 (2)	C8—H8C	0.9600
O2—C1	1.276 (2)	C9—H9A	0.9600
O5—C4	1.365 (2)	C9—H9B	0.9600
O5—C8	1.419 (2)	C9—H9C	0.9600
O6—C5	1.359 (2)	C19—C20	1.394 (3)
O6—C9	1.406 (3)	C19—H19	0.9300
N1—C19	1.331 (2)	C20—C21	1.351 (3)
N1—C23	1.355 (2)	C20—H20	0.9300
C1—C2	1.497 (3)	C21—C22	1.412 (3)
C2—C7	1.387 (3)	C21—H21	0.9300
C2—C3	1.392 (3)	C22—C23	1.396 (3)
C3—C4	1.374 (3)	C22—C29	1.429 (3)
C3—H3	0.9300	C23—C23ⁱ	1.443 (4)
C4—C5	1.406 (3)	C29—C29ⁱ	1.350 (5)
C5—C6	1.375 (3)	C29—H29	0.9300

O2ⁱ—Cu1—O2	93.72 (9)	C7—C6—H6	119.9
O2ⁱ—Cu1—N1ⁱ	170.07 (6)	C2—C7—C6	120.39 (18)
O2—Cu1—N1ⁱ	92.84 (6)	C2—C7—H7	119.8
O2ⁱ—Cu1—N1	92.84 (6)	C6—C7—H7	119.8
O2—Cu1—N1	170.07 (6)	O5—C8—H8A	109.5
N1ⁱ—Cu1—N1	81.69 (9)	O5—C8—H8B	109.5
O2ⁱ—Cu1—O1	91.61 (5)	H8A—C8—H8B	109.5
O2—Cu1—O1	57.40 (5)	O5—C8—H8C	109.5
N1ⁱ—Cu1—O1	98.20 (5)	H8A—C8—H8C	109.5
N1—Cu1—O1	114.98 (5)	H8B—C8—H8C	109.5
C1—O1—Cu1	77.28 (11)	O6—C9—H9A	109.5
C1—O2—Cu1	102.80 (12)	O6—C9—H9B	109.5
C4—O5—C8	116.78 (15)	H9A—C9—H9B	109.5
C5—O6—C9	118.78 (19)	O6—C9—H9C	109.5
C19—N1—C23	118.06 (18)	H9A—C9—H9C	109.5
C19—N1—Cu1	128.66 (15)	H9B—C9—H9C	109.5
C23—N1—Cu1	113.28 (12)	N1—C19—C20	121.5 (2)
O1—C1—O2	122.24 (17)	N1—C19—H19	119.3
O1—C1—C2	120.47 (17)	C20—C19—H19	119.3
O2—C1—C2	117.28 (16)	C21—C20—C19	120.5 (2)
C7—C2—C3	119.18 (17)	C21—C20—H20	119.7
C7—C2—C1	121.90 (17)	C19—C20—H20	119.7
C3—C2—C1	118.91 (16)	C20—C21—C22	119.9 (2)
C4—C3—C2	120.81 (17)	C20—C21—H21	120.1
C4—C3—H3	119.6	C22—C21—H21	120.1
C2—C3—H3	119.6	C23—C22—C21	115.9 (2)
O5—C4—C3	125.33 (17)	C23—C22—C29	118.47 (19)
O5—C4—C5	114.98 (16)	C21—C22—C29	125.62 (19)
C3—C4—C5	119.69 (18)	N1—C23—C22	124.09 (17)
O6—C5—C6	126.41 (18)	N1—C23—C23ⁱ	115.86 (10)
O6—C5—C4	113.81 (18)	C22—C23—C23ⁱ	120.05 (12)
C6—C5—C4	119.77 (18)	C29ⁱ—C29—C22	121.46 (12)
C5—C6—C7	120.13 (18)	C29ⁱ—C29—H29	119.3
C5—C6—H6	119.9	C22—C29—H29	119.3

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

C1 is the centroid of the C22,C23,C29,C22',C23',C29' ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1	0.96	2.98	3.642 (3)	127

Experimental details

Crystal data
Chemical formula	[Cu(C₉H₉O₄)₂(C₁₂H₈N₂)]
M_r	606.07
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	12.1639 (10), 11.4296 (9), 19.7470 (16)
β (°)	104.027 (1)
V (Å³)	2663.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.23 × 0.21 × 0.19

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.824, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	6857, 2351, 2136
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.086, 1.01
No. of reflections	2351
No. of parameters	187
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.38

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

C1 is the centroid of the C22,C23,C29,C22',C23',C29' ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1	0.96	2.979	3.642 (3)	127.44

Acknowledgements

The authors thank the Postgraduate Foundation of Taishan University for financial support (grant No.Y07-2-15).

References

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