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Acta Cryst. (2008). E64, m1526-m1527    [ doi:10.1107/S1600536808036283 ]

(2,9-Dimethyl-1,10-phenanthroline-[kappa]2N,N')bis(2-hydroxybenzoato-[kappa]O)copper(II)

C. Zhai, F. Yan and P. Zhao

Abstract top

The CuII atoms in the two independent molecules of the title compound, [Cu(C7H5O3)2(C14H12N2)], are each coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) molecule and two monodentate 2-hydroxybenzoate anions in a distorted tetrahedral geometry. The crystal packing is stabilized by intramolecular hydrogen bonding and [pi]-[pi] interactions between the dmphen rings of neighboring molecules, with distances between their ring planes of 3.5670 (4) and 3.5181 (9) Å.

Comment top

Metal-phenanthroline complexes have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Some Cu(II)-phenanthroline complexes have been synthesized and structures were determined (Cheng et al., 2007; Xuan et al., 2007; Zhao et al., 2007). Recently, we obtained the title compound copper(II) complex (I), by reaction of 2,9-dimethyl-1,10-phenanthroline, 2-hydroxybenzoic acid and Cu(NO3)2 in an ethanol/water mixture. The structure of the title compound, Cu(C14H12N2)(C6H4OHCOO)2,(I), is shown below.

There are two independent molecules in the asymmetric unit. 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 2-hydroxybenzoic anions. The CuII ion locates in the center, and CuO2N2 unit forms a distorted tetrahedral geometry (Fig.1). The Cu—N and Cu—O bond lengths in two independent molecules different slightly (Table 1). The hydroxy directions of 2-hydroxybenzoic anions in the two independent molecules are also different.

An intramolecular hydrogen bond between the hydroxy group and uncoordinated carboxyl O atom stabilizes the conformation of the hydroxybenzoate ligands (Table 2). A partially overlapped arrangement of neighboring parallel Cu1A-dmphen [symmetry code: (Cu1A) x, y - 1, z] and Cu1B-dmphen rings [symmetry code: (Cu1B) -x + 1, -y + 1, -z + 1], Cu2A-dmphen [symmetry code: (Cu2A) -x + 2, y - 1/2, -z + 3/2] and Cu2C-dmphen rings [symmetry code: (Cu2C) x, -y - 1/2, z + 3/2] are observed in the structure of (I) (Fig.2). The shorter face-to-face separation of 3.5670 (4)Å and 3.5181 (9)Å indicates the existence of π—π stacking between the dmphen ligands.

Related literature top

For the features of metal–phenanthroline complexes, see: Naing et al. (1995); Wang et al., (1996); Wall et al. (1999). For related structures, see: Cheng et al. (2007); Xuan et al. (2007); Zhao et al. (2007).

Experimental top

2-hydroxybenzoic acid (0.1389 g, 1 mmol) and NaOH (0.0370 g, 1 mmol) were dissolved in distilled water(10 ml) and Cu(NO3)2.3H2O (0.1222 g, 0.5 mmol) were added. This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C14H12N2.0.5H2O, 0.1090 g, 0.5 mmol) in ethanol (10 ml). The mixture was stirred at 323 K and then refluxed for 5 h, cooled to room temperature and filtered. Green single crystals of (I) were appeared over a period of eighteen days by slow evaporation at room temperature.

Refinement top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex(I), with atom labels and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. π—π interactions of neighboring molecules and intramolecular hydrogen bonds in the crystal structure of (I).[symmetry code: (Cu1A) x, y - 1, z; (Cu1B) -x + 1, -y + 1, -z + 1; (Cu1D) -x + 1, -y + 2, -z + 1; (Cu2A) -x + 2, y - 1/2, -z + 3/2; (Cu2B) -x + 2, y + 1/2, -z + 3/2; (Cu2C) x, -y - 1/2, z + 3/2; (Cu2D) x, -y + 1/2, z + 3/2]
(2,9-Dimethyl-1,10-phenanthroline- κ2N,N')bis(2-hydroxybenzoato-κO)copper(II) top
Crystal data top
[Cu(C7H5O3)2(C14H12N2)]F(000) = 2248
Mr = 546.02Dx = 1.496 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3270 reflections
a = 23.819 (2) Åθ = 2.4–19.2°
b = 12.2576 (11) ŵ = 0.95 mm−1
c = 17.9084 (17) ÅT = 291 K
β = 112.023 (1)°Block, green
V = 4847.0 (8) Å30.30 × 0.21 × 0.19 mm
Z = 8
Data collection top
Bruker APEXII CCD area-detector
diffractometer		8932 independent reflections
Radiation source: fine-focus sealed tube5274 reflections with I > 2σ(I)
graphiteRint = 0.060
φ and ω scansθmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −28→27
Tmin = 0.765, Tmax = 0.837k = −14→14
30637 measured reflectionsl = −21→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.051P)2 + 0.2481P]
where P = (Fo2 + 2Fc2)/3
8932 reflections(Δ/σ)max = 0.001
675 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.45 e Å−3
Crystal data top
[Cu(C7H5O3)2(C14H12N2)]V = 4847.0 (8) Å3
Mr = 546.02Z = 8
Monoclinic, P21/cMo Kα radiation
a = 23.819 (2) ŵ = 0.95 mm−1
b = 12.2576 (11) ÅT = 291 K
c = 17.9084 (17) Å0.30 × 0.21 × 0.19 mm
β = 112.023 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		8932 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		5274 reflections with I > 2σ(I)
Tmin = 0.765, Tmax = 0.837Rint = 0.060
30637 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.122Δρmax = 0.38 e Å−3
S = 1.01Δρmin = −0.45 e Å−3
8932 reflectionsAbsolute structure: ?
675 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cu10.416752 (19)0.76816 (4)0.34347 (3)0.04372 (14)
Cu20.91833 (2)0.24372 (4)0.06488 (3)0.04679 (15)
O10.42604 (14)0.5478 (3)0.36158 (18)0.0828 (10)
O20.37117 (12)0.6601 (2)0.26599 (15)0.0537 (7)
O30.4003 (2)0.3447 (3)0.3513 (2)0.1039 (13)
H30.41770.40140.37140.156*
O40.42450 (12)0.8580 (2)0.25824 (15)0.0525 (7)
O50.33691 (13)0.9202 (2)0.25654 (16)0.0636 (8)
O60.26673 (13)1.0250 (3)0.13213 (18)0.0715 (8)
H60.27740.99780.17720.107*
O70.92602 (13)0.4499 (2)0.07908 (17)0.0690 (8)
O80.85069 (12)0.3372 (2)0.06067 (17)0.0611 (7)
O90.90651 (19)0.6548 (3)0.0833 (3)0.1015 (12)
H90.92640.59950.08530.152*
O100.92554 (11)0.1888 (2)0.16999 (15)0.0540 (7)
O110.84406 (12)0.0976 (2)0.09313 (15)0.0568 (7)
O120.79075 (13)−0.0325 (2)0.15603 (18)0.0675 (8)
H120.7973−0.00090.11980.101*
N10.38290 (13)0.7629 (2)0.43145 (16)0.0390 (7)
N20.49111 (13)0.8211 (2)0.43227 (17)0.0404 (7)
N30.90189 (14)0.1985 (2)−0.05127 (18)0.0461 (8)
N41.00369 (13)0.2094 (2)0.08003 (19)0.0456 (8)
C10.35133 (17)0.4709 (3)0.2453 (2)0.0479 (10)
C20.3600 (2)0.3653 (4)0.2763 (3)0.0668 (12)
C30.3263 (3)0.2798 (4)0.2294 (4)0.0814 (16)
H3A0.33050.20980.25090.098*
C40.2874 (2)0.2979 (4)0.1529 (4)0.0787 (15)
H40.26600.23970.12200.094*
C50.27904 (19)0.4010 (4)0.1202 (3)0.0681 (12)
H50.25240.41250.06750.082*
C60.31061 (17)0.4865 (3)0.1665 (2)0.0543 (10)
H6A0.30470.55640.14480.065*
C70.38553 (18)0.5648 (4)0.2941 (2)0.0521 (10)
C80.36927 (17)0.9750 (3)0.1521 (2)0.0444 (9)
C90.3138 (2)1.0240 (3)0.1071 (2)0.0552 (11)
C100.3058 (2)1.0737 (4)0.0339 (3)0.0713 (13)
H100.26881.10550.00370.086*
C110.3519 (3)1.0761 (4)0.0061 (3)0.0842 (16)
H110.34591.1088−0.04310.101*
C120.4071 (2)1.0306 (4)0.0503 (3)0.0806 (14)
H12A0.43861.03370.03170.097*
C130.4154 (2)0.9797 (3)0.1232 (2)0.0606 (11)
H130.45270.94830.15290.073*
C140.37703 (19)0.9146 (3)0.2272 (2)0.0474 (10)
C150.32818 (16)0.7343 (3)0.4286 (2)0.0445 (9)
C160.31365 (18)0.7396 (3)0.4971 (2)0.0535 (10)
H160.27530.71830.49380.064*
C170.35443 (19)0.7751 (3)0.5680 (3)0.0545 (11)
H170.34460.77700.61360.065*
C180.41203 (17)0.8093 (3)0.5725 (2)0.0452 (9)
C190.45829 (19)0.8514 (3)0.6437 (2)0.0568 (11)
H190.45100.85550.69120.068*
C200.5121 (2)0.8852 (3)0.6438 (2)0.0603 (11)
H200.54080.91400.69050.072*
C210.52535 (16)0.8772 (3)0.5721 (2)0.0467 (10)
C220.58051 (18)0.9085 (3)0.5682 (2)0.0587 (11)
H220.61040.94030.61250.070*
C230.59019 (17)0.8921 (3)0.4987 (2)0.0579 (11)
H230.62720.91180.49620.069*
C240.54513 (16)0.8458 (3)0.4307 (2)0.0479 (10)
C250.48185 (16)0.8339 (3)0.5027 (2)0.0389 (8)
C260.42421 (16)0.8003 (3)0.5022 (2)0.0374 (8)
C270.28159 (17)0.6985 (4)0.3492 (2)0.0632 (12)
H27A0.28880.73480.30610.095*
H27B0.24190.71690.34730.095*
H27C0.28430.62100.34350.095*
C280.55725 (18)0.8220 (4)0.3559 (2)0.0657 (12)
H28A0.53620.75670.33110.099*
H28B0.60000.81220.36980.099*
H28C0.54330.88190.31900.099*
C290.83703 (17)0.5201 (3)0.0916 (2)0.0480 (10)
C300.8550 (2)0.6281 (4)0.0941 (2)0.0621 (12)
C310.8204 (3)0.7101 (4)0.1074 (3)0.0879 (18)
H310.83140.78250.10550.105*
C320.7707 (3)0.6867 (5)0.1229 (3)0.097 (2)
H320.74840.74300.13300.117*
C330.7525 (2)0.5796 (5)0.1242 (3)0.0843 (16)
H330.71860.56390.13640.101*
C340.78519 (19)0.4953 (4)0.1070 (2)0.0644 (12)
H340.77250.42330.10570.077*
C350.87370 (19)0.4315 (3)0.0756 (2)0.0495 (10)
C360.87985 (16)0.0701 (3)0.2347 (2)0.0441 (9)
C370.83292 (18)−0.0038 (3)0.2274 (3)0.0509 (10)
C380.8293 (2)−0.0506 (4)0.2951 (3)0.0703 (13)
H380.7979−0.09840.29060.084*
C390.8722 (2)−0.0267 (4)0.3695 (3)0.0769 (14)
H390.8692−0.05880.41500.092*
C400.9200 (2)0.0443 (4)0.3788 (3)0.0710 (13)
H400.94920.05870.42940.085*
C410.92263 (18)0.0929 (3)0.3104 (2)0.0570 (11)
H410.95370.14170.31530.068*
C420.88268 (18)0.1215 (3)0.1610 (2)0.0460 (9)
C430.84987 (19)0.1941 (3)−0.1155 (2)0.0556 (11)
C440.8485 (2)0.1465 (4)−0.1871 (3)0.0698 (13)
H440.81200.1430−0.23110.084*
C450.8992 (2)0.1054 (4)−0.1936 (3)0.0722 (13)
H450.89730.0744−0.24190.087*
C460.9546 (2)0.1095 (3)−0.1280 (2)0.0569 (11)
C471.0111 (3)0.0680 (3)−0.1272 (3)0.0724 (14)
H471.01250.0359−0.17350.087*
C481.0621 (2)0.0744 (3)−0.0611 (3)0.0724 (14)
H481.09800.0468−0.06270.087*
C491.0621 (2)0.1227 (3)0.0115 (3)0.0582 (11)
C501.1135 (2)0.1331 (3)0.0828 (3)0.0708 (13)
H501.15060.10600.08520.085*
C511.1092 (2)0.1825 (4)0.1482 (3)0.0721 (13)
H511.14350.19020.19500.087*
C521.05307 (18)0.2222 (3)0.1457 (3)0.0544 (11)
C531.00751 (17)0.1630 (3)0.0127 (2)0.0458 (9)
C540.95339 (18)0.1572 (3)−0.0572 (2)0.0472 (10)
C550.7945 (2)0.2406 (4)−0.1093 (3)0.0784 (14)
H55A0.78850.2097−0.06360.118*
H55B0.76020.2239−0.15740.118*
H55C0.79870.3183−0.10300.118*
C561.04876 (19)0.2811 (4)0.2161 (2)0.0688 (13)
H56A1.01790.33610.19760.103*
H56B1.08700.31480.24630.103*
H56C1.03860.23030.24990.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0443 (3)0.0543 (3)0.0349 (3)−0.0088 (2)0.0174 (2)−0.0012 (2)
Cu20.0473 (3)0.0509 (3)0.0462 (3)0.0020 (2)0.0221 (2)−0.0010 (2)
O10.079 (2)0.090 (2)0.061 (2)0.0205 (18)0.0053 (18)−0.0111 (17)
O20.0684 (18)0.0526 (17)0.0416 (15)−0.0112 (14)0.0223 (14)−0.0057 (13)
O30.164 (4)0.076 (2)0.073 (2)0.045 (3)0.046 (2)0.0203 (19)
O40.0520 (17)0.0604 (17)0.0450 (15)−0.0038 (14)0.0180 (13)0.0105 (13)
O50.071 (2)0.0692 (19)0.0609 (18)0.0028 (15)0.0367 (16)0.0050 (15)
O60.071 (2)0.067 (2)0.074 (2)0.0095 (16)0.0252 (18)0.0059 (17)
O70.0567 (19)0.073 (2)0.085 (2)−0.0001 (16)0.0352 (17)−0.0041 (17)
O80.0611 (18)0.0504 (17)0.073 (2)0.0047 (14)0.0261 (15)−0.0054 (15)
O90.119 (3)0.066 (2)0.121 (3)−0.025 (2)0.048 (3)−0.003 (2)
O100.0480 (16)0.0677 (18)0.0506 (17)−0.0042 (14)0.0235 (13)0.0045 (14)
O110.0665 (18)0.0551 (17)0.0483 (17)0.0008 (14)0.0211 (15)−0.0071 (13)
O120.066 (2)0.0548 (19)0.079 (2)−0.0062 (15)0.0244 (18)−0.0037 (16)
N10.0407 (17)0.0423 (17)0.0376 (17)−0.0067 (14)0.0189 (14)−0.0010 (14)
N20.0404 (18)0.0444 (18)0.0396 (18)−0.0016 (14)0.0184 (14)0.0023 (14)
N30.055 (2)0.0425 (18)0.0437 (19)−0.0013 (15)0.0212 (17)0.0019 (14)
N40.0475 (19)0.0410 (18)0.050 (2)−0.0027 (14)0.0208 (17)0.0015 (15)
C10.053 (2)0.047 (2)0.055 (3)−0.0010 (19)0.033 (2)−0.006 (2)
C20.091 (4)0.058 (3)0.068 (3)0.009 (3)0.049 (3)0.003 (3)
C30.114 (5)0.047 (3)0.118 (5)−0.001 (3)0.084 (4)0.001 (3)
C40.079 (4)0.067 (3)0.108 (4)−0.017 (3)0.056 (3)−0.032 (3)
C50.058 (3)0.066 (3)0.079 (3)−0.005 (2)0.024 (2)−0.020 (3)
C60.058 (3)0.048 (2)0.060 (3)0.000 (2)0.026 (2)−0.008 (2)
C70.052 (3)0.068 (3)0.045 (3)0.008 (2)0.027 (2)−0.004 (2)
C80.050 (2)0.043 (2)0.037 (2)−0.0044 (18)0.0135 (19)−0.0027 (17)
C90.070 (3)0.046 (2)0.049 (3)−0.001 (2)0.021 (2)−0.007 (2)
C100.082 (3)0.072 (3)0.047 (3)0.014 (3)0.009 (3)0.006 (2)
C110.121 (5)0.082 (4)0.048 (3)0.018 (3)0.032 (3)0.024 (3)
C120.100 (4)0.087 (4)0.067 (3)0.004 (3)0.046 (3)0.017 (3)
C130.069 (3)0.063 (3)0.051 (3)0.000 (2)0.024 (2)0.011 (2)
C140.056 (3)0.043 (2)0.041 (2)−0.012 (2)0.016 (2)−0.0079 (18)
C150.044 (2)0.045 (2)0.048 (2)−0.0004 (18)0.0222 (19)0.0019 (18)
C160.048 (2)0.060 (3)0.063 (3)−0.003 (2)0.033 (2)0.003 (2)
C170.067 (3)0.057 (3)0.056 (3)0.005 (2)0.042 (2)0.010 (2)
C180.056 (3)0.044 (2)0.043 (2)−0.0002 (18)0.026 (2)−0.0003 (18)
C190.073 (3)0.063 (3)0.039 (2)−0.002 (2)0.026 (2)−0.001 (2)
C200.068 (3)0.069 (3)0.040 (2)−0.012 (2)0.015 (2)−0.007 (2)
C210.044 (2)0.052 (2)0.039 (2)−0.0060 (18)0.0098 (18)0.0031 (18)
C220.047 (3)0.068 (3)0.049 (3)−0.010 (2)0.005 (2)−0.001 (2)
C230.035 (2)0.079 (3)0.057 (3)−0.009 (2)0.014 (2)0.011 (2)
C240.041 (2)0.058 (3)0.048 (2)0.0000 (19)0.020 (2)0.0086 (19)
C250.043 (2)0.040 (2)0.035 (2)−0.0033 (16)0.0169 (18)0.0015 (16)
C260.044 (2)0.0333 (19)0.037 (2)0.0037 (16)0.0184 (18)0.0030 (16)
C270.042 (2)0.085 (3)0.062 (3)−0.013 (2)0.020 (2)−0.006 (2)
C280.050 (3)0.097 (3)0.060 (3)−0.005 (2)0.032 (2)0.004 (2)
C290.052 (3)0.044 (2)0.038 (2)0.0078 (19)0.0053 (19)−0.0018 (18)
C300.070 (3)0.054 (3)0.051 (3)0.003 (2)0.010 (2)−0.004 (2)
C310.105 (4)0.053 (3)0.076 (4)0.026 (3)0.000 (3)−0.013 (3)
C320.092 (4)0.092 (5)0.082 (4)0.051 (4)0.003 (3)−0.019 (3)
C330.055 (3)0.117 (5)0.073 (3)0.030 (3)0.014 (3)−0.005 (3)
C340.054 (3)0.076 (3)0.060 (3)0.013 (2)0.018 (2)0.000 (2)
C350.054 (3)0.053 (3)0.039 (2)0.006 (2)0.015 (2)0.0022 (19)
C360.046 (2)0.043 (2)0.049 (2)0.0101 (18)0.024 (2)0.0017 (18)
C370.055 (3)0.045 (2)0.063 (3)0.011 (2)0.034 (2)0.005 (2)
C380.079 (3)0.061 (3)0.088 (4)0.005 (2)0.052 (3)0.010 (3)
C390.107 (4)0.071 (3)0.078 (4)0.017 (3)0.064 (3)0.016 (3)
C400.086 (4)0.078 (3)0.051 (3)0.016 (3)0.027 (3)0.006 (2)
C410.064 (3)0.057 (3)0.054 (3)0.007 (2)0.027 (2)0.000 (2)
C420.049 (2)0.039 (2)0.057 (3)0.0128 (19)0.028 (2)−0.0004 (19)
C430.063 (3)0.056 (3)0.043 (2)0.000 (2)0.015 (2)0.003 (2)
C440.087 (4)0.070 (3)0.044 (3)0.000 (3)0.016 (3)−0.005 (2)
C450.115 (4)0.064 (3)0.042 (3)0.000 (3)0.033 (3)−0.006 (2)
C460.090 (3)0.042 (2)0.053 (3)−0.001 (2)0.043 (3)−0.001 (2)
C470.109 (4)0.050 (3)0.088 (4)0.004 (3)0.071 (3)−0.001 (3)
C480.080 (4)0.051 (3)0.116 (4)0.002 (2)0.071 (3)−0.002 (3)
C490.067 (3)0.037 (2)0.087 (3)0.001 (2)0.049 (3)0.001 (2)
C500.051 (3)0.055 (3)0.114 (4)0.005 (2)0.040 (3)0.008 (3)
C510.053 (3)0.060 (3)0.092 (4)−0.004 (2)0.014 (3)0.002 (3)
C520.047 (3)0.051 (2)0.063 (3)−0.006 (2)0.017 (2)0.004 (2)
C530.056 (3)0.032 (2)0.060 (3)−0.0012 (18)0.035 (2)0.0052 (18)
C540.062 (3)0.039 (2)0.049 (2)−0.0037 (19)0.030 (2)0.0029 (18)
C550.056 (3)0.101 (4)0.064 (3)0.003 (3)0.006 (2)−0.010 (3)
C560.060 (3)0.080 (3)0.060 (3)−0.017 (2)0.015 (2)−0.011 (2)
Geometric parameters (Å, °) top
Cu1—O21.931 (2)C20—C211.436 (5)
Cu1—O41.946 (2)C20—H200.9300
Cu1—N21.994 (3)C21—C251.390 (5)
Cu1—N12.022 (3)C21—C221.396 (5)
Cu2—O101.945 (2)C22—C231.363 (5)
Cu2—O81.956 (3)C22—H220.9300
Cu2—N41.992 (3)C23—C241.405 (5)
Cu2—N32.044 (3)C23—H230.9300
O1—C71.249 (4)C24—C281.501 (5)
O2—C71.267 (4)C25—C261.431 (5)
O3—C21.350 (5)C27—H27A0.9600
O3—H30.8200C27—H27B0.9600
O4—C141.264 (4)C27—H27C0.9600
O5—C141.254 (4)C28—H28A0.9600
O6—C91.355 (5)C28—H28B0.9600
O6—H60.8200C28—H28C0.9600
O7—C351.245 (4)C29—C301.387 (6)
O8—C351.264 (4)C29—C341.395 (5)
O9—C301.351 (5)C29—C351.487 (5)
O9—H90.8200C30—C311.377 (6)
O10—C421.275 (4)C31—C321.344 (7)
O11—C421.254 (4)C31—H310.9300
O12—C371.343 (4)C32—C331.386 (8)
O12—H120.8200C32—H320.9300
N1—C151.332 (4)C33—C341.396 (6)
N1—C261.360 (4)C33—H330.9300
N2—C241.332 (4)C34—H340.9300
N2—C251.369 (4)C36—C411.384 (5)
N3—C431.339 (5)C36—C371.407 (5)
N3—C541.367 (4)C36—C421.487 (5)
N4—C521.324 (5)C37—C381.372 (5)
N4—C531.367 (4)C38—C391.372 (6)
C1—C21.392 (5)C38—H380.9300
C1—C61.394 (5)C39—C401.393 (6)
C1—C71.490 (5)C39—H390.9300
C2—C31.394 (6)C40—C411.384 (5)
C3—C41.354 (6)C40—H400.9300
C3—H3A0.9300C41—H410.9300
C4—C51.375 (6)C43—C441.397 (5)
C4—H40.9300C43—C551.479 (6)
C5—C61.373 (5)C44—C451.355 (6)
C5—H50.9300C44—H440.9300
C6—H6A0.9300C45—C461.400 (6)
C8—C131.381 (5)C45—H450.9300
C8—C91.399 (5)C46—C541.407 (5)
C8—C141.484 (5)C46—C471.434 (6)
C9—C101.392 (6)C47—C481.343 (6)
C10—C111.364 (6)C47—H470.9300
C10—H100.9300C48—C491.429 (6)
C11—C121.373 (6)C48—H480.9300
C11—H110.9300C49—C531.399 (5)
C12—C131.391 (5)C49—C501.404 (6)
C12—H12A0.9300C50—C511.356 (6)
C13—H130.9300C50—H500.9300
C15—C161.396 (5)C51—C521.407 (6)
C15—C271.504 (5)C51—H510.9300
C16—C171.350 (5)C52—C561.490 (6)
C16—H160.9300C53—C541.423 (5)
C17—C181.408 (5)C55—H55A0.9600
C17—H170.9300C55—H55B0.9600
C18—C261.399 (5)C55—H55C0.9600
C18—C191.433 (5)C56—H56A0.9600
C19—C201.346 (5)C56—H56B0.9600
C19—H190.9300C56—H56C0.9600
O2—Cu1—O491.00 (11)C21—C25—C26120.5 (3)
O2—Cu1—N2152.67 (12)N1—C26—C18123.0 (3)
O4—Cu1—N297.15 (11)N1—C26—C25117.4 (3)
O2—Cu1—N1104.90 (11)C18—C26—C25119.6 (3)
O4—Cu1—N1144.27 (11)C15—C27—H27A109.5
N2—Cu1—N183.30 (11)C15—C27—H27B109.5
O10—Cu2—O890.72 (11)H27A—C27—H27B109.5
O10—Cu2—N494.59 (12)C15—C27—H27C109.5
O8—Cu2—N4155.88 (12)H27A—C27—H27C109.5
O10—Cu2—N3143.61 (12)H27B—C27—H27C109.5
O8—Cu2—N3106.20 (12)C24—C28—H28A109.5
N4—Cu2—N382.98 (13)C24—C28—H28B109.5
C7—O2—Cu1110.6 (2)H28A—C28—H28B109.5
C2—O3—H3109.5C24—C28—H28C109.5
C14—O4—Cu1108.9 (2)H28A—C28—H28C109.5
C9—O6—H6109.5H28B—C28—H28C109.5
C35—O8—Cu2104.0 (3)C30—C29—C34119.2 (4)
C30—O9—H9109.5C30—C29—C35120.4 (4)
C42—O10—Cu2109.0 (2)C34—C29—C35120.4 (4)
C37—O12—H12109.5O9—C30—C31118.9 (5)
C15—N1—C26118.7 (3)O9—C30—C29120.9 (4)
C15—N1—Cu1130.4 (2)C31—C30—C29120.3 (5)
C26—N1—Cu1110.8 (2)C32—C31—C30120.8 (5)
C24—N2—C25118.9 (3)C32—C31—H31119.6
C24—N2—Cu1129.3 (3)C30—C31—H31119.6
C25—N2—Cu1111.8 (2)C31—C32—C33120.7 (5)
C43—N3—C54119.1 (3)C31—C32—H32119.6
C43—N3—Cu2130.4 (3)C33—C32—H32119.6
C54—N3—Cu2110.1 (2)C32—C33—C34119.5 (5)
C52—N4—C53120.1 (3)C32—C33—H33120.2
C52—N4—Cu2128.1 (3)C34—C33—H33120.2
C53—N4—Cu2111.7 (2)C29—C34—C33119.4 (5)
C2—C1—C6118.3 (4)C29—C34—H34120.3
C2—C1—C7121.2 (4)C33—C34—H34120.3
C6—C1—C7120.5 (4)O7—C35—O8121.5 (4)
O3—C2—C1121.0 (4)O7—C35—C29120.5 (4)
O3—C2—C3119.5 (5)O8—C35—C29118.0 (4)
C1—C2—C3119.5 (5)C41—C36—C37119.2 (4)
C4—C3—C2120.5 (5)C41—C36—C42121.5 (4)
C4—C3—H3A119.8C37—C36—C42119.3 (4)
C2—C3—H3A119.8O12—C37—C38117.3 (4)
C3—C4—C5121.1 (5)O12—C37—C36122.8 (4)
C3—C4—H4119.5C38—C37—C36119.9 (4)
C5—C4—H4119.5C39—C38—C37119.9 (5)
C6—C5—C4119.1 (5)C39—C38—H38120.1
C6—C5—H5120.5C37—C38—H38120.1
C4—C5—H5120.5C38—C39—C40121.7 (4)
C5—C6—C1121.5 (4)C38—C39—H39119.1
C5—C6—H6A119.3C40—C39—H39119.1
C1—C6—H6A119.3C41—C40—C39118.0 (4)
O1—C7—O2122.3 (4)C41—C40—H40121.0
O1—C7—C1119.5 (4)C39—C40—H40121.0
O2—C7—C1118.2 (4)C40—C41—C36121.2 (4)
C13—C8—C9118.6 (4)C40—C41—H41119.4
C13—C8—C14120.9 (4)C36—C41—H41119.4
C9—C8—C14120.4 (4)O11—C42—O10122.4 (4)
O6—C9—C10118.0 (4)O11—C42—C36120.1 (4)
O6—C9—C8122.2 (4)O10—C42—C36117.6 (4)
C10—C9—C8119.8 (4)N3—C43—C44120.1 (4)
C11—C10—C9120.5 (4)N3—C43—C55119.0 (4)
C11—C10—H10119.7C44—C43—C55120.9 (4)
C9—C10—H10119.7C45—C44—C43121.3 (4)
C10—C11—C12120.5 (4)C45—C44—H44119.3
C10—C11—H11119.7C43—C44—H44119.3
C12—C11—H11119.7C44—C45—C46120.3 (4)
C11—C12—C13119.6 (5)C44—C45—H45119.9
C11—C12—H12A120.2C46—C45—H45119.9
C13—C12—H12A120.2C45—C46—C54116.2 (4)
C8—C13—C12121.0 (4)C45—C46—C47125.5 (4)
C8—C13—H13119.5C54—C46—C47118.3 (4)
C12—C13—H13119.5C48—C47—C46121.6 (4)
O5—C14—O4122.8 (4)C48—C47—H47119.2
O5—C14—C8119.8 (4)C46—C47—H47119.2
O4—C14—C8117.4 (4)C47—C48—C49121.2 (4)
N1—C15—C16121.0 (3)C47—C48—H48119.4
N1—C15—C27118.5 (3)C49—C48—H48119.4
C16—C15—C27120.4 (3)C53—C49—C50116.9 (4)
C17—C16—C15121.0 (4)C53—C49—C48118.4 (4)
C17—C16—H16119.5C50—C49—C48124.7 (4)
C15—C16—H16119.5C51—C50—C49120.2 (4)
C16—C17—C18119.5 (4)C51—C50—H50119.9
C16—C17—H17120.3C49—C50—H50119.9
C18—C17—H17120.3C50—C51—C52120.3 (4)
C26—C18—C17116.9 (3)C50—C51—H51119.8
C26—C18—C19118.7 (4)C52—C51—H51119.8
C17—C18—C19124.5 (4)N4—C52—C51120.3 (4)
C20—C19—C18121.7 (4)N4—C52—C56119.3 (4)
C20—C19—H19119.2C51—C52—C56120.4 (4)
C18—C19—H19119.2N4—C53—C49122.0 (4)
C19—C20—C21120.5 (4)N4—C53—C54117.3 (3)
C19—C20—H20119.8C49—C53—C54120.7 (4)
C21—C20—H20119.8N3—C54—C46123.1 (4)
C25—C21—C22117.4 (4)N3—C54—C53117.2 (3)
C25—C21—C20119.0 (3)C46—C54—C53119.7 (4)
C22—C21—C20123.6 (4)C43—C55—H55A109.5
C23—C22—C21119.3 (4)C43—C55—H55B109.5
C23—C22—H22120.3H55A—C55—H55B109.5
C21—C22—H22120.3C43—C55—H55C109.5
C22—C23—C24121.0 (4)H55A—C55—H55C109.5
C22—C23—H23119.5H55B—C55—H55C109.5
C24—C23—H23119.5C52—C56—H56A109.5
N2—C24—C23120.2 (4)C52—C56—H56B109.5
N2—C24—C28119.0 (3)H56A—C56—H56B109.5
C23—C24—C28120.7 (3)C52—C56—H56C109.5
N2—C25—C21123.0 (3)H56A—C56—H56C109.5
N2—C25—C26116.6 (3)H56B—C56—H56C109.5
O4—Cu1—O2—C7141.8 (3)C24—N2—C25—C26−176.5 (3)
N2—Cu1—O2—C734.1 (4)Cu1—N2—C25—C264.6 (4)
N1—Cu1—O2—C7−70.5 (3)C22—C21—C25—N20.2 (5)
O2—Cu1—O4—C1483.0 (2)C20—C21—C25—N2−178.6 (3)
N2—Cu1—O4—C14−123.1 (2)C22—C21—C25—C26−179.8 (3)
N1—Cu1—O4—C14−34.7 (3)C20—C21—C25—C261.4 (5)
O10—Cu2—O8—C35104.0 (2)C15—N1—C26—C180.5 (5)
N4—Cu2—O8—C351.0 (4)Cu1—N1—C26—C18177.7 (3)
N3—Cu2—O8—C35−108.7 (2)C15—N1—C26—C25−177.9 (3)
O8—Cu2—O10—C4275.4 (2)Cu1—N1—C26—C25−0.7 (4)
N4—Cu2—O10—C42−128.2 (2)C17—C18—C26—N11.5 (5)
N3—Cu2—O10—C42−43.8 (3)C19—C18—C26—N1−178.9 (3)
O2—Cu1—N1—C15−27.3 (3)C17—C18—C26—C25179.8 (3)
O4—Cu1—N1—C1586.4 (3)C19—C18—C26—C25−0.6 (5)
N2—Cu1—N1—C15179.3 (3)N2—C25—C26—N1−2.7 (5)
O2—Cu1—N1—C26155.9 (2)C21—C25—C26—N1177.4 (3)
O4—Cu1—N1—C26−90.4 (3)N2—C25—C26—C18178.9 (3)
N2—Cu1—N1—C262.5 (2)C21—C25—C26—C18−1.1 (5)
O2—Cu1—N2—C2467.7 (4)C34—C29—C30—O9176.9 (4)
O4—Cu1—N2—C24−38.6 (3)C35—C29—C30—O9−1.1 (6)
N1—Cu1—N2—C24177.4 (3)C34—C29—C30—C31−3.3 (6)
O2—Cu1—N2—C25−113.6 (3)C35—C29—C30—C31178.7 (4)
O4—Cu1—N2—C25140.1 (2)O9—C30—C31—C32−176.1 (5)
N1—Cu1—N2—C25−3.9 (2)C29—C30—C31—C324.0 (7)
O10—Cu2—N3—C4391.7 (4)C30—C31—C32—C33−1.5 (8)
O8—Cu2—N3—C43−22.9 (4)C31—C32—C33—C34−1.6 (8)
N4—Cu2—N3—C43179.9 (3)C30—C29—C34—C330.2 (6)
O10—Cu2—N3—C54−81.1 (3)C35—C29—C34—C33178.1 (4)
O8—Cu2—N3—C54164.3 (2)C32—C33—C34—C292.3 (7)
N4—Cu2—N3—C547.1 (2)Cu2—O8—C35—O78.9 (4)
O10—Cu2—N4—C52−40.7 (3)Cu2—O8—C35—C29−169.2 (3)
O8—Cu2—N4—C5261.4 (5)C30—C29—C35—O713.4 (6)
N3—Cu2—N4—C52175.8 (3)C34—C29—C35—O7−164.5 (4)
O10—Cu2—N4—C53136.2 (2)C30—C29—C35—O8−168.4 (4)
O8—Cu2—N4—C53−121.6 (3)C34—C29—C35—O813.7 (5)
N3—Cu2—N4—C53−7.3 (2)C41—C36—C37—O12−178.0 (3)
C6—C1—C2—O3177.9 (4)C42—C36—C37—O121.6 (5)
C7—C1—C2—O3−0.8 (6)C41—C36—C37—C381.4 (5)
C6—C1—C2—C3−2.7 (6)C42—C36—C37—C38−179.0 (3)
C7—C1—C2—C3178.7 (4)O12—C37—C38—C39178.1 (4)
O3—C2—C3—C4−177.4 (5)C36—C37—C38—C39−1.3 (6)
C1—C2—C3—C43.2 (7)C37—C38—C39—C40−0.1 (7)
C2—C3—C4—C5−1.7 (7)C38—C39—C40—C411.4 (7)
C3—C4—C5—C6−0.3 (7)C39—C40—C41—C36−1.3 (6)
C4—C5—C6—C10.7 (6)C37—C36—C41—C40−0.1 (6)
C2—C1—C6—C50.7 (6)C42—C36—C41—C40−179.6 (4)
C7—C1—C6—C5179.4 (4)Cu2—O10—C42—O110.7 (4)
Cu1—O2—C7—O1−3.1 (5)Cu2—O10—C42—C36−179.8 (2)
Cu1—O2—C7—C1175.1 (3)C41—C36—C42—O11178.5 (3)
C2—C1—C7—O15.6 (6)C37—C36—C42—O11−1.1 (5)
C6—C1—C7—O1−173.1 (4)C41—C36—C42—O10−1.0 (5)
C2—C1—C7—O2−172.7 (4)C37—C36—C42—O10179.4 (3)
C6—C1—C7—O28.7 (5)C54—N3—C43—C440.8 (6)
C13—C8—C9—O6−178.6 (4)Cu2—N3—C43—C44−171.4 (3)
C14—C8—C9—O64.4 (5)C54—N3—C43—C55−178.9 (4)
C13—C8—C9—C101.6 (6)Cu2—N3—C43—C558.8 (6)
C14—C8—C9—C10−175.5 (3)N3—C43—C44—C45−0.8 (7)
O6—C9—C10—C11179.4 (4)C55—C43—C44—C45178.9 (4)
C8—C9—C10—C11−0.8 (6)C43—C44—C45—C460.3 (7)
C9—C10—C11—C12−0.7 (8)C44—C45—C46—C540.3 (6)
C10—C11—C12—C131.4 (8)C44—C45—C46—C47179.4 (4)
C9—C8—C13—C12−1.0 (6)C45—C46—C47—C48−179.4 (4)
C14—C8—C13—C12176.1 (4)C54—C46—C47—C48−0.3 (6)
C11—C12—C13—C8−0.5 (7)C46—C47—C48—C490.2 (7)
Cu1—O4—C14—O59.1 (4)C47—C48—C49—C530.4 (6)
Cu1—O4—C14—C8−170.0 (2)C47—C48—C49—C50−179.6 (4)
C13—C8—C14—O5173.0 (4)C53—C49—C50—C51−1.4 (6)
C9—C8—C14—O5−9.9 (5)C48—C49—C50—C51178.5 (4)
C13—C8—C14—O4−7.8 (5)C49—C50—C51—C521.0 (7)
C9—C8—C14—O4169.2 (3)C53—N4—C52—C51−3.6 (6)
C26—N1—C15—C16−1.6 (5)Cu2—N4—C52—C51173.1 (3)
Cu1—N1—C15—C16−178.2 (3)C53—N4—C52—C56175.1 (3)
C26—N1—C15—C27176.9 (3)Cu2—N4—C52—C56−8.2 (5)
Cu1—N1—C15—C270.3 (5)C50—C51—C52—N41.6 (6)
N1—C15—C16—C170.7 (6)C50—C51—C52—C56−177.2 (4)
C27—C15—C16—C17−177.7 (4)C52—N4—C53—C493.2 (5)
C15—C16—C17—C181.3 (6)Cu2—N4—C53—C49−174.0 (3)
C16—C17—C18—C26−2.3 (5)C52—N4—C53—C54−176.5 (3)
C16—C17—C18—C19178.1 (4)Cu2—N4—C53—C546.2 (4)
C26—C18—C19—C202.0 (6)C50—C49—C53—N4−0.6 (5)
C17—C18—C19—C20−178.4 (4)C48—C49—C53—N4179.4 (3)
C18—C19—C20—C21−1.7 (6)C50—C49—C53—C54179.1 (3)
C19—C20—C21—C250.0 (6)C48—C49—C53—C54−0.9 (5)
C19—C20—C21—C22−178.7 (4)C43—N3—C54—C46−0.2 (5)
C25—C21—C22—C23−2.4 (6)Cu2—N3—C54—C46173.5 (3)
C20—C21—C22—C23176.3 (4)C43—N3—C54—C53−179.6 (3)
C21—C22—C23—C241.1 (6)Cu2—N3—C54—C53−5.9 (4)
C25—N2—C24—C23−4.8 (5)C45—C46—C54—N3−0.4 (5)
Cu1—N2—C24—C23173.8 (3)C47—C46—C54—N3−179.5 (3)
C25—N2—C24—C28174.4 (3)C45—C46—C54—C53179.0 (4)
Cu1—N2—C24—C28−7.0 (5)C47—C46—C54—C53−0.2 (5)
C22—C23—C24—N22.6 (6)N4—C53—C54—N3−0.1 (5)
C22—C23—C24—C28−176.5 (4)C49—C53—C54—N3−179.9 (3)
C24—N2—C25—C213.4 (5)N4—C53—C54—C46−179.5 (3)
Cu1—N2—C25—C21−175.4 (3)C49—C53—C54—C460.7 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O110.821.822.549 (4)147
O9—H9···O70.821.842.561 (4)146
O6—H6···O50.821.852.572 (4)146
O3—H3···O10.821.822.553 (5)148
Table 1
Selected geometric parameters (Å, °) top
Cu1—O21.931 (2)Cu2—O101.945 (2)
Cu1—O41.946 (2)Cu2—O81.956 (3)
Cu1—N21.994 (3)Cu2—N41.992 (3)
Cu1—N12.022 (3)Cu2—N32.044 (3)
O2—Cu1—O491.00 (11)O10—Cu2—O890.72 (11)
O2—Cu1—N2152.67 (12)O10—Cu2—N494.59 (12)
O4—Cu1—N297.15 (11)O8—Cu2—N4155.88 (12)
O2—Cu1—N1104.90 (11)O10—Cu2—N3143.61 (12)
O4—Cu1—N1144.27 (11)O8—Cu2—N3106.20 (12)
N2—Cu1—N183.30 (11)N4—Cu2—N382.98 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O110.821.822.549 (4)147
O9—H9···O70.821.842.561 (4)146
O6—H6···O50.821.852.572 (4)146
O3—H3···O10.821.822.553 (5)148
Acknowledgements top

Financial support from the Science Fund of Henan Province for Distinguished Young Scholars (No. 074100510005) is gratefully acknowledged.

references
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