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Acta Cryst. (2007). E63, m1756-m1757    [ doi:10.1107/S1600536807023495 ]

(Benzoato-[kappa]2O,O')chlorido(di-2-pyridylamine-[kappa]2N,N')copper(II)

N. Okabe, A. Tsuji and M. Yodoshi

Abstract top

In the title complex, [Cu(C7H5O2)Cl(C10H9N3)], the Cu atom has a distorted CuN2O2Cl square-pyramidal geometry defined by one N,N'-bidentate 2,2'-bipyridylamine (bpa) molecule, one O,O'-bidentate benzenecarboxylate (BA) anion and one chloride ion, the latter in the apical position. The complete molecule is generated by mirror symmetry with the NH group of bpa, the Cu atom, three C atoms of BA and the Cl atom lying on the mirror plane. The complexes are connected to each other by N-H...Cl hydrogen bonds and [pi]-[pi] stacking interactions between adjacent heterocyclic rings, with distances between the ring centroids of 3.592 (4) and 3.468 (4) Å.

Comment top

The construction of novel Cu(II) complexes are important for the development of new therapeutic drug design, because some Cu(II) complexes of 1,10-phenanthroline have antitumor activity (Selvakumar et al., 2006; Li et al., 2005; Kelland, 2005; Ranford et al., 1993).

In a previous study, we have reported the structure of the ternary Cu(II) complex with 2,2'-bipyridylamine (bpa) and p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005) in which the bpa ligand has been used as the bidentate N-donor ligand and p-HB as the bidentate O-donor. In this study, we report the structure of the Cu(II) complex with bpa and benzenecarboxylate (BA), (I).

The central Cu atom in (I) (Fig. 1) has a square-pyramidal CuN2O2Cl geometry. Each Cu atom is coordinated by two N atoms from one bpa and two O atoms from one BA and one chloride anion. The bond distances and angles around the Cu atom indicate that the coordination geometry is a slightly distorted square pyramidal (Table 1).

In the complex molecule, the two pyridine rings of the bpa ligand are related by mirror symmetry and distinguished as Ring I (N1/C1—C5) and Ring II (N1i/C1i—C5i) [symmetry code: (i)(x, 1/2 - y, z)]. Four ligand atoms (N1, N1i,O1 and O1i) are neary coplanar, and the Cu atom deviates from the mean square plane towards the apical Cl atom by 0.2986 (1) Å. The bite angle N1—Cu1—N1i is in the range normally observed for the Cu(II) bpa complexes (Wang & Okabe, 2005; Youngme et al., 1999, 2004) The Cu—Cl distance is intermediate between the known values from 2.336 (2) to 2.733 (2) Å (Mao et al., 2004; Brophy et al., 1999). The long Cu—Cl bond distance is explained by the well known Jahn-Teller effect. The molecular structure of (I) is similar to that of the Cu(II) complex with bpa and p-HB (Wang & Okabe, 2005), although the hydrogen bonding and the packing modes of these are different to each other.

As shown in Figs. 2a and 2 b, the crystal structure of (I) is stabilized by hydrogen bonds (Table 2) and by two kinds of π-π stacking interactions with distances between the centroids of the aromatic rings, 3.592 (4) Å between Cg1 (Ring I) and Cg3 (Ring II) at (x, y, 1 + z) and 3.468 (4) Å between Cg2 (N1/C5/N2/C5i/N1i/Cu1) [symmetry code: (i) (x, 1/2 - y, z)] and Cg4 (BA) at (1 - x, 1 - y, 1 - z).

Related literature top

For related literature, see: Brophy et al. (1999); Kelland (2005); Li et al. (2005); Mao et al. (2004); Ranford et al. (1993); Selvakumar et al. (2006); Wang & Okabe (2005); Youngme et al. (2004).

For related literature, see: Youngme (1999).

Experimental top

2,2'-Bipyridylamine (5.0 mg, 0.03 mol) dissolved in 90%(v/v) methanol-water solution (2 ml) was reacted with benzoic acid (3.6 mg, 0.03 mol), dissolved in the same solution (2 ml) for 5 min at room temperature. This was followed by the addition of CuCl2.2H2O (5.0 mg, 0.03 mol) dissolved in H2O (1 ml) and reacted for 15 min at room temperature. After several days green plates of (I) appeared from the mother liquor.

Refinement top

All H atoms were located from the difference Fourier maps, and then were placed in idealized positions and treated as riding, with C—H = 0.93 Å, N—H = 0.86Å and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Betteridge et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997), and PLATON (Spek, 2003); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. View of (I) with the atomic numbering-scheme and displacement ellipsoid drawn at the 50% probability level (arbitrary spheres for the H atoms). Symmetry code: (i) x, 1/2 - y, z.
[Figure 2] Fig. 2. A view of the N—H···Cl hydrogen bonds (dashed lines) between the adjacent molecules of (I)
[Figure 3] Fig. 3. A view of the π-π stacking interaction in (I). See the text for the ring designations.
(Benzoato-κ2O,O')chlorido(di-2-pyridylamine- κ2N,N')copper(II) top
Crystal data top
[Cu(C7H5O2)Cl(C10H9N3)]F(000) = 796.0
Mr = 391.31Dx = 1.644 Mg m−3
Orthorhombic, PnmaMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ac 2nCell parameters from 13658 reflections
a = 19.31 (2) Åθ = 3.1–27.5°
b = 11.77 (1) ŵ = 1.57 mm−1
c = 6.958 (6) ÅT = 123 K
V = 1581 (3) Å3Plate, green
Z = 40.40 × 0.40 × 0.10 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1746 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.015
ω scansθmax = 27.5°
Absorption correction: multi-scan
(ABSCOR : Higashi,1995)		h = −25→25
Tmin = 0.587, Tmax = 0.840k = −15→15
15128 measured reflectionsl = −8→9
1893 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025 w = 1/[σ2(Fo2) + (0.0341P)2 + 1.7191P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.072(Δ/σ)max < 0.001
S = 1.12Δρmax = 0.34 e Å−3
1893 reflectionsΔρmin = −1.17 e Å−3
119 parameters
Crystal data top
[Cu(C7H5O2)Cl(C10H9N3)]V = 1581 (3) Å3
Mr = 391.31Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 19.31 (2) ŵ = 1.57 mm−1
b = 11.77 (1) ÅT = 123 K
c = 6.958 (6) Å0.40 × 0.40 × 0.10 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1893 independent reflections
Absorption correction: multi-scan
(ABSCOR : Higashi,1995)		1746 reflections with F2 > 2.0σ(F2)
Tmin = 0.587, Tmax = 0.840Rint = 0.015
15128 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.072Δρmax = 0.34 e Å−3
S = 1.12Δρmin = −1.17 e Å−3
1893 reflectionsAbsolute structure: ?
119 parametersFlack parameter: ?
? restraintsRogers parameter: ?
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.61824 (1)0.25000.18707 (4)0.0144 (1)
Cl10.50045 (3)0.25000.03740 (8)0.0198 (1)
O10.67196 (6)0.3426 (1)−0.0121 (2)0.0190 (3)
N10.60171 (7)0.3723 (1)0.3734 (2)0.0148 (3)
N20.5622 (1)0.25000.6194 (3)0.0166 (4)
C10.61517 (9)0.4801 (2)0.3141 (3)0.0201 (4)
C20.6049 (1)0.5735 (2)0.4273 (3)0.0238 (4)
C30.57907 (9)0.5576 (1)0.6132 (3)0.0210 (4)
C40.56524 (9)0.4495 (2)0.6754 (2)0.0183 (3)
C50.57716 (8)0.3570 (1)0.5513 (2)0.0146 (3)
C60.6903 (1)0.2500−0.0902 (3)0.0153 (4)
C70.7299 (1)0.2500−0.2737 (3)0.0144 (4)
C80.74776 (9)0.1475 (1)−0.3616 (3)0.0178 (3)
C90.78256 (9)0.1476 (1)−0.5363 (3)0.0203 (3)
C100.7993 (1)0.2500−0.6228 (4)0.0208 (5)
H10.63220.49080.19050.024*
H20.61480.64600.38160.028*
H30.57140.61950.69350.025*
H40.54810.43730.79860.022*
H50.53910.25000.72500.020*
H60.73630.0791−0.30300.021*
H70.79450.0793−0.59480.024*
H80.82210.2500−0.74050.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0185 (2)0.0141 (2)0.0105 (2)0.00000.0030 (1)0.0000
Cl10.0175 (3)0.0296 (3)0.0125 (3)0.00000.0023 (2)0.0000
O10.0228 (6)0.0191 (6)0.0150 (6)0.0009 (5)0.0050 (5)−0.0011 (5)
N10.0159 (6)0.0150 (6)0.0136 (6)−0.0010 (5)0.0010 (5)−0.0012 (5)
N20.020 (1)0.021 (1)0.0092 (9)0.00000.0052 (8)0.0000
C10.0234 (9)0.0182 (9)0.0187 (9)−0.0028 (6)0.0043 (6)0.0000 (7)
C20.0264 (9)0.0156 (8)0.0292 (9)−0.0030 (7)0.0046 (8)−0.0017 (7)
C30.0201 (8)0.0197 (8)0.0233 (9)0.0006 (7)−0.0007 (7)−0.0085 (7)
C40.0167 (7)0.0236 (9)0.0146 (8)0.0020 (6)−0.0001 (6)−0.0040 (6)
C50.0124 (7)0.0182 (8)0.0133 (7)0.0000 (6)−0.0011 (6)−0.0010 (6)
C60.014 (1)0.020 (1)0.012 (1)0.0000−0.0014 (9)0.0000
C70.0120 (9)0.018 (1)0.013 (1)0.0000−0.0004 (9)0.0000
C80.0182 (7)0.0167 (8)0.0185 (8)−0.0010 (6)0.0023 (6)0.0009 (7)
C90.0212 (8)0.0206 (8)0.0190 (8)0.0002 (6)0.0036 (7)−0.0053 (7)
C100.020 (1)0.030 (1)0.012 (1)0.00000.0054 (9)0.0000
Geometric parameters (Å, °) top
Cu1—Cl12.502 (3)C3—C41.370 (3)
Cu1—O12.046 (1)C3—H30.9300
Cu1—O1i2.046 (1)C4—C51.409 (2)
Cu1—N11.963 (1)C4—H40.9300
Cu1—N1i1.963 (1)C6—O1i1.269 (2)
C6—O11.269 (2)C6—C71.488 (3)
N1—C11.359 (2)C7—C81.396 (2)
N1—C51.338 (2)C7—C8i1.396 (2)
N2—C51.377 (2)C8—C91.389 (2)
N2—C5i1.377 (2)C8—H60.9300
N2—H50.8600C9—C101.386 (2)
C1—C21.367 (3)C9—H70.9300
C1—H10.9300C10—C9i1.386 (2)
C2—C31.399 (3)C10—H80.9300
C2—H20.9299
Cl1—Cu1—O1100.32 (4)H2—C2—C1120.7624
Cl1—Cu1—O1i100.32 (4)C4—C3—C2119.0 (2)
Cl1—Cu1—N197.30 (4)C4—C3—H3120.4892
Cl1—Cu1—N1i97.30 (4)H3—C3—C2120.4784
O1—Cu1—O1i64.43 (5)C5—C4—C3119.5 (2)
O1—Cu1—N197.97 (5)C5—C4—H4120.2397
O1—Cu1—N1i156.99 (5)H4—C4—C3120.2411
O1i—Cu1—N1156.99 (5)O1i—C6—O1118.5 (2)
O1i—Cu1—N1i97.97 (5)O1i—C6—C7120.7 (1)
N1—Cu1—N1i94.33 (6)C7—C6—O1i120.7 (1)
C6—O1—Cu188.5 (1)C8—C7—C6120.2 (1)
C1—N1—Cu1117.0 (1)C8—C7—C8i119.6 (2)
C1—N1—C5118.3 (1)C8i—C7—C6120.2 (1)
C5—N1—Cu1124.7 (1)C9—C8—C7120.2 (2)
C5—N2—C5i132.5 (2)C9—C8—H6119.9074
C5—N2—H5113.7538H6—C8—C7119.9042
C5i—N2—H5113.7538C10—C9—C8119.5 (2)
C2—C1—N1123.3 (2)C10—C9—H7120.2314
C2—C1—H1118.3538H7—C9—C8120.2290
H1—C1—N1118.3581C9i—C10—C9120.9 (2)
C3—C2—C1118.5 (2)C9i—C10—H8119.5321
C3—C2—H2120.7669H8—C10—C9119.5321
Cl1—Cu1—O1—C6−94.68 (11)C1—C2—C3—C40.1 (2)
Cl1—Cu1—N1—C1−89.35 (12)C2—C3—C4—C5−0.0 (2)
Cu1—O1—C6—C7174.32 (17)C3—C4—C5—N1−0.1 (2)
Cu1—N1—C1—C2178.8 (1)C3—C4—C5—N2−179.67 (17)
Cu1—N1—C5—N21.0 (2)O1—C6—C7—C8−177.83 (18)
Cu1—N1—C5—C4−178.6 (1)C6—C7—C8—C9177.7 (3)
H5—N2—C5—N1−168.0C7—C8—C9—C10−0.1 (2)
H5—N2—C5—C411.6C8—C9—C10—H8−179.2
N1—C1—C2—C3−0.1 (2)
Symmetry codes: (i) x, −y+1/2, z; i.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H5···Cl1ii0.862.33.144 (2)168
Symmetry codes: (ii) x, y, z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—Cl12.502 (3)Cu1—N11.963 (1)
Cu1—O12.046 (1)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H5···Cl1i0.862.33.144 (2)168
Symmetry codes: (i) x, y, z+1.
Acknowledgements top

The authors thank Kinki University for supporting this work.

references
References top

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