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Acta Cryst. (2007). E63, m2518-m2519    [ doi:10.1107/S1600536807043905 ]

catena-Poly[[[(2,2'-bipyridylamine-[kappa]2N,N')copper(II)]-[mu]2-L-aspartate-[kappa]3O,N:O'] monohydrate]

N. Okabe, M. Mototsuji and M. Yodoshi

Abstract top

In the title complex, {[Cu(C4H5O4N)(C10H9N3)]·H2O}n, the Cu atom has a distorted CuO2N3 square-pyramidal geometry formed by an N,O-bidentate aspartate (asp) anion and an N,N-bidentate 2,2'-bipyridylamine (bpa) molecule in the basal positions, and an O-monodentate asp ligand in the apical site. The complex forms a polymeric chain in which each metal centre is bridged to the next one by the asp anion. The crystal structure is stabilized by O-H...O and N-H...O hydrogen bonds and [pi]-[pi] stacking interactions involving the bpa ligands [centroid-centroid separation = 3.699 (4) Å].

Comment top

Recently, significant attention has focused on Cu(II) complexes in the studies of their antitumor and/or antiviral activity (Wang & Okabe, 2005; Kelland, 2005).

As part of our ongoing studies (Yodoshi et al., 2007) of mixed-ligand copper complexes, we now report the synthesis and structure of the title compound, (I), containing both aspartate (asp) anions and 2,2'-bipyridylamine (bpa) molecules (Fig. 1).

The Cu atom in (I) has a distorted square-pyramidal geometry formed by one O atom of the α-carboxylate group, one N atom of the α-amino group of an aspartate anion and two N atoms of a bidentate bpa in the basal plane and one O atom from the β-carboxylate of an aspartate in the axial position. Each complex is bridged through the O atom in the axial position, and forms polymeric chains.

Cu1 deviates by 0.289 (1) Å from the mean plane through atoms N1, N2, N4 and O1. A six-membered chelate ring Cu1/N1/C5/N3/C6/N2 and a five- membered one Cu1/O1/C11/C12/N4 are formed between the Cu1 atom and the bpa and asp ligands, respectively, where the dihedral angle between two planes, Cu1/N1/N2 and Cu1/O1/N4 is 23.1 (2)°. The two pyridine rings in the bpa ligand are also non-planar with the dihedral angle of 23.15 (8)°.

The metal coordination in (I) resembles that in monomeric Cu(asp)(bpy)H2O (Antolini et al., 1983), and the polymeric linear chain structure of (I) resembles that in [Cu(glu)(bpy)]n (Antolini et al., 1985).

The bond distances (Table 1) in the square plane in (I) are similar to those in Cu(asp)(bpy)H2O and [Cu(glu)(bpy)]n. The Cu1—O3 bond lenght is a little longer than those in the square plane because of the well known Jahn-Teller effect. The axial distance is similar to that in the polymeric complex, {Cu(glu)(bpy)]n, but a little shorter than that in Cu(asp)(bpy)H2O.

The crystal structure of (I) is stabilized by O—H···O hydrogen bonds the water molecules and the carboxylate group of asp, and N—H···O hydrogen bonds between the imino group of bpa and the carboxylate group (Table 2). Aromatic π-π stacking interactions between bpa ligands of adjacent chains also stabilizes the crystal packing (Fig. 2). The distance between the centroids of the pyridine rings Cg1 (N1/C1—C5) and Cg2 (N2/C6—C10) (symmetry code: −1/2 + x, 1/2 − y, 1 − z) is 3.699 (4) Å (Spek, 2003).

Related literature top

For related structures, see: Antolini et al. (1983, 1985). For background, see: Kelland (2005); Wang & Okabe (2005); Yodoshi et al. (2007).

Experimental top

Bpa (50.0 mg) was mixed with CuCl2·2H2O (49.8 mg), in 5 ml of 80% (v/v) methanol-water solution for 5 min at room temperature (molar ratio 1:1). The aquamarine-colored precipitate was dried under a vacuum and assumed to be [Cu(bpa)Cl2]. Then, the precipitate (5.0 mg) was reacted with aspartic acid (2.0 mg) in 2.4 ml dimethylsulfoxide for 60 min at 343 K. The reaction mixture was left to stand at room temperature, and after two months, blue needles of (I) appeared from the mother liquor.

Refinement top

The water H atoms were located in a difference map and refined as riding in their as-found relative positions with Uiso(H) = 1.5Ueq(O).

The other H atoms were located in a difference map, relocated in idealized locations (C—H = 0.93–0.97 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N)

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Betteridge et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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 (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) expanded to show the polymeric connectivity with displacement ellipsoids shown at the 50% probability level (arbitrary spheres for the H atoms). The uncoordinated water molecule is omitted for clarity. Symmetry codes: (i) 1 + x, y, z; (ii) −1 + x, y, z.
[Figure 2] Fig. 2. A view of the hydrogen bonding (blue dashed lines) and π-π stacking (purple dashed lines) interactions in (I). See the text for the designations of Cg1 and Cg2 [at (−1/2 + x, 1/2 − y, 1 − z)]. Symmetry codes: (i) x + 1/2, −y + 1/2, −z + 1; (ii) −x, y + 1/2, −z + 3/2.
catena-Poly[[[(2,2'-bipyridylamine-κ2N,N')copper(II)]- µ2-L-aspartate-κ3O,N:O'] monohydrate] top
Crystal data top
[Cu(C4H5O4N)(C10H9N3)]·H2OF000 = 788.00
Mr = 383.86Dx = 1.692 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.7107 Å
Hall symbol: P 2ac 2abCell parameters from 11236 reflections
a = 7.018 (5) Åθ = 3.1–27.5º
b = 10.364 (8) ŵ = 1.48 mm−1
c = 20.72 (2) ÅT = 123.1 K
V = 1507 (2) Å3Needle, blue
Z = 40.40 × 0.04 × 0.04 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2022 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.061
ω scansθmax = 27.5º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −9→8
Tmin = 0.931, Tmax = 0.942k = −13→13
13783 measured reflectionsl = −26→26
3469 independent reflections
Refinement top
Refinement on F2  w = 1/[σ2(Fo2) + (0.0362P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.040(Δ/σ)max < 0.001
wR(F2) = 0.079Δρmax = 0.85 e Å−3
S = 0.94Δρmin = −0.90 e Å−3
3469 reflectionsExtinction correction: none
224 parametersAbsolute structure: Flack (1983), 1416 Friedel pairs
H-atom parameters constrainedFlack parameter: 0.02 (2)
Crystal data top
[Cu(C4H5O4N)(C10H9N3)]·H2OV = 1507 (2) Å3
Mr = 383.86Z = 4
Orthorhombic, P212121Mo Kα
a = 7.018 (5) ŵ = 1.48 mm−1
b = 10.364 (8) ÅT = 123.1 K
c = 20.72 (2) Å0.40 × 0.04 × 0.04 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3469 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2022 reflections with F2 > 2.0σ(F2)
Tmin = 0.931, Tmax = 0.942Rint = 0.061
13783 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.85 e Å−3
S = 0.94Δρmin = −0.90 e Å−3
3469 reflectionsAbsolute structure: Flack (1983), 1416 Friedel pairs
224 parametersFlack parameter: 0.02 (2)
? restraints
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
Cu10.36399 (6)0.09559 (4)0.61800 (2)0.0172 (1)
O10.2334 (3)−0.0709 (2)0.6236 (1)0.0242 (6)
O20.0185 (4)−0.1830 (3)0.6789 (1)0.0292 (7)
O3−0.4093 (3)0.0429 (2)0.6832 (1)0.0209 (6)
O4−0.1666 (4)0.1431 (3)0.6343 (1)0.0297 (7)
O50.3663 (4)0.2681 (2)0.8106 (1)0.0279 (6)
N10.4276 (4)0.2784 (3)0.5966 (1)0.0168 (7)
N20.4572 (4)0.0421 (3)0.5318 (1)0.0178 (7)
N30.3895 (4)0.2443 (3)0.4851 (1)0.0197 (7)
N40.1925 (4)0.1424 (3)0.6924 (1)0.0177 (7)
C10.4647 (5)0.3616 (4)0.6454 (2)0.0209 (9)
C20.4876 (5)0.4911 (4)0.6369 (2)0.025 (1)
C30.4779 (5)0.5399 (4)0.5744 (2)0.0248 (9)
C40.4460 (5)0.4572 (4)0.5240 (2)0.0250 (9)
C50.4214 (5)0.3259 (3)0.5365 (2)0.0162 (8)
C60.4331 (5)0.1137 (4)0.4789 (2)0.0193 (8)
C70.4491 (5)0.0626 (4)0.4165 (2)0.0230 (9)
C80.4944 (5)−0.0649 (4)0.4100 (2)0.0271 (9)
C90.5273 (5)−0.1404 (4)0.4643 (2)0.0250 (9)
C100.5064 (5)−0.0835 (4)0.5240 (2)0.0235 (8)
C110.1157 (5)−0.0845 (3)0.6693 (2)0.0213 (8)
C120.0989 (5)0.0253 (3)0.7183 (2)0.0174 (8)
C13−0.1098 (5)0.0490 (3)0.7371 (2)0.0178 (8)
C14−0.2371 (5)0.0801 (4)0.6797 (2)0.0189 (8)
H10.47500.32860.68700.025*
H20.50910.54540.67190.030*
H30.49300.62780.56700.030*
H40.44070.48820.48190.030*
H50.42940.11430.38040.028*
H60.5034−0.10130.36910.033*
H70.5622−0.22660.46050.030*
H80.5271−0.13350.56050.028*
H90.33510.27890.45220.024*
H100.26150.18040.72370.021*
H110.10340.19880.67900.021*
H120.1678−0.00070.75740.021*
H13−0.1588−0.02720.75860.021*
H14−0.11530.12000.76750.021*
H150.40610.34240.81390.042*
H160.24800.27630.81310.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0183 (2)0.0164 (2)0.0169 (2)−0.0009 (2)0.0007 (2)0.0000 (2)
O10.024 (1)0.021 (1)0.028 (2)−0.005 (1)0.010 (1)−0.002 (1)
O20.029 (2)0.017 (1)0.042 (2)−0.002 (1)0.009 (1)0.001 (1)
O30.017 (1)0.024 (1)0.022 (1)−0.002 (1)−0.001 (1)0.004 (1)
O40.023 (1)0.046 (2)0.021 (2)−0.006 (1)0.000 (1)0.018 (1)
O50.027 (1)0.019 (1)0.038 (2)0.002 (2)−0.002 (2)−0.005 (1)
N10.015 (1)0.018 (2)0.018 (2)−0.002 (1)−0.001 (1)−0.001 (1)
N20.021 (2)0.018 (2)0.014 (2)−0.003 (1)0.000 (1)0.002 (1)
N30.023 (2)0.020 (2)0.015 (2)0.001 (2)−0.005 (1)0.004 (1)
N40.015 (1)0.017 (2)0.021 (2)−0.002 (1)−0.001 (1)−0.003 (1)
C10.017 (2)0.025 (2)0.020 (2)−0.002 (2)0.001 (2)−0.002 (2)
C20.019 (2)0.022 (2)0.033 (3)−0.006 (2)0.002 (2)−0.010 (2)
C30.027 (2)0.017 (2)0.030 (2)−0.001 (2)0.002 (2)0.003 (2)
C40.020 (2)0.024 (2)0.031 (2)0.003 (2)0.005 (2)0.004 (2)
C50.014 (2)0.018 (2)0.017 (2)0.004 (2)0.000 (2)0.000 (2)
C60.014 (2)0.023 (2)0.020 (2)−0.004 (2)0.001 (1)−0.002 (2)
C70.025 (2)0.026 (2)0.018 (2)−0.007 (2)0.001 (2)0.000 (2)
C80.031 (2)0.032 (3)0.018 (2)−0.006 (2)0.004 (2)−0.006 (2)
C90.032 (2)0.020 (2)0.023 (2)−0.004 (2)0.009 (2)−0.004 (2)
C100.025 (2)0.021 (2)0.025 (2)−0.001 (2)0.004 (2)0.005 (2)
C110.018 (2)0.012 (2)0.034 (2)−0.002 (2)−0.005 (2)0.005 (2)
C120.017 (2)0.018 (2)0.017 (2)−0.002 (2)−0.001 (2)0.004 (1)
C130.018 (2)0.019 (2)0.016 (2)−0.003 (2)0.001 (2)−0.001 (1)
C140.016 (2)0.019 (2)0.022 (2)0.002 (2)−0.002 (1)−0.003 (2)
Geometric parameters (Å, °) top
Cu1—O11.958 (2)C2—C31.391 (6)
Cu1—O3i2.157 (2)C2—H20.9300
Cu1—N11.997 (3)C3—C41.370 (6)
Cu1—N21.981 (3)C3—H30.9300
Cu1—N42.015 (3)C4—C51.396 (5)
O1—C111.264 (4)C4—H40.9302
O2—C111.245 (4)C6—C71.402 (5)
O3—Cu1ii2.157 (2)C7—C81.366 (6)
O3—C141.271 (4)C7—H50.9300
O4—C141.247 (4)C8—C91.390 (5)
O5—H150.8220C8—H60.9300
O5—H160.8365C9—C101.377 (5)
N1—C11.354 (5)C9—H70.9301
N1—C51.340 (5)C10—H80.9300
N2—C61.335 (5)C11—O11.264 (4)
N2—C101.357 (5)C11—O21.245 (4)
N3—C51.378 (5)C11—C121.530 (5)
N3—C61.394 (5)C12—C111.530 (5)
N3—H90.8599C12—C131.535 (5)
N4—C121.482 (4)C12—H120.9800
N4—H100.9001C13—C141.522 (5)
N4—H110.9000C13—H130.9700
C1—C21.363 (5)C13—H140.9700
C1—H10.9300H16—O50.8365
O1—Cu1—O3i94.9 (1)C4—C3—C2119.3 (4)
O1—Cu1—N1162.7 (1)C4—C3—H3120.3422
O1—Cu1—N287.8 (1)H3—C3—C2120.3249
O1—Cu1—N483.5 (1)C5—C4—C3119.3 (4)
O3i—Cu1—N1102.4 (1)C5—C4—H4120.3693
O3i—Cu1—N2104.5 (1)H4—C4—C3120.3705
O3i—Cu1—N491.3 (1)C7—C6—N2122.5 (3)
N1—Cu1—N289.5 (1)C7—C6—N3118.0 (3)
N1—Cu1—N494.3 (1)C8—C7—C6118.3 (3)
N2—Cu1—N4162.6 (1)C8—C7—H5120.8306
C11—O1—Cu1116.6 (2)H5—C7—C6120.8366
Cu1ii—O3—C14126.1 (2)C9—C8—C7120.3 (4)
H15—O5—H16103.7063C9—C8—H6119.8735
C1—N1—Cu1118.8 (2)H6—C8—C7119.8668
C1—N1—C5117.8 (3)C10—C9—C8117.9 (4)
C5—N1—Cu1123.2 (2)C10—C9—H7121.0512
C6—N2—Cu1122.9 (2)H7—C9—C8121.0527
C6—N2—C10117.8 (3)H8—C10—N2118.4655
C10—N2—Cu1117.4 (2)H8—C10—C9118.4670
C5—N3—C6129.2 (3)O1—C11—C12117.7 (3)
C5—N3—H9115.4117O1—C11—O2124.7 (3)
C6—N3—H9115.4095O2—C11—C12117.5 (3)
C12—N4—Cu1110.2 (2)C11—C12—N4109.5 (3)
C12—N4—H10109.6151C11—C12—H12107.8129
C12—N4—H11109.6255C11—C12—C13111.1 (3)
H10—N4—Cu1109.6205C13—C12—N4112.5 (3)
H10—N4—H11108.1428C13—C12—H12107.8132
H11—N4—Cu1109.6256H12—C12—N4107.8176
C2—C1—N1123.5 (4)C14—C13—C12113.3 (3)
C2—C1—H1118.2291C14—C13—H13108.8942
H1—C1—N1118.2395C14—C13—H14108.9045
C3—C2—C1118.2 (4)H13—C13—C12108.9037
C3—C2—H2120.8867H13—C13—H14107.7389
H2—C2—C1120.8839H14—C13—C12108.9029
N1—Cu1—O1—C11−87.8 (4)N1—C1—C2—C3−1.9 (6)
O1—Cu1—N1—C1124.4 (3)C1—C2—C3—C40.0 (5)
O1—Cu1—N2—C6126.6 (3)C2—C3—C4—C50.8 (5)
O1—Cu1—N4—C1211.8 (2)C3—C4—C5—N10.2 (4)
Cu1—O1—C11—O2178.5 (3)C3—C4—C5—N3−179.9 (2)
Cu1—N1—C1—C2−172.1 (3)N2—C6—C7—C8−1.1 (5)
Cu1—N1—C5—N3−7.1 (4)C6—C7—C8—C9−1.3 (5)
Cu1—N1—C5—C4172.7 (3)C7—C8—C9—C102.1 (6)
Cu1—N2—C6—N318.2 (4)C8—C9—C10—N2−0.5 (6)
Cu1—N2—C10—C9163.3 (3)O1—C11—C12—N414.4 (4)
C6—N3—C5—N1−28.1 (5)O2—C11—C12—N4−168.6 (3)
C6—N3—C5—C4152.1 (3)N4—C12—C13—C1465.7 (4)
C5—N3—C6—N222.1 (5)C12—C13—C14—O3147.9 (3)
Cu1—N4—C12—C11−16.4 (3)C12—C13—C14—O4−34.3 (5)
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H9···O4iii0.861.972.763 (4)153
N4—H10···O50.902.153.031 (4)166
N4—H11···O40.902.192.793 (4)124
O5—H15···O3iv0.822.082.867 (3)160
O5—H16···O2iv0.841.922.756 (4)173
Symmetry codes: (iii) x+1/2, −y+1/2, −z+1; (iv) −x, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.958 (2)Cu1—N21.981 (3)
Cu1—O3i2.157 (2)Cu1—N42.015 (3)
Cu1—N11.997 (3)
Symmetry codes: (i) x+1, y, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H9···O4ii0.861.972.763 (4)153
N4—H10···O50.902.153.031 (4)166
N4—H11···O40.902.192.793 (4)124
O5—H15···O3iii0.822.082.867 (3)160
O5—H16···O2iii0.841.922.756 (4)173
Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) −x, y+1/2, −z+3/2.
references
References top

Antolini, L., Marcotrigiano, G., Menabue, L., Pellacani, G. C., Saladini, M. & Sola, M. (1985). Inorg. Chem. 24, 3621–3626.

Antolini, L., Marcotrigiano, G., Menabue, L. & Pellacani, G. C. (1983). Inorg. Chem. 22, 141–145.

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Kelland, L. R. (2005). Eur. J. Cancer, 41, 971–979.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2005). or ??(2006). CrystalStructure Version 3.8. Rigaku/MSC, The Woodlands, Texas, USA. Please check date; 2005 in CIF.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Wang, Y. & Okabe, N. (2005). Inorg. Chim. Acta, 358, 3407–3416.

Yodoshi, M., Odoko, M. & Okabe, N. (2007). Chem. Pharm. Bull. 55, 853–860.