(2,2′-Bi­pyridine-κ2N,N′)bis­(nitrato-κ2O,O′)copper(II)

Liu, F.-Y.; Zhang, M.-H.; Kou, J.-F.

doi:10.1107/S1600536813028201

metal-organic compounds

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Volume 69| Part 11| November 2013| Page m609

doi:10.1107/S1600536813028201

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(2,2′-Bipyridine-κ²N,N′)bis(nitrato-κ²O,O′)copper(II)

Feng-Yi Liu,^a Ming-Hui Zhang ^a and Jun-Feng Kou ^a ^*

^aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, People's Republic of China
^*Correspondence e-mail: kjf416@163.com

(Received 6 October 2013; accepted 14 October 2013; online 19 October 2013)

In the title complex, [Cu(NO₃)₂(C₁₀H₈N₂)], the Cu^II cation is chelated by two nitrate anions and by one 2,2′-bipyridine ligand in a distorted N₂O₄ octahedral geometry. The dihedral angle between the pyridine rings is 1.92 (11)°. In the crystal, π–π stacking between parallel pyridine rings of adjacent complex molecules is observed, the centroid–centroid distance being 3.6788 (19) Å. Weak C—H⋯O hydrogen bonds further link the molecules into a three-dimensional supramolecular architecture.

CCDC reference: 966337

Related literature

For applications of copper(II) complexes in magnetochemistry, see: Garribba et al. (2000 ); Mukherjee (2000 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₀H₈N₂)]
M_r = 343.74
Monoclinic, P 2₁ /c
a = 8.4282 (17) Å
b = 11.132 (2) Å
c = 16.140 (5) Å
β = 121.39 (2)°
V = 1292.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 293 K
0.30 × 0.28 × 0.25 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer
12333 measured reflections
2955 independent reflections
2237 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.04
2955 reflections
190 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.966 (2)
Cu1—N2	1.970 (2)
Cu1—O1	2.411 (2)
Cu1—O2	1.994 (2)
Cu1—O4	2.437 (2)
Cu1—O5	1.9987 (19)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.93	2.56	3.390 (3)	149
C4—H4⋯O5ⁱⁱ	0.93	2.50	3.422 (3)	169
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) x-1, y, z.

Data collection: CrystalStructure (Rigaku/MSC, 2006 ); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 966337

Crystal structure: contains datablocks I, new_global_publ_block. DOI: 10.1107/S1600536813028201/xu5745sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028201/xu5745Isup2.hkl

checkCIF report

Comment top

Copper(II) is one of the most important transition metals in magnetochemistry (Garribba et al. 2000; Mukherjee, 2000). Herein we report the synthesis and structure of the title copper(II) complex with 2,2'-bipyridine.

As shown in Fig.1, the Cu(II) atom is chelated by two N atoms of 2,2'-bipyridine and four O atoms of from two nitrate anions, forming an irregular octahedral coordination geometry. The Cu—N bond distances are 1.9661 (19) Å and 1.9691 (18) Å with basal angle of 82.48 (8). The apical positions are occupied by O atoms of the two different bis-chelating nitrate anions [Cu—O distances of 2.4100 (19) Å, 1.9948 (18) Å, 2.28 (3) Å and 1.9983 (16) Å) with an angle of 57.76 (7), 91.89 (8) and 55.9 (7). The dihedral angle between the planes of the two pyridine rings is 1.92 (11)°. Further, π–π stacking interactions with a centroids separation of 3.6788 (19) Å between pyridine rings and weak C1—H1···O1 and C4—H4···O5 hydrogen bonds link the molecules into the three dimensional supramolecular structure in Fig. 2 and Fig. 3.

Related literature top

For applications of copper(II) complexes in magnetochemistry, see: Garribba et al. (2000); Mukherjee (2000).

Experimental top

A solution of copper(II) nitrate hydrate (0.2 mmol, 48 mg) in methanol (2 ml) was mixed with 2 ml of an aqueous solution of p-aminobenzoic acid (0.1 mmol, 17 mg) in presence of 2,2-bipyridine (0.1 mmol, 16 mg). The resulting mixture was allowed to evaporate for one week to yield a blue crystal, suitable to X-ray work.

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2006); cell refinement: CrystalStructure (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. The pi···pi stacking between two asymmetric cations.
	Fig. 3. A view of the crystal packing. Hydrogen bonds are shown as brown dashed lines.

(2,2'-Bipyridine-κ²N,N')bis(nitrato-κ²O,O')copper(II) top

Crystal data top

[Cu(NO₃)₂(C₁₀H₈N₂)]	F(000) = 692
M_r = 343.74	D_x = 1.766 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2955 reflections
a = 8.4282 (17) Å	θ = 3.0–27.5°
b = 11.132 (2) Å	µ = 1.73 mm⁻¹
c = 16.140 (5) Å	T = 293 K
β = 121.39 (2)°	Block, blue
V = 1292.7 (5) Å³	0.30 × 0.28 × 0.25 mm
Z = 4

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2237 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.038
Confocal monochromator	θ_max = 27.5°, θ_min = 3.0°
ω scans at fixed χ = 45°	h = −10→10
12333 measured reflections	k = −14→14
2955 independent reflections	l = −20→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.050P)² + 0.3548P] where P = (F_o² + 2F_c²)/3
2955 reflections	(Δ/σ)_max = 0.002
190 parameters	Δρ_max = 0.44 e Å⁻³
7 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₁₀H₈N₂)]	V = 1292.7 (5) Å³
M_r = 343.74	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4282 (17) Å	µ = 1.73 mm⁻¹
b = 11.132 (2) Å	T = 293 K
c = 16.140 (5) Å	0.30 × 0.28 × 0.25 mm
β = 121.39 (2)°

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	2237 reflections with I > 2σ(I)
12333 measured reflections	R_int = 0.038
2955 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	7 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	Δρ_max = 0.44 e Å⁻³
2955 reflections	Δρ_min = −0.45 e Å⁻³
190 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	0.85476 (4)	0.75682 (3)	1.00645 (2)	0.04079 (13)
N1	0.6302 (3)	0.85640 (18)	0.93496 (14)	0.0382 (5)
N2	0.7092 (3)	0.68048 (19)	1.05583 (16)	0.0432 (5)
N3	1.1760 (3)	0.7822 (2)	1.16329 (17)	0.0455 (5)
N4	0.9216 (4)	0.7086 (3)	0.8692 (2)	0.0665 (6)
O1	1.0825 (3)	0.87642 (17)	1.14048 (15)	0.0557 (5)
O2	1.0982 (3)	0.68978 (17)	1.10938 (14)	0.0517 (5)
O3	1.3353 (3)	0.7747 (2)	1.23263 (17)	0.0651 (6)
O4	0.8432 (3)	0.6241 (2)	0.88330 (17)	0.0742 (6)
O5	0.9581 (3)	0.80226 (19)	0.92397 (15)	0.0522 (5)
O6	0.9683 (4)	0.7076 (3)	0.8099 (2)	0.0924 (9)
C1	0.6062 (4)	0.9480 (2)	0.87584 (19)	0.0459 (6)
H1	0.7007	0.9662	0.8643	0.055*
C2	0.4471 (4)	1.0162 (3)	0.83155 (19)	0.0496 (7)
H2	0.4345	1.0798	0.7912	0.059*
C3	0.3067 (4)	0.9886 (3)	0.8480 (2)	0.0500 (7)
H3	0.1970	1.0328	0.8182	0.060*
C4	0.3301 (4)	0.8943 (2)	0.90937 (19)	0.0438 (6)
H4	0.2369	0.8749	0.9216	0.053*
C5	0.4940 (3)	0.8294 (2)	0.95232 (17)	0.0365 (5)
C6	0.5380 (4)	0.7277 (2)	1.02006 (18)	0.0377 (5)
C7	0.4185 (4)	0.6821 (3)	1.0464 (2)	0.0491 (7)
H7	0.3015	0.7159	1.0222	0.059*
C8	0.4744 (5)	0.5857 (3)	1.1093 (2)	0.0584 (8)
H8	0.3950	0.5538	1.1275	0.070*
C9	0.6479 (5)	0.5371 (3)	1.1448 (2)	0.0634 (8)
H9	0.6870	0.4716	1.1867	0.076*
C10	0.7635 (4)	0.5873 (3)	1.1170 (2)	0.0557 (7)
H10	0.8818	0.5555	1.1414	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03299 (19)	0.0431 (2)	0.0462 (2)	−0.00251 (13)	0.02050 (16)	−0.00080 (13)
N1	0.0358 (11)	0.0423 (10)	0.0365 (11)	−0.0015 (9)	0.0188 (10)	0.0014 (9)
N2	0.0410 (13)	0.0437 (12)	0.0431 (12)	−0.0026 (9)	0.0206 (11)	0.0018 (10)
N3	0.0402 (13)	0.0523 (13)	0.0418 (13)	−0.0059 (10)	0.0199 (11)	−0.0011 (10)
N4	0.0721 (14)	0.0727 (13)	0.0619 (12)	−0.0265 (11)	0.0400 (11)	−0.0237 (11)
O1	0.0553 (13)	0.0447 (11)	0.0573 (12)	0.0011 (9)	0.0224 (11)	−0.0035 (9)
O2	0.0386 (11)	0.0447 (10)	0.0592 (12)	−0.0014 (8)	0.0167 (10)	−0.0086 (9)
O3	0.0428 (13)	0.0776 (15)	0.0510 (13)	−0.0054 (10)	0.0077 (11)	0.0021 (11)
O4	0.0794 (14)	0.0738 (12)	0.0672 (12)	−0.0313 (10)	0.0366 (11)	−0.0219 (10)
O5	0.0488 (12)	0.0558 (11)	0.0627 (13)	−0.0111 (9)	0.0364 (11)	−0.0134 (10)
O6	0.107 (2)	0.119 (2)	0.0800 (19)	−0.0350 (19)	0.0689 (19)	−0.0397 (17)
C1	0.0490 (16)	0.0491 (15)	0.0432 (15)	−0.0057 (12)	0.0266 (14)	0.0033 (12)
C2	0.0590 (18)	0.0460 (15)	0.0401 (15)	0.0019 (13)	0.0234 (14)	0.0079 (12)
C3	0.0449 (16)	0.0477 (15)	0.0456 (15)	0.0049 (12)	0.0152 (14)	−0.0002 (13)
C4	0.0369 (14)	0.0487 (14)	0.0440 (14)	−0.0026 (11)	0.0198 (12)	−0.0014 (12)
C5	0.0343 (13)	0.0420 (13)	0.0314 (12)	−0.0063 (10)	0.0158 (11)	−0.0053 (10)
C6	0.0388 (14)	0.0393 (12)	0.0342 (13)	−0.0046 (10)	0.0185 (11)	−0.0013 (10)
C7	0.0463 (16)	0.0550 (16)	0.0514 (16)	−0.0056 (13)	0.0293 (14)	0.0022 (13)
C8	0.070 (2)	0.0595 (17)	0.0580 (19)	−0.0072 (16)	0.0421 (18)	0.0075 (15)
C9	0.081 (2)	0.0558 (17)	0.0531 (18)	−0.0018 (16)	0.0347 (18)	0.0170 (15)
C10	0.0571 (19)	0.0517 (16)	0.0519 (17)	0.0059 (14)	0.0239 (15)	0.0120 (14)

Geometric parameters (Å, º) top

Cu1—N1	1.966 (2)	C1—H1	0.9300
Cu1—N2	1.970 (2)	C2—C3	1.376 (4)
Cu1—O1	2.411 (2)	C2—H2	0.9300
Cu1—O2	1.994 (2)	C3—C4	1.385 (4)
Cu1—O4	2.437 (2)	C3—H3	0.9300
Cu1—O5	1.9987 (19)	C4—C5	1.383 (3)
N1—C1	1.338 (3)	C4—H4	0.9300
N1—C5	1.350 (3)	C5—C6	1.480 (3)
N2—C10	1.337 (3)	C6—C7	1.378 (3)
N2—C6	1.351 (3)	C7—C8	1.380 (4)
N3—O3	1.223 (3)	C7—H7	0.9300
N3—O1	1.247 (3)	C8—C9	1.374 (4)
N3—O2	1.285 (3)	C8—H8	0.9300
N4—O6	1.210 (3)	C9—C10	1.386 (4)
N4—O4	1.236 (3)	C9—H9	0.9300
N4—O5	1.296 (3)	C10—H10	0.9300
C1—C2	1.373 (4)

N1—Cu1—N2	82.47 (9)	N1—C1—C2	122.5 (2)
N1—Cu1—O2	163.34 (8)	N1—C1—H1	118.8
N2—Cu1—O2	95.09 (9)	C2—C1—H1	118.8
N1—Cu1—O5	94.96 (9)	C1—C2—C3	118.7 (3)
N2—Cu1—O5	163.31 (9)	C1—C2—H2	120.6
O2—Cu1—O5	91.92 (9)	C3—C2—H2	120.6
N1—Cu1—O1	106.76 (8)	C2—C3—C4	119.4 (3)
N2—Cu1—O1	104.35 (8)	C2—C3—H3	120.3
O2—Cu1—O1	57.74 (8)	C4—C3—H3	120.3
O5—Cu1—O1	92.20 (8)	C5—C4—C3	119.2 (2)
N1—Cu1—O4	104.21 (9)	C5—C4—H4	120.4
N2—Cu1—O4	107.43 (8)	C3—C4—H4	120.4
O2—Cu1—O4	92.26 (9)	N1—C5—C4	121.0 (2)
O5—Cu1—O4	57.07 (8)	N1—C5—C6	114.3 (2)
O1—Cu1—O4	137.86 (8)	C4—C5—C6	124.8 (2)
C1—N1—C5	119.2 (2)	N2—C6—C7	121.0 (2)
C1—N1—Cu1	126.18 (17)	N2—C6—C5	114.4 (2)
C5—N1—Cu1	114.53 (16)	C7—C6—C5	124.6 (2)
C10—N2—C6	119.7 (2)	C6—C7—C8	119.3 (3)
C10—N2—Cu1	126.0 (2)	C6—C7—H7	120.4
C6—N2—Cu1	114.28 (17)	C8—C7—H7	120.4
O3—N3—O1	123.4 (3)	C9—C8—C7	119.6 (3)
O3—N3—O2	119.6 (2)	C9—C8—H8	120.2
O1—N3—O2	116.9 (2)	C7—C8—H8	120.2
O6—N4—O4	124.3 (3)	C8—C9—C10	118.8 (3)
O6—N4—O5	119.2 (3)	C8—C9—H9	120.6
O4—N4—O5	116.5 (2)	C10—C9—H9	120.6
N3—O1—Cu1	83.43 (15)	N2—C10—C9	121.6 (3)
N3—O2—Cu1	101.85 (16)	N2—C10—H10	119.2
N4—O4—Cu1	83.75 (17)	C9—C10—H10	119.2
N4—O5—Cu1	102.68 (17)

N2—Cu1—N1—C1	178.0 (2)	N2—Cu1—O4—N4	172.5 (2)
O2—Cu1—N1—C1	95.5 (3)	O2—Cu1—O4—N4	−91.5 (2)
O5—Cu1—N1—C1	−18.6 (2)	O5—Cu1—O4—N4	−0.64 (19)
O1—Cu1—N1—C1	75.2 (2)	O1—Cu1—O4—N4	−50.3 (3)
O4—Cu1—N1—C1	−75.8 (2)	O6—N4—O5—Cu1	−179.7 (3)
N2—Cu1—N1—C5	0.66 (17)	O4—N4—O5—Cu1	−1.1 (3)
O2—Cu1—N1—C5	−81.9 (3)	N1—Cu1—O5—N4	−103.1 (2)
O5—Cu1—N1—C5	164.07 (17)	N2—Cu1—O5—N4	−22.8 (4)
O1—Cu1—N1—C5	−102.12 (17)	O2—Cu1—O5—N4	92.1 (2)
O4—Cu1—N1—C5	106.82 (17)	O1—Cu1—O5—N4	149.85 (19)
N1—Cu1—N2—C10	178.3 (2)	O4—Cu1—O5—N4	0.62 (19)
O2—Cu1—N2—C10	−18.3 (2)	C5—N1—C1—C2	−0.1 (4)
O5—Cu1—N2—C10	96.2 (4)	Cu1—N1—C1—C2	−177.4 (2)
O1—Cu1—N2—C10	−76.3 (2)	N1—C1—C2—C3	−0.5 (4)
O4—Cu1—N2—C10	75.7 (2)	C1—C2—C3—C4	0.8 (4)
N1—Cu1—N2—C6	0.38 (18)	C2—C3—C4—C5	−0.4 (4)
O2—Cu1—N2—C6	163.80 (18)	C1—N1—C5—C4	0.5 (3)
O5—Cu1—N2—C6	−81.7 (4)	Cu1—N1—C5—C4	178.04 (18)
O1—Cu1—N2—C6	105.83 (18)	C1—N1—C5—C6	−179.0 (2)
O4—Cu1—N2—C6	−102.22 (18)	Cu1—N1—C5—C6	−1.5 (3)
O3—N3—O1—Cu1	176.9 (2)	C3—C4—C5—N1	−0.2 (4)
O2—N3—O1—Cu1	−2.4 (2)	C3—C4—C5—C6	179.3 (2)
N1—Cu1—O1—N3	174.92 (14)	C10—N2—C6—C7	0.7 (4)
N2—Cu1—O1—N3	88.61 (15)	Cu1—N2—C6—C7	178.7 (2)
O2—Cu1—O1—N3	1.66 (14)	C10—N2—C6—C5	−179.3 (2)
O5—Cu1—O1—N3	−89.22 (15)	Cu1—N2—C6—C5	−1.3 (3)
O4—Cu1—O1—N3	−49.43 (19)	N1—C5—C6—N2	1.8 (3)
O3—N3—O2—Cu1	−176.4 (2)	C4—C5—C6—N2	−177.7 (2)
O1—N3—O2—Cu1	3.0 (2)	N1—C5—C6—C7	−178.2 (2)
N1—Cu1—O2—N3	−24.7 (4)	C4—C5—C6—C7	2.3 (4)
N2—Cu1—O2—N3	−105.41 (15)	N2—C6—C7—C8	−0.9 (4)
O5—Cu1—O2—N3	89.75 (15)	C5—C6—C7—C8	179.1 (3)
O1—Cu1—O2—N3	−1.63 (13)	C6—C7—C8—C9	0.3 (5)
O4—Cu1—O2—N3	146.86 (15)	C7—C8—C9—C10	0.6 (5)
O6—N4—O4—Cu1	179.4 (4)	C6—N2—C10—C9	0.2 (4)
O5—N4—O4—Cu1	0.9 (3)	Cu1—N2—C10—C9	−177.6 (2)
N1—Cu1—O4—N4	86.1 (2)	C8—C9—C10—N2	−0.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.56	3.390 (3)	149
C4—H4···O5ⁱⁱ	0.93	2.50	3.422 (3)	169

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x−1, y, z.

Selected bond lengths (Å) top

Cu1—N1	1.966 (2)	Cu1—O2	1.994 (2)
Cu1—N2	1.970 (2)	Cu1—O4	2.437 (2)
Cu1—O1	2.411 (2)	Cu1—O5	1.9987 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.56	3.390 (3)	149
C4—H4···O5ⁱⁱ	0.93	2.50	3.422 (3)	169

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x−1, y, z.

Acknowledgements

The work was supported by the Scientific Research Foundation of Yunnan Provincial Department of Education, China (grant No. 22012Z019).

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