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In the crystal structure of the title complex, [Cu(C10H9N3)2](ClO4)2, the CuII center is four-coordinated by the nitro­gen donors of the pyridine rings of the ligand, bis(2-pyridyl)­amine. The crystal structure reveals that the CuN4 coordination sphere has a distorted tetrahedral coordination geometry with a crystallographic C2 axis through the CuII center. The perchlorate anions link the complex cations to form a chain structure through C—H...O close contacts and N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019103/ob6011sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019103/ob6011Isup2.hkl
Contains datablock I

CCDC reference: 155841

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.043
  • wR factor = 0.108
  • Data-to-parameter ratio = 11.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Ligands containing aromatic nitrogen heterocycles, such as pyridine, 2,2'-bipyridine and 1,10-phenanthroline, have given a great impetus to metal coordination chemistry. Bis(2-pyridyl)amine has attracted a great interest in the molecular self-assembling processes that lead to macromolecular architectures (Cotton et al., 1997, 1998; Gornitzka & Stalke, 1998) and three different coordination modes were found for this feasible ligand (see below).

An structure analysis of the title complex, (I), was performed early in 1971 (Johnson et al., 1971). The structure was refined to R = 0.094 using 1167 visually estimated intensities which were not corrected for absorption and the s.u.'s reported were 0.01 Å for bond lengths and 1° for bond angles. We have now redetermined the structure of (I) using CCD data. Not only is the structure reported here more accuracy determined but some of the parameters, such as unit-cell dimensions, bond lengths and intramolecular interactions, show significantly differences from those reported earlier.

The structure (I) consists of discrete [Cu(C10H9N3)2]2+ cations and perchlorate anions. The CuII center lies on the crystallographic twofold rotation axes. The CuII atom is four coordinated and bonded in a bidentate fashion to two pyridine rings of the ligand by trans–trans mode (Fig. 1). The coordination geometry of CuII could be best described as distorted tetrahedron. The degree of distortion from planar towards tetrahedral can be reflected by the dihedral angle between the N1—Cu—N2 and N1i—Cu1—N2i planes, 54.9 (4)° [symmetry code: (i) -x, y, -z + 1/2]. The Cu—N bond distances (Table 1) are almost equivalent [1.971 (2) and 1.977 (2) Å], which are similar to the value of the analogous complexes (Ray et al., 1982; Rodig et al., 1981; Spodine et al., 1996).

The perchlorate anions act as bridges to link the complex cations through N—H···O hydrogen bonds and C—H···O close contacts, forming a chain structure, as shown in Fig. 2. The C(N)···O and H···O separations, and the bond angles are listed in Table 2, which are in the normal range of the weak interactions (Sasada, 1984; Desiraju, 1991). Furthermore, the complex cations of (I) are stacked in the b direction with the closest approach between the pyridine rings of 4.112 (4) Å, indicating no significant ππ-stacking interactions.

Experimental top

The title complex was synthesized by mixing Cu(ClO4)2 (0.37 g, 1.0 mmol) and bis(2-pyridyl)amine (0.34 g, 2.0 mmol) in methanol (20 ml). The reaction mixture was filtered and left to stand at room temperature. Blue single crystals [yield: 360 mg (60%)] suitable for X-ray analysis were obtained by slow evaporation of the solvent.

Refinement top

H atoms were located by geometry and used in the structure-factor calculations.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. View of the complex cation with 50% probability ellipsoids. [Symmetry code: (i) -x, y, 1/2 - z].
[Figure 2] Fig. 2. View of the chain structure of the complex cations and perchlorate anions.
[bis(2-pyridyl)amine-N,N']copper(II) diperchlorate top
Crystal data top
[Cu(C10H9N3)2](ClO4)2F(000) = 1228
Mr = 604.87Dx = 1.717 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 9.416 (3) ÅCell parameters from 4478 reflections
b = 12.955 (4) Åθ = 2.1–25.0°
c = 19.748 (6) ŵ = 1.22 mm1
β = 103.792 (3)°T = 298 K
V = 2339.5 (11) Å3Prism, blue
Z = 40.35 × 0.30 × 0.25 mm
Data collection top
CCD
diffractometer
1790 reflections with I > 2σ(I)
ω scansRint = 0.068
Absorption correction: integration
(Bruker, 1998)
θmax = 25.0°
Tmin = 0.674, Tmax = 0.750h = 1111
4515 measured reflectionsk = 915
1983 independent reflectionsl = 2323
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043 w = 1/[σ2(Fo2) + (0.0612P)2 + 0.9728P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108(Δ/σ)max = 0.002
S = 1.04Δρmax = 0.40 e Å3
1983 reflectionsΔρmin = 0.36 e Å3
169 parameters
Crystal data top
[Cu(C10H9N3)2](ClO4)2V = 2339.5 (11) Å3
Mr = 604.87Z = 4
Monoclinic, C2/cMo Kα radiation
a = 9.416 (3) ŵ = 1.22 mm1
b = 12.955 (4) ÅT = 298 K
c = 19.748 (6) Å0.35 × 0.30 × 0.25 mm
β = 103.792 (3)°
Data collection top
CCD
diffractometer
1983 independent reflections
Absorption correction: integration
(Bruker, 1998)
1790 reflections with I > 2σ(I)
Tmin = 0.674, Tmax = 0.750Rint = 0.068
4515 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043169 parameters
wR(F2) = 0.108H-atom parameters constrained
S = 1.04Δρmax = 0.40 e Å3
1983 reflectionsΔρmin = 0.36 e Å3
Special details top

Experimental. Yield: 360 mg (60%). FT—IR data (KBr pellet, cm-1): 3327(m), 3222(w), 1644(versus), 1592(s), 1530(s), 1484(versus), 1434(m), 1236(s), 1120(versus), 1093(versus), 1077(versus), 772(s), 625(m). Anal. Calc for C20H18CuN6Cl2O8: C 39.71, H 3.00, N 13.90; found: C 39.40, H 3.16, N 13.78%.

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. Full-MATRIX

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.00000.94442 (3)0.25000.0330 (2)
N20.1675 (2)0.99864 (17)0.32137 (11)0.0349 (5)
C60.1893 (3)0.98516 (19)0.39013 (13)0.0320 (5)
C70.3135 (3)1.0275 (2)0.43758 (15)0.0416 (7)
H7A0.32691.01660.48520.050*
C80.4118 (3)1.0834 (2)0.41342 (18)0.0491 (7)
H8A0.49321.11150.44400.059*
C90.3887 (3)1.0983 (3)0.34105 (18)0.0507 (8)
H9A0.45491.13600.32280.061*
C100.2674 (3)1.0563 (2)0.29821 (17)0.0438 (7)
H10A0.25191.06760.25050.053*
Cl10.67768 (7)0.69414 (5)0.10754 (3)0.0385 (2)
O10.6102 (3)0.7784 (2)0.06531 (19)0.0868 (10)
O20.8054 (3)0.7282 (2)0.15773 (15)0.0693 (7)
O30.7168 (3)0.6117 (2)0.06682 (15)0.0809 (9)
O40.5742 (3)0.6531 (2)0.14309 (17)0.0827 (9)
N10.1062 (2)0.89603 (17)0.31876 (11)0.0326 (5)
N30.0894 (3)0.93107 (17)0.41728 (11)0.0369 (5)
H3B0.11970.91710.46090.044*
C10.2435 (3)0.8573 (2)0.29427 (15)0.0416 (6)
H1A0.28130.85530.24630.050*
C20.3280 (4)0.8216 (3)0.33581 (18)0.0512 (8)
H2A0.42220.79760.31710.061*
C30.2686 (4)0.8221 (2)0.40798 (17)0.0497 (8)
H3A0.32330.79770.43810.060*
C40.1307 (3)0.8583 (2)0.43367 (15)0.0438 (7)
H4A0.09050.85860.48150.053*
C50.0496 (3)0.89501 (19)0.38814 (13)0.0325 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0287 (3)0.0460 (3)0.0251 (3)0.0000.00804 (19)0.000
N20.0335 (12)0.0397 (12)0.0321 (11)0.0015 (10)0.0088 (9)0.0029 (9)
C60.0302 (13)0.0329 (12)0.0321 (13)0.0043 (11)0.0057 (10)0.0009 (10)
C70.0392 (16)0.0459 (15)0.0351 (14)0.0018 (13)0.0003 (12)0.0004 (12)
C80.0353 (15)0.0482 (16)0.0571 (19)0.0068 (14)0.0023 (13)0.0037 (14)
C90.0431 (16)0.0480 (17)0.0600 (19)0.0139 (15)0.0107 (14)0.0043 (14)
C100.0428 (17)0.0464 (16)0.0440 (16)0.0062 (13)0.0137 (13)0.0070 (12)
Cl10.0375 (4)0.0408 (4)0.0370 (4)0.0049 (3)0.0089 (3)0.0008 (2)
O10.0678 (18)0.0675 (16)0.113 (2)0.0057 (15)0.0019 (16)0.0378 (17)
O20.0538 (14)0.0722 (16)0.0726 (17)0.0001 (13)0.0034 (12)0.0210 (13)
O30.0832 (19)0.095 (2)0.0606 (16)0.0202 (17)0.0107 (14)0.0334 (15)
O40.0735 (19)0.0824 (19)0.107 (2)0.0093 (15)0.0508 (17)0.0212 (17)
N10.0304 (11)0.0382 (11)0.0308 (11)0.0025 (10)0.0100 (9)0.0015 (9)
N30.0362 (12)0.0463 (12)0.0278 (11)0.0022 (10)0.0070 (9)0.0061 (9)
C10.0382 (15)0.0484 (16)0.0372 (14)0.0122 (13)0.0068 (11)0.0033 (12)
C20.0409 (16)0.0616 (19)0.0522 (17)0.0149 (15)0.0130 (14)0.0040 (15)
C30.0493 (18)0.0580 (18)0.0484 (17)0.0079 (15)0.0245 (14)0.0068 (14)
C40.0473 (17)0.0517 (16)0.0355 (15)0.0013 (14)0.0160 (12)0.0079 (12)
C50.0356 (14)0.0328 (12)0.0300 (13)0.0024 (11)0.0098 (10)0.0000 (10)
Geometric parameters (Å, º) top
Cu1—N1i1.971 (2)Cl1—O11.428 (3)
Cu1—N11.971 (2)Cl1—O41.432 (3)
Cu1—N21.977 (2)Cl1—O21.433 (2)
Cu1—N2i1.977 (2)Cl1—O31.437 (3)
N2—C61.335 (4)N1—C51.347 (3)
N2—C101.363 (4)N1—C11.364 (4)
C6—N31.380 (3)N3—C51.380 (4)
C6—C71.422 (4)C1—C21.353 (4)
C7—C81.348 (5)C2—C31.401 (5)
C8—C91.407 (5)C3—C41.360 (5)
C9—C101.362 (4)C4—C51.395 (4)
N1i—Cu1—N1142.90 (13)O1—Cl1—O2110.60 (18)
N1i—Cu1—N298.90 (9)O4—Cl1—O2109.4 (2)
N1—Cu1—N294.09 (9)O1—Cl1—O3112.3 (2)
N1i—Cu1—N2i94.09 (9)O4—Cl1—O3107.1 (2)
N1—Cu1—N2i98.90 (9)O2—Cl1—O3109.34 (16)
N2—Cu1—N2i138.37 (13)C5—N1—C1118.0 (2)
C6—N2—C10117.5 (2)C5—N1—Cu1124.17 (18)
C6—N2—Cu1125.58 (18)C1—N1—Cu1117.82 (18)
C10—N2—Cu1116.92 (19)C5—N3—C6132.6 (2)
N2—C6—N3120.5 (2)C2—C1—N1123.7 (3)
N2—C6—C7121.5 (2)C1—C2—C3117.8 (3)
N3—C6—C7118.0 (2)C4—C3—C2119.6 (3)
C8—C7—C6120.0 (3)C3—C4—C5119.9 (3)
C7—C8—C9118.7 (3)N1—C5—N3121.8 (2)
C10—C9—C8118.7 (3)N1—C5—C4121.0 (2)
C9—C10—N2123.6 (3)N3—C5—C4117.2 (2)
O1—Cl1—O4108.07 (19)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3b···O30.862.112.963 (6)174
C9—H9a···O20.962.483.331 (5)149

Experimental details

Crystal data
Chemical formula[Cu(C10H9N3)2](ClO4)2
Mr604.87
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)9.416 (3), 12.955 (4), 19.748 (6)
β (°) 103.792 (3)
V3)2339.5 (11)
Z4
Radiation typeMo Kα
µ (mm1)1.22
Crystal size (mm)0.35 × 0.30 × 0.25
Data collection
DiffractometerCCD
diffractometer
Absorption correctionIntegration
(Bruker, 1998)
Tmin, Tmax0.674, 0.750
No. of measured, independent and
observed [I > 2σ(I)] reflections
4515, 1983, 1790
Rint0.068
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.108, 1.04
No. of reflections1983
No. of parameters169
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.36

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1997).

Selected geometric parameters (Å, º) top
Cu1—N11.971 (2)Cu1—N21.977 (2)
N1i—Cu1—N1142.90 (13)N1—Cu1—N294.09 (9)
N1i—Cu1—N298.90 (9)N2—Cu1—N2i138.37 (13)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3b···O3.862.1062.963 (6)173.7
C9—H9a···O2.962.4753.331 (5)148.5
 

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