Buy article online - an online subscription or single-article purchase is required to access this article.
In the crystal structure of the title complex, [Cu(C
10H
9N
3)
2](ClO
4)
2, the Cu
II 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 CuN
4 coordination sphere has a distorted tetrahedral coordination geometry with a crystallographic
C2 axis through the Cu
II 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
CCDC reference: 155841
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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.
H atoms were located by geometry and used in the structure-factor calculations.
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).
[bis(2-pyridyl)amine-N,
N']copper(II) diperchlorate
top
Crystal data top
[Cu(C10H9N3)2](ClO4)2 | F(000) = 1228 |
Mr = 604.87 | Dx = 1.717 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.416 (3) Å | Cell parameters from 4478 reflections |
b = 12.955 (4) Å | θ = 2.1–25.0° |
c = 19.748 (6) Å | µ = 1.22 mm−1 |
β = 103.792 (3)° | T = 298 K |
V = 2339.5 (11) Å3 | Prism, blue |
Z = 4 | 0.35 × 0.30 × 0.25 mm |
Data collection top
CCD diffractometer | 1790 reflections with I > 2σ(I) |
ω scans | Rint = 0.068 |
Absorption correction: integration (Bruker, 1998) | θmax = 25.0° |
Tmin = 0.674, Tmax = 0.750 | h = −11→11 |
4515 measured reflections | k = −9→15 |
1983 independent reflections | l = −23→23 |
Refinement top
Refinement on F2 | H-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 = 1.04 | Δρmax = 0.40 e Å−3 |
1983 reflections | Δρmin = −0.36 e Å−3 |
169 parameters | |
Crystal data top
[Cu(C10H9N3)2](ClO4)2 | V = 2339.5 (11) Å3 |
Mr = 604.87 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.416 (3) Å | µ = 1.22 mm−1 |
b = 12.955 (4) Å | T = 298 K |
c = 19.748 (6) Å | 0.35 × 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 = 0.750 | Rint = 0.068 |
4515 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 169 parameters |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.40 e Å−3 |
1983 reflections | Δρmin = −0.36 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.0000 | 0.94442 (3) | 0.2500 | 0.0330 (2) | |
N2 | 0.1675 (2) | 0.99864 (17) | 0.32137 (11) | 0.0349 (5) | |
C6 | 0.1893 (3) | 0.98516 (19) | 0.39013 (13) | 0.0320 (5) | |
C7 | 0.3135 (3) | 1.0275 (2) | 0.43758 (15) | 0.0416 (7) | |
H7A | 0.3269 | 1.0166 | 0.4852 | 0.050* | |
C8 | 0.4118 (3) | 1.0834 (2) | 0.41342 (18) | 0.0491 (7) | |
H8A | 0.4932 | 1.1115 | 0.4440 | 0.059* | |
C9 | 0.3887 (3) | 1.0983 (3) | 0.34105 (18) | 0.0507 (8) | |
H9A | 0.4549 | 1.1360 | 0.3228 | 0.061* | |
C10 | 0.2674 (3) | 1.0563 (2) | 0.29821 (17) | 0.0438 (7) | |
H10A | 0.2519 | 1.0676 | 0.2505 | 0.053* | |
Cl1 | 0.67768 (7) | 0.69414 (5) | 0.10754 (3) | 0.0385 (2) | |
O1 | 0.6102 (3) | 0.7784 (2) | 0.06531 (19) | 0.0868 (10) | |
O2 | 0.8054 (3) | 0.7282 (2) | 0.15773 (15) | 0.0693 (7) | |
O3 | 0.7168 (3) | 0.6117 (2) | 0.06682 (15) | 0.0809 (9) | |
O4 | 0.5742 (3) | 0.6531 (2) | 0.14309 (17) | 0.0827 (9) | |
N1 | −0.1062 (2) | 0.89603 (17) | 0.31876 (11) | 0.0326 (5) | |
N3 | 0.0894 (3) | 0.93107 (17) | 0.41728 (11) | 0.0369 (5) | |
H3B | 0.1197 | 0.9171 | 0.4609 | 0.044* | |
C1 | −0.2435 (3) | 0.8573 (2) | 0.29427 (15) | 0.0416 (6) | |
H1A | −0.2813 | 0.8553 | 0.2463 | 0.050* | |
C2 | −0.3280 (4) | 0.8216 (3) | 0.33581 (18) | 0.0512 (8) | |
H2A | −0.4222 | 0.7976 | 0.3171 | 0.061* | |
C3 | −0.2686 (4) | 0.8221 (2) | 0.40798 (17) | 0.0497 (8) | |
H3A | −0.3233 | 0.7977 | 0.4381 | 0.060* | |
C4 | −0.1307 (3) | 0.8583 (2) | 0.43367 (15) | 0.0438 (7) | |
H4A | −0.0905 | 0.8586 | 0.4815 | 0.053* | |
C5 | −0.0496 (3) | 0.89501 (19) | 0.38814 (13) | 0.0325 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0287 (3) | 0.0460 (3) | 0.0251 (3) | 0.000 | 0.00804 (19) | 0.000 |
N2 | 0.0335 (12) | 0.0397 (12) | 0.0321 (11) | 0.0015 (10) | 0.0088 (9) | 0.0029 (9) |
C6 | 0.0302 (13) | 0.0329 (12) | 0.0321 (13) | 0.0043 (11) | 0.0057 (10) | 0.0009 (10) |
C7 | 0.0392 (16) | 0.0459 (15) | 0.0351 (14) | 0.0018 (13) | −0.0003 (12) | −0.0004 (12) |
C8 | 0.0353 (15) | 0.0482 (16) | 0.0571 (19) | −0.0068 (14) | −0.0023 (13) | −0.0037 (14) |
C9 | 0.0431 (16) | 0.0480 (17) | 0.0600 (19) | −0.0139 (15) | 0.0107 (14) | 0.0043 (14) |
C10 | 0.0428 (17) | 0.0464 (16) | 0.0440 (16) | −0.0062 (13) | 0.0137 (13) | 0.0070 (12) |
Cl1 | 0.0375 (4) | 0.0408 (4) | 0.0370 (4) | 0.0049 (3) | 0.0089 (3) | −0.0008 (2) |
O1 | 0.0678 (18) | 0.0675 (16) | 0.113 (2) | 0.0057 (15) | −0.0019 (16) | 0.0378 (17) |
O2 | 0.0538 (14) | 0.0722 (16) | 0.0726 (17) | 0.0001 (13) | −0.0034 (12) | −0.0210 (13) |
O3 | 0.0832 (19) | 0.095 (2) | 0.0606 (16) | 0.0202 (17) | 0.0107 (14) | −0.0334 (15) |
O4 | 0.0735 (19) | 0.0824 (19) | 0.107 (2) | 0.0093 (15) | 0.0508 (17) | 0.0212 (17) |
N1 | 0.0304 (11) | 0.0382 (11) | 0.0308 (11) | −0.0025 (10) | 0.0100 (9) | −0.0015 (9) |
N3 | 0.0362 (12) | 0.0463 (12) | 0.0278 (11) | −0.0022 (10) | 0.0070 (9) | 0.0061 (9) |
C1 | 0.0382 (15) | 0.0484 (16) | 0.0372 (14) | −0.0122 (13) | 0.0068 (11) | −0.0033 (12) |
C2 | 0.0409 (16) | 0.0616 (19) | 0.0522 (17) | −0.0149 (15) | 0.0130 (14) | 0.0040 (15) |
C3 | 0.0493 (18) | 0.0580 (18) | 0.0484 (17) | −0.0079 (15) | 0.0245 (14) | 0.0068 (14) |
C4 | 0.0473 (17) | 0.0517 (16) | 0.0355 (15) | 0.0013 (14) | 0.0160 (12) | 0.0079 (12) |
C5 | 0.0356 (14) | 0.0328 (12) | 0.0300 (13) | 0.0024 (11) | 0.0098 (10) | 0.0000 (10) |
Geometric parameters (Å, º) top
Cu1—N1i | 1.971 (2) | Cl1—O1 | 1.428 (3) |
Cu1—N1 | 1.971 (2) | Cl1—O4 | 1.432 (3) |
Cu1—N2 | 1.977 (2) | Cl1—O2 | 1.433 (2) |
Cu1—N2i | 1.977 (2) | Cl1—O3 | 1.437 (3) |
N2—C6 | 1.335 (4) | N1—C5 | 1.347 (3) |
N2—C10 | 1.363 (4) | N1—C1 | 1.364 (4) |
C6—N3 | 1.380 (3) | N3—C5 | 1.380 (4) |
C6—C7 | 1.422 (4) | C1—C2 | 1.353 (4) |
C7—C8 | 1.348 (5) | C2—C3 | 1.401 (5) |
C8—C9 | 1.407 (5) | C3—C4 | 1.360 (5) |
C9—C10 | 1.362 (4) | C4—C5 | 1.395 (4) |
| | | |
N1i—Cu1—N1 | 142.90 (13) | O1—Cl1—O2 | 110.60 (18) |
N1i—Cu1—N2 | 98.90 (9) | O4—Cl1—O2 | 109.4 (2) |
N1—Cu1—N2 | 94.09 (9) | O1—Cl1—O3 | 112.3 (2) |
N1i—Cu1—N2i | 94.09 (9) | O4—Cl1—O3 | 107.1 (2) |
N1—Cu1—N2i | 98.90 (9) | O2—Cl1—O3 | 109.34 (16) |
N2—Cu1—N2i | 138.37 (13) | C5—N1—C1 | 118.0 (2) |
C6—N2—C10 | 117.5 (2) | C5—N1—Cu1 | 124.17 (18) |
C6—N2—Cu1 | 125.58 (18) | C1—N1—Cu1 | 117.82 (18) |
C10—N2—Cu1 | 116.92 (19) | C5—N3—C6 | 132.6 (2) |
N2—C6—N3 | 120.5 (2) | C2—C1—N1 | 123.7 (3) |
N2—C6—C7 | 121.5 (2) | C1—C2—C3 | 117.8 (3) |
N3—C6—C7 | 118.0 (2) | C4—C3—C2 | 119.6 (3) |
C8—C7—C6 | 120.0 (3) | C3—C4—C5 | 119.9 (3) |
C7—C8—C9 | 118.7 (3) | N1—C5—N3 | 121.8 (2) |
C10—C9—C8 | 118.7 (3) | N1—C5—C4 | 121.0 (2) |
C9—C10—N2 | 123.6 (3) | N3—C5—C4 | 117.2 (2) |
O1—Cl1—O4 | 108.07 (19) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3b···O3 | 0.86 | 2.11 | 2.963 (6) | 174 |
C9—H9a···O2 | 0.96 | 2.48 | 3.331 (5) | 149 |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H9N3)2](ClO4)2 |
Mr | 604.87 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.416 (3), 12.955 (4), 19.748 (6) |
β (°) | 103.792 (3) |
V (Å3) | 2339.5 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.22 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | CCD diffractometer |
Absorption correction | Integration (Bruker, 1998) |
Tmin, Tmax | 0.674, 0.750 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4515, 1983, 1790 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.108, 1.04 |
No. of reflections | 1983 |
No. of parameters | 169 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.36 |
Selected geometric parameters (Å, º) topCu1—N1 | 1.971 (2) | Cu1—N2 | 1.977 (2) |
| | | |
N1i—Cu1—N1 | 142.90 (13) | N1—Cu1—N2 | 94.09 (9) |
N1i—Cu1—N2 | 98.90 (9) | N2—Cu1—N2i | 138.37 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3b···O3 | .86 | 2.106 | 2.963 (6) | 173.7 |
C9—H9a···O2 | .96 | 2.475 | 3.331 (5) | 148.5 |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
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 π–π-stacking interactions.