Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019103/ob6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019103/ob6011Isup2.hkl |
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.
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).
Fig. 1. View of the complex cation with 50% probability ellipsoids. [Symmetry code: (i) -x, y, 1/2 - z]. | |
Fig. 2. View of the chain structure of the complex cations and perchlorate anions. |
[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 |
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 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 |
[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)° |
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 |
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 |
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 |
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) |
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) |
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. |
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 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1997).
Cu1—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. |
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 |
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.