The title complex, [Co(C
10H
9N
3)
2(N
3)
2]ClO
4, consists of discrete cations and anions. The central Co
III ion has an approximate octahedral geometry, coordinated with four N atoms of the pyridine rings of the bis(2-pyridyl)amine ligands in a
trans–
trans mode, and with two terminal N atoms of the azide anions. The crystal structure is stabilized by N—H
O hydrogen bonds between the amino groups and the perchlorate anions.
Supporting information
CCDC reference: 159826
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.045
- wR factor = 0.120
- Data-to-parameter ratio = 12.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and
_diffrn_standards_interval_time are missing. Number of measurements
between standards or time (min) between standards.
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
A mixture of Co(ClO4)2.6H2O (0.37 g, 1.0 mmol) and bis(2-pyridyl)amine
(0.34 g, 2.0 mmol) were dissolved in methanol (40 ml). Then, an excess of
NaN3 (0.20 g, 3.0 mmol) was added to the above solution under reflux. The
resulting red solution was allowed to stand at room temperature for several
days and red block-shaped crystals were deposited slowly with the evaporation
of the solvent. Yield: 0.23 g (40%). FT—IR data (KBr pellet, cm-1): 3448
(b), 3299 (m), 2921 (w), 2030 (versus), 1631
(versus), 1586 (versus), 1524 (m), 1473 (versus),
1104 (s), 1069 (s), 775 (s), 625 (s). Analysis
calculated for the title complex: C 41.07, H 3.10, N 28.75%; found: C 40.88, H
3.34, N 28.66%.
H atoms were located by geometry and take part 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 in SHELXTL (Bruker, 1998).
Diazide[bis(2-pyridyl)amine] Co
III perchlorate
top
Crystal data top
[Co(C10H9N3)2(N3)2]ClO4 | Z = 2 |
Mr = 584.84 | F(000) = 596 |
Triclinic, P1 | Dx = 1.610 Mg m−3 |
a = 8.554 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.201 (3) Å | Cell parameters from 5012 reflections |
c = 17.036 (5) Å | θ = 1.3–25.0° |
α = 74.903 (5)° | µ = 0.88 mm−1 |
β = 78.792 (5)° | T = 298 K |
γ = 69.739 (5)° | Prism, red |
V = 1206.5 (6) Å3 | 0.25 × 0.20 × 0.20 mm |
Data collection top
Bruker SMART 1000 diffractometer | 3065 reflections with I > 2σ(I) |
ω scans | Rint = 0.025 |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | θmax = 25.0° |
Tmin = 0.810, Tmax = 0.844 | h = −9→10 |
5057 measured reflections | k = −10→10 |
4235 independent reflections | l = −20→19 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.3837P] P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.121 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.59 e Å−3 |
4235 reflections | Δρmin = −0.33 e Å−3 |
343 parameters | |
Crystal data top
[Co(C10H9N3)2(N3)2]ClO4 | γ = 69.739 (5)° |
Mr = 584.84 | V = 1206.5 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.554 (3) Å | Mo Kα radiation |
b = 9.201 (3) Å | µ = 0.88 mm−1 |
c = 17.036 (5) Å | T = 298 K |
α = 74.903 (5)° | 0.25 × 0.20 × 0.20 mm |
β = 78.792 (5)° | |
Data collection top
Bruker SMART 1000 diffractometer | 4235 independent reflections |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | 3065 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 0.844 | Rint = 0.025 |
5057 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 343 parameters |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.59 e Å−3 |
4235 reflections | Δρmin = −0.33 e Å−3 |
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. Single crystal X-ray diffraction measurements were carried out on a BRUKER
SMART 1000 CCD diffractometer. The structure was solved by direct and
difference Fourier methods and refined by full-matrix least-squares methods. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.7676 (5) | 0.7893 (4) | 0.5736 (2) | 0.0367 (9) | |
H1A | 0.7323 | 0.7811 | 0.5271 | 0.044* | |
C2 | 0.8821 (5) | 0.8655 (5) | 0.5644 (3) | 0.0462 (11) | |
H2A | 0.9268 | 0.9055 | 0.5123 | 0.055* | |
C3 | 0.9327 (5) | 0.8839 (5) | 0.6328 (3) | 0.0492 (11) | |
H3A | 1.0062 | 0.9414 | 0.6273 | 0.059* | |
C4 | 0.8720 (5) | 0.8156 (5) | 0.7087 (3) | 0.0398 (10) | |
H4A | 0.9033 | 0.8261 | 0.7557 | 0.048* | |
C5 | 0.7627 (4) | 0.7302 (4) | 0.7142 (2) | 0.0298 (8) | |
C6 | 0.6858 (4) | 0.5043 (4) | 0.8048 (2) | 0.0310 (8) | |
C7 | 0.7273 (6) | 0.3942 (5) | 0.8770 (2) | 0.0483 (11) | |
H7A | 0.7664 | 0.4199 | 0.9172 | 0.058* | |
C8 | 0.7097 (6) | 0.2475 (6) | 0.8880 (3) | 0.0611 (13) | |
H8A | 0.7353 | 0.1730 | 0.9361 | 0.073* | |
C9 | 0.6535 (6) | 0.2112 (5) | 0.8268 (3) | 0.0534 (12) | |
H9A | 0.6448 | 0.1109 | 0.8324 | 0.064* | |
C10 | 0.6112 (5) | 0.3248 (4) | 0.7584 (2) | 0.0361 (9) | |
H10A | 0.5751 | 0.2998 | 0.7170 | 0.043* | |
C11 | 0.3957 (5) | 0.9296 (4) | 0.7261 (3) | 0.0386 (10) | |
H11A | 0.4421 | 0.9746 | 0.6756 | 0.046* | |
C12 | 0.3421 (6) | 1.0144 (5) | 0.7869 (3) | 0.0523 (12) | |
H12A | 0.3541 | 1.1143 | 0.7780 | 0.063* | |
C13 | 0.2700 (6) | 0.9494 (6) | 0.8616 (3) | 0.0627 (14) | |
H13A | 0.2386 | 1.0025 | 0.9045 | 0.075* | |
C14 | 0.2450 (6) | 0.8062 (6) | 0.8718 (3) | 0.0536 (12) | |
H14A | 0.1921 | 0.7629 | 0.9208 | 0.064* | |
C15 | 0.3007 (5) | 0.7262 (5) | 0.8073 (2) | 0.0332 (9) | |
C16 | 0.2431 (4) | 0.5306 (4) | 0.7528 (2) | 0.0291 (8) | |
C17 | 0.1341 (5) | 0.4417 (4) | 0.7694 (2) | 0.0354 (9) | |
H17A | 0.0857 | 0.4135 | 0.8226 | 0.042* | |
C18 | 0.0986 (5) | 0.3960 (5) | 0.7058 (3) | 0.0406 (10) | |
H18A | 0.0268 | 0.3354 | 0.7155 | 0.049* | |
C19 | 0.1707 (5) | 0.4408 (5) | 0.6279 (2) | 0.0407 (10) | |
H19A | 0.1427 | 0.4166 | 0.5838 | 0.049* | |
C20 | 0.2836 (5) | 0.5212 (4) | 0.6157 (2) | 0.0341 (9) | |
H20A | 0.3346 | 0.5480 | 0.5630 | 0.041* | |
Cl1 | 0.80533 (15) | 0.73567 (13) | 0.97951 (6) | 0.0493 (3) | |
Co1 | 0.51255 (6) | 0.64637 (6) | 0.65952 (3) | 0.02589 (16) | |
N1 | 0.7026 (4) | 0.7245 (3) | 0.64837 (17) | 0.0277 (7) | |
N2 | 0.6196 (4) | 0.4735 (3) | 0.74800 (17) | 0.0272 (7) | |
N3 | 0.3833 (4) | 0.7827 (3) | 0.73715 (18) | 0.0298 (7) | |
N4 | 0.3242 (4) | 0.5633 (3) | 0.67755 (17) | 0.0280 (7) | |
N5 | 0.7146 (4) | 0.6479 (4) | 0.79074 (18) | 0.0332 (7) | |
H5A | 0.7020 | 0.6895 | 0.8322 | 0.040* | |
N6 | 0.2697 (4) | 0.5860 (4) | 0.81533 (18) | 0.0360 (8) | |
H6A | 0.2665 | 0.5275 | 0.8637 | 0.043* | |
N7 | 0.6284 (4) | 0.5224 (4) | 0.57756 (18) | 0.0336 (7) | |
N8 | 0.7596 (4) | 0.4174 (4) | 0.58621 (19) | 0.0354 (8) | |
N9 | 0.8830 (5) | 0.3143 (5) | 0.5897 (2) | 0.0600 (11) | |
N10 | 0.4035 (4) | 0.8227 (4) | 0.57553 (19) | 0.0386 (8) | |
N11 | 0.4306 (4) | 0.8115 (4) | 0.5044 (2) | 0.0378 (8) | |
N12 | 0.4501 (5) | 0.8100 (4) | 0.4356 (2) | 0.0607 (11) | |
O1 | 0.8988 (5) | 0.6877 (6) | 0.9072 (2) | 0.0985 (15) | |
O2 | 0.6778 (7) | 0.8716 (6) | 0.9598 (4) | 0.176 (3) | |
O3 | 0.7394 (6) | 0.6141 (6) | 1.0232 (3) | 0.1150 (16) | |
O4 | 0.9175 (6) | 0.7542 (6) | 1.0247 (3) | 0.1151 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.045 (2) | 0.036 (2) | 0.030 (2) | −0.0189 (19) | 0.0011 (18) | −0.0038 (18) |
C2 | 0.052 (3) | 0.047 (3) | 0.036 (2) | −0.026 (2) | 0.005 (2) | 0.002 (2) |
C3 | 0.054 (3) | 0.047 (3) | 0.055 (3) | −0.033 (2) | −0.006 (2) | −0.001 (2) |
C4 | 0.044 (2) | 0.039 (2) | 0.043 (2) | −0.019 (2) | −0.0093 (19) | −0.007 (2) |
C5 | 0.030 (2) | 0.027 (2) | 0.030 (2) | −0.0081 (16) | 0.0000 (16) | −0.0070 (16) |
C6 | 0.031 (2) | 0.036 (2) | 0.024 (2) | −0.0098 (17) | −0.0032 (16) | −0.0049 (17) |
C7 | 0.064 (3) | 0.055 (3) | 0.031 (2) | −0.026 (2) | −0.017 (2) | 0.002 (2) |
C8 | 0.083 (4) | 0.053 (3) | 0.045 (3) | −0.030 (3) | −0.027 (3) | 0.018 (2) |
C9 | 0.069 (3) | 0.036 (2) | 0.059 (3) | −0.025 (2) | −0.021 (2) | 0.006 (2) |
C10 | 0.041 (2) | 0.030 (2) | 0.040 (2) | −0.0134 (18) | −0.0070 (18) | −0.0062 (18) |
C11 | 0.043 (2) | 0.028 (2) | 0.043 (2) | −0.0080 (18) | −0.0048 (19) | −0.0089 (18) |
C12 | 0.060 (3) | 0.039 (3) | 0.064 (3) | −0.012 (2) | −0.006 (2) | −0.027 (2) |
C13 | 0.075 (4) | 0.062 (3) | 0.060 (3) | −0.019 (3) | 0.007 (3) | −0.042 (3) |
C14 | 0.063 (3) | 0.068 (3) | 0.038 (3) | −0.028 (3) | 0.008 (2) | −0.027 (2) |
C15 | 0.031 (2) | 0.038 (2) | 0.031 (2) | −0.0101 (18) | −0.0011 (16) | −0.0118 (18) |
C16 | 0.027 (2) | 0.029 (2) | 0.030 (2) | −0.0068 (16) | −0.0031 (16) | −0.0062 (16) |
C17 | 0.035 (2) | 0.039 (2) | 0.030 (2) | −0.0141 (18) | 0.0014 (17) | −0.0043 (18) |
C18 | 0.034 (2) | 0.044 (2) | 0.050 (3) | −0.0174 (19) | −0.0017 (19) | −0.016 (2) |
C19 | 0.040 (2) | 0.051 (3) | 0.041 (2) | −0.018 (2) | −0.0056 (19) | −0.021 (2) |
C20 | 0.033 (2) | 0.043 (2) | 0.027 (2) | −0.0112 (18) | −0.0036 (16) | −0.0113 (18) |
Cl1 | 0.0636 (7) | 0.0466 (6) | 0.0366 (6) | −0.0180 (6) | −0.0047 (5) | −0.0065 (5) |
Co1 | 0.0290 (3) | 0.0274 (3) | 0.0211 (3) | −0.0094 (2) | −0.00143 (19) | −0.0051 (2) |
N1 | 0.0306 (17) | 0.0269 (16) | 0.0237 (16) | −0.0093 (13) | −0.0006 (13) | −0.0033 (13) |
N2 | 0.0296 (16) | 0.0265 (16) | 0.0245 (16) | −0.0100 (13) | −0.0058 (13) | 0.0001 (13) |
N3 | 0.0328 (17) | 0.0268 (17) | 0.0292 (17) | −0.0072 (14) | −0.0039 (14) | −0.0075 (14) |
N4 | 0.0287 (17) | 0.0308 (17) | 0.0265 (17) | −0.0098 (13) | −0.0029 (13) | −0.0090 (14) |
N5 | 0.0442 (19) | 0.0375 (18) | 0.0243 (17) | −0.0189 (16) | −0.0020 (14) | −0.0100 (14) |
N6 | 0.048 (2) | 0.043 (2) | 0.0212 (16) | −0.0224 (16) | 0.0007 (14) | −0.0055 (15) |
N7 | 0.0323 (18) | 0.0387 (19) | 0.0275 (17) | −0.0053 (16) | −0.0029 (14) | −0.0116 (15) |
N8 | 0.035 (2) | 0.047 (2) | 0.0335 (19) | −0.0177 (19) | −0.0010 (15) | −0.0197 (16) |
N9 | 0.041 (2) | 0.071 (3) | 0.067 (3) | 0.003 (2) | −0.011 (2) | −0.038 (2) |
N10 | 0.044 (2) | 0.0376 (19) | 0.0293 (19) | −0.0069 (16) | −0.0087 (15) | −0.0030 (15) |
N11 | 0.041 (2) | 0.0298 (18) | 0.037 (2) | −0.0082 (15) | −0.0104 (16) | 0.0021 (16) |
N12 | 0.094 (3) | 0.050 (2) | 0.031 (2) | −0.015 (2) | −0.017 (2) | 0.0002 (18) |
O1 | 0.105 (3) | 0.181 (5) | 0.049 (2) | −0.086 (3) | 0.018 (2) | −0.056 (3) |
O2 | 0.134 (5) | 0.077 (3) | 0.257 (8) | 0.016 (3) | −0.055 (5) | 0.024 (4) |
O3 | 0.149 (4) | 0.108 (3) | 0.081 (3) | −0.073 (3) | 0.009 (3) | 0.022 (3) |
O4 | 0.126 (4) | 0.172 (5) | 0.087 (3) | −0.064 (3) | −0.011 (3) | −0.072 (3) |
Geometric parameters (Å, º) top
C1—C2 | 1.354 (5) | C16—N4 | 1.346 (4) |
C1—N1 | 1.359 (4) | C16—N6 | 1.380 (4) |
C2—C3 | 1.387 (6) | C16—C17 | 1.388 (5) |
C3—C4 | 1.370 (6) | C17—C18 | 1.378 (5) |
C4—C5 | 1.391 (5) | C18—C19 | 1.373 (5) |
C5—N1 | 1.342 (4) | C19—C20 | 1.364 (5) |
C5—N5 | 1.391 (4) | C20—N4 | 1.352 (4) |
C6—N2 | 1.343 (4) | Cl1—O2 | 1.358 (4) |
C6—N5 | 1.379 (5) | Cl1—O3 | 1.402 (4) |
C6—C7 | 1.392 (5) | Cl1—O4 | 1.418 (4) |
C7—C8 | 1.370 (6) | Cl1—O1 | 1.418 (3) |
C8—C9 | 1.385 (6) | Co1—N7 | 1.934 (3) |
C9—C10 | 1.360 (5) | Co1—N10 | 1.952 (3) |
C10—N2 | 1.358 (4) | Co1—N1 | 1.953 (3) |
C11—N3 | 1.354 (5) | Co1—N4 | 1.953 (3) |
C11—C12 | 1.371 (5) | Co1—N3 | 1.970 (3) |
C12—C13 | 1.383 (7) | Co1—N2 | 1.980 (3) |
C13—C14 | 1.368 (6) | N7—N8 | 1.206 (4) |
C14—C15 | 1.397 (5) | N8—N9 | 1.149 (4) |
C15—N3 | 1.342 (5) | N10—N11 | 1.213 (4) |
C15—N6 | 1.373 (5) | N11—N12 | 1.154 (5) |
| | | |
C2—C1—N1 | 122.4 (4) | N7—Co1—N10 | 90.59 (13) |
C1—C2—C3 | 119.9 (4) | N7—Co1—N1 | 90.33 (13) |
C4—C3—C2 | 118.5 (4) | N10—Co1—N1 | 92.46 (13) |
C3—C4—C5 | 119.0 (4) | N7—Co1—N4 | 91.45 (13) |
N1—C5—N5 | 119.0 (3) | N10—Co1—N4 | 90.41 (13) |
N1—C5—C4 | 122.2 (3) | N1—Co1—N4 | 176.60 (12) |
N5—C5—C4 | 118.7 (3) | N7—Co1—N3 | 175.82 (13) |
N2—C6—N5 | 119.1 (3) | N10—Co1—N3 | 85.42 (13) |
N2—C6—C7 | 121.5 (4) | N1—Co1—N3 | 91.08 (12) |
N5—C6—C7 | 119.3 (3) | N4—Co1—N3 | 87.34 (12) |
C8—C7—C6 | 119.0 (4) | N7—Co1—N2 | 91.77 (13) |
C7—C8—C9 | 119.5 (4) | N10—Co1—N2 | 177.61 (13) |
C10—C9—C8 | 118.8 (4) | N1—Co1—N2 | 87.10 (12) |
N2—C10—C9 | 122.7 (4) | N4—Co1—N2 | 89.95 (12) |
N3—C11—C12 | 122.2 (4) | N3—Co1—N2 | 92.23 (12) |
C11—C12—C13 | 119.1 (4) | C5—N1—C1 | 117.6 (3) |
C14—C13—C12 | 119.5 (4) | C5—N1—Co1 | 121.3 (2) |
C13—C14—C15 | 118.7 (4) | C1—N1—Co1 | 120.8 (2) |
N3—C15—N6 | 118.7 (3) | C6—N2—C10 | 118.1 (3) |
N3—C15—C14 | 122.0 (4) | C6—N2—Co1 | 120.6 (2) |
N6—C15—C14 | 119.3 (4) | C10—N2—Co1 | 120.9 (2) |
N4—C16—N6 | 119.3 (3) | C15—N3—C11 | 118.1 (3) |
N4—C16—C17 | 121.8 (3) | C15—N3—Co1 | 121.4 (2) |
N6—C16—C17 | 118.9 (3) | C11—N3—Co1 | 119.9 (3) |
C18—C17—C16 | 118.8 (4) | C16—N4—C20 | 118.0 (3) |
C19—C18—C17 | 119.2 (4) | C16—N4—Co1 | 121.4 (2) |
C20—C19—C18 | 119.4 (4) | C20—N4—Co1 | 120.2 (2) |
N4—C20—C19 | 122.4 (4) | C6—N5—C5 | 124.6 (3) |
O2—Cl1—O3 | 109.5 (4) | C15—N6—C16 | 125.8 (3) |
O2—Cl1—O4 | 112.3 (4) | N8—N7—Co1 | 122.8 (2) |
O3—Cl1—O4 | 110.7 (3) | N9—N8—N7 | 175.1 (4) |
O2—Cl1—O1 | 109.8 (4) | N11—N10—Co1 | 120.3 (3) |
O3—Cl1—O1 | 106.8 (3) | N12—N11—N10 | 175.9 (4) |
O4—Cl1—O1 | 107.7 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O1 | 0.86 | 2.30 | 2.922 (5) | 130 |
N6—H6A···O3i | 0.86 | 2.03 | 2.888 (5) | 179 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | [Co(C10H9N3)2(N3)2]ClO4 |
Mr | 584.84 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.554 (3), 9.201 (3), 17.036 (5) |
α, β, γ (°) | 74.903 (5), 78.792 (5), 69.739 (5) |
V (Å3) | 1206.5 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] |
Tmin, Tmax | 0.810, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5057, 4235, 3065 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.121, 1.01 |
No. of reflections | 4235 |
No. of parameters | 343 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.33 |
Selected geometric parameters (Å, º) topCo1—N7 | 1.934 (3) | Co1—N2 | 1.980 (3) |
Co1—N10 | 1.952 (3) | N7—N8 | 1.206 (4) |
Co1—N1 | 1.953 (3) | N8—N9 | 1.149 (4) |
Co1—N4 | 1.953 (3) | N10—N11 | 1.213 (4) |
Co1—N3 | 1.970 (3) | N11—N12 | 1.154 (5) |
| | | |
N7—Co1—N10 | 90.59 (13) | N4—Co1—N3 | 87.34 (12) |
N7—Co1—N1 | 90.33 (13) | N7—Co1—N2 | 91.77 (13) |
N10—Co1—N1 | 92.46 (13) | N10—Co1—N2 | 177.61 (13) |
N7—Co1—N4 | 91.45 (13) | N1—Co1—N2 | 87.10 (12) |
N10—Co1—N4 | 90.41 (13) | N4—Co1—N2 | 89.95 (12) |
N1—Co1—N4 | 176.60 (12) | N3—Co1—N2 | 92.23 (12) |
N7—Co1—N3 | 175.82 (13) | N8—N7—Co1 | 122.8 (2) |
N10—Co1—N3 | 85.42 (13) | N11—N10—Co1 | 120.3 (3) |
N1—Co1—N3 | 91.08 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···O1 | .860 | 2.295 | 2.922 (5) | 129.9 |
N6—H6A···O3i | .860 | 2.028 | 2.888 (5) | 179.0 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Ligands containing aromatic nitrogen heterocycles play a leading role in the molecular self-assembling processes that lead to macromolecules architectures (Jones, 1998; Fujita, 1998). In recent years, bis(2-pyridyl)amine has attracted great interest in the formation of directly bonded linear chains of metal centers (Cotton et al., 1997, 1998), and three different coordination modes were found for this feasible ligand (see Scheme below). In order to systematically study the coordination behavior of this ligand, we report herein the crystal structure of the first CoIII complex of bis(2-pyridyl)amine with azide coligands, namely diazido[bis(2-pyridyl)amine-N,N']cobalt(III) perchlorate, (I).
The structure of (I) comprises a discrete [Co(C10H9N3)2(N3)2]+ cation and a ClO4- anion. The central CoIII ion is six-coordinated by four N-donors of the pyridine rings, and two terminal N-donors of the azide anions, as shown in Fig. 1. In the complex cation, the CoIII center lies on the least-squares plane defined by N1, N3, N4 and N7, which deviates by only 0.0087 (4) Å from that plane. All the bond angles within the plane are very close to 90° (Table 1), and the sum of these bond angles is 360.2°. The N2—Co1—N10 bond angle deviates from linearity (180°) by only 2.39° in this complex, which can be defined as the apex of the octahedron. The six Co—N bond distances are in the range of 1.934 (3)–1.980 (3) Å (the mean bond length is 1.957 Å).
The bidentate ligands chelate CoIII atom to form two six-membered coordination rings N1—C5—N5—C6—N2—Co1 and N3—C15—N6—C16—N4—Co1. The pyridine rings in the same ligand are in normal trans–trans mode (Gornitzka & Stalke, 1998) and the dihedral angles are 39.9 (2) and 35.5 (3)°, respectively. Both azide anions are almost linear, with bond angles of 175.1 (4) and 175.9 (4)° for N9—N8—N7 and N12—N11—N10, respectively. The N—N bond lengths in the azide anions are approximately equal to each other, and the longer bonds involve the N atom linking to the metal center. The amino groups of the ligand form N—H···O hydrogen bonds with perchlorate anions, as shown in Fig. 2 (Table 2).