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The crystal structure of the title compound, [CoCl-(C16H26N6)]ClO4, consists of discrete [CoCl­(C16­H26N6)]+ cations and perchlorate anions. The five-coordinate CoII atom has four nitro­gen donors from the new mesocyclic ligand 1,5-bis(1-methyl-1H-­imidazol-2-ylmethyl)-1,5-di­aza­cyclo­octane [Co—N 2.046 (3)–2.214 (4) Å], and a chloride anion at the apical site [Co—Cl 2.3184 (13) Å]. The coordination geometry of the complex is essentially square pyramidal. The mesocyclic ligand takes a boat–chair configuration and the two imidazole pendants are not coplanar. The dihedral angle between the two imidazole planes is 15.97°. An H atom from the 1,5-diaza­cyclo­octane group effectively blocks the axial coordination site opposite the Cl ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004789/da1118sup1.cif
Contains datablocks default, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004789/da1118Isup2.hkl
Contains datablock I

CCDC reference: 147613

Comment top

1,5-Diazacyclooctane (DACO) derivatives bearing two additional functional donor pendants can strongly coordinate to transitional metal centers, forming square-pyramidal five-coordinate or square-planar four-coordinate complexes (Grapperhous & Darensbourg, 1998; Nielson et al., 1971; Bu et al., 1999).

The four donor atoms of such tetradentate ligands coordinate to the central metal ions nearly in a plane and the DACO backbone usually takes a boat-chair configuration. This configuration will force a portion of the chelate framework across to the axial coordination position, and will sterically restrict further axial coordination to the metal center. Therefore, such DACO derivatives can be used as very good ligands for the construction of metal complexes with square-planar or square-pyramidal configuration. The interesting chemistry of such DACO derivatives prompted us to create more of such ligands by modifying DACO with heterocyclic donor pendants to obtain new complexes with functional properties. We synthesized a new mesocyclic ligand functionalized by two imidazole donor pendants, 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane and its cobalt(II) complex, [Co(C16H26N6)Cl]ClO4, (I). We report herein the crystal structure of this new complex. \sch

The structure of (I) comprises discrete [CoCl(C16H26N6)]+ cations and perchlorate anions (Fig.1). In the complex cation, the CoII atom is five-coordinate. 1,5-bis(N-1-methylimidazol-2-ylmethyl)-1,5-diazacyclooctane acts as a tetradentate ligand, through one pair of nitrogen donors of the mesoocyclic ring and the two N atoms of the imidazole pendants. The coordination geometry about the CoII atom can be described as square pyramidal. The four nitrogen donors of the ligand coordinate to the central CoII in one plane, with a chloride anion occupying an apical position. The τ value used to describe the degree of trigonal distortion is 0.006 (Addison et al., 1984), i.e. nearly zero, indicating that the distortion is very small. The cobalt atom is above the mean plane formed by atoms N1, N2, N3, and N5 by 0.549 Å towards the apical Cl ligand. The two imidazole pendants are not coplanar, their planes forming an angle of 15.97°.

The six-membered CoNCH2CH2CH2N rings in [Co(C16H26N6)Cl]ClO4 adopt chair/boat configurations. The boat-form ring causes one H atom (H5B on C5) to lie about 2.509 Å from the metal, at the axial position. Thus the cobalt atom is well shielded from axial interactions opposite the Cl ligand. All of the Co—N and the Co—Cl distances are normal. The conformation of the ligand restricts the placement of the N atoms in the coordination sphere, so the N1—Co1—N2 angle is reduced to 82.41 (14)°, whereas the N3—Co1—N5 angle is 103.38 (14)°.

Experimental top

The ligand 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane dihydrochloride was prepared by the reaction of 1,5-diazacyclooctane hydrobromide and 1-methyl-2-chloromethylimidazole hydrochloride in ethanol solution in the presence of KOH (Buhle et al., 1943; Billman et al., 1962) and the details will be published elsewhere.

A mixture of Co(ClO4)2·6H2O(370 mg, 1 mmol) and 1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane hydrochloride (340 mg, 1 mmol) was dissolved in methanol (30 ml, room temperature). The ligand was neutralized by slow addition of a KOH-methanol solution to the above mixture, and the resulting solution was allowed to stand for ca 7 days. Purple block-shaped crystals were deposited slowly upon evaporation of the solvent. FT—IR data (KBr pellet, cm-1): 3127(w), 2908(w), 1628(m), 1551(w), 1501(m), 1453(m), 1082(s), 762 (m), 624(m).

Refinement top

The structure was solved by direct and difference Fourier methods and refined by full-matrix least-squares methods.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. View of the title complex drawn with 30% probability ellipsoids.
Chloro-(1,5-bis(N-1-methylimidazole-2-methyl)-1,5-diazacyclooctane) cobalt(II) perchlorate top
Crystal data top
[CoCl(C16H26N6)]ClO4Z = 2
Mr = 496.26F(000) = 514
Triclinic, P1Dx = 1.576 Mg m3
a = 7.5865 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.8102 (14) ÅCell parameters from 2632 reflections
c = 12.2307 (15) Åθ = 1.7–25.0°
α = 78.612 (3)°µ = 1.11 mm1
β = 84.519 (2)°T = 293 K
γ = 77.170 (2)°Rectangular, purple
V = 1045.9 (2) Å30.25 × 0.20 × 0.15 mm
Data collection top
Bruker SMART 1000
diffractometer
2856 reflections with I > 2σ(I)
ω scansRint = 0.048
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
θmax = 25.0°
Tmin = 0.732, Tmax = 0.808h = 89
4361 measured reflectionsk = 1411
3638 independent reflectionsl = 1114
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.064Calc. w = 1/[σ2(Fo2) + (0.1P)2] P = (Fo2 + 2Fc2)/3
wR(F2) = 0.163(Δ/σ)max = 0.012
S = 1.18Δρmax = 0.87 e Å3
3638 reflectionsΔρmin = 0.73 e Å3
263 parameters
Crystal data top
[CoCl(C16H26N6)]ClO4γ = 77.170 (2)°
Mr = 496.26V = 1045.9 (2) Å3
Triclinic, P1Z = 2
a = 7.5865 (9) ÅMo Kα radiation
b = 11.8102 (14) ŵ = 1.11 mm1
c = 12.2307 (15) ÅT = 293 K
α = 78.612 (3)°0.25 × 0.20 × 0.15 mm
β = 84.519 (2)°
Data collection top
Bruker SMART 1000
diffractometer
3638 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
2856 reflections with I > 2σ(I)
Tmin = 0.732, Tmax = 0.808Rint = 0.048
4361 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.064263 parameters
wR(F2) = 0.163H-atom parameters constrained
S = 1.18Δρmax = 0.87 e Å3
3638 reflectionsΔρmin = 0.73 e Å3
Special details top

Refinement. Full-MATRIX

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.25349 (7)0.30123 (5)0.75968 (5)0.0393 (3)
Cl10.50300 (16)0.30680 (12)0.85261 (11)0.0596 (4)
Cl20.07121 (17)0.15971 (10)0.68235 (10)0.0529 (3)
O10.2087 (8)0.1934 (5)0.7619 (6)0.134 (2)
O20.1347 (6)0.0486 (3)0.6155 (3)0.0740 (11)
O30.0724 (9)0.1545 (5)0.7456 (5)0.131 (2)
O40.0093 (11)0.2487 (4)0.6187 (4)0.133 (3)
N10.1356 (5)0.1650 (3)0.8758 (3)0.0428 (9)
N20.3591 (5)0.1558 (3)0.6716 (3)0.0443 (9)
N30.0334 (5)0.4032 (3)0.8285 (3)0.0424 (9)
N40.1669 (5)0.4201 (3)0.9686 (3)0.0434 (9)
N50.2783 (5)0.3932 (3)0.5981 (3)0.0457 (9)
N60.4029 (5)0.3888 (4)0.4305 (3)0.0537 (10)
C10.2750 (7)0.0596 (4)0.9201 (4)0.0559 (12)
C20.3653 (7)0.0126 (4)0.8352 (4)0.0577 (13)
C30.4724 (7)0.0502 (4)0.7399 (4)0.0586 (13)
C40.2019 (7)0.1249 (4)0.6286 (4)0.0519 (12)
C50.0223 (6)0.1712 (4)0.6860 (4)0.0519 (12)
C60.0009 (6)0.1341 (4)0.8119 (4)0.0490 (11)
C70.0466 (7)0.2226 (4)0.9681 (4)0.0529 (12)
C80.0327 (6)0.3476 (4)0.9235 (3)0.0419 (10)
C90.0657 (6)0.5176 (4)0.8143 (4)0.0462 (11)
C100.1880 (6)0.5286 (4)0.9010 (4)0.0480 (11)
C110.2754 (7)0.3891 (5)1.0718 (4)0.0603 (13)
C120.4744 (7)0.2029 (5)0.5775 (4)0.0597 (13)
C130.3861 (6)0.3263 (4)0.5338 (4)0.0457 (11)
C140.2248 (6)0.5012 (4)0.5333 (4)0.0509 (11)
C150.3009 (7)0.5002 (5)0.4297 (4)0.0535 (12)
C160.5132 (8)0.3461 (6)0.3360 (4)0.0721 (16)
H1A0.21830.00960.97920.067*
H1B0.36690.08570.95290.067*
H2A0.27330.04010.80380.069*
H2B0.44650.08170.87300.069*
H3A0.56800.07500.77050.070*
H3B0.52910.00510.69150.070*
H4A0.22070.03970.63810.062*
H4B0.19700.15660.54920.062*
H5A0.07130.14730.65250.062*
H5B0.00030.25680.66910.062*
H6A0.12120.17160.83670.059*
H6B0.00760.04940.82950.059*
H7A0.13390.21811.02260.064*
H7B0.04790.18271.00480.064*
H9A0.05060.57750.75440.055*
H10A0.27060.59680.91260.058*
H11A0.23260.30761.10390.090*
H11B0.40010.40151.05510.090*
H11C0.26440.43791.12390.090*
H12A0.48900.15580.51930.072*
H12B0.59320.20000.60240.072*
H14A0.14740.56560.55710.061*
H15A0.28700.56270.36950.064*
H16A0.57180.26500.35880.108*
H16B0.60300.39290.31150.108*
H16C0.43700.35250.27580.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0370 (4)0.0447 (4)0.0382 (4)0.0081 (3)0.0010 (2)0.0135 (3)
Cl10.0443 (7)0.0732 (8)0.0723 (8)0.0126 (6)0.0171 (6)0.0321 (7)
Cl20.0602 (7)0.0440 (6)0.0569 (7)0.0065 (5)0.0120 (6)0.0155 (5)
O10.103 (4)0.088 (4)0.176 (6)0.008 (3)0.038 (4)0.023 (4)
O20.089 (3)0.050 (2)0.076 (3)0.005 (2)0.004 (2)0.0053 (19)
O30.153 (5)0.114 (4)0.140 (5)0.038 (4)0.080 (4)0.012 (4)
O40.244 (7)0.066 (3)0.070 (3)0.028 (4)0.020 (4)0.027 (2)
N10.048 (2)0.039 (2)0.0403 (19)0.0057 (16)0.0040 (16)0.0067 (16)
N20.043 (2)0.048 (2)0.0403 (19)0.0007 (16)0.0036 (16)0.0128 (17)
N30.046 (2)0.043 (2)0.0367 (19)0.0038 (16)0.0038 (16)0.0122 (16)
N40.0374 (19)0.057 (2)0.040 (2)0.0107 (17)0.0036 (16)0.0185 (18)
N50.041 (2)0.053 (2)0.042 (2)0.0084 (17)0.0049 (16)0.0126 (18)
N60.043 (2)0.080 (3)0.042 (2)0.019 (2)0.0048 (17)0.017 (2)
C10.068 (3)0.048 (3)0.050 (3)0.010 (2)0.014 (2)0.000 (2)
C20.060 (3)0.041 (3)0.066 (3)0.005 (2)0.017 (3)0.005 (2)
C30.047 (3)0.054 (3)0.068 (3)0.011 (2)0.008 (2)0.019 (3)
C40.059 (3)0.055 (3)0.045 (3)0.007 (2)0.009 (2)0.019 (2)
C50.049 (3)0.049 (3)0.061 (3)0.010 (2)0.022 (2)0.012 (2)
C60.044 (2)0.041 (2)0.064 (3)0.0085 (19)0.002 (2)0.013 (2)
C70.065 (3)0.054 (3)0.039 (2)0.014 (2)0.006 (2)0.009 (2)
C80.043 (2)0.050 (3)0.036 (2)0.014 (2)0.0003 (19)0.0133 (19)
C90.046 (2)0.042 (2)0.051 (3)0.008 (2)0.006 (2)0.009 (2)
C100.041 (2)0.046 (3)0.059 (3)0.003 (2)0.001 (2)0.021 (2)
C110.052 (3)0.083 (4)0.048 (3)0.019 (3)0.016 (2)0.021 (3)
C120.052 (3)0.066 (3)0.057 (3)0.002 (2)0.014 (2)0.019 (3)
C130.039 (2)0.059 (3)0.041 (2)0.012 (2)0.0017 (19)0.012 (2)
C140.047 (3)0.054 (3)0.051 (3)0.009 (2)0.001 (2)0.011 (2)
C150.049 (3)0.063 (3)0.047 (3)0.013 (2)0.006 (2)0.005 (2)
C160.066 (4)0.108 (5)0.045 (3)0.019 (3)0.016 (3)0.028 (3)
Geometric parameters (Å, º) top
Co1—N32.046 (3)C8—N41.329 (5)
Co1—N52.071 (4)N3—C91.379 (5)
Co1—N22.169 (4)C9—C101.347 (7)
Co1—N12.214 (4)C10—N41.367 (6)
Co1—Cl12.3184 (13)N4—C111.469 (5)
N1—C71.465 (6)C12—C131.479 (7)
N1—C11.490 (6)C13—N51.322 (6)
N1—C61.500 (6)C13—N61.341 (6)
C1—C21.492 (7)N5—C141.361 (6)
C2—C31.522 (7)C14—C151.342 (7)
C3—N21.497 (6)C15—N61.369 (7)
N2—C121.473 (6)N6—C161.466 (6)
N2—C41.490 (6)Cl2—O41.402 (5)
C4—C51.512 (7)Cl2—O21.411 (4)
C5—C61.521 (7)Cl2—O31.414 (6)
C7—C81.480 (6)Cl2—O11.425 (5)
C8—N31.329 (5)
N3—Co1—N5103.38 (14)N3—C8—N4110.8 (4)
N3—Co1—N2148.09 (15)N3—C8—C7120.9 (4)
N5—Co1—N279.71 (15)N4—C8—C7128.3 (4)
N3—Co1—N178.80 (14)C8—N3—C9105.7 (4)
N5—Co1—N1147.75 (15)C8—N3—Co1113.3 (3)
N2—Co1—N182.41 (14)C9—N3—Co1140.8 (3)
N3—Co1—Cl1107.04 (11)C10—C9—N3109.1 (4)
N5—Co1—Cl1107.92 (11)C9—C10—N4106.6 (4)
N2—Co1—Cl1101.91 (10)C8—N4—C10107.8 (4)
N1—Co1—Cl1101.89 (10)C8—N4—C11126.3 (4)
C7—N1—C1109.5 (4)C10—N4—C11125.9 (4)
C7—N1—C6110.8 (4)N2—C12—C13108.1 (4)
C1—N1—C6112.2 (4)N5—C13—N6109.8 (4)
C7—N1—Co1105.4 (3)N5—C13—C12121.9 (4)
C1—N1—Co1112.7 (3)N6—C13—C12128.3 (4)
C6—N1—Co1106.1 (3)C13—N5—C14106.8 (4)
N1—C1—C2114.7 (4)C13—N5—Co1111.1 (3)
C1—C2—C3115.6 (4)C14—N5—Co1142.1 (3)
N2—C3—C2113.4 (4)C15—C14—N5109.4 (4)
C12—N2—C4109.8 (4)C14—C15—N6106.3 (4)
C12—N2—C3108.2 (4)C13—N6—C15107.7 (4)
C4—N2—C3111.5 (4)C13—N6—C16126.2 (5)
C12—N2—Co1105.4 (3)C15—N6—C16126.1 (5)
C4—N2—Co1107.4 (3)O4—Cl2—O2112.3 (3)
C3—N2—Co1114.4 (3)O4—Cl2—O3108.2 (4)
N2—C4—C5113.6 (4)O2—Cl2—O3110.4 (3)
C4—C5—C6118.2 (4)O4—Cl2—O1108.9 (4)
N1—C6—C5114.0 (4)O2—Cl2—O1111.1 (3)
N1—C7—C8109.1 (4)O3—Cl2—O1105.7 (4)

Experimental details

Crystal data
Chemical formula[CoCl(C16H26N6)]ClO4
Mr496.26
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.5865 (9), 11.8102 (14), 12.2307 (15)
α, β, γ (°)78.612 (3), 84.519 (2), 77.170 (2)
V3)1045.9 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.11
Crystal size (mm)0.25 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART 1000
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.732, 0.808
No. of measured, independent and
observed [I > 2σ(I)] reflections
4361, 3638, 2856
Rint0.048
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.163, 1.18
No. of reflections3638
No. of parameters263
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.87, 0.73

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Selected geometric parameters (Å, º) top
Co1—N32.046 (3)Co1—N12.214 (4)
Co1—N52.071 (4)Co1—Cl12.3184 (13)
Co1—N22.169 (4)
N3—Co1—N5103.38 (14)N2—Co1—N182.41 (14)
N3—Co1—N2148.09 (15)N3—Co1—Cl1107.04 (11)
N5—Co1—N279.71 (15)N5—Co1—Cl1107.92 (11)
N3—Co1—N178.80 (14)N2—Co1—Cl1101.91 (10)
N5—Co1—N1147.75 (15)N1—Co1—Cl1101.89 (10)
 

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