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In the title compound, trans-[Co(NO2)2(cyclam)]ClO4, (I), where cyclam is 1,4,8,11-tetra­aza­cyclo­tetra­decane (C10H24N4), the CoIII complex has a distorted octahedral coordination. The O atoms of each nitro ligand are disordered over two sites with 65:35% occupancy.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018778/cf6015sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018778/cf6015Isup2.hkl
Contains datablock I

CCDC reference: 155835

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.010 Å
  • Disorder in main residue
  • R factor = 0.035
  • wR factor = 0.108
  • Data-to-parameter ratio = 9.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_301 Alert C Main residue disorder ........................ 16.00 Perc. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 2554 Count of symmetry unique reflns 2329 Completeness (_total/calc) 109.66% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 225 Fraction of Friedel pairs measured 0.097 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The Co—NO2 bond distances are 1.962 (5) and 1.968 (5) Å. The Co—N bond distances of the cyclam are 1.974 (5)–1.986 (4) Å.

Experimental top

The title compound, (I), was obtained as a by-product in the synthesis of trans-[Co(cyclam)(NCS)(NO2)]ClO4 from the reaction of trans-[Co(cyclam)(NCS)Cl]ClO4 (0.5 mmol) with NaNO2 (1.5 mmol) in 30 ml 0.03 M HNO3. Crystals of (I) were grown from a dimethyl sulfoxide solution by a diffusion of diethyl ether vapour.

Refinement top

X-ray intensities were measured for ±h,+k,±l (θ< 15°) and -h,+k,+l (15 <θ < 27.5°). The O atoms of the nitro ligands show positional disorder (atoms O3–O10), suggesting that there are two possible orientations with 65:35% occupancy for each NO2 group. All H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom).

Computing details top

Data collection: WinAFC (Rigaku Corporation, 1999); cell refinement: WinAFC; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. The structure of the complex cation in (I). Displacement ellipsoids are plotted at the 50% probability level. The disordered nitro O atoms with 35% occupancy have been omitted for clarity.
(I) top
Crystal data top
[Co(NO2)2(C10H24N4)]ClO4Dx = 1.707 Mg m3
Mr = 450.72Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 25 reflections
a = 13.299 (3) Åθ = 10.3–13.9°
b = 19.820 (1) ŵ = 1.19 mm1
c = 6.6531 (7) ÅT = 297 K
V = 1753.7 (5) Å3Plate, orange
Z = 40.40 × 0.25 × 0.05 mm
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.024
θ–2θ scansθmax = 27.5°, θmin = 2.5°
Absorption correction: integration
(Coppens et al., 1965)
h = 178
Tmin = 0.752, Tmax = 0.942k = 025
3312 measured reflectionsl = 48
2554 independent reflections3 standard reflections every 150 reflections
2245 reflections with I > 2σ(I)' intensity decay: none
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.041P)2 + 3.4475P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.035(Δ/σ)max = 0.001
wR(F2) = 0.108Δρmax = 0.41 e Å3
S = 1.08Δρmin = 0.55 e Å3
2554 reflectionsAbsolute structure: (Flack, 1983), 225 Friedel pairs
271 parametersAbsolute structure parameter: 0.05 (4)
H-atom parameters constrained
Crystal data top
[Co(NO2)2(C10H24N4)]ClO4V = 1753.7 (5) Å3
Mr = 450.72Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 13.299 (3) ŵ = 1.19 mm1
b = 19.820 (1) ÅT = 297 K
c = 6.6531 (7) Å0.40 × 0.25 × 0.05 mm
Data collection top
Rigaku AFC-7R
diffractometer
2245 reflections with I > 2σ(I)'
Absorption correction: integration
(Coppens et al., 1965)
Rint = 0.024
Tmin = 0.752, Tmax = 0.9423 standard reflections every 150 reflections
3312 measured reflections intensity decay: none
2554 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.41 e Å3
S = 1.08Δρmin = 0.55 e Å3
2554 reflectionsAbsolute structure: (Flack, 1983), 225 Friedel pairs
271 parametersAbsolute structure parameter: 0.05 (4)
Special details top

Refinement. Refinement was based on F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F2, and conventional R-factor (R) was calculated on F, with F set to zero for negative F2. The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.02236 (4)0.12630 (3)0.22719 (9)0.0289 (2)
Cl20.0420 (1)0.11990 (8)0.5995 (2)0.0561 (4)
O30.0563 (7)0.0715 (6)0.601 (1)0.091 (3)0.65
O40.1886 (7)0.1029 (7)0.484 (2)0.111 (4)0.65
O50.115 (2)0.1351 (10)0.602 (2)0.094 (6)0.35
O60.122 (2)0.0389 (7)0.490 (3)0.083 (5)0.35
O70.0728 (8)0.2147 (4)0.035 (2)0.082 (3)0.65
O80.0746 (9)0.1180 (5)0.141 (1)0.086 (3)0.65
O90.136 (1)0.139 (1)0.063 (3)0.097 (8)0.35
O100.012 (2)0.1886 (10)0.141 (2)0.094 (6)0.35
O110.0280 (6)0.1258 (3)0.7629 (9)0.121 (2)
O120.1098 (5)0.1723 (4)0.613 (1)0.147 (3)
O130.0134 (4)0.1254 (3)0.4198 (8)0.098 (2)
O140.0907 (5)0.0566 (3)0.6113 (9)0.091 (2)
N150.0993 (4)0.0967 (3)0.4640 (7)0.040 (1)
N160.0528 (4)0.1568 (2)0.0097 (7)0.038 (1)
N170.0690 (3)0.1740 (2)0.4135 (7)0.036 (1)
N180.0546 (3)0.0406 (2)0.2455 (7)0.0389 (9)
N190.1121 (4)0.0776 (3)0.0406 (7)0.042 (1)
N200.0977 (3)0.2124 (2)0.2146 (7)0.0389 (10)
C210.1780 (5)0.1618 (4)0.398 (1)0.055 (2)
C220.2027 (5)0.0879 (4)0.423 (1)0.055 (2)
C230.1662 (4)0.0437 (3)0.257 (1)0.056 (2)
C240.0189 (6)0.0057 (3)0.085 (1)0.057 (2)
C250.0924 (6)0.0033 (3)0.064 (1)0.061 (2)
C260.2200 (6)0.0942 (4)0.031 (1)0.064 (2)
C270.2376 (5)0.1691 (4)0.008 (1)0.068 (2)
C280.2083 (4)0.2118 (4)0.184 (1)0.058 (2)
C290.0667 (5)0.2544 (3)0.389 (1)0.050 (2)
C300.0446 (5)0.2484 (3)0.409 (1)0.053 (2)
H170.05050.15900.54410.0438*
H180.03380.02040.36820.0467*
H190.08720.08840.08940.0508*
H200.07160.23510.10030.0466*
H21A0.20080.17650.27040.0661*
H21B0.21130.18670.50060.0661*
H22A0.27380.08350.43110.0659*
H22B0.17330.07260.54500.0659*
H23A0.19130.06060.13320.0670*
H23B0.19120.00070.27810.0670*
H24A0.05130.00490.03800.0683*
H24B0.03350.05100.12130.0683*
H25A0.11580.02020.05160.0736*
H25B0.12580.01330.17970.0736*
H26A0.24910.07150.08010.0773*
H26B0.25140.07940.15180.0773*
H27A0.20020.18410.10480.0813*
H27B0.30730.17590.01580.0813*
H28A0.23070.25670.16160.0698*
H28B0.23960.19450.30170.0698*
H29A0.08480.30020.36650.0599*
H29B0.09870.23870.50790.0599*
H30A0.07700.26930.29850.0632*
H30B0.06630.26920.53070.0632*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0312 (3)0.0309 (3)0.0246 (3)0.0012 (3)0.0035 (3)0.0001 (3)
Cl20.0669 (10)0.0504 (8)0.0509 (8)0.0029 (8)0.0089 (7)0.0043 (8)
O30.090 (7)0.141 (9)0.042 (4)0.036 (7)0.019 (5)0.037 (5)
O40.060 (6)0.19 (1)0.085 (7)0.000 (7)0.027 (5)0.063 (8)
O50.12 (1)0.11 (1)0.049 (8)0.01 (1)0.049 (10)0.026 (10)
O60.12 (2)0.046 (8)0.08 (1)0.029 (10)0.05 (1)0.001 (8)
O70.110 (8)0.053 (5)0.084 (7)0.031 (5)0.051 (6)0.003 (5)
O80.147 (10)0.064 (5)0.048 (5)0.003 (7)0.045 (6)0.003 (4)
O90.07 (1)0.16 (2)0.06 (1)0.03 (1)0.019 (9)0.05 (1)
O100.12 (2)0.11 (1)0.052 (8)0.05 (1)0.03 (1)0.040 (9)
O110.206 (7)0.075 (3)0.082 (4)0.036 (5)0.052 (5)0.001 (4)
O120.107 (5)0.114 (5)0.222 (9)0.049 (4)0.058 (6)0.062 (6)
O130.106 (4)0.120 (5)0.069 (3)0.027 (5)0.028 (3)0.000 (3)
O140.109 (4)0.074 (3)0.091 (4)0.037 (3)0.009 (4)0.005 (3)
N150.044 (3)0.042 (3)0.034 (2)0.001 (2)0.010 (2)0.001 (2)
N160.039 (2)0.044 (3)0.030 (2)0.000 (2)0.005 (2)0.003 (2)
N170.037 (2)0.039 (2)0.033 (2)0.003 (2)0.002 (2)0.002 (2)
N180.047 (2)0.040 (2)0.030 (2)0.005 (2)0.009 (2)0.000 (2)
N190.042 (3)0.052 (3)0.033 (2)0.013 (2)0.002 (2)0.001 (2)
N200.034 (2)0.048 (2)0.034 (2)0.005 (2)0.005 (2)0.007 (2)
C210.034 (3)0.078 (4)0.053 (4)0.006 (3)0.008 (3)0.005 (4)
C220.036 (3)0.076 (4)0.053 (4)0.012 (3)0.002 (3)0.000 (4)
C230.050 (3)0.069 (4)0.048 (4)0.023 (3)0.010 (4)0.004 (4)
C240.084 (4)0.036 (3)0.051 (3)0.004 (3)0.010 (4)0.009 (3)
C250.085 (5)0.042 (3)0.056 (4)0.022 (3)0.003 (4)0.011 (3)
C260.043 (4)0.084 (5)0.067 (5)0.021 (4)0.009 (3)0.003 (4)
C270.039 (3)0.087 (5)0.077 (5)0.001 (4)0.016 (4)0.007 (5)
C280.038 (3)0.075 (4)0.061 (4)0.017 (3)0.005 (3)0.009 (4)
C290.061 (4)0.035 (3)0.054 (4)0.012 (3)0.002 (3)0.009 (3)
C300.060 (4)0.043 (3)0.055 (4)0.006 (3)0.005 (3)0.013 (3)
Geometric parameters (Å, º) top
Co1—N151.968 (5)N20—C291.487 (8)
Co1—N161.962 (5)N20—H200.950
Co1—N171.976 (4)C21—C221.51 (1)
Co1—N181.986 (4)C21—H21A0.950
Co1—N191.974 (5)C21—H21B0.950
Co1—N201.981 (4)C22—C231.492 (10)
Cl2—O111.436 (7)C22—H22A0.950
Cl2—O121.379 (7)C22—H22B0.950
Cl2—O131.409 (6)C23—H23A0.950
Cl2—O141.414 (6)C23—H23B0.950
O3—N151.18 (1)C24—C251.50 (1)
O4—N151.20 (1)C24—H24A0.950
O5—N151.21 (2)C24—H24B0.950
O6—N151.20 (2)C25—H25A0.950
O7—N161.189 (10)C25—H25B0.950
O8—N161.20 (1)C26—C271.51 (1)
O9—N161.21 (2)C26—H26A0.950
O10—N161.21 (2)C26—H26B0.950
N17—C211.473 (8)C27—C281.50 (1)
N17—C301.511 (8)C27—H27A0.950
N17—H170.950C27—H27B0.950
N18—C231.487 (7)C28—H28A0.951
N18—C241.484 (8)C28—H28B0.950
N18—H180.950C29—C301.492 (10)
N19—C251.504 (9)C29—H29A0.950
N19—C261.474 (9)C29—H29B0.950
N19—H190.950C30—H30A0.950
N20—C281.485 (7)C30—H30B0.951
N15—Co1—N16179.1 (2)N17—C21—H21B108.9
N15—Co1—N1787.7 (2)C22—C21—H21A109.0
N15—Co1—N1887.9 (2)C22—C21—H21B109.0
N15—Co1—N1992.5 (2)H21A—C21—H21B109.5
N15—Co1—N2091.6 (2)C21—C22—C23114.7 (6)
N16—Co1—N1792.5 (2)C21—C22—H22A108.1
N16—Co1—N1892.9 (2)C21—C22—H22B108.2
N16—Co1—N1987.3 (2)C23—C22—H22A108.1
N16—Co1—N2087.6 (2)C23—C22—H22B108.2
N17—Co1—N1893.1 (2)H22A—C22—H22B109.4
N17—Co1—N19179.1 (2)N18—C23—C22112.7 (5)
N17—Co1—N2085.7 (2)N18—C23—H23A108.7
N18—Co1—N1986.1 (2)N18—C23—H23B108.7
N18—Co1—N20178.7 (2)C22—C23—H23A108.6
N19—Co1—N2095.1 (2)C22—C23—H23B108.6
O11—Cl2—O12108.3 (5)H23A—C23—H23B109.5
O11—Cl2—O13107.3 (4)N18—C24—C25108.2 (5)
O11—Cl2—O14109.1 (4)N18—C24—H24A109.8
O12—Cl2—O13109.8 (5)N18—C24—H24B109.8
O12—Cl2—O14111.4 (4)C25—C24—H24A109.8
O13—Cl2—O14110.8 (4)C25—C24—H24B109.8
Co1—N15—O3119.3 (6)H24A—C24—H24B109.4
Co1—N15—O4124.8 (7)N19—C25—C24107.3 (5)
Co1—N15—O5120.7 (10)N19—C25—H25A110.0
Co1—N15—O6122.3 (10)N19—C25—H25B110.0
O3—N15—O4115.9 (8)C24—C25—H25A110.0
O5—N15—O6116 (1)C24—C25—H25B110.0
Co1—N16—O7121.7 (6)H25A—C25—H25B109.4
Co1—N16—O8120.6 (6)N19—C26—C27112.0 (6)
Co1—N16—O9127 (1)N19—C26—H26A108.9
Co1—N16—O10120.8 (10)N19—C26—H26B108.9
O7—N16—O8117.5 (8)C27—C26—H26A108.8
O9—N16—O10110 (1)C27—C26—H26B108.8
Co1—N17—C21118.9 (4)H26A—C26—H26B109.5
Co1—N17—C30108.9 (4)C26—C27—C28115.8 (7)
Co1—N17—H17105.4C26—C27—H27A107.9
C21—N17—C30111.7 (5)C26—C27—H27B107.9
C21—N17—H17105.4C28—C27—H27A107.8
C30—N17—H17105.4C28—C27—H27B107.8
Co1—N18—C23118.9 (3)H27A—C27—H27B109.5
Co1—N18—C24108.6 (4)N20—C28—C27111.6 (5)
Co1—N18—H18105.2N20—C28—H28A108.9
C23—N18—C24112.4 (5)N20—C28—H28B108.9
C23—N18—H18105.3C27—C28—H28A109.0
C24—N18—H18105.2C27—C28—H28B109.0
Co1—N19—C25108.0 (4)H28A—C28—H28B109.4
Co1—N19—C26120.4 (4)N20—C29—C30107.6 (5)
Co1—N19—H19104.6N20—C29—H29A109.9
C25—N19—C26113.1 (5)N20—C29—H29B110.0
C25—N19—H19104.6C30—C29—H29A110.0
C26—N19—H19104.6C30—C29—H29B110.0
Co1—N20—C28120.0 (4)H29A—C29—H29B109.4
Co1—N20—C29108.0 (3)N17—C30—C29107.0 (5)
Co1—N20—H20104.9N17—C30—H30A110.1
C28—N20—C29112.7 (5)N17—C30—H30B110.1
C28—N20—H20104.9C29—C30—H30A110.2
C29—N20—H20104.9C29—C30—H30B110.1
N17—C21—C22111.4 (5)H30A—C30—H30B109.4
N17—C21—H21A109.0

Experimental details

Crystal data
Chemical formula[Co(NO2)2(C10H24N4)]ClO4
Mr450.72
Crystal system, space groupOrthorhombic, P212121
Temperature (K)297
a, b, c (Å)13.299 (3), 19.820 (1), 6.6531 (7)
V3)1753.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.19
Crystal size (mm)0.40 × 0.25 × 0.05
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correctionIntegration
(Coppens et al., 1965)
Tmin, Tmax0.752, 0.942
No. of measured, independent and
observed [I > 2σ(I)'] reflections
3312, 2554, 2245
Rint0.024
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.108, 1.08
No. of reflections2554
No. of parameters271
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.41, 0.55
Absolute structure(Flack, 1983), 225 Friedel pairs
Absolute structure parameter0.05 (4)

Computer programs: WinAFC (Rigaku Corporation, 1999), WinAFC, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.

 

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