trans-Dinitro(1,4,8,11-tetra­aza­cyclo­tetra­decane-N,N',N'',N''')­cobalt(III) perchlorate

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

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


 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

---

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(parent atom).

Computing details

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

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)

Crystal data

[Co(NO2)2(C10H24N4)]ClO4	Dx = 1.707 Mg m^−3
Mr = 450.72	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 13.299 (3) Å	θ = 10.3–13.9°
b = 19.820 (1) Å	µ = 1.19 mm^−1
c = 6.6531 (7) Å	T = 297 K
V = 1753.7 (5) Å^3	Plate, orange
Z = 4	0.40 × 0.25 × 0.05 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.024
θ–2θ scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: integration (Coppens et al., 1965)	h = −17→8
Tmin = 0.752, Tmax = 0.942	k = 0→25
3312 measured reflections	l = −4→8
2554 independent reflections	3 standard reflections every 150 reflections
2245 reflections with I > 2σ(I)'	intensity decay: none

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 3.4475P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.035	(Δ/σ)max = 0.001
wR(F^2) = 0.108	Δρmax = 0.41 e Å^−3
S = 1.08	Δρmin = −0.55 e Å^−3
2554 reflections	Absolute structure: (Flack, 1983), 225 Friedel pairs
271 parameters	Absolute structure parameter: −0.05 (4)
H-atom parameters constrained

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	−0.02236 (4)	−0.12630 (3)	0.22719 (9)	0.0289 (2)
Cl2	0.0420 (1)	0.11990 (8)	0.5995 (2)	0.0561 (4)
O3	−0.0563 (7)	−0.0715 (6)	0.601 (1)	0.091 (3)	0.65
O4	−0.1886 (7)	−0.1029 (7)	0.484 (2)	0.111 (4)	0.65
O5	−0.115 (2)	−0.1351 (10)	0.602 (2)	0.094 (6)	0.35
O6	−0.122 (2)	−0.0389 (7)	0.490 (3)	0.083 (5)	0.35
O7	0.0728 (8)	−0.2147 (4)	−0.035 (2)	0.082 (3)	0.65
O8	0.0746 (9)	−0.1180 (5)	−0.141 (1)	0.086 (3)	0.65
O9	0.136 (1)	−0.139 (1)	−0.063 (3)	0.097 (8)	0.35
O10	0.012 (2)	−0.1886 (10)	−0.141 (2)	0.094 (6)	0.35
O11	−0.0280 (6)	0.1258 (3)	0.7629 (9)	0.121 (2)
O12	0.1098 (5)	0.1723 (4)	0.613 (1)	0.147 (3)
O13	−0.0134 (4)	0.1254 (3)	0.4198 (8)	0.098 (2)
O14	0.0907 (5)	0.0566 (3)	0.6113 (9)	0.091 (2)
N15	−0.0993 (4)	−0.0967 (3)	0.4640 (7)	0.040 (1)
N16	0.0528 (4)	−0.1568 (2)	−0.0097 (7)	0.038 (1)
N17	0.0690 (3)	−0.1740 (2)	0.4135 (7)	0.036 (1)
N18	0.0546 (3)	−0.0406 (2)	0.2455 (7)	0.0389 (9)
N19	−0.1121 (4)	−0.0776 (3)	0.0406 (7)	0.042 (1)
N20	−0.0977 (3)	−0.2124 (2)	0.2146 (7)	0.0389 (10)
C21	0.1780 (5)	−0.1618 (4)	0.398 (1)	0.055 (2)
C22	0.2027 (5)	−0.0879 (4)	0.423 (1)	0.055 (2)
C23	0.1662 (4)	−0.0437 (3)	0.257 (1)	0.056 (2)
C24	0.0189 (6)	0.0057 (3)	0.085 (1)	0.057 (2)
C25	−0.0924 (6)	−0.0033 (3)	0.064 (1)	0.061 (2)
C26	−0.2200 (6)	−0.0942 (4)	0.031 (1)	0.064 (2)
C27	−0.2376 (5)	−0.1691 (4)	0.008 (1)	0.068 (2)
C28	−0.2083 (4)	−0.2118 (4)	0.184 (1)	0.058 (2)
C29	−0.0667 (5)	−0.2544 (3)	0.389 (1)	0.050 (2)
C30	0.0446 (5)	−0.2484 (3)	0.409 (1)	0.053 (2)
H17	0.0505	−0.1590	0.5441	0.0438*
H18	0.0338	−0.0204	0.3682	0.0467*
H19	−0.0872	−0.0884	−0.0894	0.0508*
H20	−0.0716	−0.2351	0.1003	0.0466*
H21A	0.2008	−0.1765	0.2704	0.0661*
H21B	0.2113	−0.1867	0.5006	0.0661*
H22A	0.2738	−0.0835	0.4311	0.0659*
H22B	0.1733	−0.0726	0.5450	0.0659*
H23A	0.1913	−0.0606	0.1332	0.0670*
H23B	0.1912	0.0007	0.2781	0.0670*
H24A	0.0513	−0.0049	−0.0380	0.0683*
H24B	0.0335	0.0510	0.1213	0.0683*
H25A	−0.1158	0.0202	−0.0516	0.0736*
H25B	−0.1258	0.0133	0.1797	0.0736*
H26A	−0.2491	−0.0715	−0.0801	0.0773*
H26B	−0.2514	−0.0794	0.1518	0.0773*
H27A	−0.2002	−0.1841	−0.1048	0.0813*
H27B	−0.3073	−0.1759	−0.0158	0.0813*
H28A	−0.2307	−0.2567	0.1616	0.0698*
H28B	−0.2396	−0.1945	0.3017	0.0698*
H29A	−0.0848	−0.3002	0.3665	0.0599*
H29B	−0.0987	−0.2387	0.5079	0.0599*
H30A	0.0770	−0.2693	0.2985	0.0632*
H30B	0.0663	−0.2692	0.5307	0.0632*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0312 (3)	0.0309 (3)	0.0246 (3)	0.0012 (3)	0.0035 (3)	0.0001 (3)
Cl2	0.0669 (10)	0.0504 (8)	0.0509 (8)	0.0029 (8)	−0.0089 (7)	0.0043 (8)
O3	0.090 (7)	0.141 (9)	0.042 (4)	−0.036 (7)	0.019 (5)	−0.037 (5)
O4	0.060 (6)	0.19 (1)	0.085 (7)	0.000 (7)	0.027 (5)	−0.063 (8)
O5	0.12 (1)	0.11 (1)	0.049 (8)	0.01 (1)	0.049 (10)	0.026 (10)
O6	0.12 (2)	0.046 (8)	0.08 (1)	0.029 (10)	0.05 (1)	−0.001 (8)
O7	0.110 (8)	0.053 (5)	0.084 (7)	0.031 (5)	0.051 (6)	−0.003 (5)
O8	0.147 (10)	0.064 (5)	0.048 (5)	−0.003 (7)	0.045 (6)	0.003 (4)
O9	0.07 (1)	0.16 (2)	0.06 (1)	−0.03 (1)	0.019 (9)	−0.05 (1)
O10	0.12 (2)	0.11 (1)	0.052 (8)	−0.05 (1)	0.03 (1)	−0.040 (9)
O11	0.206 (7)	0.075 (3)	0.082 (4)	0.036 (5)	0.052 (5)	−0.001 (4)
O12	0.107 (5)	0.114 (5)	0.222 (9)	−0.049 (4)	−0.058 (6)	0.062 (6)
O13	0.106 (4)	0.120 (5)	0.069 (3)	0.027 (5)	−0.028 (3)	0.000 (3)
O14	0.109 (4)	0.074 (3)	0.091 (4)	0.037 (3)	−0.009 (4)	−0.005 (3)
N15	0.044 (3)	0.042 (3)	0.034 (2)	−0.001 (2)	0.010 (2)	0.001 (2)
N16	0.039 (2)	0.044 (3)	0.030 (2)	0.000 (2)	0.005 (2)	−0.003 (2)
N17	0.037 (2)	0.039 (2)	0.033 (2)	−0.003 (2)	0.002 (2)	0.002 (2)
N18	0.047 (2)	0.040 (2)	0.030 (2)	−0.005 (2)	0.009 (2)	0.000 (2)
N19	0.042 (3)	0.052 (3)	0.033 (2)	0.013 (2)	0.002 (2)	0.001 (2)
N20	0.034 (2)	0.048 (2)	0.034 (2)	−0.005 (2)	0.005 (2)	−0.007 (2)
C21	0.034 (3)	0.078 (4)	0.053 (4)	0.006 (3)	−0.008 (3)	0.005 (4)
C22	0.036 (3)	0.076 (4)	0.053 (4)	−0.012 (3)	−0.002 (3)	0.000 (4)
C23	0.050 (3)	0.069 (4)	0.048 (4)	−0.023 (3)	0.010 (4)	−0.004 (4)
C24	0.084 (4)	0.036 (3)	0.051 (3)	−0.004 (3)	0.010 (4)	0.009 (3)
C25	0.085 (5)	0.042 (3)	0.056 (4)	0.022 (3)	0.003 (4)	0.011 (3)
C26	0.043 (4)	0.084 (5)	0.067 (5)	0.021 (4)	−0.009 (3)	−0.003 (4)
C27	0.039 (3)	0.087 (5)	0.077 (5)	−0.001 (4)	−0.016 (4)	−0.007 (5)
C28	0.038 (3)	0.075 (4)	0.061 (4)	−0.017 (3)	0.005 (3)	−0.009 (4)
C29	0.061 (4)	0.035 (3)	0.054 (4)	−0.012 (3)	−0.002 (3)	0.009 (3)
C30	0.060 (4)	0.043 (3)	0.055 (4)	0.006 (3)	−0.005 (3)	0.013 (3)

Geometric parameters (Å, º)

Co1—N15	1.968 (5)	N20—C29	1.487 (8)
Co1—N16	1.962 (5)	N20—H20	0.950
Co1—N17	1.976 (4)	C21—C22	1.51 (1)
Co1—N18	1.986 (4)	C21—H21A	0.950
Co1—N19	1.974 (5)	C21—H21B	0.950
Co1—N20	1.981 (4)	C22—C23	1.492 (10)
Cl2—O11	1.436 (7)	C22—H22A	0.950
Cl2—O12	1.379 (7)	C22—H22B	0.950
Cl2—O13	1.409 (6)	C23—H23A	0.950
Cl2—O14	1.414 (6)	C23—H23B	0.950
O3—N15	1.18 (1)	C24—C25	1.50 (1)
O4—N15	1.20 (1)	C24—H24A	0.950
O5—N15	1.21 (2)	C24—H24B	0.950
O6—N15	1.20 (2)	C25—H25A	0.950
O7—N16	1.189 (10)	C25—H25B	0.950
O8—N16	1.20 (1)	C26—C27	1.51 (1)
O9—N16	1.21 (2)	C26—H26A	0.950
O10—N16	1.21 (2)	C26—H26B	0.950
N17—C21	1.473 (8)	C27—C28	1.50 (1)
N17—C30	1.511 (8)	C27—H27A	0.950
N17—H17	0.950	C27—H27B	0.950
N18—C23	1.487 (7)	C28—H28A	0.951
N18—C24	1.484 (8)	C28—H28B	0.950
N18—H18	0.950	C29—C30	1.492 (10)
N19—C25	1.504 (9)	C29—H29A	0.950
N19—C26	1.474 (9)	C29—H29B	0.950
N19—H19	0.950	C30—H30A	0.950
N20—C28	1.485 (7)	C30—H30B	0.951
N15—Co1—N16	179.1 (2)	N17—C21—H21B	108.9
N15—Co1—N17	87.7 (2)	C22—C21—H21A	109.0
N15—Co1—N18	87.9 (2)	C22—C21—H21B	109.0
N15—Co1—N19	92.5 (2)	H21A—C21—H21B	109.5
N15—Co1—N20	91.6 (2)	C21—C22—C23	114.7 (6)
N16—Co1—N17	92.5 (2)	C21—C22—H22A	108.1
N16—Co1—N18	92.9 (2)	C21—C22—H22B	108.2
N16—Co1—N19	87.3 (2)	C23—C22—H22A	108.1
N16—Co1—N20	87.6 (2)	C23—C22—H22B	108.2
N17—Co1—N18	93.1 (2)	H22A—C22—H22B	109.4
N17—Co1—N19	179.1 (2)	N18—C23—C22	112.7 (5)
N17—Co1—N20	85.7 (2)	N18—C23—H23A	108.7
N18—Co1—N19	86.1 (2)	N18—C23—H23B	108.7
N18—Co1—N20	178.7 (2)	C22—C23—H23A	108.6
N19—Co1—N20	95.1 (2)	C22—C23—H23B	108.6
O11—Cl2—O12	108.3 (5)	H23A—C23—H23B	109.5
O11—Cl2—O13	107.3 (4)	N18—C24—C25	108.2 (5)
O11—Cl2—O14	109.1 (4)	N18—C24—H24A	109.8
O12—Cl2—O13	109.8 (5)	N18—C24—H24B	109.8
O12—Cl2—O14	111.4 (4)	C25—C24—H24A	109.8
O13—Cl2—O14	110.8 (4)	C25—C24—H24B	109.8
Co1—N15—O3	119.3 (6)	H24A—C24—H24B	109.4
Co1—N15—O4	124.8 (7)	N19—C25—C24	107.3 (5)
Co1—N15—O5	120.7 (10)	N19—C25—H25A	110.0
Co1—N15—O6	122.3 (10)	N19—C25—H25B	110.0
O3—N15—O4	115.9 (8)	C24—C25—H25A	110.0
O5—N15—O6	116 (1)	C24—C25—H25B	110.0
Co1—N16—O7	121.7 (6)	H25A—C25—H25B	109.4
Co1—N16—O8	120.6 (6)	N19—C26—C27	112.0 (6)
Co1—N16—O9	127 (1)	N19—C26—H26A	108.9
Co1—N16—O10	120.8 (10)	N19—C26—H26B	108.9
O7—N16—O8	117.5 (8)	C27—C26—H26A	108.8
O9—N16—O10	110 (1)	C27—C26—H26B	108.8
Co1—N17—C21	118.9 (4)	H26A—C26—H26B	109.5
Co1—N17—C30	108.9 (4)	C26—C27—C28	115.8 (7)
Co1—N17—H17	105.4	C26—C27—H27A	107.9
C21—N17—C30	111.7 (5)	C26—C27—H27B	107.9
C21—N17—H17	105.4	C28—C27—H27A	107.8
C30—N17—H17	105.4	C28—C27—H27B	107.8
Co1—N18—C23	118.9 (3)	H27A—C27—H27B	109.5
Co1—N18—C24	108.6 (4)	N20—C28—C27	111.6 (5)
Co1—N18—H18	105.2	N20—C28—H28A	108.9
C23—N18—C24	112.4 (5)	N20—C28—H28B	108.9
C23—N18—H18	105.3	C27—C28—H28A	109.0
C24—N18—H18	105.2	C27—C28—H28B	109.0
Co1—N19—C25	108.0 (4)	H28A—C28—H28B	109.4
Co1—N19—C26	120.4 (4)	N20—C29—C30	107.6 (5)
Co1—N19—H19	104.6	N20—C29—H29A	109.9
C25—N19—C26	113.1 (5)	N20—C29—H29B	110.0
C25—N19—H19	104.6	C30—C29—H29A	110.0
C26—N19—H19	104.6	C30—C29—H29B	110.0
Co1—N20—C28	120.0 (4)	H29A—C29—H29B	109.4
Co1—N20—C29	108.0 (3)	N17—C30—C29	107.0 (5)
Co1—N20—H20	104.9	N17—C30—H30A	110.1
C28—N20—C29	112.7 (5)	N17—C30—H30B	110.1
C28—N20—H20	104.9	C29—C30—H30A	110.2
C29—N20—H20	104.9	C29—C30—H30B	110.1
N17—C21—C22	111.4 (5)	H30A—C30—H30B	109.4
N17—C21—H21A	109.0