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The crystal structure of the low-spin (S = 1) MnIII complex [Mn(CN)2(C10H24N4)]ClO4, or trans-[Mn(CN)2(cyclam)](ClO4) (cyclam is the tetradentate amine ligand 1,4,8,11-tetra­aza­cyclo­tetra­decane), is reported. The structural parameters in the Mn(cyclam) moiety are found to be insensitive to both the spin and the oxidation state of the Mn ion. The difference between high- and low-spin MnIII complexes is that a pronounced tetragonal elongation of the coordination octahedron occurs in high-spin complexes and a slight tetragonal compression is seen in low-spin complexes, as in the title complex.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102001713/tr1013sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001713/tr1013Isup2.hkl
Contains datablock I

CCDC reference: 184455

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg, 1998) and DREAD (Blessing, 1987); program(s) used to solve structure: SIR97 (Altomare, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).

trans-Bis(cyano-κC)(1,4,8,11-tetraazacyclotetradecane-κ4N)manganese(III) perchlorate top
Crystal data top
[Mn(CN)2(C10H24N4)](ClO4)F(000) = 848
Mr = 406.76Dx = 1.572 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 474 reflections
a = 6.7599 (3) Åθ = 4.4–31.0°
b = 13.3609 (8) ŵ = 0.95 mm1
c = 19.0240 (5) ÅT = 122 K
V = 1718.22 (14) Å3Needle, yellow
Z = 40.22 × 0.08 × 0.04 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
5077 independent reflections
Radiation source: fine-focus sealed tube4366 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
θ and φ scansθmax = 30.3°, θmin = 3.2°
Absorption correction: integration
(Coppens, 1970)
h = 99
Tmin = 0.840, Tmax = 0.967k = 1818
39637 measured reflectionsl = 2626
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Only H-atom coordinates refined
wR(F2) = 0.159 w = 1/[σ2(Fo2) + (0.0705P)2 + 5.3702P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
5077 reflectionsΔρmax = 0.51 e Å3
290 parametersΔρmin = 0.94 e Å3
0 restraintsAbsolute structure: Flack (1983), 2180 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.57 (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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn0.22855 (8)0.02438 (5)0.87064 (3)0.01287 (14)
C110.4723 (6)0.1005 (4)0.8990 (2)0.0167 (8)
N110.6180 (6)0.1389 (3)0.9156 (2)0.0242 (8)
C120.0177 (6)0.0494 (4)0.8432 (2)0.0166 (8)
N120.1660 (6)0.0865 (3)0.8282 (2)0.0241 (8)
N10.2404 (5)0.0509 (3)0.96315 (16)0.0155 (6)
H1N0.357 (8)0.038 (4)0.987 (3)0.019*
C10.0798 (7)0.0080 (4)1.0073 (2)0.0193 (8)
H1A0.092 (8)0.025 (4)1.057 (3)0.023*
H1B0.043 (9)0.039 (5)0.992 (3)0.023*
C20.0811 (7)0.1040 (4)0.9977 (2)0.0210 (9)
H2A0.016 (9)0.133 (5)1.026 (3)0.025*
H2B0.208 (9)0.137 (4)1.012 (3)0.025*
N20.0547 (6)0.1249 (3)0.92146 (19)0.0177 (7)
H2N0.072 (9)0.111 (4)0.911 (3)0.021*
C30.0803 (7)0.2322 (3)0.9038 (2)0.0199 (8)
H3A0.218 (9)0.249 (4)0.918 (3)0.024*
H3B0.016 (9)0.267 (5)0.933 (3)0.024*
C40.0539 (7)0.2508 (4)0.8258 (2)0.0217 (9)
H4A0.058 (10)0.329 (5)0.817 (3)0.026*
H4B0.071 (9)0.217 (5)0.807 (3)0.026*
C50.2197 (7)0.2090 (3)0.7802 (2)0.0188 (8)
H5A0.200 (8)0.233 (4)0.730 (3)0.023*
H5B0.349 (9)0.230 (4)0.800 (3)0.023*
N30.2195 (6)0.0989 (3)0.77751 (17)0.0155 (6)
H3N0.118 (9)0.084 (4)0.754 (3)0.019*
C60.3844 (7)0.0575 (4)0.7352 (2)0.0196 (8)
H6A0.513 (9)0.086 (4)0.754 (3)0.024*
H6B0.369 (9)0.070 (4)0.690 (3)0.024*
C70.3866 (7)0.0539 (3)0.7437 (2)0.0190 (8)
H7A0.503 (9)0.091 (4)0.718 (3)0.023*
H7B0.258 (9)0.085 (4)0.729 (3)0.023*
N40.4004 (5)0.0770 (3)0.82035 (17)0.0146 (6)
H4N0.538 (8)0.062 (4)0.834 (3)0.018*
C80.3636 (7)0.1833 (3)0.8360 (2)0.0172 (8)
H8A0.460 (9)0.223 (5)0.808 (3)0.021*
H8B0.238 (10)0.193 (4)0.819 (3)0.021*
C90.3911 (7)0.2057 (4)0.9136 (2)0.0215 (9)
H9A0.388 (9)0.282 (5)0.917 (3)0.026*
H9B0.525 (10)0.184 (5)0.928 (3)0.026*
C100.2318 (8)0.1621 (3)0.9607 (2)0.0208 (8)
H10A0.093 (10)0.187 (4)0.942 (3)0.025*
H10B0.241 (10)0.182 (4)1.007 (3)0.025*
Cl0.10598 (15)0.03794 (8)0.61507 (5)0.0188 (2)
O10.0760 (5)0.0174 (3)0.61764 (18)0.0283 (7)
O20.1189 (5)0.0898 (3)0.54887 (17)0.0261 (7)
O30.2686 (5)0.0293 (3)0.62222 (17)0.0291 (7)
O40.1090 (7)0.1091 (3)0.67182 (19)0.0366 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0100 (2)0.0198 (3)0.0088 (2)0.0003 (2)0.00000 (19)0.0003 (2)
C110.0130 (18)0.023 (2)0.0140 (17)0.0018 (15)0.0013 (14)0.0010 (15)
N110.0156 (18)0.031 (2)0.0264 (19)0.0015 (16)0.0030 (15)0.0038 (16)
C120.0113 (17)0.024 (2)0.0140 (16)0.0011 (15)0.0016 (13)0.0027 (16)
N120.0162 (17)0.031 (2)0.0246 (19)0.0009 (15)0.0015 (14)0.0068 (16)
N10.0125 (15)0.0226 (16)0.0115 (13)0.0033 (14)0.0007 (12)0.0009 (11)
C10.0163 (19)0.029 (2)0.0121 (16)0.0009 (16)0.0020 (14)0.0018 (15)
C20.018 (2)0.032 (2)0.0124 (17)0.0021 (19)0.0050 (15)0.0028 (17)
N20.0146 (17)0.0249 (19)0.0136 (16)0.0014 (14)0.0007 (12)0.0022 (14)
C30.019 (2)0.019 (2)0.0217 (19)0.0010 (17)0.0012 (16)0.0038 (16)
C40.023 (2)0.020 (2)0.023 (2)0.0015 (17)0.0037 (17)0.0015 (17)
C50.0179 (18)0.0190 (19)0.0196 (18)0.0017 (16)0.0022 (16)0.0032 (14)
N30.0146 (15)0.0200 (16)0.0120 (13)0.0002 (14)0.0028 (13)0.0026 (12)
C60.019 (2)0.029 (2)0.0110 (17)0.0044 (18)0.0015 (15)0.0015 (15)
C70.020 (2)0.027 (2)0.0096 (16)0.0013 (18)0.0014 (15)0.0000 (15)
N40.0112 (15)0.0210 (17)0.0117 (14)0.0011 (13)0.0014 (12)0.0016 (12)
C80.015 (2)0.019 (2)0.0181 (19)0.0018 (15)0.0013 (15)0.0012 (15)
C90.019 (2)0.023 (2)0.023 (2)0.0014 (18)0.0033 (17)0.0034 (16)
C100.024 (2)0.0220 (19)0.0164 (17)0.0017 (19)0.0020 (17)0.0067 (14)
Cl0.0163 (4)0.0270 (5)0.0130 (4)0.0009 (4)0.0018 (3)0.0003 (3)
O10.0188 (15)0.0337 (18)0.0325 (17)0.0076 (14)0.0003 (13)0.0057 (16)
O20.0230 (17)0.0356 (19)0.0196 (15)0.0000 (15)0.0020 (13)0.0070 (13)
O30.0197 (14)0.0427 (19)0.0248 (15)0.0061 (15)0.0006 (13)0.0074 (15)
O40.051 (2)0.034 (2)0.0253 (17)0.0096 (19)0.0146 (18)0.0128 (15)
Geometric parameters (Å, º) top
Mn—C112.010 (4)C5—N31.473 (5)
Mn—C122.004 (4)C5—H5A1.02 (5)
Mn—N12.029 (3)C5—H5B0.99 (6)
Mn—N22.029 (4)N3—C61.483 (6)
Mn—N32.033 (3)N3—H3N0.84 (6)
Mn—N42.025 (4)C6—C71.497 (7)
C11—N111.154 (6)C6—H6A1.02 (6)
C12—N121.154 (6)C6—H6B0.89 (6)
N1—C11.487 (5)C7—N41.493 (5)
N1—C101.488 (5)C7—H7A1.06 (6)
N1—H1N0.92 (5)C7—H7B1.00 (6)
C1—C21.508 (7)N4—C81.472 (6)
C1—H1A0.97 (6)N4—H4N0.98 (6)
C1—H1B0.97 (6)C8—C91.518 (6)
C2—N21.488 (5)C8—H8A0.99 (6)
C2—H2A0.94 (6)C8—H8B0.92 (7)
C2—H2B1.00 (6)C9—C101.516 (7)
N2—C31.483 (6)C9—H9A1.02 (6)
N2—H2N0.90 (6)C9—H9B0.99 (7)
C3—C41.515 (6)C10—H10A1.05 (7)
C3—H3A0.99 (6)C10—H10B0.93 (6)
C3—H3B0.97 (6)Cl—O31.427 (3)
C4—C51.524 (7)Cl—O11.436 (3)
C4—H4A1.06 (6)Cl—O41.439 (4)
C4—H4B1.02 (6)Cl—O21.440 (3)
C11—Mn—N189.19 (16)N3—C5—H5A106 (3)
C11—Mn—N290.68 (17)C4—C5—H5A109 (3)
C11—Mn—N390.62 (16)N3—C5—H5B107 (3)
C11—Mn—N489.73 (16)C4—C5—H5B109 (3)
C12—Mn—C11178.88 (19)H5A—C5—H5B113 (5)
C12—Mn—N190.86 (16)C5—N3—C6113.0 (4)
C12—Mn—N288.21 (16)C5—N3—Mn117.4 (3)
C12—Mn—N389.35 (16)C6—N3—Mn105.6 (3)
C12—Mn—N491.39 (16)C5—N3—H3N104 (4)
N1—Mn—N286.42 (15)C6—N3—H3N104 (4)
N1—Mn—N3179.32 (15)Mn—N3—H3N112 (4)
N2—Mn—N394.24 (15)N3—C6—C7108.6 (4)
N4—Mn—N193.18 (14)N3—C6—H6A108 (3)
N4—Mn—N2179.43 (17)C7—C6—H6A109 (3)
N4—Mn—N386.16 (14)N3—C6—H6B112 (4)
N11—C11—Mn175.9 (4)C7—C6—H6B107 (4)
N12—C12—Mn175.7 (4)H6A—C6—H6B112 (5)
C1—N1—C10112.0 (4)N4—C7—C6108.2 (3)
C1—N1—Mn105.7 (3)N4—C7—H7A108 (3)
C10—N1—Mn117.8 (2)C6—C7—H7A115 (3)
C1—N1—H1N106 (3)N4—C7—H7B103 (3)
C10—N1—H1N104 (4)C6—C7—H7B112 (3)
Mn—N1—H1N111 (3)H7A—C7—H7B109 (4)
N1—C1—C2108.1 (4)C8—N4—C7112.8 (3)
N1—C1—H1A113 (3)C8—N4—Mn116.9 (3)
C2—C1—H1A111 (4)C7—N4—Mn106.7 (3)
N1—C1—H1B107 (3)C8—N4—H4N108 (3)
C2—C1—H1B113 (4)C7—N4—H4N106 (3)
H1A—C1—H1B105 (5)Mn—N4—H4N106 (3)
N2—C2—C1107.7 (4)N4—C8—C9111.5 (4)
N2—C2—H2A114 (4)N4—C8—H8A107 (4)
C1—C2—H2A109 (4)C9—C8—H8A109 (3)
N2—C2—H2B106 (3)N4—C8—H8B103 (3)
C1—C2—H2B114 (3)C9—C8—H8B115 (3)
H2A—C2—H2B106 (5)H8A—C8—H8B110 (5)
C3—N2—C2112.8 (4)C10—C9—C8114.3 (4)
C3—N2—Mn117.7 (3)C10—C9—H9A109 (3)
C2—N2—Mn105.7 (3)C8—C9—H9A105 (3)
C3—N2—H2N105 (4)C10—C9—H9B112 (4)
C2—N2—H2N107 (4)C8—C9—H9B109 (4)
Mn—N2—H2N108 (4)H9A—C9—H9B107 (5)
N2—C3—C4111.5 (4)N1—C10—C9112.0 (4)
N2—C3—H3A105 (3)N1—C10—H10A111 (3)
C4—C3—H3A110 (3)C9—C10—H10A108 (3)
N2—C3—H3B105 (4)N1—C10—H10B104 (3)
C4—C3—H3B113 (3)C9—C10—H10B114 (4)
H3A—C3—H3B111 (5)H10A—C10—H10B106 (5)
C3—C4—C5114.3 (4)O3—Cl—O1109.5 (2)
C3—C4—H4A109 (3)O3—Cl—O4109.5 (2)
C5—C4—H4A104 (3)O1—Cl—O4109.1 (2)
C3—C4—H4B111 (3)O3—Cl—O2109.9 (2)
C5—C4—H4B104 (3)O1—Cl—O2109.2 (2)
H4A—C4—H4B114 (5)O4—Cl—O2109.7 (2)
N3—C5—C4112.6 (4)
C12—Mn—N1—C173.5 (3)C12—Mn—N3—C5124.8 (3)
C11—Mn—N1—C1105.4 (3)C11—Mn—N3—C554.1 (3)
N4—Mn—N1—C1164.9 (3)N4—Mn—N3—C5143.8 (3)
N2—Mn—N1—C114.6 (3)N2—Mn—N3—C536.6 (3)
C12—Mn—N1—C1052.5 (3)C12—Mn—N3—C6108.3 (3)
C11—Mn—N1—C10128.7 (4)C11—Mn—N3—C672.8 (3)
N4—Mn—N1—C1039.0 (3)N4—Mn—N3—C616.9 (3)
N2—Mn—N1—C10140.6 (3)N2—Mn—N3—C6163.5 (3)
C10—N1—C1—C2171.4 (4)C5—N3—C6—C7172.5 (3)
Mn—N1—C1—C241.9 (4)Mn—N3—C6—C743.0 (4)
N1—C1—C2—N257.6 (5)N3—C6—C7—N455.8 (5)
C1—C2—N2—C3172.3 (4)C6—C7—N4—C8168.5 (4)
C1—C2—N2—Mn42.3 (4)C6—C7—N4—Mn38.8 (4)
C12—Mn—N2—C3126.6 (3)C12—Mn—N4—C850.0 (3)
C11—Mn—N2—C353.3 (3)C11—Mn—N4—C8130.1 (3)
N1—Mn—N2—C3142.4 (3)N1—Mn—N4—C840.9 (3)
N3—Mn—N2—C337.4 (3)N3—Mn—N4—C8139.2 (3)
C12—Mn—N2—C2106.3 (3)C12—Mn—N4—C777.2 (3)
C11—Mn—N2—C273.8 (3)C11—Mn—N4—C7102.6 (3)
N1—Mn—N2—C215.3 (3)N1—Mn—N4—C7168.2 (3)
N3—Mn—N2—C2164.5 (3)N3—Mn—N4—C712.0 (3)
C2—N2—C3—C4179.6 (4)C7—N4—C8—C9176.5 (4)
Mn—N2—C3—C456.0 (5)Mn—N4—C8—C959.3 (4)
N2—C3—C4—C570.0 (5)N4—C8—C9—C1070.6 (5)
C3—C4—C5—N369.9 (5)C1—N1—C10—C9178.0 (3)
C4—C5—N3—C6178.0 (3)Mn—N1—C10—C955.2 (5)
C4—C5—N3—Mn54.8 (4)C8—C9—C10—N168.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.92 (5)2.24 (6)3.078 (5)151 (5)
N2—H2N···N11ii0.90 (6)2.13 (6)2.961 (6)153 (5)
N3—H3N···O40.84 (6)2.21 (6)2.999 (5)155 (5)
N4—H4N···N12iii0.98 (6)2.03 (6)2.938 (5)152 (5)
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x1, y, z; (iii) x+1, y, z.
Comparison of structural parameters in a selection of Mn(cyclam) complexes (Å). Leq denotes the four equatorial ligands and Lax the two axial ligands in a tetragonally distorted octahedron. top
ComplexSpinLigatingaverageaaveragea
stateatomsMn-LeqMn-Lax
trans-[Mn(cyclam)(CN)2]+ bls4N,2C2.029 (4)2.007 (4)
trans-[Mn(cyclam)Cl2]+ c,dhs4N,2Cl2.035 (3)2.527 (1)
trans-[Mn(cyclam)Br2]+ chs4N,2Br2.029 (6)2.689 (1)
trans-[Mn(cyclam)I2]+ ehs4N,2I2.028 (2)2.9416 (2)
trans-[Mn(cyclam)(NCS)2]+ chs6N2.038 (4)2.166 (17)
trans-[Mn(cyclam)(NO3)2]+ chs4N,2O2.036 (7)2.221 (4)
trans-[Mn(cyclam)(N3)2]+ fhs6N2.041 (3)2.175 (3)
[Mn(CN)6]3- gls6C2.024 (2)2.013 (2)
[Mn(PhL)2]- hls4N,2O1.940 (15)1.906 (7)
trans-[Mn(tpp)(CN)2]- ils4N,2C2.00 (2)2.015 (20)
a Uncertainties for the averaged Mn-L distances are given as root-mean square deviations (r.m.s.d.).If only a single parameter is available or the s.u. is larger than the r.m.s.d., the s.u. is given. b Present work c (Daugherty et al., 1991) d (Létumier et al., 1998) e (Mossin, Weihe, Glerup, Sørensen & Søtofte, 2002) f (Meyer et al., 1998) g (Buschmann et al., 1999) h (Ganguly et al., 1997) i (Galich et al., 1998)
 

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