Tricarbonyl[tris(1-methyl-1H-imidazol-2-yl-κN3)methanol]manganese(I) trifluoromethanesulfonate

Reiss, G.J.; Kunz, P.C.

doi:10.1107/S1600536812035891

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1202-m1203

doi:10.1107/S1600536812035891

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Tricarbonyl[tris(1-methyl-1H-imidazol-2-yl-κN³)methanol]manganese(I) trifluoromethanesulfonate

Guido J. Reiss ^a and Peter C. Kunz ^b ^*

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany, and ^bInstitut für Pharmazeutische Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: peter.kunz@uni-duesseldorf.de

(Received 28 June 2012; accepted 15 August 2012; online 23 August 2012)

In the title compound, [Mn(C₁₃H₁₆N₆O)(CO)₃](CF₃O₃S), the Mn^I atom has a slightly distorted octahedral geometry. The three CO ligands have C—Mn—C angles in the range 89.44 (10)–92.31 (9)°, while the three N atoms of the tripodal ligand form significantly smaller N—Mn—N angles of 82.76 (2)–85.51 (6)°. The three N atoms of the tripodal ligand and the three carbonyl ligands coordinate facially. In the crystal, the trifluoromethanesulfonate counter anion is connected by a medium-strength O—H⋯O hydrogen bond to the hydroxyl group of the manganese complex.

Related literature

For the structures of related complexes, see: Niesel et al. (2008 ); Herrick et al. (2008 ); Kunz et al. (2009 ). For details of the chemistry of tris(imidazolyl-2-yl)carbinol ligands, see: Stamatatos et al. (2009 ); Breslow et al. (1983 ); Tang et al. (1978 ). For details of the chemistry of Mn(CO)₃ complexes, see: Kreiter et al. (1994 , 1995 ); Brückmann et al. (2011 ); Huber et al. (2012 ); Berends & Kurz (2012 ).

Experimental

Crystal data

[Mn(CO)₃(C₁₃H₁₆N₆O)](CF₃O₃S)
M_r = 560.36
Monoclinic, P 2₁ /c
a = 12.16673 (18) Å
b = 15.5692 (2) Å
c = 12.6240 (2) Å
β = 104.6721 (16)°
V = 2313.33 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 290 K
0.80 × 0.74 × 0.40 mm

Data collection

Oxford Xcalibur diffractometer with Eos detector
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd., Oxford, UK.]$ ) T_min = 0.805, T_max = 1.000
95191 measured reflections
6746 independent reflections
5888 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.084
S = 1.06
6746 reflections
330 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5	0.72 (2)	1.98 (2)	2.694 (2)	175 (2)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd., Oxford, UK.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812035891/pk2428sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035891/pk2428Isup2.hkl

checkCIF report

Comment top

The chemistry of manganese carbonyl complexes is of significant interest for at least two reasons. On the one hand there is a long standing interest in simple organometallic Mn(CO)₃ complexes, reflected by more than 2200 structures reported in the CCDC. On the other hand they are known to undergo a plethora of photochemical reactions, e.g. photochemical mediated cycloaddition reactions yielding complex organic ligand systems coordinated to a manganese center (e.g. Kreiter et al., 1994, 1995). Recently, manganese tricarbonyl complexes of tripodal N,N,N-ligands, like tris(imidazolyl)carbinols (Breslow et al., 1983; Tang et al. 1978), have been shown to be photoinduced CO-releasing molecules (photoCORMs). The CO-release characteristics, e.g. the rate and half-life time for the release, are dependent on the ligands used to stabilize the Mn(CO)₃ core (Huber et al., 2012; Berends & Kurz, 2012; Brückmann et al., 2011; Kunz et al., 2009; Niesel et al., 2008). The manganese complex cation shows N,N,N-coordination in the solid state, which has also been observed for the corresponding rhenium(I) complex, in which the carbinol OH has been methylated (Herrick et al., 2008). The spectroscopic data in solution (IR and NMR, Huber et al., 2012) of the title compound are in accord with C₃_v symmetry and therefore with the N,N,N-coordination found in the solid state. This indicates that coordination of the carbinol OH group is not favored, as found in other carbinol ligands (Stamatatos et al., 2009; Herrick et al., 2008).

The asymmetric unit of the title structure, consisting of a complex manganese cation and the trifluoromethanesulfonate counteranion, is shown in Fig. 1. The coordination polyhedron around the central manganese(I) atom is slightly distorted from octahedral symmetry. All Mn—N and Mn—C distances are in the expected range for a manganese(I) tricarbonyl complex. The three angles between the three CO ligands are near 90°, which is typical for the Mn(CO)₃ fragment (e.g. Kreiter et al., 1995). The three angles N—Mn—N are significantly smaller than 90° (82.76 (2) to 85.51 (6)°), which is a result of the bite angle the tripodal ligand. The complex cation is connected to the trifluoromethanesulfonate counter-anion by only one O—H···O hydrogen bond, between the carbinol group of the complex cation and one of the O atoms of the trifluoromethanesulfonate anion.

Related literature top

For the structures of related complexes, see: Niesel et al. (2008); Herrick et al. (2008); Kunz et al. (2009). For details of the chemistry of tris(imidazolyl-2-yl)carbinol ligands, see: Stamatatos et al. (2009); Breslow et al. (1983); Tang et al. (1978). For details of the chemistry of Mn(CO)₃ complexes, see: Kreiter et al. (1994, 1995); Brückmann et al. (2011); Huber et al. (2012); Berends & Kurz (2012).

Experimental top

The synthesis of the title compound was performed as recently reported (Huber et al. 2012). The title compound was crystallized from methanol solution by slow vapor diffusion of diethyl ether to yield yellow crystals. ¹H NMR (200 MHz, [D₄]methanol): δ = 4.12 (s, 9 H, NCH₃), 7.17 (d, ³J_H,H = 1.4 Hz, 3 H, H_im), 7.42 (d, ³J_H,H = 1.4 Hz, 3 H, H_im) p.p.m. ¹³C{¹H} NMR (125 MHz, [D₄]methanol): δ = 37.0, 78.4, 126.1, 132.0, 145.1 p.p.m. ESI-MS (MeOH): m/z (%) = 411.1 (36) [M]⁺, 354.9 (12) [M-2CO]⁺, 327.3 (100) [M-3CO]⁺. C₁₇H₁₆F₃MnN₆O₇S (560.3): calcd. C 36.44, H 2.88, N 15.00; found C 36.75, H 2.55, N 14.86. IR (KBr): ν = 2044, 1936, 1907 cm^-1. IR (CH₂Cl₂): ν = 2037, 1935 cm^-1.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Diamond (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The asymmetric unit of the title compound.

Tricarbonyl[tris(1-methyl-1H-imidazol-2-yl- κN³)methanol]manganese(I) trifluoromethanesulfonate top

Crystal data top

[Mn(C₁₃H₁₆N₆O)(CO)₃]·CF₃O₃S	F(000) = 1136
M_r = 560.36	D_x = 1.609 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 50962 reflections
a = 12.16673 (18) Å	θ = 3.0–31.7°
b = 15.5692 (2) Å	µ = 0.74 mm⁻¹
c = 12.6240 (2) Å	T = 290 K
β = 104.6721 (16)°	Block, yellow
V = 2313.33 (6) Å³	0.80 × 0.74 × 0.40 mm
Z = 4

Data collection top

Oxford Xcalibur with Eos detector? diffractometer	6746 independent reflections
Radiation source: fine-focus sealed tube	5888 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.2711 pixels mm^-1	θ_max = 30.0°, θ_min = 3.0°
ω scans	h = −17→17
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	k = −21→21
T_min = 0.805, T_max = 1.000	l = −17→17
95191 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.015P)² + 2.P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6746 reflections	Δρ_max = 0.37 e Å⁻³
330 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00166 (17)

Crystal data top

[Mn(C₁₃H₁₆N₆O)(CO)₃]·CF₃O₃S	V = 2313.33 (6) Å³
M_r = 560.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.16673 (18) Å	µ = 0.74 mm⁻¹
b = 15.5692 (2) Å	T = 290 K
c = 12.6240 (2) Å	0.80 × 0.74 × 0.40 mm
β = 104.6721 (16)°

Data collection top

Oxford Xcalibur with Eos detector? diffractometer	6746 independent reflections
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	5888 reflections with I > 2σ(I)
T_min = 0.805, T_max = 1.000	R_int = 0.027
95191 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.37 e Å⁻³
6746 reflections	Δρ_min = −0.51 e Å⁻³
330 parameters

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

	x	y	z	U_iso*/U_eq
Mn1	0.10254 (2)	0.295254 (17)	0.16048 (2)	0.03656 (8)
O1	0.35083 (11)	0.49536 (9)	0.35279 (11)	0.0412 (3)
H1	0.4054 (19)	0.4867 (14)	0.3424 (18)	0.044 (6)*
N1	0.19095 (13)	0.38711 (10)	0.10358 (12)	0.0389 (3)
C1	0.27555 (12)	0.43432 (10)	0.29428 (13)	0.0315 (3)
O2	−0.11219 (16)	0.32763 (15)	−0.00447 (16)	0.0896 (6)
N2	0.07555 (11)	0.39388 (10)	0.26080 (12)	0.0354 (3)
C2	0.25808 (13)	0.44160 (10)	0.17035 (14)	0.0333 (3)
O3	−0.02144 (16)	0.17630 (12)	0.27000 (15)	0.0730 (5)
N3	0.25271 (12)	0.27691 (9)	0.27527 (12)	0.0370 (3)
C3	0.18358 (19)	0.41522 (14)	−0.00092 (16)	0.0503 (5)
H3	0.1420	0.3890	−0.0647	0.060 (7)*
O4	0.16020 (19)	0.15860 (12)	0.02292 (16)	0.0834 (6)
N4	0.29270 (13)	0.50443 (10)	0.11247 (13)	0.0416 (3)
C4	0.2463 (2)	0.48683 (15)	0.00382 (17)	0.0542 (5)
H4	0.2563	0.5185	−0.0555	0.070 (8)*
N5	0.11867 (12)	0.50560 (9)	0.37074 (12)	0.0369 (3)
C5	0.35957 (19)	0.58200 (14)	0.1479 (2)	0.0597 (6)
H5A	0.3280	0.6129	0.1991	0.090*
H5B	0.3579	0.6177	0.0855	0.090*
H5C	0.4367	0.5664	0.1823	0.090*
N6	0.38841 (12)	0.31476 (10)	0.41865 (13)	0.0418 (3)
C6	0.15755 (13)	0.44636 (10)	0.31180 (13)	0.0314 (3)
C7	−0.02132 (14)	0.42127 (13)	0.28780 (16)	0.0434 (4)
H7	−0.0929	0.3967	0.2634	0.051 (6)*
C8	0.00426 (15)	0.48947 (13)	0.35522 (16)	0.0452 (4)
H8	−0.0459	0.5200	0.3857	0.052 (6)*
C9	0.18119 (19)	0.57170 (14)	0.44384 (18)	0.0539 (5)
H9A	0.2387	0.5451	0.5008	0.081*
H9B	0.1297	0.6031	0.4758	0.081*
H9C	0.2163	0.6103	0.4030	0.081*
C10	0.30911 (13)	0.34236 (11)	0.32977 (13)	0.0332 (3)
C11	0.30031 (17)	0.20377 (13)	0.32892 (18)	0.0476 (4)
H11	0.2788	0.1478	0.3077	0.051 (6)*
C12	0.38308 (18)	0.22648 (14)	0.41719 (18)	0.0522 (5)
H12	0.4282	0.1894	0.4678	0.064 (7)*
C13	0.46166 (19)	0.36356 (16)	0.50876 (17)	0.0602 (6)
H13A	0.5207	0.3913	0.4834	0.090*
H13B	0.4950	0.3252	0.5677	0.090*
H13C	0.4172	0.4061	0.5342	0.090*
C14	−0.02874 (18)	0.31700 (15)	0.05903 (18)	0.0533 (5)
C15	0.13726 (19)	0.21210 (14)	0.07542 (17)	0.0511 (5)
C16	0.02768 (17)	0.22112 (13)	0.22707 (17)	0.0473 (4)
S1	0.61262 (4)	0.42786 (4)	0.23478 (5)	0.05368 (14)
F1	0.7020 (2)	0.30397 (12)	0.36557 (18)	0.1337 (10)
F2	0.7028 (2)	0.28311 (15)	0.2001 (2)	0.1324 (9)
F3	0.55074 (19)	0.26955 (13)	0.24881 (19)	0.1151 (7)
O5	0.55176 (13)	0.45179 (12)	0.31485 (14)	0.0660 (4)
O6	0.72136 (14)	0.46749 (12)	0.25442 (18)	0.0790 (6)
O7	0.54709 (19)	0.42639 (18)	0.12357 (16)	0.1040 (8)
C17	0.6452 (2)	0.31564 (18)	0.2657 (3)	0.0738 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.03490 (13)	0.03877 (14)	0.03562 (13)	−0.00670 (10)	0.00821 (10)	−0.00727 (10)
O1	0.0303 (6)	0.0422 (7)	0.0499 (7)	−0.0083 (5)	0.0082 (5)	−0.0103 (6)
N1	0.0442 (8)	0.0417 (8)	0.0332 (7)	−0.0027 (6)	0.0141 (6)	−0.0036 (6)
C1	0.0252 (7)	0.0340 (8)	0.0351 (8)	−0.0031 (6)	0.0074 (6)	−0.0034 (6)
O2	0.0612 (11)	0.1112 (17)	0.0761 (13)	0.0058 (11)	−0.0201 (9)	−0.0129 (12)
N2	0.0264 (6)	0.0435 (8)	0.0372 (7)	−0.0023 (5)	0.0095 (5)	−0.0053 (6)
C2	0.0310 (7)	0.0340 (8)	0.0373 (8)	0.0012 (6)	0.0131 (6)	0.0011 (6)
O3	0.0760 (11)	0.0740 (12)	0.0726 (11)	−0.0295 (9)	0.0254 (9)	0.0044 (9)
N3	0.0336 (7)	0.0352 (7)	0.0427 (8)	−0.0006 (5)	0.0105 (6)	0.0001 (6)
C3	0.0645 (13)	0.0548 (12)	0.0345 (9)	−0.0001 (10)	0.0178 (9)	−0.0020 (8)
O4	0.1109 (16)	0.0656 (11)	0.0833 (13)	−0.0103 (11)	0.0426 (12)	−0.0355 (10)
N4	0.0414 (8)	0.0384 (8)	0.0477 (8)	−0.0001 (6)	0.0160 (7)	0.0078 (6)
C4	0.0674 (13)	0.0569 (12)	0.0432 (10)	0.0030 (10)	0.0234 (10)	0.0109 (9)
N5	0.0364 (7)	0.0379 (7)	0.0371 (7)	0.0036 (6)	0.0104 (6)	−0.0036 (6)
C5	0.0559 (12)	0.0425 (11)	0.0765 (15)	−0.0102 (9)	0.0092 (11)	0.0172 (10)
N6	0.0339 (7)	0.0481 (9)	0.0410 (8)	−0.0008 (6)	0.0049 (6)	0.0074 (7)
C6	0.0279 (7)	0.0362 (8)	0.0304 (7)	0.0006 (6)	0.0081 (6)	−0.0021 (6)
C7	0.0271 (7)	0.0551 (11)	0.0496 (10)	0.0005 (7)	0.0130 (7)	−0.0011 (8)
C8	0.0361 (9)	0.0535 (11)	0.0503 (10)	0.0088 (8)	0.0190 (8)	−0.0022 (9)
C9	0.0560 (12)	0.0498 (11)	0.0540 (12)	0.0018 (9)	0.0103 (9)	−0.0200 (9)
C10	0.0265 (7)	0.0385 (8)	0.0351 (8)	−0.0007 (6)	0.0085 (6)	0.0012 (6)
C11	0.0474 (10)	0.0362 (9)	0.0606 (12)	0.0013 (8)	0.0165 (9)	0.0071 (8)
C12	0.0461 (10)	0.0480 (11)	0.0603 (12)	0.0050 (9)	0.0095 (9)	0.0173 (9)
C13	0.0546 (12)	0.0722 (15)	0.0428 (11)	−0.0089 (11)	−0.0080 (9)	0.0071 (10)
C14	0.0488 (11)	0.0585 (12)	0.0485 (11)	−0.0059 (9)	0.0046 (9)	−0.0109 (9)
C15	0.0586 (12)	0.0473 (11)	0.0498 (11)	−0.0125 (9)	0.0180 (9)	−0.0102 (9)
C16	0.0444 (10)	0.0491 (11)	0.0464 (10)	−0.0101 (8)	0.0080 (8)	−0.0088 (8)
S1	0.0363 (2)	0.0724 (4)	0.0550 (3)	0.0099 (2)	0.0165 (2)	0.0156 (3)
F1	0.190 (2)	0.0667 (11)	0.1016 (15)	0.0248 (13)	−0.0427 (15)	0.0090 (10)
F2	0.1315 (18)	0.1085 (16)	0.174 (2)	0.0228 (14)	0.0696 (17)	−0.0448 (16)
F3	0.1188 (16)	0.0877 (13)	0.1425 (18)	−0.0411 (12)	0.0400 (14)	−0.0251 (13)
O5	0.0524 (9)	0.0804 (12)	0.0741 (11)	0.0120 (8)	0.0325 (8)	0.0101 (9)
O6	0.0489 (9)	0.0765 (12)	0.1204 (16)	−0.0028 (8)	0.0379 (10)	0.0115 (11)
O7	0.0862 (14)	0.161 (2)	0.0569 (11)	0.0263 (15)	0.0037 (10)	0.0251 (13)
C17	0.0713 (16)	0.0631 (15)	0.0827 (19)	−0.0039 (13)	0.0116 (14)	−0.0165 (14)

Geometric parameters (Å, º) top

Mn1—C15	1.799 (2)	N5—C8	1.379 (2)
Mn1—C16	1.804 (2)	N5—C9	1.461 (2)
Mn1—C14	1.808 (2)	C5—H5A	0.9600
Mn1—N1	2.0273 (15)	C5—H5B	0.9600
Mn1—N3	2.0441 (15)	C5—H5C	0.9600
Mn1—N2	2.0688 (14)	N6—C10	1.351 (2)
O1—C1	1.3946 (19)	N6—C12	1.376 (3)
O1—H1	0.72 (2)	N6—C13	1.467 (3)
N1—C2	1.322 (2)	C7—C8	1.347 (3)
N1—C3	1.371 (2)	C7—H7	0.9300
C1—C6	1.519 (2)	C8—H8	0.9300
C1—C10	1.525 (2)	C9—H9A	0.9600
C1—C2	1.529 (2)	C9—H9B	0.9600
O2—C14	1.135 (3)	C9—H9C	0.9600
N2—C6	1.324 (2)	C11—C12	1.346 (3)
N2—C7	1.375 (2)	C11—H11	0.9300
C2—N4	1.351 (2)	C12—H12	0.9300
O3—C16	1.141 (2)	C13—H13A	0.9600
N3—C10	1.320 (2)	C13—H13B	0.9600
N3—C11	1.376 (2)	C13—H13C	0.9600
C3—C4	1.343 (3)	S1—O6	1.4234 (17)
C3—H3	0.9300	S1—O7	1.428 (2)
O4—C15	1.142 (3)	S1—O5	1.4449 (16)
N4—C4	1.372 (3)	S1—C17	1.812 (3)
N4—C5	1.462 (3)	F1—C17	1.288 (3)
C4—H4	0.9300	F2—C17	1.314 (3)
N5—C6	1.344 (2)	F3—C17	1.325 (3)

C15—Mn1—C16	92.31 (9)	H5A—C5—H5C	109.5
C15—Mn1—C14	90.62 (10)	H5B—C5—H5C	109.5
C16—Mn1—C14	89.44 (10)	C10—N6—C12	106.58 (16)
C15—Mn1—N1	94.03 (8)	C10—N6—C13	130.15 (17)
C16—Mn1—N1	172.75 (7)	C12—N6—C13	123.03 (17)
C14—Mn1—N1	93.99 (9)	N2—C6—N5	111.42 (14)
C15—Mn1—N3	91.13 (8)	N2—C6—C1	118.49 (14)
C16—Mn1—N3	92.66 (8)	N5—C6—C1	130.06 (14)
C14—Mn1—N3	177.21 (8)	C8—C7—N2	109.01 (16)
N1—Mn1—N3	83.72 (6)	C8—C7—H7	125.5
C15—Mn1—N2	175.58 (8)	N2—C7—H7	125.5
C16—Mn1—N2	90.71 (8)	C7—C8—N5	107.26 (15)
C14—Mn1—N2	92.63 (8)	C7—C8—H8	126.4
N1—Mn1—N2	82.76 (6)	N5—C8—H8	126.4
N3—Mn1—N2	85.51 (6)	N5—C9—H9A	109.5
C1—O1—H1	106.7 (18)	N5—C9—H9B	109.5
C2—N1—C3	106.73 (16)	H9A—C9—H9B	109.5
C2—N1—Mn1	121.61 (11)	N5—C9—H9C	109.5
C3—N1—Mn1	130.91 (14)	H9A—C9—H9C	109.5
O1—C1—C6	110.92 (13)	H9B—C9—H9C	109.5
O1—C1—C10	113.15 (13)	N3—C10—N6	110.77 (15)
C6—C1—C10	105.41 (13)	N3—C10—C1	120.42 (14)
O1—C1—C2	113.20 (13)	N6—C10—C1	128.64 (15)
C6—C1—C2	104.38 (12)	C12—C11—N3	108.87 (18)
C10—C1—C2	109.14 (13)	C12—C11—H11	125.6
C6—N2—C7	106.01 (14)	N3—C11—H11	125.6
C6—N2—Mn1	122.61 (11)	C11—C12—N6	107.24 (17)
C7—N2—Mn1	131.37 (12)	C11—C12—H12	126.4
N1—C2—N4	110.29 (15)	N6—C12—H12	126.4
N1—C2—C1	120.54 (14)	N6—C13—H13A	109.5
N4—C2—C1	128.73 (15)	N6—C13—H13B	109.5
C10—N3—C11	106.49 (15)	H13A—C13—H13B	109.5
C10—N3—Mn1	120.98 (12)	N6—C13—H13C	109.5
C11—N3—Mn1	130.84 (13)	H13A—C13—H13C	109.5
C4—C3—N1	108.91 (18)	H13B—C13—H13C	109.5
C4—C3—H3	125.5	O2—C14—Mn1	177.5 (2)
N1—C3—H3	125.5	O4—C15—Mn1	178.9 (2)
C2—N4—C4	106.87 (16)	O3—C16—Mn1	177.9 (2)
C2—N4—C5	131.21 (17)	O6—S1—O7	116.17 (14)
C4—N4—C5	121.81 (17)	O6—S1—O5	112.63 (12)
C3—C4—N4	107.19 (17)	O7—S1—O5	115.74 (12)
C3—C4—H4	126.4	O6—S1—C17	103.75 (12)
N4—C4—H4	126.4	O7—S1—C17	103.49 (15)
C6—N5—C8	106.29 (14)	O5—S1—C17	102.74 (13)
C6—N5—C9	129.29 (15)	F1—C17—F2	108.8 (3)
C8—N5—C9	124.30 (16)	F1—C17—F3	108.1 (3)
N4—C5—H5A	109.5	F2—C17—F3	105.6 (2)
N4—C5—H5B	109.5	F1—C17—S1	112.37 (19)
H5A—C5—H5B	109.5	F2—C17—S1	111.0 (2)
N4—C5—H5C	109.5	F3—C17—S1	110.8 (2)

C15—Mn1—N1—C2	−135.39 (15)	C7—N2—C6—C1	−177.73 (15)
C14—Mn1—N1—C2	133.71 (15)	Mn1—N2—C6—C1	1.0 (2)
N3—Mn1—N1—C2	−44.69 (14)	C8—N5—C6—N2	−0.3 (2)
N2—Mn1—N1—C2	41.56 (13)	C9—N5—C6—N2	175.87 (18)
C15—Mn1—N1—C3	55.91 (19)	C8—N5—C6—C1	177.59 (17)
C14—Mn1—N1—C3	−35.00 (19)	C9—N5—C6—C1	−6.2 (3)
N3—Mn1—N1—C3	146.60 (18)	O1—C1—C6—N2	179.32 (15)
N2—Mn1—N1—C3	−127.15 (18)	C10—C1—C6—N2	−57.86 (18)
C16—Mn1—N2—C6	132.48 (15)	C2—C1—C6—N2	57.08 (19)
C14—Mn1—N2—C6	−138.05 (15)	O1—C1—C6—N5	1.5 (2)
N1—Mn1—N2—C6	−44.36 (14)	C10—C1—C6—N5	124.35 (18)
N3—Mn1—N2—C6	39.86 (14)	C2—C1—C6—N5	−120.71 (18)
C16—Mn1—N2—C7	−49.16 (17)	C6—N2—C7—C8	−0.4 (2)
C14—Mn1—N2—C7	40.31 (18)	Mn1—N2—C7—C8	−178.98 (13)
N1—Mn1—N2—C7	134.01 (17)	N2—C7—C8—N5	0.2 (2)
N3—Mn1—N2—C7	−141.77 (17)	C6—N5—C8—C7	0.1 (2)
C3—N1—C2—N4	0.9 (2)	C9—N5—C8—C7	−176.38 (18)
Mn1—N1—C2—N4	−170.19 (11)	C11—N3—C10—N6	−2.23 (19)
C3—N1—C2—C1	173.97 (15)	Mn1—N3—C10—N6	164.50 (11)
Mn1—N1—C2—C1	2.9 (2)	C11—N3—C10—C1	−178.01 (15)
O1—C1—C2—N1	178.58 (15)	Mn1—N3—C10—C1	−11.3 (2)
C6—C1—C2—N1	−60.70 (19)	C12—N6—C10—N3	1.9 (2)
C10—C1—C2—N1	51.60 (19)	C13—N6—C10—N3	−172.51 (19)
O1—C1—C2—N4	−9.8 (2)	C12—N6—C10—C1	177.26 (17)
C6—C1—C2—N4	110.93 (18)	C13—N6—C10—C1	2.8 (3)
C10—C1—C2—N4	−136.77 (17)	O1—C1—C10—N3	−173.45 (14)
C15—Mn1—N3—C10	143.22 (14)	C6—C1—C10—N3	65.17 (18)
C16—Mn1—N3—C10	−124.41 (14)	C2—C1—C10—N3	−46.45 (19)
N1—Mn1—N3—C10	49.29 (13)	O1—C1—C10—N6	11.6 (2)
N2—Mn1—N3—C10	−33.90 (13)	C6—C1—C10—N6	−109.79 (18)
C15—Mn1—N3—C11	−53.69 (18)	C2—C1—C10—N6	138.60 (17)
C16—Mn1—N3—C11	38.68 (18)	C10—N3—C11—C12	1.7 (2)
N1—Mn1—N3—C11	−147.62 (17)	Mn1—N3—C11—C12	−163.23 (14)
N2—Mn1—N3—C11	129.18 (17)	N3—C11—C12—N6	−0.5 (2)
C2—N1—C3—C4	−0.2 (2)	C10—N6—C12—C11	−0.8 (2)
Mn1—N1—C3—C4	169.76 (15)	C13—N6—C12—C11	174.13 (19)
N1—C2—N4—C4	−1.3 (2)	O6—S1—C17—F1	60.3 (3)
C1—C2—N4—C4	−173.59 (17)	O7—S1—C17—F1	−178.0 (2)
N1—C2—N4—C5	174.82 (19)	O5—S1—C17—F1	−57.2 (3)
C1—C2—N4—C5	2.5 (3)	O6—S1—C17—F2	−61.8 (2)
N1—C3—C4—N4	−0.6 (2)	O7—S1—C17—F2	59.9 (2)
C2—N4—C4—C3	1.1 (2)	O5—S1—C17—F2	−179.2 (2)
C5—N4—C4—C3	−175.44 (19)	O6—S1—C17—F3	−178.7 (2)
C7—N2—C6—N5	0.5 (2)	O7—S1—C17—F3	−57.0 (2)
Mn1—N2—C6—N5	179.18 (11)	O5—S1—C17—F3	63.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.72 (2)	1.98 (2)	2.694 (2)	175 (2)

Experimental details

Crystal data
Chemical formula	[Mn(C₁₃H₁₆N₆O)(CO)₃]·CF₃O₃S
M_r	560.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	12.16673 (18), 15.5692 (2), 12.6240 (2)
β (°)	104.6721 (16)
V (Å³)	2313.33 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.80 × 0.74 × 0.40

Data collection
Diffractometer	Oxford Xcalibur with Eos detector? diffractometer
Absorption correction	Multi-scan CrysAlis PRO (Oxford Diffraction, 2009)
T_min, T_max	0.805, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	95191, 6746, 5888
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.084, 1.06
No. of reflections	6746
No. of parameters	330
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.51

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Diamond (Brandenburg, 2011), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.72 (2)	1.98 (2)	2.694 (2)	175 (2)

Acknowledgements

This publication was funded by the German Research Foundation (DFG) and Heinrich-Heine-Universität Düsseldorf under the funding programme Open Access Publishing.

References

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