trans-Dichlorido(1,4,8,11-tetra-azacyclo-tetra-deca-ne)manganese(III) tetra-fluorido-borate.

In the title manganese(III) complex, [MnCl(2)(C(10)H(24)N(4))]BF(4) or trans-[MnCl(2)(cyclam)]BF(4) (cyclam is the tetra-dentate amine ligand 1,4,8,11-tetra-azacyclo-tetra-deca-ne), the Mn(III) ions occupy the center of a distorted octa-hedron coordinated by all four ligand nitro-gen donors in the macrobicyclic cavity and two chloride ions occupy the axial positions. Intra-molecular hydrogen bonding involving the coordinated chloride ions and the hydrogen atoms of the cyclam ligand is observed. Inter-molecular hydrogen bonding involving the tetrafluoridoborate anion and hydrogen atoms of the cyclam ligand leads to an infinite one-dimensional chain along the a axis. The tetra-fluoridoborate and inorganic units are linked by N-H⋯F hydrogen bonds. The structure may be compared with those of analogous compounds [MnCl(2)(cyclam)]ClO(4) and [Mn(CN)(2)(cyclam)]ClO(4).

Related literature

For applications of cyclams, see: Lindoy (1992 ▶); Izatt et al. (1991 ▶, 1995 ▶); Enoki et al. (2003 ▶); Steward & McLaughlin (2004 ▶); Sibert (2002 ▶); Volkert & Hoffman (1999 ▶); Anderson & Welch (1999 ▶); Caravan et al. (1999 ▶). For isostructural compounds, see: Shaikh et al. (2004 ▶); Mossin et al. (2002 ▶). For other n class="Chemical">cyclam-containing structures, see: Brewer et al. (1989 ▶); Letumier et al. (1998 ▶); Bakac & Espenson (1987 ▶); Mossin et al. (2005 ▶); Blessing (1987 ▶); Sosa-Torres & Toscano (1997 ▶).

Experimental

Crystal data

[MnCl2(C10H24N4)]BF4

M = 412.98

Orthorhombic,

a = 6.5660 (3) Å

b = 13.3760 (2) Å

c = 19.5846 (3) Å

V = 1720.05 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.12 mm−1

T = 298 K

0.40 × 0.40 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.674, T max = 0.814

3013 measured reflections

2735 independent reflections

2442 reflections with I > 2σ(I)

R int = 0.020

2 standard reflections every 120 min intensity decay: 3%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.097

S = 1.05

2735 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.50 e Å−3

Absolute structure: Flack (1983 ▶), 569 Friedel pairs

Flack parameter: 0.00 (3)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004058/br2133sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004058/br2133Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[MnCl2(C10H24N4)]BF4	F(000) = 848
Mr = 412.98	Dx = 1.59 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 6.5660 (3) Å	θ = 10–15°
b = 13.3760 (2) Å	µ = 1.12 mm−1
c = 19.5846 (3) Å	T = 298 K
V = 1720.05 (9) Å3	Prism, green
Z = 4	0.40 × 0.40 × 0.20 mm

Enraf–Nonius CAD-4 diffractometer	2442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
graphite	θmax = 27.0°, θmin = 2.1°
non–profiled ω/2θ scans	h = −8→2
Absorption correction: ψ scan (North et al., 1968)	k = −1→17
Tmin = 0.674, Tmax = 0.814	l = −1→24
3013 measured reflections	2 standard reflections every 120 min
2735 independent reflections	intensity decay: 3%

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)] = 0.034	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0545P)2 + 1.0781P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2735 reflections	Δρmax = 0.70 e Å−3
199 parameters	Δρmin = −0.50 e Å−3
0 restraints	Absolute structure: Flack (1983), 569 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (3)

Experimental. Absorption correction: Number of psi-scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

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.

	x	y	z	Uiso*/Ueq
Mn	0.77998 (8)	0.47206 (4)	0.37355 (2)	0.02124 (13)
Cl1	1.08555 (14)	0.57065 (7)	0.33104 (5)	0.0340 (2)
Cl2	0.47956 (13)	0.37068 (8)	0.41610 (5)	0.0350 (2)
C1	0.6089 (7)	0.4243 (3)	0.24327 (19)	0.0355 (9)
H1A	0.4871	0.3929	0.2613	0.043*
H1B	0.6247	0.4045	0.1959	0.043*
C2	0.5915 (7)	0.5364 (3)	0.24847 (18)	0.0347 (9)
H2A	0.4700	0.5592	0.2251	0.042*
H2B	0.7089	0.5679	0.2275	0.042*
C3	0.6006 (7)	0.6724 (3)	0.3358 (2)	0.0337 (9)
H3A	0.4972	0.7077	0.3099	0.040*
H3B	0.7328	0.6948	0.3198	0.040*
C4	0.5780 (7)	0.6979 (3)	0.4115 (2)	0.0401 (10)
H4A	0.4539	0.6674	0.4284	0.048*
H4B	0.5633	0.7698	0.4160	0.048*
C5	0.7560 (7)	0.6637 (3)	0.4564 (2)	0.0393 (9)
H5A	0.8826	0.6880	0.4371	0.047*
H5B	0.7413	0.6927	0.5016	0.047*
C6	0.9408 (7)	0.5187 (4)	0.50530 (19)	0.0403 (10)
H6A	0.9178	0.5363	0.5527	0.048*
H6B	1.0654	0.5508	0.4903	0.048*
C7	0.9609 (7)	0.4063 (4)	0.4985 (2)	0.0409 (11)
H7A	1.0804	0.3831	0.5230	0.049*
H7B	0.8420	0.3736	0.5176	0.049*
C8	0.9738 (7)	0.2730 (3)	0.4095 (2)	0.0405 (10)
H8A	0.8453	0.2457	0.4252	0.049*
H8B	1.0824	0.2398	0.4343	0.049*
C9	0.9975 (8)	0.2522 (3)	0.3335 (3)	0.0445 (11)
H9A	1.0221	0.1813	0.3273	0.053*
H9B	1.1168	0.2876	0.3171	0.053*
C10	0.8144 (7)	0.2825 (3)	0.2895 (2)	0.0388 (10)
H10A	0.8304	0.2544	0.2442	0.047*
H10B	0.6914	0.2546	0.3093	0.047*
N1	0.7920 (5)	0.3928 (2)	0.28397 (15)	0.0283 (6)
H1	0.9032	0.4152	0.2609	0.034*
N2	0.5806 (5)	0.5632 (2)	0.32309 (14)	0.0245 (6)
H2	0.4538	0.5456	0.3375	0.029*
N3	0.7654 (5)	0.5538 (2)	0.46247 (14)	0.0294 (7)
H3	0.6498	0.5344	0.4844	0.035*
N4	0.9798 (5)	0.3817 (2)	0.42444 (16)	0.0271 (7)
H4	1.1063	0.4026	0.4118	0.032*
F1	1.2555 (6)	0.4764 (4)	0.62517 (17)	0.0960 (13)
F2	1.5921 (6)	0.4961 (3)	0.62145 (19)	0.0869 (12)
F3	1.3893 (6)	0.5936 (3)	0.55560 (14)	0.0730 (10)
F4	1.3937 (9)	0.6116 (3)	0.67105 (19)	0.1155 (18)
B1	1.4102 (9)	0.5490 (5)	0.6183 (3)	0.0480 (13)

	U11	U22	U33	U12	U13	U23
Mn	0.0161 (2)	0.0242 (2)	0.0234 (2)	0.0004 (2)	−0.0017 (2)	0.0004 (2)
Cl1	0.0189 (4)	0.0365 (5)	0.0467 (5)	−0.0043 (4)	0.0023 (4)	0.0101 (4)
Cl2	0.0190 (4)	0.0414 (5)	0.0445 (5)	−0.0054 (4)	0.0022 (4)	0.0095 (4)
C1	0.033 (2)	0.046 (2)	0.0278 (17)	−0.005 (2)	−0.0042 (17)	−0.0046 (18)
C2	0.032 (2)	0.044 (2)	0.0276 (17)	0.000 (2)	−0.0093 (17)	0.0073 (17)
C3	0.030 (2)	0.0259 (18)	0.045 (2)	0.0040 (18)	−0.002 (2)	0.0064 (16)
C4	0.034 (2)	0.0282 (19)	0.058 (2)	0.0078 (19)	0.001 (2)	−0.0099 (18)
C5	0.037 (2)	0.0372 (19)	0.044 (2)	−0.002 (2)	−0.002 (2)	−0.0129 (17)
C6	0.034 (2)	0.060 (3)	0.0263 (18)	−0.005 (2)	−0.0107 (17)	−0.004 (2)
C7	0.031 (2)	0.056 (3)	0.035 (2)	−0.004 (2)	−0.0072 (18)	0.015 (2)
C8	0.032 (2)	0.030 (2)	0.059 (3)	0.0023 (19)	−0.001 (2)	0.015 (2)
C9	0.040 (2)	0.028 (2)	0.066 (3)	0.004 (2)	0.004 (2)	−0.006 (2)
C10	0.035 (2)	0.0306 (19)	0.051 (2)	−0.0004 (19)	0.003 (2)	−0.0123 (17)
N1	0.0253 (15)	0.0300 (14)	0.0295 (13)	−0.0021 (15)	0.0012 (15)	−0.0027 (11)
N2	0.0179 (13)	0.0265 (14)	0.0291 (14)	−0.0010 (13)	0.0000 (13)	0.0033 (12)
N3	0.0212 (15)	0.0399 (16)	0.0271 (12)	−0.0027 (15)	0.0024 (13)	−0.0055 (12)
N4	0.0179 (13)	0.0304 (16)	0.0330 (15)	−0.0017 (14)	−0.0018 (13)	0.0075 (13)
F1	0.069 (2)	0.143 (4)	0.076 (2)	−0.037 (3)	−0.004 (2)	0.026 (2)
F2	0.0534 (19)	0.094 (3)	0.113 (3)	0.0194 (19)	−0.014 (2)	0.024 (2)
F3	0.065 (2)	0.102 (3)	0.0516 (15)	0.001 (2)	−0.0040 (16)	0.0232 (17)
F4	0.166 (5)	0.104 (3)	0.076 (2)	0.041 (4)	−0.031 (3)	−0.028 (2)
B1	0.043 (3)	0.065 (3)	0.036 (2)	0.011 (3)	−0.009 (2)	0.004 (2)

Mn—N2	2.043 (3)	C6—C7	1.516 (6)
Mn—N4	2.043 (3)	C6—H6A	0.9700
Mn—N1	2.052 (3)	C6—H6B	0.9700
Mn—N3	2.059 (3)	C7—N4	1.492 (5)
Mn—Cl2	2.5346 (10)	C7—H7A	0.9700
Mn—Cl1	2.5412 (10)	C7—H7B	0.9700
C1—N1	1.503 (5)	C8—N4	1.484 (5)
C1—C2	1.506 (6)	C8—C9	1.521 (7)
C1—H1A	0.9700	C8—H8A	0.9700
C1—H1B	0.9700	C8—H8B	0.9700
C2—N2	1.506 (4)	C9—C10	1.533 (6)
C2—H2A	0.9700	C9—H9A	0.9700
C2—H2B	0.9700	C9—H9B	0.9700
C3—N2	1.488 (5)	C10—N1	1.486 (5)
C3—C4	1.529 (6)	C10—H10A	0.9700
C3—H3A	0.9700	C10—H10B	0.9700
C3—H3B	0.9700	N1—H1	0.9100
C4—C5	1.532 (6)	N2—H2	0.9100
C4—H4A	0.9700	N3—H3	0.9100
C4—H4B	0.9700	N4—H4	0.9100
C5—N3	1.476 (5)	F1—B1	1.412 (7)
C5—H5A	0.9700	F2—B1	1.389 (7)
C5—H5B	0.9700	F3—B1	1.373 (6)
C6—N3	1.500 (5)	F4—B1	1.333 (7)
N2—Mn—N4	179.62 (14)	C6—C7—H7A	110.1
N2—Mn—N1	85.38 (12)	N4—C7—H7B	110.1
N4—Mn—N1	94.96 (13)	C6—C7—H7B	110.1
N2—Mn—N3	93.58 (12)	H7A—C7—H7B	108.4
N4—Mn—N3	86.07 (13)	N4—C8—C9	111.7 (4)
N1—Mn—N3	178.93 (13)	N4—C8—H8A	109.3
N2—Mn—Cl2	88.83 (9)	C9—C8—H8A	109.3
N4—Mn—Cl2	91.32 (9)	N4—C8—H8B	109.3
N1—Mn—Cl2	91.98 (10)	C9—C8—H8B	109.3
N3—Mn—Cl2	88.27 (9)	H8A—C8—H8B	107.9
N2—Mn—Cl1	92.17 (9)	C8—C9—C10	114.9 (4)
N4—Mn—Cl1	87.68 (9)	C8—C9—H9A	108.5
N1—Mn—Cl1	87.58 (10)	C10—C9—H9A	108.5
N3—Mn—Cl1	92.20 (9)	C8—C9—H9B	108.5
Cl2—Mn—Cl1	178.87 (4)	C10—C9—H9B	108.5
N1—C1—C2	107.7 (3)	H9A—C9—H9B	107.5
N1—C1—H1A	110.2	N1—C10—C9	112.4 (3)
C2—C1—H1A	110.2	N1—C10—H10A	109.1
N1—C1—H1B	110.2	C9—C10—H10A	109.1
C2—C1—H1B	110.2	N1—C10—H10B	109.1
H1A—C1—H1B	108.5	C9—C10—H10B	109.1
C1—C2—N2	107.8 (3)	H10A—C10—H10B	107.9
C1—C2—H2A	110.1	C10—N1—C1	113.4 (3)
N2—C2—H2A	110.1	C10—N1—Mn	117.0 (2)
C1—C2—H2B	110.1	C1—N1—Mn	106.1 (2)
N2—C2—H2B	110.1	C10—N1—H1	106.6
H2A—C2—H2B	108.5	C1—N1—H1	106.6
N2—C3—C4	111.9 (3)	Mn—N1—H1	106.6
N2—C3—H3A	109.2	C3—N2—C2	113.0 (3)
C4—C3—H3A	109.2	C3—N2—Mn	116.6 (2)
N2—C3—H3B	109.2	C2—N2—Mn	107.3 (2)
C4—C3—H3B	109.2	C3—N2—H2	106.4
H3A—C3—H3B	107.9	C2—N2—H2	106.4
C3—C4—C5	114.6 (4)	Mn—N2—H2	106.4
C3—C4—H4A	108.6	C5—N3—C6	112.9 (3)
C5—C4—H4A	108.6	C5—N3—Mn	117.6 (2)
C3—C4—H4B	108.6	C6—N3—Mn	105.7 (2)
C5—C4—H4B	108.6	C5—N3—H3	106.7
H4A—C4—H4B	107.6	C6—N3—H3	106.7
N3—C5—C4	112.0 (3)	Mn—N3—H3	106.7
N3—C5—H5A	109.2	C8—N4—C7	113.9 (3)
C4—C5—H5A	109.2	C8—N4—Mn	117.8 (3)
N3—C5—H5B	109.2	C7—N4—Mn	106.9 (3)
C4—C5—H5B	109.2	C8—N4—H4	105.8
H5A—C5—H5B	107.9	C7—N4—H4	105.8
N3—C6—C7	109.2 (4)	Mn—N4—H4	105.8
N3—C6—H6A	109.8	F4—B1—F3	114.3 (5)
C7—C6—H6A	109.8	F4—B1—F2	110.8 (5)
N3—C6—H6B	109.8	F3—B1—F2	110.3 (5)
C7—C6—H6B	109.8	F4—B1—F1	107.5 (5)
H6A—C6—H6B	108.3	F3—B1—F1	108.2 (4)
N4—C7—C6	108.1 (3)	F2—B1—F1	105.3 (4)
N4—C7—H7A	110.1

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F4i	0.91	2.24	3.025 (6)	145
N2—H2···Cl1ii	0.91	2.44	3.256 (3)	149
N3—H3···F3ii	0.91	2.34	3.116 (5)	143
N4—H4···Cl2iii	0.91	2.49	3.289 (3)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯F4i	0.91	2.24	3.025 (6)	145
N2—H2⋯Cl1ii	0.91	2.44	3.256 (3)	149
N3—H3⋯F3ii	0.91	2.34	3.116 (5)	143
N4—H4⋯Cl2iii	0.91	2.49	3.289 (3)	147

Symmetry codes: (i) ; (ii) ; (iii) .