A tetra­nuclear chlorido-bridged manganese(II) cluster with imidazole ligands

Kurawa, M.A.; Adams, C.J.; Orpen, A.G.

doi:10.1107/S1600536808029139

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1276-m1277

doi:10.1107/S1600536808029139

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A tetranuclear chlorido-bridged manganese(II) cluster with imidazole ligands

Mukhtar A. Kurawa,^a Christopher J. Adams ^a ^* and A. Guy. Orpen ^a

^aSchool of Chemistry, University of Bristol, Bristol, BS8 1TS, UK
^*Correspondence e-mail: C.J.Adams@bris.ac.uk

(Received 8 September 2008; accepted 11 September 2008; online 20 September 2008)

The crystal structure of di-μ₃-chlorido-tetra-μ₂-chlorido-dichloridoocta(imidazole-κN)tetramanganese(II) ethanol 1.234 solvate, [Mn₄Cl₈(C₃H₄N₂)₈]·1.234C₂H₅O or [Mn₄Cl₈(Him)₈]·1.234EtOH, where Him is imidazole (C₃H₄N₂), is based upon two Mn₄Cl₄ cubes which share one face, and which each lack one manganese vertex, giving a Mn₄Cl₆ unit. This contains two different octahedral coordination environments for the Mn atoms. Mn1 is coordinated by four bridging chlorido ligands and two imidazole N atoms, whereas Mn2 is coordinated by three bridging and one terminal Cl and two imidazole N atoms. The remaining two Mn centres are generated by inversion symmetry. A partial occupancy solvent molecule (ethanol) is present. The crystal structure displays several N—H⋯Cl and N—H⋯O hydrogen bonds.

Related literature

Lee et al. (2000 ) reported the structure and magnetic properties of a similar chlorido-bridged tetranuclear cluster of cadmium(II) with 2(2-pyridyl)-4,4′,5,5′-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy-3-N-oxide (NIToPY). For the structure of [{CdCl₂(Him)₂}_n], see: Flook et al. (1973 ).

Experimental

Crystal data

[Mn₄Cl₈(C₃H₄N₂)₈]·1.234C₂H₅O
M_r = 1103.45
Triclinic, $[P \overline 1]$
a = 8.4763 (16) Å
b = 10.696 (2) Å
c = 12.764 (2) Å
α = 99.206 (3)°
β = 105.706 (4)°
γ = 96.187 (3)°
V = 1085.7 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.68 mm⁻¹
T = 173 (2) K
0.35 × 0.10 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.815, T_max = 0.850
11294 measured reflections
4920 independent reflections
3315 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.142
S = 1.04
4920 reflections
265 parameters
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8⋯O1ⁱ	0.88	2.09	2.865 (15)	147
N4—H6A⋯Cl3ⁱⁱ	0.88	2.49	3.289 (4)	152
N6—H10A⋯Cl4ⁱⁱ	0.88	2.48	3.247 (4)	146
N2—H2A⋯Cl4ⁱⁱⁱ	0.88	2.55	3.292 (4)	143
Symmetry codes: (i) x, y-1, z; (ii) x+1, y, z; (iii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808029139/sg2263sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029139/sg2263Isup2.hkl

checkCIF report

Comment top

During our exploration of solid state routes for accessing coordination compounds, we ground CdCl₂ with imidazole to form polymeric [{CdCl₂(Him)₂}_n], whose structure was reported by Flook et al. (1973). We sought to synthesize the manganese analogue in a similar fashion by grinding MnCl₂.4H₂O with an equimolar amount of imidazole. The resulting polycrystalline powder (of unknown structure) was recrystallized from absolute ethanol to afford a single-crystal. The title compound I was obtained, which crystallizes in the triclinic crystal system in the P1 space group. The molecule is centrosymmetric, containing four manganese atoms in two different coordination environments and crystallizes across an inversion centre so there is a half a molecule in the asymmetric unit. One type of manganese atom is bonded to four bridging (two µ₂-Cl and two µ₃-Cl) chlorine atoms, and two imidazole N atoms, completing an octahedral coordination sphere. The second is type is bonded to three bridging (two µ₂-Cl and one µ₃-Cl) and one terminal chlorine atoms, again with two imidazole N atoms completing octahedral coordination. One of the imidazole ligands shows a carbon-nitrogen disorder, and a partial occupancy solvent molecule (ethanol) is present in the crystal structure, giving rise to N—H···O hydrogen bonds in addition to the N—H···Cl bonds between the chlorine atoms and the imidazole NH donors. The calculated powder pattern of I does not match that obtained from the crude material.

Related literature top

Lee et al. (2000) reported the structure and magnetic properties of a similar chloro-bridged tetranuclear cluster of cadmium(II) with 2(2-pyridyl)-4,4',5,5'-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy 3-N-oxide (NIToPY). For the structure of [{CdCl₂(Him)₂}_n], see: Flook et al. (1973).

Experimental top

1 mmol of MnCl₂.4H₂O was ground with 2 mmol of imidazole resulting in the formation of an off-white polycrystalline powder. This was dissolved in absolute alcohol and the resulting solution allowed to evaporate slowly at room temperature, leading to the formation of colourless needle-like crystals.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

	Fig. 1. The molecular structure of I with atom labels and 50% probability displacement ellipsoids for non-H atoms. [Symmetry code (A):-x, -y, -z + 1]
	Fig. 2. Hydrogen bond environment for I, showing only chlorine atoms of the neighbouring cluster.

di-µ₃-chlorido-tetra-µ₂-chlorido-dichloridoocta(imidazole- κN)tetramanganese(II) ethanol 1.234-solvate top

Crystal data top

[Mn₄Cl₈(C₃H₄N₂)₈]·1.234C₂H₅O	Z = 1
M_r = 1103.45	F(000) = 554.8
Triclinic, P1	D_x = 1.688 Mg m⁻³
a = 8.4763 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.696 (2) Å	Cell parameters from 3784 reflections
c = 12.764 (2) Å	θ = 2.3–27.5°
α = 99.206 (3)°	µ = 1.68 mm⁻¹
β = 105.706 (4)°	T = 173 K
γ = 96.187 (3)°	Needle, colourless
V = 1085.7 (3) Å³	0.35 × 0.10 × 0.10 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	4920 independent reflections
Radiation source: fine-focus sealed tube	3315 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
phi and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→10
T_min = 0.815, T_max = 0.850	k = −13→13
11294 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.055P)² + 2.417P] where P = (F_o² + 2F_c²)/3
4920 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 1.17 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

[Mn₄Cl₈(C₃H₄N₂)₈]·1.234C₂H₅O	γ = 96.187 (3)°
M_r = 1103.45	V = 1085.7 (3) Å³
Triclinic, P1	Z = 1
a = 8.4763 (16) Å	Mo Kα radiation
b = 10.696 (2) Å	µ = 1.68 mm⁻¹
c = 12.764 (2) Å	T = 173 K
α = 99.206 (3)°	0.35 × 0.10 × 0.10 mm
β = 105.706 (4)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4920 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	3315 reflections with I > 2σ(I)
T_min = 0.815, T_max = 0.850	R_int = 0.048
11294 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.04	Δρ_max = 1.17 e Å⁻³
4920 reflections	Δρ_min = −0.77 e Å⁻³
265 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	Occ. (<1)
Mn1	0.11612 (8)	0.13627 (6)	0.44334 (5)	0.01743 (18)
Mn2	0.14342 (8)	0.17089 (6)	0.75623 (5)	0.01930 (19)
Cl1	0.15783 (14)	−0.04351 (11)	0.30310 (9)	0.0227 (3)
Cl2	−0.18410 (13)	0.00684 (10)	0.40027 (9)	0.0191 (2)
Cl3	0.05611 (13)	0.29485 (10)	0.59545 (9)	0.0194 (2)
Cl4	0.07690 (15)	0.33793 (11)	0.88887 (9)	0.0258 (3)
N1	0.0440 (5)	0.2621 (4)	0.3243 (3)	0.0242 (9)
N2	−0.0167 (5)	0.4279 (4)	0.2492 (3)	0.0319 (10)
H2A	−0.0456	0.5033	0.2418	0.038*
N3	0.3775 (5)	0.2228 (3)	0.4924 (3)	0.0208 (8)
N4	0.6483 (5)	0.2509 (4)	0.5285 (4)	0.0313 (10)
H6A	0.7486	0.2343	0.5312	0.038*
N5	0.4062 (5)	0.2587 (4)	0.7973 (3)	0.0273 (9)
N6	0.6744 (5)	0.2843 (4)	0.8230 (4)	0.0339 (10)
H10A	0.7720	0.2686	0.8176	0.041*
N7	0.2169 (5)	0.0477 (4)	0.8769 (3)	0.0305 (10)
C11	0.2455 (11)	−0.0398 (8)	1.0273 (6)	0.093 (4)	0.14 (9)
H11	0.2351	−0.0564	1.0963	0.111*
N8'	0.2455 (11)	−0.0398 (8)	1.0273 (6)	0.093 (4)	0.86 (9)
C1	−0.0020 (6)	0.3753 (5)	0.3382 (4)	0.0276 (11)
H1A	−0.0224	0.4151	0.4043	0.033*
C2	0.0570 (9)	0.2431 (6)	0.2190 (4)	0.0452 (16)
H4B	0.0877	0.1684	0.1835	0.054*
C3	0.0209 (8)	0.3439 (5)	0.1723 (5)	0.0419 (15)
H3B	0.0216	0.3543	0.0999	0.050*
C4	0.5062 (6)	0.1690 (5)	0.4816 (4)	0.0274 (11)
H5A	0.4992	0.0830	0.4451	0.033*
C5	0.6102 (6)	0.3629 (5)	0.5705 (5)	0.0346 (13)
H7B	0.6861	0.4390	0.6082	0.042*
C6	0.4431 (6)	0.3469 (5)	0.5491 (4)	0.0280 (11)
H8A	0.3811	0.4105	0.5697	0.034*
C7	0.5294 (6)	0.2089 (5)	0.7709 (4)	0.0266 (11)
H9A	0.5164	0.1296	0.7212	0.032*
C8	0.6458 (8)	0.3888 (6)	0.8853 (6)	0.0563 (19)
H11A	0.7259	0.4591	0.9312	0.068*
C9	0.4800 (8)	0.3732 (6)	0.8693 (6)	0.060 (2)
H12B	0.4230	0.4321	0.9026	0.072*
C10	0.1834 (11)	0.0537 (8)	0.9716 (6)	0.071 (2)
H13A	0.1235	0.1149	0.9989	0.085*
N8	0.3293 (11)	−0.1058 (8)	0.9569 (8)	0.079 (4)	0.14 (9)
H8	0.3828	−0.1704	0.9700	0.095*
C11'	0.3293 (11)	−0.1058 (8)	0.9569 (8)	0.079 (4)	0.86 (9)
C12	0.3115 (11)	−0.0513 (9)	0.8673 (8)	0.090 (3)
H16A	0.3556	−0.0757	0.8075	0.108*
O1	0.5305 (15)	0.7035 (11)	0.9177 (10)	0.111 (4)	0.617 (10)
C13	0.443 (2)	0.6632 (16)	0.7342 (11)	0.097 (6)	0.617 (10)
H17A	0.3723	0.7299	0.7260	0.145*	0.617 (10)
H18B	0.3765	0.5830	0.7359	0.145*	0.617 (10)
H19C	0.4887	0.6497	0.6713	0.145*	0.617 (10)
C14	0.548 (3)	0.694 (2)	0.8143 (16)	0.128 (8)	0.617 (10)
H20A	0.6028	0.7797	0.8117	0.154*	0.617 (10)
H21B	0.6291	0.6350	0.8098	0.154*	0.617 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0148 (4)	0.0163 (4)	0.0199 (4)	0.0015 (3)	0.0049 (3)	0.0011 (3)
Mn2	0.0151 (4)	0.0200 (4)	0.0188 (4)	0.0021 (3)	0.0003 (3)	0.0009 (3)
Cl1	0.0185 (6)	0.0204 (6)	0.0263 (6)	0.0020 (5)	0.0062 (5)	−0.0021 (4)
Cl2	0.0148 (6)	0.0177 (5)	0.0223 (5)	0.0032 (4)	0.0025 (4)	0.0014 (4)
Cl3	0.0173 (6)	0.0194 (6)	0.0200 (5)	0.0041 (4)	0.0040 (4)	0.0013 (4)
Cl4	0.0244 (6)	0.0255 (6)	0.0237 (6)	0.0007 (5)	0.0069 (5)	−0.0036 (5)
N1	0.026 (2)	0.025 (2)	0.0202 (19)	0.0022 (18)	0.0055 (17)	0.0034 (16)
N2	0.036 (3)	0.024 (2)	0.035 (2)	0.008 (2)	0.006 (2)	0.0108 (19)
N3	0.017 (2)	0.016 (2)	0.030 (2)	0.0015 (16)	0.0058 (17)	0.0050 (16)
N4	0.011 (2)	0.036 (3)	0.046 (3)	0.0024 (18)	0.0052 (19)	0.012 (2)
N5	0.016 (2)	0.028 (2)	0.030 (2)	0.0015 (18)	0.0011 (17)	−0.0047 (18)
N6	0.016 (2)	0.042 (3)	0.038 (2)	0.006 (2)	0.0026 (19)	0.003 (2)
N7	0.031 (3)	0.030 (2)	0.027 (2)	0.006 (2)	−0.0024 (19)	0.0121 (18)
C11	0.119 (7)	0.097 (7)	0.067 (5)	0.025 (6)	0.014 (5)	0.049 (5)
N8'	0.119 (7)	0.097 (7)	0.067 (5)	0.025 (6)	0.014 (5)	0.049 (5)
C1	0.037 (3)	0.021 (3)	0.028 (3)	0.012 (2)	0.013 (2)	0.007 (2)
C2	0.081 (5)	0.034 (3)	0.030 (3)	0.019 (3)	0.028 (3)	0.008 (2)
C3	0.065 (4)	0.035 (3)	0.029 (3)	0.004 (3)	0.019 (3)	0.010 (2)
C4	0.020 (3)	0.027 (3)	0.036 (3)	0.006 (2)	0.007 (2)	0.009 (2)
C5	0.021 (3)	0.031 (3)	0.048 (3)	−0.005 (2)	0.008 (2)	0.008 (2)
C6	0.020 (3)	0.022 (3)	0.040 (3)	0.004 (2)	0.008 (2)	0.004 (2)
C7	0.020 (3)	0.030 (3)	0.026 (2)	0.007 (2)	0.003 (2)	0.002 (2)
C8	0.026 (3)	0.052 (4)	0.069 (4)	−0.004 (3)	0.004 (3)	−0.025 (3)
C9	0.033 (4)	0.045 (4)	0.081 (5)	−0.009 (3)	0.017 (3)	−0.038 (3)
C10	0.103 (7)	0.069 (5)	0.053 (4)	0.032 (5)	0.025 (4)	0.031 (4)
N8	0.076 (6)	0.059 (5)	0.087 (7)	0.011 (4)	−0.011 (5)	0.033 (5)
C11'	0.076 (6)	0.059 (5)	0.087 (7)	0.011 (4)	−0.011 (5)	0.033 (5)
C12	0.075 (6)	0.087 (7)	0.091 (6)	−0.005 (5)	−0.014 (5)	0.050 (6)
O1	0.111 (10)	0.106 (9)	0.117 (9)	0.045 (7)	0.025 (8)	0.015 (7)
C13	0.145 (17)	0.109 (13)	0.043 (8)	0.071 (12)	0.023 (9)	0.009 (8)
C14	0.15 (2)	0.18 (2)	0.097 (14)	0.066 (17)	0.072 (15)	0.041 (15)

Geometric parameters (Å, º) top

Mn1—N3	2.186 (4)	N6—H10A	0.8800
Mn1—N1	2.196 (4)	N7—C10	1.308 (8)
Mn1—Cl1	2.5328 (13)	N7—C12	1.405 (10)
Mn1—Cl3	2.5636 (13)	C11—C10	1.387 (10)
Mn1—Cl2	2.6332 (13)	C11—N8	1.436 (11)
Mn1—Cl2ⁱ	2.6841 (13)	C11—H11	0.9500
Mn2—N7	2.192 (4)	C1—H1A	0.9500
Mn2—N5	2.208 (4)	C2—C3	1.338 (8)
Mn2—Cl4	2.4784 (14)	C2—H4B	0.9500
Mn2—Cl3	2.6033 (13)	C3—H3B	0.9500
Mn2—Cl1ⁱ	2.6121 (14)	C4—H5A	0.9500
Mn2—Cl2ⁱ	2.6498 (13)	C5—C6	1.355 (7)
Cl1—Mn2ⁱ	2.6121 (14)	C5—H7B	0.9500
Cl2—Mn2ⁱ	2.6498 (13)	C6—H8A	0.9500
Cl2—Mn1ⁱ	2.6841 (13)	C7—H9A	0.9500
N1—C1	1.311 (6)	C8—C9	1.353 (8)
N1—C2	1.364 (6)	C8—H11A	0.9500
N2—C1	1.329 (6)	C9—H12B	0.9500
N2—C3	1.349 (7)	C10—H13A	0.9500
N2—H2A	0.8800	N8—C12	1.345 (10)
N3—C4	1.316 (6)	N8—H8	0.8800
N3—C6	1.382 (6)	C12—H16A	0.9500
N4—C4	1.338 (6)	O1—C14	1.356 (18)
N4—C5	1.341 (7)	C13—C14	1.13 (2)
N4—H6A	0.8800	C13—H17A	0.9800
N5—C7	1.319 (6)	C13—H18B	0.9800
N5—C9	1.378 (7)	C13—H19C	0.9800
N6—C7	1.332 (6)	C14—H20A	0.9900
N6—C8	1.349 (7)	C14—H21B	0.9900

N3—Mn1—N1	92.56 (14)	C7—N6—H10A	125.9
N3—Mn1—Cl1	92.29 (10)	C8—N6—H10A	125.9
N1—Mn1—Cl1	95.12 (11)	C10—N7—C12	107.3 (6)
N3—Mn1—Cl3	92.37 (10)	C10—N7—Mn2	126.6 (5)
N1—Mn1—Cl3	90.64 (11)	C12—N7—Mn2	126.1 (5)
Cl1—Mn1—Cl3	172.42 (5)	C10—C11—N8	104.1 (7)
N3—Mn1—Cl2	171.84 (10)	C10—C11—H11	128.0
N1—Mn1—Cl2	95.45 (11)	N8—C11—H11	128.0
Cl1—Mn1—Cl2	85.48 (4)	N1—C1—N2	112.2 (4)
Cl3—Mn1—Cl2	89.08 (4)	N1—C1—H1A	123.9
N3—Mn1—Cl2ⁱ	90.21 (10)	N2—C1—H1A	123.9
N1—Mn1—Cl2ⁱ	174.19 (11)	C3—C2—N1	110.8 (5)
Cl1—Mn1—Cl2ⁱ	89.87 (4)	C3—C2—H4B	124.6
Cl3—Mn1—Cl2ⁱ	84.14 (4)	N1—C2—H4B	124.6
Cl2—Mn1—Cl2ⁱ	81.95 (4)	C2—C3—N2	105.9 (5)
N7—Mn2—N5	89.13 (16)	C2—C3—H3B	127.0
N7—Mn2—Cl4	94.57 (12)	N2—C3—H3B	127.0
N5—Mn2—Cl4	94.27 (11)	N3—C4—N4	111.4 (4)
N7—Mn2—Cl3	173.40 (12)	N3—C4—H5A	124.3
N5—Mn2—Cl3	91.82 (11)	N4—C4—H5A	124.3
Cl4—Mn2—Cl3	91.88 (4)	N4—C5—C6	107.0 (5)
N7—Mn2—Cl1ⁱ	88.65 (12)	N4—C5—H7B	126.5
N5—Mn2—Cl1ⁱ	173.48 (11)	C6—C5—H7B	126.5
Cl4—Mn2—Cl1ⁱ	92.01 (4)	C5—C6—N3	108.8 (5)
Cl3—Mn2—Cl1ⁱ	89.69 (4)	C5—C6—H8A	125.6
N7—Mn2—Cl2ⁱ	89.40 (12)	N3—C6—H8A	125.6
N5—Mn2—Cl2ⁱ	90.27 (11)	N5—C7—N6	111.2 (4)
Cl4—Mn2—Cl2ⁱ	174.01 (5)	N5—C7—H9A	124.4
Cl3—Mn2—Cl2ⁱ	84.06 (4)	N6—C7—H9A	124.4
Cl1ⁱ—Mn2—Cl2ⁱ	83.58 (4)	N6—C8—C9	106.0 (5)
Mn1—Cl1—Mn2ⁱ	97.01 (4)	N6—C8—H11A	127.0
Mn1—Cl2—Mn2ⁱ	93.69 (4)	C9—C8—H11A	127.0
Mn1—Cl2—Mn1ⁱ	98.05 (4)	C8—C9—N5	109.6 (5)
Mn2ⁱ—Cl2—Mn1ⁱ	93.71 (4)	C8—C9—H12B	125.2
Mn1—Cl3—Mn2	97.74 (4)	N5—C9—H12B	125.2
C1—N1—C2	104.0 (4)	N7—C10—C11	112.0 (8)
C1—N1—Mn1	130.2 (3)	N7—C10—H13A	124.0
C2—N1—Mn1	125.4 (4)	C11—C10—H13A	124.0
C1—N2—C3	107.1 (4)	C12—N8—C11	107.9 (8)
C1—N2—H2A	126.4	C12—N8—H8	126.1
C3—N2—H2A	126.4	C11—N8—H8	126.1
C4—N3—C6	105.2 (4)	N8—C12—N7	108.7 (9)
C4—N3—Mn1	128.8 (3)	N8—C12—H16A	125.7
C6—N3—Mn1	125.9 (3)	N7—C12—H16A	125.7
C4—N4—C5	107.7 (4)	C13—C14—O1	125 (2)
C4—N4—H6A	126.2	C13—C14—H20A	106.1
C5—N4—H6A	126.2	O1—C14—H20A	106.1
C7—N5—C9	105.0 (4)	C13—C14—H21B	106.1
C7—N5—Mn2	128.7 (3)	O1—C14—H21B	106.1
C9—N5—Mn2	125.9 (4)	H20A—C14—H21B	106.3
C7—N6—C8	108.2 (5)

N3—Mn1—Cl1—Mn2ⁱ	175.98 (10)	N7—Mn2—N5—C9	−98.3 (5)
N1—Mn1—Cl1—Mn2ⁱ	−91.24 (11)	Cl4—Mn2—N5—C9	−3.8 (5)
Cl2—Mn1—Cl1—Mn2ⁱ	3.85 (4)	Cl3—Mn2—N5—C9	88.3 (5)
Cl2ⁱ—Mn1—Cl1—Mn2ⁱ	85.78 (4)	Cl2ⁱ—Mn2—N5—C9	172.3 (5)
N1—Mn1—Cl2—Mn2ⁱ	90.95 (11)	N5—Mn2—N7—C10	110.9 (6)
Cl1—Mn1—Cl2—Mn2ⁱ	−3.77 (4)	Cl4—Mn2—N7—C10	16.7 (6)
Cl3—Mn1—Cl2—Mn2ⁱ	−178.49 (4)	Cl1ⁱ—Mn2—N7—C10	−75.2 (6)
Cl2ⁱ—Mn1—Cl2—Mn2ⁱ	−94.28 (4)	Cl2ⁱ—Mn2—N7—C10	−158.8 (6)
N1—Mn1—Cl2—Mn1ⁱ	−174.77 (11)	N5—Mn2—N7—C12	−68.0 (5)
Cl1—Mn1—Cl2—Mn1ⁱ	90.51 (4)	Cl4—Mn2—N7—C12	−162.2 (5)
Cl3—Mn1—Cl2—Mn1ⁱ	−84.21 (4)	Cl1ⁱ—Mn2—N7—C12	105.9 (5)
Cl2ⁱ—Mn1—Cl2—Mn1ⁱ	0.0	Cl2ⁱ—Mn2—N7—C12	22.3 (5)
N3—Mn1—Cl3—Mn2	−85.49 (10)	C2—N1—C1—N2	−0.6 (6)
N1—Mn1—Cl3—Mn2	−178.08 (11)	Mn1—N1—C1—N2	172.4 (3)
Cl2—Mn1—Cl3—Mn2	86.47 (4)	C3—N2—C1—N1	0.4 (6)
Cl2ⁱ—Mn1—Cl3—Mn2	4.47 (4)	C1—N1—C2—C3	0.6 (7)
N5—Mn2—Cl3—Mn1	85.55 (11)	Mn1—N1—C2—C3	−172.9 (4)
Cl4—Mn2—Cl3—Mn1	179.89 (5)	N1—C2—C3—N2	−0.4 (8)
Cl1ⁱ—Mn2—Cl3—Mn1	−88.11 (4)	C1—N2—C3—C2	0.0 (7)
Cl2ⁱ—Mn2—Cl3—Mn1	−4.53 (4)	C6—N3—C4—N4	0.4 (5)
N3—Mn1—N1—C1	−89.6 (5)	Mn1—N3—C4—N4	−175.7 (3)
Cl1—Mn1—N1—C1	177.8 (4)	C5—N4—C4—N3	−0.6 (6)
Cl3—Mn1—N1—C1	2.8 (4)	C4—N4—C5—C6	0.5 (6)
Cl2—Mn1—N1—C1	91.9 (4)	N4—C5—C6—N3	−0.2 (6)
N3—Mn1—N1—C2	82.0 (5)	C4—N3—C6—C5	−0.1 (5)
Cl1—Mn1—N1—C2	−10.5 (5)	Mn1—N3—C6—C5	176.2 (3)
Cl3—Mn1—N1—C2	174.4 (5)	C9—N5—C7—N6	0.8 (6)
Cl2—Mn1—N1—C2	−96.5 (5)	Mn2—N5—C7—N6	−171.6 (3)
N1—Mn1—N3—C4	−117.3 (4)	C8—N6—C7—N5	−0.7 (6)
Cl1—Mn1—N3—C4	−22.1 (4)	C7—N6—C8—C9	0.3 (8)
Cl3—Mn1—N3—C4	151.9 (4)	N6—C8—C9—N5	0.2 (9)
Cl2ⁱ—Mn1—N3—C4	67.8 (4)	C7—N5—C9—C8	−0.6 (8)
N1—Mn1—N3—C6	67.3 (4)	Mn2—N5—C9—C8	172.1 (5)
Cl1—Mn1—N3—C6	162.5 (4)	C12—N7—C10—C11	−2.1 (9)
Cl3—Mn1—N3—C6	−23.4 (4)	Mn2—N7—C10—C11	178.9 (5)
Cl2ⁱ—Mn1—N3—C6	−107.6 (4)	N8—C11—C10—N7	1.7 (10)
N7—Mn2—N5—C7	72.7 (4)	C10—C11—N8—C12	−0.6 (10)
Cl4—Mn2—N5—C7	167.2 (4)	C11—N8—C12—N7	−0.6 (9)
Cl3—Mn2—N5—C7	−100.8 (4)	C10—N7—C12—N8	1.6 (9)
Cl2ⁱ—Mn2—N5—C7	−16.7 (4)	Mn2—N7—C12—N8	−179.3 (5)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···O1ⁱⁱ	0.88	2.09	2.865 (15)	147
N4—H6A···Cl3ⁱⁱⁱ	0.88	2.49	3.289 (4)	152
N6—H10A···Cl4ⁱⁱⁱ	0.88	2.48	3.247 (4)	146
N2—H2A···Cl4^iv	0.88	2.55	3.292 (4)	143

Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn₄Cl₈(C₃H₄N₂)₈]·1.234C₂H₅O
M_r	1103.45
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.4763 (16), 10.696 (2), 12.764 (2)
α, β, γ (°)	99.206 (3), 105.706 (4), 96.187 (3)
V (Å³)	1085.7 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.68
Crystal size (mm)	0.35 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.815, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	11294, 4920, 3315
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.142, 1.04
No. of reflections	4920
No. of parameters	265
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −0.77

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···O1ⁱ	0.88	2.09	2.865 (15)	146.6
N4—H6A···Cl3ⁱⁱ	0.88	2.49	3.289 (4)	151.6
N6—H10A···Cl4ⁱⁱ	0.88	2.48	3.247 (4)	145.9
N2—H2A···Cl4ⁱⁱⁱ	0.88	2.55	3.292 (4)	142.7

Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x, −y+1, −z+1.

Acknowledgements

MAK thanks Bayero University, Kano, Nigeria for funding.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flook, R. J., Freeman, H. C., Huq, F. & Rosalky, J. M. (1973). Acta Cryst. B29, 903–906. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Lee, C.-J., Wei, H.-H., Lee, G.-H. & Wang, Y. (2000). Inorg. Chem. Commun. 3, 690–693. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar