{4,6-Bis[(E)-1-methyl-2-(pyridin-2-yl­methyl­idene)hydrazinyl]pyrimidine-κ3N,N′,N′′}dichloridomanganese(II)

Marzec, B.; Mahimaidoss, M.; Zhang, L.; McCabe, T.; Schmitt, W.

doi:10.1107/S1600536811043352

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1676

https://doi.org/10.1107/S1600536811043352

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{4,6-Bis[(E)-1-methyl-2-(pyridin-2-ylmethylidene)hydrazinyl]pyrimidine-κ³N,N′,N′′}dichloridomanganese(II)

Bartosz Marzec,^a Mariyatra Mahimaidoss,^a Lei Zhang,^a Thomas McCabe ^a and Wolfgang Schmitt ^a ^*

^aSchool of Chemistry and CRANN, Trinity College, University of Dublin, College Green, Dublin 2, Republic of Ireland
^*Correspondence e-mail: schmittw@tcd.ie

(Received 11 October 2011; accepted 19 October 2011; online 5 November 2011)

In the title compound, [MnCl₂(C₁₈H₁₈N₈)], the geometry around the Mn^II centre is distorted square-pyramidal. In the crystal structure, molecules pack via weak C—H⋯N and C—H⋯Cl interactions.

Related literature

For the synthesis of the ligand, see: Schmitt et al. (2003 ). For the coordination chemistry of similar ligand types, see: Stadler et al. (2005 , 2006 ). For coordination chemistry of similar complexes that contain Mn—N bonds, see: Romain et al. (2011 ). For a related structure containing copper(II) ions, see: Marzec et al. (2011 ).

Experimental

Crystal data

[MnCl₂(C₁₈H₁₈N₈)]
M_r = 472.24
Triclinic, $[P \overline 1]$
a = 8.8355 (12) Å
b = 10.0972 (14) Å
c = 12.1466 (17) Å
α = 72.571 (3)°
β = 77.694 (3)°
γ = 75.700 (3)°
V = 990.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 123 K
0.15 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Blessing, 1995 ) T_min = 0.891, T_max = 0.926
13578 measured reflections
4889 independent reflections
4095 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.088
S = 1.04
4889 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N3ⁱ	0.95	2.50	3.358 (3)	151
C18—H18⋯Cl3ⁱⁱ	0.95	2.80	3.508 (2)	133
Symmetry codes: (i) -x-1, -y+2, -z+1; (ii) -x+2, -y, -z+2.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2011 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811043352/su2330sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811043352/su2330Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811043352/su2330Isup3.mol

checkCIF report

Comment top

(Pyridin-2-ylmethylene)hydrazinyl)pyrimidine-based ligands are an interesting class of compounds due to their functionalities and their geometrical features that might contribute significantly to the field of supramolecular chemistry. Lehn and coworkers recently reported that this class of compounds can systematically and modularly be extended resulting in N-functional ligand strands with varying dimensions (Stadler et al., 2005, 2006; Schmitt et al., 2003). The modular nature of the ligands enhances their appeal to be used in coordination chemistry. We present herein, the crystal structure of a manganese(II) complex of the above mentioned ligand.

In the title complex the manganese(II) atom is penta-coordinated by three N atoms of the organic ligand (4,6-bis[(N-methyl-2-(pyrindin-2-ylmethylene)hydrazinyl]pyrimidine) and two Cl atoms (Fig. 1). The coordination geometry of the central Mn^II ion can be best described as distorted square pyramidal. The N5, N7, N8 and Cl3 atoms form the basal plane and the Cl6 Cl atom occupys the apical position. The bond distances between the N atoms and the metal ion vary between 2.2227 (16) Å [Mn1—N5] and 2.2628 (16) Å [Mn1—N7]. The Mn—Cl bond distances are 2.3695 (6) Å for Mn1—Cl3 and 2.3453 (7) Å for Mn1—Cl6. The angle between the central metal ion and the Cl atoms [Cl3—Mn1—Cl6] is equal to 113.06 (2)°. The angles between the Mn^II ion and the coordinating atoms located in the basal plane vary between 69.14 (6)° [N5—Mn1—N7] and 103.08 (4)° [Cl3—Mn1—N8]. The configuration around atoms C6 and C13 is assigned to be E, as the torsion angles N2—N1—C6—C1 and N6—N7—C13—C14 are 176.36 (17)° and -177.09 (16)°, respectively.

In the crystal the complex molecules are connected by intermolecular C—H···Cl and C—H···N hydrogen bonds (Fig. 2). The former exists between the non-coordinating N atom N3 and C atom C2, and the latter between the Cl atom Cl3 and C atom C18, see Table 1 for details.

A related structure that contains copper(II) ions was reported on by us recently (Marzec et al., 2011).

Related literature top

For the synthesis of the ligand, see: Schmitt et al. (2003). For the coordination chemistry of similar ligand types, see: Stadler et al. (2005,2006). For coordination chemistry of similar ligands that contain Mn—N bonds, see: Romain et al. (2011). For a related structure containing copper(II) ions, see: Marzec et al. (2011).

Experimental top

4,6-Bis[N-methyl-2-(pyrindin-2-ylmethylene)hydrazinyl]pyrimidine (0.007 g, 0.025 mmol) was dissolved in 5 ml of dichloromethane and 4.50 ml of methanol. Then 0.50 ml of a methanolic 0.1 M manganese(II)chloride tetrahydrate solution was added and the mixture was left for slow evaporation. Orange, block-shaped crystals of the title compound were collected after 4 d. Yield: ca 85%.

Structure description top

A related structure that contains copper(II) ions was reported on by us recently (Marzec et al., 2011).

For the synthesis of the ligand, see: Schmitt et al. (2003). For the coordination chemistry of similar ligand types, see: Stadler et al. (2005,2006). For coordination chemistry of similar ligands that contain Mn—N bonds, see: Romain et al. (2011). For a related structure containing copper(II) ions, see: Marzec et al. (2011).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2011) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, showing the numbering scheme and displacement ellipsoids drawn at 50% probability level (H atoms have been omitted for clarity).
	Fig. 2. Crystal packing of the title complex, viewed along the a-axis, showing the C—H···Cl interactions as dashed red lines (H atoms have been omitted for clarity).

{4,6-Bis[(E)-1-methyl-2-(pyridin-2-ylmethylidene)hydrazinyl]pyrimidine- κ³N,N',N''}dichloridomanganese(II) top

Crystal data top

[MnCl₂(C₁₈H₁₈N₈)]	Z = 2
M_r = 472.24	F(000) = 482
Triclinic, P1	D_x = 1.583 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8355 (12) Å	Cell parameters from 209 reflections
b = 10.0972 (14) Å	θ = 1.8–28.4°
c = 12.1466 (17) Å	µ = 0.96 mm⁻¹
α = 72.571 (3)°	T = 123 K
β = 77.694 (3)°	Block, orange
γ = 75.700 (3)°	0.15 × 0.10 × 0.08 mm
V = 990.4 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	4889 independent reflections
Radiation source: fine-focus sealed tube	4095 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −11→11
T_min = 0.891, T_max = 0.926	k = −13→13
13578 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0408P)² + 0.5107P] where P = (F_o² + 2F_c²)/3
4889 reflections	(Δ/σ)_max = 0.001
264 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[MnCl₂(C₁₈H₁₈N₈)]	γ = 75.700 (3)°
M_r = 472.24	V = 990.4 (2) Å³
Triclinic, P1	Z = 2
a = 8.8355 (12) Å	Mo Kα radiation
b = 10.0972 (14) Å	µ = 0.96 mm⁻¹
c = 12.1466 (17) Å	T = 123 K
α = 72.571 (3)°	0.15 × 0.10 × 0.08 mm
β = 77.694 (3)°

Data collection top

Bruker SMART CCD diffractometer	4889 independent reflections
Absorption correction: multi-scan (SADABS; Blessing, 1995)	4095 reflections with I > 2σ(I)
T_min = 0.891, T_max = 0.926	R_int = 0.029
13578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
4889 reflections	Δρ_min = −0.24 e Å⁻³
264 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	0.67993 (3)	0.16794 (3)	0.82771 (3)	0.01792 (9)
Cl3	0.79147 (6)	0.23004 (5)	0.96172 (5)	0.02639 (12)
Cl6	0.83681 (6)	0.18893 (6)	0.64375 (4)	0.02952 (13)
N1	0.01708 (19)	0.67410 (17)	0.66222 (14)	0.0208 (3)
N2	0.14098 (19)	0.69997 (17)	0.69778 (15)	0.0212 (3)
N3	−0.3287 (2)	0.85135 (18)	0.53910 (16)	0.0256 (4)
N4	0.37974 (19)	0.59915 (17)	0.76727 (15)	0.0213 (3)
N5	0.47733 (18)	0.34990 (17)	0.80430 (14)	0.0191 (3)
N6	0.32711 (18)	0.19442 (17)	0.79741 (15)	0.0201 (3)
N7	0.45792 (18)	0.09592 (16)	0.82524 (14)	0.0183 (3)
N8	0.72286 (18)	−0.07073 (17)	0.88859 (14)	0.0193 (3)
C1	−0.2119 (2)	0.7419 (2)	0.57423 (17)	0.0213 (4)
C2	−0.4426 (2)	0.8238 (2)	0.49708 (19)	0.0282 (5)
H2	−0.5268	0.8997	0.4731	0.034*
C3	−0.4455 (3)	0.6926 (2)	0.48639 (19)	0.0291 (5)
H3	−0.5288	0.6789	0.4553	0.035*
C4	−0.3236 (3)	0.5808 (2)	0.52218 (19)	0.0294 (5)
H4	−0.3217	0.4888	0.5160	0.035*
C5	−0.2060 (2)	0.6057 (2)	0.56669 (18)	0.0257 (4)
H5	−0.1215	0.5309	0.5921	0.031*
C6	−0.0873 (2)	0.7771 (2)	0.61700 (17)	0.0219 (4)
H6	−0.0844	0.8724	0.6113	0.026*
C7	0.1690 (2)	0.8430 (2)	0.6747 (2)	0.0269 (4)
H7A	0.0817	0.8981	0.7172	0.040*
H7B	0.1756	0.8885	0.5908	0.040*
H7C	0.2683	0.8385	0.7006	0.040*
C8	0.2476 (2)	0.5803 (2)	0.74022 (16)	0.0192 (4)
C9	0.2191 (2)	0.4463 (2)	0.75266 (17)	0.0202 (4)
H9	0.1217	0.4339	0.7398	0.024*
C10	0.3397 (2)	0.3324 (2)	0.78463 (16)	0.0178 (4)
C11	0.4861 (2)	0.4824 (2)	0.79677 (18)	0.0218 (4)
H11	0.5805	0.4943	0.8149	0.026*
C12	0.1896 (2)	0.1539 (2)	0.7783 (2)	0.0257 (4)
H12A	0.1624	0.0739	0.8428	0.039*
H12B	0.2136	0.1263	0.7047	0.039*
H12C	0.1001	0.2341	0.7744	0.039*
C13	0.4659 (2)	−0.0363 (2)	0.83818 (17)	0.0211 (4)
H13	0.3820	−0.0705	0.8253	0.025*
C14	0.6114 (2)	−0.1315 (2)	0.87384 (16)	0.0189 (4)
C15	0.6297 (2)	−0.2762 (2)	0.89248 (18)	0.0236 (4)
H15	0.5485	−0.3155	0.8816	0.028*
C16	0.7687 (2)	−0.3630 (2)	0.92733 (18)	0.0252 (4)
H16	0.7850	−0.4627	0.9400	0.030*
C17	0.8830 (2)	−0.3016 (2)	0.94323 (18)	0.0243 (4)
H17	0.9791	−0.3585	0.9675	0.029*
C18	0.8557 (2)	−0.1558 (2)	0.92326 (17)	0.0217 (4)
H18	0.9348	−0.1145	0.9347	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01333 (14)	0.01712 (15)	0.02342 (16)	−0.00139 (10)	−0.00637 (11)	−0.00423 (11)
Cl3	0.0216 (2)	0.0294 (3)	0.0326 (3)	−0.00431 (19)	−0.0116 (2)	−0.0098 (2)
Cl6	0.0247 (3)	0.0315 (3)	0.0265 (3)	−0.0013 (2)	−0.0011 (2)	−0.0043 (2)
N1	0.0168 (8)	0.0219 (8)	0.0227 (8)	−0.0002 (6)	−0.0064 (6)	−0.0049 (7)
N2	0.0178 (8)	0.0173 (8)	0.0283 (9)	0.0002 (6)	−0.0094 (7)	−0.0047 (7)
N3	0.0191 (8)	0.0237 (9)	0.0309 (9)	0.0026 (7)	−0.0094 (7)	−0.0042 (7)
N4	0.0189 (8)	0.0192 (8)	0.0273 (9)	−0.0003 (6)	−0.0082 (7)	−0.0075 (7)
N5	0.0149 (7)	0.0200 (8)	0.0234 (8)	−0.0008 (6)	−0.0065 (6)	−0.0068 (6)
N6	0.0130 (7)	0.0175 (8)	0.0294 (9)	−0.0005 (6)	−0.0083 (6)	−0.0041 (7)
N7	0.0135 (7)	0.0185 (8)	0.0211 (8)	0.0012 (6)	−0.0057 (6)	−0.0039 (6)
N8	0.0175 (8)	0.0189 (8)	0.0213 (8)	−0.0021 (6)	−0.0062 (6)	−0.0038 (6)
C1	0.0180 (9)	0.0223 (9)	0.0205 (9)	0.0003 (7)	−0.0052 (7)	−0.0030 (8)
C2	0.0185 (10)	0.0324 (11)	0.0302 (11)	−0.0001 (8)	−0.0087 (8)	−0.0036 (9)
C3	0.0233 (10)	0.0387 (12)	0.0266 (11)	−0.0096 (9)	−0.0074 (8)	−0.0050 (9)
C4	0.0326 (12)	0.0275 (11)	0.0287 (11)	−0.0073 (9)	−0.0070 (9)	−0.0055 (9)
C5	0.0245 (10)	0.0232 (10)	0.0265 (10)	0.0001 (8)	−0.0075 (8)	−0.0034 (8)
C6	0.0199 (9)	0.0190 (9)	0.0244 (10)	0.0000 (7)	−0.0051 (8)	−0.0039 (8)
C7	0.0236 (10)	0.0183 (9)	0.0391 (12)	−0.0005 (8)	−0.0115 (9)	−0.0061 (9)
C8	0.0170 (9)	0.0216 (9)	0.0174 (9)	−0.0001 (7)	−0.0034 (7)	−0.0052 (7)
C9	0.0143 (9)	0.0209 (9)	0.0247 (10)	0.0001 (7)	−0.0073 (7)	−0.0048 (8)
C10	0.0153 (8)	0.0193 (9)	0.0191 (9)	−0.0020 (7)	−0.0034 (7)	−0.0060 (7)
C11	0.0175 (9)	0.0225 (10)	0.0275 (10)	−0.0017 (7)	−0.0082 (8)	−0.0079 (8)
C12	0.0159 (9)	0.0231 (10)	0.0401 (12)	−0.0034 (7)	−0.0101 (8)	−0.0075 (9)
C13	0.0176 (9)	0.0210 (9)	0.0254 (10)	−0.0031 (7)	−0.0071 (8)	−0.0048 (8)
C14	0.0164 (9)	0.0189 (9)	0.0202 (9)	−0.0023 (7)	−0.0041 (7)	−0.0036 (7)
C15	0.0225 (10)	0.0205 (9)	0.0293 (11)	−0.0035 (8)	−0.0082 (8)	−0.0064 (8)
C16	0.0282 (10)	0.0168 (9)	0.0291 (11)	0.0008 (8)	−0.0076 (9)	−0.0055 (8)
C17	0.0209 (10)	0.0245 (10)	0.0242 (10)	0.0039 (8)	−0.0087 (8)	−0.0044 (8)
C18	0.0176 (9)	0.0236 (10)	0.0238 (10)	−0.0025 (7)	−0.0072 (8)	−0.0045 (8)

Geometric parameters (Å, º) top

Mn1—N5	2.2227 (16)	C3—H3	0.9500
Mn1—N8	2.2580 (16)	C4—C5	1.373 (3)
Mn1—N7	2.2628 (16)	C4—H4	0.9500
Mn1—Cl6	2.3453 (7)	C5—H5	0.9500
Mn1—Cl3	2.3695 (6)	C6—H6	0.9500
N1—C6	1.279 (2)	C7—H7A	0.9800
N1—N2	1.365 (2)	C7—H7B	0.9800
N2—C8	1.373 (2)	C7—H7C	0.9800
N2—C7	1.459 (3)	C8—C9	1.396 (3)
N3—C2	1.339 (3)	C9—C10	1.382 (2)
N3—C1	1.345 (2)	C9—H9	0.9500
N4—C11	1.320 (2)	C11—H11	0.9500
N4—C8	1.348 (2)	C12—H12A	0.9800
N5—C11	1.334 (2)	C12—H12B	0.9800
N5—C10	1.350 (2)	C12—H12C	0.9800
N6—N7	1.355 (2)	C13—C14	1.463 (3)
N6—C10	1.385 (2)	C13—H13	0.9500
N6—C12	1.457 (2)	C14—C15	1.384 (3)
N7—C13	1.282 (2)	C15—C16	1.387 (3)
N8—C18	1.338 (2)	C15—H15	0.9500
N8—C14	1.348 (2)	C16—C17	1.380 (3)
C1—C5	1.394 (3)	C16—H16	0.9500
C1—C6	1.468 (3)	C17—C18	1.385 (3)
C2—C3	1.376 (3)	C17—H17	0.9500
C2—H2	0.9500	C18—H18	0.9500
C3—C4	1.389 (3)

N5—Mn1—N8	138.73 (6)	N1—C6—H6	121.4
N5—Mn1—N7	69.14 (6)	C1—C6—H6	121.4
N8—Mn1—N7	71.34 (6)	N2—C7—H7A	109.5
N5—Mn1—Cl6	105.58 (5)	N2—C7—H7B	109.5
N8—Mn1—Cl6	98.09 (4)	H7A—C7—H7B	109.5
N7—Mn1—Cl6	109.23 (4)	N2—C7—H7C	109.5
N5—Mn1—Cl3	98.11 (4)	H7A—C7—H7C	109.5
N8—Mn1—Cl3	103.08 (4)	H7B—C7—H7C	109.5
N7—Mn1—Cl3	137.70 (4)	N4—C8—N2	117.01 (17)
Cl6—Mn1—Cl3	113.06 (2)	N4—C8—C9	122.41 (17)
C6—N1—N2	120.08 (17)	N2—C8—C9	120.58 (17)
N1—N2—C8	114.05 (15)	C10—C9—C8	116.66 (17)
N1—N2—C7	121.98 (15)	C10—C9—H9	121.7
C8—N2—C7	123.26 (16)	C8—C9—H9	121.7
C2—N3—C1	116.94 (18)	N5—C10—C9	121.65 (17)
C11—N4—C8	115.07 (17)	N5—C10—N6	116.17 (16)
C11—N5—C10	115.84 (16)	C9—C10—N6	122.17 (17)
C11—N5—Mn1	123.94 (12)	N4—C11—N5	128.05 (18)
C10—N5—Mn1	119.88 (12)	N4—C11—H11	116.0
N7—N6—C10	114.64 (15)	N5—C11—H11	116.0
N7—N6—C12	120.81 (15)	N6—C12—H12A	109.5
C10—N6—C12	124.50 (15)	N6—C12—H12B	109.5
C13—N7—N6	122.20 (16)	H12A—C12—H12B	109.5
C13—N7—Mn1	118.24 (12)	N6—C12—H12C	109.5
N6—N7—Mn1	119.14 (12)	H12A—C12—H12C	109.5
C18—N8—C14	117.69 (16)	H12B—C12—H12C	109.5
C18—N8—Mn1	125.94 (13)	N7—C13—C14	116.34 (17)
C14—N8—Mn1	115.79 (12)	N7—C13—H13	121.8
N3—C1—C5	122.57 (18)	C14—C13—H13	121.8
N3—C1—C6	115.26 (17)	N8—C14—C15	122.81 (17)
C5—C1—C6	122.13 (17)	N8—C14—C13	116.59 (16)
N3—C2—C3	124.18 (19)	C15—C14—C13	120.59 (17)
N3—C2—H2	117.9	C14—C15—C16	118.86 (18)
C3—C2—H2	117.9	C14—C15—H15	120.6
C2—C3—C4	118.28 (19)	C16—C15—H15	120.6
C2—C3—H3	120.9	C17—C16—C15	118.62 (18)
C4—C3—H3	120.9	C17—C16—H16	120.7
C5—C4—C3	118.8 (2)	C15—C16—H16	120.7
C5—C4—H4	120.6	C16—C17—C18	119.14 (18)
C3—C4—H4	120.6	C16—C17—H17	120.4
C4—C5—C1	119.22 (19)	C18—C17—H17	120.4
C4—C5—H5	120.4	N8—C18—C17	122.87 (18)
C1—C5—H5	120.4	N8—C18—H18	118.6
N1—C6—C1	117.14 (18)	C17—C18—H18	118.6

C6—N1—N2—C8	−177.44 (18)	N3—C1—C6—N1	173.05 (18)
C6—N1—N2—C7	−6.8 (3)	C5—C1—C6—N1	−9.2 (3)
N8—Mn1—N5—C11	160.34 (14)	C11—N4—C8—N2	−173.62 (17)
N7—Mn1—N5—C11	177.93 (17)	C11—N4—C8—C9	5.6 (3)
Cl6—Mn1—N5—C11	−77.03 (16)	N1—N2—C8—N4	174.36 (16)
Cl3—Mn1—N5—C11	39.75 (16)	C7—N2—C8—N4	3.8 (3)
N8—Mn1—N5—C10	−26.59 (19)	N1—N2—C8—C9	−4.8 (3)
N7—Mn1—N5—C10	−9.01 (13)	C7—N2—C8—C9	−175.38 (19)
Cl6—Mn1—N5—C10	96.04 (14)	N4—C8—C9—C10	−5.5 (3)
Cl3—Mn1—N5—C10	−147.19 (14)	N2—C8—C9—C10	173.61 (17)
C10—N6—N7—C13	−178.82 (18)	C11—N5—C10—C9	3.3 (3)
C12—N6—N7—C13	−1.4 (3)	Mn1—N5—C10—C9	−170.32 (14)
C10—N6—N7—Mn1	−6.4 (2)	C11—N5—C10—N6	−177.21 (17)
C12—N6—N7—Mn1	171.03 (14)	Mn1—N5—C10—N6	9.2 (2)
N5—Mn1—N7—C13	−179.21 (16)	C8—C9—C10—N5	0.8 (3)
N8—Mn1—N7—C13	−11.35 (14)	C8—C9—C10—N6	−178.64 (17)
Cl6—Mn1—N7—C13	80.91 (15)	N7—N6—C10—N5	−1.6 (2)
Cl3—Mn1—N7—C13	−100.42 (15)	C12—N6—C10—N5	−178.96 (18)
N5—Mn1—N7—N6	8.07 (13)	N7—N6—C10—C9	177.86 (17)
N8—Mn1—N7—N6	175.93 (15)	C12—N6—C10—C9	0.5 (3)
Cl6—Mn1—N7—N6	−91.81 (13)	C8—N4—C11—N5	−0.9 (3)
Cl3—Mn1—N7—N6	86.86 (14)	C10—N5—C11—N4	−3.4 (3)
N5—Mn1—N8—C18	−161.13 (14)	Mn1—N5—C11—N4	169.90 (16)
N7—Mn1—N8—C18	−178.46 (17)	N6—N7—C13—C14	−177.09 (16)
Cl6—Mn1—N8—C18	73.90 (16)	Mn1—N7—C13—C14	10.4 (2)
Cl3—Mn1—N8—C18	−42.16 (16)	C18—N8—C14—C15	−0.3 (3)
N5—Mn1—N8—C14	27.89 (18)	Mn1—N8—C14—C15	171.45 (15)
N7—Mn1—N8—C14	10.56 (13)	C18—N8—C14—C13	178.80 (17)
Cl6—Mn1—N8—C14	−97.09 (13)	Mn1—N8—C14—C13	−9.4 (2)
Cl3—Mn1—N8—C14	146.86 (13)	N7—C13—C14—N8	−0.5 (3)
C2—N3—C1—C5	0.8 (3)	N7—C13—C14—C15	178.61 (19)
C2—N3—C1—C6	178.55 (18)	N8—C14—C15—C16	−0.3 (3)
C1—N3—C2—C3	−1.0 (3)	C13—C14—C15—C16	−179.37 (19)
N3—C2—C3—C4	0.6 (3)	C14—C15—C16—C17	0.6 (3)
C2—C3—C4—C5	0.1 (3)	C15—C16—C17—C18	−0.4 (3)
C3—C4—C5—C1	−0.2 (3)	C14—N8—C18—C17	0.6 (3)
N3—C1—C5—C4	−0.2 (3)	Mn1—N8—C18—C17	−170.26 (15)
C6—C1—C5—C4	−177.8 (2)	C16—C17—C18—N8	−0.2 (3)
N2—N1—C6—C1	176.38 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.95	2.50	3.358 (3)	151
C18—H18···Cl3ⁱⁱ	0.95	2.80	3.508 (2)	133

Symmetry codes: (i) −x−1, −y+2, −z+1; (ii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₁₈H₁₈N₈)]
M_r	472.24
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	8.8355 (12), 10.0972 (14), 12.1466 (17)
α, β, γ (°)	72.571 (3), 77.694 (3), 75.700 (3)
V (Å³)	990.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Blessing, 1995)
T_min, T_max	0.891, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	13578, 4889, 4095
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.088, 1.04
No. of reflections	4889
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.24

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2011) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3ⁱ	0.95	2.50	3.358 (3)	151
C18—H18···Cl3ⁱⁱ	0.95	2.80	3.508 (2)	133

Symmetry codes: (i) −x−1, −y+2, −z+1; (ii) −x+2, −y, −z+2.

Acknowledgements

The authors thank the Science Foundation Ireland (SFI) for financial support (grant Nos 06/RFP/CHE174 and 08/IN.1/I2047). BM gratefully acknowledges financial support from DRHEA and Trinity College.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA Google Scholar
Marzec, B., Mariyatra, M. B., McCabe, T. & Schmitt, W. (2011). Acta Cryst. E67, m1073–m1074. Web of Science CSD CrossRef IUCr Journals Google Scholar
Palmer, D. (2011). CrystalMaker. Crystal Maker Software Ltd, Yarnton, Oxfordshire, England. Google Scholar
Romain, S., Rich, J., Sens, C., Stoll, T., Benet-Buchholz, J., Llobet, A., Rodriguez, M., Romero, I., Clerac, R., Mathoniere, C., Duboc, C., Deronzier, A. & Collomb, M.-N. (2011). Inorg. Chem. 50, 8427–8436. Web of Science CrossRef CAS PubMed Google Scholar
Schmitt, J.-L., Stadler, A.-M., Kyritsakas, N. & Lehn, J. M. (2003). Helv. Chim. Acta, 86, 1598–1624. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stadler, A.-M., Kyritsakas, N., Graff, R. & Lehn, J.-M. (2006). Chem. Eur. J. 12, 4503–4522. Web of Science CSD CrossRef PubMed CAS Google Scholar
Stadler, A.-M., Puntoriero, F., Campagna, S., Kyritsakas, N., Welter, R. & Lehn, J.-M. (2005). Chem. Eur. J. 11, 3997–4009. Web of Science CSD CrossRef PubMed CAS Google Scholar

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