cis-Dichloridobis­(5,5′-dimethyl-2,2′-bipyridine)­manganese(II) 2.5-hydrate

Lopes, L.B.; Corrêa, C.C.; Diniz, R.

doi:10.1107/S1600536811021805

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m906-m907

doi:10.1107/S1600536811021805

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cis-Dichloridobis(5,5′-dimethyl-2,2′-bipyridine)manganese(II) 2.5-hydrate

Lívia Batista Lopes,^a Charlane Cimini Corrêa ^a and Renata Diniz ^a ^*

^aNúcleo de Espectroscopia e Estrutura Molecular (NEEM), Department of Chemistry - Federal University of Juiz de Fora - Minas Gerais, 36036-900, Brazil
^*Correspondence e-mail: renata.diniz@ufjf.edu.br

(Received 4 May 2011; accepted 6 June 2011; online 11 June 2011)

The metal site in the title compound [MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O has a distorted octahedral geometry, coordinated by four N atoms of two 5,5′-dimethyl-2,2′-dipyridine ligands and two Cl atoms. Two and a half water molecules of hydration per complex unit are observed in the crystal structure. The compounds extend along the c axis with O—H⋯Cl, O—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds and π–π interactions [centroid-centroid distance = 3.70 (2) Å] contributing substantially to the crystal packing. The Mn and one of the water O atoms, the latter being half-occupied, are located on special positions, in this case a rotation axis of order 2.

Related literature

For the structures and applications of bipyridine and analogous ligands, see: Hazell (2004 ); Bakir et al. (1992 ); Cordes et al. (1982 ); Hung-Low et al. (2009 ). For the structure and applications of 5,5′-dimethyl-2,2′-dipyridine, see: Marandi et al. (2009 ); van Albada et al. (2005 ). For weak intermolecular interactions, see: Calhorda (2000 ); Desiraju (1996 ); Janiak (2000 ).

Experimental

Crystal data

[MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O
M_r = 539.35
Monoclinic, C 2/c
a = 18.6703 (9) Å
b = 14.0598 (4) Å
c = 12.0536 (7) Å
β = 122.430 (7)°
V = 2670.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.47 × 0.35 × 0.34 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) based on expressions derived by Clark & Reid (1995 )] T_min = 0.470, T_max = 0.697
11860 measured reflections
3317 independent reflections
2499 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.150
S = 1.09
3317 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1	0.84	2.42	3.243 (3)	168
O1—H1B⋯Cl1ⁱ	0.81	2.73	3.358 (4)	136
O2—H2A⋯O1	0.86	2.16	2.951 (6)	153
C3—H3⋯O1ⁱⁱ	0.93	2.49	3.257 (5)	140
C6—H6A⋯Cl1ⁱ	0.96	2.79	3.717 (4)	162
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021805/im2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021805/im2285Isup2.hkl

checkCIF report

Comment top

Bipyridine and analogous ligands are commonly used in the formation of different complexes with a general variety of transition metals (Hazell, 2004; Bakir et al., 1992; Cordes et al.,1982; Hung-Low et al.,2009;). The ligand 5,5'-Dimethyl-2,2'-dipyridine (abbreviated as dmdpy) acts as a chelator and usually gives rise to monomeric compounds (Marandi et al., 2009). Only a limited number of X-ray crystal structures with the ligand dmdpy has been published (van Albada et al., 2005). In this study we used the ligand 5,5'-dimethyl-2,2'-dipyridine and manganese chloride tetrahydrate. This mixture resulted in the compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O (Scheme 1).

The molecular structure of the complex unit of the titlecompound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O is shown in Figure 1. The metal site is coordinated by four nitrogen atoms N1, N2, N1ⁱ and N2ⁱ of the ligand dmdpy and two chlorides Cl1 and Cl1ⁱ adopting a distorted octahedral geometry as evidenced by the Mn—N1 distances (2.3111 (19) Å), Mn—N2 (2.245 (2) Å) and Mn—Cl1 (2.4702 (6) Å). The Mn atom is located in a special position, which in this case is a rotation axis of order 2.

The compound crystallizes in the monoclinic system and its unit cell is shown in Figure 2. The compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O is a complex that stretches along the crystallographic c axis with the molecular entities being interconnected by weak hydrogen bonds (Desiraju, 1996; Calhorda, 2000) shown in Figure 2. These hydrogen bonds are formed by the interaction between oxygen atoms of water molecules O1 and O2 and the chlorine atom Cl1 which is coordinated to the metal. The distances O1—O2 and O1—Cl1 charge 2.951 (6) Å and 3.243 (3) Å, respectively. π-π interactions between aromatic rings of the nitrogen ligand dmdpy are also shown in Figure 2. These interactions contribute substantially to the crystal packing (Janiak, 2000). In this compound the centroid-centroid distance is 3.70 (2) Å, and there was a substantial overlap between the aromatic rings of the ligand dmdpy, being centroid-plane distance of 3.45 (1)Å and the horizontal displacement of 1.37 (2) Å.

Related literature top

For the structures and applications of bipyridine and analogous ligands, see: Hazell (2004); Bakir et al. (1992); Cordes et al. (1982); Hung-Low et al. (2009). For the structure and applications of 5,5'-dimethyl-2,2'-dipyridine, see: Marandi et al. (2009); van Albada et al. (2005). For weak intermolecular interactions, see: Calhorda (2000); Desiraju (1996); Janiak (2000).

Experimental top

All chemicals were obtained commercially and used without further purification. The complex was synthesized by mixing of 0.38 mmol of dmdpy dissolved in ethanol and 0.38 mmol of MnCl₂ × 4 H₂O dissolved in water. The mixture was placed under agitation for 40 h. After a few weeks, yellow single crystals suitable for the analysis of X-ray diffraction were obtained (yield: 39%).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2008); cell refinement: CrysAlis PRO (Oxford Diffraction, 2008); data reduction: CrysAlis PRO (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the complex unit of the title compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O. Water molecules were omitted for better visualization. Symmetry code: i (1 - x, y, 1/2 - z).
	Fig. 2. Unit cell of the compound [Mn(C₁₂H₁₂N₂)₂Cl₂] × 2.5 H₂O (z = 4), hydrogen bonds chain extending along the c axis and π-π interactions between the rings aromatic ligand dmdpy are depicted as dashed lines.

cis-Dichloridobis(5,5'-dimethyl-2,2'-bipyridine)manganese(II) 2.5-hydrate top

Crystal data top

[MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O	F(000) = 1120
M_r = 539.35	D_x = 1.341 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6304 reflections
a = 18.6703 (9) Å	θ = 2.9–29.4°
b = 14.0598 (4) Å	µ = 0.72 mm⁻¹
c = 12.0536 (7) Å	T = 293 K
β = 122.430 (7)°	Prismatic, yellow
V = 2670.6 (2) Å³	0.47 × 0.35 × 0.34 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	3317 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2499 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 10.4186 pixels mm^-1	θ_max = 29.4°, θ_min = 2.9°
ω scans	h = −25→23
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008) based on expressions derived by Clark & Reid (1995)]	k = −14→18
T_min = 0.470, T_max = 0.697	l = −16→16
11860 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.094P)² + 0.4813P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3317 reflections	Δρ_max = 0.72 e Å⁻³
155 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Absolute structure: no

Crystal data top

[MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O	V = 2670.6 (2) Å³
M_r = 539.35	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.6703 (9) Å	µ = 0.72 mm⁻¹
b = 14.0598 (4) Å	T = 293 K
c = 12.0536 (7) Å	0.47 × 0.35 × 0.34 mm
β = 122.430 (7)°

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	3317 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008) based on expressions derived by Clark & Reid (1995)]	2499 reflections with I > 2σ(I)
T_min = 0.470, T_max = 0.697	R_int = 0.025
11860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.09	Δρ_max = 0.72 e Å⁻³
3317 reflections	Δρ_min = −0.31 e Å⁻³
155 parameters	Absolute structure: no

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)
Mn	0.5000	0.31073 (3)	0.2500	0.03326 (18)
Cl1	0.56731 (3)	0.43196 (4)	0.42532 (6)	0.0429 (2)
N1	0.42155 (12)	0.19415 (12)	0.0968 (2)	0.0391 (4)
N2	0.38759 (11)	0.27687 (13)	0.26398 (18)	0.0359 (4)
C1	0.37348 (15)	0.32044 (16)	0.3488 (2)	0.0407 (5)
H1	0.4120	0.3667	0.4034	0.049*
C5	0.33239 (14)	0.20969 (15)	0.1835 (2)	0.0368 (5)
C4	0.26252 (15)	0.18577 (17)	0.1891 (3)	0.0466 (6)
H4	0.2249	0.1393	0.1334	0.056*
C2	0.30477 (16)	0.30103 (17)	0.3606 (3)	0.0447 (6)
C3	0.24897 (16)	0.2312 (2)	0.2779 (3)	0.0523 (7)
H3	0.2023	0.2150	0.2824	0.063*
C7	0.35069 (14)	0.16493 (14)	0.0903 (2)	0.0386 (5)
C8	0.29693 (17)	0.09802 (17)	−0.0022 (2)	0.0511 (6)
H8	0.2475	0.0794	−0.0072	0.061*
C11	0.43965 (16)	0.15765 (17)	0.0132 (2)	0.0477 (6)
H11	0.4884	0.1792	0.0182	0.057*
C10	0.39085 (19)	0.08913 (18)	−0.0818 (3)	0.0552 (7)
C9	0.3180 (2)	0.05955 (18)	−0.0865 (3)	0.0580 (7)
H9	0.2833	0.0135	−0.1470	0.070*
C6	0.2939 (2)	0.3543 (2)	0.4579 (3)	0.0689 (9)
H6A	0.3391	0.3995	0.5036	0.103*
H6B	0.2950	0.3105	0.5199	0.103*
H6C	0.2405	0.3872	0.4128	0.103*
C12	0.4172 (2)	0.0531 (2)	−0.1719 (3)	0.0782 (10)
H12A	0.4692	0.0834	−0.1506	0.117*
H12B	0.3737	0.0673	−0.2613	0.117*
H12C	0.4257	−0.0145	−0.1614	0.117*
O1	0.5956 (2)	0.4141 (2)	0.7145 (3)	0.1311 (14)
H1A	0.5803	0.4187	0.6356	0.197*
H1B	0.5699	0.4548	0.7272	0.197*
O2	0.5000	0.2629 (5)	0.7500	0.112 (3)	0.50
H2A	0.5382	0.2904	0.7422	0.168*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0241 (3)	0.0282 (3)	0.0388 (3)	0.000	0.0111 (2)	0.000
Cl1	0.0341 (3)	0.0394 (3)	0.0431 (3)	−0.0026 (2)	0.0127 (3)	−0.0082 (2)
N1	0.0330 (10)	0.0304 (9)	0.0398 (10)	0.0005 (7)	0.0101 (8)	−0.0025 (7)
N2	0.0286 (9)	0.0321 (9)	0.0364 (9)	−0.0054 (7)	0.0105 (8)	0.0017 (7)
C1	0.0339 (11)	0.0390 (12)	0.0416 (12)	−0.0089 (9)	0.0153 (10)	−0.0011 (9)
C5	0.0307 (11)	0.0281 (10)	0.0350 (11)	−0.0042 (8)	0.0067 (9)	0.0071 (8)
C4	0.0370 (12)	0.0404 (13)	0.0477 (14)	−0.0143 (10)	0.0130 (11)	0.0020 (10)
C2	0.0415 (13)	0.0437 (13)	0.0475 (14)	−0.0073 (10)	0.0230 (11)	0.0053 (10)
C3	0.0403 (13)	0.0560 (16)	0.0563 (15)	−0.0153 (12)	0.0231 (12)	0.0050 (12)
C7	0.0364 (11)	0.0249 (9)	0.0354 (11)	−0.0015 (9)	0.0065 (9)	0.0046 (8)
C8	0.0501 (14)	0.0383 (12)	0.0428 (13)	−0.0147 (11)	0.0102 (12)	−0.0001 (10)
C11	0.0422 (13)	0.0402 (12)	0.0487 (14)	0.0020 (10)	0.0163 (11)	−0.0068 (11)
C10	0.0615 (17)	0.0373 (13)	0.0454 (14)	0.0039 (12)	0.0146 (13)	−0.0061 (10)
C9	0.0666 (18)	0.0354 (13)	0.0454 (15)	−0.0120 (12)	0.0125 (13)	−0.0077 (10)
C6	0.0645 (18)	0.080 (2)	0.079 (2)	−0.0247 (17)	0.0493 (17)	−0.0175 (17)
C12	0.092 (3)	0.068 (2)	0.060 (2)	0.0055 (18)	0.0315 (19)	−0.0192 (15)
O1	0.166 (3)	0.157 (3)	0.110 (2)	0.121 (3)	0.101 (2)	0.068 (2)
O2	0.092 (5)	0.047 (4)	0.135 (7)	0.000	0.020 (5)	0.000

Geometric parameters (Å, º) top

Mn—Cl1	2.4702 (6)	C7—C8	1.391 (3)
Mn—N1	2.3111 (19)	C8—C9	1.382 (5)
Mn—N2	2.245 (2)	C9—C10	1.394 (6)
O1—H1B	0.8100	C10—C12	1.502 (6)
O1—H1A	0.8400	C10—C11	1.397 (4)
O2—H2A	0.8600	C1—H1	0.9300
O2—H2Aⁱ	0.8600	C3—H3	0.9300
N1—C11	1.326 (4)	C4—H4	0.9300
N1—C7	1.347 (3)	C6—H6A	0.9600
N2—C5	1.350 (2)	C6—H6B	0.9600
N2—C1	1.334 (3)	C6—H6C	0.9600
C1—C2	1.391 (5)	C8—H8	0.9300
C2—C3	1.389 (4)	C9—H9	0.9300
C2—C6	1.494 (5)	C11—H11	0.9300
C3—C4	1.381 (4)	C12—H12B	0.9600
C4—C5	1.383 (4)	C12—H12C	0.9600
C5—C7	1.480 (3)	C12—H12A	0.9600

Cl1···C1	3.581 (3)	O1^iv···C3ⁱⁱ	3.257 (5)
Cl1···O1	3.243 (3)	N1···N1ⁱⁱ	3.259 (3)
Cl1···Cl1ⁱⁱ	3.5759 (9)	N1···N2ⁱⁱ	3.233 (3)
Cl1···N1ⁱⁱ	3.3695 (18)	N1···N2	2.681 (3)
Cl1···O1ⁱⁱⁱ	3.358 (4)	N2···C11ⁱⁱ	3.337 (4)
O1···O2	2.951 (6)	C3···O1^v	3.257 (5)
O1···Cl1ⁱⁱⁱ	3.358 (4)

Cl1—Mn—N1	170.62 (6)	N1—C7—C5	116.49 (19)
Cl1—Mn—N2	98.59 (5)	C5—C7—C8	122.4 (3)
Cl1—Mn—Cl1ⁱⁱ	92.74 (2)	C7—C8—C9	119.1 (3)
Cl1—Mn—N1ⁱⁱ	89.55 (5)	C8—C9—C10	120.7 (3)
Cl1—Mn—N2ⁱⁱ	98.24 (5)	C9—C10—C12	124.2 (3)
N1—Mn—N2	72.07 (8)	C11—C10—C12	120.2 (4)
Cl1ⁱⁱ—Mn—N1	89.55 (5)	C9—C10—C11	115.6 (3)
N1—Mn—N1ⁱⁱ	89.65 (7)	N1—C11—C10	124.8 (3)
N1—Mn—N2ⁱⁱ	90.40 (8)	C2—C1—H1	118.00
Cl1ⁱⁱ—Mn—N2	98.24 (5)	N2—C1—H1	118.00
N1ⁱⁱ—Mn—N2	90.40 (8)	C4—C3—H3	120.00
N2—Mn—N2ⁱⁱ	155.51 (7)	C2—C3—H3	120.00
Cl1ⁱⁱ—Mn—N1ⁱⁱ	170.62 (6)	C5—C4—H4	120.00
Cl1ⁱⁱ—Mn—N2ⁱⁱ	98.59 (5)	C3—C4—H4	120.00
N1ⁱⁱ—Mn—N2ⁱⁱ	72.07 (8)	C2—C6—H6C	109.00
H1A—O1—H1B	107.00	C2—C6—H6A	110.00
H2A—O2—H2Aⁱ	127.00	C2—C6—H6B	110.00
Mn—N1—C11	124.8 (2)	H6B—C6—H6C	109.00
Mn—N1—C7	116.40 (15)	H6A—C6—H6C	109.00
C7—N1—C11	118.7 (2)	H6A—C6—H6B	110.00
C1—N2—C5	118.9 (2)	C9—C8—H8	120.00
Mn—N2—C5	118.63 (17)	C7—C8—H8	120.00
Mn—N2—C1	122.49 (17)	C8—C9—H9	120.00
N2—C1—C2	124.1 (2)	C10—C9—H9	120.00
C3—C2—C6	123.5 (3)	N1—C11—H11	118.00
C1—C2—C3	116.3 (3)	C10—C11—H11	118.00
C1—C2—C6	120.2 (3)	C10—C12—H12B	109.00
C2—C3—C4	120.3 (3)	C10—C12—H12C	109.00
C3—C4—C5	119.6 (3)	H12A—C12—H12C	110.00
N2—C5—C7	116.4 (2)	H12B—C12—H12C	109.00
N2—C5—C4	120.8 (2)	H12A—C12—H12B	110.00
C4—C5—C7	122.8 (2)	C10—C12—H12A	109.00
N1—C7—C8	121.1 (2)

N2—Mn—N1—C7	0.40 (15)	Mn—N2—C1—C2	−179.72 (19)
N2—Mn—N1—C11	177.7 (2)	C5—N2—C1—C2	0.1 (3)
Cl1ⁱⁱ—Mn—N1—C7	−98.41 (15)	Mn—N2—C5—C4	179.52 (18)
Cl1ⁱⁱ—Mn—N1—C11	78.9 (2)	Mn—N2—C5—C7	−1.1 (2)
N1ⁱⁱ—Mn—N1—C7	90.94 (16)	C1—N2—C5—C4	−0.3 (3)
N1ⁱⁱ—Mn—N1—C11	−91.8 (2)	C1—N2—C5—C7	179.10 (19)
N2ⁱⁱ—Mn—N1—C7	163.01 (16)	N2—C1—C2—C3	0.4 (4)
N2ⁱⁱ—Mn—N1—C11	−19.7 (2)	N2—C1—C2—C6	−179.4 (3)
Cl1—Mn—N2—C1	1.11 (17)	C1—C2—C3—C4	−0.7 (4)
Cl1—Mn—N2—C5	−178.73 (15)	C6—C2—C3—C4	179.1 (3)
N1—Mn—N2—C1	−179.78 (19)	C2—C3—C4—C5	0.5 (4)
N1—Mn—N2—C5	0.38 (15)	C3—C4—C5—N2	0.0 (4)
Cl1ⁱⁱ—Mn—N2—C1	−92.95 (17)	C3—C4—C5—C7	−179.4 (2)
Cl1ⁱⁱ—Mn—N2—C5	87.21 (16)	N2—C5—C7—N1	1.4 (3)
N1ⁱⁱ—Mn—N2—C1	90.71 (17)	N2—C5—C7—C8	−176.9 (2)
N1ⁱⁱ—Mn—N2—C5	−89.13 (16)	C4—C5—C7—N1	−179.2 (2)
N2ⁱⁱ—Mn—N2—C1	134.05 (18)	C4—C5—C7—C8	2.5 (3)
N2ⁱⁱ—Mn—N2—C5	−45.8 (3)	N1—C7—C8—C9	1.5 (3)
Mn—N1—C7—C5	−1.1 (2)	C5—C7—C8—C9	179.7 (2)
Mn—N1—C7—C8	177.24 (16)	C7—C8—C9—C10	−1.8 (4)
C11—N1—C7—C5	−178.5 (2)	C8—C9—C10—C11	0.8 (4)
C11—N1—C7—C8	−0.2 (3)	C8—C9—C10—C12	−178.3 (3)
Mn—N1—C11—C10	−178.1 (2)	C9—C10—C11—N1	0.6 (4)
C7—N1—C11—C10	−0.9 (4)	C12—C10—C11—N1	179.7 (3)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, −y+1/2, −z+1; (v) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.84	2.42	3.243 (3)	168
O1—H1B···Cl1ⁱⁱⁱ	0.81	2.73	3.358 (4)	136
O2—H2A···O1	0.86	2.16	2.951 (6)	153
C3—H3···O1^v	0.93	2.49	3.257 (5)	140
C6—H6A···Cl1ⁱⁱⁱ	0.96	2.79	3.717 (4)	162

Symmetry codes: (iii) −x+1, −y+1, −z+1; (v) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₁₂H₁₂N₂)₂]·2.5H₂O
M_r	539.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.6703 (9), 14.0598 (4), 12.0536 (7)
β (°)	122.430 (7)
V (Å³)	2670.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.47 × 0.35 × 0.34

Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2008) based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.470, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	11860, 3317, 2499
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.692

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.150, 1.09
No. of reflections	3317
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.31
Absolute structure	No

Computer programs: CrysAlis PRO (Oxford Diffraction, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.84	2.42	3.243 (3)	168
O1—H1B···Cl1ⁱ	0.81	2.73	3.358 (4)	136
O2—H2A···O1	0.86	2.16	2.951 (6)	153
C3—H3···O1ⁱⁱ	0.93	2.49	3.257 (5)	140
C6—H6A···Cl1ⁱ	0.96	2.79	3.717 (4)	162

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

Acknowledgements

The authors thank CNPq, CAPES and FAPEMIG (Brazilian agencies) for financial support, and LabCri (Federal University of Minas Gerais) for measuring the X-ray diffraction data.

References

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