cis-Dichloridobis(di-2-pyridyl­amine-κ2N,N′)manganese(II)

Ha, K.

doi:10.1107/S1600536811052834

metal-organic compounds

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Volume 68| Part 1| January 2012| Page m45

doi:10.1107/S1600536811052834

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cis-Dichloridobis(di-2-pyridylamine-κ²N,N′)manganese(II)

Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 7 December 2011; accepted 7 December 2011; online 14 December 2011)

In the title complex, [MnCl₂(C₁₀H₉N₃)₂], the Mn^II ion is six-coordinated in a considerably distorted cis-N₄Cl₂ octahedral environment defined by four N atoms of two chelating di-2-pyridylamine (dpa) ligands and two Cl⁻ anions. In the crystal, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.3 (2) and 30.9 (2)°. The complex molecules are stacked in columns along the c axis and are connected by intermolecular N—H⋯Cl hydrogen bonds, forming a three-dimensional network. Weak inter- and intramolecular π–π interactions are present between the pyridine rings, the shortest centroid—centroid distance being 4.406 (3) Å.

Related literature

For the crystal structures of related Mn^II complexes with dpa, see: Bose et al. (2005 ); Ha (2011a ,b ).

Experimental

Crystal data

[MnCl₂(C₁₀H₉N₃)₂]
M_r = 468.24
Orthorhombic, P n a 2₁
a = 16.236 (3) Å
b = 12.542 (2) Å
c = 9.9233 (17) Å
V = 2020.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 200 K
0.31 × 0.28 × 0.19 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.849, T_max = 1.000
14151 measured reflections
4293 independent reflections
2982 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.092
S = 1.01
4293 reflections
262 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983 ), 1616 Friedel pairs
Flack parameter: 0.04 (2)

Table 1
Selected geometric parameters (Å, °)

Mn1—N3	2.276 (3)
Mn1—N1	2.278 (3)
Mn1—N4	2.280 (3)
Mn1—N6	2.353 (3)
Mn1—Cl2	2.4637 (12)
Mn1—Cl1	2.5122 (10)

N3—Mn1—N1	77.32 (13)
N4—Mn1—N6	77.12 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Cl2ⁱ	0.92	2.30	3.211 (3)	171
N5—H5N⋯Cl1ⁱⁱ	0.92	2.45	3.355 (4)	170
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811052834/wm2573sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052834/wm2573Isup2.hkl

checkCIF report

Comment top

Neutral and cationic Mn^II complexes of the di-2-pyridylamine (dpa; C₁₀H₉N₃) ligand, such as [MnX₂(dpa)₂]^.H₂O, [MnX(dpa)₂(H₂O)]ClO₄ (X = N₃^-, NCO^-) (Bose et al., 2005) and [MnX(dpa)₂(H₂O)]X (X = I, Br) (Ha, 2011a,b), have been investigated previously.

In the title complex, [MnCl₂(dpa)₂], the Mn^II ion is six-coordinated in a considerably distorted cis-N₄Cl₂ octahedral environment defined by four N atoms of two chelating dpa ligands and two Cl^- anions (Fig. 1). The main contributions to the distortion are the tight N—Mn—N chelating angles (Table 1), which results in non-linear trans axes [N3—Mn1—N4 = 161.55 (11)°, N6—Mn1—Cl1 = 173.54 (11)° and N1—Mn1—Cl2 = 170.18 (10)°]. Because the Mn—N bond lengths are nearly equivalent (Table 1), the different trans effects of the Cl and N atoms cannot be observed reliably. In the crystal structure, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.3 (2)° and 30.9 (2)°. The complex molecules are stacked in columns along the c axis and connected by intermolecular N—H···Cl hydrogen bonds, forming a three-dimensional network (Fig. 2, Table 2). In the columns, numerous weak inter- and intramolecular π—π interactions are present between the pyridine rings, the shortest centroid-centroid distance being 4.406 (3) Å.

Related literature top

For the crystal structures of related Mn^II complexes with dpa, see: Bose et al. (2005); Ha (2011a,b).

Experimental top

To a solution of MnCl₂.4H₂O (0.1988 g, 1.005 mmol) in EtOH (20 ml) was added di-2-pyridylamine (0.3465 g, 2.024 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with EtOH and acetone, and dried at 323 K, to give a white powder (0.2982 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 40% probability level for non-H atoms.
	Fig. 2. View of the unit-cell contents of the title complex. Hydrogen-bonding interactions are drawn with dashed lines.

cis-Dichloridobis(di-2-pyridylamine-κ²N,N')manganese(II) top

Crystal data top

[MnCl₂(C₁₀H₉N₃)₂]	F(000) = 956
M_r = 468.24	D_x = 1.539 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4041 reflections
a = 16.236 (3) Å	θ = 2.5–27.8°
b = 12.542 (2) Å	µ = 0.94 mm⁻¹
c = 9.9233 (17) Å	T = 200 K
V = 2020.7 (6) Å³	Block, colorless
Z = 4	0.31 × 0.28 × 0.19 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4293 independent reflections
Radiation source: fine-focus sealed tube	2982 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −21→21
T_min = 0.849, T_max = 1.000	k = −16→15
14151 measured reflections	l = −13→9

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0271P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
4293 reflections	Δρ_max = 0.51 e Å⁻³
262 parameters	Δρ_min = −0.57 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1616 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

Crystal data top

[MnCl₂(C₁₀H₉N₃)₂]	V = 2020.7 (6) Å³
M_r = 468.24	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 16.236 (3) Å	µ = 0.94 mm⁻¹
b = 12.542 (2) Å	T = 200 K
c = 9.9233 (17) Å	0.31 × 0.28 × 0.19 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4293 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2982 reflections with I > 2σ(I)
T_min = 0.849, T_max = 1.000	R_int = 0.072
14151 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.092	Δρ_max = 0.51 e Å⁻³
S = 1.01	Δρ_min = −0.57 e Å⁻³
4293 reflections	Absolute structure: Flack (1983), 1616 Friedel pairs
262 parameters	Absolute structure parameter: 0.04 (2)
1 restraint

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	0.20798 (3)	0.33815 (4)	0.89348 (7)	0.02448 (14)
Cl1	0.14448 (5)	0.52067 (7)	0.88475 (14)	0.0317 (2)
Cl2	0.09525 (6)	0.25950 (9)	1.02667 (13)	0.0376 (3)
N1	0.3262 (2)	0.4028 (3)	0.8006 (4)	0.0270 (8)
N2	0.4152 (2)	0.3360 (3)	0.9693 (4)	0.0293 (8)
H2N	0.4643	0.3016	0.9842	0.044*
N3	0.28805 (19)	0.3701 (2)	1.0774 (3)	0.0251 (8)
N4	0.16475 (18)	0.2772 (2)	0.6889 (4)	0.0285 (8)
N5	0.2814 (2)	0.1689 (3)	0.6387 (4)	0.0301 (8)
H5N	0.3074	0.1343	0.5690	0.045*
N6	0.27298 (17)	0.1710 (2)	0.8770 (4)	0.0246 (7)
C1	0.3191 (3)	0.4552 (3)	0.6826 (5)	0.0330 (10)
H1	0.2652	0.4722	0.6518	0.040*
C2	0.3842 (3)	0.4853 (3)	0.6045 (5)	0.0363 (11)
H2	0.3758	0.5225	0.5222	0.044*
C3	0.4629 (3)	0.4602 (3)	0.6481 (5)	0.0421 (12)
H3	0.5095	0.4787	0.5950	0.051*
C4	0.4730 (2)	0.4089 (3)	0.7678 (5)	0.0346 (11)
H4	0.5265	0.3909	0.7991	0.042*
C5	0.4036 (2)	0.3830 (3)	0.8440 (4)	0.0266 (10)
C6	0.3676 (2)	0.3427 (3)	1.0850 (4)	0.0257 (9)
C7	0.4062 (3)	0.3193 (3)	1.2082 (4)	0.0356 (11)
H7	0.4618	0.2956	1.2100	0.043*
C8	0.3632 (3)	0.3312 (3)	1.3248 (5)	0.0410 (11)
H8	0.3879	0.3145	1.4090	0.049*
C9	0.2820 (3)	0.3684 (4)	1.3191 (5)	0.0393 (12)
H9	0.2519	0.3827	1.3992	0.047*
C10	0.2472 (2)	0.3836 (3)	1.1952 (5)	0.0318 (10)
H10	0.1911	0.4048	1.1915	0.038*
C11	0.0903 (2)	0.3143 (3)	0.6470 (4)	0.0294 (10)
H11	0.0612	0.3608	0.7056	0.035*
C12	0.0546 (3)	0.2892 (3)	0.5268 (5)	0.0386 (11)
H12	0.0029	0.3186	0.5020	0.046*
C13	0.0957 (3)	0.2196 (4)	0.4416 (5)	0.0446 (13)
H13	0.0726	0.2011	0.3567	0.054*
C14	0.1699 (3)	0.1775 (3)	0.4811 (5)	0.0361 (11)
H14	0.1984	0.1287	0.4246	0.043*
C15	0.2032 (2)	0.2078 (3)	0.6067 (4)	0.0261 (9)
C16	0.3129 (3)	0.1420 (3)	0.7646 (5)	0.0256 (10)
C17	0.3864 (2)	0.0827 (3)	0.7674 (5)	0.0302 (11)
H17	0.4141	0.0650	0.6861	0.036*
C18	0.4171 (2)	0.0510 (3)	0.8890 (6)	0.0369 (10)
H18	0.4680	0.0139	0.8936	0.044*
C19	0.3733 (3)	0.0735 (4)	1.0062 (5)	0.0366 (12)
H19	0.3918	0.0487	1.0914	0.044*
C20	0.3017 (3)	0.1336 (3)	0.9945 (5)	0.0298 (11)
H20	0.2715	0.1489	1.0742	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0197 (3)	0.0278 (3)	0.0260 (3)	0.0000 (2)	−0.0022 (3)	−0.0011 (4)
Cl1	0.0290 (5)	0.0306 (5)	0.0355 (6)	0.0023 (4)	−0.0053 (6)	−0.0022 (6)
Cl2	0.0253 (5)	0.0455 (6)	0.0421 (6)	−0.0082 (5)	0.0032 (5)	0.0019 (6)
N1	0.0235 (18)	0.0270 (18)	0.031 (2)	0.0015 (14)	0.0000 (15)	0.0022 (16)
N2	0.0211 (18)	0.038 (2)	0.029 (2)	0.0048 (15)	−0.0009 (16)	−0.0002 (17)
N3	0.0195 (18)	0.0309 (18)	0.025 (2)	0.0009 (14)	−0.0034 (15)	−0.0008 (16)
N4	0.0236 (18)	0.0278 (18)	0.034 (2)	0.0006 (14)	−0.0041 (16)	−0.0060 (16)
N5	0.0285 (19)	0.037 (2)	0.024 (2)	0.0072 (15)	−0.0035 (16)	−0.0052 (16)
N6	0.0213 (15)	0.0248 (15)	0.028 (2)	−0.0013 (12)	−0.0028 (17)	0.0002 (18)
C1	0.035 (2)	0.033 (2)	0.032 (3)	0.0018 (18)	0.003 (2)	0.003 (2)
C2	0.048 (3)	0.033 (2)	0.028 (3)	−0.005 (2)	0.006 (2)	0.005 (2)
C3	0.042 (3)	0.041 (3)	0.043 (3)	−0.012 (2)	0.014 (2)	0.001 (2)
C4	0.023 (2)	0.037 (2)	0.044 (3)	−0.0021 (18)	0.005 (2)	−0.004 (2)
C5	0.022 (2)	0.025 (2)	0.033 (3)	−0.0015 (17)	−0.0012 (18)	−0.0053 (18)
C6	0.020 (2)	0.028 (2)	0.028 (2)	0.0009 (16)	−0.0025 (18)	−0.0011 (19)
C7	0.026 (2)	0.048 (3)	0.033 (3)	0.0042 (19)	−0.005 (2)	−0.005 (2)
C8	0.044 (3)	0.048 (3)	0.031 (3)	0.002 (2)	−0.008 (2)	−0.003 (2)
C9	0.043 (3)	0.046 (3)	0.029 (3)	−0.001 (2)	−0.001 (2)	−0.005 (2)
C10	0.028 (2)	0.034 (2)	0.033 (3)	0.0005 (18)	0.001 (2)	−0.007 (2)
C11	0.028 (2)	0.029 (2)	0.031 (3)	0.0005 (17)	−0.0078 (19)	−0.004 (2)
C12	0.029 (2)	0.038 (2)	0.048 (3)	0.0030 (19)	−0.014 (2)	0.000 (2)
C13	0.036 (3)	0.057 (3)	0.041 (3)	−0.002 (2)	−0.020 (2)	−0.009 (2)
C14	0.035 (3)	0.044 (3)	0.029 (3)	0.000 (2)	−0.006 (2)	−0.011 (2)
C15	0.025 (2)	0.028 (2)	0.025 (2)	0.0007 (16)	−0.0013 (18)	0.0000 (19)
C16	0.023 (2)	0.029 (2)	0.025 (3)	−0.0015 (18)	−0.0042 (19)	0.000 (2)
C17	0.021 (2)	0.035 (3)	0.035 (3)	0.0047 (18)	0.003 (2)	0.000 (2)
C18	0.027 (2)	0.034 (2)	0.050 (3)	0.0023 (16)	−0.003 (3)	0.004 (3)
C19	0.034 (3)	0.037 (3)	0.039 (3)	−0.001 (2)	−0.005 (2)	0.013 (2)
C20	0.033 (3)	0.022 (2)	0.035 (3)	−0.0028 (19)	−0.003 (2)	0.004 (2)

Geometric parameters (Å, º) top

Mn1—N3	2.276 (3)	C4—C5	1.395 (5)
Mn1—N1	2.278 (3)	C4—H4	0.9500
Mn1—N4	2.280 (3)	C6—C7	1.405 (6)
Mn1—N6	2.353 (3)	C7—C8	1.360 (6)
Mn1—Cl2	2.4637 (12)	C7—H7	0.9500
Mn1—Cl1	2.5122 (10)	C8—C9	1.399 (6)
N1—C1	1.348 (5)	C8—H8	0.9500
N1—C5	1.351 (5)	C9—C10	1.367 (6)
N2—C6	1.386 (5)	C9—H9	0.9500
N2—C5	1.389 (5)	C10—H10	0.9500
N2—H2N	0.9200	C11—C12	1.363 (6)
N3—C6	1.339 (4)	C11—H11	0.9500
N3—C10	1.355 (5)	C12—C13	1.386 (6)
N4—C15	1.346 (5)	C12—H12	0.9500
N4—C11	1.360 (5)	C13—C14	1.373 (6)
N5—C16	1.392 (6)	C13—H13	0.9500
N5—C15	1.396 (5)	C14—C15	1.411 (6)
N5—H5N	0.9200	C14—H14	0.9500
N6—C16	1.340 (6)	C16—C17	1.405 (6)
N6—C20	1.341 (6)	C17—C18	1.365 (7)
C1—C2	1.365 (6)	C17—H17	0.9500
C1—H1	0.9500	C18—C19	1.392 (7)
C2—C3	1.385 (6)	C18—H18	0.9500
C2—H2	0.9500	C19—C20	1.389 (6)
C3—C4	1.361 (6)	C19—H19	0.9500
C3—H3	0.9500	C20—H20	0.9500

N3—Mn1—N1	77.32 (13)	N2—C5—C4	118.3 (4)
N3—Mn1—N4	161.55 (11)	N3—C6—N2	120.4 (4)
N1—Mn1—N4	91.06 (12)	N3—C6—C7	122.2 (4)
N3—Mn1—N6	87.50 (12)	N2—C6—C7	117.4 (3)
N1—Mn1—N6	84.90 (11)	C8—C7—C6	119.2 (4)
N4—Mn1—N6	77.12 (12)	C8—C7—H7	120.4
N3—Mn1—Cl2	93.71 (9)	C6—C7—H7	120.4
N1—Mn1—Cl2	170.18 (10)	C7—C8—C9	119.1 (4)
N4—Mn1—Cl2	96.59 (9)	C7—C8—H8	120.4
N6—Mn1—Cl2	90.79 (9)	C9—C8—H8	120.4
N3—Mn1—Cl1	95.84 (8)	C10—C9—C8	118.2 (4)
N1—Mn1—Cl1	90.43 (9)	C10—C9—H9	120.9
N4—Mn1—Cl1	98.55 (9)	C8—C9—H9	120.9
N6—Mn1—Cl1	173.54 (11)	N3—C10—C9	123.8 (4)
Cl2—Mn1—Cl1	94.50 (4)	N3—C10—H10	118.1
C1—N1—C5	116.5 (4)	C9—C10—H10	118.1
C1—N1—Mn1	116.9 (3)	N4—C11—C12	124.5 (4)
C5—N1—Mn1	126.1 (3)	N4—C11—H11	117.8
C6—N2—C5	129.8 (3)	C12—C11—H11	117.8
C6—N2—H2N	112.2	C11—C12—C13	118.4 (4)
C5—N2—H2N	117.4	C11—C12—H12	120.8
C6—N3—C10	117.1 (3)	C13—C12—H12	120.8
C6—N3—Mn1	123.5 (3)	C14—C13—C12	119.4 (4)
C10—N3—Mn1	115.7 (3)	C14—C13—H13	120.3
C15—N4—C11	116.7 (3)	C12—C13—H13	120.3
C15—N4—Mn1	127.8 (3)	C13—C14—C15	119.0 (4)
C11—N4—Mn1	115.5 (3)	C13—C14—H14	120.5
C16—N5—C15	128.6 (4)	C15—C14—H14	120.5
C16—N5—H5N	113.0	N4—C15—N5	120.6 (4)
C15—N5—H5N	114.3	N4—C15—C14	122.1 (4)
C16—N6—C20	117.4 (3)	N5—C15—C14	117.1 (4)
C16—N6—Mn1	121.1 (3)	N6—C16—N5	120.2 (4)
C20—N6—Mn1	114.0 (3)	N6—C16—C17	122.5 (4)
N1—C1—C2	124.2 (4)	N5—C16—C17	117.3 (4)
N1—C1—H1	117.9	C18—C17—C16	118.8 (4)
C2—C1—H1	117.9	C18—C17—H17	120.6
C1—C2—C3	118.3 (4)	C16—C17—H17	120.6
C1—C2—H2	120.8	C17—C18—C19	119.5 (3)
C3—C2—H2	120.8	C17—C18—H18	120.2
C4—C3—C2	119.4 (4)	C19—C18—H18	120.2
C4—C3—H3	120.3	C20—C19—C18	117.9 (5)
C2—C3—H3	120.3	C20—C19—H19	121.1
C3—C4—C5	119.1 (4)	C18—C19—H19	121.1
C3—C4—H4	120.5	N6—C20—C19	123.6 (5)
C5—C4—H4	120.5	N6—C20—H20	118.2
N1—C5—N2	119.3 (4)	C19—C20—H20	118.2
N1—C5—C4	122.4 (4)

N3—Mn1—N1—C1	−150.8 (3)	Mn1—N1—C5—C4	167.7 (3)
N4—Mn1—N1—C1	43.7 (3)	C6—N2—C5—N1	−30.3 (6)
N6—Mn1—N1—C1	120.6 (3)	C6—N2—C5—C4	149.2 (4)
Cl1—Mn1—N1—C1	−54.9 (3)	C3—C4—C5—N1	3.1 (6)
N3—Mn1—N1—C5	37.5 (3)	C3—C4—C5—N2	−176.5 (4)
N4—Mn1—N1—C5	−128.0 (3)	C10—N3—C6—N2	−174.7 (4)
N6—Mn1—N1—C5	−51.1 (3)	Mn1—N3—C6—N2	28.0 (5)
Cl1—Mn1—N1—C5	133.4 (3)	C10—N3—C6—C7	5.6 (6)
N1—Mn1—N3—C6	−44.8 (3)	Mn1—N3—C6—C7	−151.8 (3)
N4—Mn1—N3—C6	7.3 (6)	C5—N2—C6—N3	21.9 (6)
N6—Mn1—N3—C6	40.6 (3)	C5—N2—C6—C7	−158.3 (4)
Cl2—Mn1—N3—C6	131.2 (3)	N3—C6—C7—C8	−4.2 (6)
Cl1—Mn1—N3—C6	−133.9 (3)	N2—C6—C7—C8	176.0 (4)
N1—Mn1—N3—C10	157.6 (3)	C6—C7—C8—C9	−1.3 (7)
N4—Mn1—N3—C10	−150.4 (3)	C7—C8—C9—C10	4.9 (7)
N6—Mn1—N3—C10	−117.1 (3)	C6—N3—C10—C9	−1.6 (6)
Cl2—Mn1—N3—C10	−26.5 (3)	Mn1—N3—C10—C9	157.5 (4)
Cl1—Mn1—N3—C10	68.4 (3)	C8—C9—C10—N3	−3.6 (7)
N3—Mn1—N4—C15	7.8 (6)	C15—N4—C11—C12	−2.7 (6)
N1—Mn1—N4—C15	58.1 (3)	Mn1—N4—C11—C12	178.5 (3)
N6—Mn1—N4—C15	−26.4 (3)	N4—C11—C12—C13	1.3 (7)
Cl2—Mn1—N4—C15	−115.7 (3)	C11—C12—C13—C14	0.7 (7)
Cl1—Mn1—N4—C15	148.7 (3)	C12—C13—C14—C15	−1.1 (7)
N3—Mn1—N4—C11	−173.6 (3)	C11—N4—C15—N5	177.4 (4)
N1—Mn1—N4—C11	−123.3 (3)	Mn1—N4—C15—N5	−4.1 (5)
N6—Mn1—N4—C11	152.2 (3)	C11—N4—C15—C14	2.2 (6)
Cl2—Mn1—N4—C11	62.9 (3)	Mn1—N4—C15—C14	−179.2 (3)
Cl1—Mn1—N4—C11	−32.7 (3)	C16—N5—C15—N4	37.4 (6)
N3—Mn1—N6—C16	−122.6 (3)	C16—N5—C15—C14	−147.1 (4)
N1—Mn1—N6—C16	−45.1 (3)	C13—C14—C15—N4	−0.4 (6)
N4—Mn1—N6—C16	47.1 (3)	C13—C14—C15—N5	−175.7 (4)
Cl2—Mn1—N6—C16	143.7 (3)	C20—N6—C16—N5	173.4 (4)
N3—Mn1—N6—C20	26.5 (3)	Mn1—N6—C16—N5	−38.6 (5)
N1—Mn1—N6—C20	103.9 (3)	C20—N6—C16—C17	−5.6 (5)
N4—Mn1—N6—C20	−163.8 (3)	Mn1—N6—C16—C17	142.5 (3)
Cl2—Mn1—N6—C20	−67.2 (3)	C15—N5—C16—N6	−12.8 (6)
C5—N1—C1—C2	2.3 (6)	C15—N5—C16—C17	166.2 (4)
Mn1—N1—C1—C2	−170.2 (3)	N6—C16—C17—C18	1.8 (6)
N1—C1—C2—C3	0.4 (6)	N5—C16—C17—C18	−177.2 (4)
C1—C2—C3—C4	−1.4 (6)	C16—C17—C18—C19	3.0 (6)
C2—C3—C4—C5	−0.2 (6)	C17—C18—C19—C20	−3.7 (6)
C1—N1—C5—N2	175.5 (4)	C16—N6—C20—C19	4.8 (5)
Mn1—N1—C5—N2	−12.7 (5)	Mn1—N6—C20—C19	−145.5 (3)
C1—N1—C5—C4	−4.0 (6)	C18—C19—C20—N6	−0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl2ⁱ	0.92	2.30	3.211 (3)	171
N5—H5N···Cl1ⁱⁱ	0.92	2.45	3.355 (4)	170

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

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₁₀H₉N₃)₂]
M_r	468.24
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	200
a, b, c (Å)	16.236 (3), 12.542 (2), 9.9233 (17)
V (Å³)	2020.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.31 × 0.28 × 0.19

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.849, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14151, 4293, 2982
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.092, 1.01
No. of reflections	4293
No. of parameters	262
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.57
Absolute structure	Flack (1983), 1616 Friedel pairs
Absolute structure parameter	0.04 (2)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Mn1—N3	2.276 (3)	Mn1—N6	2.353 (3)
Mn1—N1	2.278 (3)	Mn1—Cl2	2.4637 (12)
Mn1—N4	2.280 (3)	Mn1—Cl1	2.5122 (10)

N3—Mn1—N1	77.32 (13)	N4—Mn1—N6	77.12 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl2ⁱ	0.92	2.30	3.211 (3)	171.4
N5—H5N···Cl1ⁱⁱ	0.92	2.45	3.355 (4)	169.7

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

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

References

Bose, D., Mostafa, G., Fun, H.-K. & Ghosh, B. K. (2005). Polyhedron, 24, 747–758. Web of Science CSD CrossRef CAS Google Scholar
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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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