cis-Aqua­bis­(di-2-pyridyl­amine-κ2N,N′)iodidomanganese(II) iodide

Ha, K.

doi:10.1107/S1600536811047349

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1751

https://doi.org/10.1107/S1600536811047349

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cis-Aquabis(di-2-pyridylamine-κ²N,N′)iodidomanganese(II) iodide

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 November 2011; accepted 9 November 2011; online 12 November 2011)

The asymmetric unit of the title compound, [MnI(C₁₀H₉N₃)₂(H₂O)]I, contains a cationic Mn^II complex and an I⁻ anion. In the complex, the Mn^II ion is six-coordinated in a considerably distorted cis-N₄IO octahedral environment defined by four N atoms of the two chelating di-2-pyridylamine (dpa) ligands, one I⁻ anion and one O atom of a water ligand. As a result of the different trans effects of the I, N and O atoms, the Mn—N bond trans to the I atom is slightly longer than the Mn—N bond trans to the N or O atoms. The dpa ligands are not planar, with dihedral angles between the two pyridine rings of 26.2 (4) and 26.5 (4)°. The complex cations are stacked in columns along the a axis and are linked to the anions by intermolecular O—H⋯I and N—H⋯I hydrogen bonds.

Related literature

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

Experimental

Crystal data

[MnI(C₁₀H₉N₃)₂(H₂O)]I
M_r = 669.16
Triclinic, $[P \overline 1]$
a = 8.598 (3) Å
b = 10.156 (3) Å
c = 13.909 (4) Å
α = 93.091 (6)°
β = 104.402 (6)°
γ = 98.262 (6)°
V = 1159.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.26 mm⁻¹
T = 200 K
0.28 × 0.23 × 0.19 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.725, T_max = 1.000
7310 measured reflections
4509 independent reflections
3069 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.134
S = 1.06
4509 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn1—O1	2.164 (6)
Mn1—N4	2.215 (6)
Mn1—N3	2.238 (6)
Mn1—N6	2.249 (6)
Mn1—N1	2.312 (6)
Mn1—I1	2.8785 (15)

N4—Mn1—N6	81.0 (2)
N3—Mn1—N1	78.8 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯I2ⁱ	0.84	2.76	3.500 (6)	148
O1—H1B⋯I1ⁱⁱ	0.84	2.73	3.490 (6)	152
N2—H2N⋯I2ⁱⁱⁱ	0.92	2.77	3.681 (7)	172
N5—H5N⋯I2^iv	0.92	2.80	3.710 (6)	173
Symmetry codes: (i) x+1, y+1, z; (ii) -x+2, -y+2, -z; (iii) -x+1, -y+1, -z+1; (iv) x+1, y, z.

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: https://doi.org/10.1107/S1600536811047349/wm2558sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047349/wm2558Isup2.hkl

checkCIF report

Comment top

Cationic Mn^II complexes with the di-2-pyridylamine (dpa; C₁₀H₉N₃) ligand, such as [MnX(dpa)₂(H₂O)]ClO₄ (X = N₃^-, NCO^-), have been investigated previously (Bose et al., 2005).

The asymmetric unit of the title compound, [MnI(dpa)₂(H₂O)]I, consists of a cationic Mn^II complex and an I^- anion (Fig. 1). In the complex, the Mn^II ion is six-coordinated in a considerably distorted cis-N₄IO octahedral environment defined by four N atoms of the two chelating dpa ligands, one I^- anion and one O atom of a water ligand. The main contribution to the distortion is the tight N—Mn—N chelating angles (Table 1), which results in non-linear trans axes [N3—Mn1—N4 = 165.7 (2)° and O1—Mn1—N6 = 171.7 (2)°]. However, the apical I1—Mn1—N1 bond is almost linear with a bond angle of 177.61 (17)°. The Mn—N(dpa) bond lengths are somewhat different and longer than the Mn—O(H₂O) bond (Table 1). As a result of the different trans effects of the I, N and O atoms, the Mn1—N1 bond trans to the I atom is slightly longer than the Mn—N bond trans to the N or O atoms. In the crystal structure, the dpa ligands are not planar. The dihedral angles between the two pyridyl rings of dpa are 26.2 (4)° and 26.5 (4)°.

The complexes are stacked in columns along the a axis, and the component cations and anions are linked by intermolecular O—H···I and N—H···I hydrogen bonds (Fig. 2, Table 2). In the column, numerous inter- and intramolecular π-π interactions between the pyridyl rings are present, the shortest centroid-centroid distance being 3.728 (5) Å.

Related literature top

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

Experimental top

To a solution of di-2-pyridylamine (0.3432 g, 2.005 mmol) in acetone (50 ml) was added MnI₂ (0.3108 g, 1.007 mmol) and refluxed for 7 h. The formed precipitate was separated by filtration and washed with acetone, and dried at 323 K, to give a white powder (0.1571 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from an MeOH solution.

Structure description top

Cationic Mn^II complexes with the di-2-pyridylamine (dpa; C₁₀H₉N₃) ligand, such as [MnX(dpa)₂(H₂O)]ClO₄ (X = N₃^-, NCO^-), have been investigated previously (Bose et al., 2005).

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

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 the title compound, with displacement ellipsoids drawn at the 40% probability level for non-H atoms.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

cis-Aquabis(di-2-pyridylamine-κ²N,N')iodidomanganese(II) iodide top

Crystal data top

[MnI(C₁₀H₉N₃)₂(H₂O)]I	Z = 2
M_r = 669.16	F(000) = 642
Triclinic, P1	D_x = 1.917 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.598 (3) Å	Cell parameters from 2534 reflections
b = 10.156 (3) Å	θ = 2.5–25.7°
c = 13.909 (4) Å	µ = 3.26 mm⁻¹
α = 93.091 (6)°	T = 200 K
β = 104.402 (6)°	Block, colorless
γ = 98.262 (6)°	0.28 × 0.23 × 0.19 mm
V = 1159.0 (6) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	4509 independent reflections
Radiation source: fine-focus sealed tube	3069 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→10
T_min = 0.725, T_max = 1.000	k = −12→12
7310 measured reflections	l = −17→15

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0448P)² + 2.3714P] where P = (F_o² + 2F_c²)/3
4509 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 1.01 e Å⁻³
0 restraints	Δρ_min = −1.13 e Å⁻³

Crystal data top

[MnI(C₁₀H₉N₃)₂(H₂O)]I	γ = 98.262 (6)°
M_r = 669.16	V = 1159.0 (6) Å³
Triclinic, P1	Z = 2
a = 8.598 (3) Å	Mo Kα radiation
b = 10.156 (3) Å	µ = 3.26 mm⁻¹
c = 13.909 (4) Å	T = 200 K
α = 93.091 (6)°	0.28 × 0.23 × 0.19 mm
β = 104.402 (6)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4509 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3069 reflections with I > 2σ(I)
T_min = 0.725, T_max = 1.000	R_int = 0.041
7310 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.06	Δρ_max = 1.01 e Å⁻³
4509 reflections	Δρ_min = −1.13 e Å⁻³
271 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	0.92450 (15)	0.83226 (11)	0.17727 (9)	0.0334 (3)
I1	0.70020 (7)	0.84510 (6)	−0.01259 (4)	0.0439 (2)
O1	1.0782 (8)	1.0190 (6)	0.1727 (5)	0.0597 (19)
H1A	1.1370	1.0566	0.2276	0.090*
H1B	1.1097	1.0741	0.1359	0.090*
N1	1.0972 (8)	0.8255 (6)	0.3329 (5)	0.0330 (15)
N2	0.8918 (8)	0.8161 (7)	0.4170 (5)	0.0399 (17)
H2N	0.8627	0.7822	0.4712	0.060*
N3	0.7974 (8)	0.9327 (6)	0.2754 (5)	0.0362 (16)
N4	1.0645 (8)	0.7020 (6)	0.1115 (5)	0.0320 (15)
N5	1.0185 (8)	0.5213 (6)	0.2056 (5)	0.0348 (16)
H5N	1.0725	0.4583	0.2387	0.052*
N6	0.7948 (8)	0.6322 (6)	0.1996 (5)	0.0318 (15)
C1	1.2452 (10)	0.7983 (8)	0.3321 (6)	0.040 (2)
H1	1.2943	0.8345	0.2831	0.048*
C2	1.3298 (11)	0.7210 (10)	0.3981 (7)	0.051 (3)
H2	1.4363	0.7076	0.3966	0.061*
C3	1.2553 (12)	0.6636 (9)	0.4664 (7)	0.048 (2)
H3	1.3062	0.6038	0.5094	0.057*
C4	1.1086 (11)	0.6936 (8)	0.4715 (6)	0.040 (2)
H4	1.0567	0.6577	0.5194	0.048*
C5	1.0354 (10)	0.7785 (8)	0.4046 (6)	0.0348 (19)
C6	0.7953 (9)	0.9056 (7)	0.3694 (6)	0.0304 (18)
C7	0.6994 (10)	0.9603 (8)	0.4199 (6)	0.0371 (19)
H7	0.7061	0.9430	0.4872	0.045*
C8	0.5937 (10)	1.0399 (8)	0.3740 (7)	0.040 (2)
H8	0.5243	1.0762	0.4082	0.048*
C9	0.5890 (11)	1.0668 (8)	0.2771 (6)	0.042 (2)
H9	0.5148	1.1198	0.2424	0.051*
C10	0.6939 (11)	1.0151 (8)	0.2330 (6)	0.042 (2)
H10	0.6950	1.0382	0.1679	0.050*
C11	1.1421 (10)	0.7549 (9)	0.0432 (6)	0.038 (2)
H11	1.1232	0.8405	0.0232	0.046*
C12	1.2430 (10)	0.6932 (10)	0.0028 (6)	0.046 (2)
H12	1.2942	0.7343	−0.0436	0.055*
C13	1.2698 (10)	0.5664 (10)	0.0317 (6)	0.046 (2)
H13	1.3415	0.5209	0.0055	0.055*
C14	1.1937 (10)	0.5088 (9)	0.0966 (6)	0.041 (2)
H14	1.2095	0.4222	0.1155	0.050*
C15	1.0906 (9)	0.5798 (7)	0.1355 (6)	0.0314 (18)
C16	0.8692 (9)	0.5266 (7)	0.2229 (6)	0.0303 (18)
C17	0.7977 (11)	0.4190 (8)	0.2649 (6)	0.042 (2)
H17	0.8529	0.3454	0.2814	0.050*
C18	0.6502 (12)	0.4210 (8)	0.2814 (6)	0.046 (2)
H18	0.6030	0.3504	0.3125	0.055*
C19	0.5665 (10)	0.5270 (8)	0.2529 (6)	0.038 (2)
H19	0.4609	0.5288	0.2620	0.046*
C20	0.6419 (9)	0.6271 (8)	0.2117 (6)	0.0312 (18)
H20	0.5845	0.6979	0.1900	0.037*
I2	0.23491 (7)	0.28327 (5)	0.35974 (4)	0.03842 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0398 (7)	0.0302 (6)	0.0334 (7)	0.0067 (6)	0.0144 (6)	0.0048 (5)
I1	0.0482 (4)	0.0497 (4)	0.0375 (3)	0.0134 (3)	0.0131 (3)	0.0129 (3)
O1	0.084 (5)	0.040 (3)	0.054 (4)	−0.021 (3)	0.034 (4)	−0.003 (3)
N1	0.034 (4)	0.031 (4)	0.033 (4)	−0.001 (3)	0.012 (3)	0.000 (3)
N2	0.043 (4)	0.047 (4)	0.036 (4)	0.015 (3)	0.016 (3)	0.011 (3)
N3	0.045 (4)	0.031 (4)	0.040 (4)	0.017 (3)	0.018 (3)	0.002 (3)
N4	0.030 (4)	0.026 (3)	0.042 (4)	0.003 (3)	0.014 (3)	−0.001 (3)
N5	0.034 (4)	0.033 (4)	0.042 (4)	0.013 (3)	0.013 (3)	0.011 (3)
N6	0.035 (4)	0.028 (3)	0.029 (4)	0.002 (3)	0.005 (3)	0.005 (3)
C1	0.031 (5)	0.051 (5)	0.032 (5)	−0.003 (4)	0.008 (4)	−0.017 (4)
C2	0.032 (5)	0.064 (6)	0.051 (6)	0.013 (5)	0.003 (4)	−0.014 (5)
C3	0.057 (6)	0.048 (5)	0.037 (5)	0.021 (5)	0.002 (5)	−0.003 (4)
C4	0.054 (6)	0.030 (4)	0.033 (5)	0.002 (4)	0.009 (4)	0.001 (4)
C5	0.032 (5)	0.031 (4)	0.037 (5)	0.003 (4)	0.004 (4)	−0.004 (4)
C6	0.031 (4)	0.019 (4)	0.040 (5)	−0.002 (3)	0.009 (4)	0.005 (3)
C7	0.039 (5)	0.036 (5)	0.039 (5)	0.005 (4)	0.018 (4)	−0.002 (4)
C8	0.037 (5)	0.031 (4)	0.055 (6)	0.010 (4)	0.015 (4)	−0.005 (4)
C9	0.056 (6)	0.030 (4)	0.043 (5)	0.018 (4)	0.011 (4)	0.008 (4)
C10	0.053 (6)	0.039 (5)	0.038 (5)	0.011 (4)	0.019 (4)	0.005 (4)
C11	0.031 (5)	0.047 (5)	0.041 (5)	0.006 (4)	0.015 (4)	0.005 (4)
C12	0.036 (5)	0.070 (6)	0.034 (5)	0.000 (5)	0.015 (4)	0.005 (5)
C13	0.027 (5)	0.073 (7)	0.040 (5)	0.016 (4)	0.011 (4)	−0.008 (5)
C14	0.033 (5)	0.047 (5)	0.039 (5)	0.011 (4)	−0.001 (4)	−0.011 (4)
C15	0.019 (4)	0.031 (4)	0.036 (4)	−0.003 (3)	0.000 (3)	−0.011 (4)
C16	0.035 (4)	0.023 (4)	0.029 (4)	0.001 (3)	0.002 (3)	0.002 (3)
C17	0.042 (5)	0.032 (4)	0.051 (5)	0.013 (4)	0.007 (4)	0.005 (4)
C18	0.062 (6)	0.034 (5)	0.040 (5)	−0.006 (4)	0.017 (5)	0.006 (4)
C19	0.038 (5)	0.035 (5)	0.042 (5)	0.004 (4)	0.014 (4)	−0.002 (4)
C20	0.025 (4)	0.038 (4)	0.034 (4)	0.014 (4)	0.007 (3)	0.003 (4)
I2	0.0426 (3)	0.0392 (3)	0.0373 (3)	0.0124 (3)	0.0130 (2)	0.0094 (2)

Geometric parameters (Å, º) top

Mn1—O1	2.164 (6)	C3—H3	0.9500
Mn1—N4	2.215 (6)	C4—C5	1.399 (11)
Mn1—N3	2.238 (6)	C4—H4	0.9500
Mn1—N6	2.249 (6)	C6—C7	1.364 (10)
Mn1—N1	2.312 (6)	C7—C8	1.366 (11)
Mn1—I1	2.8785 (15)	C7—H7	0.9500
O1—H1A	0.8400	C8—C9	1.383 (12)
O1—H1B	0.8400	C8—H8	0.9500
N1—C5	1.321 (10)	C9—C10	1.356 (11)
N1—C1	1.343 (9)	C9—H9	0.9500
N2—C5	1.391 (10)	C10—H10	0.9500
N2—C6	1.401 (9)	C11—C12	1.349 (11)
N2—H2N	0.9200	C11—H11	0.9500
N3—C6	1.355 (10)	C12—C13	1.403 (13)
N3—C10	1.359 (10)	C12—H12	0.9500
N4—C15	1.338 (10)	C13—C14	1.351 (12)
N4—C11	1.381 (10)	C13—H13	0.9500
N5—C16	1.371 (10)	C14—C15	1.407 (11)
N5—C15	1.395 (10)	C14—H14	0.9500
N5—H5N	0.9200	C16—C17	1.403 (11)
N6—C16	1.339 (9)	C17—C18	1.347 (12)
N6—C20	1.361 (9)	C17—H17	0.9500
C1—C2	1.378 (12)	C18—C19	1.401 (11)
C1—H1	0.9500	C18—H18	0.9500
C2—C3	1.382 (13)	C19—C20	1.356 (11)
C2—H2	0.9500	C19—H19	0.9500
C3—C4	1.358 (12)	C20—H20	0.9500

O1—Mn1—N4	96.3 (2)	N1—C5—N2	119.4 (7)
O1—Mn1—N3	91.1 (2)	N1—C5—C4	123.5 (8)
N4—Mn1—N3	165.7 (2)	N2—C5—C4	117.1 (8)
O1—Mn1—N6	171.7 (2)	N3—C6—C7	122.5 (7)
N4—Mn1—N6	81.0 (2)	N3—C6—N2	119.7 (7)
N3—Mn1—N6	89.9 (2)	C7—C6—N2	117.8 (7)
O1—Mn1—N1	85.5 (2)	C6—C7—C8	120.1 (8)
N4—Mn1—N1	89.6 (2)	C6—C7—H7	120.0
N3—Mn1—N1	78.8 (2)	C8—C7—H7	120.0
N6—Mn1—N1	86.7 (2)	C7—C8—C9	119.0 (8)
O1—Mn1—I1	94.82 (18)	C7—C8—H8	120.5
N4—Mn1—I1	92.68 (17)	C9—C8—H8	120.5
N3—Mn1—I1	98.81 (18)	C10—C9—C8	117.8 (8)
N6—Mn1—I1	93.11 (16)	C10—C9—H9	121.1
N1—Mn1—I1	177.61 (17)	C8—C9—H9	121.1
Mn1—O1—H1A	116.6	C9—C10—N3	124.7 (8)
Mn1—O1—H1B	145.6	C9—C10—H10	117.6
H1A—O1—H1B	97.7	N3—C10—H10	117.6
C5—N1—C1	116.5 (7)	C12—C11—N4	124.4 (8)
C5—N1—Mn1	118.9 (5)	C12—C11—H11	117.8
C1—N1—Mn1	114.9 (5)	N4—C11—H11	117.8
C5—N2—C6	131.9 (7)	C11—C12—C13	117.8 (8)
C5—N2—H2N	112.5	C11—C12—H12	121.1
C6—N2—H2N	115.2	C13—C12—H12	121.1
C6—N3—C10	115.7 (7)	C14—C13—C12	120.1 (8)
C6—N3—Mn1	126.3 (5)	C14—C13—H13	119.9
C10—N3—Mn1	117.4 (5)	C12—C13—H13	119.9
C15—N4—C11	115.9 (7)	C13—C14—C15	118.6 (8)
C15—N4—Mn1	126.9 (5)	C13—C14—H14	120.7
C11—N4—Mn1	117.1 (5)	C15—C14—H14	120.7
C16—N5—C15	130.6 (6)	N4—C15—N5	119.0 (7)
C16—N5—H5N	114.2	N4—C15—C14	123.1 (8)
C15—N5—H5N	114.4	N5—C15—C14	117.8 (7)
C16—N6—C20	117.4 (7)	N6—C16—N5	120.3 (7)
C16—N6—Mn1	123.8 (5)	N6—C16—C17	121.6 (8)
C20—N6—Mn1	117.2 (5)	N5—C16—C17	118.2 (7)
N1—C1—C2	123.8 (8)	C18—C17—C16	119.3 (8)
N1—C1—H1	118.1	C18—C17—H17	120.3
C2—C1—H1	118.1	C16—C17—H17	120.3
C1—C2—C3	118.1 (9)	C17—C18—C19	120.1 (8)
C1—C2—H2	121.0	C17—C18—H18	120.0
C3—C2—H2	121.0	C19—C18—H18	120.0
C4—C3—C2	119.2 (8)	C20—C19—C18	117.5 (8)
C4—C3—H3	120.4	C20—C19—H19	121.3
C2—C3—H3	120.4	C18—C19—H19	121.3
C3—C4—C5	118.5 (8)	C19—C20—N6	124.0 (7)
C3—C4—H4	120.8	C19—C20—H20	118.0
C5—C4—H4	120.8	N6—C20—H20	118.0

O1—Mn1—N1—C5	142.6 (6)	Mn1—N1—C5—C4	138.1 (6)
N4—Mn1—N1—C5	−121.0 (6)	C6—N2—C5—N1	−4.3 (12)
N3—Mn1—N1—C5	50.6 (6)	C6—N2—C5—C4	174.6 (7)
N6—Mn1—N1—C5	−40.0 (6)	C3—C4—C5—N1	3.9 (12)
O1—Mn1—N1—C1	−72.4 (6)	C3—C4—C5—N2	−174.9 (7)
N4—Mn1—N1—C1	23.9 (6)	C10—N3—C6—C7	−1.9 (11)
N3—Mn1—N1—C1	−164.5 (6)	Mn1—N3—C6—C7	−172.1 (6)
N6—Mn1—N1—C1	105.0 (6)	C10—N3—C6—N2	176.7 (7)
O1—Mn1—N3—C6	−117.8 (6)	Mn1—N3—C6—N2	6.5 (10)
N4—Mn1—N3—C6	3.7 (14)	C5—N2—C6—N3	26.0 (12)
N6—Mn1—N3—C6	54.0 (6)	C5—N2—C6—C7	−155.4 (8)
N1—Mn1—N3—C6	−32.6 (6)	N3—C6—C7—C8	3.7 (12)
I1—Mn1—N3—C6	147.1 (6)	N2—C6—C7—C8	−174.9 (7)
O1—Mn1—N3—C10	72.1 (6)	C6—C7—C8—C9	−1.8 (12)
N4—Mn1—N3—C10	−166.3 (8)	C7—C8—C9—C10	−1.7 (12)
N6—Mn1—N3—C10	−116.1 (6)	C8—C9—C10—N3	3.7 (13)
N1—Mn1—N3—C10	157.3 (6)	C6—N3—C10—C9	−1.9 (12)
I1—Mn1—N3—C10	−22.9 (6)	Mn1—N3—C10—C9	169.2 (7)
O1—Mn1—N4—C15	143.8 (6)	C15—N4—C11—C12	−1.9 (12)
N3—Mn1—N4—C15	22.8 (14)	Mn1—N4—C11—C12	174.1 (7)
N6—Mn1—N4—C15	−28.3 (6)	N4—C11—C12—C13	0.6 (13)
N1—Mn1—N4—C15	58.4 (6)	C11—C12—C13—C14	1.1 (13)
I1—Mn1—N4—C15	−121.0 (6)	C12—C13—C14—C15	−1.2 (12)
O1—Mn1—N4—C11	−31.7 (6)	C11—N4—C15—N5	178.8 (7)
N3—Mn1—N4—C11	−152.7 (9)	Mn1—N4—C15—N5	3.2 (10)
N6—Mn1—N4—C11	156.2 (6)	C11—N4—C15—C14	1.6 (11)
N1—Mn1—N4—C11	−117.1 (6)	Mn1—N4—C15—C14	−173.9 (5)
I1—Mn1—N4—C11	63.4 (5)	C16—N5—C15—N4	36.6 (11)
N4—Mn1—N6—C16	36.5 (6)	C16—N5—C15—C14	−146.2 (8)
N3—Mn1—N6—C16	−132.5 (6)	C13—C14—C15—N4	−0.2 (12)
N1—Mn1—N6—C16	−53.7 (6)	C13—C14—C15—N5	−177.3 (7)
I1—Mn1—N6—C16	128.7 (6)	C20—N6—C16—N5	175.3 (7)
N4—Mn1—N6—C20	−158.5 (6)	Mn1—N6—C16—N5	−19.7 (9)
N3—Mn1—N6—C20	32.5 (5)	C20—N6—C16—C17	−4.4 (10)
N1—Mn1—N6—C20	111.3 (5)	Mn1—N6—C16—C17	160.5 (6)
I1—Mn1—N6—C20	−66.3 (5)	C15—N5—C16—N6	−27.0 (12)
C5—N1—C1—C2	2.9 (11)	C15—N5—C16—C17	152.7 (8)
Mn1—N1—C1—C2	−142.9 (7)	N6—C16—C17—C18	0.6 (12)
N1—C1—C2—C3	2.8 (12)	N5—C16—C17—C18	−179.2 (8)
C1—C2—C3—C4	−5.2 (13)	C16—C17—C18—C19	2.7 (12)
C2—C3—C4—C5	2.1 (12)	C17—C18—C19—C20	−2.0 (12)
C1—N1—C5—N2	172.5 (6)	C18—C19—C20—N6	−2.1 (12)
Mn1—N1—C5—N2	−43.2 (9)	C16—N6—C20—C19	5.3 (11)
C1—N1—C5—C4	−6.3 (11)	Mn1—N6—C20—C19	−160.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···I2ⁱ	0.84	2.76	3.500 (6)	148
O1—H1B···I1ⁱⁱ	0.84	2.73	3.490 (6)	152
N2—H2N···I2ⁱⁱⁱ	0.92	2.77	3.681 (7)	172
N5—H5N···I2^iv	0.92	2.80	3.710 (6)	173

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

Experimental details

Crystal data
Chemical formula	[MnI(C₁₀H₉N₃)₂(H₂O)]I
M_r	669.16
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	8.598 (3), 10.156 (3), 13.909 (4)
α, β, γ (°)	93.091 (6), 104.402 (6), 98.262 (6)
V (Å³)	1159.0 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.26
Crystal size (mm)	0.28 × 0.23 × 0.19

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.725, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7310, 4509, 3069
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.134, 1.06
No. of reflections	4509
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −1.13

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—O1	2.164 (6)	Mn1—N6	2.249 (6)
Mn1—N4	2.215 (6)	Mn1—N1	2.312 (6)
Mn1—N3	2.238 (6)	Mn1—I1	2.8785 (15)

N4—Mn1—N6	81.0 (2)	N3—Mn1—N1	78.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···I2ⁱ	0.84	2.76	3.500 (6)	148.3
O1—H1B···I1ⁱⁱ	0.84	2.73	3.490 (6)	151.5
N2—H2N···I2ⁱⁱⁱ	0.92	2.77	3.681 (7)	171.7
N5—H5N···I2^iv	0.92	2.80	3.710 (6)	173.3

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

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
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar