Diaqua­iodido(2,3,5,6-tetra-2-pyridyl­pyrazine-κ3N2,N1,N6)manganese(II) iodide monohydrate

Ha, K.

doi:10.1107/S1600536811035434

Diaquaiodido(2,3,5,6-tetra-2-pyridylpyrazine-κ³N²,N¹,N⁶)manganese(II) iodide monohydrate

The asymmetric unit of the title compound, [MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O, consists of a cationic Mn^II complex, an I⁻ anion and a solvent water molecule. In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz) ligand, one I⁻ anion and two O atoms of two water ligands. The dihedral angles between the pyridyl rings [maximum deviation = 0.034 (6) Å] and their carrier pyrazine ring [maximum deviation = 0.020 (6) Å] are 26.5 (2) and 27.0 (2)° for the coordinated pyridyl rings, and 51.3 (3) and 43.2 (2)° for the uncoordinated pyridyl rings. Intermolecular O—H

O, O—H

N and O—H

I hydrogen bonds stabilize the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811035434/zq2121sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811035434/zq2121Isup2.hkl Contains datablock I

CCDC reference: 850333

checkCIF report

Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.013 Å
R factor = 0.040
wR factor = 0.115
Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.979
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0135 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         16
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         56
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................         64 Perc.
PLAT925_ALERT_1_C The Reported and Calculated Rho(max) Differ by .       1.17 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       2.23 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       2.02 eA-3

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.39
           From the CIF: _reflns_number_total               5463
           Count of symmetry unique reflns         3483
           Completeness (_total/calc)            156.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1980
           Fraction of Friedel pairs measured     0.568
           Are heavy atom types Z>Si present        yes
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       7.66
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  I1     --  Mn1     ..        6.6 su

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Mono- and dinuclear Mn^II complexes of 2,3,5,6-tetra-2-pyridylpyrazine (tppz; C₂₄H₁₆N₆) ligand, such as [Mn(C₂N₃)(NO₃)(tppz)(H₂O)] (Callejo et al., 2009) and [Mn₂Cl₄(tppz)₂] (Ha, 2011), have been investigated previously.

The asymmetric unit of the title compound, [MnI(tppz)(H₂O)₂]I.H₂O, consists of a cationic Mn^II complex, an I^- anion and a solvent water molecule (Fig. 1). In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by three N atoms of the tridentate tppz ligand, one I^- anion and two O atoms of two water ligands. The main contribution to the distortion is the tight N—Mn—N chelating angles (Table 1), which results in non-linear trans arrangement of the N3—Mn1—N6 bond [N3—Mn1—N6 = 143.1 (3)°]. The apical O1—Mn1—O2 and I1—Mn1—N1 bond angles are 167.0 (2)° and 173.04 (19)°, respectively. The three Mn—N(pyrazine or pyridyl) bond lengths are roughly equivalent and slightly longer than the Mn—O(H₂O) bonds (Table 1). In the crystal structure, the pyrazine and pyridyl rings are nearly planar [maximum deviation = 0.020 (6) Å for pyrazine and 0.034 (6) Å for pyridyl]. The dihedral angles between the pyridyl rings and their carrier pyrazine ring are 26.5 (2)° and 27.0 (2)° for the coordinated pyridyl rings, and 51.3 (3)° and 43.2 (2)° for the uncoordinated pyridyl rings, respectively. The complex, anion and solvent water molecule are linked by intermolecular O—H···O, O—H···N and O—H···I hydrogen bonds (Fig. 2, Table 2). In addition, the complex displays numerous inter- and intramolecular π-π interactions between adjacent six-membered rings, the shortest ring centroid-centroid distance being 4.032 (5) Å.

Related literature top

For the crystal structures of mono- and dinuclear Mn^II complexes with tppz, see: Callejo et al. (2009); Ha (2011).

Experimental top

To a suspension of 2,3,5,6-tetra-2-pyridylpyrazine (0.1945 g, 0.501 mmol) in acetone (20 ml) was added MnI₂ (0.1575 g, 0.510 mmol) in acetone (30 ml) and refluxed for 5 h. The formed precipitate was separated by filtration, washed with acetone and dried at 50 °C, to give an orange powder (0.0779 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a 2-butanone solution.

Structure description top

For the crystal structures of mono- and dinuclear Mn^II complexes with tppz, see: Callejo et al. (2009); Ha (2011).

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. A structure detail of 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.

Diaquaiodido(2,3,5,6-tetra-2-pyridylpyrazine- κ³N²,N¹,N⁶)manganese(II) iodide monohydrate top

Crystal data top

[MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O	F(000) = 726
M_r = 751.22	D_x = 1.875 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5752 reflections
a = 7.977 (3) Å	θ = 2.6–28.3°
b = 13.880 (5) Å	µ = 2.85 mm⁻¹
c = 12.134 (4) Å	T = 200 K
β = 97.944 (7)°	Plate, orange
V = 1330.5 (8) Å³	0.28 × 0.20 × 0.12 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD diffractometer	5463 independent reflections
Radiation source: fine-focus sealed tube	4463 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.828, T_max = 1.000	k = −18→14
9685 measured reflections	l = −16→13

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.P)² + 7.6642P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max < 0.001
5463 reflections	Δρ_max = 1.06 e Å⁻³
325 parameters	Δρ_min = −1.41 e Å⁻³
1 restraint	Absolute structure: Flack (1983); 2033 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)

Crystal data top

[MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O	V = 1330.5 (8) Å³
M_r = 751.22	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.977 (3) Å	µ = 2.85 mm⁻¹
b = 13.880 (5) Å	T = 200 K
c = 12.134 (4) Å	0.28 × 0.20 × 0.12 mm
β = 97.944 (7)°

Data collection top

Bruker SMART 1000 CCD diffractometer	5463 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4463 reflections with I > 2σ(I)
T_min = 0.828, T_max = 1.000	R_int = 0.030
9685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.115	Δρ_max = 1.06 e Å⁻³
S = 1.23	Δρ_min = −1.41 e Å⁻³
5463 reflections	Absolute structure: Flack (1983); 2033 Friedel pairs
325 parameters	Absolute structure parameter: −0.01 (4)
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	0.73505 (17)	0.72431 (9)	0.04312 (11)	0.0215 (3)
I1	0.72966 (9)	0.92402 (4)	0.05631 (6)	0.03842 (18)
O1	1.0067 (8)	0.7096 (5)	0.0533 (6)	0.0328 (16)
H1A	1.0537	0.6728	0.1032	0.049*
H1B	1.0648	0.7508	0.0246	0.049*
O2	0.4663 (7)	0.7099 (5)	0.0564 (5)	0.0263 (14)
H2A	0.4295	0.7353	0.1111	0.039*
H2B	0.4199	0.7271	−0.0070	0.039*
N1	0.7180 (9)	0.5642 (5)	0.0129 (6)	0.0187 (15)
N2	0.7871 (9)	0.3757 (5)	−0.0207 (6)	0.0233 (16)
N3	0.6873 (9)	0.6981 (5)	−0.1423 (6)	0.0207 (15)
N4	0.6763 (9)	0.3041 (5)	−0.2331 (6)	0.0247 (17)
N5	0.7592 (9)	0.2438 (5)	0.1416 (6)	0.0242 (17)
N6	0.7658 (10)	0.6496 (6)	0.2088 (6)	0.0238 (17)
C1	0.7137 (11)	0.5310 (6)	−0.0902 (7)	0.0193 (18)
C2	0.6586 (12)	0.6064 (7)	−0.1792 (7)	0.0230 (19)
C3	0.5767 (12)	0.5849 (7)	−0.2810 (8)	0.027 (2)
H3	0.5502	0.5199	−0.3011	0.032*
C4	0.5320 (12)	0.6590 (7)	−0.3557 (8)	0.028 (2)
H4	0.4761	0.6454	−0.4284	0.034*
C5	0.5696 (11)	0.7531 (7)	−0.3233 (6)	0.0245 (19)
H5	0.5455	0.8049	−0.3743	0.029*
C6	0.6431 (12)	0.7699 (7)	−0.2151 (8)	0.027 (2)
H6	0.6631	0.8346	−0.1912	0.033*
C7	0.7493 (10)	0.4348 (7)	−0.1073 (8)	0.0236 (19)
C8	0.7618 (12)	0.3885 (6)	−0.2172 (8)	0.0201 (18)
C9	0.8629 (11)	0.4246 (8)	−0.2909 (7)	0.0260 (18)
H9	0.9222	0.4836	−0.2759	0.031*
C10	0.8765 (15)	0.3728 (8)	−0.3881 (8)	0.037 (3)
H10	0.9445	0.3957	−0.4409	0.044*
C11	0.7875 (15)	0.2869 (8)	−0.4052 (9)	0.039 (3)
H11	0.7936	0.2499	−0.4704	0.047*
C12	0.6904 (13)	0.2556 (8)	−0.3268 (8)	0.032 (2)
H12	0.6304	0.1966	−0.3398	0.038*
C13	0.7855 (11)	0.4058 (6)	0.0817 (7)	0.0183 (18)
C14	0.8309 (11)	0.3302 (7)	0.1689 (7)	0.0241 (18)
C15	0.9449 (11)	0.3464 (6)	0.2615 (7)	0.026 (2)
H15	0.9938	0.4083	0.2763	0.031*
C16	0.9871 (12)	0.2702 (7)	0.3332 (8)	0.030 (2)
H16	1.0673	0.2788	0.3980	0.036*
C17	0.9129 (12)	0.1821 (7)	0.3106 (8)	0.029 (2)
H17	0.9379	0.1296	0.3604	0.035*
C18	0.8011 (12)	0.1713 (8)	0.2139 (9)	0.031 (2)
H18	0.7514	0.1098	0.1976	0.037*
C19	0.7492 (11)	0.5042 (6)	0.1010 (7)	0.0212 (18)
C20	0.7376 (11)	0.5527 (6)	0.2092 (7)	0.0203 (18)
C21	0.6956 (13)	0.5065 (8)	0.3028 (7)	0.031 (2)
H21	0.6684	0.4399	0.3008	0.038*
C22	0.6940 (13)	0.5593 (8)	0.3988 (8)	0.032 (2)
H22	0.6659	0.5291	0.4640	0.039*
C23	0.7325 (14)	0.6542 (8)	0.3998 (9)	0.037 (2)
H23	0.7372	0.6902	0.4668	0.045*
C24	0.7651 (12)	0.6983 (7)	0.3031 (8)	0.026 (2)
H24	0.7877	0.7656	0.3038	0.032*
I2	0.25693 (9)	0.48423 (5)	0.46473 (6)	0.0427 (2)
O3	0.1465 (11)	0.5575 (6)	0.1752 (7)	0.053 (2)
H3A	0.2127	0.5245	0.1425	0.079*
H3B	0.1894	0.5500	0.2419	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0255 (7)	0.0152 (7)	0.0231 (7)	0.0003 (5)	0.0012 (5)	−0.0020 (5)
I1	0.0437 (4)	0.0208 (3)	0.0499 (4)	−0.0005 (3)	0.0033 (3)	−0.0050 (3)
O1	0.023 (3)	0.029 (4)	0.046 (4)	0.002 (3)	0.002 (3)	0.015 (3)
O2	0.021 (3)	0.033 (4)	0.026 (3)	0.002 (3)	0.004 (3)	−0.003 (3)
N1	0.025 (4)	0.012 (3)	0.019 (4)	−0.007 (3)	0.000 (3)	−0.007 (3)
N2	0.021 (4)	0.024 (4)	0.025 (4)	0.005 (3)	0.003 (3)	−0.005 (3)
N3	0.027 (4)	0.010 (3)	0.026 (4)	0.000 (3)	0.006 (3)	−0.002 (3)
N4	0.025 (4)	0.023 (4)	0.028 (4)	0.002 (3)	0.011 (3)	−0.010 (3)
N5	0.029 (4)	0.019 (4)	0.026 (4)	0.002 (3)	0.007 (3)	0.001 (3)
N6	0.035 (5)	0.023 (4)	0.012 (3)	0.006 (3)	−0.002 (3)	−0.001 (3)
C1	0.020 (4)	0.015 (4)	0.022 (4)	0.004 (3)	−0.002 (3)	−0.006 (3)
C2	0.033 (5)	0.022 (4)	0.012 (4)	−0.001 (4)	−0.003 (4)	−0.002 (3)
C3	0.029 (5)	0.025 (5)	0.027 (5)	0.004 (4)	0.008 (4)	−0.002 (4)
C4	0.032 (5)	0.022 (5)	0.031 (5)	0.001 (4)	0.006 (4)	−0.006 (4)
C5	0.032 (5)	0.035 (5)	0.008 (4)	0.005 (4)	0.008 (3)	0.000 (3)
C6	0.032 (5)	0.015 (4)	0.033 (5)	0.003 (4)	0.000 (4)	−0.002 (4)
C7	0.017 (4)	0.018 (5)	0.035 (5)	0.001 (4)	0.001 (3)	−0.002 (4)
C8	0.024 (5)	0.013 (4)	0.026 (5)	0.005 (3)	0.012 (4)	−0.001 (3)
C9	0.036 (5)	0.015 (4)	0.028 (4)	−0.006 (4)	0.008 (4)	0.001 (4)
C10	0.051 (7)	0.045 (6)	0.014 (4)	0.004 (5)	0.005 (4)	0.001 (4)
C11	0.054 (7)	0.038 (6)	0.025 (5)	0.010 (5)	0.002 (5)	−0.013 (5)
C12	0.043 (6)	0.033 (5)	0.021 (5)	−0.003 (5)	0.009 (4)	−0.007 (4)
C13	0.023 (4)	0.009 (4)	0.021 (4)	−0.001 (3)	−0.002 (3)	−0.001 (3)
C14	0.028 (4)	0.020 (4)	0.022 (4)	0.002 (4)	−0.003 (3)	0.000 (4)
C15	0.022 (4)	0.021 (5)	0.032 (5)	−0.001 (3)	−0.007 (4)	−0.005 (4)
C16	0.031 (5)	0.024 (5)	0.032 (5)	0.004 (4)	−0.004 (4)	−0.004 (4)
C17	0.031 (5)	0.032 (5)	0.026 (5)	0.010 (4)	0.008 (4)	0.007 (4)
C18	0.028 (5)	0.029 (5)	0.039 (6)	0.001 (4)	0.011 (4)	0.005 (4)
C19	0.023 (4)	0.019 (5)	0.021 (4)	−0.003 (3)	0.004 (3)	−0.006 (3)
C20	0.019 (4)	0.019 (4)	0.026 (5)	0.000 (3)	0.011 (3)	0.002 (4)
C21	0.044 (6)	0.033 (6)	0.017 (4)	−0.005 (5)	0.007 (4)	0.000 (4)
C22	0.040 (6)	0.038 (6)	0.022 (5)	0.002 (5)	0.011 (4)	0.009 (4)
C23	0.045 (6)	0.038 (6)	0.027 (5)	0.002 (5)	−0.001 (5)	−0.010 (4)
C24	0.033 (5)	0.017 (5)	0.030 (5)	−0.005 (4)	0.010 (4)	−0.003 (4)
I2	0.0438 (4)	0.0399 (4)	0.0443 (4)	−0.0125 (4)	0.0054 (3)	−0.0141 (4)
O3	0.059 (6)	0.046 (5)	0.053 (5)	0.013 (4)	0.009 (4)	0.013 (4)

Geometric parameters (Å, º) top

Mn1—O1	2.163 (6)	C6—H6	0.9500
Mn1—O2	2.182 (6)	C7—C8	1.497 (13)
Mn1—N6	2.245 (7)	C8—C9	1.378 (12)
Mn1—N1	2.253 (7)	C9—C10	1.399 (13)
Mn1—N3	2.259 (7)	C9—H9	0.9500
Mn1—I1	2.7772 (16)	C10—C11	1.389 (15)
O1—H1A	0.8400	C10—H10	0.9500
O1—H1B	0.8400	C11—C12	1.377 (15)
O2—H2A	0.8400	C11—H11	0.9500
O2—H2B	0.8400	C12—H12	0.9500
N1—C1	1.328 (10)	C13—C19	1.423 (12)
N1—C19	1.350 (11)	C13—C14	1.498 (12)
N2—C13	1.314 (11)	C14—C15	1.362 (11)
N2—C7	1.334 (11)	C15—C16	1.382 (13)
N3—C6	1.346 (11)	C15—H15	0.9500
N3—C2	1.358 (11)	C16—C17	1.369 (13)
N4—C12	1.339 (11)	C16—H16	0.9500
N4—C8	1.356 (11)	C17—C18	1.380 (13)
N5—C18	1.347 (12)	C17—H17	0.9500
N5—C14	1.351 (12)	C18—H18	0.9500
N6—C24	1.330 (11)	C19—C20	1.489 (12)
N6—C20	1.363 (11)	C20—C21	1.385 (12)
C1—C7	1.387 (11)	C21—C22	1.377 (13)
C1—C2	1.525 (12)	C21—H21	0.9500
C2—C3	1.349 (12)	C22—C23	1.352 (15)
C3—C4	1.385 (13)	C22—H22	0.9500
C3—H3	0.9500	C23—C24	1.381 (14)
C4—C5	1.385 (13)	C23—H23	0.9500
C4—H4	0.9500	C24—H24	0.9500
C5—C6	1.381 (12)	O3—H3A	0.8400
C5—H5	0.9500	O3—H3B	0.8400

O1—Mn1—O2	167.0 (2)	C1—C7—C8	126.0 (8)
O1—Mn1—N6	85.5 (3)	N4—C8—C9	123.4 (8)
O2—Mn1—N6	83.0 (3)	N4—C8—C7	113.8 (7)
O1—Mn1—N1	87.4 (3)	C9—C8—C7	122.6 (8)
O2—Mn1—N1	83.3 (3)	C8—C9—C10	118.7 (10)
N6—Mn1—N1	71.7 (3)	C8—C9—H9	120.6
O1—Mn1—N3	94.1 (3)	C10—C9—H9	120.6
O2—Mn1—N3	91.5 (2)	C11—C10—C9	118.0 (10)
N6—Mn1—N3	143.1 (3)	C11—C10—H10	121.0
N1—Mn1—N3	71.4 (2)	C9—C10—H10	121.0
O1—Mn1—I1	96.54 (18)	C12—C11—C10	119.5 (9)
O2—Mn1—I1	93.67 (17)	C12—C11—H11	120.3
N6—Mn1—I1	114.2 (2)	C10—C11—H11	120.3
N1—Mn1—I1	173.04 (19)	N4—C12—C11	123.3 (10)
N3—Mn1—I1	102.48 (18)	N4—C12—H12	118.4
Mn1—O1—H1A	116.2	C11—C12—H12	118.4
Mn1—O1—H1B	121.2	N2—C13—C19	119.3 (8)
H1A—O1—H1B	119.7	N2—C13—C14	114.4 (7)
Mn1—O2—H2A	118.3	C19—C13—C14	126.2 (8)
Mn1—O2—H2B	102.7	N5—C14—C15	124.1 (9)
H2A—O2—H2B	116.6	N5—C14—C13	113.3 (7)
C1—N1—C19	120.6 (7)	C15—C14—C13	122.4 (8)
C1—N1—Mn1	119.2 (6)	C14—C15—C16	118.0 (8)
C19—N1—Mn1	118.6 (5)	C14—C15—H15	121.0
C13—N2—C7	121.2 (8)	C16—C15—H15	121.0
C6—N3—C2	117.4 (7)	C17—C16—C15	119.8 (8)
C6—N3—Mn1	121.8 (6)	C17—C16—H16	120.1
C2—N3—Mn1	118.5 (5)	C15—C16—H16	120.1
C12—N4—C8	117.1 (8)	C16—C17—C18	118.6 (9)
C18—N5—C14	116.4 (8)	C16—C17—H17	120.7
C24—N6—C20	118.6 (8)	C18—C17—H17	120.7
C24—N6—Mn1	121.5 (6)	N5—C18—C17	123.1 (10)
C20—N6—Mn1	117.5 (6)	N5—C18—H18	118.5
N1—C1—C7	119.7 (8)	C17—C18—H18	118.5
N1—C1—C2	113.3 (7)	N1—C19—C13	118.8 (8)
C7—C1—C2	126.9 (8)	N1—C19—C20	113.1 (7)
C3—C2—N3	123.2 (8)	C13—C19—C20	128.1 (8)
C3—C2—C1	123.5 (8)	N6—C20—C21	121.2 (8)
N3—C2—C1	113.0 (7)	N6—C20—C19	114.3 (7)
C2—C3—C4	118.9 (9)	C21—C20—C19	124.5 (8)
C2—C3—H3	120.5	C22—C21—C20	118.6 (9)
C4—C3—H3	120.5	C22—C21—H21	120.7
C3—C4—C5	119.2 (9)	C20—C21—H21	120.7
C3—C4—H4	120.4	C23—C22—C21	119.8 (9)
C5—C4—H4	120.4	C23—C22—H22	120.1
C6—C5—C4	118.4 (8)	C21—C22—H22	120.1
C6—C5—H5	120.8	C22—C23—C24	119.6 (9)
C4—C5—H5	120.8	C22—C23—H23	120.2
N3—C6—C5	122.5 (8)	C24—C23—H23	120.2
N3—C6—H6	118.8	N6—C24—C23	121.9 (9)
C5—C6—H6	118.8	N6—C24—H24	119.0
N2—C7—C1	120.2 (9)	C23—C24—H24	119.0
N2—C7—C8	113.7 (8)	H3A—O3—H3B	100.9

O1—Mn1—N1—C1	−86.0 (7)	N1—C1—C7—C8	−175.3 (8)
O2—Mn1—N1—C1	103.1 (7)	C2—C1—C7—C8	8.2 (15)
N6—Mn1—N1—C1	−172.1 (7)	C12—N4—C8—C9	−1.2 (13)
N3—Mn1—N1—C1	9.2 (6)	C12—N4—C8—C7	−176.0 (8)
O1—Mn1—N1—C19	79.9 (6)	N2—C7—C8—N4	51.0 (10)
O2—Mn1—N1—C19	−91.0 (6)	C1—C7—C8—N4	−133.2 (9)
N6—Mn1—N1—C19	−6.2 (6)	N2—C7—C8—C9	−123.8 (10)
N3—Mn1—N1—C19	175.1 (7)	C1—C7—C8—C9	52.0 (14)
O1—Mn1—N3—C6	−106.4 (7)	N4—C8—C9—C10	1.1 (14)
O2—Mn1—N3—C6	85.3 (7)	C7—C8—C9—C10	175.4 (9)
N6—Mn1—N3—C6	165.7 (6)	C8—C9—C10—C11	−0.3 (15)
N1—Mn1—N3—C6	167.8 (7)	C9—C10—C11—C12	−0.2 (15)
I1—Mn1—N3—C6	−8.8 (7)	C8—N4—C12—C11	0.7 (15)
O1—Mn1—N3—C2	91.2 (7)	C10—C11—C12—N4	0.0 (16)
O2—Mn1—N3—C2	−77.0 (7)	C7—N2—C13—C19	−2.5 (13)
N6—Mn1—N3—C2	3.3 (9)	C7—N2—C13—C14	180.0 (8)
N1—Mn1—N3—C2	5.4 (6)	C18—N5—C14—C15	2.3 (14)
I1—Mn1—N3—C2	−171.1 (6)	C18—N5—C14—C13	176.9 (8)
O1—Mn1—N6—C24	101.1 (7)	N2—C13—C14—N5	−42.3 (11)
O2—Mn1—N6—C24	−85.0 (7)	C19—C13—C14—N5	140.4 (9)
N1—Mn1—N6—C24	−170.2 (8)	N2—C13—C14—C15	132.4 (9)
N3—Mn1—N6—C24	−168.2 (6)	C19—C13—C14—C15	−44.9 (14)
I1—Mn1—N6—C24	5.9 (8)	N5—C14—C15—C16	−1.4 (15)
O1—Mn1—N6—C20	−97.0 (7)	C13—C14—C15—C16	−175.6 (9)
O2—Mn1—N6—C20	77.0 (7)	C14—C15—C16—C17	−0.9 (14)
N1—Mn1—N6—C20	−8.3 (6)	C15—C16—C17—C18	2.1 (14)
N3—Mn1—N6—C20	−6.2 (9)	C14—N5—C18—C17	−0.9 (14)
I1—Mn1—N6—C20	167.9 (6)	C16—C17—C18—N5	−1.2 (15)
C19—N1—C1—C7	−3.1 (13)	C1—N1—C19—C13	3.1 (12)
Mn1—N1—C1—C7	162.5 (6)	Mn1—N1—C19—C13	−162.6 (6)
C19—N1—C1—C2	173.9 (8)	C1—N1—C19—C20	−176.1 (8)
Mn1—N1—C1—C2	−20.5 (10)	Mn1—N1—C19—C20	18.2 (9)
C6—N3—C2—C3	−5.4 (14)	N2—C13—C19—N1	−0.3 (13)
Mn1—N3—C2—C3	157.7 (8)	C14—C13—C19—N1	176.9 (8)
C6—N3—C2—C1	179.9 (8)	N2—C13—C19—C20	178.7 (8)
Mn1—N3—C2—C1	−17.0 (10)	C14—C13—C19—C20	−4.0 (15)
N1—C1—C2—C3	−150.6 (9)	C24—N6—C20—C21	5.2 (13)
C7—C1—C2—C3	26.1 (15)	Mn1—N6—C20—C21	−157.3 (7)
N1—C1—C2—N3	24.1 (11)	C24—N6—C20—C19	−177.2 (8)
C7—C1—C2—N3	−159.2 (9)	Mn1—N6—C20—C19	20.3 (10)
N3—C2—C3—C4	5.7 (15)	N1—C19—C20—N6	−24.9 (11)
C1—C2—C3—C4	179.8 (9)	C13—C19—C20—N6	156.0 (9)
C2—C3—C4—C5	−1.2 (14)	N1—C19—C20—C21	152.6 (9)
C3—C4—C5—C6	−3.3 (13)	C13—C19—C20—C21	−26.5 (15)
C2—N3—C6—C5	0.6 (13)	N6—C20—C21—C22	−4.5 (15)
Mn1—N3—C6—C5	−161.9 (7)	C19—C20—C21—C22	178.2 (9)
C4—C5—C6—N3	3.6 (14)	C20—C21—C22—C23	0.2 (16)
C13—N2—C7—C1	2.6 (13)	C21—C22—C23—C24	3.2 (16)
C13—N2—C7—C8	178.6 (8)	C20—N6—C24—C23	−1.7 (14)
N1—C1—C7—N2	0.3 (13)	Mn1—N6—C24—C23	160.1 (8)
C2—C1—C7—N2	−176.2 (8)	C22—C23—C24—N6	−2.5 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱ	0.84	1.92	2.726 (10)	160
O1—H1B···N2ⁱⁱ	0.84	2.10	2.890 (10)	156
O2—H2A···N4ⁱⁱⁱ	0.84	2.04	2.876 (10)	174
O2—H2B···N5ⁱⁱⁱ	0.84	2.03	2.834 (10)	160
O3—H3A···I1^iv	0.84	2.88	3.615 (9)	148
O3—H3B···I2	0.84	2.83	3.646 (8)	163

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

Experimental details

Crystal data
Chemical formula	[MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O
M_r	751.22
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	200
a, b, c (Å)	7.977 (3), 13.880 (5), 12.134 (4)
β (°)	97.944 (7)
V (Å³)	1330.5 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.85
Crystal size (mm)	0.28 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.828, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9685, 5463, 4463
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.23
No. of reflections	5463
No. of parameters	325
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.06, −1.41
Absolute structure	Flack (1983); 2033 Friedel pairs
Absolute structure parameter	−0.01 (4)

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	2.163 (6)	Mn1—N1	2.253 (7)
Mn1—O2	2.182 (6)	Mn1—N3	2.259 (7)
Mn1—N6	2.245 (7)	Mn1—I1	2.7772 (16)

N6—Mn1—N1	71.7 (3)	N1—Mn1—N3	71.4 (2)