catena-Poly[[manganese(III)-bis­{μ-2-[(2-hy­droxy­eth­yl)imino­meth­yl]-6-meth­oxy­phenolato-κ³O¹,N:O²;κ³O²:N,O¹}] iodide]

In the title one-dimensional coordination polymer, {[Mn(C₁₀H₁₂NO₃)₂]I}_n, the potentially tetra­dentate (O,O,O,N) 2-[(2-hy­droxy­eth­yl)imino­meth­yl]-6-meth­oxy­phenol (H₂L) ligands are mono-deprotonated (as HL⁻) and coordinated by the metal ions in a tridentate chelate-bridging fashion [2.01₁1₁1₂]. The Mn^III atom possesses a distorted trans-MnO₄N₂ octa­hedral coordination environment. The bridging ligands lead to [010]-chain polymeric cations {[Mn(HL)₂]⁺}_n in the crystal. The charge-balancing iodide ions are disordered over two sites in a 0.690 (2):0.310 (2) ratio and a weak O—H...I hydrogen bond occurs. The crystal studied was found to be a racemic twin.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.017 Å
• Disorder in solvent or counterion
• R factor = 0.076
• wR factor = 0.173
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry .....        100 %Fit
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O2     --  C3      ..        8.0 su
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O4
PLAT420_ALERT_2_B D-H Without Acceptor       O6     -   H6     ...          ?
PLAT915_ALERT_3_B Low Friedel Pair Coverage ......................         38 %

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.590
           From the CIF: _refine_ls_abs_structure_Flack_su    0.030
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 %
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.27
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C11     ..        6.3 su
PLAT234_ALERT_4_C Large Hirshfeld Difference N2     --  C15     ..       0.19 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference N2     --  C20     ..       0.17 Ang.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0171 Ang
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     11.083
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.328
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.119
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         16

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined Donor-H Atoms ........          2
PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem...          b
PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space-group.       Pbca
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  N1      ..        5.4 su
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................        100 %
PLAT335_ALERT_2_G Check Large C6 Ring    C-C Range C9     -C14           0.17 Ang.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O3  -MN1 -O1  -C2     10.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            N2  -MN1 -N1  -C7     96.00 30.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N2  -MN1 -N1  -C17   -89.00 30.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -MN1 -N2  -C15    86.00 30.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         23
            N1  -MN1 -N2  -C20   -97.00 30.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         32
            O1  -MN1 -O3  -C10     9.00  0.00   1.555   1.555   1.555   1.555
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

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

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

---

S1. Comment

Developing the "direct synthesis" approach (Babich et al., 1996; Vinogradova et al., 2002; Makhankova et al., 2002), our research group are now interested in the preparation of manganese-based heterometallic "salen-type" Schiff bases complexes as promising objects for search and production of new materials with useful properties. Synthesis from metal powders as reagents has been recently demonstrated to be an alternative and efficient way to similar Fe/Co complexes (Nesterov et al., 2012; Chygorin et al., 2012). But in some cases instead of heterometallic compounds we can obtain monometallic ones or a mixture of different compounds as more thermodinamically favorable products in selected conditions. Such a case is observed with the investigated system

Mn⁰ – Fe⁰ – {3(o-vanillin) – 3(Hea)} – 2NH₄I – CH₃OH (t=50 ⁰C, in open air),

where o-vanillin = 2-hydroxy-3-methoxybenzaldehyde; Hea = 2-aminoethanol;

from which the new polymeric complex [Mn(HL)₂]I (H₂L = 2-hydroxyiminomethyl-6-methoxyphenol), (I), was isolated.

The total dissolution of metal powders was observed within 6 h resulting into intensive dark brown solution. The block brown crystalls precipitate after 24 h with 45% yield. Interestingly that the stechiometric system

Mn⁰ – {2(o-vanillin) – 2(Hea)} – NH₄I – CH₃OH

produces the same complex, but the dissolution of metal powders is longer (more than 7 h) and the yield is lower (26%).

The {[Mn(HL)₂]}_n unit (Fig.1) demonstrates the [O₄N₂] coordination environment with a distorted octahedral geometry around the central atom. The metal assignment and its oxidation state were confirmed by considering coordination bond lengths, existence of Jahn-Teller elongation and bond valence sum calculation [BVS(Mn) = 3.07 (Brown & Altermatt, 1985)].

The one-dimensional polymeric structure of the crystal (Fig. 2) is realised by means of chelate-bridging function of the ligand, [2.01₁1₁1₂] by Harris notation (Coxall et al., 2000), which is firstly observed for H₂L.

The disodered iodide anions occupy channels between polymeric cationic chains joining to them through weak O–H···I hydrogen bonds (H···I 2.62 - 2.86 Å, O—H···I 131 - 172°) forming neutral chains along (010) direction (Fig. 2, 3). It is worth noting that in the similar complex {[Mn(HL')₂]Cl}_n, where H₂L'= 2-[(2-hydroxyethyl)iminomethyl]-phenol (Zhang et al., 2005), the polymeric chains interlink with numerous O–H···Cl hydrogen bonds and C–H···π contacts yielding two-dimensional network. This difference can be caused by at least two factors: (1) greater electronegativeness and notably smaller radius of Cl^- anions, and (2) absence of methoxy-group, and so additional steric hindrance, in H₂L'.

Related literature

For the related structure of {[Mn(C₉H₁₀NO₂)₂]Cl}_n, see: Zhang et al. (2005). For further synthetic details, see: Babich et al. (1996); Vinogradova et al. (2002); Makhankova et al. (2002); Nesterov et al. (2012); Chygorin et al. (2012). For bond-valence sum calculations, see: Brown & Altermatt (1985). For coordination mode notation, see: Coxall et al. (2000).

S2. Experimental

2-Aminoethanol (0.18 g, 3 mmol) and o-vanillin (0.457 g, 3 mmol) were added to 30 ml of methanol and stirred magnetically for 15 min until the colour of the solution turned in yellow. After manganese powder (0.055 g, 1 mmol), iron powder (0.058 g, 1 mmol) and NH₄I (0.29 g, 2 mmol) were added to the solution, the reaction mixture was stirred at 50°C for ca 6 h. Almost total dissolution of metal powders was observed. Dark brown crystals that precipitated after 1 day were collected by filtration and dried in air; yield 45%. Elemental analysis for C₂₀H₂₄I₂MnN₂O₆ (Mr = 570.26). Calcd: Mn, 9.63%. Found: Mn, 9.3%. IR(KBr, cm^-1): 3457(b), 3411(w), 3248(b), 3193(w), 2993(w), 2939(w), 2830(w), 1615(s), 1552(m), 1459(s), 1443(s), 1406(m), 1343(m), 1316(s), 1243(s), 1216(m) 1161(w), 1107(w), 1071(m), 1017(m), 980(m), 898(w), 871(m), 789(w), 726(s), 635(m), 599(w), 526(w), 454(w), 417(w).

S3. Refinement

All H atoms were placed in idealized positions (C–H = 0.93 – 0.97 Å, O–H = 0.86 Å) and constrained to ride on their parent atoms, with U_iso = 1.2Ueq (except U_iso = 1.5Ueq for methyl and hydroxyl groups). It should be noted that the mean value of the |E²-1| is 0.816 and the structure can be solved in both polar (Pca2₁) and centrosymmetric (Pbca) groups, however, the R₁ value in the latter case is consistently higher (ca. 0.24) that in the former (less than 0.10), so the noncentrosymmetric space group is believed to be the correct choice. Flack parameter value (Flack, 1983) of 0.48 (5) was obtained in the final structure factor calculation, indicating a racemic twin. for Futher full-matrix refinement of the Flack parameter slightly improved the agreement index R (from 0.077 to 0.076). Content of the the major component in the refined racemic twin structure is 59 (3)%. Iodine atom was found to be disordered over two sites with with occupancy factors 0.69 and 0.31.

Computing details

Data collection: CrysAlis CCD (Agilent, 2011); cell refinement: CrysAlis RED (Agilent, 2011); data reduction: CrysAlis RED (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of (I) with 30% probability ellipsoids for non-H atoms. C—H hydrogen atoms are ommited for clarity. Iodide ion is disodered in two positions I1A and I1B with occupancy ratio 0.69:0.31, respectively.
	Fig. 2. Fragment of chain polymeric structure of (I).
	Fig. 3. Packing of (I) viewed down the (010) direction.

catena-Poly[[manganese(III)-bis{µ-2-[(2-hydroxyethyl)iminomethyl]-6-methoxyphenolato-κ³O¹,N:O²;κ³O²:N,O¹}] iodide]

Crystal data

[Mn(C10H12NO3)2]I	F(000) = 1136
Mr = 570.25	Dx = 1.626 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 861 reflections
a = 18.880 (2) Å	θ = 2.9–32.3°
b = 5.8979 (10) Å	µ = 1.93 mm^−1
c = 20.916 (2) Å	T = 298 K
V = 2329.1 (5) Å^3	Block, brown
Z = 4	0.40 × 0.20 × 0.20 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer	4752 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2094 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 16.1827 pixels mm^-1	θmax = 30.0°, θmin = 3.5°
ω scans	h = −26→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −6→8
Tmin = 0.513, Tmax = 0.699	l = −29→28
7841 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.076	H-atom parameters constrained
wR(F^2) = 0.173	w = 1/[σ^2(Fo^2) + (0.055P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max < 0.001
4752 reflections	Δρmax = 1.49 e Å^−3
282 parameters	Δρmin = −0.66 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1276 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.59 (3)

Special details

Experimental. Absorption correction: CrysAlis PRO (Agilent, 2011). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1A	0.08961 (6)	0.43638 (19)	0.26350 (5)	0.0583 (4)	0.690 (2)
I1B	0.08839 (17)	−0.0686 (6)	0.20195 (17)	0.0752 (12)	0.310 (2)
Mn1	−0.00346 (8)	−0.2483 (4)	−0.01586 (13)	0.0360 (3)
O1	0.0867 (4)	−0.3014 (13)	−0.0471 (4)	0.046 (2)
N1	−0.0240 (4)	−0.0371 (15)	−0.0905 (5)	0.036 (2)
C1	0.0895 (7)	−0.0934 (19)	−0.1467 (5)	0.045 (3)
N2	0.0178 (4)	−0.4584 (16)	0.0605 (4)	0.036 (2)
O2	0.2049 (4)	−0.5108 (13)	−0.0732 (4)	0.057 (2)
C2	0.1194 (6)	−0.2539 (19)	−0.1020 (6)	0.041 (3)
O3	−0.0923 (4)	−0.1935 (15)	0.0153 (4)	0.049 (2)
C3	0.1822 (6)	−0.354 (3)	−0.1174 (7)	0.058 (4)
O4	−0.2124 (5)	0.0167 (19)	0.0405 (6)	0.095 (4)
C4	0.2190 (7)	−0.297 (2)	−0.1702 (6)	0.060 (4)
H4	0.2633	−0.3603	−0.1782	0.072*
O5	−0.0455 (4)	0.4550 (13)	−0.0775 (4)	0.048 (2)
H5	−0.0337	0.4208	−0.1158	0.072*
C5	0.1889 (7)	−0.138 (2)	−0.2134 (6)	0.067 (4)
H5A	0.2124	−0.1046	−0.2514	0.081*
O6	0.0391 (4)	−0.9640 (12)	0.0445 (4)	0.047 (2)
H6	0.0484	−0.9805	0.0846	0.071*
C6	0.1268 (7)	−0.035 (2)	−0.2004 (6)	0.053 (3)
H6A	0.1093	0.0758	−0.2279	0.063*
C7	0.0196 (6)	0.000 (2)	−0.1382 (6)	0.042 (3)
H7	0.0037	0.0981	−0.1700	0.050*
C8	0.2479 (9)	−0.695 (2)	−0.0966 (9)	0.078 (5)
H8A	0.2609	−0.7920	−0.0616	0.117*
H8B	0.2900	−0.6354	−0.1162	0.117*
H8C	0.2216	−0.7807	−0.1275	0.117*
C9	−0.0945 (6)	−0.3948 (19)	0.1152 (5)	0.040 (3)
C10	−0.1217 (6)	−0.256 (2)	0.0695 (6)	0.039 (3)
C11	−0.1901 (6)	−0.1460 (19)	0.0850 (6)	0.041 (3)
C12	−0.2257 (6)	−0.200 (2)	0.1367 (7)	0.056 (4)
H12	−0.2695	−0.1327	0.1443	0.067*
C13	−0.1983 (6)	−0.358 (2)	0.1810 (8)	0.065 (4)
H13	−0.2246	−0.4019	0.2165	0.078*
C14	−0.1321 (7)	−0.445 (2)	0.1705 (6)	0.060 (4)
H14	−0.1119	−0.5401	0.2010	0.072*
C15	−0.0250 (6)	−0.496 (2)	0.1054 (6)	0.048 (3)
H15	−0.0105	−0.6015	0.1359	0.058*
C16	−0.2537 (8)	0.190 (2)	0.0618 (7)	0.065 (4)
H16A	−0.2654	0.2880	0.0267	0.098*
H16B	−0.2285	0.2746	0.0937	0.098*
H16C	−0.2964	0.1298	0.0800	0.098*
C17	−0.0928 (5)	0.0769 (15)	−0.0985 (7)	0.049 (3)
H17A	−0.1310	−0.0249	−0.0869	0.059*
H17B	−0.0993	0.1225	−0.1427	0.059*
C18	−0.0929 (6)	0.2899 (19)	−0.0539 (6)	0.044 (3)
H18A	−0.1403	0.3529	−0.0517	0.053*
H18B	−0.0789	0.2458	−0.0110	0.053*
C19	0.0885 (6)	−0.7926 (19)	0.0222 (7)	0.048 (4)
H19A	0.0769	−0.7521	−0.0215	0.058*
H19B	0.1360	−0.8551	0.0224	0.058*
C20	0.0869 (5)	−0.5841 (19)	0.0628 (5)	0.040 (3)
H20A	0.1244	−0.4829	0.0491	0.048*
H20B	0.0966	−0.6267	0.1068	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1A	0.0828 (7)	0.0563 (6)	0.0359 (5)	−0.0091 (7)	−0.0043 (9)	−0.0054 (10)
I1B	0.087 (2)	0.0596 (19)	0.079 (2)	−0.0057 (18)	0.011 (2)	−0.002 (2)
Mn1	0.0441 (6)	0.0298 (5)	0.0340 (6)	0.0027 (6)	0.0010 (7)	0.0055 (6)
O1	0.054 (5)	0.049 (5)	0.036 (4)	0.008 (4)	−0.007 (5)	0.010 (4)
N1	0.039 (5)	0.027 (5)	0.042 (5)	−0.009 (4)	0.005 (5)	−0.015 (5)
C1	0.070 (8)	0.034 (6)	0.031 (5)	0.014 (6)	0.010 (7)	0.000 (5)
N2	0.038 (5)	0.038 (5)	0.033 (5)	0.017 (4)	0.003 (4)	0.014 (5)
O2	0.079 (5)	0.051 (5)	0.040 (5)	0.039 (4)	0.013 (5)	0.008 (5)
C2	0.044 (6)	0.038 (7)	0.043 (7)	−0.003 (5)	0.005 (6)	−0.007 (6)
O3	0.056 (5)	0.054 (6)	0.038 (5)	0.011 (4)	0.014 (5)	0.015 (5)
C3	0.044 (7)	0.087 (10)	0.044 (7)	−0.012 (7)	0.023 (6)	−0.027 (8)
O4	0.075 (6)	0.146 (11)	0.065 (7)	0.057 (7)	−0.009 (6)	−0.006 (8)
C4	0.069 (8)	0.077 (11)	0.034 (7)	0.018 (8)	0.011 (7)	−0.013 (8)
O5	0.069 (5)	0.043 (5)	0.033 (4)	−0.011 (4)	−0.010 (4)	−0.008 (5)
C5	0.097 (10)	0.076 (10)	0.028 (6)	−0.005 (9)	0.020 (7)	−0.011 (7)
O6	0.069 (5)	0.030 (4)	0.043 (4)	−0.010 (4)	−0.009 (5)	0.006 (5)
C6	0.076 (8)	0.048 (7)	0.035 (6)	0.004 (7)	0.008 (7)	0.003 (7)
C7	0.054 (7)	0.028 (7)	0.044 (7)	0.002 (5)	−0.008 (6)	−0.001 (6)
C8	0.085 (8)	0.043 (8)	0.106 (15)	0.012 (7)	0.006 (11)	−0.004 (10)
C9	0.045 (6)	0.041 (7)	0.035 (5)	−0.008 (5)	−0.003 (6)	0.010 (6)
C10	0.051 (7)	0.042 (7)	0.025 (5)	0.002 (5)	−0.003 (6)	−0.004 (6)
C11	0.040 (6)	0.041 (7)	0.041 (6)	0.011 (5)	−0.014 (6)	0.013 (6)
C12	0.048 (7)	0.061 (10)	0.057 (9)	0.006 (7)	−0.009 (7)	0.002 (9)
C13	0.058 (7)	0.065 (9)	0.071 (10)	0.002 (7)	0.036 (8)	0.018 (8)
C14	0.078 (8)	0.062 (9)	0.040 (7)	0.020 (7)	0.007 (7)	0.004 (8)
C15	0.063 (8)	0.042 (8)	0.039 (6)	0.000 (6)	−0.022 (7)	0.007 (6)
C16	0.067 (8)	0.069 (10)	0.059 (9)	0.016 (7)	0.010 (8)	−0.016 (9)
C17	0.029 (5)	0.016 (5)	0.102 (10)	−0.005 (4)	−0.018 (7)	0.016 (7)
C18	0.046 (6)	0.049 (8)	0.037 (6)	−0.010 (6)	−0.010 (6)	0.011 (6)
C19	0.048 (7)	0.025 (7)	0.072 (10)	0.008 (5)	0.006 (7)	−0.010 (7)
C20	0.042 (5)	0.048 (7)	0.030 (5)	−0.010 (5)	−0.018 (6)	0.005 (6)

Geometric parameters (Å, º)

Mn1—O3	1.829 (8)	O6—H6	0.8625
Mn1—O1	1.849 (8)	C6—H6A	0.9300
Mn1—N1	2.035 (10)	C7—H7	0.9300
Mn1—N2	2.061 (9)	C8—H8A	0.9600
Mn1—O6^i	2.247 (8)	C8—H8B	0.9600
Mn1—O5^ii	2.315 (8)	C8—H8C	0.9600
O1—C2	1.335 (14)	C9—C10	1.358 (15)
N1—C7	1.312 (14)	C9—C14	1.391 (16)
N1—C17	1.473 (13)	C9—C15	1.457 (17)
C1—C6	1.371 (16)	C10—C11	1.482 (16)
C1—C7	1.443 (16)	C11—C12	1.312 (17)
C1—C2	1.445 (16)	C12—C13	1.414 (19)
N2—C15	1.259 (15)	C12—H12	0.9300
N2—C20	1.502 (13)	C13—C14	1.369 (16)
O2—C3	1.376 (17)	C13—H13	0.9300
O2—C8	1.442 (14)	C14—H14	0.9300
C2—C3	1.363 (16)	C15—H15	0.9300
O3—C10	1.315 (13)	C16—H16A	0.9600
C3—C4	1.349 (18)	C16—H16B	0.9600
O4—C16	1.361 (14)	C16—H16C	0.9600
O4—C11	1.401 (14)	C17—C18	1.566 (16)
C4—C5	1.421 (18)	C17—H17A	0.9700
C4—H4	0.9300	C17—H17B	0.9700
O5—C18	1.412 (12)	C18—H18A	0.9700
O5—Mn1^i	2.315 (8)	C18—H18B	0.9700
O5—H5	0.8547	C19—C20	1.496 (17)
C5—C6	1.348 (17)	C19—H19A	0.9700
C5—H5A	0.9300	C19—H19B	0.9700
O6—C19	1.453 (13)	C20—H20A	0.9700
O6—Mn1^ii	2.247 (8)	C20—H20B	0.9700
O3—Mn1—O1	179.5 (5)	O2—C8—H8C	109.5
O3—Mn1—N1	89.5 (4)	H8A—C8—H8C	109.5
O1—Mn1—N1	90.5 (3)	H8B—C8—H8C	109.5
O3—Mn1—N2	90.5 (4)	C10—C9—C14	121.4 (11)
O1—Mn1—N2	89.6 (3)	C10—C9—C15	119.3 (10)
N1—Mn1—N2	179.2 (5)	C14—C9—C15	119.2 (11)
O3—Mn1—O6^i	89.8 (4)	O3—C10—C9	128.1 (11)
O1—Mn1—O6^i	89.8 (3)	O3—C10—C11	115.6 (10)
N1—Mn1—O6^i	92.4 (3)	C9—C10—C11	116.1 (11)
N2—Mn1—O6^i	86.8 (3)	C12—C11—O4	124.0 (10)
O3—Mn1—O5^ii	91.0 (4)	C12—C11—C10	121.4 (11)
O1—Mn1—O5^ii	89.5 (3)	O4—C11—C10	114.6 (10)
N1—Mn1—O5^ii	88.3 (3)	C11—C12—C13	120.8 (11)
N2—Mn1—O5^ii	92.5 (4)	C11—C12—H12	119.6
O6^i—Mn1—O5^ii	179.0 (4)	C13—C12—H12	119.6
C2—O1—Mn1	134.0 (7)	C14—C13—C12	118.6 (12)
C7—N1—C17	113.0 (10)	C14—C13—H13	120.7
C7—N1—Mn1	124.6 (7)	C12—C13—H13	120.7
C17—N1—Mn1	122.3 (8)	C13—C14—C9	121.2 (13)
C6—C1—C7	118.3 (12)	C13—C14—H14	119.4
C6—C1—C2	119.7 (12)	C9—C14—H14	119.4
C7—C1—C2	121.9 (11)	N2—C15—C9	127.5 (11)
C15—N2—C20	116.4 (9)	N2—C15—H15	116.3
C15—N2—Mn1	124.1 (7)	C9—C15—H15	116.3
C20—N2—Mn1	119.4 (7)	O4—C16—H16A	109.5
C3—O2—C8	117.0 (11)	O4—C16—H16B	109.5
O1—C2—C3	121.0 (12)	H16A—C16—H16B	109.5
O1—C2—C1	120.9 (10)	O4—C16—H16C	109.5
C3—C2—C1	118.1 (12)	H16A—C16—H16C	109.5
C10—O3—Mn1	130.1 (8)	H16B—C16—H16C	109.5
C4—C3—C2	122.2 (15)	N1—C17—C18	107.4 (9)
C4—C3—O2	123.9 (11)	N1—C17—H17A	110.2
C2—C3—O2	113.8 (11)	C18—C17—H17A	110.2
C16—O4—C11	118.0 (12)	N1—C17—H17B	110.2
C3—C4—C5	118.7 (13)	C18—C17—H17B	110.2
C3—C4—H4	120.7	H17A—C17—H17B	108.5
C5—C4—H4	120.7	O5—C18—C17	110.1 (9)
C18—O5—Mn1^i	122.9 (7)	O5—C18—H18A	109.6
C18—O5—H5	109.4	C17—C18—H18A	109.6
Mn1^i—O5—H5	127.6	O5—C18—H18B	109.6
C6—C5—C4	121.1 (12)	C17—C18—H18B	109.6
C6—C5—H5A	119.4	H18A—C18—H18B	108.2
C4—C5—H5A	119.4	O6—C19—C20	112.1 (10)
C19—O6—Mn1^ii	124.6 (8)	O6—C19—H19A	109.2
C19—O6—H6	105.1	C20—C19—H19A	109.2
Mn1^ii—O6—H6	122.3	O6—C19—H19B	109.2
C5—C6—C1	119.9 (13)	C20—C19—H19B	109.2
C5—C6—H6A	120.0	H19A—C19—H19B	107.9
C1—C6—H6A	120.0	C19—C20—N2	113.9 (9)
N1—C7—C1	127.1 (11)	C19—C20—H20A	108.8
N1—C7—H7	116.5	N2—C20—H20A	108.8
C1—C7—H7	116.5	C19—C20—H20B	108.8
O2—C8—H8A	109.5	N2—C20—H20B	108.8
O2—C8—H8B	109.5	H20A—C20—H20B	107.7
H8A—C8—H8B	109.5
O3—Mn1—O1—C2	−95 (59)	C8—O2—C3—C2	151.0 (12)
N1—Mn1—O1—C2	−10.8 (10)	C2—C3—C4—C5	−4 (2)
N2—Mn1—O1—C2	170.0 (11)	O2—C3—C4—C5	177.9 (11)
O6^i—Mn1—O1—C2	−103.2 (10)	C3—C4—C5—C6	4 (2)
O5^ii—Mn1—O1—C2	77.5 (10)	C4—C5—C6—C1	−4 (2)
O3—Mn1—N1—C7	−176.6 (9)	C7—C1—C6—C5	−172.8 (12)
O1—Mn1—N1—C7	3.9 (9)	C2—C1—C6—C5	4.3 (19)
N2—Mn1—N1—C7	96 (30)	C17—N1—C7—C1	−177.0 (11)
O6^i—Mn1—N1—C7	93.7 (8)	Mn1—N1—C7—C1	−1.4 (16)
O5^ii—Mn1—N1—C7	−85.6 (9)	C6—C1—C7—N1	179.4 (12)
O3—Mn1—N1—C17	−1.3 (8)	C2—C1—C7—N1	2.3 (18)
O1—Mn1—N1—C17	179.1 (8)	Mn1—O3—C10—C9	−5.3 (18)
N2—Mn1—N1—C17	−89 (30)	Mn1—O3—C10—C11	168.8 (8)
O6^i—Mn1—N1—C17	−91.1 (8)	C14—C9—C10—O3	179.7 (12)
O5^ii—Mn1—N1—C17	89.7 (8)	C15—C9—C10—O3	−1.5 (18)
O3—Mn1—N2—C15	−1.5 (10)	C14—C9—C10—C11	5.7 (17)
O1—Mn1—N2—C15	178.0 (10)	C15—C9—C10—C11	−175.6 (11)
N1—Mn1—N2—C15	86 (30)	C16—O4—C11—C12	28.4 (19)
O6^i—Mn1—N2—C15	88.2 (10)	C16—O4—C11—C10	−151.5 (12)
O5^ii—Mn1—N2—C15	−92.5 (10)	O3—C10—C11—C12	177.8 (11)
O3—Mn1—N2—C20	175.9 (8)	C9—C10—C11—C12	−7.4 (18)
O1—Mn1—N2—C20	−4.6 (8)	O3—C10—C11—O4	−2.3 (15)
N1—Mn1—N2—C20	−97 (30)	C9—C10—C11—O4	172.5 (10)
O6^i—Mn1—N2—C20	−94.4 (8)	O4—C11—C12—C13	−177.0 (12)
O5^ii—Mn1—N2—C20	84.8 (8)	C10—C11—C12—C13	3 (2)
Mn1—O1—C2—C3	−166.4 (9)	C11—C12—C13—C14	3 (2)
Mn1—O1—C2—C1	14.1 (16)	C12—C13—C14—C9	−5 (2)
C6—C1—C2—O1	175.1 (11)	C10—C9—C14—C13	0 (2)
C7—C1—C2—O1	−7.9 (17)	C15—C9—C14—C13	−178.4 (13)
C6—C1—C2—C3	−4.5 (17)	C20—N2—C15—C9	178.8 (11)
C7—C1—C2—C3	172.5 (12)	Mn1—N2—C15—C9	−3.7 (18)
O1—Mn1—O3—C10	−90 (59)	C10—C9—C15—N2	6.1 (19)
N1—Mn1—O3—C10	−173.4 (10)	C14—C9—C15—N2	−175.1 (13)
N2—Mn1—O3—C10	5.8 (10)	C7—N1—C17—C18	−103.3 (12)
O6^i—Mn1—O3—C10	−80.9 (10)	Mn1—N1—C17—C18	81.0 (9)
O5^ii—Mn1—O3—C10	98.4 (10)	Mn1^i—O5—C18—C17	−162.6 (6)
O1—C2—C3—C4	−175.0 (12)	N1—C17—C18—O5	70.0 (12)
C1—C2—C3—C4	4.6 (19)	Mn1^ii—O6—C19—C20	159.0 (7)
O1—C2—C3—O2	2.9 (17)	O6—C19—C20—N2	−65.1 (13)
C1—C2—C3—O2	−177.5 (11)	C15—N2—C20—C19	97.8 (13)
C8—O2—C3—C4	−31.1 (19)	Mn1—N2—C20—C19	−79.8 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···I1A^iii	0.86	2.86	3.488 (8)	131

Symmetry code: (iii) −x, −y+1, z−1/2.