Bis(ethanamidinium) (1,10-phen­an­thro­line-2,9-dicarboxyl­ato)manganate(II) hepta­hydrate

In the title complex, (C₂H₇N₂)₂[Mn(C₁₄H₆N₂O₄)₂]·7H₂O, the Mn^II atom is coordinated by four N atoms and four O atoms from two 1,10-phenanthroline-2,9-dicarboxyl­ate ligands in a distorted dodeca­hedral geometry. The double negative charge is balanced by two ethanamidinium cations. A three-dimensional supra­molecular structure is formed through N—H...O and O—H...O hydrogen bonds and π–π stacking inter­actions [centroid–centroid distance = 3.553 (2) Å].

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.102
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5617
PLAT023_ALERT_3_B Resolution (too) Low [sin(theta)/Lambda < 0.6]..      60.00 Deg.

Alert level C
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C28 H12 Mn N4 O8
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.562         86

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............         22
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00500 Deg.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         14
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2
              C2 H7 N2
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              C2 H7 N2
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          5
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          6
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          7
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          8
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          9
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #         10
              H2 O
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Mn1     (I)           0.44
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          64 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   2 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

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

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S1. Comment

1,10-Phenanthroline and its substituted derivatives have versatile chelating and bridging capability(Kaes et al., 2000; Albores & Rentschler, 2008) which have played an important role in the development of coordination chemistry while the oxime, similar to the cyanide, can link two magnetic moment carriers with the shortest pairwise exchange pathway (Sreerama & Pal, 2004). Preliminary study on the coordination chemistry of 1,10-phenanthroline-2,9-dicarboxylate (H₂phenda) found that it chelates the metal ions such as Ca(II), Cu(II), Th(III), Eu(III) and Tb(III) as a tridentate or tetradentate ligand by the phenanthroline and one or both of the oxygen atoms on the carboxylate groups (Dean et al., 2008; Gephart et al., 2008; Moghimi et al., 2005; Fan et al., 2008). We report here the crystal structure of the title compound, (I).

The title compound is ionic and contains discrete 1,10-phenanthroline- 2,9-dicarboxylate manganese(II) anions, ethanamidinium cations and water molecules (Fig. 1). The Mn atom is coordinated by four N atoms and four O atoms from two 1,10-phenanthroline-2,9-dicarboxylate ligands in a distorted dodecahedron geometry.

In the crystal structure, intermolecular π-π interactions (Figure 2) between the neighboring aromatic rings of phenda ligands link the molecules into an infinite layer. The centroid to centroid distance between pyridine rings is 3.553 (2) Å. The crystal packing is further stabilized by N—H···O and O—H···O hydrogen bonds (Table 1 and Figure 3), which link the layers into a three dimensional framework (Figure 4).

Related literature

For general background to 1,10-phenanthroline derivatives, see: Kaes et al. (2000); Albores & Rentschler (2008); Sreerama & Pal (2004) and to 1,10-phenanthroline-2,9-dicarboxylate (H₂phenda) see: Dean et al. (2008); Gephart et al. (2008); Moghimi et al. (2005); Fan et al. (2008). For the synthesis, see: Chandler et al. (1981).

S2. Experimental

Hydrothermal treatment of manganese chloride tetrahydrate (0.2 mmol, 0.039 g), 1,10-phenanthroline-2,9-dicarboxylate (0.2 mmol, 0.054 g) synthesized according to C. J. Chandler et al. (1981), triethylamine (0.080 g, 0.4 mmol), and methanol/acetonitrile (15 ml,V/V = 5/1) over 72 h at 418 K yielded light yellow block-shaped crystals.

S3. Refinement

Diffraction data for compound I were recorded on Oxford Diffraction Gemini R CCD diffractometer at 150 (2) K. The data collection routine, unit cell refinement, and data processing were carried out with the program CrysAlis PRO for I.

All H atoms were placed in idealized positions, and were refined using as riding model with C—H distances of 0.95, 0.98, 0.90 and 0.85 Å, for aryl, methyl, amido and water, respectively, with U_iso(H) = 1.5U_eq (methyl C-atoms) and 1.2U_eq(non-methyl C-atoms). The hightest peak is located 1.13 Å from O5W and the deepest hole is located 0.68 Å from N5.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
	Fig. 2. The off-set π-π stacking interaction in the distance of 3.553 (2) Å between phenda^2- groups from the neighboring units (the H-atoms on the phenda^2- are omitted for clarity)
	Fig. 3. A perspective view of hydrogen bonding interactions shown as dashed lines.
	Fig. 4. The three-dimensional framework of the title compound through intermolecular π-π stacking interactions and all hydrogen bonds.

Bis(ethanamidinium) (1,10-phenanthroline-2,9-dicarboxylato)manganate(II) heptahydrate

Crystal data

(C2H7N2)2[Mn(C14H6N2O4)2]·7H2O	Z = 2
Mr = 831.66	F(000) = 866
Triclinic, P1	Dx = 1.522 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 9.6330 (6) Å	Cell parameters from 2456 reflections
b = 13.8174 (7) Å	θ = 3.8–60.5°
c = 15.4828 (8) Å	µ = 3.69 mm^−1
α = 66.151 (5)°	T = 150 K
β = 78.949 (5)°	Block, yellow
γ = 75.397 (5)°	0.29 × 0.26 × 0.16 mm
V = 1814.56 (19) Å^3

Data collection

Agilent Gemini S Ultra CCD diffractometer	5310 independent reflections
Radiation source: Ultra (Cu) X-ray Source	4336 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
ω and ψ scan	θmax = 60.0°, θmin = 3.1°
Absorption correction: multi-scan (Blessing, 1995)	h = −10→10
Tmin = 0.395, Tmax = 0.554	k = −15→15
10581 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0694P)^2] where P = (Fo^2 + 2Fc^2)/3
5310 reflections	(Δ/σ)max < 0.001
507 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

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
Mn1	0.38224 (4)	−0.32469 (3)	−0.30135 (3)	0.02456 (13)
O1	0.62034 (19)	−0.44480 (14)	−0.29790 (12)	0.0315 (4)
O2	0.7512 (2)	−0.60690 (15)	−0.22274 (14)	0.0405 (5)
O3	0.19195 (19)	−0.18187 (14)	−0.36856 (13)	0.0322 (4)
O4	−0.0144 (2)	−0.07603 (17)	−0.34049 (16)	0.0526 (6)
O5	0.4381 (2)	−0.21686 (15)	−0.22559 (12)	0.0342 (4)
O6	0.5792 (2)	−0.10790 (16)	−0.23117 (14)	0.0429 (5)
O7	0.27142 (19)	−0.45336 (14)	−0.31506 (12)	0.0316 (4)
O8	0.2046 (2)	−0.51264 (15)	−0.41261 (13)	0.0352 (4)
N1	0.4178 (2)	−0.46684 (16)	−0.15591 (14)	0.0247 (5)
N2	0.1863 (2)	−0.31304 (16)	−0.19121 (15)	0.0266 (5)
N3	0.5253 (2)	−0.20108 (16)	−0.39983 (14)	0.0249 (5)
N4	0.4184 (2)	−0.32404 (16)	−0.45354 (14)	0.0238 (5)
C1	0.5334 (3)	−0.5458 (2)	−0.14235 (18)	0.0275 (6)
C2	0.5504 (3)	−0.6328 (2)	−0.05494 (19)	0.0327 (6)
H2	0.6323	−0.6896	−0.0479	0.039*
C3	0.4479 (3)	−0.6348 (2)	0.01978 (19)	0.0361 (7)
H3	0.4594	−0.6924	0.0796	0.043*
C4	0.3259 (3)	−0.5520 (2)	0.00840 (19)	0.0328 (6)
C5	0.3154 (3)	−0.4703 (2)	−0.08246 (17)	0.0264 (6)
C6	0.1906 (3)	−0.3847 (2)	−0.10117 (18)	0.0276 (6)
C7	0.0811 (3)	−0.3796 (2)	−0.0278 (2)	0.0355 (7)
C8	−0.0404 (3)	−0.2954 (2)	−0.0534 (2)	0.0398 (7)
H8	−0.1181	−0.2882	−0.0069	0.048*
C9	−0.0455 (3)	−0.2239 (2)	−0.1460 (2)	0.0392 (7)
H9	−0.1277	−0.1681	−0.1643	0.047*
C10	0.0723 (3)	−0.2344 (2)	−0.2135 (2)	0.0317 (6)
C11	0.2133 (3)	−0.5429 (2)	0.08190 (19)	0.0386 (7)
H11	0.2200	−0.5962	0.1442	0.046*
C12	0.0976 (3)	−0.4606 (2)	0.0651 (2)	0.0398 (7)
H12	0.0263	−0.4567	0.1159	0.048*
C13	0.6447 (3)	−0.5317 (2)	−0.22789 (19)	0.0280 (6)
C14	0.0830 (3)	−0.1565 (2)	−0.3165 (2)	0.0333 (6)
C15	0.5761 (3)	−0.1406 (2)	−0.37003 (18)	0.0271 (6)
C16	0.6643 (3)	−0.0680 (2)	−0.4304 (2)	0.0331 (6)
H16	0.6989	−0.0256	−0.4069	0.040*
C17	0.7004 (3)	−0.0583 (2)	−0.5229 (2)	0.0337 (6)
H17	0.7605	−0.0096	−0.5639	0.040*
C18	0.6479 (3)	−0.1210 (2)	−0.55703 (19)	0.0299 (6)
C19	0.5597 (3)	−0.19174 (19)	−0.49131 (18)	0.0250 (5)
C20	0.5006 (3)	−0.2583 (2)	−0.52032 (17)	0.0248 (5)
C21	0.5305 (3)	−0.2531 (2)	−0.61455 (18)	0.0292 (6)
C22	0.4655 (3)	−0.3189 (2)	−0.63757 (19)	0.0326 (6)
H22	0.4809	−0.3179	−0.7004	0.039*
C23	0.3805 (3)	−0.3840 (2)	−0.57014 (18)	0.0308 (6)
H23	0.3358	−0.4279	−0.5857	0.037*
C24	0.3596 (3)	−0.3856 (2)	−0.47696 (18)	0.0264 (6)
C25	0.6768 (3)	−0.1183 (2)	−0.65205 (19)	0.0333 (6)
H25	0.7367	−0.0717	−0.6969	0.040*
C26	0.6210 (3)	−0.1805 (2)	−0.67956 (19)	0.0349 (6)
H26	0.6420	−0.1761	−0.7434	0.042*
C27	0.5275 (3)	−0.1559 (2)	−0.26719 (19)	0.0301 (6)
C28	0.2712 (3)	−0.4568 (2)	−0.39516 (18)	0.0276 (6)
N5	0.8010 (3)	−0.8300 (2)	−0.1744 (2)	0.0640 (8)
H5A	0.7521	−0.8547	−0.2026	0.077*
H5B	0.7762	−0.7619	−0.1765	0.077*
N6	0.9723 (3)	−0.9812 (2)	−0.1703 (2)	0.0604 (8)
H6A	0.9292	−0.9846	−0.2154	0.073*
H6B	1.0600	−1.0209	−0.1545	0.073*
C29	0.9287 (4)	−0.8931 (3)	−0.1516 (2)	0.0517 (8)
C30	1.0219 (4)	−0.8639 (3)	−0.1027 (3)	0.0615 (10)
H30A	0.9621	−0.8381	−0.0545	0.092*
H30B	1.0707	−0.8069	−0.1493	0.092*
H30C	1.0939	−0.9275	−0.0721	0.092*
N7	0.1675 (2)	−0.59460 (18)	−0.54617 (16)	0.0329 (5)
H7A	0.1679	−0.5739	−0.4981	0.039*
H7B	0.2252	−0.5741	−0.6008	0.039*
N8	0.0118 (2)	−0.70915 (18)	−0.45609 (16)	0.0349 (5)
H8A	0.0121	−0.6954	−0.4041	0.042*
H8B	−0.0380	−0.7590	−0.4501	0.042*
C31	0.0874 (3)	−0.6628 (2)	−0.53660 (19)	0.0309 (6)
C32	0.0816 (3)	−0.6870 (2)	−0.6215 (2)	0.0375 (7)
H32A	0.1707	−0.6759	−0.6639	0.056*
H32B	−0.0011	−0.6389	−0.6551	0.056*
H32C	0.0715	−0.7621	−0.6010	0.056*
O1W	0.7167 (2)	−0.93913 (18)	−0.26699 (16)	0.0517 (6)
H1WB	0.6725	−0.9894	−0.2567	0.062*
H1WA	0.7559	−0.9119	−0.3232	0.062*
O2W	0.8697 (2)	−0.87175 (15)	−0.44941 (13)	0.0374 (5)
H2WA	0.9239	−0.9339	−0.4315	0.045*
H2WB	0.8510	−0.8574	−0.5052	0.045*
O3W	0.0311 (2)	−0.64852 (16)	−0.29789 (14)	0.0433 (5)
H3WA	0.0748	−0.5962	−0.3280	0.052*
H3WB	−0.0544	−0.6172	−0.2865	0.052*
O4W	0.2349 (2)	−0.65284 (17)	−0.17187 (14)	0.0455 (5)
H4WA	0.1802	−0.6675	−0.2001	0.055*
H4WB	0.2411	−0.5878	−0.2062	0.055*
O5W	0.4446 (4)	−0.8419 (2)	−0.1000 (2)	0.0860 (10)
H5WA	0.3813	−0.7841	−0.1141	0.103*
H5WB	0.4500	−0.8624	−0.0409	0.103*
O6W	0.5485 (3)	−0.94350 (19)	0.07739 (16)	0.0579 (6)
H6WA	0.5041	−0.9299	0.1255	0.069*
H6WB	0.5758	−1.0060	0.0752	0.069*
O7W	0.7721 (2)	−0.87078 (19)	0.10478 (17)	0.0560 (6)
H7WA	0.7217	−0.8988	0.0853	0.067*
H7WB	0.7133	−0.8399	0.1386	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0283 (2)	0.0252 (2)	0.0204 (2)	−0.00653 (17)	−0.00202 (16)	−0.00818 (17)
O1	0.0312 (10)	0.0301 (10)	0.0291 (10)	−0.0049 (8)	−0.0017 (8)	−0.0083 (9)
O2	0.0352 (11)	0.0331 (11)	0.0472 (12)	0.0015 (9)	−0.0024 (9)	−0.0146 (9)
O3	0.0336 (10)	0.0295 (10)	0.0315 (10)	−0.0048 (8)	−0.0076 (8)	−0.0084 (8)
O4	0.0449 (13)	0.0370 (12)	0.0569 (14)	0.0085 (10)	−0.0079 (10)	−0.0069 (10)
O5	0.0441 (11)	0.0353 (11)	0.0285 (10)	−0.0152 (9)	−0.0045 (8)	−0.0127 (9)
O6	0.0539 (13)	0.0485 (12)	0.0396 (11)	−0.0203 (10)	−0.0067 (9)	−0.0230 (10)
O7	0.0396 (11)	0.0334 (10)	0.0273 (10)	−0.0131 (8)	−0.0031 (8)	−0.0134 (8)
O8	0.0372 (11)	0.0407 (11)	0.0379 (11)	−0.0153 (9)	−0.0038 (8)	−0.0204 (9)
N1	0.0286 (11)	0.0243 (11)	0.0247 (11)	−0.0051 (9)	−0.0060 (9)	−0.0113 (9)
N2	0.0281 (12)	0.0257 (11)	0.0289 (12)	−0.0063 (9)	−0.0039 (9)	−0.0122 (10)
N3	0.0272 (11)	0.0215 (11)	0.0269 (11)	−0.0028 (9)	−0.0064 (9)	−0.0095 (9)
N4	0.0249 (11)	0.0221 (11)	0.0260 (11)	−0.0026 (9)	−0.0060 (9)	−0.0102 (9)
C1	0.0333 (14)	0.0247 (14)	0.0293 (14)	−0.0079 (11)	−0.0086 (11)	−0.0112 (12)
C2	0.0386 (16)	0.0259 (14)	0.0316 (15)	−0.0056 (12)	−0.0113 (12)	−0.0057 (12)
C3	0.0480 (18)	0.0325 (15)	0.0273 (15)	−0.0142 (13)	−0.0128 (13)	−0.0031 (12)
C4	0.0425 (16)	0.0357 (16)	0.0262 (14)	−0.0176 (13)	−0.0055 (12)	−0.0108 (12)
C5	0.0333 (14)	0.0277 (14)	0.0236 (13)	−0.0123 (11)	−0.0040 (11)	−0.0108 (11)
C6	0.0319 (14)	0.0295 (14)	0.0275 (14)	−0.0116 (11)	−0.0003 (11)	−0.0149 (12)
C7	0.0378 (16)	0.0438 (17)	0.0356 (16)	−0.0180 (13)	0.0044 (12)	−0.0233 (14)
C8	0.0350 (16)	0.0457 (18)	0.0457 (18)	−0.0128 (14)	0.0090 (13)	−0.0269 (15)
C9	0.0321 (16)	0.0356 (16)	0.0527 (19)	−0.0052 (12)	0.0012 (13)	−0.0225 (15)
C10	0.0291 (15)	0.0290 (15)	0.0419 (16)	−0.0047 (12)	−0.0056 (12)	−0.0181 (13)
C11	0.0515 (19)	0.0471 (18)	0.0229 (14)	−0.0254 (15)	−0.0001 (12)	−0.0110 (13)
C12	0.0467 (18)	0.0498 (19)	0.0296 (15)	−0.0222 (15)	0.0081 (13)	−0.0192 (14)
C13	0.0270 (14)	0.0278 (15)	0.0337 (15)	−0.0054 (12)	−0.0062 (11)	−0.0145 (13)
C14	0.0336 (16)	0.0270 (15)	0.0402 (16)	−0.0053 (12)	−0.0077 (13)	−0.0122 (13)
C15	0.0262 (13)	0.0239 (13)	0.0318 (14)	−0.0022 (11)	−0.0074 (11)	−0.0105 (11)
C16	0.0336 (15)	0.0295 (15)	0.0410 (17)	−0.0105 (12)	−0.0068 (12)	−0.0142 (13)
C17	0.0310 (15)	0.0300 (15)	0.0383 (16)	−0.0107 (12)	−0.0022 (12)	−0.0086 (13)
C18	0.0261 (14)	0.0261 (14)	0.0339 (15)	−0.0027 (11)	−0.0038 (11)	−0.0086 (12)
C19	0.0235 (13)	0.0212 (13)	0.0280 (14)	−0.0010 (10)	−0.0044 (10)	−0.0079 (11)
C20	0.0236 (13)	0.0240 (13)	0.0248 (13)	−0.0001 (10)	−0.0065 (10)	−0.0080 (11)
C21	0.0291 (14)	0.0303 (15)	0.0259 (14)	0.0001 (11)	−0.0052 (11)	−0.0106 (12)
C22	0.0360 (15)	0.0380 (16)	0.0259 (14)	−0.0030 (12)	−0.0048 (12)	−0.0160 (13)
C23	0.0354 (15)	0.0321 (15)	0.0299 (14)	−0.0059 (12)	−0.0057 (12)	−0.0160 (13)
C24	0.0267 (13)	0.0246 (13)	0.0293 (14)	−0.0004 (11)	−0.0073 (11)	−0.0122 (11)
C25	0.0307 (15)	0.0349 (15)	0.0281 (14)	−0.0090 (12)	0.0030 (11)	−0.0066 (12)
C26	0.0356 (15)	0.0404 (17)	0.0251 (14)	−0.0062 (13)	0.0006 (12)	−0.0111 (13)
C27	0.0347 (15)	0.0261 (14)	0.0327 (14)	−0.0051 (12)	−0.0106 (12)	−0.0115 (12)
C28	0.0268 (14)	0.0242 (14)	0.0319 (15)	−0.0005 (11)	−0.0062 (11)	−0.0118 (12)
N5	0.070 (2)	0.0449 (17)	0.083 (2)	0.0005 (15)	−0.0239 (17)	−0.0293 (16)
N6	0.0657 (19)	0.0425 (16)	0.081 (2)	0.0048 (14)	−0.0284 (16)	−0.0308 (16)
C29	0.055 (2)	0.046 (2)	0.054 (2)	−0.0131 (16)	−0.0062 (16)	−0.0152 (16)
C30	0.073 (3)	0.059 (2)	0.059 (2)	−0.0178 (19)	−0.0177 (19)	−0.0208 (19)
N7	0.0352 (13)	0.0374 (13)	0.0304 (12)	−0.0120 (11)	−0.0006 (10)	−0.0155 (11)
N8	0.0334 (13)	0.0360 (13)	0.0359 (13)	−0.0091 (10)	−0.0043 (10)	−0.0123 (11)
C31	0.0266 (14)	0.0299 (15)	0.0345 (15)	−0.0010 (12)	−0.0046 (12)	−0.0124 (12)
C32	0.0351 (16)	0.0399 (16)	0.0428 (17)	−0.0070 (13)	−0.0063 (13)	−0.0200 (14)
O1W	0.0516 (13)	0.0528 (14)	0.0579 (14)	−0.0179 (11)	0.0000 (11)	−0.0261 (12)
O2W	0.0433 (11)	0.0324 (10)	0.0354 (10)	−0.0074 (9)	−0.0120 (9)	−0.0081 (9)
O3W	0.0378 (11)	0.0422 (12)	0.0452 (12)	−0.0079 (9)	0.0024 (9)	−0.0145 (10)
O4W	0.0535 (13)	0.0419 (12)	0.0386 (11)	−0.0154 (10)	−0.0028 (10)	−0.0096 (10)
O5W	0.135 (3)	0.0618 (17)	0.0708 (18)	0.0146 (17)	−0.0524 (18)	−0.0365 (15)
O6W	0.0748 (16)	0.0636 (15)	0.0467 (13)	−0.0144 (12)	−0.0092 (11)	−0.0304 (12)
O7W	0.0481 (13)	0.0637 (15)	0.0654 (15)	−0.0037 (11)	−0.0068 (11)	−0.0373 (13)

Geometric parameters (Å, º)

Mn1—N2	2.309 (2)	C17—H17	0.9500
Mn1—N4	2.312 (2)	C18—C19	1.412 (4)
Mn1—N3	2.327 (2)	C18—C25	1.431 (4)
Mn1—N1	2.329 (2)	C19—C20	1.439 (4)
Mn1—O3	2.3630 (18)	C20—C21	1.407 (4)
Mn1—O7	2.3863 (18)	C21—C22	1.407 (4)
Mn1—O5	2.4382 (17)	C21—C26	1.438 (4)
Mn1—O1	2.4645 (18)	C22—C23	1.361 (4)
O1—C13	1.255 (3)	C22—H22	0.9500
O2—C13	1.251 (3)	C23—C24	1.410 (4)
O3—C14	1.262 (3)	C23—H23	0.9500
O4—C14	1.237 (3)	C24—C28	1.517 (4)
O5—C27	1.258 (3)	C25—C26	1.351 (4)
O6—C27	1.253 (3)	C25—H25	0.9500
O7—C28	1.261 (3)	C26—H26	0.9500
O8—C28	1.250 (3)	N5—C29	1.332 (4)
N1—C1	1.329 (3)	N5—H5A	0.9000
N1—C5	1.348 (3)	N5—H5B	0.9000
N2—C10	1.321 (3)	N6—C29	1.313 (4)
N2—C6	1.345 (3)	N6—H6A	0.9000
N3—C15	1.325 (3)	N6—H6B	0.9000
N3—C19	1.351 (3)	C29—C30	1.493 (5)
N4—C24	1.322 (3)	C30—H30A	0.9800
N4—C20	1.345 (3)	C30—H30B	0.9800
C1—C2	1.405 (4)	C30—H30C	0.9800
C1—C13	1.514 (4)	N7—C31	1.310 (4)
C2—C3	1.365 (4)	N7—H7A	0.8999
C2—H2	0.9500	N7—H7B	0.9000
C3—C4	1.400 (4)	N8—C31	1.317 (4)
C3—H3	0.9500	N8—H8A	0.9000
C4—C5	1.406 (4)	N8—H8B	0.8999
C4—C11	1.436 (4)	C31—C32	1.495 (4)
C5—C6	1.439 (4)	C32—H32A	0.9800
C6—C7	1.405 (4)	C32—H32B	0.9800
C7—C8	1.414 (4)	C32—H32C	0.9800
C7—C12	1.430 (4)	O1W—H1WB	0.8501
C8—C9	1.375 (4)	O1W—H1WA	0.8499
C8—H8	0.9500	O2W—H2WA	0.8500
C9—C10	1.409 (4)	O2W—H2WB	0.8499
C9—H9	0.9500	O3W—H3WA	0.8498
C10—C14	1.523 (4)	O3W—H3WB	0.8501
C11—C12	1.354 (4)	O4W—H4WA	0.8499
C11—H11	0.9500	O4W—H4WB	0.8500
C12—H12	0.9500	O5W—H5WA	0.8500
C15—C16	1.403 (4)	O5W—H5WB	0.8499
C15—C27	1.514 (4)	O6W—H6WA	0.8501
C16—C17	1.368 (4)	O6W—H6WB	0.8499
C16—H16	0.9500	O7W—H7WA	0.8500
C17—C18	1.407 (4)	O7W—H7WB	0.8501
N2—Mn1—N4	136.11 (7)	O4—C14—O3	126.9 (3)
N2—Mn1—N3	132.09 (7)	O4—C14—C10	117.4 (2)
N4—Mn1—N3	69.49 (7)	O3—C14—C10	115.6 (2)
N2—Mn1—N1	69.13 (7)	N3—C15—C16	122.0 (2)
N4—Mn1—N1	130.55 (7)	N3—C15—C27	113.8 (2)
N3—Mn1—N1	131.49 (7)	C16—C15—C27	124.1 (2)
N2—Mn1—O3	67.82 (7)	C17—C16—C15	119.9 (2)
N4—Mn1—O3	80.79 (7)	C17—C16—H16	120.0
N3—Mn1—O3	83.18 (7)	C15—C16—H16	120.0
N1—Mn1—O3	136.69 (7)	C16—C17—C18	119.6 (3)
N2—Mn1—O7	83.15 (7)	C16—C17—H17	120.2
N4—Mn1—O7	67.47 (7)	C18—C17—H17	120.2
N3—Mn1—O7	136.91 (7)	C17—C18—C19	116.6 (2)
N1—Mn1—O7	78.60 (7)	C17—C18—C25	125.2 (3)
O3—Mn1—O7	91.77 (6)	C19—C18—C25	118.2 (2)
N2—Mn1—O5	75.67 (7)	N3—C19—C18	123.4 (2)
N4—Mn1—O5	135.37 (7)	N3—C19—C20	116.3 (2)
N3—Mn1—O5	66.19 (7)	C18—C19—C20	120.3 (2)
N1—Mn1—O5	85.00 (7)	N4—C20—C21	123.3 (2)
O3—Mn1—O5	88.98 (6)	N4—C20—C19	116.7 (2)
O7—Mn1—O5	156.79 (6)	C21—C20—C19	120.0 (2)
N2—Mn1—O1	135.12 (7)	C22—C21—C20	116.3 (3)
N4—Mn1—O1	79.20 (6)	C22—C21—C26	125.4 (2)
N3—Mn1—O1	79.36 (7)	C20—C21—C26	118.3 (2)
N1—Mn1—O1	66.09 (6)	C23—C22—C21	120.2 (2)
O3—Mn1—O1	157.04 (6)	C23—C22—H22	119.9
O7—Mn1—O1	90.89 (6)	C21—C22—H22	119.9
O5—Mn1—O1	97.40 (6)	C22—C23—C24	119.4 (2)
C13—O1—Mn1	119.48 (16)	C22—C23—H23	120.3
C14—O3—Mn1	120.52 (16)	C24—C23—H23	120.3
C27—O5—Mn1	120.15 (16)	N4—C24—C23	121.7 (3)
C28—O7—Mn1	120.22 (17)	N4—C24—C28	114.0 (2)
C1—N1—C5	118.4 (2)	C23—C24—C28	124.3 (2)
C1—N1—Mn1	122.99 (17)	C26—C25—C18	121.6 (3)
C5—N1—Mn1	118.63 (16)	C26—C25—H25	119.2
C10—N2—C6	119.0 (2)	C18—C25—H25	119.2
C10—N2—Mn1	121.43 (18)	C25—C26—C21	121.6 (2)
C6—N2—Mn1	119.54 (16)	C25—C26—H26	119.2
C15—N3—C19	118.5 (2)	C21—C26—H26	119.2
C15—N3—Mn1	123.05 (17)	O6—C27—O5	126.0 (3)
C19—N3—Mn1	118.41 (16)	O6—C27—C15	118.0 (3)
C24—N4—C20	119.1 (2)	O5—C27—C15	116.0 (2)
C24—N4—Mn1	121.88 (17)	O8—C28—O7	126.0 (3)
C20—N4—Mn1	119.00 (15)	O8—C28—C24	118.0 (2)
N1—C1—C2	122.1 (2)	O7—C28—C24	116.0 (2)
N1—C1—C13	114.2 (2)	C29—N5—H5A	113.1
C2—C1—C13	123.7 (2)	C29—N5—H5B	123.4
C3—C2—C1	119.3 (3)	H5A—N5—H5B	121.6
C3—C2—H2	120.4	C29—N6—H6A	116.3
C1—C2—H2	120.4	C29—N6—H6B	117.8
C2—C3—C4	120.1 (3)	H6A—N6—H6B	122.1
C2—C3—H3	120.0	N6—C29—N5	120.7 (3)
C4—C3—H3	120.0	N6—C29—C30	119.8 (3)
C3—C4—C5	116.7 (3)	N5—C29—C30	119.5 (3)
C3—C4—C11	125.5 (3)	C29—C30—H30A	109.5
C5—C4—C11	117.9 (3)	C29—C30—H30B	109.5
N1—C5—C4	123.4 (2)	H30A—C30—H30B	109.5
N1—C5—C6	116.4 (2)	C29—C30—H30C	109.5
C4—C5—C6	120.2 (2)	H30A—C30—H30C	109.5
N2—C6—C7	123.6 (2)	H30B—C30—H30C	109.5
N2—C6—C5	116.1 (2)	C31—N7—H7A	120.3
C7—C6—C5	120.2 (2)	C31—N7—H7B	116.6
C6—C7—C8	116.4 (3)	H7A—N7—H7B	122.9
C6—C7—C12	118.5 (3)	C31—N8—H8A	121.6
C8—C7—C12	125.0 (3)	C31—N8—H8B	121.0
C9—C8—C7	119.6 (3)	H8A—N8—H8B	117.3
C9—C8—H8	120.2	N7—C31—N8	122.6 (2)
C7—C8—H8	120.2	N7—C31—C32	117.9 (2)
C8—C9—C10	119.3 (3)	N8—C31—C32	119.6 (2)
C8—C9—H9	120.4	C31—C32—H32A	109.5
C10—C9—H9	120.4	C31—C32—H32B	109.5
N2—C10—C9	122.0 (3)	H32A—C32—H32B	109.5
N2—C10—C14	113.9 (2)	C31—C32—H32C	109.5
C9—C10—C14	124.1 (2)	H32A—C32—H32C	109.5
C12—C11—C4	122.0 (3)	H32B—C32—H32C	109.5
C12—C11—H11	119.0	H1WB—O1W—H1WA	115.9
C4—C11—H11	119.0	H2WA—O2W—H2WB	107.1
C11—C12—C7	121.1 (3)	H3WA—O3W—H3WB	103.0
C11—C12—H12	119.4	H4WA—O4W—H4WB	103.6
C7—C12—H12	119.4	H5WA—O5W—H5WB	105.4
O2—C13—O1	126.1 (2)	H6WA—O6W—H6WB	125.3
O2—C13—C1	117.7 (2)	H7WA—O7W—H7WB	105.6
O1—C13—C1	116.2 (2)
N2—Mn1—O1—C13	13.5 (2)	C3—C4—C5—N1	−2.4 (4)
N4—Mn1—O1—C13	−134.56 (18)	C11—C4—C5—N1	176.4 (2)
N3—Mn1—O1—C13	154.53 (18)	C3—C4—C5—C6	177.5 (2)
N1—Mn1—O1—C13	9.39 (17)	C11—C4—C5—C6	−3.7 (4)
O3—Mn1—O1—C13	−164.36 (18)	C10—N2—C6—C7	−1.4 (4)
O7—Mn1—O1—C13	−67.71 (18)	Mn1—N2—C6—C7	175.47 (19)
O5—Mn1—O1—C13	90.55 (18)	C10—N2—C6—C5	177.9 (2)
N2—Mn1—O3—C14	7.74 (18)	Mn1—N2—C6—C5	−5.2 (3)
N4—Mn1—O3—C14	156.4 (2)	N1—C5—C6—N2	3.0 (3)
N3—Mn1—O3—C14	−133.32 (19)	C4—C5—C6—N2	−176.8 (2)
N1—Mn1—O3—C14	14.4 (2)	N1—C5—C6—C7	−177.6 (2)
O7—Mn1—O3—C14	89.61 (19)	C4—C5—C6—C7	2.6 (4)
O5—Mn1—O3—C14	−67.18 (19)	N2—C6—C7—C8	1.9 (4)
O1—Mn1—O3—C14	−173.92 (18)	C5—C6—C7—C8	−177.4 (2)
N2—Mn1—O5—C27	−158.4 (2)	N2—C6—C7—C12	179.9 (2)
N4—Mn1—O5—C27	−15.3 (2)	C5—C6—C7—C12	0.5 (4)
N3—Mn1—O5—C27	−8.08 (18)	C6—C7—C8—C9	−0.3 (4)
N1—Mn1—O5—C27	131.87 (19)	C12—C7—C8—C9	−178.1 (3)
O3—Mn1—O5—C27	−91.07 (19)	C7—C8—C9—C10	−1.6 (4)
O7—Mn1—O5—C27	176.82 (18)	C6—N2—C10—C9	−0.7 (4)
O1—Mn1—O5—C27	66.80 (19)	Mn1—N2—C10—C9	−177.49 (19)
N2—Mn1—O7—C28	140.83 (18)	C6—N2—C10—C14	177.9 (2)
N4—Mn1—O7—C28	−5.86 (17)	Mn1—N2—C10—C14	1.1 (3)
N3—Mn1—O7—C28	−8.5 (2)	C8—C9—C10—N2	2.2 (4)
N1—Mn1—O7—C28	−149.16 (18)	C8—C9—C10—C14	−176.3 (3)
O3—Mn1—O7—C28	73.41 (18)	C3—C4—C11—C12	−179.4 (3)
O5—Mn1—O7—C28	164.95 (17)	C5—C4—C11—C12	1.9 (4)
O1—Mn1—O7—C28	−83.78 (18)	C4—C11—C12—C7	1.2 (4)
N2—Mn1—N1—C1	176.7 (2)	C6—C7—C12—C11	−2.4 (4)
N4—Mn1—N1—C1	43.1 (2)	C8—C7—C12—C11	175.3 (3)
N3—Mn1—N1—C1	−55.0 (2)	Mn1—O1—C13—O2	168.8 (2)
O3—Mn1—N1—C1	170.03 (16)	Mn1—O1—C13—C1	−11.0 (3)
O7—Mn1—N1—C1	89.71 (19)	N1—C1—C13—O2	−174.7 (2)
O5—Mn1—N1—C1	−106.80 (19)	C2—C1—C13—O2	6.8 (4)
O1—Mn1—N1—C1	−6.42 (17)	N1—C1—C13—O1	5.1 (3)
N2—Mn1—N1—C5	−2.20 (16)	C2—C1—C13—O1	−173.4 (2)
N4—Mn1—N1—C5	−135.73 (16)	Mn1—O3—C14—O4	170.2 (2)
N3—Mn1—N1—C5	126.16 (17)	Mn1—O3—C14—C10	−9.9 (3)
O3—Mn1—N1—C5	−8.8 (2)	N2—C10—C14—O4	−174.3 (2)
O7—Mn1—N1—C5	−89.14 (17)	C9—C10—C14—O4	4.2 (4)
O5—Mn1—N1—C5	74.35 (17)	N2—C10—C14—O3	5.8 (3)
O1—Mn1—N1—C5	174.73 (19)	C9—C10—C14—O3	−175.7 (2)
N4—Mn1—N2—C10	−51.9 (2)	C19—N3—C15—C16	−0.2 (4)
N3—Mn1—N2—C10	53.1 (2)	Mn1—N3—C15—C16	178.83 (18)
N1—Mn1—N2—C10	−179.3 (2)	C19—N3—C15—C27	178.6 (2)
O3—Mn1—N2—C10	−4.16 (18)	Mn1—N3—C15—C27	−2.4 (3)
O7—Mn1—N2—C10	−98.89 (19)	N3—C15—C16—C17	−0.1 (4)
O5—Mn1—N2—C10	90.68 (19)	C27—C15—C16—C17	−178.8 (2)
O1—Mn1—N2—C10	176.76 (17)	C15—C16—C17—C18	0.4 (4)
N4—Mn1—N2—C6	131.34 (17)	C16—C17—C18—C19	−0.3 (4)
N3—Mn1—N2—C6	−123.72 (17)	C16—C17—C18—C25	179.7 (3)
N1—Mn1—N2—C6	3.94 (17)	C15—N3—C19—C18	0.3 (4)
O3—Mn1—N2—C6	179.04 (19)	Mn1—N3—C19—C18	−178.78 (18)
O7—Mn1—N2—C6	84.31 (18)	C15—N3—C19—C20	−179.4 (2)
O5—Mn1—N2—C6	−86.12 (18)	Mn1—N3—C19—C20	1.6 (3)
O1—Mn1—N2—C6	0.0 (2)	C17—C18—C19—N3	−0.1 (4)
N2—Mn1—N3—C15	45.3 (2)	C25—C18—C19—N3	180.0 (2)
N4—Mn1—N3—C15	179.7 (2)	C17—C18—C19—C20	179.6 (2)
N1—Mn1—N3—C15	−53.8 (2)	C25—C18—C19—C20	−0.4 (4)
O3—Mn1—N3—C15	96.98 (19)	C24—N4—C20—C21	−1.5 (4)
O7—Mn1—N3—C15	−177.74 (16)	Mn1—N4—C20—C21	179.14 (18)
O5—Mn1—N3—C15	5.08 (18)	C24—N4—C20—C19	178.9 (2)
O1—Mn1—N3—C15	−97.99 (19)	Mn1—N4—C20—C19	−0.5 (3)
N2—Mn1—N3—C19	−135.64 (16)	N3—C19—C20—N4	−0.7 (3)
N4—Mn1—N3—C19	−1.30 (16)	C18—C19—C20—N4	179.6 (2)
N1—Mn1—N3—C19	125.27 (17)	N3—C19—C20—C21	179.7 (2)
O3—Mn1—N3—C19	−83.99 (17)	C18—C19—C20—C21	0.0 (4)
O7—Mn1—N3—C19	1.3 (2)	N4—C20—C21—C22	2.0 (4)
O5—Mn1—N3—C19	−175.89 (19)	C19—C20—C21—C22	−178.4 (2)
O1—Mn1—N3—C19	81.04 (17)	N4—C20—C21—C26	−179.4 (2)
N2—Mn1—N4—C24	−48.4 (2)	C19—C20—C21—C26	0.2 (4)
N3—Mn1—N4—C24	−178.4 (2)	C20—C21—C22—C23	−0.9 (4)
N1—Mn1—N4—C24	53.9 (2)	C26—C21—C22—C23	−179.4 (2)
O3—Mn1—N4—C24	−92.32 (19)	C21—C22—C23—C24	−0.6 (4)
O7—Mn1—N4—C24	3.49 (17)	C20—N4—C24—C23	−0.1 (4)
O5—Mn1—N4—C24	−171.37 (16)	Mn1—N4—C24—C23	179.22 (17)
O1—Mn1—N4—C24	99.01 (19)	C20—N4—C24—C28	179.3 (2)
N2—Mn1—N4—C20	130.95 (17)	Mn1—N4—C24—C28	−1.4 (3)
N3—Mn1—N4—C20	0.90 (16)	C22—C23—C24—N4	1.2 (4)
N1—Mn1—N4—C20	−126.74 (17)	C22—C23—C24—C28	−178.2 (2)
O3—Mn1—N4—C20	87.01 (17)	C17—C18—C25—C26	−179.3 (3)
O7—Mn1—N4—C20	−177.19 (19)	C19—C18—C25—C26	0.6 (4)
O5—Mn1—N4—C20	8.0 (2)	C18—C25—C26—C21	−0.5 (4)
O1—Mn1—N4—C20	−81.66 (17)	C22—C21—C26—C25	178.5 (3)
C5—N1—C1—C2	1.1 (4)	C20—C21—C26—C25	0.1 (4)
Mn1—N1—C1—C2	−177.75 (18)	Mn1—O5—C27—O6	−170.0 (2)
C5—N1—C1—C13	−177.5 (2)	Mn1—O5—C27—C15	9.8 (3)
Mn1—N1—C1—C13	3.7 (3)	N3—C15—C27—O6	174.7 (2)
N1—C1—C2—C3	−2.5 (4)	C16—C15—C27—O6	−6.5 (4)
C13—C1—C2—C3	175.9 (2)	N3—C15—C27—O5	−5.0 (3)
C1—C2—C3—C4	1.4 (4)	C16—C15—C27—O5	173.7 (2)
C2—C3—C4—C5	0.9 (4)	Mn1—O7—C28—O8	−172.32 (19)
C2—C3—C4—C11	−177.8 (3)	Mn1—O7—C28—C24	7.3 (3)
C1—N1—C5—C4	1.4 (4)	N4—C24—C28—O8	175.7 (2)
Mn1—N1—C5—C4	−179.72 (18)	C23—C24—C28—O8	−4.9 (4)
C1—N1—C5—C6	−178.4 (2)	N4—C24—C28—O7	−3.9 (3)
Mn1—N1—C5—C6	0.5 (3)	C23—C24—C28—O7	175.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1W	0.90	1.93	2.792 (4)	159
N5—H5B···O2	0.90	1.93	2.797 (3)	161
N6—H6A···O1W	0.90	2.19	2.938 (4)	140
N6—H6B···O7W^i	0.90	1.94	2.830 (3)	169
N7—H7A···O8	0.90	1.96	2.840 (3)	167
N7—H7B···O1^ii	0.90	1.93	2.812 (3)	168
N8—H8A···O3W	0.90	2.05	2.941 (3)	172
N8—H8B···O2W^iii	0.90	1.98	2.871 (3)	173
O1W—H1WB···O6^iv	0.85	1.93	2.780 (3)	178
O1W—H1WA···O2W	0.85	1.98	2.826 (3)	171
O2W—H2WA···O4^v	0.85	1.92	2.709 (3)	154
O2W—H2WB···O3^ii	0.85	1.90	2.753 (3)	177
O3W—H3WA···O8	0.85	1.87	2.687 (3)	161
O3W—H3WB···O2^iii	0.85	1.94	2.741 (3)	156
O4W—H4WA···O3W	0.85	2.18	2.996 (3)	161
O4W—H4WB···O7	0.85	1.98	2.808 (3)	164
O5W—H5WA···O4W	0.85	1.99	2.828 (3)	168
O5W—H5WB···O6W	0.85	1.99	2.783 (3)	154
O6W—H6WA···O6^vi	0.85	1.89	2.737 (3)	174
O6W—H6WB···O5W^vii	0.85	2.03	2.826 (4)	155
O7W—H7WA···O6W	0.85	1.96	2.760 (3)	157
O7W—H7WB···O5^vi	0.85	2.02	2.865 (3)	173

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