Reversible high-temperature phase transition of a manganese(II) formate framework with imidazolium cations

A new metal–formate framework, poly[1H-imidazol-3-ium [tri-μ₂-formato-manganese(II)]], {(C₃H₅N₂)[Mn(HCOO)₃]}_n, was synthesized and its structural phase transition was studied by thermal analysis and variable-temperature X-ray diffraction analysis. The transition temperature is around 435 K. The high-temperature phase is tetra­gonal and the low-temperature phase is monoclinic, with a β angle close to 90°. The relationship of the unit cells between the two phases can be described as: a_HT = 0.5a_LT + 0.5b_LT; b_HT = −0.5a_LT + 0.5b_LT; c_HT = 0.5c_LT. In the high-temperature phase, both the frame­work and the guest 1H-imidazol-3-ium (HIm) cations are disordered; the HIm cations are located about 2mm sites and were modelled as fourfold disordered. The Mn and a formate C atom are located on fourfold rotary inversion axes, while another formate C atom is on a mirror plane. The low-temperature structure is ordered and consists of two crystallographically independent HIm cations and two crystallographically independent Mn²⁺ ions. The phase transition is attributable to the order–disorder transition of the HIm cations.

S1. Comment

Recently developed metal formate frameworks (AmineH⁺)[M(HCOO)₃^-] [AmineH⁺ = (CH₃)₂NH₂⁺, (CH₂)₃NH₂⁺, NH₄⁺ etc.; M = Mn²⁺, Fe²⁺, Cu²⁺, Zn²⁺ etc.) (Xu et al. 2010; Zhou et al., 2011; Wang, Zhang et al., 2004; Jain et al., 2009) are of interest in terms of structural phase transition. The key feature of the structures is the anionic NaCl framework of [M²⁺(HCOO)₃^-], where the cavity is occupied by the alkylammonium cations. The guest alkylammonium cations tend to be disordered due to relative larger freedom of motion, and become ordered at lower temperature, which leads to phase transitions. Some transitions have been found to be accompanied by interesting and/or useful physical properties. For example, [(CH₃)₂NH₂⁺][Mn(HCOO)₃^-] (Jain et al., 2009) was found to undergo a paraelectric-to-ferroelectric phase transition at 183 K due to the ordering of the (CH₃)₂NH₂⁺ cations. Another example is the phase transition of [(CH₂)₃NH₂⁺][Cu(HCOO)₃^-](Zhou et al., 2011). This phase transition is related to the ring-puckering of the organic cations, and is accompanied by unusually large dielectric response (Zhou et al., 2011).

It has been found that the crystal structures and their phase transitions in this series of compounds depend greatly on the shape and the size of the guest alkylammonium cations (Wang, Zhang et al., 2004). The introduction of new organic ammonium cations into the metal formate framework will enrich the structures of [and?] properties of this series. As a simple organic rotator, imidazole has been utilized to develop artificial molecular motors or potential dielectric rotors (Zhang et al., 2010; Sun, et al., 2010; Pająk et al., 2006). Among them, the perovskite-type cage compound (HIm)₂[KFe(CN)₆] (HIm is 1H-imidazol-3-ium; Zhang et al., 2010) are structurally analogous to the metal formate frameworks, and exhibits interesting phase transitions. Therefore, it is expected that inclusion of HIm cations into the metal formate frameworks would lead to formation of structures with interesting phase transitions. Here, we describe the phase transition of a new member of this series, {(HIm)[Mn(HCOO)₃]}_n, (I).

At room temperature, (I) crystallizes in a monoclinic system, with β = 91.31 (3)°. The crystal structure has the common feature of the three-dimensional metal formate framework (Wang, Gan et al., 2004), i.e. the HIm cations occupy the cavities of the three-dimensional metal formate framework formed by the octahedral coordinated Mn²⁺ ions and the bidentate formate ligands (Fig. 1). The crystal structure consists of two crystallographically independent HIm cations. They have the same geometry and adopt configurations suitable for the formation of hydrogen bonds to the formate groups (Table 2). The structure of the manganese(II) formate framework is comparable to that of the analogue with (CH₂)₃NH₂⁺ (Wang, Zhang et al., 2004). The two crystallographically independent Mn²⁺ ions have similar coordination geometries with Mn—O bonds ranging from 2.1430 (14) to 2.2053 (14) Å (Table 1). The average distance of two neighbouring Mn²⁺ ions is about 6.28 Å. It has been shown that the size of the guest cation is mainly responsible for the apparent breathing nature of the framework brought about by the change of the Mn–O–C angles. Compared with those cations, including CH₃NH₃⁺, CH₃CH₂NH₃⁺, (CH₃)₂NH₂⁺ and (CH₂)₃NH₂⁺ (Wang, Zhang et al., 2004), the imidazolium cation has a larger size. Correspondingly, the average Mn—O—C angle (135.1°) and the volume per four cages (987 ų) in (I) are somewhat larger than those (121.9–128.7° and 847.1–948.6 ų, respectively) in the analogues with smaller amines.

Qualitatively, the larger size of the HIm cations will decrease the freedom of their motion in the cavities. At room temperature, smaller cations, such as (CH₃)₂NH₂⁺, (CH₂)₃NH₂⁺ and NH₄⁺, are all disordered in their corresponding metal formate frameworks; while in (I), the HIm cations are ordered, and the C and N atoms are definitely distinguishable. The hydrogen bonds also contribute to the formation of an ordered structure at room temperature. In the above-mentioned cage compound (HIm)₂[KFe(CN)₆] (Zhang et al., 2010), the average distance of between two neighbouringd Fe³⁺ and K⁺ ions is about 5.97 Å, a little shorter than that in (I). However, this compound has a totally disordered room-temperature structure, and the ordering temperature is about 160 K. This can be ascribed to the fact that the there are additional N—H···O hydrogen bonds and C—H···O interactions in (I).

Differential scanning calorimetry (DSC) measurements show that (I) undergoes a high-temperature phase transition at around 435 K (Fig. 2). Compared with other metal formate frameworks of type (AmineH⁺)[M(HCOO)₃^-] {T_c = 183, 286 and 192 K for [(CH₃)₂NH₂⁺][Mn(HCOO)₃^-], [(CH₂)₃NH₂⁺][Cu(HCOO)₃^-] and [NH₄⁺][Zn(HCOO)₃^- respectively}, (I) has a significantly higher phase transition temperature. At 448 K, (I) was tetragonal, with space group P42₁m. The relationship of the unit cells between the two phases is a_HT = 0.5a_LT + 0.5b_LT; b_HT = -0.5 a_LT + 0.5b_LT; c_HT = 0.5c_LT. The Mn²⁺ ion is located on the rotoinversion centre; the formate groups along the direction of the c axis become disordered over two orientations, with atom C2 located on the rotoinversion centres; atom C1 is positioned on a mirror plane. The volume of the cages does not show significant change, with the average distance between two neighbouring Mn²⁺ ions being about 6.31 Å. As expected, the HIm cation is totally disordered. It is located on a 2mm site, inconsistent with its own symmetry. The crystal symmetry requirement is satisfied by the orientation disorder. As revealed in artificial molecular motors (Zhang et al., 2010; Pająk et al., 2006), the HIm cation tends to show in-plane disorder at high temperature. In this case, the orientation disorder is due to the rotation about the twofold axis which is inclined to the plane and thus leads to formation of fourfold disorder.

The transition observed in (I) is a new type of reversible temperature phase transition due to the order–disorder transition of HIm cations. The ordering of the cations breaks the 2 mm symmetry and lead to a little change of the β angle and the doubling of the c axis.

Related literature

For related literature, see: Jain et al. (2009); Pająk et al. (2006); Sun et al. (2010); Wang, Gan, Zhang & Gao (2004); Wang, Zhang, Otsuka, Inoue, Kobayashi & Kurmoo (2004); Xu et al. (2010); Zhang et al. (2010); Zhou et al. (2011).

S2. Experimental

Crystals of (I) was prepared according to a similar procedure to that used for the preparation of the NH4⁺ analogue (Xu et al., 2010) but using imidazole instead of HCOONH₄. In a typical synthesis procedure, an aqueous solution of Mn(ClO₄)₂.6H₂O (0.8 mmol) and an aqueous solution containing imidazole (6.4 mmol) and formic acid (9.6 mmol) were loaded into two parts of an H-shape tube and allowed to diffuse slowly at room temperature. After 10 d, the precipitated crystals were collected and dried in a vacuum. The DSC measurements were performed using a Rigaku Thermal series instrument.

S3. Refinement

All H atoms were generated geometrically and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N). In the high-temperature phase, only two atoms of the HIm cation could be located on a Fourier difference map. The geometry of the HIm ring was constrained to be an ideal five-membered ring, and the U_eq values are restrained to be the same with a default value (0.08) of the standard deviation. The crystal structure was refined with two inversion domains.

Computing details

For both compounds, data collection: RAPID-AUTO (Rigaku, 2000); cell refinement: RAPID-AUTO (Rigaku, 2000); data reduction: RAPID-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Putz, 2005) for I_RT; DIAMOND (Brandenburg & Putz, 2005) for I_HT. For both compounds, software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The crystal structure of the three-dimensional perovskite cage compound (I) at room temperature. H atoms bonded to formate C atoms have been omitted for clarity. The non-H atoms of an asymmetric unit are labelled. The atom with suffix is generated by symmetry operation. Displacement ellipsoids were drawn at the 30% probability level. Dashed lines indicate hydrogen-bond interactions.[Symmetry code: (A) -x+3/2, y-1/2, -z+1/2.]
	Fig. 2. The differential scanning calorimetry (DSC) plot for (I).
	Fig. 3. The crystal structure of the three-dimensional perovskite cage compound (I) at 453 K. H atoms have been omitted for clarity. The non-H atoms of the asymmetric unit are labelled. The four orientations of the disordered HIm cation are indicated by bonds with different colours. The two orientations for each disordered formate group along the c axis are indicated by bonds with different colors. Displacement ellipsoids were drawn at the 30% probability level.

(I_RT) Poly[1H-imidazol-3-ium [tri-µ₂-formato-manganese(II)]]

Crystal data

(C3H5N2)[Mn(CHO2)3]	F(000) = 1048
Mr = 259.08	Dx = 1.743 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10994 reflections
a = 12.332 (3) Å	θ = 3.2–27.4°
b = 12.461 (3) Å	µ = 1.35 mm^−1
c = 12.850 (3) Å	T = 293 K
β = 91.31 (3)°	Block, colourless
V = 1974.1 (7) Å^3	0.5 × 0.45 × 0.45 mm
Z = 8

Data collection

Rigaku Rapid diffractometer	4488 independent reflections
Radiation source: Rotating anode	3025 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2000)	h = −15→15
Tmin = 0.446, Tmax = 0.545	k = −16→16
18874 measured reflections	l = −16→16

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0263P)^2 + 0.9936P] where P = (Fo^2 + 2Fc^2)/3
4488 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.35 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	0.23949 (2)	0.75287 (2)	0.00823 (2)	0.01852 (8)
Mn2	0.73998 (2)	0.74768 (2)	0.00685 (2)	0.01818 (8)
C1	0.48867 (16)	0.78333 (19)	0.00373 (16)	0.0305 (5)
H1	0.4900	0.7308	0.0551	0.037*
C2	−0.00834 (16)	0.72988 (19)	0.04414 (18)	0.0342 (5)
H2	−0.0054	0.7993	0.0706	0.041*
C3	0.24711 (17)	0.7810 (2)	0.25854 (16)	0.0314 (5)
H3	0.1994	0.8388	0.2594	0.038*
C4	0.73572 (17)	0.72935 (19)	0.25561 (16)	0.0316 (5)
H4	0.7880	0.6755	0.2573	0.038*
C5	0.78179 (17)	0.99722 (17)	−0.02302 (18)	0.0305 (5)
H5	0.7297	0.9968	−0.0765	0.037*
C6	0.72475 (17)	0.49882 (17)	0.01305 (17)	0.0288 (5)
H6	0.7851	0.5006	0.0578	0.035*
O1	0.07757 (11)	0.69195 (13)	0.01836 (13)	0.0397 (4)
O3	0.27906 (14)	0.75159 (15)	0.17279 (11)	0.0462 (5)
O6	0.39848 (11)	0.81763 (13)	−0.02546 (12)	0.0373 (4)
O7	0.57760 (10)	0.81345 (13)	−0.03009 (11)	0.0329 (4)
O8	0.79963 (13)	0.91219 (13)	0.02088 (13)	0.0428 (4)
O10	0.68150 (12)	0.58561 (12)	−0.00958 (13)	0.0367 (4)
O11	0.70120 (14)	0.75907 (15)	0.17015 (11)	0.0473 (5)
N3	0.02918 (17)	0.54480 (18)	0.30825 (16)	0.0449 (5)
H3A	0.0430	0.5884	0.3587	0.054*
N4	−0.04583 (16)	0.42174 (17)	0.21481 (16)	0.0412 (5)
H4A	−0.0893	0.3718	0.1940	0.049*
C10	0.0858 (2)	0.5365 (2)	0.2205 (2)	0.0458 (6)
H10A	0.1462	0.5769	0.2035	0.055*
C11	0.0397 (2)	0.4598 (2)	0.16248 (19)	0.0422 (6)
H11A	0.0624	0.4367	0.0977	0.051*
C12	−0.0511 (2)	0.4751 (2)	0.3041 (2)	0.0491 (7)
H12A	−0.1026	0.4649	0.3549	0.059*
N1	0.44428 (16)	0.5487 (2)	0.19223 (17)	0.0500 (6)
H1A	0.3943	0.5695	0.1491	0.060*
N2	0.54806 (16)	0.54070 (19)	0.32563 (16)	0.0434 (5)
H2A	0.5780	0.5553	0.3851	0.052*
C7	0.5102 (2)	0.4642 (3)	0.1784 (2)	0.0586 (8)
H7A	0.5104	0.4182	0.1214	0.070*
C8	0.5755 (2)	0.4597 (2)	0.2629 (2)	0.0524 (7)
H8A	0.6299	0.4095	0.2757	0.063*
C9	0.4679 (2)	0.5940 (2)	0.2811 (2)	0.0506 (7)
H9A	0.4338	0.6540	0.3083	0.061*
O9	0.27267 (15)	0.74094 (15)	0.34257 (11)	0.0484 (5)
O12	−0.09929 (11)	0.68830 (14)	0.03988 (14)	0.0434 (4)
O4	0.69399 (11)	0.40918 (12)	−0.01921 (12)	0.0323 (3)
O5	0.70566 (13)	0.76626 (14)	0.34045 (11)	0.0398 (4)
O2	0.82668 (11)	1.08493 (12)	−0.00308 (12)	0.0341 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01965 (14)	0.01808 (16)	0.01777 (14)	0.00002 (11)	−0.00090 (10)	0.00093 (12)
Mn2	0.01980 (14)	0.01772 (16)	0.01700 (14)	−0.00074 (11)	−0.00027 (10)	−0.00025 (12)
C1	0.0289 (11)	0.0307 (13)	0.0317 (11)	−0.0042 (9)	−0.0021 (9)	0.0091 (9)
C2	0.0247 (10)	0.0310 (13)	0.0470 (13)	−0.0017 (9)	0.0031 (9)	−0.0091 (11)
C3	0.0340 (11)	0.0344 (13)	0.0258 (11)	0.0036 (9)	0.0009 (9)	−0.0028 (9)
C4	0.0331 (11)	0.0354 (14)	0.0263 (11)	0.0033 (9)	0.0008 (9)	−0.0007 (10)
C5	0.0327 (11)	0.0253 (13)	0.0331 (12)	−0.0026 (9)	−0.0112 (9)	−0.0025 (10)
C6	0.0292 (10)	0.0258 (13)	0.0311 (11)	0.0003 (9)	−0.0057 (8)	−0.0002 (9)
O1	0.0227 (7)	0.0363 (10)	0.0605 (11)	−0.0049 (7)	0.0085 (7)	−0.0051 (8)
O3	0.0583 (11)	0.0611 (13)	0.0190 (7)	0.0092 (9)	−0.0026 (7)	−0.0022 (8)
O6	0.0217 (7)	0.0407 (10)	0.0494 (10)	−0.0021 (7)	0.0007 (6)	0.0142 (8)
O7	0.0206 (7)	0.0386 (10)	0.0396 (9)	0.0011 (6)	0.0015 (6)	0.0145 (7)
O8	0.0554 (10)	0.0206 (10)	0.0514 (10)	−0.0099 (7)	−0.0206 (8)	0.0036 (8)
O10	0.0364 (8)	0.0184 (9)	0.0546 (10)	−0.0021 (6)	−0.0109 (7)	−0.0004 (7)
O11	0.0583 (11)	0.0649 (13)	0.0188 (7)	0.0191 (9)	0.0029 (7)	0.0014 (8)
N3	0.0562 (13)	0.0376 (13)	0.0401 (11)	0.0027 (10)	−0.0121 (10)	−0.0151 (10)
N4	0.0451 (11)	0.0330 (12)	0.0451 (12)	−0.0090 (9)	−0.0085 (9)	−0.0052 (10)
C10	0.0537 (15)	0.0389 (15)	0.0449 (15)	−0.0131 (12)	0.0010 (12)	0.0001 (12)
C11	0.0516 (14)	0.0408 (15)	0.0343 (12)	−0.0051 (12)	0.0049 (11)	−0.0080 (12)
C12	0.0502 (15)	0.0608 (19)	0.0365 (14)	0.0022 (14)	0.0072 (11)	0.0017 (13)
N1	0.0388 (11)	0.0623 (17)	0.0479 (13)	−0.0077 (11)	−0.0166 (10)	0.0241 (12)
N2	0.0453 (11)	0.0487 (14)	0.0355 (11)	−0.0025 (10)	−0.0133 (9)	0.0019 (10)
C7	0.0681 (18)	0.062 (2)	0.0459 (16)	−0.0029 (16)	−0.0002 (14)	−0.0136 (15)
C8	0.0467 (14)	0.0455 (17)	0.0645 (19)	0.0129 (13)	−0.0068 (13)	0.0011 (15)
C9	0.0419 (14)	0.0439 (17)	0.0660 (18)	0.0080 (12)	0.0015 (13)	0.0039 (15)
O9	0.0646 (11)	0.0613 (13)	0.0196 (7)	0.0174 (9)	0.0079 (7)	0.0024 (8)
O12	0.0210 (7)	0.0374 (10)	0.0717 (12)	−0.0002 (7)	−0.0013 (7)	0.0035 (9)
O4	0.0349 (8)	0.0199 (9)	0.0415 (9)	0.0036 (6)	−0.0093 (6)	−0.0031 (7)
O5	0.0520 (10)	0.0488 (11)	0.0183 (7)	0.0084 (8)	−0.0027 (7)	−0.0005 (7)
O2	0.0347 (8)	0.0176 (8)	0.0495 (9)	−0.0001 (6)	−0.0110 (7)	0.0002 (7)

Geometric parameters (Å, º)

Mn1—O1	2.1430 (14)	C5—O2	1.249 (2)
Mn1—O3	2.1594 (16)	C5—H5	0.9300
Mn1—O6	2.1728 (14)	C6—O10	1.238 (2)
Mn1—O2^i	2.1801 (16)	C6—O4	1.247 (2)
Mn1—O4^ii	2.1828 (16)	C6—H6	0.9300
Mn1—O5^iii	2.1996 (15)	N3—C12	1.318 (3)
Mn1—Mn2	6.1727 (13)	N3—C10	1.343 (3)
Mn2—O12^iv	2.1489 (15)	N3—H3A	0.8600
Mn2—O10	2.1531 (16)	N4—C12	1.329 (3)
Mn2—O9^v	2.1629 (15)	N4—C11	1.350 (3)
Mn2—O11	2.1675 (15)	N4—H4A	0.8600
Mn2—O8	2.1839 (17)	C10—C11	1.331 (4)
Mn2—O7	2.2053 (14)	C10—H10A	0.9300
Mn2—Mn1^iv	6.1598 (13)	C11—H11A	0.9300
Mn2—Mn1^i	6.2318 (13)	C12—H12A	0.9300
Mn2—Mn1^ii	6.2454 (13)	N1—C9	1.301 (3)
Mn2—Mn1^v	6.4073 (13)	N1—C7	1.344 (4)
Mn2—Mn1^vi	6.4430 (14)	N1—H1A	0.8600
C1—O6	1.242 (2)	N2—C9	1.312 (3)
C1—O7	1.247 (2)	N2—C8	1.340 (3)
C1—H1	0.9300	N2—H2A	0.8600
C2—O1	1.213 (2)	C7—C8	1.338 (4)
C2—O12	1.235 (2)	C7—H7A	0.9300
C2—H2	0.9300	C8—H8A	0.9300
C3—O9	1.224 (3)	C9—H9A	0.9300
C3—O3	1.234 (2)	O9—Mn2^vii	2.1629 (15)
C3—H3	0.9300	O12—Mn2^viii	2.1489 (15)
C4—O11	1.226 (3)	O4—Mn1^ii	2.1828 (16)
C4—O5	1.247 (2)	O5—Mn1^vi	2.1996 (15)
C4—H4	0.9300	O2—Mn1^i	2.1801 (16)
C5—O8	1.218 (3)
O1—Mn1—O3	97.35 (7)	Mn1^i—Mn2—Mn1^v	88.228 (5)
O1—Mn1—O6	171.86 (6)	Mn1^ii—Mn2—Mn1^v	88.111 (5)
O3—Mn1—O6	90.75 (7)	O12^iv—Mn2—Mn1^vi	79.87 (6)
O1—Mn1—O2^i	88.95 (6)	O10—Mn2—Mn1^vi	95.11 (5)
O3—Mn1—O2^i	96.47 (7)	O9^v—Mn2—Mn1^vi	168.68 (5)
O6—Mn1—O2^i	89.34 (6)	O11—Mn2—Mn1^vi	13.27 (5)
O1—Mn1—O4^ii	91.01 (6)	O8—Mn2—Mn1^vi	85.78 (5)
O3—Mn1—O4^ii	81.58 (6)	O7—Mn2—Mn1^vi	101.19 (5)
O6—Mn1—O4^ii	90.97 (6)	Mn1^iv—Mn2—Mn1^vi	91.20 (3)
O2^i—Mn1—O4^ii	178.03 (6)	Mn1—Mn2—Mn1^vi	88.47 (3)
O1—Mn1—O5^iii	82.24 (7)	Mn1^i—Mn2—Mn1^vi	91.897 (5)
O3—Mn1—O5^iii	173.05 (7)	Mn1^ii—Mn2—Mn1^vi	91.772 (5)
O6—Mn1—O5^iii	89.82 (7)	Mn1^v—Mn2—Mn1^vi	179.838 (8)
O2^i—Mn1—O5^iii	90.47 (6)	O6—C1—O7	125.5 (2)
O4^ii—Mn1—O5^iii	91.48 (6)	O6—C1—H1	117.3
O1—Mn1—Mn2	158.37 (5)	O7—C1—H1	117.3
O3—Mn1—Mn2	78.42 (5)	O1—C2—O12	128.5 (2)
O6—Mn1—Mn2	25.38 (4)	O1—C2—H2	115.8
O2^i—Mn1—Mn2	112.53 (4)	O12—C2—H2	115.8
O4^ii—Mn1—Mn2	67.43 (4)	O9—C3—O3	125.8 (2)
O5^iii—Mn1—Mn2	99.40 (5)	O9—C3—H3	117.1
O12^iv—Mn2—O10	90.10 (6)	O3—C3—H3	117.1
O12^iv—Mn2—O9^v	91.36 (8)	O11—C4—O5	124.6 (2)
O10—Mn2—O9^v	92.02 (7)	O11—C4—H4	117.7
O12^iv—Mn2—O11	93.11 (7)	O5—C4—H4	117.7
O10—Mn2—O11	94.33 (7)	O8—C5—O2	126.3 (2)
O9^v—Mn2—O11	172.22 (7)	O8—C5—H5	116.9
O12^iv—Mn2—O8	89.97 (6)	O2—C5—H5	116.9
O10—Mn2—O8	179.10 (6)	O10—C6—O4	125.3 (2)
O9^v—Mn2—O8	87.08 (7)	O10—C6—H6	117.3
O11—Mn2—O8	86.55 (7)	O4—C6—H6	117.3
O12^iv—Mn2—O7	177.95 (6)	C2—O1—Mn1	134.38 (16)
O10—Mn2—O7	91.55 (6)	C3—O3—Mn1	143.36 (16)
O9^v—Mn2—O7	87.37 (7)	C1—O6—Mn1	128.18 (14)
O11—Mn2—O7	87.98 (6)	C1—O7—Mn2	127.93 (14)
O8—Mn2—O7	88.36 (6)	C5—O8—Mn2	136.17 (15)
O12^iv—Mn2—Mn1^iv	23.83 (5)	C6—O10—Mn2	130.92 (14)
O10—Mn2—Mn1^iv	110.05 (4)	C4—O11—Mn2	140.14 (15)
O9^v—Mn2—Mn1^iv	78.08 (6)	C12—N3—C10	108.6 (2)
O11—Mn2—Mn1^iv	103.84 (6)	C12—N3—H3A	125.7
O8—Mn2—Mn1^iv	69.82 (5)	C10—N3—H3A	125.7
O7—Mn2—Mn1^iv	154.12 (4)	C12—N4—C11	108.0 (2)
O12^iv—Mn2—Mn1	157.05 (5)	C12—N4—H4A	126.0
O10—Mn2—Mn1	71.18 (4)	C11—N4—H4A	126.0
O9^v—Mn2—Mn1	102.17 (6)	C11—C10—N3	107.6 (2)
O11—Mn2—Mn1	75.75 (6)	C11—C10—H10A	126.2
O8—Mn2—Mn1	108.95 (5)	N3—C10—H10A	126.2
O7—Mn2—Mn1	25.00 (4)	C10—C11—N4	107.5 (2)
Mn1^iv—Mn2—Mn1	178.753 (7)	C10—C11—H11A	126.2
O12^iv—Mn2—Mn1^i	108.18 (5)	N4—C11—H11A	126.2
O10—Mn2—Mn1^i	161.33 (4)	N3—C12—N4	108.2 (2)
O9^v—Mn2—Mn1^i	84.01 (5)	N3—C12—H12A	125.9
O11—Mn2—Mn1^i	88.55 (5)	N4—C12—H12A	125.9
O8—Mn2—Mn1^i	18.44 (4)	C9—N1—C7	109.4 (2)
O7—Mn2—Mn1^i	70.09 (4)	C9—N1—H1A	125.3
Mn1^iv—Mn2—Mn1^i	87.035 (5)	C7—N1—H1A	125.3
Mn1—Mn2—Mn1^i	91.773 (5)	C9—N2—C8	108.5 (2)
O12^iv—Mn2—Mn1^ii	67.94 (5)	C9—N2—H2A	125.8
O10—Mn2—Mn1^ii	22.18 (4)	C8—N2—H2A	125.8
O9^v—Mn2—Mn1^ii	91.53 (5)	C8—C7—N1	106.3 (3)
O11—Mn2—Mn1^ii	96.05 (5)	C8—C7—H7A	126.9
O8—Mn2—Mn1^ii	157.84 (5)	N1—C7—H7A	126.9
O7—Mn2—Mn1^ii	113.69 (4)	C7—C8—N2	107.5 (2)
Mn1^iv—Mn2—Mn1^ii	88.244 (5)	C7—C8—H8A	126.2
Mn1—Mn2—Mn1^ii	92.969 (5)	N2—C8—H8A	126.2
Mn1^i—Mn2—Mn1^ii	174.079 (7)	N1—C9—N2	108.3 (3)
O12^iv—Mn2—Mn1^v	100.19 (6)	N1—C9—H9A	125.8
O10—Mn2—Mn1^v	84.74 (5)	N2—C9—H9A	125.8
O9^v—Mn2—Mn1^v	11.46 (5)	C3—O9—Mn2^vii	141.63 (16)
O11—Mn2—Mn1^v	166.66 (5)	C2—O12—Mn2^viii	134.15 (17)
O8—Mn2—Mn1^v	94.37 (5)	C6—O4—Mn1^ii	134.09 (14)
O7—Mn2—Mn1^v	78.76 (5)	C4—O5—Mn1^vi	139.75 (15)
Mn1^iv—Mn2—Mn1^v	88.91 (3)	C5—O2—Mn1^i	129.88 (14)
Mn1—Mn2—Mn1^v	91.42 (3)

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1, y, z; (v) x+1/2, −y+3/2, z−1/2; (vi) x+1/2, −y+3/2, z+1/2; (vii) x−1/2, −y+3/2, z+1/2; (viii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O7^vii	0.86	1.92	2.781 (3)	179
N4—H4A···O5^ix	0.86	1.99	2.842 (3)	172
N1—H1A···O4^ii	0.86	1.99	2.820 (3)	162
N2—H2A···O2^x	0.86	1.93	2.780 (3)	168
C9—H9A···O9	0.93	2.31	3.140 (3)	148
C11—H11A···O12^xi	0.93	2.41	3.286 (3)	157

Symmetry codes: (ii) −x+1, −y+1, −z; (vii) x−1/2, −y+3/2, z+1/2; (ix) −x+1/2, y−1/2, −z+1/2; (x) −x+3/2, y−1/2, −z+1/2; (xi) −x, −y+1, −z.

(I_HT) Poly[1H-imidazol-3-ium [tri-µ₂-formato-manganese(II)]]

Crystal data

(C3H5N2)[Mn(CHO2)3]	Dx = 1.713 Mg m^−3
Mr = 259.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421m	Cell parameters from 4770 reflections
Hall symbol: P -4 2ab	θ = 3.2–27.4°
a = 8.8324 (12) Å	µ = 1.33 mm^−1
c = 6.4406 (13) Å	T = 453 K
V = 502.44 (14) Å^3	Block, colorless
Z = 2	0.5 × 0.45 × 0.45 mm
F(000) = 262

Data collection

Rigaku Rapid diffractometer	623 independent reflections
Radiation source: rotating anode	460 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ω scans	θmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2000)	h = −10→11
Tmin = 0.462, Tmax = 0.551	k = −11→11
4803 measured reflections	l = −8→8

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.085P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
623 reflections	Δρmax = 0.28 e Å^−3
66 parameters	Δρmin = −0.33 e Å^−3
30 restraints	Absolute structure: Flack (1983), 247 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.3 (2)

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.

Compared with the metal atom Mn1, the coordinated O atoms show relatively larger ADP, and thus an alert B related to this is given when checked the cif file with PLATON. This indicates possible disorder of the coordinated O1 atom. However, we didn't try to model this disorder because it is not a typical disorder with easily distinguishable two sites. The imidazolium cation is modeled with fourfold disorder, its geometry and ADP have to be constrained. The crystal structure was refined with two inversion domains. The detail of the command used for this purpose is attached at the end of this cif.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.5000	0.5000	0.5000	0.0341 (4)
C1	0.7225 (6)	0.2225 (6)	0.515 (3)	0.096 (4)
H1	0.7953	0.2953	0.5494	0.115*
O1	0.6013 (3)	0.2766 (3)	0.4996 (9)	0.0804 (11)
C2	0.5000	0.5000	1.0000	0.115 (6)
H2	0.4363	0.5881	1.0000	0.138*	0.25
O2	0.5374 (13)	0.503 (6)	0.8329 (9)	0.089 (6)	0.50
N2	0.6237 (16)	0.0341 (17)	0.886 (2)	0.066 (6)	0.25
H2A	0.7121	0.0378	0.8167	0.080*	0.25
C5	0.5974 (17)	−0.027 (2)	1.0868 (16)	0.066 (9)	0.25
H5A	0.6725	−0.0698	1.1770	0.079*	0.25
N1	0.4404 (19)	−0.0133 (17)	1.1306 (17)	0.051 (7)	0.25
H1A	0.3939	−0.0434	1.2479	0.062*	0.25
C4	0.3698 (14)	0.056 (2)	0.957 (2)	0.117 (11)	0.25
H4A	0.2639	0.0791	0.9441	0.140*	0.25
C3	0.483 (2)	0.085 (2)	0.8058 (17)	0.109 (10)	0.25
H3A	0.4673	0.1317	0.6727	0.131*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0352 (4)	0.0352 (4)	0.0319 (5)	0.000	0.000	0.000
C1	0.054 (2)	0.054 (2)	0.178 (12)	0.013 (3)	−0.054 (6)	−0.054 (6)
O1	0.0628 (18)	0.0498 (16)	0.128 (3)	0.0147 (14)	0.013 (3)	−0.012 (3)
C2	0.149 (10)	0.149 (10)	0.047 (8)	0.000	0.000	0.000
O2	0.098 (13)	0.138 (10)	0.030 (4)	−0.010 (12)	−0.006 (4)	0.024 (15)
N2	0.035 (9)	0.038 (10)	0.126 (14)	−0.019 (6)	−0.012 (10)	0.014 (9)
C5	0.077 (17)	0.049 (16)	0.072 (13)	0.027 (12)	−0.033 (13)	−0.048 (10)
N1	0.054 (12)	0.049 (14)	0.051 (6)	0.024 (12)	0.026 (6)	0.032 (8)
C4	0.091 (17)	0.111 (18)	0.15 (2)	−0.014 (15)	0.056 (16)	−0.075 (16)
C3	0.114 (19)	0.054 (13)	0.16 (2)	−0.043 (13)	0.057 (18)	0.026 (15)

Geometric parameters (Å, º)

Mn1—O1^i	2.166 (3)	C5—N1	1.4200
Mn1—O1^ii	2.166 (3)	C5—C5^viii	1.553 (15)
Mn1—O1	2.166 (3)	C5—C5^xi	1.79 (2)
Mn1—O1^iii	2.166 (3)	C5—C3^viii	1.815 (3)
Mn1—O2^ii	2.170 (6)	C5—N2^xii	1.94 (3)
Mn1—O2^iii	2.170 (6)	C5—H5A	0.9600
Mn1—O2	2.170 (6)	N1—C5^xi	0.564 (18)
Mn1—O2^i	2.170 (6)	N1—N1^viii	0.58 (2)
Mn1—Mn1^iv	6.2455 (9)	N1—N1^xii	0.91 (4)
Mn1—Mn1^v	6.2455 (9)	N1—C5^viii	1.058 (7)
Mn1—Mn1^vi	6.2454 (9)	N1—N1^xi	1.08 (4)
Mn1—Mn1^vii	6.2454 (9)	N1—C5^xii	1.1021
C1—O1^viii	1.177 (4)	N1—C4	1.4200
C1—O1	1.177 (4)	N1—N2^xi	1.68 (3)
C1—H1	0.9346	N1—C4^xii	1.69 (2)
C2—O2^i	1.126 (7)	N1—C4^viii	1.83 (2)
C2—O2	1.126 (7)	N1—N2^xii	1.87 (2)
C2—O2^ix	1.126 (7)	N1—H1A	0.9000
C2—O2^x	1.126 (7)	C4—N2^xi	0.92 (3)
C2—H2	0.9600	C4—C5^xi	0.922 (9)
O2—O2^i	0.66 (2)	C4—C4^xii	0.93 (4)
N2—C3^viii	0.765 (4)	C4—C3^xii	1.1066 (14)
N2—C4^xi	0.92 (2)	C4—C5^viii	1.290 (5)
N2—N2^viii	1.12 (3)	C4—C3	1.4200
N2—C3	1.4200	C4—N2^viii	1.63 (2)
N2—C5	1.4200	C4—N1^xii	1.69 (2)
N2—C3^xi	1.51 (3)	C4—N1^viii	1.833 (17)
N2—C4^viii	1.635 (10)	C4—N2^xii	1.858 (19)
N2—N1^xi	1.684 (14)	C4—H4A	0.9600
N2—C4^xii	1.858 (10)	C3—N2^viii	0.765 (14)
N2—N1^xii	1.867 (12)	C3—C3^xii	0.85 (4)
N2—C3^xii	1.92 (3)	C3—C4^xii	1.1066 (12)
N2—C5^xii	1.94 (3)	C3—C3^viii	1.28 (4)
N2—H2A	0.9000	C3—N2^xi	1.51 (3)
C5—N1^xi	0.564 (15)	C3—C3^xi	1.54 (4)
C5—C5^xii	0.88 (4)	C3—C5^viii	1.8149 (12)
C5—C4^xi	0.921 (8)	C3—N2^xii	1.92 (3)
C5—N1^viii	1.058 (10)	C3—C5^xi	2.012 (15)
C5—N1^xii	1.1021	C3—H3A	0.9600
C5—C4^viii	1.290 (8)
O1^i—Mn1—O1^ii	89.999 (1)	C5^xi—C5—N2^xii	62.6 (6)
O1^i—Mn1—O1	179.9 (3)	C3^viii—C5—N2^xii	47.2 (10)
O1^ii—Mn1—O1	90.001 (1)	N1^xi—C5—H5A	110.8
O1^i—Mn1—O1^iii	90.001 (2)	C5^xii—C5—H5A	102.1
O1^ii—Mn1—O1^iii	179.9 (3)	C4^xi—C5—H5A	102.8
O1—Mn1—O1^iii	90.000 (1)	N1^viii—C5—H5A	111.7
O1^i—Mn1—O2^ii	81.7 (6)	N1^xii—C5—H5A	125.7
O1^ii—Mn1—O2^ii	87.1 (13)	C4^viii—C5—H5A	108.0
O1—Mn1—O2^ii	98.2 (6)	N1—C5—H5A	126.0
O1^iii—Mn1—O2^ii	93.0 (12)	N2—C5—H5A	126.0
O1^i—Mn1—O2^iii	98.2 (6)	C5^viii—C5—H5A	140.2
O1^ii—Mn1—O2^iii	93.0 (12)	C5^xi—C5—H5A	140.5
O1—Mn1—O2^iii	81.7 (6)	C3^viii—C5—H5A	131.5
O1^iii—Mn1—O2^iii	87.1 (13)	N2^xii—C5—H5A	130.1
O2^ii—Mn1—O2^iii	17.6 (6)	C5^xi—N1—N1^viii	149.9 (11)
O1^i—Mn1—O2	93.0 (12)	C5^xi—N1—N1^xii	88 (4)
O1^ii—Mn1—O2	81.7 (6)	N1^viii—N1—N1^xii	90.0
O1—Mn1—O2	87.1 (13)	C5^xi—N1—C5^viii	56 (4)
O1^iii—Mn1—O2	98.2 (6)	N1^viii—N1—C5^viii	117.4 (7)
O2^ii—Mn1—O2	167.6 (4)	N1^xii—N1—C5^viii	32.2 (6)
O2^iii—Mn1—O2	167.6 (4)	C5^xi—N1—N1^xi	116 (4)
O1^i—Mn1—O2^i	87.1 (13)	N1^viii—N1—N1^xi	57.6 (16)
O1^ii—Mn1—O2^i	98.2 (6)	N1^xii—N1—N1^xi	32.4 (16)
O1—Mn1—O2^i	93.0 (12)	C5^viii—N1—N1^xi	62.1 (13)
O1^iii—Mn1—O2^i	81.7 (6)	C5^xi—N1—C5^xii	135.0 (11)
O2^ii—Mn1—O2^i	167.6 (4)	N1^viii—N1—C5^xii	14.88 (13)
O2^iii—Mn1—O2^i	167.6 (4)	N1^xii—N1—C5^xii	89 (2)
O2—Mn1—O2^i	17.6 (6)	C5^viii—N1—C5^xii	111 (2)
O1^i—Mn1—Mn1^iv	69.39 (8)	N1^xi—N1—C5^xii	58.1 (12)
O1^ii—Mn1—Mn1^iv	20.60 (8)	C5^xi—N1—C5	122 (3)
O1—Mn1—Mn1^iv	110.60 (8)	N1^viii—N1—C5	41.4
O1^iii—Mn1—Mn1^iv	159.40 (8)	N1^xii—N1—C5	50.9
O2^ii—Mn1—Mn1^iv	84.3 (10)	C5^viii—N1—C5	76.0 (7)
O2^iii—Mn1—Mn1^iv	95.7 (10)	N1^xi—N1—C5	20.9 (13)
O2—Mn1—Mn1^iv	83.3 (9)	C5^xii—N1—C5	38 (2)
O2^i—Mn1—Mn1^iv	96.7 (9)	C5^xi—N1—C4	22.0 (11)
O1^i—Mn1—Mn1^v	110.61 (8)	N1^viii—N1—C4	128.0
O1^ii—Mn1—Mn1^v	159.40 (8)	N1^xii—N1—C4	90.3
O1—Mn1—Mn1^v	69.40 (8)	C5^viii—N1—C4	60.7 (4)
O1^iii—Mn1—Mn1^v	20.60 (8)	N1^xi—N1—C4	109.6 (9)
O2^ii—Mn1—Mn1^v	95.7 (10)	C5^xii—N1—C4	113.2
O2^iii—Mn1—Mn1^v	84.3 (10)	C5—N1—C4	108.0
O2—Mn1—Mn1^v	96.7 (9)	C5^xi—N1—N2^xi	53.2 (18)
O2^i—Mn1—Mn1^v	83.3 (9)	N1^viii—N1—N2^xi	99.3 (10)
Mn1^iv—Mn1—Mn1^v	180.0	N1^xii—N1—N2^xi	108.4 (11)
O1^i—Mn1—Mn1^vi	159.39 (8)	C5^viii—N1—N2^xi	86.7 (10)
O1^ii—Mn1—Mn1^vi	69.40 (8)	N1^xi—N1—N2^xi	110.6 (11)
O1—Mn1—Mn1^vi	20.60 (8)	C5^xii—N1—N2^xi	85.4 (11)
O1^iii—Mn1—Mn1^vi	110.60 (8)	C5—N1—N2^xi	97.7 (11)
O2^ii—Mn1—Mn1^vi	96.7 (9)	C4—N1—N2^xi	33.1 (9)
O2^iii—Mn1—Mn1^vi	83.3 (9)	C5^xi—N1—C4^xii	38 (3)
O2—Mn1—Mn1^vi	84.3 (10)	N1^viii—N1—C4^xii	121.2 (4)
O2^i—Mn1—Mn1^vi	95.7 (10)	N1^xii—N1—C4^xii	57.1 (11)
Mn1^iv—Mn1—Mn1^vi	90.0	C5^viii—N1—C4^xii	29.0 (9)
Mn1^v—Mn1—Mn1^vi	90.0	N1^xi—N1—C4^xii	79.5 (14)
O1^i—Mn1—Mn1^vii	20.61 (8)	C5^xii—N1—C4^xii	108.8 (13)
O1^ii—Mn1—Mn1^vii	110.60 (8)	C5—N1—C4^xii	85.1 (7)
O1—Mn1—Mn1^vii	159.40 (8)	C4—N1—C4^xii	33.2 (11)
O1^iii—Mn1—Mn1^vii	69.40 (8)	N2^xi—N1—C4^xii	57.9 (7)
O2^ii—Mn1—Mn1^vii	83.3 (9)	C5^xi—N1—C4^viii	112.3 (7)
O2^iii—Mn1—Mn1^vii	96.7 (9)	N1^viii—N1—C4^viii	37.6 (5)
O2—Mn1—Mn1^vii	95.7 (10)	N1^xii—N1—C4^viii	90.3
O2^i—Mn1—Mn1^vii	84.3 (10)	C5^viii—N1—C4^viii	101.9 (6)
Mn1^iv—Mn1—Mn1^vii	90.0	N1^xi—N1—C4^viii	65.1 (11)
Mn1^v—Mn1—Mn1^vii	90.0	C5^xii—N1—C4^viii	22.8 (5)
Mn1^vi—Mn1—Mn1^vii	180.0	C5—N1—C4^viii	44.5 (2)
O1^viii—C1—O1	137.0 (7)	C4—N1—C4^viii	90.4 (5)
O1^viii—C1—H1	111.5	N2^xi—N1—C4^viii	63.6 (7)
O1—C1—H1	111.5	C4^xii—N1—C4^viii	90.5 (4)
C1—O1—Mn1	138.2 (4)	C5^xi—N1—N2^xii	88.7 (15)
O2^i—C2—O2	34.3 (12)	N1^viii—N1—N2^xii	63.0 (9)
O2^i—C2—O2^ix	155.9 (8)	N1^xii—N1—N2^xii	106.5 (9)
O2—C2—O2^ix	156.0 (8)	C5^viii—N1—N2^xii	103.0 (10)
O2^i—C2—O2^x	155.9 (8)	N1^xi—N1—N2^xii	89.8 (10)
O2—C2—O2^x	156.0 (8)	C5^xii—N1—N2^xii	49.3 (5)
O2^ix—C2—O2^x	34.3 (12)	C5—N1—N2^xii	70.7 (9)
O2^i—C2—H2	81.2	C4—N1—N2^xii	67.3 (9)
O2—C2—H2	98.8	N2^xi—N1—N2^xii	36.3 (11)
O2^ix—C2—H2	75.4	C4^xii—N1—N2^xii	80.3 (7)
O2^x—C2—H2	104.6	C4^viii—N1—N2^xii	28.8 (7)
O2^i—O2—C2	72.9 (6)	C5^xi—N1—H1A	109.6
O2^i—O2—Mn1	81.2 (3)	N1^viii—N1—H1A	96.5
C2—O2—Mn1	154.1 (9)	N1^xii—N1—H1A	122.1
C3^viii—N2—C4^xi	82 (2)	C5^viii—N1—H1A	128.4
C3^viii—N2—N2^viii	96 (2)	N1^xi—N1—H1A	120.7
C4^xi—N2—N2^viii	131.0 (15)	C5^xii—N1—H1A	109.4
C3^viii—N2—C3	64 (3)	C5—N1—H1A	126.0
C4^xi—N2—C3	120.8 (19)	C4—N1—H1A	126.0
N2^viii—N2—C3	32.4 (7)	N2^xi—N1—H1A	126.8
C3^viii—N2—C5	108.6 (5)	C4^xii—N1—H1A	141.7
C4^xi—N2—C5	39.6 (7)	C4^viii—N1—H1A	126.9
N2^viii—N2—C5	98.8 (5)	N2^xii—N1—H1A	127.5
C3—N2—C5	108.0	N2^xi—C4—C5^xi	101 (2)
C3^viii—N2—C3^xi	22.8 (5)	N2^xi—C4—C4^xii	125 (2)
C4^xi—N2—C3^xi	66.6 (16)	C5^xi—C4—C4^xii	89 (2)
N2^viii—N2—C3^xi	93.0 (12)	N2^xi—C4—C3^xii	43.1 (9)
C3—N2—C3^xi	63.3 (15)	C5^xi—C4—C3^xii	126.7 (11)
C5—N2—C3^xi	86.8 (5)	C4^xii—C4—C3^xii	88 (2)
C3^viii—N2—C4^viii	60.2 (9)	N2^xi—C4—C5^viii	121.5 (18)
C4^xi—N2—C4^viii	27.8 (15)	C5^xi—C4—C5^viii	43 (2)
N2^viii—N2—C4^viii	111.7 (8)	C4^xii—C4—C5^viii	45.6 (2)
C3—N2—C4^viii	93.7 (8)	C3^xii—C4—C5^viii	114 (2)
C5—N2—C4^viii	49.36 (11)	N2^xi—C4—C3	77 (2)
C3^xi—N2—C4^viii	41.0 (6)	C5^xi—C4—C3	116.8 (17)
C3^viii—N2—N1^xi	114.7 (15)	C4^xii—C4—C3	51.2
C4^xi—N2—N1^xi	57.5 (11)	C3^xii—C4—C3	37 (2)
N2^viii—N2—N1^xi	80.7 (7)	C5^viii—C4—C3	83.9 (2)
C3—N2—N1^xi	94.6 (8)	N2^xi—C4—N1	89.4 (17)
C5—N2—N1^xi	18.5 (8)	C5^xi—C4—N1	13.2 (12)
C3^xi—N2—N1^xi	91.9 (16)	C4^xii—C4—N1	89.7
C4^viii—N2—N1^xi	61.2 (15)	C3^xii—C4—N1	113.6
C3^viii—N2—C4^xii	93 (3)	C5^viii—C4—N1	45.6 (4)
C4^xi—N2—C4^xii	109.1 (17)	C3—C4—N1	108.0
N2^viii—N2—C4^xii	21.9 (6)	N2^xi—C4—N2^viii	97 (3)
C3—N2—C4^xii	36.5 (3)	C5^xi—C4—N2^viii	94 (2)
C5—N2—C4^xii	79.0 (4)	C4^xii—C4—N2^viii	27.6 (8)
C3^xi—N2—C4^xii	82.5 (16)	C3^xii—C4—N2^viii	63 (2)
C4^viii—N2—C4^xii	91.4 (10)	C5^viii—C4—N2^viii	56.6 (5)
N1^xi—N2—C4^xii	62.1 (7)	C3—C4—N2^viii	27.9 (5)
C3^viii—N2—N1^xii	114.2 (17)	N1—C4—N2^viii	89.3 (5)
C4^xi—N2—N1^xii	73.6 (12)	N2^xi—C4—N1^xii	107.3 (12)
N2^viii—N2—N1^xii	63.0 (5)	C5^xi—C4—N1^xii	33.8 (11)
C3—N2—N1^xii	79.1 (4)	C4^xii—C4—N1^xii	57.1 (12)
C5—N2—N1^xii	36.1 (3)	C3^xii—C4—N1^xii	108.6 (13)
C3^xi—N2—N1^xii	92.7 (15)	C5^viii—C4—N1^xii	15.4 (11)
C4^viii—N2—N1^xii	71.3 (13)	C3—C4—N1^xii	85.5 (8)
N1^xi—N2—N1^xii	17.8 (6)	N1—C4—N1^xii	32.6 (12)
C4^xii—N2—N1^xii	44.8 (2)	N2^viii—C4—N1^xii	60.8 (10)
C3^viii—N2—C3^xii	49 (2)	N2^xi—C4—N1^viii	77.6 (18)
C4^xi—N2—C3^xii	97 (2)	C5^xi—C4—N1^viii	27.6 (8)
N2^viii—N2—C3^xii	51.4 (7)	C4^xii—C4—N1^viii	89.7
C3—N2—C3^xii	24.1 (9)	C3^xii—C4—N1^viii	99.3 (4)
C5—N2—C3^xii	93.3 (6)	C5^viii—C4—N1^viii	50.5 (5)
C3^xi—N2—C3^xii	41.6 (16)	C3—C4—N1^viii	97.1 (3)
C4^viii—N2—C3^xii	69.8 (9)	N1—C4—N1^viii	14.4 (4)
N1^xi—N2—C3^xii	85.4 (10)	N2^viii—C4—N1^viii	82.8 (6)
C4^xii—N2—C3^xii	44.1 (6)	N1^xii—C4—N1^viii	35.3 (11)
N1^xii—N2—C3^xii	74.6 (8)	N2^xi—C4—N2^xii	27.0 (11)
C3^viii—N2—C5^xii	84.4 (9)	C5^xi—C4—N2^xii	80.8 (17)
C4^xi—N2—C5^xii	34.6 (14)	C4^xii—C4—N2^xii	106.3 (9)
N2^viii—N2—C5^xii	96.4 (5)	C3^xii—C4—N2^xii	49.7 (5)
C3—N2—C5^xii	92.7 (6)	C5^viii—C4—N2^xii	94.5 (10)
C5—N2—C5^xii	24.8 (9)	C3—C4—N2^xii	70.4 (10)
C3^xi—N2—C5^xii	62.1 (9)	N1—C4—N2^xii	67.9 (10)
C4^viii—N2—C5^xii	28.3 (9)	N2^viii—C4—N2^xii	80.7 (13)
N1^xi—N2—C5^xii	33.0 (7)	N1^xii—C4—N2^xii	80.5 (6)
C4^xii—N2—C5^xii	74.5 (8)	N1^viii—C4—N2^xii	54.3 (11)
N1^xii—N2—C5^xii	43.8 (6)	N2^xi—C4—H4A	101.6
C3^xii—N2—C5^xii	73.0 (8)	C5^xi—C4—H4A	116.4
C3^viii—N2—H2A	94.1	C4^xii—C4—H4A	122.6
C4^xi—N2—H2A	102.9	C3^xii—C4—H4A	109.8
N2^viii—N2—H2A	126.0	C5^viii—C4—H4A	133.2
C3—N2—H2A	124.6	C3—C4—H4A	126.0
C5—N2—H2A	127.4	N1—C4—H4A	126.0
C3^xi—N2—H2A	113.5	N2^viii—C4—H4A	139.7
C4^viii—N2—H2A	119.2	N1^xii—C4—H4A	141.6
N1^xi—N2—H2A	139.4	N1^viii—C4—H4A	136.0
C4^xii—N2—H2A	147.9	N2^xii—C4—H4A	127.2
N1^xii—N2—H2A	150.2	N2^viii—C3—C3^xii	136.9 (6)
C3^xii—N2—H2A	134.6	N2^viii—C3—C4^xii	55.3 (19)
C5^xii—N2—H2A	137.4	C3^xii—C3—C4^xii	91.9 (19)
N1^xi—C5—C5^xii	92 (5)	N2^viii—C3—C3^viii	84 (2)
N1^xi—C5—C4^xi	144.8 (18)	C3^xii—C3—C3^viii	90.0
C5^xii—C5—C4^xi	91 (2)	C4^xii—C3—C3^viii	118.3
N1^xi—C5—N1^viii	59 (5)	N2^viii—C3—N2	52 (2)
C5^xii—C5—N1^viii	32.2 (8)	C3^xii—C3—N2	113.2
C4^xi—C5—N1^viii	117 (2)	C4^xii—C3—N2	93.9 (8)
N1^xi—C5—N1^xii	15.2 (9)	C3^viii—C3—N2	32.4
C5^xii—C5—N1^xii	91 (2)	N2^viii—C3—C4	91.9 (15)
C4^xi—C5—N1^xii	129.7 (11)	C3^xii—C3—C4	51.2
N1^viii—C5—N1^xii	60 (2)	C4^xii—C3—C4	40.7 (19)
N1^xi—C5—C4^viii	127 (4)	C3^viii—C3—C4	111.7
C5^xii—C5—C4^viii	45.6 (4)	N2—C3—C4	108.0
C4^xi—C5—C4^viii	46 (2)	N2^viii—C3—N2^xi	116.6 (13)
N1^viii—C5—C4^viii	73.7 (5)	C3^xii—C3—N2^xi	20.3 (9)
N1^xii—C5—C4^viii	118 (2)	C4^xii—C3—N2^xi	76 (2)
N1^xi—C5—N1	43 (4)	C3^viii—C3—N2^xi	87.0 (11)
C5^xii—C5—N1	50.9	N2—C3—N2^xi	101.5 (10)
C4^xi—C5—N1	120.8 (18)	C4—C3—N2^xi	36.5 (11)
N1^viii—C5—N1	21.2 (10)	N2^viii—C3—C3^xi	109 (2)
N1^xii—C5—N1	40 (2)	C3^xii—C3—C3^xi	56.2 (15)
C4^viii—C5—N1	85.0 (9)	C4^xii—C3—C3^xi	114.3 (12)
N1^xi—C5—N2	108 (2)	C3^viii—C3—C3^xi	33.8 (15)
C5^xii—C5—N2	112.6	N2—C3—C3^xi	61.1 (13)
C4^xi—C5—N2	39.5 (16)	C4—C3—C3^xi	87.6 (11)
N1^viii—C5—N2	119.9 (5)	N2^xi—C3—C3^xi	55.6 (9)
N1^xii—C5—N2	94.6 (8)	N2^viii—C3—C5^viii	47.9 (12)
C4^viii—C5—N2	74.0 (3)	C3^xii—C3—C5^viii	90.4
N1—C5—N2	108.0	C4^xii—C3—C5^viii	24.0 (5)
N1^xi—C5—C5^viii	30.1 (9)	C3^viii—C3—C5^viii	94.3 (5)
C5^xii—C5—C5^viii	90.0	N2—C3—C5^viii	72.4 (4)
C4^xi—C5—C5^viii	114.8 (11)	C4—C3—C5^viii	45.0 (2)
N1^viii—C5—C5^viii	62.6 (10)	N2^xi—C3—C5^viii	70.7 (10)
N1^xii—C5—C5^viii	14.88 (11)	C3^xi—C3—C5^viii	93.8 (4)
C4^viii—C5—C5^viii	107.5 (12)	N2^viii—C3—N2^xii	106.9 (13)
N1—C5—C5^viii	41.4	C3^xii—C3—N2^xii	42.7 (9)
N2—C5—C5^viii	81.2	C4^xii—C3—N2^xii	94.8 (16)
N1^xi—C5—C5^xi	42 (3)	C3^viii—C3—N2^xii	51.4 (8)
C5^xii—C5—C5^xi	60.4 (11)	N2—C3—N2^xii	70.4 (9)
C4^xi—C5—C5^xi	112.2 (15)	C4—C3—N2^xii	65.5 (8)
N1^viii—C5—C5^xi	35.1 (11)	N2^xi—C3—N2^xii	35.5 (11)
N1^xii—C5—C5^xi	33.5 (13)	C3^xi—C3—N2^xii	22.1 (6)
C4^viii—C5—C5^xi	85.2 (11)	C5^viii—C3—N2^xii	77.6 (8)
N1—C5—C5^xi	15.5 (7)	N2^viii—C3—C5^xi	73.4 (12)
N2—C5—C5^xi	93.3 (4)	C3^xii—C3—C5^xi	64.5 (9)
C5^viii—C5—C5^xi	29.6 (11)	C4^xii—C3—C5^xi	35.9 (10)
N1^xi—C5—C3^viii	115.8 (14)	C3^viii—C3—C5^xi	93.9 (6)
C5^xii—C5—C3^viii	89.6	N2—C3—C5^xi	84.3 (6)
C4^xi—C5—C3^viii	29.2 (5)	C4—C3—C5^xi	24.1 (7)
N1^viii—C5—C3^viii	103.0 (6)	N2^xi—C3—C5^xi	44.8 (8)
N1^xii—C5—C3^viii	100.5 (11)	C3^xi—C3—C5^xi	79.5 (7)
C4^viii—C5—C3^viii	51.1 (4)	C5^viii—C3—C5^xi	26.0 (9)
N1—C5—C3^viii	97.9 (8)	N2^xii—C3—C5^xi	58.9 (7)
N2—C5—C3^viii	23.5 (2)	N2^viii—C3—H3A	120.0
C5^viii—C5—C3^viii	85.7 (11)	C3^xii—C3—H3A	101.5
C5^xi—C5—C3^viii	86.0 (10)	C4^xii—C3—H3A	126.0
N1^xi—C5—N2^xii	105 (3)	C3^viii—C3—H3A	113.8
C5^xii—C5—N2^xii	42.6 (10)	N2—C3—H3A	126.0
C4^xi—C5—N2^xii	57.3 (18)	C4—C3—H3A	126.0
N1^viii—C5—N2^xii	60.2 (9)	N2^xi—C3—H3A	120.9
N1^xii—C5—N2^xii	94.2 (16)	C3^xi—C3—H3A	116.5
C4^viii—C5—N2^xii	23.9 (9)	C5^viii—C3—H3A	149.1
N1—C5—N2^xii	65.5 (8)	N2^xii—C3—H3A	129.6
N2—C5—N2^xii	70.0 (10)	C5^xi—C3—H3A	149.5
C5^viii—C5—N2^xii	83.6 (7)

Symmetry codes: (i) −x+1, −y+1, z; (ii) −y+1, x, −z+1; (iii) y, −x+1, −z+1; (iv) −x+3/2, y+1/2, −z+1; (v) −x+1/2, y−1/2, −z+1; (vi) −x+3/2, y−1/2, −z+1; (vii) −x+1/2, y+1/2, −z+1; (viii) y+1/2, x−1/2, z; (ix) −y+1, x, −z+2; (x) y, −x+1, −z+2; (xi) −x+1, −y, z; (xii) −y+1/2, −x+1/2, z.