Bis(9-amino-acridinium) bis-(pyridine-2,6-dicarboxyl-ato-κO,N,O)manganate(II) trihydrate.

The asymmetric unit of the title compound, (C(13)H(11)N(2))(2)[Mn(C(7)H(3)NO(4))(2)]·3H(2)O, consists of a discrete mononuclear [Mn(2,6-pydc)(2)](2-) anionic complex (2,6-pydc is pyridine-2,6-dicarboxyl-ate) associated with two 9-amino-acridinium counter-ions for neutralization of charge and three uncoordin-ated water mol-ecules. The Mn(II) atom is six-coordinated by (2,6-pydc)(2-) anions in a tridentate fashion and is at the centre of a distorted octa-hedron formed by the MnO(4)N(2) bonding set. In the crystal, various inter-molecular inter-actions between different moieties can be found, such as different kinds of hydrogen bonds, offset or slipped π-π [centroid-centroid distances in the range 3.3704 (12) to 3.8674 (13)Å] and C=O⋯π [3.563 Å] inter-actions, which lead to the formation of a three-dimensional supra-molecular network.

Related literature

For complexes derived from Mn(II) atoms and pyridine-2,6-dicarboxlic acid, see: Aghabozorg et al. (2010 ▶, 2011 ▶). For similar compounds, see: Mirzaei et al. (2011 ▶); Derikvand et al. (2010 ▶); Eshtiagh-Hosseini, Aghabozorg et al. (2010 ▶); Eshtiagh-Hosseini, Alfi et al. (2010 ▶); Eshtiagh-Hosseini, Gschwind et al. (2010 ▶); Eshtiagh-Hosseini, Yousefi et al. (2010 ▶) ; Mei & Wolf (2004 ▶); MacDonald et al. (2000 ▶); Aghabozorg et al. (2008 ▶).

Experimental

Crystal data

(C13H11N2)2[Mn(C7H3NO4)2]·3H2O

M = 829.67

Triclinic,

a = 10.8202 (4) Å

b = 13.5186 (5) Å

c = 13.9844 (5) Å

α = 102.351 (3)°

β = 103.466 (3)°

γ = 104.868 (3)°

V = 1839.42 (12) Å3

Z = 2

Cu Kα radiation

μ = 3.55 mm−1

T = 293 K

0.20 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Nova diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.538, T max = 0.718

17948 measured reflections

7606 independent reflections

6791 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.114

S = 1.08

7606 reflections

572 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek; 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036981/om2447sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036981/om2447Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C13H11N2)2[Mn(C7H3NO4)2]·3H2O	Z = 2
Mr = 829.67	F(000) = 858
Triclinic, P1	Dx = 1.498 Mg m−3
a = 10.8202 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 13.5186 (5) Å	Cell parameters from 11391 reflections
c = 13.9844 (5) Å	θ = 3.4–75.9°
α = 102.351 (3)°	µ = 3.55 mm−1
β = 103.466 (3)°	T = 293 K
γ = 104.868 (3)°	Prism, yellow
V = 1839.42 (12) Å3	0.20 × 0.12 × 0.10 mm

Oxford Diffraction Xcalibur Nova diffractometer	7606 independent reflections
Radiation source: Enhance (Cu) X-ray Source	6791 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 10.4323 pixels mm-1	θmax = 76.1°, θmin = 3.4°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→16
Tmin = 0.538, Tmax = 0.718	l = −17→12
17948 measured reflections

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0654P)2 + 0.2228P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.038	(Δ/σ)max < 0.001
wR(F2) = 0.114	Δρmax = 0.25 e Å−3
S = 1.08	Δρmin = −0.31 e Å−3
7606 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
572 parameters	Extinction coefficient: 0.00077 (19)
9 restraints

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Mn1	0.64063 (3)	0.25673 (2)	0.40959 (2)	0.04394 (10)
O1	0.44381 (15)	0.20160 (11)	0.28655 (10)	0.0518 (3)
O2	0.26457 (17)	0.05818 (15)	0.19184 (12)	0.0669 (4)
O3	0.79344 (15)	0.20184 (11)	0.50812 (11)	0.0535 (3)
O4	0.84704 (14)	0.06026 (11)	0.53782 (11)	0.0529 (3)
N1	0.56149 (14)	0.08499 (11)	0.37675 (10)	0.0360 (3)
C1	0.43716 (17)	0.03411 (14)	0.31346 (11)	0.0377 (3)
C2	0.37476 (18)	−0.07366 (15)	0.29815 (13)	0.0451 (4)
H2	0.2881	−0.1084	0.2535	0.054*
C3	0.44423 (19)	−0.12868 (14)	0.35074 (14)	0.0447 (4)
H3	0.4042	−0.2009	0.3422	0.054*
C4	0.57380 (18)	−0.07533 (13)	0.41616 (12)	0.0404 (3)
H4	0.6221	−0.1111	0.4517	0.048*
C5	0.62957 (16)	0.03236 (13)	0.42732 (11)	0.0356 (3)
C6	0.37496 (19)	0.10379 (16)	0.25923 (13)	0.0444 (4)
C7	0.76853 (18)	0.10354 (14)	0.49707 (12)	0.0407 (3)
O5	0.54528 (17)	0.30295 (10)	0.52945 (11)	0.0543 (3)
O6	0.52901 (17)	0.43798 (12)	0.64314 (11)	0.0581 (4)
O7	0.76616 (18)	0.31403 (12)	0.31869 (11)	0.0609 (4)
O8	0.91391 (19)	0.45506 (14)	0.30369 (13)	0.0657 (4)
N2	0.71790 (16)	0.42813 (11)	0.47040 (10)	0.0416 (3)
C8	0.67712 (19)	0.47705 (14)	0.54468 (12)	0.0425 (4)
C9	0.7249 (2)	0.58709 (15)	0.58508 (14)	0.0528 (4)
H9	0.6945	0.6213	0.6354	0.063*
C10	0.8191 (3)	0.64496 (16)	0.54865 (17)	0.0605 (5)
H10	0.8542	0.719	0.5757	0.073*
C11	0.8613 (2)	0.59309 (16)	0.47198 (16)	0.0567 (5)
H11	0.9251	0.6313	0.4474	0.068*
C12	0.8062 (2)	0.48295 (14)	0.43303 (13)	0.0453 (4)
C13	0.5753 (2)	0.40030 (14)	0.57584 (12)	0.0435 (4)
C14	0.8333 (2)	0.41252 (16)	0.34409 (14)	0.0493 (4)
N3	0.14305 (15)	0.10470 (12)	0.02023 (11)	0.0411 (3)
H3N	0.181 (2)	0.0906 (19)	0.0761 (19)	0.050 (6)*
N4	−0.01292 (19)	0.18331 (17)	−0.24082 (13)	0.0553 (4)
H4A	−0.029 (3)	0.141 (2)	−0.300 (2)	0.065 (7)*
H4B	−0.029 (3)	0.248 (2)	−0.236 (2)	0.073 (8)*
C15	0.03526 (17)	0.15624 (15)	−0.15714 (13)	0.0428 (4)
C16	0.05018 (16)	0.22265 (14)	−0.05743 (13)	0.0397 (3)
C17	0.01312 (18)	0.31667 (16)	−0.04250 (15)	0.0475 (4)
H17	−0.0232	0.3373	−0.0991	0.057*
C18	0.0302 (2)	0.37710 (17)	0.05400 (17)	0.0525 (4)
H18	0.0065	0.4391	0.0627	0.063*
C19	0.0832 (2)	0.34669 (18)	0.14030 (15)	0.0539 (4)
H19	0.0924	0.3879	0.2056	0.065*
C20	0.12132 (19)	0.25721 (16)	0.12938 (14)	0.0468 (4)
H20	0.1576	0.238	0.187	0.056*
C21	0.10539 (16)	0.19399 (14)	0.03001 (12)	0.0389 (3)
C22	0.12958 (16)	0.03901 (14)	−0.07291 (13)	0.0414 (3)
C23	0.1714 (2)	−0.05174 (16)	−0.07770 (16)	0.0500 (4)
H23	0.2069	−0.0672	−0.0175	0.06*
C24	0.1597 (2)	−0.11733 (17)	−0.17090 (18)	0.0589 (5)
H24	0.1881	−0.177	−0.1737	0.071*
C25	0.1055 (2)	−0.09545 (19)	−0.26169 (17)	0.0628 (5)
H25	0.0982	−0.1406	−0.3246	0.075*
C26	0.0634 (2)	−0.00866 (19)	−0.25909 (15)	0.0586 (5)
H26	0.0271	0.0046	−0.3204	0.07*
C27	0.07390 (17)	0.06234 (15)	−0.16393 (13)	0.0445 (4)
N5	0.66357 (16)	0.67352 (14)	1.11671 (11)	0.0465 (3)
H5N	0.677 (3)	0.680 (2)	1.180 (2)	0.073 (8)*
N6	0.54690 (18)	0.61190 (14)	0.80226 (11)	0.0475 (3)
H6A	0.556 (2)	0.5560 (19)	0.7592 (19)	0.053 (6)*
H6B	0.523 (3)	0.661 (2)	0.7753 (19)	0.060 (7)*
C28	0.58159 (16)	0.62845 (13)	0.90294 (12)	0.0375 (3)
C29	0.56236 (17)	0.71798 (13)	0.96725 (12)	0.0393 (3)
C30	0.4940 (2)	0.78319 (15)	0.92699 (14)	0.0466 (4)
H30	0.4611	0.7694	0.8562	0.056*
C31	0.4756 (2)	0.86606 (17)	0.99064 (18)	0.0569 (5)
H31	0.4295	0.9079	0.963	0.068*
C32	0.5257 (3)	0.88850 (18)	1.09755 (18)	0.0627 (6)
H32	0.5154	0.9468	1.1403	0.075*
C33	0.5889 (2)	0.82645 (17)	1.13944 (15)	0.0559 (5)
H33	0.6208	0.8416	1.2105	0.067*
C34	0.60641 (17)	0.73838 (15)	1.07472 (13)	0.0424 (4)
C35	0.67653 (16)	0.58457 (15)	1.05882 (13)	0.0424 (4)
C36	0.73090 (19)	0.51809 (18)	1.10862 (17)	0.0542 (5)
H36	0.7585	0.5358	1.18	0.065*
C37	0.7427 (2)	0.42785 (19)	1.05168 (19)	0.0594 (5)
H37	0.7766	0.3832	1.0846	0.071*
C38	0.7046 (2)	0.40105 (17)	0.94423 (19)	0.0584 (5)
H38	0.7144	0.3395	0.9065	0.07*
C39	0.65279 (19)	0.46540 (15)	0.89438 (15)	0.0476 (4)
H39	0.6283	0.4474	0.823	0.057*
C40	0.63637 (16)	0.55866 (14)	0.95048 (13)	0.0396 (3)
O9	0.88560 (18)	−0.13804 (14)	0.47029 (16)	0.0717 (4)
H9A	0.866 (3)	−0.0741 (19)	0.486 (3)	0.096 (11)*
H9B	0.971 (2)	−0.119 (3)	0.463 (3)	0.103 (12)*
O10	1.0899 (2)	0.63986 (16)	0.28914 (14)	0.0766 (5)
H10A	1.135 (3)	0.684 (2)	0.3551 (16)	0.087 (10)*
H10B	1.036 (3)	0.580 (2)	0.298 (3)	0.114 (13)*
O11	0.6811 (2)	0.69942 (17)	1.31723 (11)	0.0742 (5)
H11A	0.618 (3)	0.657 (2)	1.338 (3)	0.100 (11)*
H11B	0.744 (3)	0.750 (2)	1.3740 (19)	0.089 (10)*

	U11	U22	U33	U12	U13	U23
Mn1	0.0648 (2)	0.03080 (15)	0.03618 (15)	0.01615 (12)	0.01555 (12)	0.00863 (10)
O1	0.0674 (8)	0.0479 (7)	0.0453 (7)	0.0261 (6)	0.0124 (6)	0.0202 (6)
O2	0.0601 (9)	0.0752 (10)	0.0585 (8)	0.0199 (8)	−0.0034 (7)	0.0314 (8)
O3	0.0560 (8)	0.0393 (7)	0.0511 (7)	0.0095 (6)	0.0022 (6)	0.0079 (5)
O4	0.0479 (7)	0.0520 (7)	0.0527 (7)	0.0204 (6)	0.0020 (6)	0.0123 (6)
N1	0.0452 (7)	0.0343 (6)	0.0295 (6)	0.0150 (5)	0.0110 (5)	0.0090 (5)
C1	0.0442 (8)	0.0426 (8)	0.0285 (7)	0.0162 (7)	0.0117 (6)	0.0118 (6)
C2	0.0437 (9)	0.0473 (9)	0.0385 (8)	0.0089 (7)	0.0084 (7)	0.0120 (7)
C3	0.0532 (10)	0.0353 (8)	0.0447 (9)	0.0101 (7)	0.0160 (7)	0.0140 (7)
C4	0.0518 (9)	0.0385 (8)	0.0370 (8)	0.0207 (7)	0.0147 (7)	0.0146 (6)
C5	0.0426 (8)	0.0364 (8)	0.0303 (7)	0.0162 (6)	0.0126 (6)	0.0091 (6)
C6	0.0491 (9)	0.0548 (10)	0.0344 (7)	0.0223 (8)	0.0115 (7)	0.0180 (7)
C7	0.0457 (9)	0.0409 (8)	0.0348 (7)	0.0157 (7)	0.0103 (6)	0.0091 (6)
O5	0.0814 (10)	0.0353 (6)	0.0494 (7)	0.0152 (6)	0.0312 (7)	0.0112 (5)
O6	0.0752 (9)	0.0496 (8)	0.0451 (7)	0.0153 (7)	0.0266 (7)	0.0016 (6)
O7	0.0890 (11)	0.0468 (7)	0.0525 (8)	0.0196 (7)	0.0377 (8)	0.0110 (6)
O8	0.0794 (10)	0.0665 (10)	0.0610 (9)	0.0203 (8)	0.0370 (8)	0.0254 (7)
N2	0.0566 (8)	0.0335 (7)	0.0335 (6)	0.0140 (6)	0.0127 (6)	0.0090 (5)
C8	0.0561 (10)	0.0368 (8)	0.0304 (7)	0.0147 (7)	0.0081 (6)	0.0067 (6)
C9	0.0733 (13)	0.0380 (9)	0.0383 (8)	0.0150 (8)	0.0125 (8)	0.0021 (7)
C10	0.0792 (14)	0.0332 (9)	0.0544 (11)	0.0049 (9)	0.0154 (10)	0.0046 (8)
C11	0.0662 (12)	0.0426 (10)	0.0539 (11)	0.0062 (9)	0.0169 (9)	0.0143 (8)
C12	0.0567 (10)	0.0401 (9)	0.0375 (8)	0.0130 (7)	0.0112 (7)	0.0147 (7)
C13	0.0600 (10)	0.0402 (9)	0.0304 (7)	0.0182 (7)	0.0130 (7)	0.0089 (6)
C14	0.0649 (11)	0.0473 (10)	0.0409 (9)	0.0198 (8)	0.0193 (8)	0.0177 (7)
N3	0.0403 (7)	0.0457 (8)	0.0354 (7)	0.0127 (6)	0.0078 (5)	0.0137 (6)
N4	0.0621 (10)	0.0606 (10)	0.0367 (8)	0.0191 (8)	0.0042 (7)	0.0139 (7)
C15	0.0351 (8)	0.0483 (9)	0.0374 (8)	0.0065 (7)	0.0050 (6)	0.0123 (7)
C16	0.0316 (7)	0.0459 (9)	0.0396 (8)	0.0097 (6)	0.0087 (6)	0.0144 (7)
C17	0.0403 (8)	0.0532 (10)	0.0501 (9)	0.0169 (7)	0.0096 (7)	0.0198 (8)
C18	0.0466 (10)	0.0519 (10)	0.0625 (11)	0.0214 (8)	0.0195 (8)	0.0137 (9)
C19	0.0554 (11)	0.0572 (11)	0.0465 (9)	0.0188 (9)	0.0175 (8)	0.0066 (8)
C20	0.0484 (9)	0.0531 (10)	0.0375 (8)	0.0139 (8)	0.0130 (7)	0.0131 (7)
C21	0.0326 (7)	0.0431 (8)	0.0385 (8)	0.0083 (6)	0.0102 (6)	0.0125 (7)
C22	0.0359 (8)	0.0415 (8)	0.0418 (8)	0.0070 (6)	0.0107 (6)	0.0098 (7)
C23	0.0471 (9)	0.0464 (10)	0.0556 (10)	0.0140 (8)	0.0146 (8)	0.0152 (8)
C24	0.0576 (11)	0.0439 (10)	0.0700 (13)	0.0145 (9)	0.0218 (10)	0.0063 (9)
C25	0.0663 (13)	0.0557 (12)	0.0523 (11)	0.0120 (10)	0.0180 (9)	−0.0030 (9)
C26	0.0613 (12)	0.0601 (12)	0.0390 (9)	0.0110 (9)	0.0072 (8)	0.0027 (8)
C27	0.0390 (8)	0.0477 (9)	0.0383 (8)	0.0067 (7)	0.0080 (6)	0.0083 (7)
N5	0.0428 (7)	0.0589 (9)	0.0324 (7)	0.0093 (7)	0.0104 (6)	0.0122 (6)
N6	0.0635 (10)	0.0470 (8)	0.0335 (7)	0.0255 (7)	0.0120 (6)	0.0086 (6)
C28	0.0350 (7)	0.0380 (8)	0.0348 (7)	0.0078 (6)	0.0097 (6)	0.0074 (6)
C29	0.0392 (8)	0.0391 (8)	0.0360 (8)	0.0085 (6)	0.0124 (6)	0.0074 (6)
C30	0.0515 (10)	0.0445 (9)	0.0450 (9)	0.0162 (8)	0.0169 (7)	0.0119 (7)
C31	0.0651 (12)	0.0478 (10)	0.0647 (12)	0.0238 (9)	0.0276 (10)	0.0147 (9)
C32	0.0794 (15)	0.0491 (11)	0.0640 (12)	0.0218 (10)	0.0390 (11)	0.0054 (9)
C33	0.0649 (12)	0.0561 (11)	0.0404 (9)	0.0106 (9)	0.0237 (8)	0.0037 (8)
C34	0.0385 (8)	0.0474 (9)	0.0356 (8)	0.0063 (7)	0.0142 (6)	0.0069 (7)
C35	0.0317 (7)	0.0504 (9)	0.0428 (8)	0.0067 (6)	0.0102 (6)	0.0183 (7)
C36	0.0397 (9)	0.0676 (13)	0.0569 (11)	0.0109 (8)	0.0109 (8)	0.0333 (10)
C37	0.0427 (9)	0.0623 (12)	0.0828 (14)	0.0169 (9)	0.0170 (9)	0.0431 (11)
C38	0.0491 (10)	0.0470 (10)	0.0811 (14)	0.0169 (8)	0.0191 (10)	0.0219 (10)
C39	0.0438 (9)	0.0434 (9)	0.0532 (10)	0.0139 (7)	0.0122 (7)	0.0126 (8)
C40	0.0341 (7)	0.0402 (8)	0.0404 (8)	0.0076 (6)	0.0092 (6)	0.0111 (6)
O9	0.0588 (9)	0.0509 (9)	0.0911 (12)	0.0094 (7)	0.0181 (8)	0.0069 (8)
O10	0.0891 (13)	0.0703 (11)	0.0565 (9)	0.0100 (9)	0.0071 (8)	0.0260 (8)
O11	0.0774 (11)	0.0874 (12)	0.0363 (7)	−0.0017 (9)	0.0132 (7)	0.0133 (7)

Mn1—N2	2.1501 (14)	C18—H18	0.93
Mn1—N1	2.1622 (14)	C19—C20	1.365 (3)
Mn1—O7	2.1786 (15)	C19—H19	0.93
Mn1—O5	2.2254 (13)	C20—C21	1.413 (2)
Mn1—O1	2.2319 (15)	C20—H20	0.93
Mn1—O3	2.2780 (14)	C22—C23	1.406 (3)
O1—C6	1.263 (2)	C22—C27	1.412 (3)
O2—C6	1.243 (2)	C23—C24	1.368 (3)
O3—C7	1.254 (2)	C23—H23	0.93
O4—C7	1.249 (2)	C24—C25	1.395 (4)
N1—C1	1.333 (2)	C24—H24	0.93
N1—C5	1.338 (2)	C25—C26	1.360 (4)
C1—C2	1.385 (2)	C25—H25	0.93
C1—C6	1.519 (2)	C26—C27	1.425 (3)
C2—C3	1.387 (3)	C26—H26	0.93
C2—H2	0.93	N5—C34	1.351 (3)
C3—C4	1.387 (3)	N5—C35	1.358 (3)
C3—H3	0.93	N5—H5N	0.84 (3)
C4—C5	1.384 (2)	N6—C28	1.323 (2)
C4—H4	0.93	N6—H6A	0.90 (2)
C5—C7	1.520 (2)	N6—H6B	0.90 (3)
O5—C13	1.255 (2)	C28—C40	1.434 (2)
O6—C13	1.241 (2)	C28—C29	1.438 (2)
O7—C14	1.268 (3)	C29—C34	1.408 (2)
O8—C14	1.233 (3)	C29—C30	1.413 (3)
N2—C12	1.330 (2)	C30—C31	1.363 (3)
N2—C8	1.334 (2)	C30—H30	0.93
C8—C9	1.382 (3)	C31—C32	1.402 (3)
C8—C13	1.520 (3)	C31—H31	0.93
C9—C10	1.383 (3)	C32—C33	1.354 (4)
C9—H9	0.93	C32—H32	0.93
C10—C11	1.387 (3)	C33—C34	1.416 (3)
C10—H10	0.93	C33—H33	0.93
C11—C12	1.384 (3)	C35—C36	1.410 (3)
C11—H11	0.93	C35—C40	1.412 (2)
C12—C14	1.532 (3)	C36—C37	1.360 (4)
N3—C21	1.360 (2)	C36—H36	0.93
N3—C22	1.363 (2)	C37—C38	1.400 (3)
N3—H3N	0.88 (2)	C37—H37	0.93
N4—C15	1.331 (2)	C38—C39	1.373 (3)
N4—H4A	0.85 (3)	C38—H38	0.93
N4—H4B	0.93 (3)	C39—C40	1.412 (3)
C15—C27	1.426 (3)	C39—H39	0.93
C15—C16	1.436 (2)	O9—H9A	0.933 (18)
C16—C21	1.408 (2)	O9—H9B	0.926 (18)
C16—C17	1.417 (3)	O10—H10A	0.924 (18)
C17—C18	1.363 (3)	O10—H10B	0.922 (18)
C17—H17	0.93	O11—H11A	0.923 (18)
C18—C19	1.402 (3)	O11—H11B	0.914 (18)
N2—Mn1—N1	169.44 (5)	C18—C17—H17	119.7
N2—Mn1—O7	73.33 (5)	C16—C17—H17	119.7
N1—Mn1—O7	115.96 (5)	C17—C18—C19	120.64 (19)
N2—Mn1—O5	72.69 (5)	C17—C18—H18	119.7
N1—Mn1—O5	98.33 (5)	C19—C18—H18	119.7
O7—Mn1—O5	145.68 (5)	C20—C19—C18	120.60 (18)
N2—Mn1—O1	112.02 (5)	C20—C19—H19	119.7
N1—Mn1—O1	72.97 (5)	C18—C19—H19	119.7
O7—Mn1—O1	97.13 (6)	C19—C20—C21	119.58 (18)
O5—Mn1—O1	91.08 (6)	C19—C20—H20	120.2
N2—Mn1—O3	103.37 (5)	C21—C20—H20	120.2
N1—Mn1—O3	71.55 (5)	N3—C21—C16	120.66 (15)
O7—Mn1—O3	96.10 (6)	N3—C21—C20	118.95 (16)
O5—Mn1—O3	96.27 (6)	C16—C21—C20	120.38 (17)
O1—Mn1—O3	144.44 (5)	N3—C22—C23	119.67 (17)
C6—O1—Mn1	118.13 (11)	N3—C22—C27	119.93 (17)
C7—O3—Mn1	118.29 (11)	C23—C22—C27	120.40 (17)
C1—N1—C5	120.32 (14)	C24—C23—C22	120.0 (2)
C1—N1—Mn1	118.51 (11)	C24—C23—H23	120
C5—N1—Mn1	120.76 (11)	C22—C23—H23	120
N1—C1—C2	121.49 (15)	C23—C24—C25	120.5 (2)
N1—C1—C6	114.05 (15)	C23—C24—H24	119.7
C2—C1—C6	124.43 (16)	C25—C24—H24	119.7
C1—C2—C3	118.59 (16)	C26—C25—C24	120.59 (19)
C1—C2—H2	120.7	C26—C25—H25	119.7
C3—C2—H2	120.7	C24—C25—H25	119.7
C2—C3—C4	119.62 (16)	C25—C26—C27	121.0 (2)
C2—C3—H3	120.2	C25—C26—H26	119.5
C4—C3—H3	120.2	C27—C26—H26	119.5
C5—C4—C3	118.45 (15)	C22—C27—C26	117.47 (19)
C5—C4—H4	120.8	C22—C27—C15	119.44 (16)
C3—C4—H4	120.8	C26—C27—C15	123.06 (18)
N1—C5—C4	121.53 (15)	C34—N5—C35	122.46 (15)
N1—C5—C7	112.96 (14)	C34—N5—H5N	120 (2)
C4—C5—C7	125.51 (15)	C35—N5—H5N	117 (2)
O2—C6—O1	127.50 (17)	C28—N6—H6A	122.2 (15)
O2—C6—C1	116.80 (17)	C28—N6—H6B	120.0 (16)
O1—C6—C1	115.68 (15)	H6A—N6—H6B	117 (2)
O4—C7—O3	125.91 (17)	N6—C28—C40	121.98 (16)
O4—C7—C5	118.23 (16)	N6—C28—C29	119.49 (16)
O3—C7—C5	115.85 (15)	C40—C28—C29	118.52 (15)
C13—O5—Mn1	118.71 (12)	C34—C29—C30	118.19 (16)
C14—O7—Mn1	119.60 (12)	C34—C29—C28	119.07 (16)
C12—N2—C8	121.52 (16)	C30—C29—C28	122.64 (15)
C12—N2—Mn1	118.88 (12)	C31—C30—C29	120.82 (18)
C8—N2—Mn1	119.60 (12)	C31—C30—H30	119.6
N2—C8—C9	120.87 (18)	C29—C30—H30	119.6
N2—C8—C13	113.30 (15)	C30—C31—C32	120.3 (2)
C9—C8—C13	125.81 (17)	C30—C31—H31	119.9
C8—C9—C10	118.25 (19)	C32—C31—H31	119.9
C8—C9—H9	120.9	C33—C32—C31	120.89 (19)
C10—C9—H9	120.9	C33—C32—H32	119.6
C9—C10—C11	120.29 (18)	C31—C32—H32	119.6
C9—C10—H10	119.9	C32—C33—C34	119.79 (19)
C11—C10—H10	119.9	C32—C33—H33	120.1
C12—C11—C10	118.25 (19)	C34—C33—H33	120.1
C12—C11—H11	120.9	N5—C34—C29	120.45 (16)
C10—C11—H11	120.9	N5—C34—C33	119.60 (17)
N2—C12—C11	120.78 (18)	C29—C34—C33	119.95 (18)
N2—C12—C14	113.29 (16)	N5—C35—C36	118.89 (17)
C11—C12—C14	125.90 (18)	N5—C35—C40	120.82 (16)
O6—C13—O5	125.91 (18)	C36—C35—C40	120.29 (19)
O6—C13—C8	118.40 (16)	C37—C36—C35	119.61 (19)
O5—C13—C8	115.69 (15)	C37—C36—H36	120.2
O8—C14—O7	126.68 (19)	C35—C36—H36	120.2
O8—C14—C12	118.80 (18)	C36—C37—C38	121.07 (19)
O7—C14—C12	114.51 (16)	C36—C37—H37	119.5
C21—N3—C22	122.48 (15)	C38—C37—H37	119.5
C21—N3—H3N	118.6 (15)	C39—C38—C37	120.2 (2)
C22—N3—H3N	118.9 (15)	C39—C38—H38	119.9
C15—N4—H4A	119.1 (19)	C37—C38—H38	119.9
C15—N4—H4B	121.4 (18)	C38—C39—C40	120.57 (19)
H4A—N4—H4B	119 (2)	C38—C39—H39	119.7
N4—C15—C27	121.37 (17)	C40—C39—H39	119.7
N4—C15—C16	119.93 (18)	C39—C40—C35	118.27 (17)
C27—C15—C16	118.70 (16)	C39—C40—C28	123.25 (16)
C21—C16—C17	118.15 (16)	C35—C40—C28	118.48 (16)
C21—C16—C15	118.76 (16)	H9A—O9—H9B	105 (3)
C17—C16—C15	123.09 (16)	H10A—O10—H10B	104 (3)
C18—C17—C16	120.63 (18)	H11A—O11—H11B	108 (3)
N2—Mn1—O1—C6	−165.89 (13)	Mn1—O5—C13—O6	178.93 (16)
N1—Mn1—O1—C6	4.23 (13)	Mn1—O5—C13—C8	−0.7 (2)
O7—Mn1—O1—C6	119.25 (13)	N2—C8—C13—O6	−178.68 (17)
O5—Mn1—O1—C6	−94.15 (13)	C9—C8—C13—O6	0.3 (3)
O3—Mn1—O1—C6	8.22 (18)	N2—C8—C13—O5	1.0 (2)
N2—Mn1—O3—C7	173.32 (13)	C9—C8—C13—O5	179.98 (19)
N1—Mn1—O3—C7	2.96 (13)	Mn1—O7—C14—O8	175.59 (18)
O7—Mn1—O3—C7	−112.41 (14)	Mn1—O7—C14—C12	−5.7 (2)
O5—Mn1—O3—C7	99.67 (14)	N2—C12—C14—O8	−179.84 (19)
O1—Mn1—O3—C7	−1.07 (19)	C11—C12—C14—O8	2.1 (3)
N2—Mn1—N1—C1	112.5 (3)	N2—C12—C14—O7	1.3 (3)
O7—Mn1—N1—C1	−97.01 (12)	C11—C12—C14—O7	−176.8 (2)
O5—Mn1—N1—C1	81.29 (12)	N4—C15—C16—C21	−178.00 (17)
O1—Mn1—N1—C1	−7.29 (11)	C27—C15—C16—C21	1.5 (2)
O3—Mn1—N1—C1	175.16 (12)	N4—C15—C16—C17	1.4 (3)
N2—Mn1—N1—C5	−60.2 (4)	C27—C15—C16—C17	−179.12 (16)
O7—Mn1—N1—C5	90.30 (12)	C21—C16—C17—C18	−0.3 (3)
O5—Mn1—N1—C5	−91.40 (12)	C15—C16—C17—C18	−179.62 (17)
O1—Mn1—N1—C5	−179.98 (12)	C16—C17—C18—C19	−0.8 (3)
O3—Mn1—N1—C5	2.47 (11)	C17—C18—C19—C20	1.4 (3)
C5—N1—C1—C2	0.1 (2)	C18—C19—C20—C21	−0.9 (3)
Mn1—N1—C1—C2	−172.62 (12)	C22—N3—C21—C16	−0.1 (2)
C5—N1—C1—C6	−178.14 (13)	C22—N3—C21—C20	179.29 (16)
Mn1—N1—C1—C6	9.13 (17)	C17—C16—C21—N3	−179.84 (15)
N1—C1—C2—C3	0.3 (2)	C15—C16—C21—N3	−0.4 (2)
C6—C1—C2—C3	178.37 (16)	C17—C16—C21—C20	0.8 (2)
C1—C2—C3—C4	−0.6 (3)	C15—C16—C21—C20	−179.84 (16)
C2—C3—C4—C5	0.4 (3)	C19—C20—C21—N3	−179.59 (17)
C1—N1—C5—C4	−0.3 (2)	C19—C20—C21—C16	−0.2 (3)
Mn1—N1—C5—C4	172.30 (11)	C21—N3—C22—C23	179.56 (16)
C1—N1—C5—C7	−179.10 (13)	C21—N3—C22—C27	−0.4 (2)
Mn1—N1—C5—C7	−6.54 (17)	N3—C22—C23—C24	−179.19 (18)
C3—C4—C5—N1	0.0 (2)	C27—C22—C23—C24	0.8 (3)
C3—C4—C5—C7	178.68 (15)	C22—C23—C24—C25	−0.5 (3)
Mn1—O1—C6—O2	−179.12 (17)	C23—C24—C25—C26	−0.1 (4)
Mn1—O1—C6—C1	−1.0 (2)	C24—C25—C26—C27	0.3 (4)
N1—C1—C6—O2	173.11 (17)	N3—C22—C27—C26	179.45 (17)
C2—C1—C6—O2	−5.1 (3)	C23—C22—C27—C26	−0.5 (3)
N1—C1—C6—O1	−5.2 (2)	N3—C22—C27—C15	1.5 (2)
C2—C1—C6—O1	176.59 (16)	C23—C22—C27—C15	−178.46 (16)
Mn1—O3—C7—O4	172.80 (14)	C25—C26—C27—C22	0.0 (3)
Mn1—O3—C7—C5	−7.1 (2)	C25—C26—C27—C15	177.8 (2)
N1—C5—C7—O4	−171.07 (15)	N4—C15—C27—C22	177.46 (17)
C4—C5—C7—O4	10.1 (2)	C16—C15—C27—C22	−2.0 (2)
N1—C5—C7—O3	8.9 (2)	N4—C15—C27—C26	−0.4 (3)
C4—C5—C7—O3	−169.90 (16)	C16—C15—C27—C26	−179.86 (17)
N2—Mn1—O5—C13	0.21 (14)	N6—C28—C29—C34	−176.52 (16)
N1—Mn1—O5—C13	174.50 (15)	C40—C28—C29—C34	4.4 (2)
O7—Mn1—O5—C13	−8.2 (2)	N6—C28—C29—C30	7.2 (3)
O1—Mn1—O5—C13	−112.55 (15)	C40—C28—C29—C30	−171.89 (16)
O3—Mn1—O5—C13	102.30 (15)	C34—C29—C30—C31	2.4 (3)
N2—Mn1—O7—C14	5.78 (16)	C28—C29—C30—C31	178.69 (18)
N1—Mn1—O7—C14	−168.81 (15)	C29—C30—C31—C32	0.6 (3)
O5—Mn1—O7—C14	14.2 (2)	C30—C31—C32—C33	−2.3 (4)
O1—Mn1—O7—C14	116.70 (17)	C31—C32—C33—C34	0.8 (3)
O3—Mn1—O7—C14	−96.39 (17)	C35—N5—C34—C29	−2.7 (3)
N1—Mn1—N2—C12	147.6 (3)	C35—N5—C34—C33	176.34 (17)
O7—Mn1—N2—C12	−4.85 (14)	C30—C29—C34—N5	175.17 (16)
O5—Mn1—N2—C12	−179.90 (15)	C28—C29—C34—N5	−1.3 (2)
O1—Mn1—N2—C12	−95.92 (14)	C30—C29—C34—C33	−3.8 (3)
O3—Mn1—N2—C12	87.60 (14)	C28—C29—C34—C33	179.73 (16)
N1—Mn1—N2—C8	−32.1 (4)	C32—C33—C34—N5	−176.72 (19)
O7—Mn1—N2—C8	175.43 (15)	C32—C33—C34—C29	2.3 (3)
O5—Mn1—N2—C8	0.38 (13)	C34—N5—C35—C36	−176.67 (16)
O1—Mn1—N2—C8	84.37 (14)	C34—N5—C35—C40	3.3 (3)
O3—Mn1—N2—C8	−92.12 (14)	N5—C35—C36—C37	179.03 (17)
C12—N2—C8—C9	0.4 (3)	C40—C35—C36—C37	−1.0 (3)
Mn1—N2—C8—C9	−179.87 (14)	C35—C36—C37—C38	1.5 (3)
C12—N2—C8—C13	179.48 (16)	C36—C37—C38—C39	−0.8 (3)
Mn1—N2—C8—C13	−0.8 (2)	C37—C38—C39—C40	−0.5 (3)
N2—C8—C9—C10	−1.9 (3)	C38—C39—C40—C35	1.0 (3)
C13—C8—C9—C10	179.18 (19)	C38—C39—C40—C28	−179.30 (17)
C8—C9—C10—C11	1.4 (3)	N5—C35—C40—C39	179.74 (16)
C9—C10—C11—C12	0.5 (4)	C36—C35—C40—C39	−0.3 (2)
C8—N2—C12—C11	1.6 (3)	N5—C35—C40—C28	0.0 (2)
Mn1—N2—C12—C11	−178.14 (15)	C36—C35—C40—C28	−179.99 (15)
C8—N2—C12—C14	−176.62 (16)	N6—C28—C40—C39	−2.5 (3)
Mn1—N2—C12—C14	3.7 (2)	C29—C28—C40—C39	176.53 (16)
C10—C11—C12—N2	−2.0 (3)	N6—C28—C40—C35	177.18 (16)
C10—C11—C12—C14	176.0 (2)	C29—C28—C40—C35	−3.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.88 (2)	1.86 (2)	2.736 (2)	178 (2)
N4—H4A···O4i	0.85 (3)	2.22 (3)	2.994 (2)	152 (3)
N4—H4B···O10ii	0.93 (3)	2.01 (3)	2.884 (3)	156 (2)
N5—H5N···O11	0.84 (3)	1.87 (3)	2.706 (2)	171 (3)
N6—H6A···O6	0.90 (2)	1.92 (3)	2.801 (2)	164 (2)
N6—H6B···O1iii	0.89 (3)	2.20 (3)	3.029 (2)	155 (3)
O9—H9A···O4	0.94 (3)	1.89 (3)	2.815 (2)	171 (3)
O9—H9B···O4iv	0.93 (3)	1.93 (3)	2.851 (3)	172 (3)
O10—H10A···O3v	0.92 (2)	2.02 (2)	2.926 (2)	168 (3)
O10—H10B···O8	0.92 (3)	1.89 (3)	2.805 (3)	175 (4)
O11—H11A···O6vi	0.92 (3)	1.88 (3)	2.790 (3)	170 (4)
O11—H11B···O9vii	0.92 (3)	1.85 (3)	2.756 (3)	169 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.88 (2)	1.86 (2)	2.736 (2)	178 (2)
N4—H4A⋯O4i	0.85 (3)	2.22 (3)	2.994 (2)	152 (3)
N4—H4B⋯O10ii	0.93 (3)	2.01 (3)	2.884 (3)	156 (2)
N5—H5N⋯O11	0.84 (3)	1.87 (3)	2.706 (2)	171 (3)
N6—H6A⋯O6	0.90 (2)	1.92 (3)	2.801 (2)	164 (2)
N6—H6B⋯O1iii	0.89 (3)	2.20 (3)	3.029 (2)	155 (3)
O9—H9A⋯O4	0.94 (3)	1.89 (3)	2.815 (2)	171 (3)
O9—H9B⋯O4iv	0.93 (3)	1.93 (3)	2.851 (3)	172 (3)
O10—H10A⋯O3v	0.92 (2)	2.02 (2)	2.926 (2)	168 (3)
O10—H10B⋯O8	0.92 (3)	1.89 (3)	2.805 (3)	175 (4)
O11—H11A⋯O6vi	0.92 (3)	1.88 (3)	2.790 (3)	170 (4)
O11—H11B⋯O9vii	0.92 (3)	1.85 (3)	2.756 (3)	169 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .