metal-organic compounds
Diaqua[N,N′-bis(2-pyridylmethylene)propane-1,3-diamine]manganese(II) dibromide–aquabromido[N,N′-bis(2-pyridylmethylene)propane-1,3-diamine]manganese(II) bromide–dibromido[N,N′-bis(2-pyridylmethylene)propane-1,3-diamine]manganese(II) (1/2/1)
aDepartment of Chemistry, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea, and bSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
There are three different MnII complexes in the of the title compound, [Mn(C15H16N4)(H2O)2]Br2·2{[MnBr(C15H16N4)(H2O)]Br}·[MnBr2(C15H16N4)]. In the neutral complex, the Mn2+ ion is six-coordinated in a distorted octahedral environment by four N atoms of the tetradentate ligand N,N′-bis(2-pyridylmethylene)propane-1,3-diamine (bppd) and two bromide ligands. In the two cationic complexes, the Mn2+ ions are also six-coordinated in similar environments, but one Mn ion is coordinated by four N atoms of bppd, one Br atom and one O atom of a coordinating water molecule, whereas the other Mn ion is coordinated by four N atoms of bppd and two O atoms of water ligands. The complexes with two coordinated Br atoms or two H2O ligands are disposed about a twofold axis through Mn and C atoms with the special positions (, y, 0) and (0, y, ), respectively. The compound displays intermolecular O—H⋯Br hydrogen bonding. There are intermolecular π–π interactions between adjacent pyridine rings, with centroid–centroid distances of 3.822 and 3.833 Å, and a C—H⋯O interaction is also present.
Experimental
Crystal data
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808041731/im2090sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808041731/im2090Isup2.hkl
A solution of MnBr2 (0.25 g, 1.16 mmol) and N,N'-bis-(pyridin-2-ylmethylene)-propane-1,3-diamine (0.30 g, 1.19 mmol) in EtOH (20 ml) was stirred for 1 h at room temparature. After adding diethyl ether to the solution, the formed precipitate was separated by filtration and washed with acetone and dried under vacuum, to give a dark yellow powder (0.50 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanolic solution. MS (FAB): m/z 386, 388 (Mn(bppd)Br+); IR (KBr): 3287 cm-1 (broad).
H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 (aromatic) or 0.97 (CH2) Å and Uiso(H) = 1.2Ueq(C)]. The H atoms of the water ligands were located from Fourier difference maps, but not refined. C23 and C31 which lie on special positions are highly disordered and were therfore refined with isotropic thermal parameters Uiso = 0.08 Å2.
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Mn(C15H16N4)(H2O)2]Br2·2{[MnBr(C15H16N4)(H2O)]Br}·[MnBr2(C15H16N4)] | F(000) = 1912 |
Mr = 1940.38 | Dx = 1.781 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 5299 reflections |
a = 28.559 (2) Å | θ = 2.3–24.7° |
b = 9.2318 (6) Å | µ = 5.16 mm−1 |
c = 13.8990 (9) Å | T = 293 K |
β = 99.111 (2)° | Plate, yellow |
V = 3618.2 (4) Å3 | 0.25 × 0.20 × 0.08 mm |
Z = 2 |
Bruker SMART 1000 CCD diffractometer | 6854 independent reflections |
Radiation source: fine-focus sealed tube | 5483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −32→35 |
Tmin = 0.361, Tmax = 0.662 | k = −10→11 |
14779 measured reflections | l = −16→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0674P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.007 |
6854 reflections | Δρmax = 1.30 e Å−3 |
413 parameters | Δρmin = −2.37 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 2901 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (1) |
[Mn(C15H16N4)(H2O)2]Br2·2{[MnBr(C15H16N4)(H2O)]Br}·[MnBr2(C15H16N4)] | V = 3618.2 (4) Å3 |
Mr = 1940.38 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 28.559 (2) Å | µ = 5.16 mm−1 |
b = 9.2318 (6) Å | T = 293 K |
c = 13.8990 (9) Å | 0.25 × 0.20 × 0.08 mm |
β = 99.111 (2)° |
Bruker SMART 1000 CCD diffractometer | 6854 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 5483 reflections with I > 2σ(I) |
Tmin = 0.361, Tmax = 0.662 | Rint = 0.035 |
14779 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.116 | Δρmax = 1.30 e Å−3 |
S = 0.98 | Δρmin = −2.37 e Å−3 |
6854 reflections | Absolute structure: Flack (1983), 2901 Friedel pairs |
413 parameters | Absolute structure parameter: 0.06 (1) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.23354 (3) | 0.67117 (10) | 0.21033 (6) | 0.0378 (2) | |
Br1 | 0.21279 (2) | 0.65427 (9) | 0.02208 (4) | 0.0549 (2) | |
Br2 | 0.29708 (2) | 0.33983 (8) | 0.47346 (5) | 0.05364 (19) | |
O1 | 0.24730 (16) | 0.6324 (5) | 0.3731 (3) | 0.0525 (12) | |
H1WA | 0.2627 | 0.5465 | 0.3944 | 0.22 (7)* | |
H1WB | 0.2500 | 0.6545 | 0.4331 | 0.17 (5)* | |
N1 | 0.30105 (16) | 0.5427 (6) | 0.2189 (3) | 0.0385 (11) | |
N2 | 0.2915 (2) | 0.8352 (6) | 0.2394 (4) | 0.0481 (13) | |
N3 | 0.1850 (2) | 0.8506 (7) | 0.2407 (4) | 0.0519 (14) | |
N4 | 0.16399 (18) | 0.5636 (7) | 0.2259 (4) | 0.0448 (13) | |
C1 | 0.3072 (2) | 0.4038 (8) | 0.2018 (5) | 0.0508 (17) | |
H1 | 0.2804 | 0.3481 | 0.1808 | 0.061* | |
C2 | 0.3508 (3) | 0.3360 (10) | 0.2131 (5) | 0.0605 (19) | |
H2 | 0.3535 | 0.2376 | 0.2006 | 0.073* | |
C3 | 0.3906 (3) | 0.4207 (11) | 0.2441 (5) | 0.065 (2) | |
H3 | 0.4207 | 0.3794 | 0.2530 | 0.078* | |
C4 | 0.3853 (2) | 0.5630 (10) | 0.2611 (5) | 0.060 (2) | |
H4 | 0.4117 | 0.6200 | 0.2826 | 0.072* | |
C5 | 0.3401 (2) | 0.6250 (8) | 0.2463 (4) | 0.0493 (17) | |
C6 | 0.3324 (3) | 0.7804 (8) | 0.2573 (5) | 0.054 (2) | |
H6 | 0.3583 | 0.8401 | 0.2779 | 0.065* | |
C7 | 0.2857 (3) | 0.9905 (8) | 0.2476 (5) | 0.068 (2) | |
H7A | 0.2797 | 1.0323 | 0.1827 | 0.081* | |
H7B | 0.3149 | 1.0317 | 0.2815 | 0.081* | |
C8 | 0.2468 (3) | 1.0300 (9) | 0.2995 (6) | 0.083 (3) | |
H8A | 0.2501 | 1.1317 | 0.3167 | 0.099* | |
H8B | 0.2505 | 0.9755 | 0.3599 | 0.099* | |
C9 | 0.1979 (3) | 1.0063 (9) | 0.2477 (6) | 0.078 (3) | |
H9A | 0.1951 | 1.0466 | 0.1825 | 0.094* | |
H9B | 0.1757 | 1.0574 | 0.2817 | 0.094* | |
C10 | 0.1444 (3) | 0.8098 (10) | 0.2559 (5) | 0.060 (2) | |
H10 | 0.1231 | 0.8777 | 0.2731 | 0.072* | |
C11 | 0.1306 (2) | 0.6568 (10) | 0.2468 (4) | 0.0523 (18) | |
C12 | 0.0858 (3) | 0.6059 (13) | 0.2581 (5) | 0.073 (3) | |
H12 | 0.0632 | 0.6699 | 0.2745 | 0.087* | |
C13 | 0.0751 (3) | 0.4644 (13) | 0.2454 (6) | 0.075 (3) | |
H13 | 0.0450 | 0.4310 | 0.2511 | 0.090* | |
C14 | 0.1082 (3) | 0.3719 (12) | 0.2245 (6) | 0.075 (3) | |
H14 | 0.1016 | 0.2737 | 0.2162 | 0.090* | |
C15 | 0.1534 (3) | 0.4265 (9) | 0.2153 (5) | 0.059 (2) | |
H15 | 0.1765 | 0.3625 | 0.2011 | 0.070* | |
Mn2 | 0.5000 | 0.51666 (15) | 0.0000 | 0.0429 (3) | |
Br3 | 0.47098 (2) | 0.53137 (8) | −0.19582 (5) | 0.0545 (2) | |
N5 | 0.43259 (17) | 0.6317 (6) | 0.0202 (4) | 0.0448 (13) | |
N6 | 0.4462 (2) | 0.3436 (6) | 0.0014 (3) | 0.0492 (13) | |
C16 | 0.4249 (2) | 0.7700 (8) | 0.0343 (5) | 0.0545 (18) | |
H16 | 0.4510 | 0.8315 | 0.0457 | 0.065* | |
C17 | 0.3804 (3) | 0.8294 (10) | 0.0331 (5) | 0.064 (2) | |
H17 | 0.3770 | 0.9284 | 0.0423 | 0.077* | |
C18 | 0.3419 (3) | 0.7424 (11) | 0.0184 (5) | 0.063 (2) | |
H18 | 0.3116 | 0.7806 | 0.0164 | 0.075* | |
C19 | 0.3483 (2) | 0.5952 (10) | 0.0063 (5) | 0.0551 (19) | |
H19 | 0.3226 | 0.5321 | −0.0024 | 0.066* | |
C20 | 0.3946 (2) | 0.5435 (9) | 0.0075 (4) | 0.0490 (17) | |
C21 | 0.4047 (3) | 0.3865 (9) | 0.0003 (5) | 0.0542 (19) | |
H21 | 0.3800 | 0.3199 | −0.0051 | 0.065* | |
C22 | 0.4544 (3) | 0.1870 (9) | −0.0035 (6) | 0.070 (2) | |
H22A | 0.4430 | 0.1393 | 0.0506 | 0.084* | |
H22B | 0.4369 | 0.1486 | −0.0636 | 0.084* | |
C23 | 0.5000 | 0.1605 (15) | 0.0000 | 0.080* | |
H23A | 0.5033 | 0.0954 | 0.0555 | 0.096* | 0.50 |
H23B | 0.4967 | 0.0954 | −0.0555 | 0.096* | 0.50 |
Mn3 | 0.0000 | 0.20194 (14) | 0.5000 | 0.0406 (3) | |
Br4 | 0.05416 (3) | 0.54204 (10) | 0.73983 (7) | 0.0786 (3) | |
O2 | 0.01481 (15) | 0.2422 (5) | 0.6552 (3) | 0.0505 (11) | |
H2WA | 0.0279 | 0.3279 | 0.6786 | 0.044 (17)* | |
H2WB | 0.0013 | 0.1642 | 0.6970 | 0.045 (17)* | |
N7 | 0.07095 (18) | 0.3114 (6) | 0.4971 (4) | 0.0422 (13) | |
N8 | 0.0515 (2) | 0.0231 (7) | 0.4885 (4) | 0.0524 (14) | |
C24 | 0.0825 (3) | 0.4523 (9) | 0.5045 (5) | 0.0551 (19) | |
H24 | 0.0589 | 0.5179 | 0.5141 | 0.066* | |
C25 | 0.1267 (3) | 0.5054 (10) | 0.4988 (5) | 0.061 (2) | |
H25 | 0.1332 | 0.6040 | 0.5048 | 0.073* | |
C26 | 0.1613 (3) | 0.4073 (13) | 0.4840 (5) | 0.072 (3) | |
H26 | 0.1916 | 0.4396 | 0.4786 | 0.087* | |
C27 | 0.1512 (2) | 0.2644 (11) | 0.4771 (5) | 0.060 (2) | |
H27 | 0.1745 | 0.1974 | 0.4687 | 0.071* | |
C28 | 0.1051 (2) | 0.2195 (8) | 0.4830 (5) | 0.0470 (16) | |
C29 | 0.0923 (3) | 0.0629 (9) | 0.4800 (5) | 0.059 (2) | |
H29 | 0.1150 | −0.0060 | 0.4715 | 0.071* | |
C30 | 0.0429 (3) | −0.1332 (9) | 0.4859 (7) | 0.085 (3) | |
H30A | 0.0481 | −0.1700 | 0.4231 | 0.102* | |
H30B | 0.0659 | −0.1789 | 0.5353 | 0.102* | |
C31 | 0.0000 | −0.1720 (16) | 0.5000 | 0.080* | |
H31A | 0.0083 | −0.2366 | 0.5551 | 0.096* | 0.50 |
H31B | −0.0083 | −0.2366 | 0.4449 | 0.096* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0336 (5) | 0.0370 (6) | 0.0422 (5) | −0.0022 (4) | 0.0043 (4) | −0.0030 (4) |
Br1 | 0.0469 (4) | 0.0742 (5) | 0.0422 (3) | 0.0010 (4) | 0.0025 (3) | −0.0013 (3) |
Br2 | 0.0557 (4) | 0.0429 (4) | 0.0644 (4) | 0.0008 (3) | 0.0158 (3) | 0.0081 (3) |
O1 | 0.067 (3) | 0.053 (3) | 0.038 (2) | 0.011 (3) | 0.009 (2) | 0.002 (2) |
N1 | 0.034 (3) | 0.043 (3) | 0.039 (2) | −0.004 (2) | 0.005 (2) | 0.002 (2) |
N2 | 0.065 (4) | 0.038 (3) | 0.040 (3) | −0.016 (3) | 0.005 (3) | 0.000 (2) |
N3 | 0.061 (4) | 0.043 (3) | 0.048 (3) | 0.015 (3) | −0.005 (3) | −0.005 (3) |
N4 | 0.037 (3) | 0.055 (4) | 0.043 (3) | −0.007 (3) | 0.007 (2) | −0.003 (3) |
C1 | 0.046 (4) | 0.051 (4) | 0.058 (4) | 0.000 (3) | 0.017 (3) | 0.012 (3) |
C2 | 0.062 (5) | 0.058 (5) | 0.067 (5) | 0.010 (4) | 0.027 (4) | 0.012 (4) |
C3 | 0.045 (4) | 0.099 (7) | 0.052 (4) | 0.024 (4) | 0.011 (3) | 0.006 (4) |
C4 | 0.037 (4) | 0.093 (7) | 0.050 (4) | 0.000 (4) | 0.006 (3) | −0.001 (4) |
C5 | 0.038 (4) | 0.069 (5) | 0.041 (3) | −0.010 (3) | 0.008 (3) | −0.001 (3) |
C6 | 0.058 (5) | 0.063 (5) | 0.040 (4) | −0.035 (4) | 0.004 (3) | −0.007 (3) |
C7 | 0.105 (7) | 0.043 (4) | 0.053 (4) | −0.027 (4) | 0.005 (4) | −0.009 (3) |
C8 | 0.133 (8) | 0.032 (4) | 0.073 (5) | −0.005 (5) | −0.012 (5) | −0.006 (4) |
C9 | 0.107 (7) | 0.040 (5) | 0.080 (5) | 0.019 (5) | −0.009 (5) | −0.006 (4) |
C10 | 0.059 (5) | 0.071 (6) | 0.049 (4) | 0.016 (4) | 0.005 (3) | −0.008 (4) |
C11 | 0.039 (4) | 0.079 (6) | 0.038 (3) | 0.011 (4) | 0.003 (3) | 0.004 (4) |
C12 | 0.043 (4) | 0.125 (9) | 0.051 (4) | 0.010 (5) | 0.012 (3) | 0.011 (5) |
C13 | 0.047 (5) | 0.122 (9) | 0.057 (5) | −0.027 (5) | 0.006 (4) | 0.011 (5) |
C14 | 0.063 (5) | 0.101 (8) | 0.062 (5) | −0.036 (5) | 0.010 (4) | 0.007 (5) |
C15 | 0.054 (4) | 0.064 (5) | 0.059 (4) | −0.017 (4) | 0.013 (3) | −0.006 (4) |
Mn2 | 0.0395 (7) | 0.0358 (8) | 0.0548 (8) | 0.000 | 0.0117 (6) | 0.000 |
Br3 | 0.0571 (4) | 0.0607 (5) | 0.0463 (3) | −0.0058 (4) | 0.0098 (3) | 0.0110 (3) |
N5 | 0.031 (3) | 0.050 (4) | 0.054 (3) | −0.005 (2) | 0.011 (2) | 0.002 (3) |
N6 | 0.067 (4) | 0.043 (3) | 0.037 (3) | −0.011 (3) | 0.006 (2) | 0.003 (2) |
C16 | 0.044 (4) | 0.060 (5) | 0.060 (4) | 0.002 (3) | 0.009 (3) | −0.005 (3) |
C17 | 0.051 (4) | 0.068 (5) | 0.077 (5) | 0.017 (4) | 0.024 (4) | 0.005 (4) |
C18 | 0.040 (4) | 0.102 (7) | 0.048 (4) | 0.004 (4) | 0.013 (3) | 0.011 (4) |
C19 | 0.033 (4) | 0.091 (6) | 0.043 (4) | −0.007 (4) | 0.013 (3) | 0.005 (3) |
C20 | 0.040 (4) | 0.066 (5) | 0.042 (3) | −0.009 (3) | 0.009 (3) | 0.010 (3) |
C21 | 0.047 (4) | 0.071 (6) | 0.046 (4) | −0.026 (4) | 0.009 (3) | 0.001 (3) |
C22 | 0.079 (5) | 0.050 (5) | 0.075 (5) | −0.014 (4) | −0.008 (4) | 0.004 (4) |
Mn3 | 0.0376 (7) | 0.0312 (8) | 0.0555 (8) | 0.000 | 0.0152 (6) | 0.000 |
Br4 | 0.0802 (6) | 0.0722 (6) | 0.0899 (6) | −0.0243 (5) | 0.0334 (5) | −0.0249 (5) |
O2 | 0.051 (3) | 0.050 (3) | 0.051 (3) | −0.002 (2) | 0.012 (2) | 0.002 (2) |
N7 | 0.035 (3) | 0.046 (4) | 0.046 (3) | −0.002 (3) | 0.010 (2) | 0.001 (2) |
N8 | 0.062 (4) | 0.042 (3) | 0.056 (3) | 0.010 (3) | 0.018 (3) | −0.001 (3) |
C24 | 0.055 (4) | 0.054 (5) | 0.058 (4) | −0.012 (4) | 0.012 (3) | 0.001 (3) |
C25 | 0.048 (4) | 0.068 (6) | 0.063 (4) | −0.026 (4) | −0.001 (3) | 0.006 (4) |
C26 | 0.045 (5) | 0.124 (9) | 0.047 (4) | −0.024 (5) | 0.001 (3) | 0.014 (5) |
C27 | 0.034 (4) | 0.087 (6) | 0.057 (4) | 0.003 (4) | 0.006 (3) | 0.007 (4) |
C28 | 0.039 (4) | 0.060 (5) | 0.043 (3) | 0.005 (3) | 0.007 (3) | −0.005 (3) |
C29 | 0.057 (5) | 0.060 (5) | 0.060 (4) | 0.027 (4) | 0.011 (4) | 0.003 (4) |
C30 | 0.102 (7) | 0.043 (5) | 0.122 (7) | 0.015 (5) | 0.056 (6) | −0.003 (5) |
Mn1—N2 | 2.232 (6) | Mn2—Br3 | 2.7200 (7) |
Mn1—N3 | 2.244 (6) | N5—C16 | 1.315 (9) |
Mn1—N1 | 2.250 (5) | N5—C20 | 1.345 (8) |
Mn1—N4 | 2.262 (5) | N6—C21 | 1.247 (9) |
Mn1—O1 | 2.263 (4) | N6—C22 | 1.468 (10) |
Mn1—Br1 | 2.5944 (10) | C16—C17 | 1.382 (10) |
O1—H1WA | 0.932 | C16—H16 | 0.9300 |
O1—H1WB | 0.850 | C17—C18 | 1.352 (11) |
N1—C1 | 1.321 (9) | C17—H17 | 0.9300 |
N1—C5 | 1.352 (8) | C18—C19 | 1.385 (11) |
N2—C6 | 1.263 (9) | C18—H18 | 0.9300 |
N2—C7 | 1.450 (9) | C19—C20 | 1.403 (9) |
N3—C10 | 1.268 (9) | C19—H19 | 0.9300 |
N3—C9 | 1.483 (10) | C20—C21 | 1.484 (11) |
N4—C15 | 1.303 (9) | C21—H21 | 0.9300 |
N4—C11 | 1.349 (9) | C22—C23 | 1.319 (8) |
C1—C2 | 1.382 (10) | C22—H22A | 0.9700 |
C1—H1 | 0.9300 | C22—H22B | 0.9700 |
C2—C3 | 1.390 (11) | C23—C22i | 1.319 (8) |
C2—H2 | 0.9300 | C23—H23A | 0.9700 |
C3—C4 | 1.347 (12) | C23—H23B | 0.9700 |
C3—H3 | 0.9300 | Mn3—O2 | 2.164 (4) |
C4—C5 | 1.398 (10) | Mn3—O2ii | 2.164 (4) |
C4—H4 | 0.9300 | Mn3—N8ii | 2.234 (6) |
C5—C6 | 1.462 (11) | Mn3—N8 | 2.234 (6) |
C6—H6 | 0.9300 | Mn3—N7 | 2.270 (5) |
C7—C8 | 1.464 (11) | Mn3—N7ii | 2.270 (5) |
C7—H7A | 0.9700 | O2—H2WA | 0.913 |
C7—H7B | 0.9700 | O2—H2WB | 1.037 |
C8—C9 | 1.483 (11) | N7—C28 | 1.330 (8) |
C8—H8A | 0.9700 | N7—C24 | 1.341 (9) |
C8—H8B | 0.9700 | N8—C29 | 1.244 (9) |
C9—H9A | 0.9700 | N8—C30 | 1.463 (10) |
C9—H9B | 0.9700 | C24—C25 | 1.370 (10) |
C10—C11 | 1.467 (12) | C24—H24 | 0.9300 |
C10—H10 | 0.9300 | C25—C26 | 1.378 (12) |
C11—C12 | 1.397 (11) | C25—H25 | 0.9300 |
C12—C13 | 1.347 (13) | C26—C27 | 1.350 (11) |
C12—H12 | 0.9300 | C26—H26 | 0.9300 |
C13—C14 | 1.339 (13) | C27—C28 | 1.394 (10) |
C13—H13 | 0.9300 | C27—H27 | 0.9300 |
C14—C15 | 1.410 (10) | C28—C29 | 1.491 (11) |
C14—H14 | 0.9300 | C29—H29 | 0.9300 |
C15—H15 | 0.9300 | C30—C31 | 1.319 (9) |
Mn2—N6 | 2.219 (6) | C30—H30A | 0.9700 |
Mn2—N6i | 2.219 (6) | C30—H30B | 0.9700 |
Mn2—N5 | 2.255 (5) | C31—C30ii | 1.319 (9) |
Mn2—N5i | 2.255 (5) | C31—H31A | 0.9700 |
Mn2—Br3i | 2.7200 (7) | C31—H31B | 0.9700 |
N2—Mn1—N3 | 85.9 (2) | N6i—Mn2—Br3 | 97.41 (13) |
N2—Mn1—N1 | 75.1 (2) | N5—Mn2—Br3 | 88.29 (13) |
N3—Mn1—N1 | 158.3 (2) | N5i—Mn2—Br3 | 89.01 (13) |
N2—Mn1—N4 | 156.6 (2) | Br3i—Mn2—Br3 | 174.28 (7) |
N3—Mn1—N4 | 74.2 (2) | C16—N5—C20 | 117.2 (6) |
N1—Mn1—N4 | 121.4 (2) | C16—N5—Mn2 | 129.9 (5) |
N2—Mn1—O1 | 85.40 (18) | C20—N5—Mn2 | 112.6 (5) |
N3—Mn1—O1 | 86.76 (19) | C21—N6—C22 | 118.1 (6) |
N1—Mn1—O1 | 81.49 (17) | C21—N6—Mn2 | 115.4 (5) |
N4—Mn1—O1 | 81.42 (17) | C22—N6—Mn2 | 126.4 (5) |
N2—Mn1—Br1 | 105.54 (13) | N5—C16—C17 | 123.9 (7) |
N3—Mn1—Br1 | 100.65 (13) | N5—C16—H16 | 118.0 |
N1—Mn1—Br1 | 94.51 (12) | C17—C16—H16 | 118.0 |
N4—Mn1—Br1 | 90.37 (13) | C18—C17—C16 | 119.4 (8) |
O1—Mn1—Br1 | 167.08 (13) | C18—C17—H17 | 120.3 |
Mn1—O1—H1WA | 116.8 | C16—C17—H17 | 120.3 |
Mn1—O1—H1WB | 156.5 | C17—C18—C19 | 118.7 (8) |
H1WA—O1—H1WB | 85.9 | C17—C18—H18 | 120.7 |
C1—N1—C5 | 118.0 (6) | C19—C18—H18 | 120.7 |
C1—N1—Mn1 | 129.7 (4) | C18—C19—C20 | 118.4 (7) |
C5—N1—Mn1 | 112.3 (5) | C18—C19—H19 | 120.8 |
C6—N2—C7 | 119.6 (6) | C20—C19—H19 | 120.8 |
C6—N2—Mn1 | 113.6 (5) | N5—C20—C19 | 122.3 (7) |
C7—N2—Mn1 | 126.5 (5) | N5—C20—C21 | 116.1 (6) |
C10—N3—C9 | 120.1 (7) | C19—C20—C21 | 121.6 (7) |
C10—N3—Mn1 | 114.9 (5) | N6—C21—C20 | 120.2 (6) |
C9—N3—Mn1 | 125.0 (5) | N6—C21—H21 | 119.9 |
C15—N4—C11 | 119.0 (7) | C20—C21—H21 | 119.9 |
C15—N4—Mn1 | 127.3 (5) | C23—C22—N6 | 110.2 (9) |
C11—N4—Mn1 | 113.7 (5) | C23—C22—H22A | 109.6 |
N1—C1—C2 | 124.2 (7) | N6—C22—H22A | 109.6 |
N1—C1—H1 | 117.9 | C23—C22—H22B | 109.6 |
C2—C1—H1 | 117.9 | N6—C22—H22B | 109.6 |
C1—C2—C3 | 117.3 (8) | H22A—C22—H22B | 108.1 |
C1—C2—H2 | 121.4 | C22i—C23—C22 | 158.6 (14) |
C3—C2—H2 | 121.4 | C22i—C23—H23A | 96.6 |
C4—C3—C2 | 119.6 (7) | C22—C23—H23A | 96.6 |
C4—C3—H3 | 120.2 | C22i—C23—H23B | 96.6 |
C2—C3—H3 | 120.2 | C22—C23—H23B | 96.6 |
C3—C4—C5 | 120.1 (8) | H23A—C23—H23B | 103.5 |
C3—C4—H4 | 120.0 | O2—Mn3—O2ii | 160.2 (3) |
C5—C4—H4 | 120.0 | O2—Mn3—N8ii | 94.74 (19) |
N1—C5—C4 | 120.8 (7) | O2ii—Mn3—N8ii | 99.85 (19) |
N1—C5—C6 | 116.8 (6) | O2—Mn3—N8 | 99.85 (19) |
C4—C5—C6 | 122.4 (7) | O2ii—Mn3—N8 | 94.74 (19) |
N2—C6—C5 | 121.4 (6) | N8ii—Mn3—N8 | 84.7 (3) |
N2—C6—H6 | 119.3 | O2—Mn3—N7 | 84.67 (17) |
C5—C6—H6 | 119.3 | O2ii—Mn3—N7 | 86.56 (17) |
N2—C7—C8 | 112.9 (6) | N8ii—Mn3—N7 | 158.4 (2) |
N2—C7—H7A | 109.0 | N8—Mn3—N7 | 74.2 (2) |
C8—C7—H7A | 109.0 | O2—Mn3—N7ii | 86.56 (17) |
N2—C7—H7B | 109.0 | O2ii—Mn3—N7ii | 84.67 (17) |
C8—C7—H7B | 109.0 | N8ii—Mn3—N7ii | 74.2 (2) |
H7A—C7—H7B | 107.8 | N8—Mn3—N7ii | 158.4 (2) |
C7—C8—C9 | 116.9 (7) | N7—Mn3—N7ii | 127.1 (3) |
C7—C8—H8A | 108.1 | Mn3—O2—H2WA | 120.5 |
C9—C8—H8A | 108.1 | Mn3—O2—H2WB | 114.1 |
C7—C8—H8B | 108.1 | H2WA—O2—H2WB | 124.8 |
C9—C8—H8B | 108.1 | C28—N7—C24 | 116.9 (6) |
H8A—C8—H8B | 107.3 | C28—N7—Mn3 | 113.3 (5) |
C8—C9—N3 | 112.3 (7) | C24—N7—Mn3 | 129.7 (5) |
C8—C9—H9A | 109.1 | C29—N8—C30 | 116.5 (7) |
N3—C9—H9A | 109.1 | C29—N8—Mn3 | 115.2 (5) |
C8—C9—H9B | 109.1 | C30—N8—Mn3 | 128.3 (5) |
N3—C9—H9B | 109.1 | N7—C24—C25 | 124.0 (8) |
H9A—C9—H9B | 107.9 | N7—C24—H24 | 118.0 |
N3—C10—C11 | 120.7 (7) | C25—C24—H24 | 118.0 |
N3—C10—H10 | 119.6 | C24—C25—C26 | 117.5 (8) |
C11—C10—H10 | 119.6 | C24—C25—H25 | 121.2 |
N4—C11—C12 | 120.1 (9) | C26—C25—H25 | 121.2 |
N4—C11—C10 | 116.4 (6) | C27—C26—C25 | 120.1 (8) |
C12—C11—C10 | 123.5 (8) | C27—C26—H26 | 119.9 |
C13—C12—C11 | 120.2 (9) | C25—C26—H26 | 119.9 |
C13—C12—H12 | 119.9 | C26—C27—C28 | 118.6 (8) |
C11—C12—H12 | 119.9 | C26—C27—H27 | 120.7 |
C14—C13—C12 | 119.6 (8) | C28—C27—H27 | 120.7 |
C14—C13—H13 | 120.2 | N7—C28—C27 | 122.7 (7) |
C12—C13—H13 | 120.2 | N7—C28—C29 | 116.1 (6) |
C13—C14—C15 | 118.7 (9) | C27—C28—C29 | 121.1 (7) |
C13—C14—H14 | 120.7 | N8—C29—C28 | 120.9 (7) |
C15—C14—H14 | 120.7 | N8—C29—H29 | 119.6 |
N4—C15—C14 | 122.4 (8) | C28—C29—H29 | 119.6 |
N4—C15—H15 | 118.8 | C31—C30—N8 | 114.9 (9) |
C14—C15—H15 | 118.8 | C31—C30—H30A | 108.6 |
N6—Mn2—N6i | 87.9 (3) | N8—C30—H30A | 108.6 |
N6—Mn2—N5 | 74.5 (2) | C31—C30—H30B | 108.6 |
N6i—Mn2—N5 | 161.2 (2) | N8—C30—H30B | 108.6 |
N6—Mn2—N5i | 161.2 (2) | H30A—C30—H30B | 107.5 |
N6i—Mn2—N5i | 74.5 (2) | C30—C31—C30ii | 148.5 (14) |
N5—Mn2—N5i | 123.8 (3) | C30—C31—H31A | 99.6 |
N6—Mn2—Br3i | 97.41 (13) | C30ii—C31—H31A | 99.6 |
N6i—Mn2—Br3i | 86.73 (13) | C30—C31—H31B | 99.6 |
N5—Mn2—Br3i | 89.01 (13) | C30ii—C31—H31B | 99.6 |
N5i—Mn2—Br3i | 88.29 (13) | H31A—C31—H31B | 104.1 |
N6—Mn2—Br3 | 86.73 (13) | ||
N2—Mn1—N1—C1 | −174.0 (6) | N6—Mn2—N5—C16 | 176.3 (6) |
N3—Mn1—N1—C1 | 156.5 (6) | N6i—Mn2—N5—C16 | 155.2 (6) |
N4—Mn1—N1—C1 | 24.1 (6) | N5i—Mn2—N5—C16 | −8.9 (6) |
O1—Mn1—N1—C1 | 98.6 (5) | Br3i—Mn2—N5—C16 | 78.4 (6) |
Br1—Mn1—N1—C1 | −69.1 (5) | Br3—Mn2—N5—C16 | −96.6 (6) |
N2—Mn1—N1—C5 | 6.4 (4) | N6—Mn2—N5—C20 | −9.6 (4) |
N3—Mn1—N1—C5 | −23.2 (7) | N6i—Mn2—N5—C20 | −30.7 (8) |
N4—Mn1—N1—C5 | −155.5 (4) | N5i—Mn2—N5—C20 | 165.1 (5) |
O1—Mn1—N1—C5 | −81.1 (4) | Br3i—Mn2—N5—C20 | −107.6 (4) |
Br1—Mn1—N1—C5 | 111.3 (4) | Br3—Mn2—N5—C20 | 77.4 (4) |
N3—Mn1—N2—C6 | 162.0 (5) | N6i—Mn2—N6—C21 | −178.5 (6) |
N1—Mn1—N2—C6 | −7.5 (4) | N5—Mn2—N6—C21 | 8.2 (5) |
N4—Mn1—N2—C6 | 130.7 (6) | N5i—Mn2—N6—C21 | −158.2 (6) |
O1—Mn1—N2—C6 | 74.9 (5) | Br3i—Mn2—N6—C21 | 95.1 (5) |
Br1—Mn1—N2—C6 | −98.1 (4) | Br3—Mn2—N6—C21 | −80.9 (5) |
N3—Mn1—N2—C7 | −12.3 (5) | N6i—Mn2—N6—C22 | −3.1 (4) |
N1—Mn1—N2—C7 | 178.3 (6) | N5—Mn2—N6—C22 | −176.5 (6) |
N4—Mn1—N2—C7 | −43.5 (8) | N5i—Mn2—N6—C22 | 17.2 (9) |
O1—Mn1—N2—C7 | −99.3 (5) | Br3i—Mn2—N6—C22 | −89.6 (5) |
Br1—Mn1—N2—C7 | 87.7 (5) | Br3—Mn2—N6—C22 | 94.4 (5) |
N2—Mn1—N3—C10 | −164.7 (5) | C20—N5—C16—C17 | −2.5 (10) |
N1—Mn1—N3—C10 | −136.1 (6) | Mn2—N5—C16—C17 | 171.3 (5) |
N4—Mn1—N3—C10 | 2.9 (5) | N5—C16—C17—C18 | 1.2 (11) |
O1—Mn1—N3—C10 | −79.1 (5) | C16—C17—C18—C19 | 0.9 (11) |
Br1—Mn1—N3—C10 | 90.3 (5) | C17—C18—C19—C20 | −1.5 (11) |
N2—Mn1—N3—C9 | 12.7 (6) | C16—N5—C20—C19 | 1.8 (9) |
N1—Mn1—N3—C9 | 41.3 (9) | Mn2—N5—C20—C19 | −173.0 (5) |
N4—Mn1—N3—C9 | −179.7 (6) | C16—N5—C20—C21 | −174.9 (6) |
O1—Mn1—N3—C9 | 98.3 (6) | Mn2—N5—C20—C21 | 10.2 (7) |
Br1—Mn1—N3—C9 | −92.3 (5) | C18—C19—C20—N5 | 0.2 (10) |
N2—Mn1—N4—C15 | −150.2 (6) | C18—C19—C20—C21 | 176.7 (6) |
N3—Mn1—N4—C15 | 177.3 (6) | C22—N6—C21—C20 | 178.5 (6) |
N1—Mn1—N4—C15 | −19.2 (7) | Mn2—N6—C21—C20 | −5.7 (8) |
O1—Mn1—N4—C15 | −93.7 (6) | N5—C20—C21—N6 | −3.4 (9) |
Br1—Mn1—N4—C15 | 76.3 (6) | C19—C20—C21—N6 | 179.9 (6) |
N2—Mn1—N4—C11 | 31.2 (8) | C21—N6—C22—C23 | −179.0 (5) |
N3—Mn1—N4—C11 | −1.4 (4) | Mn2—N6—C22—C23 | 5.8 (8) |
N1—Mn1—N4—C11 | 162.1 (4) | N6—C22—C23—C22i | −3.2 (5) |
O1—Mn1—N4—C11 | 87.7 (4) | O2—Mn3—N7—C28 | 106.6 (4) |
Br1—Mn1—N4—C11 | −102.4 (4) | O2ii—Mn3—N7—C28 | −91.2 (4) |
C5—N1—C1—C2 | 2.2 (9) | N8ii—Mn3—N7—C28 | 17.2 (8) |
Mn1—N1—C1—C2 | −177.5 (5) | N8—Mn3—N7—C28 | 4.8 (4) |
N1—C1—C2—C3 | −0.3 (10) | N7ii—Mn3—N7—C28 | −171.8 (5) |
C1—C2—C3—C4 | −0.3 (10) | O2—Mn3—N7—C24 | −75.6 (6) |
C2—C3—C4—C5 | −0.9 (11) | O2ii—Mn3—N7—C24 | 86.7 (6) |
C1—N1—C5—C4 | −3.3 (8) | N8ii—Mn3—N7—C24 | −165.0 (6) |
Mn1—N1—C5—C4 | 176.4 (5) | N8—Mn3—N7—C24 | −177.4 (6) |
C1—N1—C5—C6 | 175.4 (6) | N7ii—Mn3—N7—C24 | 6.0 (5) |
Mn1—N1—C5—C6 | −4.9 (7) | O2—Mn3—N8—C29 | −85.7 (5) |
C3—C4—C5—N1 | 2.8 (10) | O2ii—Mn3—N8—C29 | 80.9 (5) |
C3—C4—C5—C6 | −175.8 (6) | N8ii—Mn3—N8—C29 | −179.6 (6) |
C7—N2—C6—C5 | −177.6 (6) | N7—Mn3—N8—C29 | −4.2 (5) |
Mn1—N2—C6—C5 | 7.7 (8) | N7ii—Mn3—N8—C29 | 168.4 (5) |
N1—C5—C6—N2 | −1.9 (9) | O2—Mn3—N8—C30 | 97.0 (7) |
C4—C5—C6—N2 | 176.8 (6) | O2ii—Mn3—N8—C30 | −96.4 (7) |
C6—N2—C7—C8 | −134.6 (7) | N8ii—Mn3—N8—C30 | 3.1 (6) |
Mn1—N2—C7—C8 | 39.4 (9) | N7—Mn3—N8—C30 | 178.5 (7) |
N2—C7—C8—C9 | −72.3 (10) | N7ii—Mn3—N8—C30 | −8.9 (10) |
C7—C8—C9—N3 | 72.7 (10) | C28—N7—C24—C25 | −0.3 (10) |
C10—N3—C9—C8 | 137.2 (8) | Mn3—N7—C24—C25 | −178.0 (5) |
Mn1—N3—C9—C8 | −40.1 (9) | N7—C24—C25—C26 | 0.4 (11) |
C9—N3—C10—C11 | 178.3 (6) | C24—C25—C26—C27 | −1.1 (11) |
Mn1—N3—C10—C11 | −4.1 (8) | C25—C26—C27—C28 | 1.6 (12) |
C15—N4—C11—C12 | 1.0 (9) | C24—N7—C28—C27 | 0.8 (9) |
Mn1—N4—C11—C12 | 179.7 (5) | Mn3—N7—C28—C27 | 178.9 (5) |
C15—N4—C11—C10 | −178.8 (6) | C24—N7—C28—C29 | 177.0 (6) |
Mn1—N4—C11—C10 | −0.1 (7) | Mn3—N7—C28—C29 | −4.8 (7) |
N3—C10—C11—N4 | 2.9 (9) | C26—C27—C28—N7 | −1.4 (11) |
N3—C10—C11—C12 | −176.9 (6) | C26—C27—C28—C29 | −177.5 (7) |
N4—C11—C12—C13 | −2.0 (11) | C30—N8—C29—C28 | −179.2 (7) |
C10—C11—C12—C13 | 177.8 (7) | Mn3—N8—C29—C28 | 3.2 (9) |
C11—C12—C13—C14 | 1.9 (13) | N7—C28—C29—N8 | 1.2 (10) |
C12—C13—C14—C15 | −0.7 (12) | C27—C28—C29—N8 | 177.6 (6) |
C11—N4—C15—C14 | 0.2 (11) | C29—N8—C30—C31 | 176.8 (7) |
Mn1—N4—C15—C14 | −178.4 (5) | Mn3—N8—C30—C31 | −6.0 (11) |
C13—C14—C15—N4 | −0.3 (12) | N8—C30—C31—C30ii | 3.2 (6) |
Symmetry codes: (i) −x+1, y, −z; (ii) −x, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1WA···Br2 | 0.932 | 2.34 | 3.261 (5) | 170.1 |
O1—H1WB···Br2iii | 0.850 | 2.64 | 3.268 (5) | 131.6 |
O2—H2WA···Br4 | 0.913 | 2.23 | 3.145 (5) | 175.2 |
O2—H2WB···Br3iv | 1.037 | 2.21 | 3.234 (4) | 169.5 |
C4—H4···O2iii | 0.93 | 2.42 | 3.344 (9) | 173 |
C29—H29···Br2v | 0.93 | 2.88 | 3.742 (7) | 154 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z+1; (iv) x−1/2, y−1/2, z+1; (v) −x+1/2, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C15H16N4)(H2O)2]Br2·2{[MnBr(C15H16N4)(H2O)]Br}·[MnBr2(C15H16N4)] |
Mr | 1940.38 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 28.559 (2), 9.2318 (6), 13.8990 (9) |
β (°) | 99.111 (2) |
V (Å3) | 3618.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.16 |
Crystal size (mm) | 0.25 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.361, 0.662 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14779, 6854, 5483 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.116, 0.98 |
No. of reflections | 6854 |
No. of parameters | 413 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −2.37 |
Absolute structure | Flack (1983), 2901 Friedel pairs |
Absolute structure parameter | 0.06 (1) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1WA···Br2 | 0.932 | 2.34 | 3.261 (5) | 170.1 |
O1—H1WB···Br2i | 0.850 | 2.64 | 3.268 (5) | 131.6 |
O2—H2WA···Br4 | 0.913 | 2.23 | 3.145 (5) | 175.2 |
O2—H2WB···Br3ii | 1.037 | 2.21 | 3.234 (4) | 169.5 |
C4—H4···O2i | 0.93 | 2.42 | 3.344 (9) | 173.3 |
C29—H29···Br2iii | 0.93 | 2.88 | 3.742 (7) | 154.3 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) x−1/2, y−1/2, z+1; (iii) −x+1/2, y−1/2, −z+1. |
Acknowledgements
This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).
References
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hwang, I.-C. & Ha, K. (2007). Acta Cryst. E63, m2465. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The crystal structure of the title compound, [Mn(C15H16N4)(H2O)2]Br2[MnBr(C15H16N4)(H2O)]Br [MnBr2(C15H16N4)], contains three different MnII complexes in the unit cell (Fig. 1). In the neutral complex, the Mn2+ ion is six-coordinated in a distorted octahedral environment by four N atoms of the tetradentate ligand N,N'-bis-(pyridin-2-ylmethylene)-propane-1,3-diamine (bppd) occupying equatorial positions and two Br atoms occupying axial positions. The complex is disposed about a twofold axis passing through Mn2 and C23 which lie on the special positions (1/2, y, 0). Within the equatorial plane, the chelating angles lie in the range of 74.5 (2)°–87.9 (3)°. The apical Br3—Mn2—Br3a [Symmetry code: (a) 1 - x, y, -z] bond angle is 174.28 (7)°. In the two cationic complexes, the Mn2+ ions are also six-coordinated in distorted octahedral environments, but one Mn ion is coordinated by four N atoms of bppd, one Br atom and one O atom of a water ligand, whereas the other Mn ion is coordinated by four N atoms of bppd and two O atoms of water ligands. The cationic diaqua complex is disposed about a twofold axis passing through Mn3 and C31 which lie on the special positions (0, y, 1/2). Within the equatorial planes, the chelating angles lie in the range of 74.2 (2)°–85.9 (2)°. The apical Br1—Mn1—O1 and O2—Mn3—O2b [Symmetry code: (b) -x, y, 1 - z] bond angles are 167.08 (13)° and 160.2 (3)°, respectively. The compound displays intermolecular hydrogen bonds between the O atoms and the Br atoms (Fig. 2, Table 1). There are also intermolecular π-π interactions between adjacent pyridine rings, with centroid-to-centroid distances of 3.822 Å and 3.833 Å, and with dihedral angles between the ring planes of 9.8° and 4.4°.