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)

Hwang, I.-C.; Ha, K.

doi:10.1107/S1600536808041731

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)

There are three different Mn^II complexes in the asymmetric unit 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 ( ${\script{1\over 2}}$ , y, 0) and (0, y, ${\script{1\over 2}}$ ), 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.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808041731/im2090sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808041731/im2090Isup2.hkl Contains datablock I

CCDC reference: 717194

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.012 Å
R factor = 0.045
wR factor = 0.116
Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) .......          2

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.361     0.662
            Tmin and Tmax expected:      0.302     0.662
            RR =      1.194
            Please check that your absorption correction is appropriate.
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.61 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Br3    --  Mn2     ..       9.97 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C30
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         12
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O2     -   H2WB   ...       1.04 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C30    -   C31    ...       1.32 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C22    -   C23    ...       1.32 Ang.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT060_ALERT_4_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.20
PLAT234_ALERT_4_C Large Hirshfeld Difference C25    --  C26     ..       0.15  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C26    --  C27     ..       0.16  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference N1     --  C1      ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference N2     --  C6      ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C7     --  C8      ..       0.19  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C12    --  C13     ..       0.13  Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.39
           From the CIF: _reflns_number_total               6854
           Count of symmetry unique reflns         3955
           Completeness (_total/calc)            173.30%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2899
           Fraction of Friedel pairs measured     0.733
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  16 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

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

Comment top

The crystal structure of the title compound, [Mn(C₁₅H₁₆N₄)(H₂O)₂]Br₂[MnBr(C₁₅H₁₆N₄)(H₂O)]Br [MnBr₂(C₁₅H₁₆N₄)], contains three different Mn^II 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°.

Related literature top

For a structurally related complex, see: Hwang & Ha (2007).

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: 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).

Figures top

	Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

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) top

Crystal data top

[Mn(C₁₅H₁₆N₄)(H₂O)₂]Br₂·2{[MnBr(C₁₅H₁₆N₄)(H₂O)]Br}·[MnBr₂(C₁₅H₁₆N₄)]	F(000) = 1912
M_r = 1940.38	D_x = 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

Data collection top

Bruker SMART 1000 CCD diffractometer	6854 independent reflections
Radiation source: fine-focus sealed tube	5483 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −32→35
T_min = 0.361, T_max = 0.662	k = −10→11
14779 measured reflections	l = −16→17

Refinement top

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(F_o²) + (0.0674P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.007
6854 reflections	Δρ_max = 1.30 e Å⁻³
413 parameters	Δρ_min = −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)

Crystal data top

[Mn(C₁₅H₁₆N₄)(H₂O)₂]Br₂·2{[MnBr(C₁₅H₁₆N₄)(H₂O)]Br}·[MnBr₂(C₁₅H₁₆N₄)]	V = 3618.2 (4) Å³
M_r = 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)°

Data collection top

Bruker SMART 1000 CCD diffractometer	6854 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	5483 reflections with I > 2σ(I)
T_min = 0.361, T_max = 0.662	R_int = 0.035
14779 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.116	Δρ_max = 1.30 e Å⁻³
S = 0.98	Δρ_min = −2.37 e Å⁻³
6854 reflections	Absolute structure: Flack (1983), 2901 Friedel pairs
413 parameters	Absolute structure parameter: 0.06 (1)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···Br3^iv	1.037	2.21	3.234 (4)	169.5
C4—H4···O2ⁱⁱⁱ	0.93	2.42	3.344 (9)	173
C29—H29···Br2^v	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)]
M_r	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)
T_min, T_max	0.361, 0.662
No. of measured, independent and observed [I > 2σ(I)] reflections	14779, 6854, 5483
R_int	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
Δρ_max, Δρ_min (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).