metal-organic compounds
Aqua(4-bromobenzoato-κO)bis(1,10-phenanthroline-κ2N,N′)manganese(II) 4-bromobenzoate dihydrate
aCollge of Pharmaceutics and Material Engineering, Jinhua Polytechnic, Jinhua, Zhejiang 321007, People's Republic of China
*Correspondence e-mail: zbs_jy@163.com
The 7H4BrO2)(C12H8N2)2(H2O)](C7H4BrO2)·2H2O, consists of a monovalent [Mn(C7H4BrO2)(C12H8N2)2(H2O)]+ complex cation, a 4-bromobenzoate anion and two lattice water molecules. In the complex cation, the MnII atom is coordinated by four N atoms from two bidentate chelating 1,10-phenanthroline (phen) ligands and two O atoms, one from a 4-bromobenzoate anion and the other from a coordinating water molecule. This completes an MnN4O2 coordination sphere with a distorted octahedral geometry. The Br atom of the bromobenzoato ligand is equally disordered over two sites. In the crystal, the complex cations are connected to each other via O—H⋯O, O—H⋯Br and C—H⋯O hydrogen bonds and π–π stacking interactions [closest separation = 3.492 (4) Å]. π–π contacts [closest separation = 3.771 (4) Å] also link the complex cations to both the coordinated and non-coordinating 4-bromobenzoate anions. Overall, these contacts generate a three-dimensional network structure.
of the title compound, [Mn(CKeywords: crystal structure; MnII complex; hydrogen bonds; π–π stacking.
CCDC reference: 1481227
Structure description
The structures [Mn(phen)2(H2O)(C7H4FO2)](C7H4FO2)·2H2O, (Li et al., 2011) and [Mn2(phen)4(H2O)(C7H4IO2)](I)2·2H2O (Zhang, 2007) with Mn2+ cations and 1,10-phenanthroline (phen) ligands have been reported. We report here the synthesis and structure of the related complex aqua(4-bromobenzoato-κO)bis(1,10-phenanthroline-κ2N,N′)-manganese(II) 4-bromobenzoate dihydrate. The title complex is closely related to the compounds [Mn(phen)2(H2O)(C7H4FO2)](C7H4FO2)·2H2O, (Li et al., 2011) and [Zn(H2O)(phen)2(C7H4BrO2)](C7H4BrO2)·2H2O, (Zhang et al., 2010).
The title compound comprises an [Mn(H2O)(phen)2(C7H4BrO2)]+complex cation with the charge-balanced by a 4-bromobenzoate anion. Two lattice water molecules complete the (Fig. 1). Within the cation, the MnII atom is coordinated by four N atoms from two bidentate chelating 1,10-phenanthroline (phen)ligands and two O atoms, one from a 4-bromobenzoate anion and the other from a coordinating water molecule. This completes an MnN4O2 coordination sphere with distorted octahedral geometry. The Mn—N bond lengths are in the range of 2.282 (5)–2.343 (5) Å with Mn—O bond lengths of 2.114 (5) and 2.128 (5) Å. The two crystallographically independent chelating phen ligands are almost perfectly planar (r.m.s. deviations = 0.018 and 0.032 Å, respectively). The dihedral angle between the mean planes of the phen ligands is 87.9 (1)°.
In the crystal, an extensive series of O—H⋯O, O—H⋯Br and C—H⋯O hydrogen bonds stabilize the structure (Table 1 and Fig. 2). In addition, inversion-related offset π–π contacts occur between adjacent N3,N4 phen ligands with Cg6⋯Cg6v = 3.492 (4) and Cg6⋯Cg9v = 3.689 (4) Å [symmetry code: (v) 1 − x, −y, −z; Cg6 and Cg9 are the centroids of the N4/C28–C31 and C24–C27/C21/C32 rings, respectively]. Furthermore there are other significant π–π contacts Cg4⋯Cg8vi =3.948 (4) Å and Cg3⋯Cg10vii = 3.771 (4) Å between the aromatic rings of the other phen ligand and the benzene rings of both the coordinating and non-coordinating anions [symmetry codes: (vi) − x, + y, − z; (vii) − x, − + y, − z; Cg3, Cg4, Cg8 and Cg10 are the centroids of the N1/C1–C4/C12, N2/C7–C11, C13–C18 and C33–C38 rings, respectively]. This extensive series of contacts combines to generate a three dimensional network structure.
Synthesis and crystallization
MnCl2·2H2O (0.0811 g, 0.50 mmol) was dissolved in an appropriate amount of water, and then 1 M Na2CO3 solution was added. MnCO3 was separated by filtration and was then washed five times with distilled water. The freshly prepared MnCO3, 1,10-phenanthroline(phen)·H2O, 0.0493 g, 0.25 mmol) and 4-bromobenzoic acid (0.0516 g, 0.25 mmol), CH3OH/H2O (v/v = 1:2, 15 ml) were mixed and stirred for 2.0 h. Subsequently, the resulting suspension was heated in a 23 ml Teflon- lined stainless steel autoclave at 433 K for 5800 minutes. After the autoclave was cooled to room temperature over 2600 minutes, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation over 1 month afforded yellow block-like single crystals.
Refinement
Crystal data, data collection and structure . Atom Br1 of the bromobenzoato ligand is equally disordered over two sites.
details are summarized in Table 2
|
Structural data
CCDC reference: 1481227
10.1107/S2414314616008336/sj4035sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616008336/sj4035Isup2.hkl
MnCl2.2H2O (0.0811 g, 0.50 mmol) was dissolved in an appropriate amount of water, and then 1M Na2CO3 solution was added. MnCO3 was separated by filtration and was then washed 5 times with distilled water. The freshly prepared MnCO3, 1,10-phenanthroline(phen).H2O, 0.0493 g, 0.25 mmol) and 4-bromobenzoic acid (0.0516 g, 0.25 mmol), CH3OH/H2O (v/v = 1:2, 15 ml) were mixed and stirred for 2.0 h. Subsequently, the resulting suspension was heated in a 23 ml Teflon- lined stainless steel autoclave at 433 K for 5800 minutes. After the autoclave was cooled to room temperature over 2600 minutes, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation over 1 month afforded yellow block-like single crystals.
MnCl2·2H2O (0.0811 g, 0.50 mmol) was dissolved in an appropriate amount of water, and then 1 M Na2CO3 solution was added. MnCO3 was separated by filtration and was then washed five times with distilled water. The freshly prepared MnCO3, 1,10-phenanthroline(phen)·H2O, 0.0493 g, 0.25 mmol) and 4-bromobenzoic acid (0.0516 g, 0.25 mmol), CH3OH/H2O (v/v = 1:2, 15 ml) were mixed and stirred for 2.0 h. Subsequently, the resulting suspension was heated in a 23 ml Teflon- lined stainless steel autoclave at 433 K for 5800 minutes. After the autoclave was cooled to room temperature over 2600 minutes, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation over 1 month afforded yellow block-like single crystals.
Crystal data, data collection and structure
details are summarized in Table 2. Atom Br1 of the bromobenzoato ligand is equally disordered over two sites.The structures [Mn(phen)2(H2O)(C7H4FO2)](C7H4FO2)·2H2O, (Li et al., 2011) and [Mn2(phen)4(H2O)(C7H4IO2)](I)2·2H2O (Zhang, 2007) with Mn2+ cations and 1,10-phenanthroline (phen) ligands have been reported. We report here the synthesis and structure of the related complex aqua(4-bromobenzoato-κO)bis(1,10-phenanthroline-κ2N,N')-manganese(II) 4-bromobenzoate dihydrate. The title complex is also closely related to the compounds [Mn(phen)2(H2O)(C7H4FO2)](C7H4FO2)·2H2O, (Li et al., 2011) and [Zn(H2O)(phen)2(C7H4BrO2)](C7H4BrO2)·2H2O, (Zhang et al., 2010).
The title compound comprises an [Mn(H2O)(phen)2(C7H4BrO2)]+complex cation with the charge-balanced by a 4-bromobenzoate anion. Two lattice water molecules complete the
(Fig.1). Within the cation, the MnII atom is coordinated by four N atoms from two bidentate chelating 1,10-phenanthroline (phen)ligands and two O atoms, one from a 4-bromobenzoate anion and the other from a coordinating water molecule. This completes an MnN4O2 coordination sphere with distorted octahedral geometry. The Mn—N bond lengths are in the range of 2.282 (5)–2.343 (5) Å with Mn—O bond lengths of 2.114 (5) and 2.128 (5) Å. The two crystallographically independent chelating phen ligands are almost perfectly planar [give r.m.s. deviations]. The dihedral angle between the mean planes of the phen ligands is 87.9 (1)°.In the crystal, an extensive series of O—H···O, O—H···Br and C—H···O hydrogen bonds stabilize the structure (Table 1). In addition, inversion-related offset π–π contacts occur between adjacent N3,N4 phen ligands with Cg6···Cg6v = 3.492 (4) and Cg6···Cg9v = 3.689 (4) Å [symmetry code: (v) 1 - x, -y, -z; Cg6 and Cg9 are the centroids of the N4/C28–C31 and C24–C27/C21/C32 rings, respectively]. Furthermore there are other significant π–π contacts Cg4···Cg8vi =3.948 (4) Å and Cg3···Cg10vii = 3.771 (4) Å between the aromatic rings of the other phen ligand and the benzene rings of both the coordinating and non-coordinating anions [symmetry codes: (vi) 3/2 - x, 1/2 + y, 1/2 - z; (vii) 3/2 - x, -1/2 + y, 1/2 - z; Cg3, Cg4, Cg8 and Cg10 are the centroids of the N1/C1–C4/C12, N2/C7–C11, C13–C18 and C33–C38 rings, respectively]. This extensive series of contacts combines to generate a three dimensional network structure.
Data collection: RAPID-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A packing diagram, viewed along the b axis. Dashed lines indicate hydrogen bonds. |
[Mn(C7H4BrO2)(C12H8N2)2(H2O)](C7H4BrO2)·2H2O | F(000) = 1748 |
Mr = 869.42 | Dx = 1.611 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 14746 reflections |
a = 14.193 (3) Å | θ = 3.0–24.5° |
b = 11.912 (2) Å | µ = 2.65 mm−1 |
c = 21.253 (4) Å | T = 293 K |
β = 93.86 (3)° | Block, yellow |
V = 3584.9 (12) Å3 | 0.49 × 0.40 × 0.35 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 5952 independent reflections |
Radiation source: fine-focus sealed tube | 3857 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
ω scans | θmax = 24.5°, θmin = 3.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −16→16 |
Tmin = 0.289, Tmax = 0.399 | k = −12→13 |
26000 measured reflections | l = −24→24 |
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)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.205 | w = 1/[σ2(Fo2) + (0.0898P)2 + 6.5748P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
5952 reflections | Δρmax = 0.66 e Å−3 |
473 parameters | Δρmin = −1.01 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0053 (6) |
[Mn(C7H4BrO2)(C12H8N2)2(H2O)](C7H4BrO2)·2H2O | V = 3584.9 (12) Å3 |
Mr = 869.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.193 (3) Å | µ = 2.65 mm−1 |
b = 11.912 (2) Å | T = 293 K |
c = 21.253 (4) Å | 0.49 × 0.40 × 0.35 mm |
β = 93.86 (3)° |
Rigaku R-AXIS RAPID diffractometer | 5952 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3857 reflections with I > 2σ(I) |
Tmin = 0.289, Tmax = 0.399 | Rint = 0.093 |
26000 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 6 restraints |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.66 e Å−3 |
5952 reflections | Δρmin = −1.01 e Å−3 |
473 parameters |
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. |
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 > 2sigma(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 | 0.56915 (7) | 0.11055 (8) | 0.18912 (4) | 0.0445 (3) | |
N1 | 0.4353 (4) | 0.1308 (4) | 0.2469 (2) | 0.0484 (13) | |
N2 | 0.6170 (4) | 0.1671 (5) | 0.2888 (2) | 0.0506 (13) | |
N3 | 0.5305 (4) | −0.0764 (4) | 0.1816 (2) | 0.0487 (13) | |
N4 | 0.4701 (4) | 0.0841 (4) | 0.0990 (2) | 0.0449 (12) | |
Br1 | 1.1551 (5) | 0.0191 (13) | 0.0874 (6) | 0.0857 (12) | 0.50 |
Br1' | 1.1764 (5) | 0.0103 (13) | 0.0992 (6) | 0.0857 (12) | 0.50 |
Br2 | 0.93834 (5) | 0.38650 (7) | 0.10085 (4) | 0.0712 (3) | |
O1 | 0.7019 (3) | 0.0811 (4) | 0.1526 (2) | 0.0626 (13) | |
O2 | 0.7475 (4) | −0.0247 (5) | 0.2351 (2) | 0.0722 (14) | |
O3 | 0.5724 (3) | 0.2821 (4) | 0.1613 (2) | 0.0631 (12) | |
H3WA | 0.5294 | 0.3289 | 0.1687 | 0.076* | |
H3WB | 0.6186 | 0.3240 | 0.1534 | 0.076* | |
O4 | 1.4147 (4) | 0.4000 (5) | 0.1686 (2) | 0.0690 (14) | |
O5 | 1.4133 (3) | 0.4581 (5) | 0.0697 (2) | 0.0701 (14) | |
O6 | 1.4030 (4) | 0.4556 (5) | −0.0600 (3) | 0.0849 (16) | |
H6WA | 1.3986 | 0.4925 | −0.0261 | 0.102* | |
H6WB | 1.4264 | 0.5015 | −0.0853 | 0.102* | |
O7 | 0.7205 (4) | 0.4136 (5) | 0.1376 (3) | 0.0854 (17) | |
H7WA | 0.7754 | 0.3885 | 0.1480 | 0.102* | |
H7WB | 0.7147 | 0.4419 | 0.1009 | 0.102* | |
C1 | 0.3473 (5) | 0.1152 (6) | 0.2263 (3) | 0.0599 (18) | |
H1A | 0.3350 | 0.0931 | 0.1846 | 0.072* | |
C2 | 0.2707 (5) | 0.1299 (7) | 0.2636 (4) | 0.072 (2) | |
H2A | 0.2092 | 0.1169 | 0.2472 | 0.086* | |
C3 | 0.2883 (5) | 0.1638 (6) | 0.3245 (4) | 0.069 (2) | |
H3A | 0.2385 | 0.1757 | 0.3499 | 0.082* | |
C4 | 0.3804 (5) | 0.1807 (6) | 0.3485 (3) | 0.0576 (17) | |
C5 | 0.4046 (6) | 0.2155 (7) | 0.4125 (3) | 0.069 (2) | |
H5A | 0.3571 | 0.2261 | 0.4400 | 0.082* | |
C6 | 0.4940 (7) | 0.2325 (7) | 0.4325 (3) | 0.074 (2) | |
H6A | 0.5078 | 0.2538 | 0.4742 | 0.088* | |
C7 | 0.5697 (5) | 0.2192 (6) | 0.3921 (3) | 0.0557 (17) | |
C8 | 0.6649 (6) | 0.2411 (6) | 0.4104 (3) | 0.071 (2) | |
H8A | 0.6819 | 0.2644 | 0.4514 | 0.085* | |
C9 | 0.7325 (6) | 0.2282 (7) | 0.3684 (3) | 0.072 (2) | |
H9A | 0.7954 | 0.2441 | 0.3801 | 0.086* | |
C10 | 0.7060 (5) | 0.1913 (7) | 0.3082 (3) | 0.0642 (19) | |
H10A | 0.7526 | 0.1829 | 0.2798 | 0.077* | |
C11 | 0.5493 (5) | 0.1832 (5) | 0.3304 (3) | 0.0463 (15) | |
C12 | 0.4530 (4) | 0.1634 (5) | 0.3078 (3) | 0.0464 (15) | |
C13 | 0.8606 (5) | 0.0191 (5) | 0.1618 (3) | 0.0489 (15) | |
C14 | 0.8805 (5) | 0.0655 (7) | 0.1047 (4) | 0.067 (2) | |
H14A | 0.8325 | 0.0988 | 0.0793 | 0.080* | |
C15 | 0.9710 (6) | 0.0628 (8) | 0.0853 (4) | 0.078 (2) | |
H15A | 0.9837 | 0.0934 | 0.0465 | 0.093* | |
C16 | 1.0420 (5) | 0.0158 (6) | 0.1224 (4) | 0.0591 (18) | |
C17 | 1.0244 (5) | −0.0307 (6) | 0.1787 (4) | 0.0615 (19) | |
H17A | 1.0733 | −0.0632 | 0.2038 | 0.074* | |
C18 | 0.9340 (5) | −0.0297 (6) | 0.1986 (3) | 0.0519 (16) | |
H18A | 0.9220 | −0.0620 | 0.2371 | 0.062* | |
C19 | 0.7627 (5) | 0.0248 (6) | 0.1851 (3) | 0.0571 (18) | |
C21 | 0.5591 (5) | −0.1556 (6) | 0.2225 (3) | 0.0543 (17) | |
H21A | 0.5965 | −0.1346 | 0.2582 | 0.065* | |
C22 | 0.5360 (5) | −0.2685 (6) | 0.2146 (4) | 0.0649 (19) | |
H22A | 0.5569 | −0.3210 | 0.2448 | 0.078* | |
C23 | 0.4827 (5) | −0.3015 (6) | 0.1623 (4) | 0.0620 (19) | |
H23A | 0.4673 | −0.3768 | 0.1562 | 0.074* | |
C24 | 0.4514 (4) | −0.2215 (6) | 0.1179 (3) | 0.0508 (16) | |
C25 | 0.3961 (5) | −0.2478 (7) | 0.0603 (3) | 0.0630 (19) | |
H25A | 0.3812 | −0.3222 | 0.0511 | 0.076* | |
C26 | 0.3658 (5) | −0.1671 (7) | 0.0197 (3) | 0.0620 (19) | |
H26A | 0.3297 | −0.1868 | −0.0168 | 0.074* | |
C27 | 0.3875 (4) | −0.0527 (6) | 0.0312 (3) | 0.0500 (16) | |
C28 | 0.3580 (5) | 0.0365 (7) | −0.0096 (3) | 0.0597 (19) | |
H28A | 0.3205 | 0.0217 | −0.0462 | 0.072* | |
C29 | 0.3845 (5) | 0.1437 (6) | 0.0047 (3) | 0.0561 (17) | |
H29A | 0.3646 | 0.2025 | −0.0217 | 0.067* | |
C30 | 0.4409 (4) | 0.1644 (6) | 0.0587 (3) | 0.0495 (15) | |
H30A | 0.4595 | 0.2379 | 0.0673 | 0.059* | |
C31 | 0.4436 (4) | −0.0226 (5) | 0.0856 (3) | 0.0441 (14) | |
C32 | 0.4752 (4) | −0.1087 (5) | 0.1296 (3) | 0.0465 (15) | |
C33 | 1.2670 (5) | 0.4084 (5) | 0.1103 (3) | 0.0472 (15) | |
C34 | 1.2206 (5) | 0.3675 (6) | 0.1606 (3) | 0.0594 (18) | |
H34A | 1.2552 | 0.3462 | 0.1974 | 0.071* | |
C35 | 1.1240 (6) | 0.3579 (7) | 0.1569 (4) | 0.070 (2) | |
H35A | 1.0938 | 0.3285 | 0.1908 | 0.084* | |
C36 | 1.0719 (5) | 0.3915 (6) | 0.1036 (3) | 0.0579 (17) | |
C37 | 1.1172 (5) | 0.4316 (6) | 0.0528 (3) | 0.0599 (18) | |
H37A | 1.0823 | 0.4527 | 0.0161 | 0.072* | |
C38 | 1.2146 (5) | 0.4403 (6) | 0.0564 (3) | 0.0591 (18) | |
H38A | 1.2450 | 0.4678 | 0.0222 | 0.071* | |
C39 | 1.3731 (5) | 0.4228 (6) | 0.1165 (3) | 0.0524 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0424 (6) | 0.0504 (6) | 0.0409 (5) | 0.0014 (4) | 0.0039 (4) | −0.0048 (4) |
N1 | 0.040 (3) | 0.058 (3) | 0.048 (3) | 0.002 (2) | 0.008 (2) | −0.003 (2) |
N2 | 0.051 (3) | 0.057 (3) | 0.044 (3) | 0.002 (3) | 0.005 (2) | −0.009 (2) |
N3 | 0.054 (3) | 0.046 (3) | 0.046 (3) | 0.002 (3) | 0.003 (2) | −0.003 (2) |
N4 | 0.047 (3) | 0.049 (3) | 0.038 (3) | 0.007 (2) | −0.001 (2) | 0.000 (2) |
Br1 | 0.020 (3) | 0.134 (2) | 0.103 (4) | −0.005 (3) | 0.003 (2) | −0.019 (3) |
Br1' | 0.020 (3) | 0.134 (2) | 0.103 (4) | −0.005 (3) | 0.003 (2) | −0.019 (3) |
Br2 | 0.0485 (5) | 0.0924 (7) | 0.0734 (5) | −0.0039 (4) | 0.0098 (4) | 0.0010 (4) |
O1 | 0.043 (3) | 0.072 (3) | 0.072 (3) | 0.012 (2) | 0.000 (2) | −0.006 (3) |
O2 | 0.054 (3) | 0.100 (4) | 0.063 (3) | −0.005 (3) | 0.009 (2) | −0.010 (3) |
O3 | 0.050 (3) | 0.051 (3) | 0.089 (3) | 0.000 (2) | 0.004 (2) | 0.000 (2) |
O4 | 0.051 (3) | 0.095 (4) | 0.060 (3) | 0.008 (3) | 0.004 (2) | 0.004 (3) |
O5 | 0.053 (3) | 0.095 (4) | 0.064 (3) | −0.007 (3) | 0.015 (2) | 0.014 (3) |
O6 | 0.0841 (18) | 0.0868 (18) | 0.0837 (18) | −0.0013 (10) | 0.0060 (10) | −0.0003 (10) |
O7 | 0.061 (3) | 0.108 (5) | 0.089 (4) | −0.010 (3) | 0.011 (3) | 0.009 (3) |
C1 | 0.038 (4) | 0.082 (5) | 0.061 (4) | −0.006 (3) | 0.014 (3) | −0.006 (3) |
C2 | 0.042 (4) | 0.080 (6) | 0.095 (6) | −0.004 (4) | 0.011 (4) | 0.005 (4) |
C3 | 0.063 (5) | 0.068 (5) | 0.079 (5) | 0.007 (4) | 0.035 (4) | 0.005 (4) |
C4 | 0.058 (4) | 0.051 (4) | 0.066 (4) | 0.002 (3) | 0.020 (3) | 0.004 (3) |
C5 | 0.083 (6) | 0.068 (5) | 0.058 (4) | 0.002 (4) | 0.029 (4) | −0.005 (4) |
C6 | 0.105 (7) | 0.067 (5) | 0.050 (4) | −0.004 (5) | 0.016 (4) | −0.009 (3) |
C7 | 0.075 (5) | 0.053 (4) | 0.039 (3) | 0.003 (4) | 0.006 (3) | −0.003 (3) |
C8 | 0.097 (6) | 0.068 (5) | 0.045 (4) | −0.002 (4) | −0.011 (4) | −0.010 (3) |
C9 | 0.069 (5) | 0.082 (6) | 0.062 (4) | 0.004 (4) | −0.013 (4) | −0.015 (4) |
C10 | 0.042 (4) | 0.087 (6) | 0.063 (4) | 0.002 (4) | −0.002 (3) | −0.023 (4) |
C11 | 0.056 (4) | 0.043 (4) | 0.040 (3) | 0.007 (3) | 0.006 (3) | 0.001 (3) |
C12 | 0.051 (4) | 0.045 (4) | 0.044 (3) | 0.007 (3) | 0.015 (3) | −0.003 (3) |
C13 | 0.051 (4) | 0.044 (4) | 0.052 (4) | 0.000 (3) | 0.001 (3) | −0.012 (3) |
C14 | 0.058 (5) | 0.076 (5) | 0.066 (5) | 0.005 (4) | 0.003 (4) | 0.015 (4) |
C15 | 0.059 (5) | 0.100 (6) | 0.077 (5) | −0.010 (5) | 0.025 (4) | 0.018 (5) |
C16 | 0.040 (4) | 0.063 (5) | 0.074 (5) | −0.003 (3) | 0.001 (3) | −0.009 (4) |
C17 | 0.053 (4) | 0.055 (4) | 0.075 (5) | 0.009 (3) | −0.010 (4) | −0.013 (4) |
C18 | 0.045 (4) | 0.056 (4) | 0.054 (4) | 0.008 (3) | 0.004 (3) | −0.006 (3) |
C19 | 0.058 (4) | 0.057 (4) | 0.058 (4) | −0.006 (4) | 0.010 (4) | −0.019 (3) |
C21 | 0.045 (4) | 0.068 (5) | 0.050 (4) | 0.001 (3) | 0.008 (3) | 0.006 (3) |
C22 | 0.059 (5) | 0.058 (5) | 0.079 (5) | 0.005 (4) | 0.014 (4) | 0.016 (4) |
C23 | 0.054 (4) | 0.046 (4) | 0.088 (5) | −0.001 (3) | 0.020 (4) | 0.006 (4) |
C24 | 0.041 (3) | 0.055 (4) | 0.057 (4) | −0.003 (3) | 0.013 (3) | −0.007 (3) |
C25 | 0.061 (5) | 0.061 (5) | 0.068 (5) | −0.013 (4) | 0.015 (4) | −0.015 (4) |
C26 | 0.046 (4) | 0.085 (6) | 0.056 (4) | −0.011 (4) | 0.007 (3) | −0.020 (4) |
C27 | 0.038 (3) | 0.067 (5) | 0.045 (3) | −0.001 (3) | 0.004 (3) | −0.011 (3) |
C28 | 0.050 (4) | 0.089 (6) | 0.040 (3) | 0.004 (4) | 0.004 (3) | −0.006 (3) |
C29 | 0.051 (4) | 0.071 (5) | 0.045 (4) | 0.012 (4) | −0.003 (3) | 0.004 (3) |
C30 | 0.049 (4) | 0.053 (4) | 0.046 (3) | 0.008 (3) | −0.002 (3) | −0.005 (3) |
C31 | 0.045 (4) | 0.050 (4) | 0.038 (3) | −0.002 (3) | 0.011 (3) | −0.002 (3) |
C32 | 0.044 (4) | 0.053 (4) | 0.044 (3) | 0.000 (3) | 0.013 (3) | −0.004 (3) |
C33 | 0.047 (4) | 0.045 (4) | 0.050 (4) | 0.004 (3) | 0.006 (3) | −0.002 (3) |
C34 | 0.043 (4) | 0.072 (5) | 0.064 (4) | 0.007 (3) | 0.006 (3) | 0.018 (3) |
C35 | 0.071 (5) | 0.076 (5) | 0.066 (5) | −0.001 (4) | 0.033 (4) | 0.016 (4) |
C36 | 0.058 (4) | 0.060 (4) | 0.057 (4) | 0.001 (3) | 0.014 (3) | 0.007 (3) |
C37 | 0.052 (4) | 0.079 (5) | 0.048 (4) | 0.000 (4) | −0.004 (3) | 0.003 (3) |
C38 | 0.057 (4) | 0.071 (5) | 0.050 (4) | −0.003 (4) | 0.003 (3) | −0.001 (3) |
C39 | 0.050 (4) | 0.049 (4) | 0.059 (4) | −0.001 (3) | 0.003 (3) | −0.007 (3) |
Mn1—O1 | 2.114 (5) | C10—H10A | 0.9300 |
Mn1—O3 | 2.128 (5) | C11—C12 | 1.438 (9) |
Mn1—N2 | 2.282 (5) | C13—C14 | 1.380 (9) |
Mn1—N3 | 2.297 (5) | C13—C18 | 1.387 (9) |
Mn1—N4 | 2.320 (5) | C13—C19 | 1.508 (9) |
Mn1—N1 | 2.343 (5) | C14—C15 | 1.376 (11) |
N1—C1 | 1.310 (8) | C14—H14A | 0.9300 |
N1—C12 | 1.358 (7) | C15—C16 | 1.357 (11) |
N2—C10 | 1.334 (8) | C15—H15A | 0.9300 |
N2—C11 | 1.363 (7) | C16—C17 | 1.358 (10) |
N3—C21 | 1.328 (8) | C17—C18 | 1.379 (10) |
N3—C32 | 1.367 (8) | C17—H17A | 0.9300 |
N4—C30 | 1.331 (8) | C18—H18A | 0.9300 |
N4—C31 | 1.351 (8) | C21—C22 | 1.392 (10) |
Br1—C16 | 1.814 (13) | C21—H21A | 0.9300 |
Br1'—C16 | 2.003 (12) | C22—C23 | 1.360 (10) |
Br2—C36 | 1.894 (7) | C22—H22A | 0.9300 |
O1—C19 | 1.261 (8) | C23—C24 | 1.393 (10) |
O2—C19 | 1.246 (8) | C23—H23A | 0.9300 |
O3—H3WA | 0.8500 | C24—C32 | 1.404 (9) |
O3—H3WB | 0.8501 | C24—C25 | 1.443 (9) |
O4—C39 | 1.250 (8) | C25—C26 | 1.343 (10) |
O5—C39 | 1.253 (8) | C25—H25A | 0.9300 |
O6—H6WA | 0.8500 | C26—C27 | 1.415 (10) |
O6—H6WB | 0.8499 | C26—H26A | 0.9300 |
O7—H7WA | 0.8500 | C27—C31 | 1.404 (9) |
O7—H7WB | 0.8499 | C27—C28 | 1.417 (10) |
C1—C2 | 1.398 (10) | C28—C29 | 1.359 (10) |
C1—H1A | 0.9300 | C28—H28A | 0.9300 |
C2—C3 | 1.363 (11) | C29—C30 | 1.376 (9) |
C2—H2A | 0.9300 | C29—H29A | 0.9300 |
C3—C4 | 1.385 (10) | C30—H30A | 0.9300 |
C3—H3A | 0.9300 | C31—C32 | 1.439 (9) |
C4—C12 | 1.404 (8) | C33—C38 | 1.375 (9) |
C4—C5 | 1.442 (10) | C33—C34 | 1.382 (9) |
C5—C6 | 1.326 (11) | C33—C39 | 1.513 (9) |
C5—H5A | 0.9300 | C34—C35 | 1.372 (10) |
C6—C7 | 1.429 (10) | C34—H34A | 0.9300 |
C6—H6A | 0.9300 | C35—C36 | 1.371 (10) |
C7—C11 | 1.392 (8) | C35—H35A | 0.9300 |
C7—C8 | 1.404 (10) | C36—C37 | 1.378 (10) |
C8—C9 | 1.363 (11) | C37—C38 | 1.384 (10) |
C8—H8A | 0.9300 | C37—H37A | 0.9300 |
C9—C10 | 1.380 (9) | C38—H38A | 0.9300 |
C9—H9A | 0.9300 | ||
O1—Mn1—O3 | 91.20 (19) | C16—C15—C14 | 120.4 (7) |
O1—Mn1—N2 | 99.94 (19) | C16—C15—H15A | 119.8 |
O3—Mn1—N2 | 87.91 (19) | C14—C15—H15A | 119.8 |
O1—Mn1—N3 | 91.62 (19) | C15—C16—C17 | 120.5 (7) |
O3—Mn1—N3 | 157.11 (18) | C15—C16—Br1 | 113.3 (7) |
N2—Mn1—N3 | 113.92 (19) | C17—C16—Br1 | 126.2 (7) |
O1—Mn1—N4 | 100.37 (18) | C15—C16—Br1' | 123.5 (7) |
O3—Mn1—N4 | 85.67 (18) | C17—C16—Br1' | 116.0 (6) |
N2—Mn1—N4 | 158.80 (18) | Br1—C16—Br1' | 10.4 (7) |
N3—Mn1—N4 | 71.48 (18) | C16—C17—C18 | 119.8 (7) |
O1—Mn1—N1 | 169.49 (19) | C16—C17—H17A | 120.1 |
O3—Mn1—N1 | 94.60 (18) | C18—C17—H17A | 120.1 |
N2—Mn1—N1 | 71.58 (19) | C17—C18—C13 | 120.7 (6) |
N3—Mn1—N1 | 86.44 (18) | C17—C18—H18A | 119.7 |
N4—Mn1—N1 | 88.82 (18) | C13—C18—H18A | 119.7 |
C1—N1—C12 | 118.1 (5) | O2—C19—O1 | 124.6 (7) |
C1—N1—Mn1 | 126.8 (4) | O2—C19—C13 | 118.3 (7) |
C12—N1—Mn1 | 115.1 (4) | O1—C19—C13 | 117.1 (6) |
C10—N2—C11 | 117.6 (5) | N3—C21—C22 | 123.3 (7) |
C10—N2—Mn1 | 124.6 (4) | N3—C21—H21A | 118.4 |
C11—N2—Mn1 | 117.7 (4) | C22—C21—H21A | 118.4 |
C21—N3—C32 | 117.5 (6) | C23—C22—C21 | 119.4 (7) |
C21—N3—Mn1 | 125.6 (5) | C23—C22—H22A | 120.3 |
C32—N3—Mn1 | 116.8 (4) | C21—C22—H22A | 120.3 |
C30—N4—C31 | 118.0 (5) | C22—C23—C24 | 119.4 (7) |
C30—N4—Mn1 | 125.4 (4) | C22—C23—H23A | 120.3 |
C31—N4—Mn1 | 116.5 (4) | C24—C23—H23A | 120.3 |
C19—O1—Mn1 | 118.7 (4) | C23—C24—C32 | 118.2 (6) |
Mn1—O3—H3WA | 123.4 | C23—C24—C25 | 123.8 (7) |
Mn1—O3—H3WB | 130.6 | C32—C24—C25 | 117.9 (6) |
H3WA—O3—H3WB | 103.0 | C26—C25—C24 | 121.5 (7) |
H6WA—O6—H6WB | 105.0 | C26—C25—H25A | 119.3 |
H7WA—O7—H7WB | 114.2 | C24—C25—H25A | 119.3 |
N1—C1—C2 | 123.6 (7) | C25—C26—C27 | 121.4 (6) |
N1—C1—H1A | 118.2 | C25—C26—H26A | 119.3 |
C2—C1—H1A | 118.2 | C27—C26—H26A | 119.3 |
C3—C2—C1 | 118.4 (7) | C31—C27—C26 | 119.5 (6) |
C3—C2—H2A | 120.8 | C31—C27—C28 | 116.1 (6) |
C1—C2—H2A | 120.8 | C26—C27—C28 | 124.3 (6) |
C2—C3—C4 | 120.0 (6) | C29—C28—C27 | 120.1 (6) |
C2—C3—H3A | 120.0 | C29—C28—H28A | 120.0 |
C4—C3—H3A | 120.0 | C27—C28—H28A | 120.0 |
C3—C4—C12 | 117.8 (6) | C28—C29—C30 | 119.4 (7) |
C3—C4—C5 | 123.2 (6) | C28—C29—H29A | 120.3 |
C12—C4—C5 | 119.0 (7) | C30—C29—H29A | 120.3 |
C6—C5—C4 | 120.5 (7) | N4—C30—C29 | 123.1 (7) |
C6—C5—H5A | 119.7 | N4—C30—H30A | 118.4 |
C4—C5—H5A | 119.7 | C29—C30—H30A | 118.4 |
C5—C6—C7 | 122.2 (7) | N4—C31—C27 | 123.2 (6) |
C5—C6—H6A | 118.9 | N4—C31—C32 | 117.6 (5) |
C7—C6—H6A | 118.9 | C27—C31—C32 | 119.2 (6) |
C11—C7—C8 | 116.9 (6) | N3—C32—C24 | 122.1 (6) |
C11—C7—C6 | 118.9 (7) | N3—C32—C31 | 117.5 (6) |
C8—C7—C6 | 124.2 (6) | C24—C32—C31 | 120.4 (6) |
C9—C8—C7 | 120.3 (6) | C38—C33—C34 | 118.9 (6) |
C9—C8—H8A | 119.8 | C38—C33—C39 | 121.4 (6) |
C7—C8—H8A | 119.8 | C34—C33—C39 | 119.7 (6) |
C8—C9—C10 | 118.9 (7) | C35—C34—C33 | 120.8 (7) |
C8—C9—H9A | 120.6 | C35—C34—H34A | 119.6 |
C10—C9—H9A | 120.6 | C33—C34—H34A | 119.6 |
N2—C10—C9 | 123.3 (7) | C36—C35—C34 | 120.2 (6) |
N2—C10—H10A | 118.4 | C36—C35—H35A | 119.9 |
C9—C10—H10A | 118.4 | C34—C35—H35A | 119.9 |
N2—C11—C7 | 123.0 (6) | C35—C36—C37 | 119.7 (7) |
N2—C11—C12 | 117.1 (5) | C35—C36—Br2 | 119.9 (5) |
C7—C11—C12 | 119.9 (6) | C37—C36—Br2 | 120.4 (6) |
N1—C12—C4 | 122.1 (6) | C36—C37—C38 | 119.9 (7) |
N1—C12—C11 | 118.4 (5) | C36—C37—H37A | 120.1 |
C4—C12—C11 | 119.4 (6) | C38—C37—H37A | 120.1 |
C14—C13—C18 | 118.2 (6) | C33—C38—C37 | 120.5 (6) |
C14—C13—C19 | 121.2 (6) | C33—C38—H38A | 119.7 |
C18—C13—C19 | 120.5 (6) | C37—C38—H38A | 119.7 |
C15—C14—C13 | 120.4 (7) | O4—C39—O5 | 124.4 (6) |
C15—C14—H14A | 119.8 | O4—C39—C33 | 117.5 (6) |
C13—C14—H14A | 119.8 | O5—C39—C33 | 118.2 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3WA···O4i | 0.85 | 1.83 | 2.656 (7) | 162 |
O3—H3WB···O7 | 0.85 | 1.85 | 2.696 (7) | 179 |
O6—H6WA···O5 | 0.85 | 2.07 | 2.751 (8) | 136 |
O6—H6WB···O5ii | 0.85 | 2.33 | 2.823 (7) | 118 |
O6—H6WB···O7iii | 0.85 | 2.51 | 2.798 (9) | 101 |
O7—H7WA···Br2 | 0.85 | 2.58 | 3.256 (6) | 137 |
O7—H7WB···O6iii | 0.85 | 2.20 | 2.798 (9) | 127 |
C21—H21A···O2 | 0.93 | 2.59 | 3.091 (9) | 115 |
C28—H28A···O1iv | 0.93 | 2.57 | 3.402 (8) | 149 |
C30—H30A···O3 | 0.93 | 2.53 | 3.107 (8) | 121 |
Symmetry codes: (i) x−1, y, z; (ii) −x+3, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3WA···O4i | 0.85 | 1.83 | 2.656 (7) | 162 |
O3—H3WB···O7 | 0.85 | 1.85 | 2.696 (7) | 179 |
O6—H6WA···O5 | 0.85 | 2.07 | 2.751 (8) | 136 |
O6—H6WB···O5ii | 0.85 | 2.33 | 2.823 (7) | 118 |
O6—H6WB···O7iii | 0.85 | 2.51 | 2.798 (9) | 101 |
O7—H7WA···Br2 | 0.85 | 2.58 | 3.256 (6) | 137 |
O7—H7WB···O6iii | 0.85 | 2.20 | 2.798 (9) | 127 |
C21—H21A···O2 | 0.93 | 2.59 | 3.091 (9) | 115 |
C28—H28A···O1iv | 0.93 | 2.57 | 3.402 (8) | 149 |
C30—H30A···O3 | 0.93 | 2.53 | 3.107 (8) | 121 |
Symmetry codes: (i) x−1, y, z; (ii) −x+3, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H4BrO2)(C12H8N2)2(H2O)](C7H4BrO2)·2H2O |
Mr | 869.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 14.193 (3), 11.912 (2), 21.253 (4) |
β (°) | 93.86 (3) |
V (Å3) | 3584.9 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.65 |
Crystal size (mm) | 0.49 × 0.40 × 0.35 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.289, 0.399 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26000, 5952, 3857 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.583 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.205, 1.13 |
No. of reflections | 5952 |
No. of parameters | 473 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −1.01 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (grant No. 51343003).
References
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Rigaku (1998). RAPID-AUTO. Rigaku Corporation. Tokyo Japan. Google Scholar
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Zhang, B.-S. (2007). Z. Kristallogr. New Cryst. Struct. 222, 274–276. CAS Google Scholar
Zhang, B.-S., Wu, C.-S. & Xu, W. (2010). Acta Cryst. E66, m1426. Web of Science CSD CrossRef IUCr Journals Google Scholar
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