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5,6-Dioxo-1,10-phenanthroline-2,9-dicarb­oxy­lic acid dihydrate (H2pdda·2H2O), C14H6N2O6·2H2O, was obtained by car­bonyl­ation of 1,10-phenanthroline-2,9-dicarb­oxy­lic acid. Its first coordination compound, [MnCl(C14H6N2O6)(H2O)2]Cl·2H2O, in which the H2pdda ligand remains protonated, was synthesized in aqueous acetic acid. H2pdda chelates one water mol­ecule via hydrogen bonds in H2pdda·2H2O, whereas in the coordination compound it chelates one hepta­coordinate MnII atom via coordination bonds. The N atoms in H2pdda·2H2O and the Cl atoms in the coordination compound are also involved in hydrogen bonds. Extensive hydrogen bonding results in supra­molecular networks in both com­pounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112017763/tp3010sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112017763/tp3010Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112017763/tp3010IIsup3.hkl
Contains datablock II

CCDC references: 854367; 860768

Comment top

1,10-Phenanthroline is among the most extensively studied chelators and its numerous derivatives have played key roles in coordination and supramolecular chemistry (Bencini & Lippolis, 2010; Luman & Castellano, 2004). 1,10-Phenanthroline-5,6-dione (Ma et al., 2010; Braband et al., 2010; Dong et al., 2010; Liu et al., 2008; Wang et al., 2006; Zheng et al., 2010; Patel et al., 2010; Goswami & Chakrabarty, 2010; Si et al., 2009; Ettedgui & Neumann, 2009; Zhao et al., 2008; Bodige & MacDonnell, 1997; Lenaerts et al., 2005; Cardinaels et al., 2008; Beaudoin & Obare, 2008) and 1,10-phenanthroline-2,9-dicarboxylic acid (Miao et al., 2010; Chen et al., 2010; Williams et al., 2009; Harbuzaru et al., 2009; Dean et al., 2008; Fan et al., 2008; Melton et al., 2006; Garas & Vagg, 2000) are two of the important derivatives, whereas 5,6-dioxo-1,10-phenanthroline-2,9-dicarboxylic acid (H2pdda), which combines both the 5,6-dicarbonyl and 2,9-dicarboxyl groups, has received little attention (Lamarque et al., 2010; Echavarren & Porcel, 2006; Garas & Vagg, 2000; Evangelista & Pollak, 1986). No coordination compound of H2pdda has been reported. Continuing our interested in polypyridine compounds and their coordination behaviour (Wu et al., 1997, 2002, 2005), we discuss here the synthesis and structure of of H2pdda.2H2O, (I), and its first coordination compound [MnCl(H2pdda)(H2O)2]Cl.2H2O, (II).

Two previous procedures for obtaining (I) were reported (Evangelista & Pollak, 1986; Garas & Vagg, 2000) using 2,9-dimethyl-1,10-phenanthroline-5,6-dione as the reactant, but the yields were not high and the handling procedures were somewhat complicated. Here we used a new synthetic route with 1,10-phenanthroline-2,9-dicarboxylic acid as the starting material. The main advantages of this route are the improved yield and product separation is much simpler. The normal carbonylation procedure for 1,10-phenanthroline-type compounds includes oxidation with H2SO4/HNO3/KBr (or NaBr), neutralization of the resulting acidic solution, extraction of the quinone with dichloromethane, drying and distilling of the organic solution (Ma et al., 2010; Braband et al., 2010; Dong et al., 2010; Liu et al., 2008; Wang et al., 2006; Zheng et al., 2010; Patel et al., 2010; Goswami & Chakrabarty, 2010; Si et al., 2009; Ettedgui & Neumann, 2009; Zhao et al., 2008; Bodige & MacDonnell, 1997; Lenaerts et al., 2005; Cardinaels et al., 2008; Beaudoin & Obare, 2008). For 1,10-phenanthroline-2,9-dicarboxylic acid, the solution remains acidic after oxidation and, on pouring into cold water, the product precipitated directly with a high yield. This is reasonable since the two carboxyl groups should make H2pdda less soluble in acidic solution. The proton NMR spectrum of (I) shows three kinds of protons, including the carboxyl protons, and their integration areas are fully consistent with the structure of H2pdda. Interestingly, the X-ray structural analysis confirms that H2pdda preferentially exists as the dihydrate, just like those reported previously without X-ray analysis (Evangelista & Pollak, 1986; Garas & Vagg, 2000).

Complex (II) is the first reported coordination compound of H2pdda and it is noteworthy that this crystalline solid was obtained in acetic acid/water solution. The acidic solution favours the protonation form of H2pdda, which is supported by the infrared spectrum of the complex since the characteristic strong band around 1600 cm-1 corresponding to the asymmetric stretching of a deprotonated carboxyl group (Nakamoto, 2009) was not observed. The X-ray diffraction data for both (I) and (II) are of high quality and the protons are generally visible in the difference Fourier maps. Therefore, we believe the detailed description of the structures (specifically the hydrogen bonding) is reliable.

The asymmetric unit of (I) is shown in Fig. 1 and consists of one H2pdda molecule and two water molecules. The lengths of the C7—O3 and C8—O4 carbonyl bonds are 1.203 (3) and 1.210 (3) Å, respectively, comparable to the corresponding data in 1,10-phenanthroline-5,6-dione which range from 1.207 (3) to 1.214 (3) Å (Calderazzo et al., 1999). This reflects [the fact] that the two carboxyl groups at the 2- and 9-positions do not have a significant influence on the carbonyl groups. The location of the carboxyl H atoms which are clearly visible in the difference Fourier map is also confirmed by the C—O bond lengths: the C1O1 and C14O5 double-bond lengths are 1.219 (3) and 1.200 (3) Å, respectively, whereas the C1—O2 and C14—O6 single-bond lengths are significantly longer at 1.298 (3) and 1.305 (3) Å, respectively. The two carboxyl groups are approximately coplanar with the phenanthroline unit, particularly that defined by C1 as the N1—C2—C1—O1 and N2—C13—C14—O5 torsion angles of 176.5 (2) and 15.3 (4)°, respectively. It is interesting that the O1W water molecule is situated such that the O atom and its attached H atom (H2W) look to be chelated by two N atoms and two carboxyl groups through O—H···O and O—H···N hydrogen bonds (Table 1, and Figs. 1 and 2). This water molecule donates the other hydrogen atom (H1W) to carboxyl atom O1 in an adjacent H2pdda molecule (symmetry code: x, -y+5/2, z-1/2). These classical hydrogen bonds, together with nonclassical intermolecular C—H···O hydrogen bonds (Steiner, 1996) between C12 and O4(x, -y+3/2, z-1/2), lead to the formation of a corrugated layer parallel to the (001) direction, as shown in Fig. 2. The other water molecule (O2W) forms three hydrogen bonds with three H2pdda molecules. These hydrogen bonds further link two adjacent antiparallel layers, giving rise to a double-layer network (Fig. 2b).

The molecular structure of (II) is shown in Fig. 3. The MnII atom is seven coordinate, ligated by a tetradentate H2pdda molecule, two water molecules and one chloride ion, forming the pentagonal– bipyramidal geometry. The H2pdda ligand remains protonated and binds to the MnII atom in a planar N2O2 chelation manner. The rigid nature of the ligand ensures that the Mn—O(carboxyl) bond lengths [2.430 (3) and 2.461 (3) Å for O5 and O1, respectively] are longer than the Mn—O(water) bond lengths [2.204 (3) and 2.248 (3) Å for O1W and O2W, respectively], which are comparable to the Mn—N bond lengths [2.295 (3) and 2.298 (3) Å for N1 and N2, respectively]. The Mn—Cl bond length [2.4945 (1) Å] falls into the expected range. Inspection of the bond lengths for H2pdda in (I) and (II) reveals no remarkable difference in the corresponding data, indicative of similar environments for the H2pdda molecule in the two compounds. This is reasonable if the H2pdda molecule in (I) is considered to `chelate' the water molecule in a similar fashion to the binding of H2pdda in (II), where the tetradentate H2pdda chelates the MnII atom. The discrepency in binding guests and bonding nature does not induce significant change in the structure of H2pdda.

There are also extensive hydrogen bonds (Table 2) in (II). As shown in Fig. 4, water molecules O4W or O5W are located on the same twofold axis. They connect two symmetry-related manganese complexes via hydrogen bonds to form a dimer. The O3W water molecule and the Cl- counter-ion are also involved in the formation of the dimer. Continuous hydrogen-bonding linkage among the dimers throughout the crystal lattice leads to a pillar-layer-like three-dimensional supramolecular network, as illustrated in Fig. 5.

Related literature top

For related literature, see: Beaudoin & Obare (2008); Bencini & Lippolis (2010); Bodige & MacDonnell (1997); Braband et al. (2010); Calderazzo et al. (1999); Cardinaels et al. (2008); Chen et al. (2010); Cooper et al. (2010); De Cian, DeLemos, Mergny, Teulade-Fichou & Monchaud (2007); Dean et al. (2008); Dong et al. (2010); Echavarren & Porcel (2006); Ettedgui & Neumann (2009); Evangelista & Pollak (1986); Fan et al. (2008); Garas & Vagg (2000); Goswami & Chakrabarty (2010); Harbuzaru et al. (2009); Lamarque et al. (2010); Lenaerts et al. (2005); Liu et al. (2008); Luman & Castellano (2004); Ma et al. (2010); Melton et al. (2006); Miao et al. (2010); Nakamoto (2009); Patel et al. (2010); Si et al. (2009); Steiner (1996); Wang et al. (2006); Williams et al. (2009); Wu et al. (1997, 2002, 2005); Zhao et al. (2008); Zheng et al. (2010).

Experimental top

For the synthesis of (I), cold concentrated H2SO4 (20 ml) and then concentrated HNO3 (10 ml) were added dropwise to a three-necked reaction flask loaded with 1,10-phenanthroline-2,9-dicarboxylic acid (De Cian et al., 2007) (2.68 g, 10 mmol) and potassium bromide (1.78 g, 15 mmol) in an ice-salt bath. After further stirring for 30 min, the mixture was heated to 358 K and refluxed for 4 h. The condenser tube was then removed and the solution allowed to cool to room temperature. The solution was poured into ice water (200 ml). The yellow precipitate was collected and washed (yield 2.70 g, 8.1 mmol, 81%). Recrystallization from acetone afforded crystals suitable for X-ray crystallographic analysis. 1H NMR (d6-DMSO): δ 13.70 (br, 2H, COOH), 8.60 (d, 2H, J = 8.0 Hz, 3-H), 8.27 (d, 2H, J = 8.0 Hz, 4-H). m.p.: 478 K. IR (KBr) ν/cm-1: 3514 (s), 3092 (m), 1927 (m), 1701 (vs), 1630 (m), 1570 (s), 1431 (m), 1385 (s), 1294 (m), 1229 (m), 1155 (m), 992 (m), 931 (m), 726 (m), 531 (s).

For the synthesis of (II), a solution of MnCl2.4H2O (19.8 mg, 0.1 mmol) in water (5 ml) was added dropwise to to a solution of H2pdda.2H2O (33.4 mg, 0.1 mmol) in glacial acetic acid (10 ml). The mixture was stirred for 2 h at 358 K and the resulting clear solution was evaporated for 2 weeks at room temperature to yield yellow crystals. IR (KBr) ν/cm-1: 3414 (b s), 2466 (m), 1876 (m), 1703 (vs), 1608 (m), 1575 (s), 1468 (m), 1389 (m), 1262 (s), 1242 (m), 936 (m), 812 (m), 714 (m), 528 (m).

Refinement top

H atoms attached to C atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). H atoms bound to O atoms were located from difference Fourier maps and treated in the riding-model approximation, with Uiso(H) = 1.5Ueq(O). The method described by Cooper et al. (2010) was applied to assist the location of the H atoms, especially H3W and H4W, for more rational hydrogen bonds and short contacts.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 30% probability level and dashed lines represent hydrogen bonds.
[Figure 2] Fig. 2. Three views of the hydrogen-bonding networks in (I). The H2pdda layer and the O1W water molecule are shown in (a), viewed down the a axis. These layers are bridged by O2W water molecules to form the double layers shown in (c) viewed down the c axis. part (b) ?.
[Figure 3] Fig. 3. The molecular structure of (II), with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x+1, y, -z+1/2.]
[Figure 4] Fig. 4. The dimer composed of two twofold-axis-related molecules in (II), formed by hydrogen bonds (dashed bonds). The twofold axis which bisects water molecules O4W and O5W is shown.
[Figure 5] Fig. 5. The pillar-layer-like hydrogen-bond network in (II).
(I) 5,6-dioxo-1,10-phenanthroline-2,9-dicarboxylic acid dihydrate top
Crystal data top
C14H6N2O6·2H2OF(000) = 688
Mr = 334.24Dx = 1.631 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1820 reflections
a = 7.206 (2) Åθ = 2.6–25.8°
b = 15.968 (6) ŵ = 0.14 mm1
c = 13.055 (3) ÅT = 296 K
β = 115.049 (13)°Block, colourless
V = 1360.9 (7) Å30.20 × 0.13 × 0.12 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2517 independent reflections
Radiation source: fine-focus sealed tube1610 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 88
Tmin = 0.973, Tmax = 0.984k = 1719
6770 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.4185P]
where P = (Fo2 + 2Fc2)/3
2517 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C14H6N2O6·2H2OV = 1360.9 (7) Å3
Mr = 334.24Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.206 (2) ŵ = 0.14 mm1
b = 15.968 (6) ÅT = 296 K
c = 13.055 (3) Å0.20 × 0.13 × 0.12 mm
β = 115.049 (13)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2517 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
1610 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.984Rint = 0.034
6770 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 1.03Δρmax = 0.18 e Å3
2517 reflectionsΔρmin = 0.29 e Å3
217 parameters
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
xyzUiso*/Ueq
O10.0582 (3)1.29993 (11)0.64417 (16)0.0557 (6)
O20.0660 (3)1.25251 (11)0.48964 (15)0.0551 (6)
H20.08331.20770.46430.083*
O30.4382 (4)0.91298 (14)0.89740 (17)0.0776 (7)
O40.4696 (3)0.79054 (12)0.76275 (17)0.0605 (6)
O50.2200 (3)1.01996 (12)0.24213 (15)0.0548 (5)
O60.2272 (3)0.88409 (11)0.20723 (16)0.0596 (6)
H60.19290.90010.14210.089*
N10.1997 (3)1.10060 (12)0.58679 (16)0.0339 (5)
N20.2549 (3)0.98064 (11)0.45496 (16)0.0327 (5)
C10.0962 (4)1.24268 (16)0.5943 (2)0.0422 (6)
C20.1736 (4)1.16042 (15)0.6506 (2)0.0366 (6)
C30.2129 (4)1.14979 (17)0.7632 (2)0.0441 (7)
H30.19161.19320.80450.053*
C40.2841 (4)1.07343 (17)0.8122 (2)0.0445 (7)
H40.31301.06420.88780.053*
C50.3123 (4)1.01008 (15)0.7475 (2)0.0376 (6)
C60.2667 (4)1.02579 (14)0.6342 (2)0.0328 (6)
C70.3919 (4)0.92756 (17)0.7992 (2)0.0453 (7)
C80.4134 (4)0.85965 (17)0.7239 (2)0.0419 (6)
C90.3658 (4)0.88056 (15)0.6053 (2)0.0366 (6)
C100.2959 (3)0.96023 (14)0.56153 (19)0.0315 (5)
C110.3927 (4)0.82113 (16)0.5368 (2)0.0432 (6)
H110.43930.76780.56440.052*
C120.3501 (4)0.84143 (16)0.4269 (2)0.0424 (7)
H120.36620.80230.37860.051*
C130.2826 (4)0.92140 (15)0.3900 (2)0.0356 (6)
C140.2373 (4)0.94806 (17)0.2715 (2)0.0392 (6)
O1W0.0457 (3)1.13852 (11)0.34725 (15)0.0538 (6)
H1W0.05821.15160.28800.081*
H2W0.10901.09410.37000.081*
O2W0.1357 (4)0.93251 (14)0.00342 (16)0.0728 (7)
H3W0.06240.89640.04600.109*
H4W0.21980.96620.00700.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0749 (15)0.0419 (11)0.0533 (12)0.0079 (10)0.0300 (11)0.0058 (9)
O20.0826 (16)0.0399 (11)0.0459 (11)0.0067 (10)0.0303 (11)0.0000 (8)
O30.116 (2)0.0759 (15)0.0421 (13)0.0238 (14)0.0344 (13)0.0151 (11)
O40.0706 (15)0.0529 (12)0.0614 (13)0.0133 (11)0.0313 (12)0.0188 (10)
O50.0773 (15)0.0488 (12)0.0430 (11)0.0019 (10)0.0301 (11)0.0004 (9)
O60.0897 (17)0.0506 (12)0.0448 (12)0.0007 (11)0.0345 (12)0.0084 (9)
N10.0324 (12)0.0372 (12)0.0343 (11)0.0030 (9)0.0163 (10)0.0027 (9)
N20.0297 (12)0.0373 (11)0.0333 (11)0.0019 (9)0.0156 (9)0.0007 (9)
C10.0448 (17)0.0395 (15)0.0431 (16)0.0028 (12)0.0193 (13)0.0067 (12)
C20.0324 (15)0.0382 (14)0.0401 (14)0.0039 (11)0.0161 (12)0.0037 (11)
C30.0472 (18)0.0466 (16)0.0419 (16)0.0046 (13)0.0221 (14)0.0107 (12)
C40.0477 (18)0.0556 (17)0.0336 (14)0.0024 (13)0.0204 (13)0.0013 (12)
C50.0319 (15)0.0455 (15)0.0363 (14)0.0034 (12)0.0155 (12)0.0016 (11)
C60.0280 (14)0.0373 (14)0.0356 (13)0.0038 (11)0.0160 (11)0.0010 (11)
C70.0455 (17)0.0551 (17)0.0354 (15)0.0005 (13)0.0172 (13)0.0067 (12)
C80.0350 (16)0.0417 (15)0.0498 (16)0.0026 (12)0.0187 (13)0.0098 (12)
C90.0312 (14)0.0390 (14)0.0421 (15)0.0009 (11)0.0180 (12)0.0025 (11)
C100.0253 (13)0.0357 (13)0.0346 (13)0.0038 (10)0.0137 (11)0.0002 (10)
C110.0414 (17)0.0372 (14)0.0514 (16)0.0047 (12)0.0201 (14)0.0019 (12)
C120.0449 (17)0.0397 (15)0.0471 (16)0.0002 (12)0.0239 (14)0.0068 (11)
C130.0304 (14)0.0393 (14)0.0396 (14)0.0045 (11)0.0171 (12)0.0055 (11)
C140.0353 (15)0.0451 (16)0.0408 (15)0.0021 (12)0.0196 (12)0.0063 (13)
O1W0.0754 (15)0.0500 (11)0.0442 (11)0.0114 (10)0.0331 (11)0.0055 (9)
O2W0.0940 (18)0.0766 (15)0.0490 (13)0.0245 (13)0.0315 (13)0.0065 (10)
Geometric parameters (Å, º) top
O1—C11.219 (3)C4—H40.9300
O2—C11.298 (3)C5—C61.396 (3)
O2—H20.8201C5—C71.481 (4)
O3—C71.202 (3)C6—C101.486 (3)
O4—C81.210 (3)C7—C81.515 (4)
O5—C141.200 (3)C8—C91.475 (4)
O6—C141.305 (3)C9—C111.373 (3)
O6—H60.8200C9—C101.398 (3)
N1—C21.333 (3)C11—C121.372 (4)
N1—C61.338 (3)C11—H110.9300
N2—C101.335 (3)C12—C131.379 (4)
N2—C131.340 (3)C12—H120.9300
C1—C21.493 (4)C13—C141.501 (4)
C2—C31.384 (3)O1W—H1W0.8420
C3—C41.371 (4)O1W—H2W0.8276
C3—H30.9300O2W—H3W0.8597
C4—C51.387 (3)O2W—H4W0.8629
C1—O2—H2109.5C5—C7—C8117.8 (2)
C14—O6—H6109.5O4—C8—C9122.3 (2)
C2—N1—C6118.0 (2)O4—C8—C7119.2 (2)
C10—N2—C13117.4 (2)C9—C8—C7118.5 (2)
O1—C1—O2119.7 (2)C11—C9—C10119.2 (2)
O1—C1—C2121.2 (2)C11—C9—C8119.6 (2)
O2—C1—C2119.1 (2)C10—C9—C8121.2 (2)
N1—C2—C3123.8 (2)N2—C10—C9122.0 (2)
N1—C2—C1116.4 (2)N2—C10—C6117.7 (2)
C3—C2—C1119.8 (2)C9—C10—C6120.3 (2)
C4—C3—C2118.2 (2)C12—C11—C9119.1 (2)
C4—C3—H3120.9C12—C11—H11120.4
C2—C3—H3120.9C9—C11—H11120.4
C3—C4—C5119.1 (2)C11—C12—C13118.3 (2)
C3—C4—H4120.4C11—C12—H12120.9
C5—C4—H4120.4C13—C12—H12120.9
C4—C5—C6119.0 (2)N2—C13—C12123.9 (2)
C4—C5—C7120.0 (2)N2—C13—C14115.2 (2)
C6—C5—C7121.0 (2)C12—C13—C14120.9 (2)
N1—C6—C5121.8 (2)O5—C14—O6125.0 (2)
N1—C6—C10117.0 (2)O5—C14—C13123.3 (2)
C5—C6—C10121.1 (2)O6—C14—C13111.7 (2)
O3—C7—C5122.5 (2)H1W—O1W—H2W106.6
O3—C7—C8119.6 (2)H3W—O2W—H4W123.3
C6—N1—C2—C30.4 (4)O4—C8—C9—C112.5 (4)
C6—N1—C2—C1179.3 (2)C7—C8—C9—C11177.2 (2)
O1—C1—C2—N1176.5 (2)O4—C8—C9—C10178.3 (3)
O2—C1—C2—N12.4 (4)C7—C8—C9—C102.1 (4)
O1—C1—C2—C33.3 (4)C13—N2—C10—C90.2 (3)
O2—C1—C2—C3177.9 (2)C13—N2—C10—C6179.6 (2)
N1—C2—C3—C40.4 (4)C11—C9—C10—N20.2 (4)
C1—C2—C3—C4179.9 (2)C8—C9—C10—N2179.0 (2)
C2—C3—C4—C50.5 (4)C11—C9—C10—C6179.6 (2)
C3—C4—C5—C60.2 (4)C8—C9—C10—C60.4 (4)
C3—C4—C5—C7179.1 (2)N1—C6—C10—N20.5 (3)
C2—N1—C6—C51.2 (3)C5—C6—C10—N2178.0 (2)
C2—N1—C6—C10179.7 (2)N1—C6—C10—C9179.9 (2)
C4—C5—C6—N11.1 (4)C5—C6—C10—C91.4 (3)
C7—C5—C6—N1178.2 (2)C10—C9—C11—C120.1 (4)
C4—C5—C6—C10179.5 (2)C8—C9—C11—C12179.3 (2)
C7—C5—C6—C100.2 (4)C9—C11—C12—C130.4 (4)
C4—C5—C7—O31.6 (4)C10—N2—C13—C120.1 (4)
C6—C5—C7—O3177.7 (3)C10—N2—C13—C14179.1 (2)
C4—C5—C7—C8178.1 (2)C11—C12—C13—N20.4 (4)
C6—C5—C7—C82.6 (4)C11—C12—C13—C14178.8 (2)
O3—C7—C8—O42.9 (4)N2—C13—C14—O515.3 (4)
C5—C7—C8—O4176.8 (2)C12—C13—C14—O5164.0 (3)
O3—C7—C8—C9176.8 (3)N2—C13—C14—O6167.1 (2)
C5—C7—C8—C93.5 (4)C12—C13—C14—O613.6 (3)
Hydrogen-bond geometry (Å, º) top
Table 1
D—H···AD—HH···AD···AD—H···A
C12—H12···O4i0.932.453.367 (1)170
O1W—H1W···O1ii0.842.032.865 (3)170
O2—H2···O1W0.821.812.561 (2)152
O1W—H2W···O50.832.442.917 (3)117
O1W—H2W···N20.832.152.968 (3)169
O2W—H3W···O1iii0.861.962.805 (3)169
O2W—H4W···O3iv0.862.533.053 (3)120
O6—H6···O2W0.821.762.574 (3)176
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+5/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x, y, z1.
(II) cis-diaquachlorido(5,6-dioxo-1,10-phenanthroline-2,9-dicarboxylic acid-κ4O2,N,N',O9)manganese(II) chloride dihydrate top
Crystal data top
[MnCl(C14H6N2O6)(H2O)2]Cl·2H2OF(000) = 2008
Mr = 496.11Dx = 1.758 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 2414 reflections
a = 17.195 (6) Åθ = 2.3–21.5°
b = 12.411 (5) ŵ = 1.05 mm1
c = 17.569 (6) ÅT = 296 K
V = 3750 (2) Å3Block, yellow
Z = 80.42 × 0.40 × 0.30 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3372 independent reflections
Radiation source: fine-focus sealed tube2021 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
ϕ and ω scansθmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1720
Tmin = 0.667, Tmax = 0.744k = 1414
17437 measured reflectionsl = 1921
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.0578P)2]
where P = (Fo2 + 2Fc2)/3
3372 reflections(Δ/σ)max = 0.001
265 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
[MnCl(C14H6N2O6)(H2O)2]Cl·2H2OV = 3750 (2) Å3
Mr = 496.11Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 17.195 (6) ŵ = 1.05 mm1
b = 12.411 (5) ÅT = 296 K
c = 17.569 (6) Å0.42 × 0.40 × 0.30 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3372 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2021 reflections with I > 2σ(I)
Tmin = 0.667, Tmax = 0.744Rint = 0.082
17437 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 0.98Δρmax = 0.48 e Å3
3372 reflectionsΔρmin = 0.33 e Å3
265 parameters
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
xyzUiso*/Ueq
C10.5332 (2)0.1261 (3)0.4605 (2)0.0298 (9)
C20.6055 (2)0.1135 (3)0.5084 (2)0.0293 (9)
C30.6061 (2)0.1024 (3)0.5866 (2)0.0351 (10)
H30.55980.09900.61400.042*
C40.6777 (2)0.0963 (3)0.6236 (2)0.0341 (10)
H40.68000.08870.67620.041*
C50.7457 (2)0.1018 (3)0.5810 (2)0.0305 (9)
C60.7396 (2)0.1113 (3)0.5021 (2)0.0260 (9)
C70.8248 (2)0.0974 (3)0.6183 (2)0.0356 (10)
C80.8972 (2)0.1048 (3)0.5651 (2)0.0362 (10)
C90.8851 (2)0.1166 (3)0.4818 (2)0.0292 (9)
C100.8087 (2)0.1196 (3)0.4520 (2)0.0270 (9)
C110.9467 (2)0.1244 (3)0.4305 (2)0.0376 (10)
H110.99780.12250.44790.045*
C120.9315 (2)0.1349 (3)0.3534 (2)0.0407 (11)
H120.97200.14080.31850.049*
C130.8549 (2)0.1366 (3)0.3294 (2)0.0335 (9)
C140.8288 (2)0.1492 (3)0.2480 (2)0.0372 (10)
Cl10.66197 (6)0.07431 (9)0.32957 (6)0.0452 (3)
Cl20.66507 (6)0.37138 (8)0.53645 (6)0.0394 (3)
Mn10.66806 (3)0.12632 (5)0.33544 (3)0.0327 (2)
N10.67083 (16)0.1169 (2)0.46588 (16)0.0272 (7)
N20.79438 (17)0.1286 (3)0.37808 (17)0.0298 (7)
O10.53707 (15)0.1347 (2)0.39159 (15)0.0420 (7)
O20.46892 (15)0.1262 (2)0.50065 (15)0.0426 (7)
H20.43220.14240.47320.064*
O30.83346 (16)0.0893 (3)0.68621 (16)0.0494 (8)
O40.96201 (16)0.1034 (2)0.59366 (16)0.0508 (8)
O50.75973 (15)0.1493 (2)0.23147 (15)0.0459 (8)
O60.88584 (15)0.1576 (3)0.19872 (14)0.0465 (8)
H60.86820.15590.15540.070*
O1W0.59722 (15)0.1543 (2)0.23277 (14)0.0432 (8)
H1W0.56630.10360.22120.065*
H2W0.57240.20980.23830.065*
O2W0.66687 (16)0.3062 (2)0.35021 (15)0.0473 (8)
H3W0.66200.32500.39600.071*
H4W0.70700.34100.34800.071*
O3W0.34424 (15)0.1721 (2)0.42079 (15)0.0442 (8)
H5W0.29750.15640.42590.066*
H6W0.35190.16340.37560.066*
O4W0.50000.3286 (4)0.25000.0576 (12)
H7W0.50100.36850.21300.086*
O5W0.50000.0309 (4)0.25000.0614 (13)
H8W0.53200.06900.27200.092*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.025 (2)0.027 (2)0.038 (2)0.0022 (17)0.0089 (18)0.0003 (18)
C20.025 (2)0.029 (2)0.034 (2)0.0003 (17)0.0046 (17)0.0022 (17)
C30.031 (2)0.039 (3)0.035 (2)0.0030 (19)0.0056 (19)0.0000 (18)
C40.040 (3)0.037 (3)0.025 (2)0.0013 (19)0.0048 (19)0.0017 (17)
C50.034 (2)0.024 (2)0.034 (2)0.0018 (17)0.0035 (18)0.0024 (16)
C60.023 (2)0.025 (2)0.030 (2)0.0019 (16)0.0008 (16)0.0010 (16)
C70.036 (2)0.035 (3)0.036 (2)0.0010 (19)0.0039 (19)0.0042 (18)
C80.034 (3)0.031 (3)0.043 (2)0.0014 (19)0.005 (2)0.0035 (19)
C90.027 (2)0.027 (2)0.033 (2)0.0026 (17)0.0040 (17)0.0011 (17)
C100.025 (2)0.030 (2)0.026 (2)0.0006 (16)0.0010 (16)0.0030 (17)
C110.021 (2)0.048 (3)0.044 (2)0.0020 (19)0.0018 (18)0.002 (2)
C120.025 (2)0.058 (3)0.039 (3)0.000 (2)0.0052 (18)0.002 (2)
C130.026 (2)0.042 (3)0.033 (2)0.0032 (18)0.0001 (17)0.0011 (19)
C140.026 (2)0.045 (3)0.041 (2)0.0019 (19)0.008 (2)0.0022 (19)
Cl10.0459 (7)0.0423 (7)0.0475 (6)0.0036 (5)0.0032 (5)0.0030 (5)
Cl20.0403 (6)0.0391 (6)0.0390 (6)0.0006 (5)0.0004 (5)0.0003 (5)
Mn10.0248 (3)0.0433 (4)0.0299 (3)0.0009 (3)0.0007 (3)0.0002 (3)
N10.0214 (17)0.0287 (18)0.0316 (17)0.0005 (14)0.0015 (14)0.0011 (13)
N20.0198 (16)0.036 (2)0.0340 (18)0.0012 (14)0.0037 (14)0.0012 (15)
O10.0269 (15)0.060 (2)0.0390 (17)0.0021 (14)0.0023 (12)0.0029 (14)
O20.0224 (15)0.059 (2)0.0467 (17)0.0017 (15)0.0042 (13)0.0006 (15)
O30.0466 (19)0.066 (2)0.0355 (18)0.0020 (16)0.0089 (14)0.0005 (14)
O40.0331 (18)0.076 (2)0.0436 (18)0.0050 (15)0.0112 (14)0.0060 (15)
O50.0228 (16)0.080 (3)0.0352 (16)0.0017 (14)0.0030 (12)0.0043 (14)
O60.0293 (16)0.079 (2)0.0309 (15)0.0047 (15)0.0068 (13)0.0022 (16)
O1W0.0270 (15)0.066 (2)0.0363 (16)0.0008 (14)0.0017 (12)0.0037 (14)
O2W0.0443 (19)0.050 (2)0.0479 (17)0.0055 (15)0.0077 (14)0.0019 (14)
O3W0.0307 (17)0.055 (2)0.0465 (17)0.0012 (14)0.0000 (13)0.0050 (14)
O4W0.059 (3)0.067 (3)0.047 (3)0.0000.002 (2)0.000
O5W0.041 (3)0.078 (4)0.065 (3)0.0000.009 (2)0.000
Geometric parameters (Å, º) top
C1—O11.217 (4)C12—H120.9300
C1—O21.311 (4)C13—N21.351 (5)
C1—C21.508 (5)C13—C141.506 (6)
C2—N11.350 (4)C14—O51.222 (4)
C2—C31.382 (5)C14—O61.313 (5)
C3—C41.395 (5)Cl1—Mn12.4945 (15)
C3—H30.9300Mn1—O1W2.204 (3)
C4—C51.391 (5)Mn1—O2W2.248 (3)
C4—H40.9300Mn1—N12.295 (3)
C5—C61.395 (5)Mn1—N22.298 (3)
C5—C71.510 (5)Mn1—O52.430 (3)
C6—N11.345 (4)Mn1—O12.461 (3)
C6—C101.482 (5)O2—H20.8200
C7—O31.207 (5)O6—H60.8200
C7—C81.559 (6)O1W—H1W0.8476
C8—O41.222 (5)O1W—H2W0.8169
C8—C91.485 (5)O2W—H3W0.8416
C9—C111.395 (5)O2W—H4W0.8142
C9—C101.414 (5)O3W—H5W0.8312
C10—N21.326 (5)O3W—H6W0.8126
C11—C121.386 (5)O4W—H7W0.8173
C11—H110.9300O5W—H8W0.8221
C12—C131.384 (5)
O1—C1—O2125.5 (3)O5—C14—C13121.1 (3)
O1—C1—C2121.2 (3)O6—C14—C13114.3 (3)
O2—C1—C2113.2 (3)O1W—Mn1—O2W86.16 (10)
N1—C2—C3123.2 (3)O1W—Mn1—N1146.79 (10)
N1—C2—C1112.0 (3)O2W—Mn1—N186.30 (10)
C3—C2—C1124.8 (3)O1W—Mn1—N2141.93 (10)
C2—C3—C4118.4 (4)O2W—Mn1—N287.65 (11)
C2—C3—H3120.8N1—Mn1—N269.84 (10)
C4—C3—H3120.8O1W—Mn1—O574.02 (10)
C5—C4—C3119.3 (4)O2W—Mn1—O588.62 (10)
C5—C4—H4120.3N1—Mn1—O5138.00 (10)
C3—C4—H4120.3N2—Mn1—O568.31 (10)
C4—C5—C6118.4 (3)O1W—Mn1—O179.38 (10)
C4—C5—C7121.4 (3)O2W—Mn1—O184.47 (10)
C6—C5—C7120.2 (3)N1—Mn1—O167.72 (9)
N1—C6—C5122.7 (3)N2—Mn1—O1137.21 (11)
N1—C6—C10114.9 (3)O5—Mn1—O1152.90 (9)
C5—C6—C10122.4 (3)O1W—Mn1—Cl195.75 (8)
O3—C7—C5122.9 (4)O2W—Mn1—Cl1174.84 (8)
O3—C7—C8119.9 (4)N1—Mn1—Cl189.51 (8)
C5—C7—C8117.2 (3)N2—Mn1—Cl193.74 (8)
O4—C8—C9122.3 (4)O5—Mn1—Cl196.51 (8)
O4—C8—C7118.8 (4)O1—Mn1—Cl191.16 (7)
C9—C8—C7118.9 (3)C6—N1—C2118.0 (3)
C11—C9—C10117.6 (3)C6—N1—Mn1119.5 (2)
C11—C9—C8122.5 (3)C2—N1—Mn1122.4 (2)
C10—C9—C8119.9 (3)C10—N2—C13118.9 (3)
N2—C10—C9122.5 (3)C10—N2—Mn1119.6 (2)
N2—C10—C6116.0 (3)C13—N2—Mn1121.5 (2)
C9—C10—C6121.5 (3)C1—O1—Mn1116.4 (2)
C12—C11—C9119.7 (4)C1—O2—H2109.5
C12—C11—H11120.1C14—O5—Mn1116.8 (2)
C9—C11—H11120.1C14—O6—H6109.5
C13—C12—C11118.6 (4)Mn1—O1W—H1W115.2
C13—C12—H12120.7Mn1—O1W—H2W108.9
C11—C12—H12120.7H1W—O1W—H2W109.1
N2—C13—C12122.6 (4)Mn1—O2W—H3W112.7
N2—C13—C14112.3 (3)Mn1—O2W—H4W120.9
C12—C13—C14125.1 (3)H3W—O2W—H4W89.1
O5—C14—O6124.6 (4)H5W—O3W—H6W103.4
Hydrogen-bond geometry (Å, º) top
Table 2
D—H···AD—HH···AD···AD—H···A
C11—H11···Cl2i0.932.893.799 (3)166
C12—H12···O6ii0.932.473.283 (5)146
C4—H4···Cl1iii0.932.723.640 (4)171
O5W—H8W···Cl10.822.453.1625 (16)145
O4W—H7W···O4iv0.822.222.947 (3)149
O3W—H6W···O5v0.812.693.230 (4)125
O3W—H6W···O1Wv0.812.102.888 (4)164
O3W—H5W···Cl2vi0.832.403.217 (3)169
O2W—H4W···Cl1vii0.822.513.315 (3)172
O2W—H3W···Cl20.842.533.371 (3)172
O1W—H2W···O4W0.821.942.751 (4)172
O1W—H1W···O5W0.852.082.858 (5)151
O6—H6···Cl2iv0.822.193.004 (3)170
O2—H2···O3W0.821.812.625 (4)174
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+2, y, z+1/2; (iii) x, y, z+1/2; (iv) x+3/2, y+1/2, z1/2; (v) x+1, y, z+1/2; (vi) x1/2, y+1/2, z+1; (vii) x+3/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H6N2O6·2H2O[MnCl(C14H6N2O6)(H2O)2]Cl·2H2O
Mr334.24496.11
Crystal system, space groupMonoclinic, P21/cOrthorhombic, Pbcn
Temperature (K)296296
a, b, c (Å)7.206 (2), 15.968 (6), 13.055 (3)17.195 (6), 12.411 (5), 17.569 (6)
α, β, γ (°)90, 115.049 (13), 9090, 90, 90
V3)1360.9 (7)3750 (2)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.141.05
Crystal size (mm)0.20 × 0.13 × 0.120.42 × 0.40 × 0.30
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Multi-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.973, 0.9840.667, 0.744
No. of measured, independent and
observed [I > 2σ(I)] reflections
6770, 2517, 1610 17437, 3372, 2021
Rint0.0340.082
(sin θ/λ)max1)0.6060.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.138, 1.03 0.046, 0.121, 0.98
No. of reflections25173372
No. of parameters217265
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.290.48, 0.33

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
Table 1
D—H···AD—HH···AD···AD—H···A
C12—H12···O4i0.932.453.367 (1)169.8
O1W—H1W···O1ii0.842.032.865 (3)170.3
O2—H2···O1W0.821.812.561 (2)151.6
O1W—H2W···O50.832.442.917 (3)117.4
O1W—H2W···N20.832.152.968 (3)169.0
O2W—H3W···O1iii0.861.962.805 (3)168.8
O2W—H4W···O3iv0.862.533.053 (3)119.5
O6—H6···O2W0.821.762.574 (3)176.2
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+5/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x, y, z1.
Hydrogen-bond geometry (Å, º) for (II) top
Table 2
D—H···AD—HH···AD···AD—H···A
C11—H11···Cl2i0.932.893.799 (3)165.9
C12—H12···O6ii0.932.473.283 (5)145.8
C4—H4···Cl1iii0.932.723.640 (4)170.8
O5W—H8W···Cl10.822.453.1625 (16)145.0
O4W—H7W···O4iv0.822.222.947 (3)148.5
O3W—H6W···O5v0.812.693.230 (4)125.1
O3W—H6W···O1Wv0.812.102.888 (4)164.2
O3W—H5W···Cl2vi0.832.403.217 (3)169.0
O2W—H4W···Cl1vii0.822.513.315 (3)171.5
O2W—H3W···Cl20.842.533.371 (3)172.4
O1W—H2W···O4W0.821.942.751 (4)171.7
O1W—H1W···O5W0.852.082.858 (5)151.4
O6—H6···Cl2iv0.822.193.004 (3)170.1
O2—H2···O3W0.821.812.625 (4)173.6
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+2, y, z+1/2; (iii) x, y, z+1/2; (iv) x+3/2, y+1/2, z1/2; (v) x+1, y, z+1/2; (vi) x1/2, y+1/2, z+1; (vii) x+3/2, y+1/2, z.
 

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