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Double-layer structures consisting of alternating polar and non-polar layers have been prepared using Mn2+ ions and o-hydroxy­naphthoic acids. The polar layers contain the Mn2+ ions, carboxylate groups, hydr­oxy groups and water mol­ecules. The non-polar layers are built up from the naphthalene moieties. In catena-poly[[diaqua­manganese(II)]bis­([mu]-3-hy­droxy-2-naphthoato-[kappa]2O:O')] (also called manganese 3-hy­droxy-2-naphthoate dihydrate), [Mn(C11H7O3)2(H2O)2]n, (I), the Mn2+ ions are connected by carboxylate groups to form two-dimensional networks. This compound shows distinct antiferromagnetic inter­actions and long-range ordering at low temperature. In contrast, tetra­aqua­bis(1-hydr­oxy-2-naph­thoato-[kappa]O)manganese(II), [Mn(C11H7O3)2(H2O)4], (II), which lacks a close linkage between the Mn2+ ions, reveals purely paramagnetic behaviour. In (II), the Mn2+ ion lies on an inversion centre.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105015659/ta1467sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015659/ta1467Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015659/ta1467IIsup3.hkl
Contains datablock II

CCDC references: 278548; 278549

Comment top

Low-dimensional spin systems are a topic of current research because of their unusual magnetic properties. In the course of searching for molecule-based new materials, we have designed double-layer structures consisting of alternating polar and non-polar layers (Fig. 1). Each polar layer contains a two-dimensional network of metal ions, carboxylic acid groups and water molecules, and these networks are separated by non-polar layers of naphthalene fragments of considerable thickness. The structures are built from Mn2+ ions and 3-hydroxy-2-naphthoate or 1-hydroxy-2-naphthoate anions. 3-Hydroxy-2-naphthoic acid is also known as β-oxy-naphthoic acid (BONA) and is used industrially for the synthesis of red azo pigments (Herbst & Hunger, 2004).

Transition metal complexes with hydroxy-naphthoates as ligands have rarely been synthesized or crystallized, although the starting materials are readily available. Crystal structures have not been reported to date, except for some lanthanoid complexes (Ohki et al., 1986; Ohki, Suzuki & Ouchi, 1987; Ohki, Suzuki et al., 1987). Reasons include problems in growing single crystals as well as synthetic difficulties: hydroxy-naphthoic acids are insoluble in water and acids, while Mn2+ salts are often insoluble in alkaline media and organic solvents. Therefore, most synthetic attempts result in mixtures of starting materials (cf. Schmidt et al., 2002). Furthermore, the synthesized metal complexes reveal very low solubilities in most media, which renders the growth of single crystals suitable for X-ray analysis difficult. We finally succeeded in growing single crystals of the title compounds, (I) and (II), by slow reaction of a mixture of Mn(OH)2 suspensions and hydroxy-naphthoic acid suspensions in water. The crystals form plate-like species, as expected for layer structures with strong hydrogen bonds and Coulomb interactions within the layers and weak van der Waals interactions between the layers. The crystal structures of (I) and (II) were determined by single-crystal X-ray diffraction. As intended, both compounds form double-layer structures. The crystal of (I) was found to be a non-merohedral twin.

In both compounds, the Mn2+ ions are coordinated octahedrally by six O atoms. In (I), the Mn2+ ion is coordinated by four carboxylic acid groups of four different molecules of 3-hydroxy-2-naphthoate in a square-planar type arrangement. The remaining two axial positions of the octahedra are occupied by water molecules (Fig. 2). Each carboxylic acid group connects two Mn2+ ions. The closest Mn···Mn distances are 4.392 (1) and 5.135 (1) Å. The shorter distance is bridged simultaneously by two carboxylic acid groups and the longer distance by only one carboxylic acid group. Accordingly, the structure contains two crystallographically independent 3-hydroxy-2-naphthoate moieties. The Mn2+ ions are situated on a general position. The closest Mn···Mn distances between Mn2+ ions of different layers is as large as 17.262 (2) Å.

In compound (II), the Mn2+ ion is coordinated by only two molecules of 1-hydroxy-2-naphthoate in the axial positions and four water molecules arranged in the equatorial square plane of the coordination octahedra (Fig. 3). The Mn2+ ions are positioned on a crystallographic inversion centre. The closest Mn···Mn distance is 5.2121 (3) Å.

The Mn—O distances are between 2.109 (6) and 2.246 (6) Å for both compounds (Tables 1 and 3). All O—Mn—O angles are in the range 83.5 (2)–98.8 (2)° for O atoms in cis positions and from 167.4 (3)–180° for O atoms in trans positions. In both compounds, the hydroxy groups do not participate in the octahedral coordination of the Mn2+ ions; the OH groups only form intramolecular hydrogen bonds to neighbouring carboxylic acid groups.

Despite this similarity, the structures differ in various aspects. The crystal structure of (I) contains a parallel arrangement of naphthalene moieties within the non-polar layer (Fig. 4); this packing motif is also known for aromatic compounds, e.g. for hexamethylbenzene (Lonsdale, 1929). In contrast, in (II) the naphthalene moieties form a herringbone arrangement (Fig. 5), as in naphthalene itself (Bragg, 1921) and many other aromatic compounds. Furthermore, both compounds show different types of connection pattern for the Mn2+ ions. In compound (I), neighbouring Mn2+ ions are connected by carboxylic acid groups which provide a magnetic exchange path via Mn—O—C—O—Mn (Fig. 6). In fact, susceptibility measurements on this material revealed a significant antiferromagnetic interaction between the Mn2+ ions. For high temperatures 50 K T 300 K, the susceptibility follows a Curie–Weiss-like temperature dependence, χ(T) = C/(T+θ), corresponding to Mn2+ (S = 5/2) ions with an average antiferromagnetic interaction θAF = (12±0.2) K (Fig. 7). With decreasing temperature, the susceptibility shows a distinct maximum at Tmax = 8 K. Such a temperature dependence is known for Mn2+ systems with quasi one- or two-dimensional antiferromagnetic interactions (Smith & Friedberg, 1968). We assigned the kink in χ(T) at TN = (3±0.2) K to the onset of three-dimensional antiferromagnetic ordering. Since low-range magnetic order at a finite temperature is not expected for Heisenberg interactions in dimensions d < 3 (Mermin & Wagner, 1966), this observation implies a significant magnetic coupling between the layers, probably mediated via the naphthalene fragments.

In contrast, compound (II) does not show such an exchange path. The two-dimensional network is built by isolated Mn–bis-naphthoate moieties which are connected by water molecules. This leads to an arrangement which is not expected to mediate magnetic interaction between the Mn2+ ions. Indeed, the compound shows paramagnetic behaviour. The temperature dependence of the magnetic susceptibility was found to follow a simple Curie law, with a Curie constant corresponding to uncoupled S = 5/2 spins and an isotropic g factor g = 2. This observation of magnetically isolated paramagnetic centres is consistent with the crystal structure, where the Mn2+ ions in their 6S5/2 ground-state configuration lack any obvious magnetic exchange path to neighbouring Mn2+ ions. As an upper limit for a possible magnetic Mn2+–Mn2+ interaction, we estimate an antiferromagnetic Weiss temperature of θAF = (0.7±0.5) K.

Experimental top

Compound (I) was prepared as follows. A suspension of Mn(OH)2 (0.25 g) in H2O (65 ml) was added to a suspension of 3-hydroxy-2-naphthoic acid (BONA; 1.50 g) in water (100 ml). The mixture was heated to 313 K for 6 weeks. The crystals grew as brownish thin plates with sizes up to 1 mm. They were separated by decantation and dried in air at room temperature (yield ca 90%). Compound (II) was prepared as follows. A suspension of Mn(OH)2 (0.35 g) in H2O (60 ml) was added to a suspension of 1-hydroxy-2-naphthoic acid (1.75 g, 1,2-HNA) in water (100 ml). The mixture was heated to 313 K for 6 weeks. Red–brown crystals of sizes up to 1 mm were obtained after decantation and dried in air at room temperature (yield ca 90%). In both cases, X-ray powder investigation did not give any hint of additional compounds or phases, or of remains of the starting materials. Magnetic measurements of samples of (I) and (II) were carried out as follows. Variable-temperature magnetic susceptibility measurements in the temperature range 2–300 K and magnetic fields of 0.5–2 T were carried out on single crystalline samples of (I) (m = 0.65 mg) and (II) (m = 2.35 mg) using a Quantum Design SQUID magnetometer. These measurements were complemented by isothermal magnetization runs at temperatures of 2–200 K and fields up to 5 T. The data were corrected for the contribution of the sample holder and for the diamagnetic core contribution.

Refinement top

H atoms bonded to C were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C)] using a riding model, with C—Haromatic = 0.95 Å. The H atoms bonded to O in (II) were refined freely. The H atoms bonded to O in (I) were refined using a riding model with fixed individual displacement parameters [O—H = 0.84 Å Please check added text and Uiso(H) = 1.2 Ueq(O)]. The crystal of (I) is a non-merohedral twin. Two different domains could be identified when the crystal was on the diffractometer. The twin law (1 0 0.456/0 − 1 0/0 0 − 1) was evaluated using the program TWINLAW (Bolte, 2004) and the reflection data file for refinement was prepared using the program TWINLAW. The highest peak in the final difference map of (I) of 1.08 e Å−3 is at (0.4826, 0.0635, 0.0383) (1.46 Å from Mn1) and the deepest hole of −1.27 e Å−3 is at (0.4823, 0.4303, 0.4493) (1.68 Å from O2W).

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A schematic view of the designed structures consisting of alternating polar and non-polar layers.
[Figure 2] Fig. 2. The coordination of the Mn2+ ions in (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by spheres of arbitrary size. The H atoms of the naphthalene moieties have been omitted for clarity. Hydrogen bonds are indicated by dashed lines. Please check added text.
[Figure 3] Fig. 3. The coordination of the Mn2+ ions in (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by spheres of arbitrary size. The H atoms of the naphthalene fragments have been omitted for clarity. Hydrogen bonds are indicated by dashed lines. Please check added text.
[Figure 4] Fig. 4. The structure of (I), viewed along the [010] direction. Hydrogen bonds are indicated by dashed lines. Please check added text.
[Figure 5] Fig. 5. The structure of (II), viewed along the [100] direction. Hydrogen bonds are indicated by dashed lines. Please check added text.
[Figure 6] Fig. 6. The magnetic exchange path in (I), viewed along the [100] direction.
[Figure 7] Fig. 7. The magnetic susceptibility of (I). The inset shows the low-temperature region. The arrow indicates the onset of long-range antiferromagnetic order (see text).
(I) catena-poly[[diaquamanganese(II)]bis(µ-3-hydroxy-2-naphthoato-κ2O:O')] top
Crystal data top
[Mn(C11H7O3)2(H2O)2]F(000) = 956
Mr = 465.30Dx = 1.602 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 20695 reflections
a = 17.2616 (17) Åθ = 2.5–27.3°
b = 7.3476 (5) ŵ = 0.74 mm1
c = 15.5360 (15) ÅT = 173 K
β = 101.815 (8)°Plate, light brown
V = 1928.7 (3) Å30.42 × 0.32 × 0.13 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
4535 independent reflections
Radiation source: fine-focus sealed tube3911 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
ω scansθmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 2222
Tmin = 0.748, Tmax = 0.911k = 99
17865 measured reflectionsl = 2020
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)] = 0.087Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.316H-atom parameters constrained
S = 1.21 w = 1/[σ2(Fo2) + (0.0999P)2 + 24.9072P]
where P = (Fo2 + 2Fc2)/3
4535 reflections(Δ/σ)max < 0.001
281 parametersΔρmax = 1.08 e Å3
0 restraintsΔρmin = 1.27 e Å3
Crystal data top
[Mn(C11H7O3)2(H2O)2]V = 1928.7 (3) Å3
Mr = 465.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.2616 (17) ŵ = 0.74 mm1
b = 7.3476 (5) ÅT = 173 K
c = 15.5360 (15) Å0.42 × 0.32 × 0.13 mm
β = 101.815 (8)°
Data collection top
Stoe IPDS II two-circle
diffractometer
4535 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
3911 reflections with I > 2σ(I)
Tmin = 0.748, Tmax = 0.911Rint = 0.083
17865 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0870 restraints
wR(F2) = 0.316H-atom parameters constrained
S = 1.21 w = 1/[σ2(Fo2) + (0.0999P)2 + 24.9072P]
where P = (Fo2 + 2Fc2)/3
4535 reflectionsΔρmax = 1.08 e Å3
281 parametersΔρmin = 1.27 e Å3
Special details top

Experimental. No standard reflections measured

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
Mn10.51716 (8)0.57041 (16)0.36795 (9)0.0204 (3)
O1W0.5828 (4)0.8207 (9)0.3530 (4)0.0312 (15)
H1WA0.57760.91900.32470.037*
H1WB0.62530.79410.33750.037*
O2W0.4604 (4)0.3071 (8)0.3562 (5)0.0279 (13)
H2WA0.49140.26160.32680.033*
H2WB0.44090.22370.38200.033*
C10.7360 (5)0.2761 (13)0.4748 (6)0.0269 (18)
H10.74010.40160.46180.032*
C20.6716 (5)0.2165 (11)0.5058 (5)0.0207 (16)
C210.6079 (5)0.3488 (12)0.5182 (6)0.0232 (17)
O210.6062 (4)0.5034 (9)0.4831 (4)0.0268 (13)
O220.5581 (4)0.2933 (9)0.5621 (4)0.0264 (13)
C30.6655 (5)0.0289 (12)0.5264 (6)0.0234 (17)
O30.6034 (4)0.0341 (9)0.5590 (5)0.0317 (15)
H30.57610.05410.56990.048*
C40.7217 (5)0.0924 (13)0.5109 (6)0.0275 (18)
H40.71580.21810.52250.033*
C50.7884 (5)0.0333 (14)0.4778 (6)0.0298 (19)
C60.8452 (6)0.1569 (17)0.4592 (7)0.040 (2)
H60.83930.28350.46850.047*
C70.9092 (7)0.094 (2)0.4277 (8)0.046 (3)
H70.94690.17800.41430.056*
C80.9193 (6)0.093 (2)0.4150 (8)0.046 (3)
H80.96480.13560.39560.055*
C90.8635 (6)0.2153 (18)0.4308 (7)0.038 (2)
H90.87010.34140.42070.046*
C100.7966 (5)0.1548 (15)0.4617 (6)0.0290 (19)
C1A0.2826 (5)0.6092 (13)0.2772 (6)0.0237 (17)
H1A0.31610.50620.27840.028*
C2A0.3089 (5)0.7748 (12)0.2562 (5)0.0226 (16)
C21A0.3899 (5)0.7946 (11)0.2377 (5)0.0202 (16)
O21A0.4349 (4)0.6537 (8)0.2427 (4)0.0228 (12)
O22A0.4129 (4)0.9514 (8)0.2189 (4)0.0263 (13)
C3A0.2585 (5)0.9301 (13)0.2533 (7)0.0276 (18)
O3A0.2797 (4)1.0989 (10)0.2304 (6)0.0382 (17)
H3A0.32621.09560.22160.057*
C4A0.1847 (5)0.9118 (13)0.2743 (7)0.031 (2)
H4A0.15181.01590.27320.037*
C5A0.1578 (5)0.7426 (13)0.2970 (6)0.0273 (18)
C6A0.0817 (6)0.7196 (15)0.3179 (7)0.035 (2)
H6A0.04820.82200.31870.042*
C7A0.0565 (6)0.5488 (17)0.3370 (8)0.042 (3)
H7A0.00540.53450.34980.050*
C8A0.1050 (6)0.3975 (15)0.3379 (8)0.037 (2)
H8A0.08700.28140.35230.044*
C9A0.1781 (6)0.4140 (14)0.3182 (7)0.034 (2)
H9A0.21030.30900.31840.040*
C10A0.2066 (5)0.5861 (12)0.2973 (7)0.0256 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0238 (6)0.0172 (6)0.0206 (6)0.0011 (5)0.0056 (5)0.0006 (5)
O1W0.034 (3)0.025 (3)0.031 (3)0.009 (3)0.000 (3)0.003 (3)
O2W0.035 (3)0.019 (3)0.034 (3)0.004 (2)0.016 (3)0.000 (3)
C10.028 (4)0.027 (4)0.025 (4)0.004 (4)0.005 (3)0.003 (4)
C20.022 (4)0.019 (4)0.021 (4)0.002 (3)0.002 (3)0.003 (3)
C210.024 (4)0.024 (4)0.021 (4)0.002 (3)0.004 (3)0.003 (3)
O210.028 (3)0.021 (3)0.028 (3)0.002 (3)0.001 (3)0.005 (3)
O220.029 (3)0.025 (3)0.027 (3)0.001 (3)0.008 (3)0.001 (3)
C30.026 (4)0.020 (4)0.024 (4)0.002 (3)0.004 (3)0.002 (3)
O30.032 (3)0.023 (3)0.045 (4)0.001 (3)0.020 (3)0.003 (3)
C40.027 (4)0.023 (4)0.032 (5)0.001 (3)0.007 (4)0.003 (4)
C50.026 (4)0.038 (5)0.024 (4)0.006 (4)0.002 (3)0.006 (4)
C60.039 (5)0.043 (6)0.038 (6)0.013 (5)0.011 (4)0.007 (5)
C70.036 (5)0.069 (9)0.036 (5)0.018 (6)0.013 (4)0.003 (5)
C80.026 (5)0.069 (9)0.045 (6)0.005 (5)0.016 (5)0.003 (6)
C90.029 (5)0.054 (6)0.032 (5)0.002 (5)0.007 (4)0.004 (5)
C100.024 (4)0.042 (5)0.022 (4)0.004 (4)0.005 (3)0.001 (4)
C1A0.021 (4)0.023 (4)0.028 (4)0.001 (3)0.006 (3)0.001 (3)
C2A0.022 (4)0.023 (4)0.022 (4)0.001 (3)0.003 (3)0.001 (3)
C21A0.019 (4)0.020 (4)0.021 (4)0.000 (3)0.004 (3)0.005 (3)
O21A0.023 (3)0.022 (3)0.022 (3)0.000 (2)0.002 (2)0.001 (2)
O22A0.032 (3)0.019 (3)0.030 (3)0.001 (2)0.012 (3)0.002 (2)
C3A0.020 (4)0.025 (4)0.037 (5)0.002 (3)0.005 (4)0.000 (4)
O3A0.030 (4)0.025 (3)0.063 (5)0.004 (3)0.019 (4)0.009 (3)
C4A0.022 (4)0.026 (4)0.043 (6)0.002 (3)0.006 (4)0.002 (4)
C5A0.023 (4)0.028 (4)0.030 (4)0.002 (3)0.006 (3)0.004 (4)
C6A0.026 (5)0.038 (5)0.044 (6)0.002 (4)0.015 (4)0.006 (5)
C7A0.029 (5)0.047 (6)0.053 (7)0.004 (5)0.016 (5)0.002 (5)
C8A0.029 (5)0.033 (5)0.049 (6)0.007 (4)0.012 (4)0.005 (5)
C9A0.027 (4)0.031 (5)0.044 (6)0.003 (4)0.010 (4)0.001 (4)
C10A0.020 (4)0.028 (4)0.028 (4)0.004 (3)0.004 (4)0.001 (4)
Geometric parameters (Å, º) top
Mn1—O22i2.109 (6)C7—H70.9500
Mn1—O2W2.159 (6)C8—C91.373 (16)
Mn1—O212.163 (6)C8—H80.9500
Mn1—O22Aii2.170 (6)C9—C101.411 (13)
Mn1—O1W2.198 (7)C9—H90.9500
Mn1—O21A2.246 (6)C1A—C2A1.361 (13)
O1W—H1WA0.8400C1A—C10A1.419 (12)
O1W—H1WB0.8399C1A—H1A0.9500
O2W—H2WA0.8399C2A—C3A1.429 (12)
O2W—H2WB0.8400C2A—C21A1.492 (11)
C1—C21.370 (12)C21A—O22A1.272 (10)
C1—C101.421 (13)C21A—O21A1.287 (10)
C1—H10.9500O22A—Mn1iii2.170 (6)
C2—C31.424 (12)C3A—O3A1.361 (12)
C2—C211.510 (12)C3A—C4A1.385 (13)
C21—O211.258 (11)O3A—H3A0.8429
C21—O221.269 (11)C4A—C5A1.397 (13)
O22—Mn1i2.109 (6)C4A—H4A0.9500
C3—O31.356 (11)C5A—C10A1.425 (12)
C3—C41.375 (12)C5A—C6A1.428 (12)
O3—H30.8400C6A—C7A1.379 (16)
C4—C51.421 (13)C6A—H6A0.9500
C4—H40.9500C7A—C8A1.390 (16)
C5—C61.409 (13)C7A—H7A0.9500
C5—C101.417 (15)C8A—C9A1.363 (14)
C6—C71.378 (17)C8A—H8A0.9500
C6—H60.9500C9A—C10A1.418 (13)
C7—C81.41 (2)C9A—H9A0.9500
O22i—Mn1—O2W98.8 (2)C8—C7—H7119.7
O22i—Mn1—O2195.2 (3)C9—C8—C7120.2 (11)
O2W—Mn1—O2195.7 (3)C9—C8—H8119.9
O22i—Mn1—O22Aii172.4 (3)C7—C8—H8119.9
O2W—Mn1—O22Aii83.5 (2)C8—C9—C10120.5 (12)
O21—Mn1—O22Aii91.8 (3)C8—C9—H9119.7
O22i—Mn1—O1W92.4 (3)C10—C9—H9119.7
O2W—Mn1—O1W167.4 (3)C5—C10—C1118.8 (9)
O21—Mn1—O1W89.0 (2)C5—C10—C9119.1 (9)
O22Aii—Mn1—O1W84.7 (3)C1—C10—C9122.0 (10)
O22i—Mn1—O21A88.3 (2)C2A—C1A—C10A121.8 (8)
O2W—Mn1—O21A88.6 (2)C2A—C1A—H1A119.1
O21—Mn1—O21A174.0 (2)C10A—C1A—H1A119.1
O22Aii—Mn1—O21A84.5 (2)C1A—C2A—C3A119.4 (8)
O1W—Mn1—O21A85.9 (2)C1A—C2A—C21A120.3 (8)
Mn1—O1W—H1WA140.5C3A—C2A—C21A120.3 (8)
Mn1—O1W—H1WB109.6O22A—C21A—O21A121.9 (7)
H1WA—O1W—H1WB93.3O22A—C21A—C2A118.8 (7)
Mn1—O2W—H2WA94.3O21A—C21A—C2A119.3 (7)
Mn1—O2W—H2WB146.4C21A—O21A—Mn1122.5 (5)
H2WA—O2W—H2WB109.3C21A—O22A—Mn1iii138.4 (6)
C2—C1—C10121.6 (9)O3A—C3A—C4A117.3 (8)
C2—C1—H1119.2O3A—C3A—C2A122.8 (8)
C10—C1—H1119.2C4A—C3A—C2A119.9 (9)
C1—C2—C3119.5 (8)C3A—O3A—H3A109.4
C1—C2—C21120.2 (8)C3A—C4A—C5A120.9 (9)
C3—C2—C21120.3 (8)C3A—C4A—H4A119.5
O21—C21—O22124.4 (8)C5A—C4A—H4A119.5
O21—C21—C2118.6 (8)C4A—C5A—C10A119.5 (8)
O22—C21—C2116.9 (8)C4A—C5A—C6A122.1 (9)
C21—O21—Mn1120.9 (6)C10A—C5A—C6A118.3 (9)
C21—O22—Mn1i132.9 (6)C7A—C6A—C5A120.1 (10)
O3—C3—C4118.9 (8)C7A—C6A—H6A119.9
O3—C3—C2121.1 (8)C5A—C6A—H6A119.9
C4—C3—C2120.0 (8)C6A—C7A—C8A120.9 (9)
C3—O3—H3109.4C6A—C7A—H7A119.5
C3—C4—C5121.2 (9)C8A—C7A—H7A119.5
C3—C4—H4119.4C9A—C8A—C7A120.7 (10)
C5—C4—H4119.4C9A—C8A—H8A119.7
C6—C5—C10119.5 (10)C7A—C8A—H8A119.7
C6—C5—C4121.8 (10)C8A—C9A—C10A120.7 (10)
C10—C5—C4118.7 (8)C8A—C9A—H9A119.6
C7—C6—C5120.0 (12)C10A—C9A—H9A119.6
C7—C6—H6120.0C5A—C10A—C9A119.2 (8)
C5—C6—H6120.0C5A—C10A—C1A118.3 (8)
C6—C7—C8120.6 (11)C9A—C10A—C1A122.5 (8)
C6—C7—H7119.7
C10—C1—C2—C30.8 (13)C10A—C1A—C2A—C3A0.7 (14)
C10—C1—C2—C21179.5 (8)C10A—C1A—C2A—C21A178.4 (8)
C1—C2—C21—O2114.7 (12)C1A—C2A—C21A—O22A179.6 (8)
C3—C2—C21—O21165.5 (8)C3A—C2A—C21A—O22A0.4 (12)
C1—C2—C21—O22167.2 (8)C1A—C2A—C21A—O21A0.7 (12)
C3—C2—C21—O2212.6 (12)C3A—C2A—C21A—O21A178.4 (8)
O22—C21—O21—Mn172.0 (10)O22A—C21A—O21A—Mn189.2 (9)
C2—C21—O21—Mn1106.0 (8)C2A—C21A—O21A—Mn189.6 (8)
O22i—Mn1—O21—C2198.1 (7)O22i—Mn1—O21A—C21A25.1 (6)
O2W—Mn1—O21—C211.3 (7)O2W—Mn1—O21A—C21A123.9 (6)
O22Aii—Mn1—O21—C2184.9 (7)O22Aii—Mn1—O21A—C21A152.5 (6)
O1W—Mn1—O21—C21169.5 (7)O1W—Mn1—O21A—C21A67.5 (6)
O21—C21—O22—Mn1i24.2 (13)O21A—C21A—O22A—Mn1iii38.7 (14)
C2—C21—O22—Mn1i157.8 (6)C2A—C21A—O22A—Mn1iii142.5 (7)
C1—C2—C3—O3178.6 (8)C1A—C2A—C3A—O3A178.0 (9)
C21—C2—C3—O31.2 (12)C21A—C2A—C3A—O3A2.8 (14)
C1—C2—C3—C43.4 (13)C1A—C2A—C3A—C4A1.9 (14)
C21—C2—C3—C4176.8 (8)C21A—C2A—C3A—C4A177.2 (9)
O3—C3—C4—C5179.2 (8)O3A—C3A—C4A—C5A178.9 (9)
C2—C3—C4—C52.7 (14)C2A—C3A—C4A—C5A1.0 (15)
C3—C4—C5—C6178.1 (9)C3A—C4A—C5A—C10A1.0 (15)
C3—C4—C5—C100.6 (14)C3A—C4A—C5A—C6A179.3 (9)
C10—C5—C6—C71.6 (15)C4A—C5A—C6A—C7A177.8 (10)
C4—C5—C6—C7179.7 (10)C10A—C5A—C6A—C7A0.6 (15)
C5—C6—C7—C81.0 (18)C5A—C6A—C7A—C8A1.2 (18)
C6—C7—C8—C92.6 (19)C6A—C7A—C8A—C9A1.2 (19)
C7—C8—C9—C101.5 (17)C7A—C8A—C9A—C10A0.6 (17)
C6—C5—C10—C1175.6 (9)C4A—C5A—C10A—C9A178.3 (9)
C4—C5—C10—C13.2 (13)C6A—C5A—C10A—C9A0.1 (14)
C6—C5—C10—C92.7 (14)C4A—C5A—C10A—C1A2.1 (14)
C4—C5—C10—C9178.5 (9)C6A—C5A—C10A—C1A179.5 (9)
C2—C1—C10—C52.5 (13)C8A—C9A—C10A—C5A0.1 (16)
C2—C1—C10—C9179.2 (9)C8A—C9A—C10A—C1A179.5 (10)
C8—C9—C10—C51.1 (15)C2A—C1A—C10A—C5A1.2 (14)
C8—C9—C10—C1177.1 (10)C2A—C1A—C10A—C9A179.2 (9)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O220.841.782.533 (9)148
O3A—H3A···O22A0.841.842.582 (9)146
O1W—H1WA···O21Aiii0.842.012.846 (9)180
O1W—H1WB···O3Aii0.842.563.351 (10)157
O2W—H2WA···O21Aii0.841.992.834 (9)180
O2W—H2WB···O3iv0.841.912.751 (9)180
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y, z+1.
(II) tetraaquabis(1-hydroxy-2-naphthoato)manganese(II) top
Crystal data top
[Mn(C11H7O3)2(H2O)4]F(000) = 518
Mr = 501.34Dx = 1.586 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25353 reflections
a = 6.8188 (5) Åθ = 2.6–28.2°
b = 5.2121 (3) ŵ = 0.69 mm1
c = 29.639 (3) ÅT = 173 K
β = 94.917 (7)°Plate, light brown
V = 1049.51 (13) Å30.26 × 0.22 × 0.13 mm
Z = 2
Data collection top
Stoe IPDS II two-circle
diffractometer
2576 independent reflections
Radiation source: fine-focus sealed tube2158 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
ω scansθmax = 28.2°, θmin = 2.8°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 99
Tmin = 0.841, Tmax = 0.916k = 66
22886 measured reflectionsl = 3939
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0366P)2 + 1.434P]
where P = (Fo2 + 2Fc2)/3
2576 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Mn(C11H7O3)2(H2O)4]V = 1049.51 (13) Å3
Mr = 501.34Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.8188 (5) ŵ = 0.69 mm1
b = 5.2121 (3) ÅT = 173 K
c = 29.639 (3) Å0.26 × 0.22 × 0.13 mm
β = 94.917 (7)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2576 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
2158 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 0.916Rint = 0.062
22886 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.38 e Å3
2576 reflectionsΔρmin = 0.31 e Å3
171 parameters
Special details top

Experimental. No standard reflections measured

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
Mn10.00001.00000.50000.02768 (15)
O1W0.2138 (3)1.3077 (4)0.50283 (7)0.0373 (4)
H1A0.317 (7)1.250 (10)0.5177 (14)0.081 (14)*
H1B0.233 (5)1.440 (8)0.4895 (12)0.055 (11)*
O2W0.1855 (3)0.7823 (4)0.45438 (6)0.0307 (4)
H2A0.276 (6)0.838 (7)0.4468 (11)0.047 (10)*
H2B0.132 (5)0.752 (7)0.4305 (11)0.041 (9)*
C10.2719 (3)0.4782 (5)0.62196 (8)0.0283 (5)
O10.0781 (2)0.4873 (4)0.60730 (6)0.0333 (4)
H10.070 (5)0.621 (8)0.5850 (12)0.056 (10)*
C20.4078 (3)0.6472 (5)0.60601 (7)0.0277 (5)
C210.3459 (3)0.8458 (5)0.57165 (8)0.0284 (5)
O210.1599 (2)0.8499 (4)0.55818 (6)0.0324 (4)
O220.4646 (2)0.9986 (4)0.55685 (6)0.0366 (4)
C30.6077 (3)0.6301 (5)0.62380 (8)0.0319 (5)
H30.70200.74340.61290.038*
C40.6667 (4)0.4536 (5)0.65627 (8)0.0345 (5)
H40.80100.44680.66770.041*
C50.5300 (4)0.2807 (5)0.67305 (8)0.0328 (5)
C60.5842 (4)0.0955 (6)0.70697 (9)0.0392 (6)
H60.71700.08660.71940.047*
C70.4491 (5)0.0699 (6)0.72196 (9)0.0419 (6)
H70.48880.19210.74470.050*
C80.2518 (4)0.0610 (5)0.70410 (9)0.0399 (6)
H80.15900.17770.71470.048*
C90.1925 (4)0.1153 (5)0.67144 (8)0.0342 (5)
H90.05890.11980.65940.041*
C100.3294 (4)0.2910 (5)0.65551 (8)0.0301 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0248 (2)0.0259 (3)0.0322 (3)0.0009 (2)0.00186 (17)0.0030 (2)
O1W0.0304 (9)0.0278 (9)0.0527 (11)0.0052 (7)0.0016 (8)0.0072 (8)
O2W0.0269 (8)0.0292 (9)0.0364 (9)0.0025 (7)0.0041 (7)0.0004 (7)
C10.0264 (10)0.0293 (11)0.0294 (10)0.0010 (9)0.0032 (8)0.0023 (9)
O10.0259 (8)0.0345 (9)0.0392 (9)0.0032 (7)0.0007 (6)0.0055 (8)
C20.0264 (10)0.0273 (11)0.0294 (10)0.0004 (9)0.0028 (8)0.0014 (9)
C210.0256 (10)0.0298 (12)0.0300 (10)0.0004 (9)0.0037 (8)0.0011 (9)
O210.0249 (8)0.0343 (9)0.0372 (9)0.0024 (7)0.0013 (6)0.0077 (7)
O220.0279 (8)0.0397 (10)0.0425 (9)0.0058 (8)0.0039 (7)0.0105 (8)
C30.0265 (11)0.0331 (13)0.0362 (12)0.0010 (10)0.0038 (9)0.0004 (10)
C40.0284 (11)0.0370 (14)0.0377 (12)0.0033 (10)0.0001 (9)0.0005 (10)
C50.0347 (12)0.0331 (13)0.0308 (11)0.0056 (10)0.0032 (9)0.0014 (10)
C60.0408 (14)0.0401 (14)0.0362 (13)0.0087 (12)0.0011 (10)0.0027 (11)
C70.0571 (17)0.0349 (14)0.0342 (12)0.0103 (12)0.0065 (11)0.0065 (10)
C80.0514 (15)0.0313 (13)0.0387 (13)0.0001 (11)0.0144 (11)0.0036 (10)
C90.0364 (13)0.0314 (12)0.0358 (12)0.0015 (10)0.0085 (10)0.0004 (10)
C100.0332 (12)0.0283 (12)0.0294 (11)0.0026 (10)0.0056 (9)0.0016 (9)
Geometric parameters (Å, º) top
Mn1—O21i2.1100 (16)C21—O221.242 (3)
Mn1—O212.1100 (16)C21—O211.297 (3)
Mn1—O1Wi2.1639 (19)C3—C41.367 (4)
Mn1—O1W2.1639 (19)C3—H30.9500
Mn1—O2W2.2381 (18)C4—C51.417 (4)
Mn1—O2Wi2.2381 (18)C4—H40.9500
O1W—H1A0.85 (5)C5—C61.419 (4)
O1W—H1B0.81 (4)C5—C101.422 (3)
O2W—H2A0.74 (4)C6—C71.364 (4)
O2W—H2B0.78 (3)C6—H60.9500
C1—O11.356 (3)C7—C81.404 (4)
C1—C21.391 (3)C7—H70.9500
C1—C101.424 (3)C8—C91.371 (4)
O1—H10.96 (4)C8—H80.9500
C2—C31.421 (3)C9—C101.417 (4)
C2—C211.488 (3)C9—H90.9500
O21i—Mn1—O21180.00 (6)O22—C21—O21122.1 (2)
O21i—Mn1—O1Wi86.78 (7)O22—C21—C2122.2 (2)
O21—Mn1—O1Wi93.22 (7)O21—C21—C2115.8 (2)
O21i—Mn1—O1W93.22 (7)C21—O21—Mn1132.91 (15)
O21—Mn1—O1W86.78 (7)C4—C3—C2121.2 (2)
O1Wi—Mn1—O1W180.00 (7)C4—C3—H3119.4
O21i—Mn1—O2W88.48 (7)C2—C3—H3119.4
O21—Mn1—O2W91.52 (7)C3—C4—C5120.8 (2)
O1Wi—Mn1—O2W90.85 (7)C3—C4—H4119.6
O1W—Mn1—O2W89.15 (7)C5—C4—H4119.6
O21i—Mn1—O2Wi91.52 (7)C4—C5—C6122.8 (2)
O21—Mn1—O2Wi88.48 (7)C4—C5—C10119.3 (2)
O1Wi—Mn1—O2Wi89.15 (7)C6—C5—C10117.9 (2)
O1W—Mn1—O2Wi90.85 (7)C7—C6—C5121.2 (3)
O2W—Mn1—O2Wi179.999 (1)C7—C6—H6119.4
Mn1—O1W—H1A107 (3)C5—C6—H6119.4
Mn1—O1W—H1B138 (3)C6—C7—C8120.6 (2)
H1A—O1W—H1B113 (4)C6—C7—H7119.7
Mn1—O2W—H2A121 (3)C8—C7—H7119.7
Mn1—O2W—H2B114 (2)C9—C8—C7120.2 (3)
H2A—O2W—H2B98 (3)C9—C8—H8119.9
O1—C1—C2121.9 (2)C7—C8—H8119.9
O1—C1—C10116.7 (2)C8—C9—C10120.4 (3)
C2—C1—C10121.3 (2)C8—C9—H9119.8
C1—O1—H1104 (2)C10—C9—H9119.8
C1—C2—C3118.7 (2)C9—C10—C5119.6 (2)
C1—C2—C21121.0 (2)C9—C10—C1121.7 (2)
C3—C2—C21120.3 (2)C5—C10—C1118.7 (2)
O1—C1—C2—C3178.5 (2)C3—C4—C5—C6179.5 (3)
C10—C1—C2—C30.1 (3)C3—C4—C5—C100.4 (4)
O1—C1—C2—C210.4 (4)C4—C5—C6—C7179.3 (3)
C10—C1—C2—C21178.7 (2)C10—C5—C6—C70.8 (4)
C1—C2—C21—O22179.9 (2)C5—C6—C7—C80.0 (4)
C3—C2—C21—O221.3 (4)C6—C7—C8—C90.3 (4)
C1—C2—C21—O210.3 (3)C7—C8—C9—C100.3 (4)
C3—C2—C21—O21178.6 (2)C8—C9—C10—C51.1 (4)
O22—C21—O21—Mn120.7 (4)C8—C9—C10—C1179.3 (2)
C2—C21—O21—Mn1159.52 (16)C4—C5—C10—C9178.7 (2)
O1Wi—Mn1—O21—C21145.1 (2)C6—C5—C10—C91.3 (4)
O1W—Mn1—O21—C2134.9 (2)C4—C5—C10—C10.9 (3)
O2W—Mn1—O21—C2154.1 (2)C6—C5—C10—C1179.0 (2)
O2Wi—Mn1—O21—C21125.9 (2)O1—C1—C10—C92.6 (3)
C1—C2—C3—C40.6 (4)C2—C1—C10—C9179.0 (2)
C21—C2—C3—C4178.2 (2)O1—C1—C10—C5177.8 (2)
C2—C3—C4—C50.4 (4)C2—C1—C10—C50.7 (3)
Symmetry code: (i) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O210.96 (4)1.59 (4)2.478 (3)153 (3)
O1W—H1A···O220.85 (5)1.97 (5)2.760 (3)154 (4)
O1W—H1B···O2Wii0.81 (4)2.08 (4)2.859 (3)162 (4)
O2W—H2A···O22iii0.74 (4)1.97 (4)2.691 (3)165 (4)
O2W—H2B···O1iv0.78 (3)2.14 (4)2.826 (3)146 (3)
Symmetry codes: (ii) x, y+1, z; (iii) x+1, y+2, z+1; (iv) x, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Mn(C11H7O3)2(H2O)2][Mn(C11H7O3)2(H2O)4]
Mr465.30501.34
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)173173
a, b, c (Å)17.2616 (17), 7.3476 (5), 15.5360 (15)6.8188 (5), 5.2121 (3), 29.639 (3)
β (°) 101.815 (8) 94.917 (7)
V3)1928.7 (3)1049.51 (13)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.740.69
Crystal size (mm)0.42 × 0.32 × 0.130.26 × 0.22 × 0.13
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 1990; Blessing, 1995)
Multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.748, 0.9110.841, 0.916
No. of measured, independent and
observed [I > 2σ(I)] reflections
17865, 4535, 3911 22886, 2576, 2158
Rint0.0830.062
(sin θ/λ)max1)0.6600.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.087, 0.316, 1.21 0.043, 0.113, 1.11
No. of reflections45352576
No. of parameters281171
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0999P)2 + 24.9072P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0366P)2 + 1.434P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.08, 1.270.38, 0.31

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97 and PLATON (Spek, 2003).

Selected bond lengths (Å) for (I) top
Mn1—O22i2.109 (6)Mn1—O22Aii2.170 (6)
Mn1—O2W2.159 (6)Mn1—O1W2.198 (7)
Mn1—O212.163 (6)Mn1—O21A2.246 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O220.841.782.533 (9)148
O3A—H3A···O22A0.841.842.582 (9)146
O1W—H1WA···O21Aiii0.842.012.846 (9)180
O1W—H1WB···O3Aii0.842.563.351 (10)157
O2W—H2WA···O21Aii0.841.992.834 (9)180
O2W—H2WB···O3iv0.841.912.751 (9)180
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y, z+1.
Selected bond lengths (Å) for (II) top
Mn1—O212.1100 (16)Mn1—O2W2.2381 (18)
Mn1—O1W2.1639 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O210.96 (4)1.59 (4)2.478 (3)153 (3)
O1W—H1A···O220.85 (5)1.97 (5)2.760 (3)154 (4)
O1W—H1B···O2Wi0.81 (4)2.08 (4)2.859 (3)162 (4)
O2W—H2A···O22ii0.74 (4)1.97 (4)2.691 (3)165 (4)
O2W—H2B···O1iii0.78 (3)2.14 (4)2.826 (3)146 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+2, z+1; (iii) x, y+1, z+1.
 

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