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In the title complex, [Mn(C8H4NO6)2(H2O)4]·2H2O, cyclic water tetra­mers forming one-dimensional metal–water chains have been observed. The water clusters are trapped by the co-­operative association of coordination inter­actions and hydrogen bonds. The MnII ion resides on a center of symmetry and is in an octa­hedral coordination environment comprising two O atoms from two 5-carboxy-2-nitrobenzoate ligands and four O atoms from water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106056010/av3055sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106056010/av3055Isup2.hkl
Contains datablock I

CCDC reference: 602561

Comment top

Water clusters are bridges between a single water molecule and liquid water or ice. Recent years have witnessed intense studies of small water clusters (Mascal et al., 2006) from the theoretical (Xantheas 1994, 1995; Kim et al., 1994, 1999) and experimental aspects (Buck & Huisken, 2000; Barbour et al., 1998; Raghuraman et al., 2003; Janiak & Scharamann, 2002). Among them, the cyclic water tetramer is of great interest since it is a simple two-structure model for liquid water (Benson & Siebert, 1992; Ludwig, 2001). Their configurations have been predicted by ab initio electronic structure calculations (Gregory & Clary, 1996; Udalde et al., 2000; Radhakrishnan & Herndon, 1991), and some of them have been characterized by far-IR vibration–rotation tunneling spectroscopy (Cruzan et al., 1996) or found in different crystal hosts (Mascal et al., 2006; Xu et al., 2000; Supriya & Das, 2003; Long et al., 2004; Zuhayra et al., 2006). We report here the title metal–water chain complex [Mn(NO2—HBDC)2·4H2O]·2H2O [NO2—H2BDC is 4-nitro-1,3-benzenedicarboxylic acid], (I), which contains the cyclic water tetramer.

The asymmetric unit of complex (I) consists of one Mn atom, two NO2—H2BDC ligands, four coordinated water molecules and two solvent water molecules (Fig. 1). The MnII ion is located on a symmetry center and is coordinated by two O atoms of two monodentate carboxylate groups from two NO2—HBDC ligands [Mn—O1 = 2.1493 (17) Å; symmetry code: (i) -x, -y + 2, -z + 1] and two O atoms from two water molecules [Mn—O7 = 2.1815 (19) Å] forming the equatorial plane, and two O atoms from the other two water molecules [Mn—O8 = 2.2060 (18) Å] at the axial positions. The coordination geometry around the MnII ion can be described as a slightly distorted octahedron. The distortion arises from the axis O8—Mn1—O8i, which is not actually perpendicular to the coordination plane (O1/O7/O1i/O7i/Mn1). In fact, the angle O1—Mn1—O8 is 89.26 (6)°. In the NO2—H2BDC ligand, the dihedral angles between the benzene ring (C2–C7; plane I) and the planes formed by carboxylate groups atoms are 68.8 (3) and 27.9 (2) ° for the O1/C1/O2 plane and the O3/C8/O4 plane, respectively; that between plane I and the O5/N1/O6 plane is 26.1 (2)°.

There are O—H···O hydrogen bonds between the coordination water molecules and carboxylate O atoms [O8···O4iii = 2.725 (2) Å; see Table 2 fro symmetry codes], which bridge molecules, forming an infinite one-dimensional chain along the c axis. The NO2—H2BDC ligands are parallel to each other in the chain; the distance between the benzene rings of the NO2—HBDC ligands is 3.588 (2) Å. These chains are further interconnected by solvent water molecules via hydrogen bonds [O9···O2v = 2.665 (3) Å, O3···O9ii = 2.608 (2) Å and O7···O9 = 2.829 (2) Å], giving rise to a two-dimensional structure in the bc plane, as shown in Fig. 2.

Interestingly, a cyclic water tetramer is observed in the solid state (Fig. 3). The solvent water molecule in the cluster is in a tetrahedral environment with two water–water hydrogen bonds and two water–carboxylate hydrogen bonds. Meanwhile, the coordinated water molecule involves two water–water hydrogen bonds and one water–metal coordination bond. Within the cluster, the four water molecules are completely coplanar without regard to connectivity of the H atoms. Though the distance of O9···O7 (3.155 Å) is longer than the sum of van der Waals radii (3.04 Å), we think there still exist weak hydrogen-bonding interactions as found in a lots of compounds reported (Liu & Xu, 2005; Oscar et al., 2006). The average O···O distance is 2.99 Å. This distance is significantly longer than the 2.78 Å e stimated in the water tetramer of (D2O)4 in the gas phase (Cruzan et al., 1996), and longer than in other tetrameric clusters reported previously (2.768–2.94 Å; Supriya & Das, 2003; Long et al., 2004; Zuhayra et al., 2006; Tao et al., 2004; Ye et al., 2005). However, it is shorter than that observed in 1,4,7,10-tetraazacyclododecane·3H2O (3.004 Å; Pal et al., 2003). Two of the water molecules in the cyclic tetramers of (I) bind to the MnII ions, resulting in an infinite metal–water chain along the a axis. To the best of our knowledge, such cyclic water clusters containing metal–water chains are not common (Turner et al., 2004; Ghosh & Bharadwaj, 2003; Ye et al., 2004; Liu & Xu, 2005; Li et al., 2006). Another remarkable feature is that the two-dimensional structure is assembled into a three-dimensional network (Fig. 4) by the water tetramers through metal–water chains, indicating that the cyclic water tetramer plays a crucial role in the formation of the three-dimensional network.

Related literature top

For related literature, see: Barbour et al. (1998); Benson & Siebert (1992); Buck & Huisken (2000); Cruzan et al. (1996); Ghosh & Bharadwaj (2003); Gregory & Clary (1996); Janiak & Scharamann (2002); Kim et al. (1994, 1999); Li et al. (2006); Liu & Xu (2005); Long et al. (2004); Ludwig (2001); Mascal et al. (2006); Oscar et al. (2006); Pal et al. (2003); Radhakrishnan & Herndon (1991); Raghuraman et al. (2003); Supriya & Das (2003); Tao et al. (2004); Turner et al. (2004); Udalde et al. (2000); Xantheas (1994, 1995); Xu et al. (2000); Ye et al. (2004, 2005); Zuhayra et al. (2006).

Experimental top

A solution of MnSO4 (0.0151 g, 0.10 mmol) in water (5 ml) was added dropwise with constant stirring to an aqueous solution (5 ml) of 4-nitro-1,3-benzenedicarboxylic acid (0.0211 g, 0.1 mmol). The resulting mixture was then transferred into a Teflon-lined stainless steel vessel, which was sealed and heated to 403 K for 72 h, then cooled to room temperature. The reaction mixture was then filtered and single crystals were obtained from the filtrate at room temperature after a few days.

Refinement top

H atoms attached to C atoms were placed at calculated positions (C—H = 0.93 Å) and allowed to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)]. H atoms attached to O atoms were located in a difference map and refined as riding in their as-found positions (O—H = 0.82–0.86 Å), with Uiso(H) = 1.2Ueq(O). Please check changes to text.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-mumbering scheme. [Symmetry code: (A) - x, 2 - y, 1 - z.]
[Figure 2] Fig. 2. A view of the two-dimensional hydrogen-bonded net projected on to the bc plane in (I). Dashed lines indicate hydrogen bonds. [Symmetry codes: (A) x, y, -1 + z; (B) x, y, z; (AA) - x, 2 - y, - z; (AD) 1 - x, 1 - y, - z.]
[Figure 3] Fig. 3. A view of the cyclic water tetramer and its coordination environment in (I). Dashed lines indicate hydrogen bonds. [Symmetry codes: (A) Please provide. (B) 1 - x, 2 - y, 1 - z; (AB) 1 + x, y, z; (AC) 1 - x, 1 - y, 1 - z; (AD) x, 1 + y, z; (AE) 1 - x, 2 - y, - z; (AF) x, y, 1 + z.]
[Figure 4] Fig. 4. The crystal packing of (I) viewed down the c axis. Dashed lines indicate hydrogen bonds.
Tetraaquabis(3-carboxy-4-nitrobenzoato-κO)manganese(II) dihydrate top
Crystal data top
[Mn(C8H4NO6)2(H2O)4]·2H2OZ = 1
Mr = 583.28F(000) = 299
Triclinic, P1Dx = 1.738 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.355 (4) ÅCell parameters from 1957 reflections
b = 7.965 (4) Åθ = 3.1–26.5°
c = 11.056 (6) ŵ = 0.69 mm1
α = 73.827 (8)°T = 273 K
β = 83.588 (7)°Block, colourless
γ = 63.647 (7)°0.24 × 0.22 × 0.20 mm
V = 557.4 (5) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
1957 independent reflections
Radiation source: fine-focus sealed tube1741 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.852, Tmax = 0.875k = 95
2863 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0461P)2 + 0.1749P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1957 reflectionsΔρmax = 0.25 e Å3
171 parametersΔρmin = 0.28 e Å3
9 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.331 (13)
Crystal data top
[Mn(C8H4NO6)2(H2O)4]·2H2Oγ = 63.647 (7)°
Mr = 583.28V = 557.4 (5) Å3
Triclinic, P1Z = 1
a = 7.355 (4) ÅMo Kα radiation
b = 7.965 (4) ŵ = 0.69 mm1
c = 11.056 (6) ÅT = 273 K
α = 73.827 (8)°0.24 × 0.22 × 0.20 mm
β = 83.588 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1957 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1741 reflections with I > 2σ(I)
Tmin = 0.852, Tmax = 0.875Rint = 0.019
2863 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0309 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.04Δρmax = 0.25 e Å3
1957 reflectionsΔρmin = 0.28 e Å3
171 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
Mn10.00001.00000.50000.02650 (19)
O10.0201 (2)0.9464 (2)0.32299 (13)0.0343 (4)
O20.1911 (3)0.6336 (2)0.37183 (15)0.0513 (5)
O30.4305 (2)0.7371 (2)0.11896 (14)0.0375 (4)
H30.49980.73140.18250.056*
O40.2952 (2)0.5942 (2)0.20296 (13)0.0343 (4)
O50.5054 (2)0.8809 (3)0.20446 (17)0.0510 (5)
O60.2785 (3)0.7428 (3)0.35109 (14)0.0502 (5)
O70.3273 (2)0.9039 (2)0.48277 (15)0.0439 (4)
H7A0.40600.85760.54700.053*
H7B0.37940.85590.42020.053*
O80.0371 (2)1.2945 (2)0.39871 (13)0.0350 (4)
H8A0.11951.33940.33670.042*
H8B0.08331.34700.46000.042*
N10.3294 (3)0.8061 (2)0.24005 (17)0.0328 (4)
C10.0658 (3)0.7828 (3)0.30173 (18)0.0294 (5)
C20.0175 (3)0.7680 (3)0.17634 (17)0.0248 (4)
C30.1659 (3)0.7385 (3)0.08529 (17)0.0254 (4)
H3A0.29170.72890.10200.031*
C40.1289 (3)0.7232 (3)0.03059 (17)0.0250 (4)
C50.0604 (3)0.7434 (3)0.05823 (18)0.0300 (4)
H50.08490.73420.13630.036*
C60.2121 (3)0.7772 (3)0.02976 (19)0.0298 (4)
H60.34040.79390.01140.036*
C70.1693 (3)0.7855 (3)0.14552 (18)0.0257 (4)
C80.2910 (3)0.6791 (3)0.12654 (17)0.0259 (4)
O90.6331 (2)0.7165 (2)0.67225 (14)0.0397 (4)
H9A0.70130.78250.64460.048*
H9B0.69330.59800.66960.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0317 (3)0.0320 (3)0.0209 (3)0.0169 (2)0.00441 (16)0.01065 (18)
O10.0447 (8)0.0327 (8)0.0250 (7)0.0121 (7)0.0004 (6)0.0149 (6)
O20.0537 (10)0.0456 (10)0.0319 (8)0.0074 (8)0.0144 (7)0.0195 (7)
O30.0350 (8)0.0558 (10)0.0353 (8)0.0267 (8)0.0131 (6)0.0249 (8)
O40.0395 (8)0.0416 (8)0.0282 (7)0.0186 (7)0.0067 (6)0.0190 (7)
O50.0281 (8)0.0674 (12)0.0553 (11)0.0179 (8)0.0105 (7)0.0209 (9)
O60.0492 (10)0.0665 (12)0.0290 (9)0.0231 (9)0.0139 (7)0.0120 (8)
O70.0305 (8)0.0613 (10)0.0410 (9)0.0157 (8)0.0100 (7)0.0256 (8)
O80.0445 (8)0.0344 (8)0.0275 (7)0.0172 (7)0.0017 (6)0.0087 (6)
N10.0314 (9)0.0330 (9)0.0354 (10)0.0147 (8)0.0114 (7)0.0138 (8)
C10.0292 (10)0.0358 (11)0.0218 (10)0.0107 (9)0.0045 (8)0.0127 (9)
C20.0279 (9)0.0220 (9)0.0217 (9)0.0073 (8)0.0008 (7)0.0073 (7)
C30.0239 (9)0.0290 (10)0.0254 (10)0.0112 (8)0.0002 (7)0.0105 (8)
C40.0275 (10)0.0248 (9)0.0232 (9)0.0111 (8)0.0019 (8)0.0081 (8)
C50.0334 (10)0.0377 (11)0.0224 (10)0.0159 (9)0.0009 (8)0.0115 (8)
C60.0270 (10)0.0363 (11)0.0303 (10)0.0159 (9)0.0011 (8)0.0111 (9)
C70.0262 (9)0.0242 (9)0.0262 (10)0.0106 (8)0.0052 (8)0.0081 (8)
C80.0294 (10)0.0267 (10)0.0203 (9)0.0104 (8)0.0001 (8)0.0067 (8)
O90.0395 (8)0.0407 (8)0.0439 (9)0.0213 (7)0.0170 (7)0.0178 (7)
Geometric parameters (Å, º) top
Mn1—O1i2.1493 (17)O8—H8B0.8542
Mn1—O12.1494 (17)N1—C71.468 (3)
Mn1—O72.1815 (19)C1—C21.517 (3)
Mn1—O7i2.1815 (19)C2—C31.385 (3)
Mn1—O8i2.2062 (17)C2—C71.390 (3)
Mn1—O82.2062 (17)C3—C41.387 (3)
O1—C11.249 (3)C3—H3A0.9300
O2—C11.240 (2)C4—C51.387 (3)
O3—C81.317 (2)C4—C81.491 (3)
O3—H30.8200C5—C61.379 (3)
O4—C81.211 (2)C5—H50.9300
O5—N11.218 (2)C6—C71.377 (3)
O6—N11.221 (2)C6—H60.9300
O7—H7A0.8558O9—H9A0.8558
O7—H7B0.8543O9—H9B0.8536
O8—H8A0.8543
O1i—Mn1—O1180.0O2—C1—O1125.96 (18)
O1i—Mn1—O788.22 (6)O2—C1—C2117.33 (17)
O1—Mn1—O791.77 (6)O1—C1—C2116.67 (17)
O1i—Mn1—O7i91.78 (6)C3—C2—C7117.29 (17)
O1—Mn1—O7i88.22 (6)C3—C2—C1118.74 (17)
O7—Mn1—O7i180.00 (3)C7—C2—C1123.96 (17)
O1i—Mn1—O8i89.26 (6)C2—C3—C4120.77 (17)
O1—Mn1—O8i90.74 (6)C2—C3—H3A119.6
O7—Mn1—O8i92.13 (6)C4—C3—H3A119.6
O7i—Mn1—O8i87.87 (6)C3—C4—C5120.18 (18)
O1i—Mn1—O890.74 (6)C3—C4—C8121.44 (17)
O1—Mn1—O889.26 (6)C5—C4—C8118.36 (17)
O7—Mn1—O887.87 (6)C6—C5—C4120.16 (18)
O7i—Mn1—O892.13 (6)C6—C5—H5119.9
O8i—Mn1—O8180.0C4—C5—H5119.9
C1—O1—Mn1123.79 (13)C7—C6—C5118.46 (18)
C8—O3—H3109.5C7—C6—H6120.8
Mn1—O7—H7A122.3C5—C6—H6120.8
Mn1—O7—H7B114.8C6—C7—C2123.09 (18)
H7A—O7—H7B114.9C6—C7—N1116.83 (17)
Mn1—O8—H8A109.7C2—C7—N1120.03 (17)
Mn1—O8—H8B97.5O4—C8—O3123.24 (18)
H8A—O8—H8B114.9O4—C8—C4122.68 (17)
O5—N1—O6123.17 (18)O3—C8—C4114.07 (16)
O5—N1—C7118.78 (18)H9A—O9—H9B115.3
O6—N1—C7118.02 (17)
O7—Mn1—O1—C162.49 (17)C4—C5—C6—C71.5 (3)
O7i—Mn1—O1—C1117.51 (17)C5—C6—C7—C22.2 (3)
O8i—Mn1—O1—C129.67 (16)C5—C6—C7—N1175.23 (18)
O8—Mn1—O1—C1150.33 (16)C3—C2—C7—C60.8 (3)
Mn1—O1—C1—O28.7 (3)C1—C2—C7—C6178.08 (18)
Mn1—O1—C1—C2173.81 (12)C3—C2—C7—N1176.59 (16)
O2—C1—C2—C368.7 (3)C1—C2—C7—N14.5 (3)
O1—C1—C2—C3109.1 (2)O5—N1—C7—C625.5 (3)
O2—C1—C2—C7112.4 (2)O6—N1—C7—C6152.8 (2)
O1—C1—C2—C769.8 (3)O5—N1—C7—C2156.97 (19)
C7—C2—C3—C41.4 (3)O6—N1—C7—C224.7 (3)
C1—C2—C3—C4179.70 (17)C3—C4—C8—O4150.97 (19)
C2—C3—C4—C52.1 (3)C5—C4—C8—O427.2 (3)
C2—C3—C4—C8176.09 (17)C3—C4—C8—O327.7 (3)
C3—C4—C5—C60.6 (3)C5—C4—C8—O3154.09 (18)
C8—C4—C5—C6177.62 (17)
Symmetry code: (i) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O9ii0.821.792.608 (2)175
O7—H7A···O90.861.992.829 (2)168
O8—H8A···O4iii0.851.882.726 (2)173
O8—H8B···O2i0.851.962.764 (2)157
O9—H9A···O7iv0.862.433.155 (3)143
O9—H9A···O8iv0.862.292.956 (3)134
O9—H9B···O2v0.851.822.665 (3)168
Symmetry codes: (i) x, y+2, z+1; (ii) x, y, z1; (iii) x, y+2, z; (iv) x+1, y+2, z+1; (v) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Mn(C8H4NO6)2(H2O)4]·2H2O
Mr583.28
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)7.355 (4), 7.965 (4), 11.056 (6)
α, β, γ (°)73.827 (8), 83.588 (7), 63.647 (7)
V3)557.4 (5)
Z1
Radiation typeMo Kα
µ (mm1)0.69
Crystal size (mm)0.24 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.852, 0.875
No. of measured, independent and
observed [I > 2σ(I)] reflections
2863, 1957, 1741
Rint0.019
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.084, 1.04
No. of reflections1957
No. of parameters171
No. of restraints9
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected bond lengths (Å) top
Mn1—O1i2.1493 (17)Mn1—O82.2062 (17)
Mn1—O12.1494 (17)O1—C11.249 (3)
Mn1—O72.1815 (19)O2—C11.240 (2)
Mn1—O7i2.1815 (19)O3—C81.317 (2)
Mn1—O8i2.2062 (17)O4—C81.211 (2)
Symmetry code: (i) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O9ii0.821.792.608 (2)175
O7—H7A···O90.861.992.829 (2)168
O8—H8A···O4iii0.851.882.726 (2)173
O9—H9A···O7iv0.862.433.155 (3)143
O9—H9B···O2v0.851.822.665 (3)168
Symmetry codes: (ii) x, y, z1; (iii) x, y+2, z; (iv) x+1, y+2, z+1; (v) x+1, y+1, z+1.
 

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