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Acta Cryst. (2007). E63, m1720-m1721    [ doi:10.1107/S1600536807024270 ]

Aqua[7,11:19,23-dinitrilo-1,5,13,17-tetraazacyclotetracosa-1(24),5,7,9,12,17,20,22-octaene]bis(perchlorato-[kappa]2O,O')barium(II) monohydrate

R. Dennett, L. James and V. McKee

Abstract top

The title complex, [Ba(ClO4)2(C20H22N6)(H2O)]·H2O, contains an 11-coordinate barium ion, coordinated by a folded hexadentate macrocycle, two bidentate perchlorate anions and a water molecule. The coordinated water molecule and one of the perchlorate anions are disordered about a twofold axis running through the complex. Hydrogen-bonded sheets are linked in the third dimension by [pi]-[pi] stacking (the mean interplanar distance is 3.441 Å).

Comment top

The stucture of the title compound, [Ba(C20H22N6)(ClO4)2(H2O)].H2O, (I), was solved in C2/c and is shown in Fig. 1. The barium ion is 11-coordinate; it is bonded to all six N donors of the macrocycle, which is folded to accommodate the metal (N1—Ba—N1i , 130.69 (6)°). Two bidentate perchlorate anions are also coordinated, one on each side of the macrocycle, and the coordination sphere is completed by a water molecule (O1W) on the convex side. A non-coordinated water molecule (O2W) is H-bonded to O1W and to the perchlorate ion. A 2-fold axis runs through Ba1 and Cl1 and this requires that the perchlorate/water assembly on the convex face of the macrocycle is disordered with equal occupancy of two positions related by the 2-fold axis, as shown in Fig. 2. There is also a minor disorder in the saturated portion of the macrocycle at C9; this was modelled as 9:1 occupancy of two related sites.

The water molecules link the complex molecules into two-dimensional sheets perpendicular to a through further H-bonding (Table 1). The disorder of the groups coordinated on the convex face of the macrocycle gives rise to two possible H-bonding nets related by a 2-fold axis, one of these is shown in Fig. 3. The principal interaction between adjacent layers is π-π stacking of the pyridine-imine unit with the same section of an adjacent molecule under symmetry operation (iv) -x - 1/2, -y + 3/2, -z + 1 (Fig. 4). The mean interplanar distance between the overlapping sections (N1, N2, C1 – C6) is 3.441 Å. Interactions between layers are not affected significantly by the disorder within the two-dimensional H-bonded sheets, so the structure can be viewed as a random stack of the two H-bonded layers.

The structure was initially solved in Cc as the statistics indicated a non-centrosymmetric space group (possibly an artefact due to the presence of the heavy Ba atom). There was disorder evident on the convex side of the macrocycle, racemic twinning was indicated, the Flack parameter refined to 0.43 (2), and the anisotropic refinement required a series of restraints to prevent atoms going non-positive definite. Hence, the centrosymmetric solution was preferred.

Related literature top

In 1990, the structure of a complex formulated as [Ba(C20H22N6)(ClO4)2(C2H5OH)], (II), was determined at ambient temperature and refined in space group Aa to a value of R = 0.080 for data with I > 2σ(I) (Harding et al., 1990). Low-temperature data for the title complex gave a unit cell apparently isomorphous with that of (II) and a similar solution in Cc, but the refinement was poor (see Supplementary Material). Solution in C2/c, however, gave a much better refinement for a model with disorder between one coordinated perchlorate anion and a coordinated water molecule across the twofold axis. While it is possible that both the title complex and (II) could differ in the coordinated solvent present and still have very similar unit cells, it is also possible that the complexes are the same and that the earlier structure should be re-interpreted.

Experimental top

Complex (I), [Ba(C20H22N6)(ClO4)2(H2O)]H2O, was prepared as reported previously (Harding et al., 1990) and recrystallized from CH3CN by slow diffusion of Et2O to yield colourless crystals.

Refinement top

H atoms bonded to C were inserted at calculated positions with C—H distances of 0.99 and 0.95 Å for saturated and unsaturated C atoms, respectively; they were refined using a riding model with Uiso(H) = 1.2Ueq(C). The H atoms bonded to partial occupancy O atoms were not located or included in the model.

Computing details top

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Perspective view of complex (I); displacement ellipsoids are drawn at the 50% probability level and H-bonds are indicated by dashed lines. For clarity only one component of the disorder is shown and the H atoms are omitted. [Symmetry code (i) -x, y, -z + 3/2]
[Figure 2] Fig. 2. Perspective view showing the two components of the disorder related by the 2-fold axis through Ba1 and Cl1 [Symmetry code (i) -x, y, -z + 3/2]. Dashed lines indicate H-bonds: O1W···O2W 2.761 (6) Å; O2W···O6 2.904 (5) Å.
[Figure 3] Fig. 3. Packing diagram viewed perpendicular to a, showing the two-dimensional H-bonded sheets. Only one component of the disorder is shown.
[Figure 4] Fig. 4. The π-π stacking between pyridine diimine groups viewed perpendicular to the N1—C5 ring. H atoms and non-macrocyclic ligands omitted for clarity. [Symmetry code (iv) -x - 1/2, -y + 3/2, -z + 1]
Aqua[7,11:19,23-dinitrilo-1,5,13,17-tetraazacyclotetracosa- 1(24),5,7,9,12,17,20,22-octaene]bis(perchlorato- κ2O,O')barium(II) monohydrate top
Crystal data top
[Ba(ClO4)2(C20H22N6)(H2O)]·H2OF(000) = 1432
Mr = 718.71Dx = 1.771 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9994 reflections
a = 14.5247 (8) Åθ = 2.4–31.7°
b = 12.0634 (6) ŵ = 1.74 mm−1
c = 15.8698 (8) ÅT = 150 K
β = 104.157 (1)°Triangular prism, colourless
V = 2696.2 (2) Å30.51 × 0.31 × 0.13 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer		4334 independent reflections
Radiation source: fine-focus sealed tube4120 reflections with I > 2σ(I)
graphiteRint = 0.018
φ and ω scansθmax = 31.9°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −21→21
Tmin = 0.472, Tmax = 0.806k = −17→17
16000 measured reflectionsl = −23→23
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0204P)2 + 4.1932P]
where P = (Fo2 + 2Fc2)/3
4334 reflections(Δ/σ)max = 0.002
213 parametersΔρmax = 0.69 e Å−3
3 restraintsΔρmin = −0.63 e Å−3
Crystal data top
[Ba(ClO4)2(C20H22N6)(H2O)]·H2OV = 2696.2 (2) Å3
Mr = 718.71Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.5247 (8) ŵ = 1.74 mm−1
b = 12.0634 (6) ÅT = 150 K
c = 15.8698 (8) Å0.51 × 0.31 × 0.13 mm
β = 104.157 (1)°
Data collection top
Bruker APEXII
diffractometer		4120 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		Rint = 0.018
Tmin = 0.472, Tmax = 0.806θmax = 31.9°
16000 measured reflectionsStandard reflections: 0
4334 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.057Δρmax = 0.69 e Å−3
S = 1.19Δρmin = −0.63 e Å−3
4334 reflectionsAbsolute structure: ?
213 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
Ba10.00000.788958 (11)0.75000.01874 (4)
N1−0.10892 (11)0.68917 (13)0.59159 (10)0.0238 (3)
C1−0.06707 (14)0.65105 (15)0.53091 (12)0.0256 (3)
C2−0.11248 (16)0.57923 (18)0.46426 (13)0.0338 (4)
H2−0.08050.55330.42250.041*
C3−0.20456 (17)0.54690 (18)0.46044 (15)0.0381 (5)
H3−0.23690.49770.41630.046*
C4−0.24903 (15)0.58707 (17)0.52181 (15)0.0352 (4)
H4−0.31270.56690.52000.042*
C5−0.19879 (13)0.65772 (15)0.58645 (13)0.0267 (4)
C6−0.24753 (13)0.70665 (17)0.64921 (14)0.0302 (4)
H6−0.31250.68920.64360.036*
N2−0.20673 (11)0.77051 (14)0.70992 (11)0.0266 (3)
C7−0.26778 (15)0.8175 (2)0.76233 (14)0.0356 (4)0.90
H7A−0.33500.81130.72970.043*0.90
H7B−0.25290.89720.77260.043*0.90
C8−0.25451 (17)0.7586 (2)0.84939 (17)0.0383 (5)0.90
H8A−0.31170.77220.87140.046*0.90
H8B−0.25110.67790.83940.046*0.90
C9−0.16824 (16)0.7917 (2)0.91937 (15)0.0407 (5)0.90
H9A−0.16590.87360.92300.049*0.90
H9B−0.17600.76360.97580.049*0.90
C7'−0.26778 (15)0.8175 (2)0.76233 (14)0.0356 (4)0.10
H7'1−0.30910.75770.77520.043*0.10
H7'2−0.30950.87400.72700.043*0.10
C8'−0.2141 (14)0.8725 (14)0.8508 (9)0.032 (4)*0.10
H8'1−0.16470.92300.83960.038*0.10
H8'2−0.25980.91780.87300.038*0.10
C9'−0.16824 (16)0.7917 (2)0.91937 (15)0.0407 (5)0.10
H9'1−0.15760.82760.97700.049*0.10
H9'2−0.21130.72790.91850.049*0.10
N3−0.07714 (12)0.75158 (15)0.90665 (11)0.0275 (3)
C10−0.02915 (14)0.69174 (16)0.96740 (12)0.0280 (4)
H10−0.05640.67221.01400.034*
Cl10.00000.48758 (5)0.75000.02468 (12)
O1−0.07104 (10)0.55775 (11)0.77253 (10)0.0303 (3)
O2−0.04305 (13)0.41910 (14)0.67689 (12)0.0444 (4)
Cl2−0.00155 (6)1.03329 (8)0.62396 (6)0.02486 (16)0.50
O5−0.0806 (3)0.9790 (3)0.6470 (2)0.0381 (8)0.50
O6−0.0092 (3)1.1495 (3)0.6331 (2)0.0408 (7)0.50
O70.0840 (2)0.9913 (3)0.6816 (2)0.0342 (6)0.50
O8−0.0029 (4)1.0072 (4)0.5355 (2)0.0576 (11)0.50
O1W0.0299 (4)0.9723 (3)0.8653 (2)0.0476 (10)0.50
O2W−0.0057 (4)1.1901 (4)0.8142 (3)0.0690 (13)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.02017 (7)0.01853 (7)0.01998 (7)0.0000.00965 (5)0.000
N10.0224 (7)0.0224 (7)0.0265 (7)0.0014 (5)0.0054 (5)−0.0012 (5)
C10.0281 (8)0.0230 (8)0.0245 (8)0.0044 (7)0.0042 (7)−0.0026 (6)
C20.0399 (11)0.0295 (9)0.0289 (9)0.0056 (8)0.0024 (8)−0.0071 (7)
C30.0404 (11)0.0286 (10)0.0378 (11)−0.0005 (8)−0.0049 (9)−0.0072 (8)
C40.0270 (9)0.0284 (9)0.0449 (12)−0.0020 (8)−0.0014 (8)−0.0016 (8)
C50.0219 (8)0.0226 (8)0.0338 (9)0.0016 (6)0.0035 (7)0.0016 (7)
C60.0186 (8)0.0313 (9)0.0411 (11)0.0017 (7)0.0083 (7)0.0053 (8)
N20.0225 (7)0.0299 (8)0.0301 (8)0.0078 (6)0.0115 (6)0.0064 (6)
C70.0272 (9)0.0482 (12)0.0351 (10)0.0139 (9)0.0151 (8)0.0067 (9)
C80.0255 (10)0.0550 (15)0.0400 (12)0.0071 (10)0.0189 (9)0.0136 (11)
C90.0325 (10)0.0636 (15)0.0322 (10)0.0116 (10)0.0201 (8)0.0035 (10)
C7'0.0272 (9)0.0482 (12)0.0351 (10)0.0139 (9)0.0151 (8)0.0067 (9)
C9'0.0325 (10)0.0636 (15)0.0322 (10)0.0116 (10)0.0201 (8)0.0035 (10)
N30.0253 (7)0.0348 (8)0.0258 (7)0.0016 (6)0.0131 (6)0.0015 (6)
C100.0307 (9)0.0322 (9)0.0235 (8)−0.0059 (7)0.0115 (7)0.0018 (7)
Cl10.0260 (3)0.0175 (2)0.0348 (3)0.0000.0156 (2)0.000
O10.0296 (7)0.0251 (6)0.0411 (8)0.0065 (5)0.0178 (6)0.0012 (6)
O20.0469 (9)0.0358 (8)0.0572 (10)−0.0167 (7)0.0258 (8)−0.0204 (8)
Cl20.0288 (4)0.0247 (4)0.0219 (4)−0.0025 (3)0.0077 (3)0.0058 (3)
O50.0302 (16)0.0428 (19)0.0391 (18)−0.0088 (14)0.0041 (14)0.0120 (14)
O60.059 (2)0.0259 (15)0.0359 (17)0.0034 (14)0.0078 (15)0.0003 (13)
O70.0227 (13)0.0346 (15)0.0444 (17)0.0007 (11)0.0065 (12)0.0083 (13)
O80.095 (3)0.055 (2)0.0287 (16)0.011 (2)0.0268 (19)0.0088 (15)
O1W0.091 (3)0.0312 (18)0.0255 (16)−0.004 (2)0.022 (2)−0.0022 (13)
O2W0.093 (4)0.050 (2)0.065 (3)0.002 (2)0.022 (3)−0.003 (2)
Geometric parameters (Å, °) top
Ba1—O1W2.836 (4)N2—C71.470 (2)
Ba1—N12.8856 (16)C7—C81.523 (3)
Ba1—O52.893 (4)C7—H7A0.9900
Ba1—N22.9217 (16)C7—H7B0.9900
Ba1—N33.0002 (15)C8—C91.511 (4)
Ba1—O13.0253 (14)C8—H8A0.9900
Ba1—O73.045 (3)C8—H8B0.9900
N1—C11.340 (2)C9—N31.469 (3)
N1—C51.342 (2)C9—H9A0.9900
C1—C21.401 (3)C9—H9B0.9900
C1—C10i1.475 (3)C8'—H8'10.9900
C2—C31.380 (3)C8'—H8'20.9900
C2—H20.9500N3—C101.268 (3)
C3—C41.381 (3)C10—H100.9500
C3—H30.9500Cl1—O21.4369 (17)
C4—C51.395 (3)Cl1—O11.4455 (13)
C4—H40.9500Cl2—O61.416 (3)
C5—C61.479 (3)Cl2—O81.435 (3)
C6—N21.262 (3)Cl2—O71.442 (3)
C6—H60.9500Cl2—O51.444 (3)
O1W—Ba1—N1148.48 (11)N1—C1—C2122.83 (19)
O1W—Ba1—N1i78.38 (9)N1—C1—C10i117.85 (16)
N1—Ba1—N1i130.69 (6)C2—C1—C10i119.24 (18)
O1W—Ba1—O5i16.22 (10)C3—C2—C1118.7 (2)
N1—Ba1—O5i152.02 (8)C3—C2—H2120.7
O1W—Ba1—O573.93 (10)C1—C2—H2120.7
N1—Ba1—O577.19 (8)C2—C3—C4119.02 (19)
N1i—Ba1—O5152.02 (8)C2—C3—H3120.5
O5i—Ba1—O575.11 (15)C4—C3—H3120.5
O1W—Ba1—N2100.79 (12)C3—C4—C5118.8 (2)
N1—Ba1—N257.54 (5)C3—C4—H4120.6
N1i—Ba1—N2118.24 (4)C5—C4—H4120.6
O5i—Ba1—N2115.84 (8)N1—C5—C4122.92 (19)
O5—Ba1—N271.63 (8)N1—C5—C6117.70 (17)
O1W—Ba1—N2i86.08 (12)C4—C5—C6119.26 (18)
N1—Ba1—N2i118.24 (4)N2—C6—C5123.03 (17)
O5—Ba1—N2i115.84 (8)N2—C6—H6118.5
N2—Ba1—N2i171.27 (6)C5—C6—H6118.5
O1W—Ba1—N367.18 (9)C6—N2—C7115.58 (18)
N1—Ba1—N3115.02 (5)C6—N2—Ba1118.57 (12)
N1i—Ba1—N356.75 (4)C7—N2—Ba1125.28 (13)
O5i—Ba1—N380.34 (9)N2—C7—C8111.95 (18)
O5—Ba1—N3113.95 (9)N2—C7—H7A109.2
N2—Ba1—N366.22 (5)C8—C7—H7A109.2
N2i—Ba1—N3112.35 (5)N2—C7—H7B109.2
O1W—Ba1—N3i128.49 (9)C8—C7—H7B109.2
N1—Ba1—N3i56.75 (4)H7A—C7—H7B107.9
O5—Ba1—N3i80.34 (9)C9—C8—C7116.2 (2)
N2—Ba1—N3i112.35 (5)C9—C8—H8A108.2
N3—Ba1—N3i162.71 (7)C7—C8—H8A108.2
O1W—Ba1—O1130.24 (8)C9—C8—H8B108.2
N1—Ba1—O165.68 (4)C7—C8—H8B108.2
N1i—Ba1—O169.06 (4)H8A—C8—H8B107.4
O5i—Ba1—O1140.06 (9)N3—C9—C8115.15 (19)
O5—Ba1—O1134.03 (7)N3—C9—H9A108.5
N2—Ba1—O166.01 (4)C8—C9—H9A108.5
N2i—Ba1—O1105.43 (4)N3—C9—H9B108.5
N3—Ba1—O163.66 (4)C8—C9—H9B108.5
N3i—Ba1—O199.59 (4)H9A—C9—H9B107.5
O1W—Ba1—O1i142.43 (10)H8'1—C8'—H8'2107.6
N1—Ba1—O1i69.06 (4)C10—N3—C9115.43 (17)
O5—Ba1—O1i140.06 (9)C10—N3—Ba1117.93 (12)
N2—Ba1—O1i105.43 (4)C9—N3—Ba1126.58 (13)
N3—Ba1—O1i99.59 (4)N3—C10—C1i123.05 (17)
O1—Ba1—O1i45.57 (5)N3—C10—H10118.5
O1W—Ba1—O7i32.46 (13)C1i—C10—H10118.5
O1W—Ba1—O765.97 (10)O2—Cl1—O2i109.81 (16)
N1—Ba1—O7i117.57 (6)O2—Cl1—O1109.90 (10)
N1—Ba1—O7101.89 (7)O2i—Cl1—O1109.45 (9)
O5—Ba1—O745.97 (9)O1i—Cl1—O1108.31 (12)
O5—Ba1—O7i54.82 (11)Cl1—O1—Ba1103.06 (7)
N2—Ba1—O7i70.05 (6)O6—Cl2—O8109.6 (2)
N2—Ba1—O7117.60 (6)O6—Cl2—O7111.0 (2)
N3—Ba1—O7i64.02 (7)O8—Cl2—O7110.3 (2)
N3—Ba1—O7132.77 (7)O6—Cl2—O5109.6 (2)
O1—Ba1—O7i121.28 (6)O8—Cl2—O5109.1 (3)
O1—Ba1—O7163.58 (7)O7—Cl2—O5107.18 (19)
C1—N1—C5117.70 (16)Cl2—O5—Ba1105.37 (18)
C1—N1—Ba1121.39 (12)Cl2—O7—Ba198.60 (14)
C5—N1—Ba1119.25 (12)
Symmetry codes: (i) −x, y, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °). The H atoms of these water molecules were not located. top
D···AD···AD···AD···A
O1W···O2W2.761 (6)O2W···O62.904 (7)
O1W···O8i2.866 (5)O2W···O2ii2.846 (5)
Symmetry codes: (i) x, -y+2, z+1/2; (ii) -x, y+1, -z+3/2.
references
References top

Bruker (1998). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Harding, C., McDowell, D., Nelson, J., Raghunathan, S., Stevenson, C., Drew, M. G. B. & Yates, P. C. (1990). J. Chem. Soc. Dalton Trans. pp. 2521–2533.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.