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Acta Cryst. (2007). E63, m2515    [ doi:10.1107/S1600536807043565 ]

Diaquabis(1,10-phenanthroline-[kappa]2N,N')nickel(II) diperchlorate 0.4-hydrate

X.-Y. Tang, Y.-C. Qiu, F. Sun and S.-T. Yue

Abstract top

The title complex, [Ni(C12H8N2)2(H2O)2](ClO4)2·0.4H2O, possesses crystallographically imposed C2 symmetry. The NiII atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and two water molecules in a distorted octahedral coordination geometry. The packing is governed by intermolecular hydrogen bonds and a [pi]-[pi] stacking interaction with a centroid-to-centroid distance of 3.650 (2) Å.

Comment top

We have been recently interested in the nature of π-π stacking as it plays an important role in some biological processes (Deisenhofer & Michel, 1989). A series of metal complexes incorporating different aromatic ligands has been prepared and their crystal structures provide useful information about π-π stacking (Wu et al., 2003; Pan & Xu, 2004; Li et al., 2005). As part of ongoing investigations, the title complex, incorporating 1,10-phenanthroline, (I), has been prepared.

As illustrated in Fig. 1, the NiII atom lies on a C2 symmetry position and has a distorted octahedral geometry with six coordinating atoms: four N atoms from two 1,10-phenanthroline ligands, two O from two water molecules (Table 1). A depleted hydration water molecule (occupation: 1/5) completes the structure. Intermolecular O—H···O hydrogen bonding involving the coordinating water molecules as donors and the perchlorate O atoms as acceptors forms chains, which are further assembled via π-π stacking interactions between adjacent phen rings, thus forming a supramolecular network structure (Fig. 2; Table 2). The centroid-centroid distance of adjacent phen rings (at 1/2 − x,1/2 − y,1 − z) is 3.650 (2) Å, indicating a normal π-π interaction.

Related literature top

For related literature, see: Deisenhofer & Michel (1989); Li et al. (2005); Pan & Xu (2004); Wu et al. (2003).

Experimental top

The title complex was prepared by addition of a stoichiometric amount of 1,10-phenanthroline (2 mmol) to warm aqueous solution of nickel perchlorate (2 mmol) (about 333–343 K). The PH was then adjusted from 5.5 to 6.5 with NaOH (10 mmol). The resulting solution was put into a 30 ml stainless steel reaction bottle with the gather four fluorine ethylene inner pad, sealed up completely and stored at 443 K for 144 h. Cyan single crystals were obtained after cooling to room temperature.

Refinement top

The occupation factor of a depleted hydration water molecule (O2W) was refined in the initial stages, and kept fixed at the latest cycles of refinement; the corresponding H atoms were disregarded from the model. The disorder of perchlorate unit was refined and split into two positions with an occupancy ratio of (0.721 (1):0.279 (1)). The Cl—O distances were restrained to be 1.44 Å, both within a standard deviation of 0.01 Å. Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å.

Computing details top

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 30% probability displacement ellipsoids. The disordered perchlorate ions were omitted for clarity. Symmetry code: as in Table 1.
[Figure 2] Fig. 2. A packing view of (I), showing the intermolecular hydrogen bonds and the π-π interaction as broken lines. For clarity, H atoms and disordered perchlorate ions are not shown.
Diaquabis(1,10-phenanthroline-κ2 N,N')nickel(II) diperchlorate 0.4-hydrate top
Crystal data top
[Ni(C12H8N2)2(H2O)2](ClO4)2·0.4H2OF000 = 1352
Mr = 661.26Dx = 1.377 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1167 reflections
a = 18.2558 (6) Åθ = 1.4–28º
b = 15.9362 (6) ŵ = 0.83 mm−1
c = 11.7096 (4) ÅT = 293 (2) K
β = 110.591 (2)ºBlock, green
V = 3189.02 (19) Å30.26 × 0.20 × 0.18 mm
Z = 4
Data collection top
Bruker APEX II area-detector
diffractometer		3488 independent reflections
Radiation source: fine-focus sealed tube1861 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.071
T = 293(2) Kθmax = 27.0º
φ and ω scanθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −23→23
Tmin = 0.827, Tmax = 0.867k = −20→16
13780 measured reflectionsl = −14→14
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)] = 0.071H-atom parameters constrained
wR(F2) = 0.262  w = 1/[σ2(Fo2) + (0.144P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3488 reflectionsΔρmax = 0.64 e Å−3
241 parametersΔρmin = −0.37 e Å−3
97 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C12H8N2)2(H2O)2](ClO4)2·0.4H2OV = 3189.02 (19) Å3
Mr = 661.26Z = 4
Monoclinic, C2/cMo Kα
a = 18.2558 (6) ŵ = 0.83 mm−1
b = 15.9362 (6) ÅT = 293 (2) K
c = 11.7096 (4) Å0.26 × 0.20 × 0.18 mm
β = 110.591 (2)º
Data collection top
Bruker APEX II area-detector
diffractometer		3488 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1861 reflections with I > 2σ(I)
Tmin = 0.827, Tmax = 0.867Rint = 0.071
13780 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07197 restraints
wR(F2) = 0.262H-atom parameters constrained
S = 1.08Δρmax = 0.64 e Å−3
3488 reflectionsΔρmin = −0.37 e Å−3
241 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*/UeqOcc. (<1)
Ni10.50000.33437 (6)0.75000.0538 (4)
O1W0.5725 (2)0.4330 (3)0.7362 (4)0.0714 (11)
H1W0.61000.43240.71260.107*
H2W0.58830.46360.79690.107*
N10.5844 (3)0.2437 (3)0.7589 (4)0.0625 (12)
N20.5543 (3)0.3252 (3)0.9371 (4)0.0601 (12)
C10.5407 (4)0.3668 (4)1.0251 (6)0.0703 (16)
H10.50590.41171.00420.084*
C20.5761 (5)0.3464 (5)1.1478 (7)0.089 (2)
H20.56460.37701.20700.107*
C30.6264 (5)0.2828 (6)1.1799 (6)0.095 (2)
H30.64950.26851.26180.114*
C40.6447 (4)0.2375 (5)1.0923 (6)0.083 (2)
C50.6995 (6)0.1692 (6)1.1172 (10)0.120 (3)
H50.72410.15171.19730.144*
C60.7164 (5)0.1298 (7)1.0269 (9)0.119 (3)
H60.75290.08651.04630.143*
C70.6789 (4)0.1538 (5)0.9025 (8)0.087 (2)
C80.6946 (5)0.1164 (6)0.8020 (10)0.106 (3)
H80.73040.07270.81540.128*
C90.6579 (5)0.1443 (5)0.6911 (9)0.100 (3)
H90.66910.12140.62600.120*
C100.6021 (4)0.2082 (4)0.6696 (6)0.0759 (18)
H100.57650.22640.59000.091*
C110.6231 (3)0.2178 (4)0.8737 (6)0.0674 (16)
C120.6059 (3)0.2614 (4)0.9702 (5)0.0634 (15)
O2W0.501 (2)0.023 (2)0.449 (3)0.134 (11)0.20
Cl1A0.8269 (3)0.0925 (3)0.4969 (4)0.0610 (12)0.720 (11)
O1A0.8132 (5)0.0811 (7)0.3699 (6)0.109 (3)0.720 (11)
O2A0.8634 (8)0.1706 (5)0.5390 (10)0.124 (4)0.720 (11)
O3A0.7595 (5)0.0778 (7)0.5247 (11)0.131 (4)0.720 (11)
O4A0.8859 (5)0.0327 (6)0.5610 (8)0.132 (3)0.720 (11)
Cl1B0.8131 (10)0.0938 (11)0.4849 (14)0.103 (6)0.280 (11)
O1B0.8366 (14)0.0403 (15)0.405 (2)0.113 (7)0.280 (11)
O2B0.8446 (18)0.1755 (13)0.485 (3)0.136 (9)0.280 (11)
O3B0.7289 (9)0.1023 (18)0.432 (2)0.140 (8)0.280 (11)
O4B0.8293 (15)0.0550 (14)0.6000 (14)0.116 (8)0.280 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0576 (6)0.0605 (7)0.0444 (7)0.0000.0195 (4)0.000
O1W0.078 (3)0.074 (3)0.070 (3)−0.018 (2)0.036 (2)−0.013 (2)
N10.065 (3)0.071 (3)0.056 (3)0.003 (2)0.026 (2)−0.008 (2)
N20.062 (3)0.071 (3)0.049 (3)0.001 (2)0.022 (2)0.000 (2)
C10.078 (4)0.081 (4)0.053 (4)0.000 (3)0.025 (3)−0.007 (3)
C20.104 (5)0.107 (6)0.057 (4)−0.012 (5)0.028 (4)−0.019 (4)
C30.107 (6)0.124 (7)0.043 (4)0.006 (5)0.013 (4)0.009 (4)
C40.086 (4)0.093 (5)0.054 (4)0.004 (4)0.006 (3)0.007 (4)
C50.126 (7)0.120 (7)0.084 (6)0.039 (6)0.000 (5)0.032 (5)
C60.111 (7)0.118 (7)0.103 (8)0.054 (6)0.007 (5)0.016 (6)
C70.081 (4)0.083 (5)0.093 (6)0.026 (4)0.025 (4)0.002 (4)
C80.100 (6)0.097 (6)0.127 (8)0.037 (5)0.045 (5)0.002 (6)
C90.098 (6)0.101 (6)0.115 (8)0.015 (5)0.054 (5)−0.015 (5)
C100.082 (4)0.080 (4)0.075 (5)0.005 (4)0.040 (3)−0.009 (4)
C110.067 (4)0.071 (4)0.065 (4)0.007 (3)0.024 (3)0.006 (3)
C120.058 (3)0.074 (4)0.051 (3)0.000 (3)0.010 (2)−0.002 (3)
O2W0.124 (13)0.130 (14)0.135 (14)−0.002 (10)0.030 (9)−0.020 (10)
Cl1A0.0745 (18)0.069 (2)0.048 (2)0.0005 (14)0.0329 (15)0.0057 (15)
O1A0.103 (6)0.175 (9)0.048 (4)0.019 (6)0.024 (3)−0.002 (4)
O2A0.191 (10)0.104 (5)0.091 (7)−0.044 (5)0.068 (7)−0.018 (5)
O3A0.118 (6)0.160 (8)0.158 (9)−0.008 (6)0.102 (7)−0.009 (7)
O4A0.144 (7)0.154 (7)0.115 (6)0.063 (6)0.065 (5)0.075 (6)
Cl1B0.110 (8)0.119 (9)0.077 (8)−0.008 (7)0.027 (6)0.004 (6)
O1B0.130 (14)0.132 (14)0.098 (13)−0.020 (12)0.066 (11)−0.009 (11)
O2B0.183 (16)0.108 (12)0.104 (17)−0.019 (12)0.036 (15)0.005 (10)
O3B0.108 (10)0.210 (18)0.096 (14)0.022 (11)0.029 (10)0.019 (14)
O4B0.152 (16)0.128 (14)0.057 (9)−0.010 (13)0.023 (9)0.004 (9)
Geometric parameters (Å, °) top
Ni1—N2i2.068 (5)C5—H50.9300
Ni1—N22.068 (5)C6—C71.427 (11)
Ni1—N1i2.089 (5)C6—H60.9300
Ni1—N12.089 (5)C7—C111.397 (9)
Ni1—O1W2.098 (4)C7—C81.434 (12)
Ni1—O1Wi2.098 (4)C8—C91.312 (12)
O1W—H1W0.8234C8—H80.9300
O1W—H2W0.8268C9—C101.400 (10)
N1—C101.323 (7)C9—H90.9300
N1—C111.345 (7)C10—H100.9300
N2—C11.320 (7)C11—C121.453 (9)
N2—C121.346 (7)O2W—O2Wii1.41 (6)
C1—C21.391 (9)Cl1A—O3A1.398 (6)
C1—H10.9300Cl1A—O2A1.416 (7)
C2—C31.331 (10)Cl1A—O1A1.431 (6)
C2—H20.9300Cl1A—O4A1.435 (7)
C3—C41.387 (11)Cl1B—O4B1.416 (9)
C3—H30.9300Cl1B—O2B1.423 (10)
C4—C121.407 (8)Cl1B—O1B1.441 (10)
C4—C51.437 (11)Cl1B—O3B1.449 (10)
C5—C61.355 (13)
N2i—Ni1—N2171.9 (3)C6—C5—C4121.8 (8)
N2i—Ni1—N1i80.10 (19)C6—C5—H5119.1
N2—Ni1—N1i94.27 (18)C4—C5—H5119.1
N2i—Ni1—N194.27 (18)C5—C6—C7120.9 (8)
N2—Ni1—N180.10 (19)C5—C6—H6119.6
N1i—Ni1—N192.5 (3)C7—C6—H6119.6
N2i—Ni1—O1W92.95 (17)C11—C7—C6119.3 (8)
N2—Ni1—O1W93.11 (17)C11—C7—C8116.4 (7)
N1i—Ni1—O1W171.63 (17)C6—C7—C8124.3 (7)
N1—Ni1—O1W92.70 (18)C9—C8—C7119.5 (7)
N2i—Ni1—O1Wi93.11 (17)C9—C8—H8120.3
N2—Ni1—O1Wi92.95 (17)C7—C8—H8120.3
N1i—Ni1—O1Wi92.70 (18)C8—C9—C10120.7 (8)
N1—Ni1—O1Wi171.63 (17)C8—C9—H9119.7
O1W—Ni1—O1Wi83.0 (2)C10—C9—H9119.7
Ni1—O1W—H1W129.8N1—C10—C9122.2 (7)
Ni1—O1W—H2W114.4N1—C10—H10118.9
H1W—O1W—H2W102.5C9—C10—H10118.9
C10—N1—C11118.1 (6)N1—C11—C7123.2 (6)
C10—N1—Ni1129.5 (5)N1—C11—C12116.7 (5)
C11—N1—Ni1112.4 (4)C7—C11—C12120.1 (6)
C1—N2—C12117.3 (5)N2—C12—C4123.2 (6)
C1—N2—Ni1129.8 (4)N2—C12—C11117.3 (5)
C12—N2—Ni1112.6 (4)C4—C12—C11119.4 (6)
N2—C1—C2122.9 (7)O3A—Cl1A—O2A114.2 (7)
N2—C1—H1118.6O3A—Cl1A—O1A111.9 (7)
C2—C1—H1118.6O2A—Cl1A—O1A111.3 (6)
C3—C2—C1119.6 (7)O3A—Cl1A—O4A109.1 (6)
C3—C2—H2120.2O2A—Cl1A—O4A103.2 (7)
C1—C2—H2120.2O1A—Cl1A—O4A106.5 (6)
C2—C3—C4120.7 (7)O4B—Cl1B—O2B116.6 (13)
C2—C3—H3119.7O4B—Cl1B—O1B110.6 (13)
C4—C3—H3119.7O2B—Cl1B—O1B109.4 (13)
C3—C4—C12116.3 (7)O4B—Cl1B—O3B106.3 (12)
C3—C4—C5125.2 (8)O2B—Cl1B—O3B106.4 (13)
C12—C4—C5118.5 (7)O1B—Cl1B—O3B107.0 (13)
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1Biii0.821.992.75 (2)154
O1W—H1W···O1Aiii0.821.972.787 (9)169
O1W—H2W···O4Aiv0.831.912.733 (8)174
O1W—H2W···O4Biv0.832.142.87 (2)148
Symmetry codes: (iii) −x+3/2, −y+1/2, −z+1; (iv) −x+3/2, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Ni1—N22.068 (5)Ni1—O1W2.098 (4)
Ni1—N12.089 (5)
N2i—Ni1—N2171.9 (3)N2—Ni1—O1W93.11 (17)
N2i—Ni1—N194.27 (18)N1i—Ni1—O1W171.63 (17)
N2—Ni1—N180.10 (19)N1—Ni1—O1W92.70 (18)
N1i—Ni1—N192.5 (3)O1W—Ni1—O1Wi83.0 (2)
N2i—Ni1—O1W92.95 (17)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1Bii0.821.992.75 (2)154
O1W—H1W···O1Aii0.821.972.787 (9)169
O1W—H2W···O4Aiii0.831.912.733 (8)174
O1W—H2W···O4Biii0.832.142.87 (2)148
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1; (iii) −x+3/2, y+1/2, −z+3/2.
Acknowledgements top

The work was supported by the Natural Science Foundation of Guang Dong Province (grant No. 7005808) and South China Normal University.

references
References top

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Pan, T.-T. & Xu, D.-J. (2004). Acta Cryst. E60, m56–m58.

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