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Acta Cryst. (2007). E63, m2405    [ doi:10.1107/S1600536807040706 ]

Diaqua(benzoato-[kappa]2O,O')(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')nickel(II) nitrate dihydrate

X.-P. Xuan, P.-Z. Zhao and Q.-H. Tang

Abstract top

The title compound, [Ni(C7H5O2)(C14H12N2)(H2O)2]NO3·2H2O, consists of one NiII complex cation, two solvent water molecules and one non-coordinated nitrate anion. The NiII ion has a slightly distorted octahedral coordination geometry, bonded to two N atoms from one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, two O atoms from one benzoate anion and two water molecules. Both the cation and anion lie on a twofold rotation axis. O-H...O hydrogen bonds involving the water molecules as donors and [pi]-[pi] stacking interactions between the dmphen ligands of symmetry-related cations, with a distance between their ring planes of 3.2197 Å, seem to determine the crystal packing.

Comment top

The formula unit of (I, Fig. 1) comprises a mononuclear [Ni(dmphen)(benzoate)(H2O)2]+ cation, two uncoordinated water molecules, and a nitrate anion (dmphen is 2,9-dimethyl-1,10-phenanthroline). The NiII ion is in a distorted octahedral NiN2O4 geometry, being coordinated by two N atoms of the dmphen ligand, two O atoms of the benzoate anion and two O atoms of two water molecules. The coordination bond lengths and angles are given in Table 1. Both cation and anion have a crystallographic twofold symmetry, passing through the metal atom, dmphen molecule, benzoate anion, and nitrate anion. The non-coordinated nitrate anion is almost perpendicular to the phenyl ring of benzoate anion, with a dihedral angle of 83.05° between mean planes. In the crystal structure, one-dimensional chains along [100] are formed by intermolecular Owater—H···Onitrate and Owater—H···Owater hydrogen bonds (Fig. 2 and Table 2). The crystal packing is also stabilized by π–π interactions between the dmphen rings of neighboring molecules (Fig. 2), with a distance between their ring planes of 3.220 Å.

Related literature top

Structurally related CuII and MnII complexes have been characterized by Xuan et al. (2007) and Zhao et al. (2007), respectively.

Experimental top

To a solution of dmphen hemihydrate (C14H12N2.0.5 H2O, 0.1089 g, 0.5 mmol) and sodium benzoate (0.072 g, 0.5 mmol) in ethanol (10 ml) was added a solution of Ni(NO3)2·6H2O (0.1455 g, 0.5 mmol) in distilled water (10 ml). The resulting solution was refluxed for 5 h at 333 K and filtrated. Green single crystals of (I) were obtained after 4 d. by slow evaporation of the filtrate.

Refinement top

H atoms bonded to C atoms were placed in calculated positions (C—H = 0.93 Å for aromatic CH; 0.96 Å for methyl CH3), and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(carrier C) (aromatic CH) or Uiso(H) = 1.5Ueq(carrier C) (methyl CH3). The water H atoms were located in a difference map and were refined as riding to their O atoms, with O—H bonds fixed to 0.82 Å and Uiso(H) = 1.5 Ueq(carrier O).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry code: (A) 1 − x, y, 3/2 − z for cation; 1 − x, y, 1/2 − z for anion.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of hydrogen-bonds (dashed lines) and π–π stacking interactions between dmphen ligands.
Diaqua(benzoato-κ2O,O')(2,9-dimethyl-1,10-phenanthroline-κ2N,N')nickel(II) nitrate dihydrate top
Crystal data top
[Ni(C7H5O2)(C14H12N2)(H2O)2]NO3·2H2OF000 = 1088
Mr = 522.15Dx = 1.497 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 3407 reflections
a = 10.4453 (9) Åθ = 2.7–26.8º
b = 22.2586 (19) ŵ = 0.89 mm−1
c = 9.9660 (9) ÅT = 291 (2) K
V = 2317.1 (4) Å3Block, green
Z = 40.37 × 0.30 × 0.23 mm
Data collection top
Bruker SMART CCD
diffractometer		2129 independent reflections
Radiation source: fine-focus sealed tube1723 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −12→12
Tmin = 0.732, Tmax = 0.817k = −26→26
9175 measured reflectionsl = −10→12
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)] = 0.034H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0526P)2 + 1.0711P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2129 reflectionsΔρmax = 0.59 e Å−3
158 parametersΔρmin = −0.39 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C7H5O2)(C14H12N2)(H2O)2]NO3·2H2OV = 2317.1 (4) Å3
Mr = 522.15Z = 4
Orthorhombic, PbcnMo Kα
a = 10.4453 (9) ŵ = 0.89 mm−1
b = 22.2586 (19) ÅT = 291 (2) K
c = 9.9660 (9) Å0.37 × 0.30 × 0.23 mm
Data collection top
Bruker SMART CCD
diffractometer		2129 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1723 reflections with I > 2σ(I)
Tmin = 0.732, Tmax = 0.817Rint = 0.019
9175 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034158 parameters
wR(F2) = 0.098H-atom parameters constrained
S = 1.05Δρmax = 0.59 e Å−3
2129 reflectionsΔρmin = −0.39 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.661272 (16)0.75000.03514 (16)
O10.43542 (16)0.74343 (7)0.83637 (16)0.0478 (4)
O20.17794 (17)0.78534 (8)0.88233 (18)0.0643 (5)
H1W0.25180.77700.85870.096*
H2W0.12340.76380.84750.096*
O30.50000.7955 (2)0.25000.170 (3)
O40.5989 (3)0.87694 (15)0.2690 (3)0.1113 (9)
O50.65977 (15)0.66105 (7)0.87457 (17)0.0528 (4)
H4W0.72450.66610.82940.079*
H3W0.66250.67950.94680.079*
N10.41788 (16)0.59084 (8)0.85549 (19)0.0407 (4)
N20.50000.84737 (19)0.25000.0668 (10)
C10.2989 (3)0.65071 (12)1.0176 (3)0.0645 (8)
H1A0.37040.67781.01390.097*
H1B0.27360.64511.10940.097*
H1C0.22860.66730.96770.097*
C20.3362 (2)0.59182 (11)0.9585 (3)0.0492 (6)
C30.2870 (2)0.53789 (13)1.0127 (3)0.0627 (7)
H30.22910.53941.08350.075*
C40.3234 (3)0.48420 (13)0.9627 (3)0.0667 (8)
H4A0.29100.44890.99940.080*
C50.4098 (2)0.48161 (11)0.8558 (3)0.0568 (7)
C60.4548 (2)0.53665 (9)0.8044 (3)0.0437 (5)
C70.4568 (3)0.42671 (12)0.7992 (3)0.0718 (9)
H70.42650.39030.83190.086*
C80.50000.9625 (2)0.75000.125 (3)
H80.50001.00430.75000.150*
C90.4668 (3)0.93192 (15)0.8644 (6)0.1001 (15)
H90.44550.95310.94170.120*
C100.4648 (2)0.86985 (13)0.8653 (4)0.0662 (8)
H100.44020.84910.94220.079*
C110.50000.83864 (14)0.75000.0491 (9)
C120.50000.77188 (15)0.75000.0410 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0321 (2)0.0313 (2)0.0420 (3)0.0000.00452 (16)0.000
O10.0499 (10)0.0394 (9)0.0541 (10)0.0009 (7)0.0145 (8)0.0002 (7)
O20.0565 (11)0.0593 (11)0.0772 (13)0.0097 (9)0.0016 (9)−0.0154 (9)
O30.220 (6)0.066 (3)0.224 (6)0.0000.142 (5)0.000
O40.0621 (15)0.122 (2)0.150 (3)−0.0057 (16)−0.0105 (15)0.0139 (18)
O50.0382 (9)0.0668 (11)0.0533 (10)−0.0016 (7)−0.0021 (8)−0.0098 (8)
N10.0330 (9)0.0399 (10)0.0491 (11)−0.0007 (8)−0.0024 (8)0.0093 (8)
N20.048 (2)0.084 (3)0.069 (2)0.0000.0137 (16)0.000
C10.0607 (17)0.0714 (18)0.0614 (17)0.0167 (14)0.0241 (14)0.0206 (14)
C20.0338 (11)0.0587 (15)0.0551 (14)0.0011 (10)0.0013 (11)0.0180 (11)
C30.0396 (12)0.0765 (19)0.0719 (18)−0.0099 (13)−0.0005 (13)0.0316 (15)
C40.0518 (15)0.0595 (17)0.089 (2)−0.0187 (13)−0.0211 (15)0.0331 (15)
C50.0528 (14)0.0438 (14)0.0737 (17)−0.0105 (11)−0.0276 (14)0.0145 (12)
C60.0386 (11)0.0337 (12)0.0589 (14)−0.0037 (9)−0.0149 (10)0.0057 (10)
C70.087 (2)0.0361 (13)0.093 (2)−0.0081 (13)−0.0394 (18)0.0078 (13)
C80.050 (3)0.031 (3)0.293 (11)0.000−0.042 (4)0.000
C90.0472 (16)0.0515 (19)0.202 (5)0.0043 (14)−0.019 (2)−0.050 (2)
C100.0400 (13)0.0536 (16)0.105 (2)0.0019 (12)−0.0031 (14)−0.0244 (16)
C110.0326 (16)0.0364 (18)0.078 (3)0.0000.0001 (16)0.000
C120.0357 (16)0.0364 (17)0.0510 (19)0.0000.0030 (14)0.000
Geometric parameters (Å, °) top
Ni1—N12.0734 (18)C2—C31.413 (3)
Ni1—N1i2.0734 (18)C3—C41.349 (4)
Ni1—O52.0800 (16)C3—H30.9300
Ni1—O5i2.0800 (16)C4—C51.398 (4)
Ni1—O1i2.1307 (15)C4—H4A0.9300
Ni1—O12.1308 (15)C5—C61.409 (3)
Ni1—C122.462 (3)C5—C71.433 (4)
O1—C121.264 (2)C6—C6i1.438 (5)
O2—H1W0.8271C7—C7i1.332 (7)
O2—H2W0.8214C7—H70.9300
O3—N21.155 (5)C8—C91.373 (5)
O4—N21.239 (3)C8—C9i1.373 (5)
O5—H4W0.8200C8—H80.9300
O5—H3W0.8291C9—C101.382 (5)
N1—C21.335 (3)C9—H90.9300
N1—C61.365 (3)C10—C111.393 (3)
N2—O4ii1.239 (3)C10—H100.9300
C1—C21.489 (4)C11—C10i1.392 (3)
C1—H1A0.9600C11—C121.486 (5)
C1—H1B0.9600C12—O1i1.264 (2)
C1—H1C0.9600
N1—Ni1—N1i81.75 (10)H1B—C1—H1C109.5
N1—Ni1—O591.57 (7)N1—C2—C3120.8 (2)
N1i—Ni1—O588.22 (7)N1—C2—C1119.1 (2)
N1—Ni1—O5i88.22 (7)C3—C2—C1120.1 (2)
N1i—Ni1—O5i91.57 (7)C4—C3—C2120.6 (3)
O5—Ni1—O5i179.72 (9)C4—C3—H3119.7
N1—Ni1—O1i169.99 (7)C2—C3—H3119.7
N1i—Ni1—O1i108.25 (7)C3—C4—C5120.0 (2)
O5—Ni1—O1i89.38 (7)C3—C4—H4A120.0
O5i—Ni1—O1i90.86 (7)C5—C4—H4A120.0
N1—Ni1—O1108.25 (7)C4—C5—C6117.2 (2)
N1i—Ni1—O1169.99 (7)C4—C5—C7123.8 (2)
O5—Ni1—O190.86 (7)C6—C5—C7119.0 (3)
O5i—Ni1—O189.38 (7)N1—C6—C5122.6 (2)
O1i—Ni1—O161.76 (8)N1—C6—C6i117.83 (13)
N1—Ni1—C12139.13 (5)C5—C6—C6i119.55 (17)
N1i—Ni1—C12139.13 (5)C7i—C7—C5121.46 (17)
O5—Ni1—C1290.14 (5)C7i—C7—H7119.3
O5i—Ni1—C1290.14 (5)C5—C7—H7119.3
O1i—Ni1—C1230.88 (4)C9—C8—C9i120.5 (5)
O1—Ni1—C1230.88 (4)C9—C8—H8119.7
C12—O1—Ni189.19 (15)C9i—C8—H8119.7
H1W—O2—H2W113.3C8—C9—C10120.3 (4)
Ni1—O5—H4W109.5C8—C9—H9119.8
Ni1—O5—H3W123.0C10—C9—H9119.8
H4W—O5—H3W112.4C9—C10—C11119.3 (4)
C2—N1—C6118.81 (19)C9—C10—H10120.3
C2—N1—Ni1129.93 (16)C11—C10—H10120.3
C6—N1—Ni1111.24 (15)C10i—C11—C10120.1 (4)
O3—N2—O4ii122.1 (2)C10i—C11—C12119.93 (18)
O3—N2—O4122.1 (2)C10—C11—C12119.93 (18)
O4ii—N2—O4115.8 (5)O1—C12—O1i119.8 (3)
C2—C1—H1A109.5O1—C12—C11120.07 (15)
C2—C1—H1B109.5O1i—C12—C11120.08 (15)
H1A—C1—H1B109.5O1—C12—Ni159.93 (15)
C2—C1—H1C109.5O1i—C12—Ni159.92 (15)
H1A—C1—H1C109.5C11—C12—Ni1180.0
N1—Ni1—O1—C12−179.22 (8)C2—N1—C6—C6i−178.6 (2)
N1i—Ni1—O1—C124.2 (4)Ni1—N1—C6—C6i2.9 (3)
O5—Ni1—O1—C1288.84 (9)C4—C5—C6—N10.4 (3)
O5i—Ni1—O1—C12−91.31 (9)C7—C5—C6—N1−177.9 (2)
O1i—Ni1—O1—C120.0C4—C5—C6—C6i179.2 (3)
N1i—Ni1—N1—C2−179.3 (2)C7—C5—C6—C6i0.9 (4)
O5—Ni1—N1—C292.7 (2)C4—C5—C7—C7i−177.3 (3)
O5i—Ni1—N1—C2−87.5 (2)C6—C5—C7—C7i0.9 (5)
O1i—Ni1—N1—C2−2.7 (5)C9i—C8—C9—C10−0.8 (2)
O1—Ni1—N1—C21.3 (2)C8—C9—C10—C111.6 (4)
C12—Ni1—N1—C20.7 (2)C9—C10—C11—C10i−0.8 (2)
N1i—Ni1—N1—C6−1.03 (11)C9—C10—C11—C12179.2 (2)
O5—Ni1—N1—C6−89.00 (15)Ni1—O1—C12—O1i0.000 (1)
O5i—Ni1—N1—C690.82 (15)Ni1—O1—C12—C11180.0
O1i—Ni1—N1—C6175.6 (3)C10i—C11—C12—O1−159.65 (15)
O1—Ni1—N1—C6179.58 (14)C10—C11—C12—O120.35 (15)
C12—Ni1—N1—C6178.97 (11)C10i—C11—C12—O1i20.35 (15)
C6—N1—C2—C3−1.0 (3)C10—C11—C12—O1i−159.65 (15)
Ni1—N1—C2—C3177.21 (17)N1i—Ni1—C12—O1−178.88 (12)
C6—N1—C2—C1178.0 (2)O5—Ni1—C12—O1−91.44 (11)
Ni1—N1—C2—C1−3.8 (3)O5i—Ni1—C12—O188.56 (11)
N1—C2—C3—C41.1 (4)O1i—Ni1—C12—O1180.0
C1—C2—C3—C4−177.9 (3)N1—Ni1—C12—O1i−178.87 (12)
C2—C3—C4—C5−0.4 (4)N1i—Ni1—C12—O1i1.12 (12)
C3—C4—C5—C6−0.3 (4)O5—Ni1—C12—O1i88.56 (11)
C3—C4—C5—C7177.9 (3)O5i—Ni1—C12—O1i−91.44 (11)
C2—N1—C6—C50.2 (3)O1—Ni1—C12—O1i180.000 (1)
Ni1—N1—C6—C5−178.29 (18)
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H1W···O10.832.072.883 (2)167
O2—H2W···O3iii0.822.082.903 (3)174
O5—H3W···O2iv0.831.882.707 (2)174
O5—H4W···O4v0.822.162.860 (3)143
Symmetry codes: (iii) −x+1/2, −y+3/2, z+1/2; (iv) x+1/2, −y+3/2, −z+2; (v) −x+3/2, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H1W···O10.832.072.883 (2)167
O2—H2W···O3i0.822.082.903 (3)174
O5—H3W···O2ii0.831.882.707 (2)174
O5—H4W···O4iii0.822.162.860 (3)143
Symmetry codes: (i) −x+1/2, −y+3/2, z+1/2; (ii) x+1/2, −y+3/2, −z+2; (iii) −x+3/2, −y+3/2, z+1/2.
Acknowledgements top

Financial support by the Science Fund of Henan Province for Distinguished Young Scholars (No. 07410051005) is gratefully acknowledged.

references
References top

Bruker (1997). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

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

Xuan, X.-P., Zhao, P.-Z. & Zhang, S.-X. (2007). Acta Cryst. E63, m1817–?.

Zhao, P.-Z., Xuan, X.-P. & Wang, J.-G. (2007). Acta Cryst. E63, m2127–?.