Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The asymmetric unit of the title compound, [Ni(C7H5O3)(C14H12N2)(H2O)2]NO3, comprises one half of the NiII complex cation and one half of the non-coordinated nitrate anion, as both the Ni atom and the N and one O atoms of the anion lie on twofold rotation axes. The Ni2+ cation is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, two water mol­ecules and a bidentate 3-hydroxy­benzoate anion in a distorted octa­hedral environment. The OH group of the benzoate is disordered over two positions with equal occupancy. An extensive series of O—H...O hydrogen bonds leads to a supra­molecular network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052944/sj2386sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052944/sj2386Isup2.hkl
Contains datablock I

CCDC reference: 667248

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.033
  • wR factor = 0.084
  • Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N2 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.29 PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The crystal structure of a compound containing the [Ni(dmphen)(benzoate]2+ fragment has been reported (Xuan et al. 2007)(dmphen is 2,9-dimethyl-1,10-phenanthroline) and we report here the structure of a closely related NiII complex, (I), Fig. 1.

The NiII atom is located on a twofold symmetry axis and is six-coordinated by two N atoms from the dmphen ligand, O atoms from two water molecules and is also chelated by two O atoms from carboxyl group of the 3-hydroxy-benzoate anion. The NiO4N2unit is in a a distorted octahedral geometry, with the O atoms of two water molecules occupying axial positions with a Ni1—O3 distance of 2.0393 (15) Å. The equatorial planes are defined by the N atoms of dmphen and the carboxyl O atoms of the 3-hydroxy-benzoate anion. The OH group on phenyl ring of the benzoato ligand is disordered over two positions with site occupancy factors of 0.5.

In the crystal structure, the uncoordinated nitrate anion, lying on twofold axis, links to the NiII complex cation via O—H···O hydrogen bonds (Table 1 and Figure 2). In the crystal molecules are linked into a supramolecular network structure by OwaterH···Ocarbonyl and Owater—H···Onitrate hydrogen bonding.

Related literature top

For the structure of a closely related complex, see: Xuan et al. (2007).

Experimental top

To a solution of 2,9-dimethyl-1,10-phenanthroline (C14H12N2.0.5H2O, 0.1089 g, 0.5 mmol), 3-hydroxy-benzoate (0.0696 g, 0.5 mmol) and sodium hydroxide (0.01859 g, 0.5 mmol) in ethanol/water (v:v=1:1, 20 ml) was added a solution of Ni(NO3)2.6H2O (0.1460 g, 0.5 mmol) in distilled water (5 ml). The resulting solution was stirred for 4 h at 323 K and then a pale green precipitate was filtered. Blue single crystals of (I) were obtained by slow evaporation of the filtrate over 90 days.

Refinement top

The OH group of the benzoate anion is disordered over two symmetry-related positions with site occupancy factors of 0.5. The carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms. The hydroxyl H atoms were placed in calculated positions (O—H =0.82 Å) and refined with free torsion angles to fit the electron density, with Uiso(H) = 1.5 Ueq(O).

Structure description top

The crystal structure of a compound containing the [Ni(dmphen)(benzoate]2+ fragment has been reported (Xuan et al. 2007)(dmphen is 2,9-dimethyl-1,10-phenanthroline) and we report here the structure of a closely related NiII complex, (I), Fig. 1.

The NiII atom is located on a twofold symmetry axis and is six-coordinated by two N atoms from the dmphen ligand, O atoms from two water molecules and is also chelated by two O atoms from carboxyl group of the 3-hydroxy-benzoate anion. The NiO4N2unit is in a a distorted octahedral geometry, with the O atoms of two water molecules occupying axial positions with a Ni1—O3 distance of 2.0393 (15) Å. The equatorial planes are defined by the N atoms of dmphen and the carboxyl O atoms of the 3-hydroxy-benzoate anion. The OH group on phenyl ring of the benzoato ligand is disordered over two positions with site occupancy factors of 0.5.

In the crystal structure, the uncoordinated nitrate anion, lying on twofold axis, links to the NiII complex cation via O—H···O hydrogen bonds (Table 1 and Figure 2). In the crystal molecules are linked into a supramolecular network structure by OwaterH···Ocarbonyl and Owater—H···Onitrate hydrogen bonding.

For the structure of a closely related complex, see: Xuan et al. (2007).

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 the cation; 1 - x, y, 1/2 - z for the anion.
[Figure 2] Fig. 2. Part of the crystal packing of (I), showing the formation of hydrogen-bonds drawn as dashed lines.
Diaqua(2,9-dimethyl-1,10-phenanthroline-κ2N,N')(3-hydroxybenzoato-\ κ2O,O')nickel(II) nitrate top
Crystal data top
[Ni(C7H5O3)(C14H12N2)(H2O)2]NO3F(000) = 1036
Mr = 501.11Dx = 1.537 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2940 reflections
a = 10.9278 (15) Åθ = 2.7–25.6°
b = 28.509 (4) ŵ = 0.95 mm1
c = 7.9738 (11) ÅT = 293 K
β = 119.311 (1)°Block, blue
V = 2166.2 (5) Å30.39 × 0.18 × 0.05 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2025 independent reflections
Radiation source: fine-focus sealed tube1688 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
φ and ω scansθmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1313
Tmin = 0.708, Tmax = 0.950k = 3434
8026 measured reflectionsl = 99
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0504P)2]
where P = (Fo2 + 2Fc2)/3
2025 reflections(Δ/σ)max = 0.001
159 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
[Ni(C7H5O3)(C14H12N2)(H2O)2]NO3V = 2166.2 (5) Å3
Mr = 501.11Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.9278 (15) ŵ = 0.95 mm1
b = 28.509 (4) ÅT = 293 K
c = 7.9738 (11) Å0.39 × 0.18 × 0.05 mm
β = 119.311 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2025 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1688 reflections with I > 2σ(I)
Tmin = 0.708, Tmax = 0.950Rint = 0.055
8026 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 0.99Δρmax = 0.42 e Å3
2025 reflectionsΔρmin = 0.29 e Å3
159 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)
Ni10.50000.294675 (12)0.75000.03422 (15)
O10.39684 (13)0.22911 (5)0.7403 (2)0.0397 (4)
O20.3150 (4)0.05478 (12)0.7986 (8)0.0832 (14)0.50
H20.26660.07110.82790.125*0.50
O30.38872 (15)0.29142 (5)0.4572 (2)0.0448 (4)
H1W0.41340.30820.39480.067*
H2W0.30250.28770.39960.067*
O40.50000.33471 (10)0.25000.0957 (11)
O50.4233 (3)0.39816 (10)0.2940 (3)0.1127 (9)
N10.61633 (17)0.35019 (6)0.7301 (3)0.0410 (4)
N20.50000.37810 (10)0.25000.0479 (6)
C10.7845 (3)0.30371 (9)0.6822 (5)0.0729 (9)
H1A0.85480.29260.80590.109*
H1B0.82520.30770.60030.109*
H1C0.70940.28130.62560.109*
C20.7287 (2)0.34941 (9)0.7052 (4)0.0514 (6)
C30.7936 (3)0.39192 (10)0.6978 (4)0.0702 (8)
H3A0.87270.39100.68270.084*
C40.7417 (3)0.43345 (11)0.7125 (4)0.0780 (9)
H40.78560.46110.70860.094*
C50.6220 (3)0.43551 (9)0.7335 (4)0.0629 (7)
C60.5625 (2)0.39226 (7)0.7414 (3)0.0457 (6)
C70.5579 (4)0.47808 (9)0.7422 (5)0.0859 (11)
H70.59770.50650.73690.103*
C80.50000.20663 (10)0.75000.0362 (7)
C90.50000.15418 (10)0.75000.0408 (7)
C100.3994 (2)0.12960 (8)0.7713 (4)0.0521 (6)
H100.33140.14580.78590.063*
C110.3989 (3)0.08092 (9)0.7711 (5)0.0688 (8)
C120.50000.05679 (12)0.75000.0792 (13)
H120.50000.02420.75000.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0248 (2)0.0285 (2)0.0475 (3)0.0000.01626 (18)0.000
O10.0278 (7)0.0326 (8)0.0590 (10)0.0008 (6)0.0215 (7)0.0001 (7)
O20.075 (3)0.0368 (19)0.171 (4)0.0047 (18)0.086 (3)0.007 (2)
O30.0337 (8)0.0483 (9)0.0480 (9)0.0074 (6)0.0167 (7)0.0026 (7)
O40.179 (4)0.0497 (16)0.092 (2)0.0000.092 (2)0.000
O50.1028 (18)0.151 (2)0.0926 (17)0.0680 (17)0.0541 (15)0.0065 (15)
N10.0319 (9)0.0374 (10)0.0459 (11)0.0045 (8)0.0130 (8)0.0029 (8)
N20.0437 (15)0.0499 (17)0.0535 (17)0.0000.0266 (14)0.000
C10.0514 (16)0.0655 (18)0.122 (3)0.0110 (13)0.0580 (18)0.0287 (17)
C20.0347 (12)0.0551 (15)0.0592 (15)0.0078 (10)0.0190 (11)0.0095 (12)
C30.0497 (16)0.074 (2)0.086 (2)0.0219 (14)0.0321 (15)0.0072 (16)
C40.084 (2)0.0551 (18)0.092 (2)0.0329 (16)0.0408 (19)0.0012 (16)
C50.0782 (19)0.0424 (14)0.0647 (17)0.0178 (13)0.0324 (15)0.0047 (12)
C60.0495 (14)0.0340 (12)0.0448 (13)0.0057 (10)0.0161 (11)0.0012 (9)
C70.130 (3)0.0309 (13)0.106 (2)0.0159 (15)0.065 (3)0.0031 (15)
C80.0290 (15)0.0322 (15)0.0431 (17)0.0000.0142 (13)0.000
C90.0350 (16)0.0311 (16)0.0521 (19)0.0000.0180 (15)0.000
C100.0434 (13)0.0370 (12)0.0794 (18)0.0008 (10)0.0327 (13)0.0045 (12)
C110.0608 (17)0.0374 (13)0.114 (2)0.0041 (12)0.0470 (17)0.0067 (14)
C120.080 (3)0.0290 (18)0.139 (4)0.0000.062 (3)0.000
Geometric parameters (Å, º) top
Ni1—O3i2.0393 (15)C2—C31.420 (3)
Ni1—O32.0393 (15)C3—C41.342 (4)
Ni1—N1i2.0839 (17)C3—H3A0.9300
Ni1—N12.0840 (17)C4—C51.398 (4)
Ni1—O1i2.1645 (14)C4—H40.9300
Ni1—O12.1647 (14)C5—C61.410 (3)
O1—C81.2658 (19)C5—C71.420 (4)
O2—C111.281 (4)C6—C6i1.437 (5)
O2—H20.8200C7—C7i1.332 (7)
O3—H1W0.8251C7—H70.9300
O3—H2W0.8281C8—O1i1.2659 (19)
O4—N21.237 (4)C8—C91.495 (4)
O5—N21.200 (2)C9—C10i1.382 (3)
N1—C21.337 (3)C9—C101.382 (3)
N1—C61.358 (3)C10—C111.388 (3)
N2—O5ii1.200 (2)C10—H100.9300
C1—C21.487 (3)C11—C121.380 (3)
C1—H1A0.9600C12—C11i1.380 (3)
C1—H1B0.9600C12—H120.9300
C1—H1C0.9600
O3i—Ni1—O3174.80 (8)N1—C2—C1119.6 (2)
O3i—Ni1—N1i89.51 (6)C3—C2—C1120.0 (2)
O3—Ni1—N1i94.45 (6)C4—C3—C2120.6 (3)
O3i—Ni1—N194.44 (6)C4—C3—H3A119.7
O3—Ni1—N189.51 (6)C2—C3—H3A119.7
N1i—Ni1—N181.18 (10)C3—C4—C5120.5 (2)
O3i—Ni1—O1i84.94 (6)C3—C4—H4119.8
O3—Ni1—O1i90.56 (6)C5—C4—H4119.8
N1i—Ni1—O1i168.37 (6)C4—C5—C6116.6 (3)
N1—Ni1—O1i109.39 (6)C4—C5—C7123.7 (2)
O3i—Ni1—O190.57 (6)C6—C5—C7119.7 (3)
O3—Ni1—O184.93 (6)N1—C6—C5123.0 (2)
N1i—Ni1—O1109.40 (6)N1—C6—C6i117.96 (12)
N1—Ni1—O1168.37 (6)C5—C6—C6i119.02 (16)
O1i—Ni1—O160.57 (7)C7i—C7—C5121.26 (16)
C8—O1—Ni190.13 (13)C7i—C7—H7119.4
C11—O2—H2109.5C5—C7—H7119.4
Ni1—O3—H1W118.5O1—C8—O1i119.2 (3)
Ni1—O3—H2W121.3O1—C8—C9120.42 (13)
H1W—O3—H2W111.0O1i—C8—C9120.42 (13)
C2—N1—C6118.93 (19)C10i—C9—C10119.1 (3)
C2—N1—Ni1129.63 (16)C10i—C9—C8120.46 (15)
C6—N1—Ni1111.43 (14)C10—C9—C8120.47 (15)
O5—N2—O5ii123.1 (4)C9—C10—C11120.7 (2)
O5—N2—O4118.5 (2)C9—C10—H10119.7
O5ii—N2—O4118.5 (2)C11—C10—H10119.7
C2—C1—H1A109.5O2—C11—C12114.4 (3)
C2—C1—H1B109.5O2—C11—C10125.8 (3)
H1A—C1—H1B109.5C12—C11—C10119.7 (3)
C2—C1—H1C109.5C11—C12—C11i120.2 (3)
H1A—C1—H1C109.5C11—C12—H12119.9
H1B—C1—H1C109.5C11i—C12—H12119.9
N1—C2—C3120.4 (2)
O3i—Ni1—O1—C883.86 (8)C3—C4—C5—C7177.4 (3)
O3—Ni1—O1—C893.52 (8)C2—N1—C6—C51.8 (3)
N1i—Ni1—O1—C8173.54 (7)Ni1—N1—C6—C5179.46 (19)
N1—Ni1—O1—C831.8 (3)C2—N1—C6—C6i176.9 (2)
O1i—Ni1—O1—C80.0Ni1—N1—C6—C6i1.8 (3)
O3i—Ni1—N1—C293.27 (19)C4—C5—C6—N10.1 (4)
O3—Ni1—N1—C283.34 (19)C7—C5—C6—N1178.7 (2)
N1i—Ni1—N1—C2177.9 (2)C4—C5—C6—C6i178.6 (3)
O1i—Ni1—N1—C27.1 (2)C7—C5—C6—C6i0.1 (4)
O1—Ni1—N1—C222.0 (4)C4—C5—C7—C7i178.4 (4)
O3i—Ni1—N1—C688.19 (15)C6—C5—C7—C7i0.0 (6)
O3—Ni1—N1—C695.20 (15)Ni1—O1—C8—O1i0.000 (1)
N1i—Ni1—N1—C60.62 (11)Ni1—O1—C8—C9180.0
O1i—Ni1—N1—C6174.37 (13)O1—C8—C9—C10i169.33 (14)
O1—Ni1—N1—C6156.5 (2)O1i—C8—C9—C10i10.67 (14)
C6—N1—C2—C32.3 (3)O1—C8—C9—C1010.67 (14)
Ni1—N1—C2—C3179.25 (18)O1i—C8—C9—C10169.33 (14)
C6—N1—C2—C1176.8 (2)C10i—C9—C10—C110.10 (19)
Ni1—N1—C2—C11.6 (3)C8—C9—C10—C11179.90 (19)
N1—C2—C3—C41.1 (4)C9—C10—C11—O2176.5 (4)
C1—C2—C3—C4178.0 (3)C9—C10—C11—C120.2 (4)
C2—C3—C4—C50.6 (5)O2—C11—C12—C11i176.8 (4)
C3—C4—C5—C61.1 (4)C10—C11—C12—C11i0.10 (19)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H2W···O1iii0.831.962.784 (2)173
O3—H1W···O40.831.972.7746 (19)166
O2—H2···O5iii0.822.012.692 (4)140
Symmetry code: (iii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C7H5O3)(C14H12N2)(H2O)2]NO3
Mr501.11
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)10.9278 (15), 28.509 (4), 7.9738 (11)
β (°) 119.311 (1)
V3)2166.2 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.95
Crystal size (mm)0.39 × 0.18 × 0.05
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.708, 0.950
No. of measured, independent and
observed [I > 2σ(I)] reflections
8026, 2025, 1688
Rint0.055
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.085, 0.99
No. of reflections2025
No. of parameters159
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.29

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H2W···O1i0.831.962.784 (2)173.1
O3—H1W···O40.831.972.7746 (19)166.0
O2—H2···O5i0.822.012.692 (4)140.1
Symmetry code: (i) x+1/2, y+1/2, z+1.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds