Diaqua­(benzoato-κ²O,O′)(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)nickel(II) nitrate dihydrate

The title compound, [Ni(C₇H₅O₂)(C₁₄H₁₂N₂)(H₂O)₂]NO₃·2H₂O, consists of one Ni^II complex cation, two solvent water mol­ecules and one non-coordinated nitrate anion. The Ni^II 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 π–π 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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.098
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom C8      has ADP max/min Ratio .............       3.10 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O1      ..       6.82 su
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 ....       2.09
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 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

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S1. Comment

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 Ni^II 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 O_water—H···O_nitrate and O_water—H···O_water 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

Structurally related Cu^II and Mn^II complexes have been characterized by Xuan et al. (2007) and Zhao et al. (2007), respectively.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(carrier C) (aromatic CH) or U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.5 U_eq(carrier O).

Computing details

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

	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.
	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

Crystal data

[Ni(C7H5O2)(C14H12N2)(H2O)2]NO3·2H2O	F(000) = 1088
Mr = 522.15	Dx = 1.497 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 3407 reflections
a = 10.4453 (9) Å	θ = 2.7–26.8°
b = 22.2586 (19) Å	µ = 0.89 mm^−1
c = 9.9660 (9) Å	T = 291 K
V = 2317.1 (4) Å^3	Block, green
Z = 4	0.37 × 0.30 × 0.23 mm

Data collection

Bruker SMART CCD diffractometer	2129 independent reflections
Radiation source: fine-focus sealed tube	1723 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
Tmin = 0.732, Tmax = 0.817	k = −26→26
9175 measured reflections	l = −10→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 1.0711P] where P = (Fo^2 + 2Fc^2)/3
2129 reflections	(Δ/σ)max = 0.002
158 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.661272 (16)	0.7500	0.03514 (16)
O1	0.43542 (16)	0.74343 (7)	0.83637 (16)	0.0478 (4)
O2	0.17794 (17)	0.78534 (8)	0.88233 (18)	0.0643 (5)
H1W	0.2518	0.7770	0.8587	0.096*
H2W	0.1234	0.7638	0.8475	0.096*
O3	0.5000	0.7955 (2)	0.2500	0.170 (3)
O4	0.5989 (3)	0.87694 (15)	0.2690 (3)	0.1113 (9)
O5	0.65977 (15)	0.66105 (7)	0.87457 (17)	0.0528 (4)
H4W	0.7245	0.6661	0.8294	0.079*
H3W	0.6625	0.6795	0.9468	0.079*
N1	0.41788 (16)	0.59084 (8)	0.85549 (19)	0.0407 (4)
N2	0.5000	0.84737 (19)	0.2500	0.0668 (10)
C1	0.2989 (3)	0.65071 (12)	1.0176 (3)	0.0645 (8)
H1A	0.3704	0.6778	1.0139	0.097*
H1B	0.2736	0.6451	1.1094	0.097*
H1C	0.2286	0.6673	0.9677	0.097*
C2	0.3362 (2)	0.59182 (11)	0.9585 (3)	0.0492 (6)
C3	0.2870 (2)	0.53789 (13)	1.0127 (3)	0.0627 (7)
H3	0.2291	0.5394	1.0835	0.075*
C4	0.3234 (3)	0.48420 (13)	0.9627 (3)	0.0667 (8)
H4A	0.2910	0.4489	0.9994	0.080*
C5	0.4098 (2)	0.48161 (11)	0.8558 (3)	0.0568 (7)
C6	0.4548 (2)	0.53665 (9)	0.8044 (3)	0.0437 (5)
C7	0.4568 (3)	0.42671 (12)	0.7992 (3)	0.0718 (9)
H7	0.4265	0.3903	0.8319	0.086*
C8	0.5000	0.9625 (2)	0.7500	0.125 (3)
H8	0.5000	1.0043	0.7500	0.150*
C9	0.4668 (3)	0.93192 (15)	0.8644 (6)	0.1001 (15)
H9	0.4455	0.9531	0.9417	0.120*
C10	0.4648 (2)	0.86985 (13)	0.8653 (4)	0.0662 (8)
H10	0.4402	0.8491	0.9422	0.079*
C11	0.5000	0.83864 (14)	0.7500	0.0491 (9)
C12	0.5000	0.77188 (15)	0.7500	0.0410 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0321 (2)	0.0313 (2)	0.0420 (3)	0.000	0.00452 (16)	0.000
O1	0.0499 (10)	0.0394 (9)	0.0541 (10)	0.0009 (7)	0.0145 (8)	0.0002 (7)
O2	0.0565 (11)	0.0593 (11)	0.0772 (13)	0.0097 (9)	0.0016 (9)	−0.0154 (9)
O3	0.220 (6)	0.066 (3)	0.224 (6)	0.000	0.142 (5)	0.000
O4	0.0621 (15)	0.122 (2)	0.150 (3)	−0.0057 (16)	−0.0105 (15)	0.0139 (18)
O5	0.0382 (9)	0.0668 (11)	0.0533 (10)	−0.0016 (7)	−0.0021 (8)	−0.0098 (8)
N1	0.0330 (9)	0.0399 (10)	0.0491 (11)	−0.0007 (8)	−0.0024 (8)	0.0093 (8)
N2	0.048 (2)	0.084 (3)	0.069 (2)	0.000	0.0137 (16)	0.000
C1	0.0607 (17)	0.0714 (18)	0.0614 (17)	0.0167 (14)	0.0241 (14)	0.0206 (14)
C2	0.0338 (11)	0.0587 (15)	0.0551 (14)	0.0011 (10)	0.0013 (11)	0.0180 (11)
C3	0.0396 (12)	0.0765 (19)	0.0719 (18)	−0.0099 (13)	−0.0005 (13)	0.0316 (15)
C4	0.0518 (15)	0.0595 (17)	0.089 (2)	−0.0187 (13)	−0.0211 (15)	0.0331 (15)
C5	0.0528 (14)	0.0438 (14)	0.0737 (17)	−0.0105 (11)	−0.0276 (14)	0.0145 (12)
C6	0.0386 (11)	0.0337 (12)	0.0589 (14)	−0.0037 (9)	−0.0149 (10)	0.0057 (10)
C7	0.087 (2)	0.0361 (13)	0.093 (2)	−0.0081 (13)	−0.0394 (18)	0.0078 (13)
C8	0.050 (3)	0.031 (3)	0.293 (11)	0.000	−0.042 (4)	0.000
C9	0.0472 (16)	0.0515 (19)	0.202 (5)	0.0043 (14)	−0.019 (2)	−0.050 (2)
C10	0.0400 (13)	0.0536 (16)	0.105 (2)	0.0019 (12)	−0.0031 (14)	−0.0244 (16)
C11	0.0326 (16)	0.0364 (18)	0.078 (3)	0.000	0.0001 (16)	0.000
C12	0.0357 (16)	0.0364 (17)	0.0510 (19)	0.000	0.0030 (14)	0.000

Geometric parameters (Å, º)

Ni1—N1	2.0734 (18)	C2—C3	1.413 (3)
Ni1—N1^i	2.0734 (18)	C3—C4	1.349 (4)
Ni1—O5	2.0800 (16)	C3—H3	0.9300
Ni1—O5^i	2.0800 (16)	C4—C5	1.398 (4)
Ni1—O1^i	2.1307 (15)	C4—H4A	0.9300
Ni1—O1	2.1308 (15)	C5—C6	1.409 (3)
Ni1—C12	2.462 (3)	C5—C7	1.433 (4)
O1—C12	1.264 (2)	C6—C6^i	1.438 (5)
O2—H1W	0.8271	C7—C7^i	1.332 (7)
O2—H2W	0.8214	C7—H7	0.9300
O3—N2	1.155 (5)	C8—C9	1.373 (5)
O4—N2	1.239 (3)	C8—C9^i	1.373 (5)
O5—H4W	0.8200	C8—H8	0.9300
O5—H3W	0.8291	C9—C10	1.382 (5)
N1—C2	1.335 (3)	C9—H9	0.9300
N1—C6	1.365 (3)	C10—C11	1.393 (3)
N2—O4^ii	1.239 (3)	C10—H10	0.9300
C1—C2	1.489 (4)	C11—C10^i	1.392 (3)
C1—H1A	0.9600	C11—C12	1.486 (5)
C1—H1B	0.9600	C12—O1^i	1.264 (2)
C1—H1C	0.9600
N1—Ni1—N1^i	81.75 (10)	H1B—C1—H1C	109.5
N1—Ni1—O5	91.57 (7)	N1—C2—C3	120.8 (2)
N1^i—Ni1—O5	88.22 (7)	N1—C2—C1	119.1 (2)
N1—Ni1—O5^i	88.22 (7)	C3—C2—C1	120.1 (2)
N1^i—Ni1—O5^i	91.57 (7)	C4—C3—C2	120.6 (3)
O5—Ni1—O5^i	179.72 (9)	C4—C3—H3	119.7
N1—Ni1—O1^i	169.99 (7)	C2—C3—H3	119.7
N1^i—Ni1—O1^i	108.25 (7)	C3—C4—C5	120.0 (2)
O5—Ni1—O1^i	89.38 (7)	C3—C4—H4A	120.0
O5^i—Ni1—O1^i	90.86 (7)	C5—C4—H4A	120.0
N1—Ni1—O1	108.25 (7)	C4—C5—C6	117.2 (2)
N1^i—Ni1—O1	169.99 (7)	C4—C5—C7	123.8 (2)
O5—Ni1—O1	90.86 (7)	C6—C5—C7	119.0 (3)
O5^i—Ni1—O1	89.38 (7)	N1—C6—C5	122.6 (2)
O1^i—Ni1—O1	61.76 (8)	N1—C6—C6^i	117.83 (13)
N1—Ni1—C12	139.13 (5)	C5—C6—C6^i	119.55 (17)
N1^i—Ni1—C12	139.13 (5)	C7^i—C7—C5	121.46 (17)
O5—Ni1—C12	90.14 (5)	C7^i—C7—H7	119.3
O5^i—Ni1—C12	90.14 (5)	C5—C7—H7	119.3
O1^i—Ni1—C12	30.88 (4)	C9—C8—C9^i	120.5 (5)
O1—Ni1—C12	30.88 (4)	C9—C8—H8	119.7
C12—O1—Ni1	89.19 (15)	C9^i—C8—H8	119.7
H1W—O2—H2W	113.3	C8—C9—C10	120.3 (4)
Ni1—O5—H4W	109.5	C8—C9—H9	119.8
Ni1—O5—H3W	123.0	C10—C9—H9	119.8
H4W—O5—H3W	112.4	C9—C10—C11	119.3 (4)
C2—N1—C6	118.81 (19)	C9—C10—H10	120.3
C2—N1—Ni1	129.93 (16)	C11—C10—H10	120.3
C6—N1—Ni1	111.24 (15)	C10^i—C11—C10	120.1 (4)
O3—N2—O4^ii	122.1 (2)	C10^i—C11—C12	119.93 (18)
O3—N2—O4	122.1 (2)	C10—C11—C12	119.93 (18)
O4^ii—N2—O4	115.8 (5)	O1—C12—O1^i	119.8 (3)
C2—C1—H1A	109.5	O1—C12—C11	120.07 (15)
C2—C1—H1B	109.5	O1^i—C12—C11	120.08 (15)
H1A—C1—H1B	109.5	O1—C12—Ni1	59.93 (15)
C2—C1—H1C	109.5	O1^i—C12—Ni1	59.92 (15)
H1A—C1—H1C	109.5	C11—C12—Ni1	180.0
N1—Ni1—O1—C12	−179.22 (8)	C2—N1—C6—C6^i	−178.6 (2)
N1^i—Ni1—O1—C12	4.2 (4)	Ni1—N1—C6—C6^i	2.9 (3)
O5—Ni1—O1—C12	88.84 (9)	C4—C5—C6—N1	0.4 (3)
O5^i—Ni1—O1—C12	−91.31 (9)	C7—C5—C6—N1	−177.9 (2)
O1^i—Ni1—O1—C12	0.0	C4—C5—C6—C6^i	179.2 (3)
N1^i—Ni1—N1—C2	−179.3 (2)	C7—C5—C6—C6^i	0.9 (4)
O5—Ni1—N1—C2	92.7 (2)	C4—C5—C7—C7^i	−177.3 (3)
O5^i—Ni1—N1—C2	−87.5 (2)	C6—C5—C7—C7^i	0.9 (5)
O1^i—Ni1—N1—C2	−2.7 (5)	C9^i—C8—C9—C10	−0.8 (2)
O1—Ni1—N1—C2	1.3 (2)	C8—C9—C10—C11	1.6 (4)
C12—Ni1—N1—C2	0.7 (2)	C9—C10—C11—C10^i	−0.8 (2)
N1^i—Ni1—N1—C6	−1.03 (11)	C9—C10—C11—C12	179.2 (2)
O5—Ni1—N1—C6	−89.00 (15)	Ni1—O1—C12—O1^i	0.000 (1)
O5^i—Ni1—N1—C6	90.82 (15)	Ni1—O1—C12—C11	180.0
O1^i—Ni1—N1—C6	175.6 (3)	C10^i—C11—C12—O1	−159.65 (15)
O1—Ni1—N1—C6	179.58 (14)	C10—C11—C12—O1	20.35 (15)
C12—Ni1—N1—C6	178.97 (11)	C10^i—C11—C12—O1^i	20.35 (15)
C6—N1—C2—C3	−1.0 (3)	C10—C11—C12—O1^i	−159.65 (15)
Ni1—N1—C2—C3	177.21 (17)	N1^i—Ni1—C12—O1	−178.88 (12)
C6—N1—C2—C1	178.0 (2)	O5—Ni1—C12—O1	−91.44 (11)
Ni1—N1—C2—C1	−3.8 (3)	O5^i—Ni1—C12—O1	88.56 (11)
N1—C2—C3—C4	1.1 (4)	O1^i—Ni1—C12—O1	180.0
C1—C2—C3—C4	−177.9 (3)	N1—Ni1—C12—O1^i	−178.87 (12)
C2—C3—C4—C5	−0.4 (4)	N1^i—Ni1—C12—O1^i	1.12 (12)
C3—C4—C5—C6	−0.3 (4)	O5—Ni1—C12—O1^i	88.56 (11)
C3—C4—C5—C7	177.9 (3)	O5^i—Ni1—C12—O1^i	−91.44 (11)
C2—N1—C6—C5	0.2 (3)	O1—Ni1—C12—O1^i	180.000 (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, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1W···O1	0.83	2.07	2.883 (2)	167
O2—H2W···O3^iii	0.82	2.08	2.903 (3)	174
O5—H3W···O2^iv	0.83	1.88	2.707 (2)	174
O5—H4W···O4^v	0.82	2.16	2.860 (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.