Tetra­aqua­bis(2-methoxy­benzaldehyde isonicotinoylhydrazone)zinc dinitrate

In the title complex, [Zn(C₁₄H₁₃N₃O₂)₂(H₂O)₄](NO₃)₂, the Zn atom is located on a center of symmetry. The Zn—O bond distances are 2.0816 (19) and 2.1356 (18) Å, and the Zn—N bond distance is 2.166 (2) Å. The coordination polyhedron is a slightly distorted octa­hedron. The crystal structure is stabilized by O—H(coordinated water)...O(NO₃⁻ or carbonyl O) and N—H(imine)...O(NO₃⁻) hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.041
• wR factor = 0.101
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.42

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
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.94

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

There has been considerable interests in the design and syntheses of transition metal complexes with isonicotinoylhydrazone ligands, owing to that there are multi–dimensional structure or extended multi–dimensional structures in these complexes (Bu et al., 2000; Fu et al., 2007; Ge et al., 2006). As a continued study in these complexes, herein we report the synthesis and crystal structure of complex [Zn(C₁₄H₁₃N₃O₂)₂(H₂O)₄]·(NO₃)₂, (I), where C₁₄H₁₃N₃O₂ is 2–methoxybenzaldehyde isonicotinoylhydrazonate (L).

The complex [Cd(L)₂(H₂O)₄]·(NO₃)₂ (II) has been reported (Fu et al., 2007). The title complex I (Fig. 1) and the reported complex II form an isomorphous pair. These two complexes show similar molecular configurations and structure parameters. In I, the Zn atom placed on the center of symmetry. The Zn—O bond distances are 2.0816 (19) and 2.1356 (18) Å for Zn1—O6 and Zn1—O7, respectively. This difference between Zn—O(water) bonds in same compound is 0.054 (2) Å. It is normal among the values reported by Quirós et al., 1991; Ryu et al., 2005; Zhu et al., 2003. While the length of 2.166 (2) Å in Zn1—N1 is in agreement with the values reported by Sun et al., 2007 and Uçar et al., 2006. Therefore, the coordination environment of metal centre displays a slightly distorted octahedron (Fig. 1). The dihedral angle between the phenyl and pyridine ring is 21.5 (1)°, which is little bigger than 18.8 (2)° in II.

The crystal structure is stabilized by hydrogen bonds, and confers a three dimensional network as complex II. Every two neighboring complex molecules in complex I are linked by O7—H72···O1^iv hydrogen bonds, forming a sheet along bc plane (Fig. 2). And these sheets were connected along a axis into a three dimensional supramolecule via the O6—H61···O3, O6—H62···O(3)ⁱⁱⁱ, O7ⁱ—H71ⁱ···O4 and N2ⁱⁱ—H21ⁱⁱ···O5 hydrogen bonds (Fig. 3) (symmetry codes: (i) -x + 1, -y, -z + 1; (ii) x + 1/2, -y + 1/2, z - 1/2; (iii) -x, -y, -z + 1; (iv) x - 1/2, -y + 1/2, z - 1/2).

Related literature

For compounds containing isonicotinoylhydrazone ligands, see: Bu et al. (2000); Fu et al. (2007); Ge et al. (2006); Quirós et al. (1991); Ryu et al. (2005); Sun et al. (2007); Uçar et al. (2006); Zhu et al. (2003).

S2. Experimental

Ligand L was prepared according Fu et al., 2007. The zinc nitrate hexahydrate (59 mg, 0.2 mmol) and L (51 mg, 0.2 mmol) were mixed and dissolved in 10 ml me thanol. After stirring for an hour, the solution was filtered. Slow evaporation from the solution afforded yellow crystals suitable for X–ray diffraction.

S3. Refinement

The H atoms in water molecules were located in different Fourier maps, and then allowed to ride on the oxygen atoms with U_iso = 1.5U_eq(O). The other H atoms were placed in idealized positions and treated as riding with d(C—H) = 0.93 Å, U_iso(H) = 1.2U_eq(C) for aromatic, d(C—H) = 0.96 Å, U_iso(H) = 1.5U_eq(C) for methyl and d(N—H) = 0.86 Å, U_iso(H) = 1.2U_eq(N) for the imine group.

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of the title complex, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a spheres of arbitrary radius. Symmetry code: (i), -x + 1, -y, -z + 1.
	Fig. 2. The two–dimentional structure of I in the bc plane. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry code: (iv) x - 1/2, -y + 1/2, z - 1/2.
	Fig. 3. The three–dimentional structure of I. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) x + 1/2, -y + 1/2, z - 1/2; (iii) -x, -y, -z + 1; (iv) x - 1/2, -y + 1/2, z - 1/2).

Tetraaquabis(2-methoxybenzaldehyde isonicotinoylhydrazone)zinc dinitrate

Crystal data

[Zn(C14H13N3O2)2(H2O)4](NO3)2	F(000) = 800
Mr = 772.02	Dx = 1.559 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 14941 reflections
a = 7.970 (4) Å	θ = 3.1–27.5°
b = 17.647 (9) Å	µ = 0.83 mm^−1
c = 11.838 (4) Å	T = 293 K
β = 99.062 (16)°	Prism, yellow
V = 1644.2 (13) Å^3	0.20 × 0.15 × 0.12 mm
Z = 2

Data collection

Rigaku Weissenberg IP diffractometer	3665 independent reflections
Radiation source: Fine–focus sealed tube	2955 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ–scan	θmax = 27.5°, θmin = 3.1°
Absorption correction: empirical (TEXRAY; Molecular Structure Corporation, 1999)	h = −8→10
Tmin = 0.853, Tmax = 0.912	k = −22→22
14941 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: Direct
Least-squares matrix: Full	Secondary atom site location: Difmap
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: Geom
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 1.115P] where P = (Fo^2 + 2Fc^2)/3
3665 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.0000	0.5000	0.02783 (11)
N1	0.5422 (2)	0.11807 (10)	0.54594 (15)	0.0297 (4)
N2	0.6791 (3)	0.39700 (10)	0.53791 (16)	0.0391 (5)
H21	0.6215	0.3849	0.4728	0.047*
N3	0.7507 (3)	0.46831 (11)	0.55469 (17)	0.0407 (5)
N4	0.1088 (3)	0.09550 (13)	0.71546 (18)	0.0460 (5)
O1	0.7721 (3)	0.36189 (9)	0.72069 (14)	0.0500 (5)
O2	0.6753 (4)	0.59321 (12)	0.27438 (18)	0.0836 (9)
O3	0.0344 (3)	0.07244 (13)	0.62089 (17)	0.0603 (6)
O4	0.2662 (3)	0.09405 (17)	0.7342 (2)	0.0822 (8)
O5	0.0287 (3)	0.11849 (15)	0.78818 (17)	0.0775 (8)
O6	0.2392 (2)	0.01951 (10)	0.47521 (16)	0.0432 (4)
H61	0.1961	0.0371	0.5349	0.065*
H62	0.1652	−0.0061	0.4356	0.065*
O7	0.4919 (2)	0.02614 (10)	0.32308 (14)	0.0415 (4)
H71	0.5698	0.0062	0.2889	0.062*
H72	0.4224	0.0505	0.2806	0.062*
C1	0.4726 (3)	0.17490 (13)	0.47888 (19)	0.0368 (5)
H1	0.3919	0.1632	0.4156	0.044*
C2	0.5161 (3)	0.25000 (13)	0.49998 (19)	0.0372 (5)
H2	0.4658	0.2878	0.4513	0.045*
C3	0.6351 (3)	0.26846 (12)	0.59417 (18)	0.0309 (5)
C4	0.7015 (3)	0.21004 (13)	0.66525 (19)	0.0360 (5)
H4	0.7786	0.2203	0.7310	0.043*
C5	0.6527 (3)	0.13666 (12)	0.63803 (19)	0.0347 (5)
H5	0.6993	0.0981	0.6865	0.042*
C6	0.7003 (3)	0.34722 (12)	0.62393 (18)	0.0345 (5)
C7	0.7243 (4)	0.51018 (13)	0.4674 (2)	0.0429 (6)
H7	0.6562	0.4923	0.4018	0.051*
C8	0.7972 (3)	0.58583 (13)	0.4663 (2)	0.0387 (5)
C9	0.7676 (4)	0.62883 (14)	0.3661 (2)	0.0457 (6)
C10	0.8338 (4)	0.70137 (15)	0.3637 (3)	0.0544 (7)
H10	0.8120	0.7305	0.2975	0.065*
C11	0.9317 (4)	0.72970 (16)	0.4601 (3)	0.0584 (8)
H11	0.9745	0.7787	0.4594	0.070*
C12	0.9675 (4)	0.68698 (16)	0.5574 (3)	0.0619 (8)
H12	1.0373	0.7063	0.6212	0.074*
C13	0.8998 (4)	0.61541 (15)	0.5606 (2)	0.0494 (7)
H13	0.9236	0.5867	0.6270	0.059*
C14	0.6210 (5)	0.63421 (19)	0.1741 (3)	0.0685 (9)
H141	0.5616	0.6010	0.1171	0.103*
H142	0.7178	0.6555	0.1465	0.103*
H143	0.5465	0.6742	0.1899	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0319 (2)	0.01876 (17)	0.03134 (19)	−0.00072 (14)	0.00039 (13)	0.00013 (13)
N1	0.0360 (11)	0.0208 (8)	0.0301 (9)	−0.0031 (7)	−0.0014 (7)	−0.0001 (7)
N2	0.0580 (14)	0.0230 (9)	0.0320 (10)	−0.0104 (9)	−0.0059 (9)	0.0001 (7)
N3	0.0596 (14)	0.0224 (9)	0.0374 (11)	−0.0087 (9)	−0.0005 (9)	0.0005 (8)
N4	0.0534 (15)	0.0390 (12)	0.0420 (12)	0.0053 (10)	−0.0039 (10)	−0.0036 (9)
O1	0.0787 (14)	0.0295 (9)	0.0347 (9)	−0.0137 (9)	−0.0128 (9)	0.0005 (7)
O2	0.144 (3)	0.0406 (12)	0.0522 (13)	−0.0262 (14)	−0.0281 (14)	0.0150 (9)
O3	0.0534 (12)	0.0781 (15)	0.0476 (11)	−0.0089 (11)	0.0027 (9)	−0.0230 (10)
O4	0.0555 (16)	0.101 (2)	0.0851 (17)	−0.0147 (14)	−0.0039 (12)	−0.0202 (15)
O5	0.0921 (18)	0.0979 (19)	0.0391 (11)	0.0547 (15)	−0.0002 (11)	−0.0087 (11)
O6	0.0329 (9)	0.0440 (10)	0.0510 (10)	0.0008 (7)	0.0014 (7)	−0.0118 (8)
O7	0.0533 (11)	0.0350 (8)	0.0354 (9)	0.0093 (8)	0.0043 (7)	0.0047 (7)
C1	0.0445 (14)	0.0263 (11)	0.0348 (12)	−0.0010 (10)	−0.0082 (10)	−0.0009 (9)
C2	0.0492 (15)	0.0234 (10)	0.0337 (11)	−0.0011 (10)	−0.0097 (10)	0.0027 (8)
C3	0.0403 (13)	0.0218 (10)	0.0288 (10)	−0.0016 (9)	0.0001 (9)	−0.0001 (8)
C4	0.0435 (14)	0.0279 (11)	0.0322 (11)	−0.0054 (10)	−0.0076 (9)	0.0012 (8)
C5	0.0440 (14)	0.0239 (10)	0.0330 (11)	−0.0018 (9)	−0.0032 (9)	0.0047 (8)
C6	0.0470 (14)	0.0227 (10)	0.0314 (11)	−0.0046 (9)	−0.0016 (9)	−0.0003 (8)
C7	0.0610 (17)	0.0271 (12)	0.0371 (13)	−0.0070 (11)	−0.0029 (11)	0.0009 (9)
C8	0.0494 (15)	0.0249 (11)	0.0409 (13)	−0.0031 (10)	0.0040 (10)	0.0021 (9)
C9	0.0620 (18)	0.0283 (12)	0.0448 (14)	−0.0049 (11)	0.0024 (12)	0.0029 (10)
C10	0.077 (2)	0.0312 (13)	0.0550 (17)	−0.0067 (13)	0.0116 (14)	0.0105 (11)
C11	0.074 (2)	0.0289 (13)	0.073 (2)	−0.0169 (13)	0.0128 (16)	0.0012 (13)
C12	0.075 (2)	0.0404 (16)	0.0641 (19)	−0.0207 (15)	−0.0071 (15)	−0.0045 (13)
C13	0.0639 (19)	0.0334 (13)	0.0474 (15)	−0.0093 (12)	−0.0025 (13)	0.0028 (10)
C14	0.098 (3)	0.0541 (19)	0.0482 (17)	−0.0007 (18)	−0.0056 (16)	0.0134 (14)

Geometric parameters (Å, º)

Zn1—O6^i	2.0816 (19)	C1—H1	0.9300
Zn1—O6	2.0816 (19)	C2—C3	1.384 (3)
Zn1—O7	2.1356 (18)	C2—H2	0.9300
Zn1—O7^i	2.1356 (18)	C3—C4	1.382 (3)
Zn1—N1^i	2.166 (2)	C3—C6	1.506 (3)
Zn1—N1	2.166 (2)	C4—C5	1.376 (3)
N1—C5	1.330 (3)	C4—H4	0.9300
N1—C1	1.343 (3)	C5—H5	0.9300
N2—C6	1.335 (3)	C7—C8	1.457 (3)
N2—N3	1.383 (3)	C7—H7	0.9300
N2—H21	0.8600	C8—C13	1.378 (4)
N3—C7	1.260 (3)	C8—C9	1.397 (3)
N4—O5	1.219 (3)	C9—C10	1.386 (4)
N4—O4	1.240 (3)	C10—C11	1.372 (4)
N4—O3	1.250 (3)	C10—H10	0.9300
O1—C6	1.225 (3)	C11—C12	1.368 (4)
O2—C9	1.365 (3)	C11—H11	0.9300
O2—C14	1.399 (3)	C12—C13	1.376 (4)
O6—H61	0.8884	C12—H12	0.9300
O6—H62	0.8270	C13—H13	0.9300
O7—H71	0.8673	C14—H141	0.9600
O7—H72	0.8106	C14—H142	0.9600
C1—C2	1.383 (3)	C14—H143	0.9600
O6^i—Zn1—O6	180.0	C4—C3—C6	117.45 (19)
O6^i—Zn1—O7	92.82 (7)	C2—C3—C6	124.96 (19)
O6—Zn1—O7	87.18 (7)	C5—C4—C3	119.5 (2)
O6^i—Zn1—O7^i	87.18 (7)	C5—C4—H4	120.3
O6—Zn1—O7^i	92.82 (7)	C3—C4—H4	120.3
O7—Zn1—O7^i	180.0	N1—C5—C4	123.4 (2)
O6^i—Zn1—N1^i	89.33 (7)	N1—C5—H5	118.3
O6—Zn1—N1^i	90.67 (7)	C4—C5—H5	118.3
O7—Zn1—N1^i	88.97 (7)	O1—C6—N2	123.9 (2)
O7^i—Zn1—N1^i	91.03 (7)	O1—C6—C3	120.5 (2)
O6^i—Zn1—N1	90.67 (7)	N2—C6—C3	115.54 (19)
O6—Zn1—N1	89.33 (7)	N3—C7—C8	122.0 (2)
O7—Zn1—N1	91.03 (7)	N3—C7—H7	119.0
O7^i—Zn1—N1	88.97 (7)	C8—C7—H7	119.0
N1^i—Zn1—N1	180.00 (9)	C13—C8—C9	118.8 (2)
C5—N1—C1	117.29 (19)	C13—C8—C7	121.8 (2)
C5—N1—Zn1	119.97 (14)	C9—C8—C7	119.4 (2)
C1—N1—Zn1	122.44 (15)	O2—C9—C10	124.6 (2)
C6—N2—N3	119.29 (19)	O2—C9—C8	115.0 (2)
C6—N2—H21	120.4	C10—C9—C8	120.3 (3)
N3—N2—H21	120.4	C11—C10—C9	119.2 (3)
C7—N3—N2	113.8 (2)	C11—C10—H10	120.4
O5—N4—O4	120.5 (2)	C9—C10—H10	120.4
O5—N4—O3	120.9 (3)	C12—C11—C10	121.0 (3)
O4—N4—O3	118.6 (2)	C12—C11—H11	119.5
C9—O2—C14	119.5 (2)	C10—C11—H11	119.5
Zn1—O6—H61	116.6	C11—C12—C13	119.9 (3)
Zn1—O6—H62	126.6	C11—C12—H12	120.1
H61—O6—H62	108.1	C13—C12—H12	120.1
Zn1—O7—H71	117.2	C12—C13—C8	120.7 (3)
Zn1—O7—H72	129.4	C12—C13—H13	119.6
H71—O7—H72	113.3	C8—C13—H13	119.6
N1—C1—C2	122.7 (2)	O2—C14—H141	109.5
N1—C1—H1	118.6	O2—C14—H142	109.5
C2—C1—H1	118.6	H141—C14—H142	109.5
C1—C2—C3	119.4 (2)	O2—C14—H143	109.5
C1—C2—H2	120.3	H141—C14—H143	109.5
C3—C2—H2	120.3	H142—C14—H143	109.5
C4—C3—C2	117.6 (2)
O6^i—Zn1—N1—C5	−46.33 (18)	C4—C3—C6—O1	−19.0 (4)
O6—Zn1—N1—C5	133.67 (18)	C2—C3—C6—O1	162.2 (3)
O7—Zn1—N1—C5	−139.16 (18)	C4—C3—C6—N2	158.8 (2)
O7^i—Zn1—N1—C5	40.84 (18)	C2—C3—C6—N2	−20.0 (4)
O6^i—Zn1—N1—C1	127.22 (19)	N2—N3—C7—C8	−176.6 (2)
O6—Zn1—N1—C1	−52.78 (19)	N3—C7—C8—C13	0.3 (4)
O7—Zn1—N1—C1	34.38 (19)	N3—C7—C8—C9	178.2 (3)
O7^i—Zn1—N1—C1	−145.62 (19)	C14—O2—C9—C10	−9.4 (5)
C6—N2—N3—C7	179.2 (3)	C14—O2—C9—C8	172.3 (3)
C5—N1—C1—C2	2.4 (4)	C13—C8—C9—O2	175.3 (3)
Zn1—N1—C1—C2	−171.35 (19)	C7—C8—C9—O2	−2.6 (4)
N1—C1—C2—C3	−0.5 (4)	C13—C8—C9—C10	−3.1 (4)
C1—C2—C3—C4	−1.9 (4)	C7—C8—C9—C10	179.0 (3)
C1—C2—C3—C6	176.8 (2)	O2—C9—C10—C11	−176.8 (3)
C2—C3—C4—C5	2.4 (4)	C8—C9—C10—C11	1.4 (5)
C6—C3—C4—C5	−176.5 (2)	C9—C10—C11—C12	1.3 (5)
C1—N1—C5—C4	−1.9 (4)	C10—C11—C12—C13	−2.3 (5)
Zn1—N1—C5—C4	171.99 (19)	C11—C12—C13—C8	0.5 (5)
C3—C4—C5—N1	−0.5 (4)	C9—C8—C13—C12	2.1 (5)
N3—N2—C6—O1	4.3 (4)	C7—C8—C13—C12	179.9 (3)
N3—N2—C6—C3	−173.4 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H61···O3	0.89	1.87	2.720 (3)	159
N2—H21···O5^ii	0.86	2.19	3.022 (3)	162
O6—H62···O3^iii	0.83	2.00	2.811 (3)	165
O7—H71···O4^i	0.87	2.24	3.014 (3)	148
O7—H72···O1^iv	0.81	2.01	2.788 (3)	159

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2.