Bis(nitrato-κO)(3-oxapentane-1,5-diamine-κ3N,O,N′)zinc(II)

Jia, F.; Kou, F.; Liu, B.; Jia, B.-B.; Wu, H.-L.

doi:10.1107/S1600536811018010

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m764

doi:10.1107/S1600536811018010

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Bis(nitrato-κO)(3-oxapentane-1,5-diamine-κ³N,O,N′)zinc(II)

Fei Jia,^a Fan Kou,^a Bin Liu,^a Bei-Bei Jia ^a and Hui-Lu Wu ^a ^*

^aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: wuhuilu@163.com

(Received 9 May 2011; accepted 12 May 2011; online 20 May 2011)

In the title compound, [Zn(NO₃)₂(C₄H₁₂N₂O)], the Zn^II atom is N,O,N′-chelated by a 3-oxapentane-1,5-diamine ligand and is further coordinated by two nitrate anions in a distorted trigonal–bipyramidal geometry. Intermolecular N—H⋯O hydrogen bonding is present in the crystal structure. A short O⋯O contact of 2.816 (8) Å is observed between the nitrate anions of adjacent molecules.

Related literature

For polydentate amine ligands in metal complexes, see: Fanshawe et al. (2000 ). For applications of metal complexes with a tridentate amine ligand, see: Junk & Steed (2007 ). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[Zn(NO₃)₂(C₄H₁₂N₂O)]
M_r = 293.55
Triclinic, $[P \overline 1]$
a = 8.031 (19) Å
b = 8.034 (19) Å
c = 9.55 (2) Å
α = 103.97 (2)°
β = 101.90 (2)°
γ = 115.879 (18)°
V = 503 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.48 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.26 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.524, T_max = 0.565
2969 measured reflections
1712 independent reflections
1543 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.065
S = 1.08
1712 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H3A⋯O2ⁱ	0.90	2.39	3.217 (7)	152
N1—H3B⋯O6ⁱⁱ	0.90	2.51	3.168 (9)	130
N2—H2A⋯O4ⁱⁱⁱ	0.90	2.42	3.058 (8)	128
N2—H2B⋯O5^iv	0.90	2.41	3.201 (9)	145
N2—H2B⋯O3^iv	0.90	2.49	3.106 (6)	126
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+1; (iii) x, y+1, z; (iv) -x+2, -y+2, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018010/xu5211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018010/xu5211Isup2.hkl

checkCIF report

Comment top

Polydentate amine ligands generally coordinate to transition metal ions using all of the available nitrogen atoms as donors (Fanshawe et al., 2000). Transition metal coordination complexes involving tridentate amines as ligands have attracted solid attention for their role as model compounds for bioinorganic systems, as building blocks in supramolecular assemblies and as catalysts (Junk & Steed, 2007). 3-oxapentane-1,5-diamine as the one of the classics of polyamines behaves as a tridentate ligand that can form three coordinative bonds with a metal atom through the long pair electrons on two N atoms and one oxygen.

The Zn^II in the complex is N,O,N'-chelated by a 3-oxapentane-1,5-diamine ligand and is further coordinated by two nitrate anions. The coordination geometry of the Zn^II ion may be best described as distorted trigonal bipyramidal (tau = 2/3). The parameter tau is defined as (beta-alpha)/60) [where beta= O(5)–Zn(1)–O(1), alpha = N(2)–Zn(1)–N(1)] and its value varies from 0 (in regular square-base pyramidal) to 1 (in regular trigonal bipyramidal) (Addison et al., 1984). The equatorial plane is occupied by two N atoms of the ligand, and one O atom of nitrate anions, whereas the Zn^II ion protrudes towards O5 by 0.337 Å from the plane of atoms N1/N2/O2. The axial positions are occupied by O1 and O5 atoms. The crystal structure is mainly stabilized by the intermolecular H–bond.

Related literature top

For polydentate amine ligands in metal complexes, see: Fanshawe et al. (2000). For applications of metal complexes with a tridentate amine ligand, see: Junk & Steed (2007). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984).

Experimental top

To a stirred solution of 3-oxapentane-1,5-diamine(0.104 g, 0.10 mmol) in EtOH (10 ml) was added Zn(NO₃₎2(H₂O)₆(0.297 g 0.1 mmol) in EtOH (5 ml).A White crystalline product formed rapidly.The precipitate was filtered off, wash with EtOH and in vacuo.The dried precipitate was dissolved in DMF resulting in a colourless solutoin.The crystals suitable for X-ray diffraction studies were obtained by ether diffusion into DMF after several days at room temperature.Yield,0.115 g(28%).(found:C,16.45;H,3.99;N,19.43.Calcd.: C, 16.37; H, 4.12; N, 19.09).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

Bis(nitrato-κO)(3-oxapentane-1,5-diamine- κ³N,O,N')zinc(II) top

Crystal data top

[Zn(NO₃)₂(C₄H₁₂N₂O)]	Z = 2
M_r = 293.55	F(000) = 300
Triclinic, P1	D_x = 1.940 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.031 (19) Å	Cell parameters from 1744 reflections
b = 8.034 (19) Å	θ = 2.4–26.2°
c = 9.55 (2) Å	µ = 2.48 mm⁻¹
α = 103.97 (2)°	T = 296 K
β = 101.90 (2)°	Block, colourless
γ = 115.879 (18)°	0.30 × 0.28 × 0.26 mm
V = 503 (2) Å³

Data collection top

Bruker SMART 1000 diffractometer	1712 independent reflections
Radiation source: fine-focus sealed tube	1543 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→9
T_min = 0.524, T_max = 0.565	k = −9→9
2969 measured reflections	l = −11→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0269P)² + 0.3287P] where P = (F_o² + 2F_c²)/3
1712 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Zn(NO₃)₂(C₄H₁₂N₂O)]	γ = 115.879 (18)°
M_r = 293.55	V = 503 (2) Å³
Triclinic, P1	Z = 2
a = 8.031 (19) Å	Mo Kα radiation
b = 8.034 (19) Å	µ = 2.48 mm⁻¹
c = 9.55 (2) Å	T = 296 K
α = 103.97 (2)°	0.30 × 0.28 × 0.26 mm
β = 101.90 (2)°

Data collection top

Bruker SMART 1000 diffractometer	1712 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1543 reflections with I > 2σ(I)
T_min = 0.524, T_max = 0.565	R_int = 0.016
2969 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.08	Δρ_max = 0.39 e Å⁻³
1712 reflections	Δρ_min = −0.30 e Å⁻³
145 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

	x	y	z	U_iso*/U_eq
C1	0.1984 (4)	0.4429 (4)	0.1842 (4)	0.0421 (7)
H4A	0.0585	0.3840	0.1683	0.050*
H4B	0.2276	0.3362	0.1631	0.050*
C2	0.2448 (4)	0.5479 (4)	0.0773 (3)	0.0408 (7)
H3C	0.1756	0.4536	−0.0289	0.049*
H3D	0.2044	0.6464	0.0907	0.049*
C3	0.5347 (5)	0.8083 (5)	0.0668 (4)	0.0447 (8)
H1A	0.4661	0.8816	0.0797	0.054*
H1B	0.5209	0.7623	−0.0409	0.054*
C4	0.7451 (5)	0.9362 (5)	0.1657 (4)	0.0443 (8)
H2C	0.8153	0.8670	0.1428	0.053*
H2D	0.8031	1.0575	0.1449	0.053*
N1	0.3161 (3)	0.5833 (4)	0.3447 (3)	0.0354 (5)
H3A	0.3025	0.5149	0.4077	0.043*
H3B	0.2702	0.6660	0.3699	0.043*
N2	0.7660 (3)	0.9873 (3)	0.3291 (3)	0.0350 (5)
H2A	0.7262	1.0754	0.3551	0.042*
H2B	0.8947	1.0466	0.3874	0.042*
N3	0.8109 (4)	0.5303 (3)	0.3367 (3)	0.0344 (5)
N4	0.7273 (4)	0.9449 (3)	0.6934 (3)	0.0351 (6)
O1	0.4541 (3)	0.6427 (3)	0.1137 (2)	0.0370 (5)
O2	0.6435 (3)	0.5019 (3)	0.3413 (2)	0.0425 (5)
O3	0.9375 (3)	0.6943 (3)	0.3458 (3)	0.0538 (6)
O4	0.8395 (4)	0.3919 (4)	0.3230 (4)	0.0700 (8)
O5	0.7711 (3)	0.8330 (3)	0.6081 (2)	0.0367 (5)
O6	0.6094 (3)	0.9873 (3)	0.6285 (3)	0.0489 (6)
O7	0.8036 (4)	1.0070 (4)	0.8329 (2)	0.0556 (6)
Zn1	0.60715 (5)	0.74633 (5)	0.37628 (4)	0.03129 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0341 (16)	0.0388 (16)	0.0448 (18)	0.0122 (13)	0.0134 (14)	0.0155 (14)
C2	0.0346 (16)	0.0391 (16)	0.0352 (16)	0.0135 (13)	0.0052 (13)	0.0097 (13)
C3	0.0485 (19)	0.0457 (17)	0.0352 (17)	0.0162 (15)	0.0176 (15)	0.0209 (14)
C4	0.0460 (18)	0.0410 (17)	0.0428 (18)	0.0156 (14)	0.0213 (15)	0.0196 (14)
N1	0.0376 (13)	0.0451 (14)	0.0364 (13)	0.0247 (12)	0.0195 (11)	0.0232 (11)
N2	0.0336 (13)	0.0318 (12)	0.0356 (13)	0.0148 (10)	0.0092 (11)	0.0129 (10)
N3	0.0433 (14)	0.0363 (13)	0.0311 (13)	0.0245 (12)	0.0157 (11)	0.0145 (10)
N4	0.0397 (14)	0.0386 (13)	0.0337 (14)	0.0239 (12)	0.0139 (11)	0.0162 (11)
O1	0.0351 (11)	0.0374 (10)	0.0339 (11)	0.0131 (9)	0.0137 (9)	0.0159 (9)
O2	0.0388 (12)	0.0442 (12)	0.0500 (13)	0.0251 (10)	0.0185 (10)	0.0165 (10)
O3	0.0541 (14)	0.0401 (12)	0.0583 (15)	0.0136 (11)	0.0231 (12)	0.0227 (11)
O4	0.0750 (18)	0.0592 (15)	0.114 (2)	0.0528 (15)	0.0505 (17)	0.0426 (16)
O5	0.0444 (12)	0.0435 (11)	0.0305 (10)	0.0298 (10)	0.0135 (9)	0.0123 (9)
O6	0.0525 (13)	0.0560 (13)	0.0527 (14)	0.0402 (12)	0.0129 (11)	0.0237 (11)
O7	0.0754 (17)	0.0698 (15)	0.0279 (12)	0.0482 (14)	0.0122 (11)	0.0121 (11)
Zn1	0.03247 (19)	0.03232 (19)	0.03040 (19)	0.01648 (14)	0.01121 (14)	0.01408 (14)

Geometric parameters (Å, º) top

C1—N1	1.467 (4)	N1—H3A	0.9000
C1—C2	1.480 (5)	N1—H3B	0.9000
C1—H4A	0.9700	N2—Zn1	2.020 (4)
C1—H4B	0.9700	N2—H2A	0.9000
C2—O1	1.429 (5)	N2—H2B	0.9000
C2—H3C	0.9700	N3—O4	1.214 (4)
C2—H3D	0.9700	N3—O3	1.231 (4)
C3—O1	1.429 (4)	N3—O2	1.273 (4)
C3—C4	1.470 (5)	N4—O7	1.215 (4)
C3—H1A	0.9700	N4—O6	1.240 (3)
C3—H1B	0.9700	N4—O5	1.279 (3)
C4—N2	1.468 (5)	O1—Zn1	2.307 (5)
C4—H2C	0.9700	O2—Zn1	2.068 (5)
C4—H2D	0.9700	O5—Zn1	2.091 (4)
N1—Zn1	2.029 (5)

N1—C1—C2	110.1 (3)	H3A—N1—H3B	108.0
N1—C1—H4A	109.6	C4—N2—Zn1	112.71 (19)
C2—C1—H4A	109.6	C4—N2—H2A	109.1
N1—C1—H4B	109.6	Zn1—N2—H2A	109.1
C2—C1—H4B	109.6	C4—N2—H2B	109.1
H4A—C1—H4B	108.2	Zn1—N2—H2B	109.1
O1—C2—C1	106.9 (2)	H2A—N2—H2B	107.8
O1—C2—H3C	110.3	O4—N3—O3	122.0 (3)
C1—C2—H3C	110.3	O4—N3—O2	117.9 (3)
O1—C2—H3D	110.3	O3—N3—O2	120.0 (3)
C1—C2—H3D	110.3	O7—N4—O6	122.9 (3)
H3C—C2—H3D	108.6	O7—N4—O5	119.3 (2)
O1—C3—C4	106.7 (3)	O6—N4—O5	117.8 (3)
O1—C3—H1A	110.4	C2—O1—C3	114.1 (2)
C4—C3—H1A	110.4	C2—O1—Zn1	108.81 (17)
O1—C3—H1B	110.4	C3—O1—Zn1	109.59 (19)
C4—C3—H1B	110.4	N3—O2—Zn1	116.47 (18)
H1A—C3—H1B	108.6	N4—O5—Zn1	109.2 (2)
N2—C4—C3	110.2 (3)	N2—Zn1—N1	133.42 (10)
N2—C4—H2C	109.6	N2—Zn1—O2	124.63 (18)
C3—C4—H2C	109.6	N1—Zn1—O2	93.24 (17)
N2—C4—H2D	109.6	N2—Zn1—O5	102.15 (13)
C3—C4—H2D	109.6	N1—Zn1—O5	107.77 (13)
H2C—C4—H2D	108.1	O2—Zn1—O5	84.95 (10)
C1—N1—Zn1	111.6 (2)	N2—Zn1—O1	76.61 (12)
C1—N1—H3A	109.3	N1—Zn1—O1	77.29 (11)
Zn1—N1—H3A	109.3	O2—Zn1—O1	90.28 (10)
C1—N1—H3B	109.3	O5—Zn1—O1	173.20 (8)
Zn1—N1—H3B	109.3

N1—C1—C2—O1	55.3 (3)	C1—N1—Zn1—O5	−153.7 (2)
O1—C3—C4—N2	−53.8 (3)	C1—N1—Zn1—O1	21.62 (19)
C2—C1—N1—Zn1	−49.5 (3)	N3—O2—Zn1—N2	22.7 (2)
C3—C4—N2—Zn1	48.8 (3)	N3—O2—Zn1—N1	173.84 (19)
C1—C2—O1—C3	−157.2 (2)	N3—O2—Zn1—O5	−78.6 (2)
C1—C2—O1—Zn1	−34.5 (3)	N3—O2—Zn1—O1	96.6 (2)
C4—C3—O1—C2	156.3 (3)	N4—O5—Zn1—N2	81.0 (3)
C4—C3—O1—Zn1	34.0 (3)	N4—O5—Zn1—N1	−62.8 (2)
O4—N3—O2—Zn1	176.9 (2)	N4—O5—Zn1—O2	−154.59 (18)
O3—N3—O2—Zn1	−3.2 (3)	N4—O5—Zn1—O1	159.8 (5)
O7—N4—O5—Zn1	178.1 (2)	C2—O1—Zn1—N2	−133.23 (19)
O6—N4—O5—Zn1	−2.8 (3)	C3—O1—Zn1—N2	−7.84 (19)
C4—N2—Zn1—N1	−78.7 (2)	C2—O1—Zn1—N1	7.84 (17)
C4—N2—Zn1—O2	59.7 (2)	C3—O1—Zn1—N1	133.2 (2)
C4—N2—Zn1—O5	152.0 (2)	C2—O1—Zn1—O2	101.1 (2)
C4—N2—Zn1—O1	−21.2 (2)	C3—O1—Zn1—O2	−133.5 (2)
C1—N1—Zn1—N2	78.9 (3)	C2—O1—Zn1—O5	146.5 (6)
C1—N1—Zn1—O2	−67.9 (2)	C3—O1—Zn1—O5	−88.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3A···O2ⁱ	0.90	2.39	3.217 (7)	152
N1—H3B···O6ⁱⁱ	0.90	2.51	3.168 (9)	130
N2—H2A···O4ⁱⁱⁱ	0.90	2.42	3.058 (8)	128
N2—H2B···O5^iv	0.90	2.41	3.201 (9)	145
N2—H2B···O3^iv	0.90	2.49	3.106 (6)	126

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

Experimental details

Crystal data
Chemical formula	[Zn(NO₃)₂(C₄H₁₂N₂O)]
M_r	293.55
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.031 (19), 8.034 (19), 9.55 (2)
α, β, γ (°)	103.97 (2), 101.90 (2), 115.879 (18)
V (Å³)	503 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.48
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.524, 0.565
No. of measured, independent and observed [I > 2σ(I)] reflections	2969, 1712, 1543
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.065, 1.08
No. of reflections	1712
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3A···O2ⁱ	0.90	2.39	3.217 (7)	152
N1—H3B···O6ⁱⁱ	0.90	2.51	3.168 (9)	130
N2—H2A···O4ⁱⁱⁱ	0.90	2.42	3.058 (8)	128
N2—H2B···O5^iv	0.90	2.41	3.201 (9)	145
N2—H2B···O3^iv	0.90	2.49	3.106 (6)	126

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

Acknowledgements

The authors acknowledge financial support from the `Qing Lan' Talent Engineering Funds and the Students' Innovation Experiment Funds (grant No. 201031) of Lanzhou Jiaotong University, China.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
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