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Acta Cryst. (2007). E63, m1954    [ doi:10.1107/S1600536807029285 ]

[[mu]-10,21-Dimethyl-3,6,14,17-tetraazatricyclo[17.3.18,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diolato-[kappa]4N3,N6,O23,O24:[kappa]4N14,N17,O23,O24]bis(nitrato-[kappa]O)zinc(II)

J. Liu, J.-F. Ma, S.-L. Li and G.-J. Ping

Abstract top

The title compound, [Zn2(NO3)2(C22H30N4O2)], is a centrosymmetric dinuclear zinc compound. Each Zn atom has a square-pyramidal geometry with N2O3 donors, being coordinated by two N atoms and two O atoms from the macrocyclic 10,21-dimethyl-3,6,14,17-tetraazatricyclo[17.3.18,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diolate ligand and one O atom from a nitrate anion. In the structure, two Zn atoms are linked by two phenolate O atoms to give a four-membered Zn2O2 ring.

Comment top

Dinuclear zinc(II) cores have attracted much interest as a result of their significance in biological systems (Dealwis et al., 1995; Burley et al., 1990; Roderick & Mathews, 1993). In addition, some synthetic dinuclear zinc(II) compounds are found to have functions in dephosphorylation (Bazzicalupi et al., 1997). To further widen the scope of application of such zinc compounds, there is a need to prepare new series of dinuclear zinc compounds. In this work, a new dinuclear zinc(II) compound has been synthesized, and its structure (I) is reported here.

As shown in Fig. 1, [Zn2L(NO3)2] is a centrosymmetric dinuclear zinc compound. The coordination environment around zinc is a square-pyramid with two N atoms and two O atoms from L ligand occupying the basal positions and one O atom from NO3− anion occupying the apical position. In the crystal structure two zinc atoms are bridged by two phenolate O atoms to generate a four-membered Zn2O2 ring. The Zn—O and Zn—N distances are normal (Dutta et al., 2005).

Related literature top

For related literature, see: Dealwis et al. (1995); Burley et al. (1990); Roderick & Mathews (1993); Dutta et al. (2005); Mandal & Nag (1986); Bazzicalupi et al. (1997).

Experimental top

The ligand C22H32N4O2 (H2L) was prepared by the reported procedure (Mandal & Nag, 1986). A mixture of H2L (0.10 g, 0.26 mmol) and Zn(NO3)2. 6H2O (0.15 g, 0.52 mmol) in methanol (20 ml) was stirred for 10 min. The resulting solution was filtered. Colorless single crystals were obtained by slow evaporation of the filtrate at room temperature (yield 56%).

Refinement top

All H-atoms bound to carbon were refined using a riding model 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 imino H atoms were located in a difference Fourier map and refined isotropically with Uiso(H) = 1.5 Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
[µ-10,21-Dimethyl-3,6,14,17-tetraazatricyclo[17.3.18,12]tetracosa- 1(23),8,10,12 (24),19,21-hexaene-23,24-diolato- κ4N3,N6,O23,O24:κ4N14,N17,O23,O24]bis(nitrato-κO)zinc(II) top
Crystal data top
[Zn2(NO3)2(C22H30N4O2)]F000 = 656
Mr = 637.26Dx = 1.695 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 3000 reflections
a = 8.2190 (5) Åθ = 2.4–28.4º
b = 14.1450 (8) ŵ = 1.98 mm−1
c = 11.0550 (6) ÅT = 293 (2) K
β = 103.744 (9)ºBlock, colorless
V = 1248.43 (12) Å30.40 × 0.30 × 0.25 mm
Z = 2
Data collection top
Bruker APEX CCD area-detector
diffractometer		3027 independent reflections
Radiation source: fine-focus sealed tube2524 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 293(2) Kθmax = 28.4º
ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.495, Tmax = 0.609k = −10→18
7558 measured reflectionsl = −14→14
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)] = 0.028H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.080  w = 1/[σ2(Fo2) + (0.0446P)2 + 0.1778P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
3027 reflectionsΔρmax = 0.40 e Å−3
178 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn2(NO3)2(C22H30N4O2)]V = 1248.43 (12) Å3
Mr = 637.26Z = 2
Monoclinic, P21/cMo Kα
a = 8.2190 (5) ŵ = 1.98 mm−1
b = 14.1450 (8) ÅT = 293 (2) K
c = 11.0550 (6) Å0.40 × 0.30 × 0.25 mm
β = 103.744 (9)º
Data collection top
Bruker APEX CCD area-detector
diffractometer		3027 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2524 reflections with I > 2σ(I)
Tmin = 0.495, Tmax = 0.609Rint = 0.019
7558 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028178 parameters
wR(F2) = 0.080H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.40 e Å−3
3027 reflectionsΔρmin = −0.29 e Å−3
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*/Ueq
Zn10.52604 (3)0.398830 (14)0.56583 (2)0.03572 (9)
C11.0529 (3)0.3634 (2)0.1572 (3)0.0680 (7)
H1A1.14330.32800.20810.102*
H1B1.09670.41900.12620.102*
H1C0.99600.32510.08850.102*
C20.9306 (3)0.39238 (14)0.2345 (3)0.0509 (6)
C30.9619 (3)0.37071 (14)0.3605 (2)0.0478 (5)
H31.05620.33520.39640.057*
C40.8564 (3)0.40063 (12)0.4347 (2)0.0419 (5)
C50.9026 (3)0.38988 (14)0.5739 (2)0.0463 (5)
H5A1.00410.35250.59690.056*
H5B0.92770.45200.61080.056*
C60.8087 (3)0.36047 (16)0.7661 (2)0.0487 (5)
H6A0.83350.42670.78450.058*
H6B0.90600.32370.80690.058*
C70.6586 (3)0.33110 (16)0.8152 (2)0.0495 (5)
H7A0.64010.26370.80270.059*
H7B0.68160.34360.90390.059*
C80.7136 (2)0.45295 (13)0.3782 (2)0.0402 (4)
C90.7880 (3)0.44471 (16)0.1820 (2)0.0493 (5)
H90.76650.46040.09800.059*
C100.6769 (3)0.47418 (14)0.2512 (2)0.0437 (5)
C110.5148 (3)0.52395 (15)0.1905 (2)0.0483 (5)
H11A0.51110.53390.10310.058*
H11B0.42140.48350.19560.058*
N10.7725 (2)0.34492 (11)0.62923 (17)0.0400 (4)
N20.5050 (2)0.38322 (13)0.75088 (18)0.0435 (4)
N30.3579 (2)0.22836 (14)0.4825 (2)0.0524 (5)
O10.61249 (19)0.48312 (10)0.44910 (15)0.0504 (4)
O20.3842 (3)0.30868 (13)0.44489 (18)0.0728 (5)
O30.2602 (3)0.17463 (14)0.4146 (2)0.0801 (6)
O40.4378 (4)0.20400 (16)0.5846 (2)0.1122 (9)
H1N0.773 (7)0.290 (3)0.614 (5)0.168*
H2N0.414 (7)0.353 (4)0.749 (5)0.168*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.03569 (14)0.03053 (13)0.04245 (15)0.00473 (8)0.01229 (10)0.00441 (8)
C10.0588 (15)0.0631 (15)0.095 (2)−0.0046 (12)0.0434 (15)−0.0265 (15)
C20.0465 (12)0.0400 (11)0.0748 (16)−0.0088 (9)0.0316 (11)−0.0194 (10)
C30.0346 (10)0.0321 (9)0.0811 (16)−0.0013 (8)0.0227 (10)−0.0089 (10)
C40.0371 (10)0.0275 (9)0.0650 (13)−0.0025 (7)0.0199 (9)−0.0024 (8)
C50.0352 (10)0.0368 (10)0.0672 (14)−0.0018 (8)0.0129 (10)0.0041 (9)
C60.0458 (11)0.0436 (11)0.0527 (12)0.0066 (9)0.0035 (9)0.0043 (9)
C70.0573 (13)0.0453 (11)0.0444 (11)0.0103 (9)0.0092 (10)0.0099 (9)
C80.0410 (10)0.0279 (9)0.0583 (12)0.0013 (7)0.0247 (9)−0.0004 (8)
C90.0513 (12)0.0462 (12)0.0554 (13)−0.0061 (9)0.0226 (10)−0.0136 (9)
C100.0442 (11)0.0341 (10)0.0565 (12)−0.0024 (8)0.0193 (9)−0.0071 (8)
C110.0479 (12)0.0478 (12)0.0492 (12)0.0017 (9)0.0117 (9)−0.0077 (9)
N10.0371 (8)0.0299 (8)0.0531 (10)0.0014 (6)0.0107 (7)0.0034 (7)
N20.0460 (10)0.0402 (9)0.0450 (9)0.0038 (7)0.0124 (8)0.0023 (7)
N30.0438 (10)0.0504 (11)0.0658 (13)−0.0012 (8)0.0185 (9)−0.0124 (9)
O10.0557 (9)0.0413 (8)0.0654 (10)0.0207 (6)0.0365 (8)0.0171 (7)
O20.0836 (13)0.0563 (11)0.0666 (11)−0.0142 (9)−0.0057 (10)0.0032 (8)
O30.0671 (12)0.0692 (12)0.1050 (16)−0.0187 (9)0.0225 (11)−0.0374 (11)
O40.144 (2)0.0728 (14)0.0964 (17)−0.0331 (15)−0.0171 (17)0.0208 (13)
Geometric parameters (Å, °) top
Zn1—O1i2.0057 (13)C6—H6A0.9700
Zn1—O12.0068 (14)C6—H6B0.9700
Zn1—O22.0079 (18)C7—N21.489 (3)
Zn1—N22.1051 (19)C7—H7A0.9700
Zn1—N12.1216 (16)C7—H7B0.9700
C1—C21.523 (3)C8—O11.340 (2)
C1—H1A0.9600C8—C101.397 (3)
C1—H1B0.9600C9—C101.388 (3)
C1—H1C0.9600C9—H90.9300
C2—C31.389 (4)C10—C111.515 (3)
C2—C91.391 (3)C11—N2i1.490 (3)
C3—C41.394 (3)C11—H11A0.9700
C3—H30.9300C11—H11B0.9700
C4—C81.402 (3)N1—H1N0.80 (5)
C4—C51.503 (3)N2—C11i1.490 (3)
C5—N11.494 (3)N2—H2N0.86 (5)
C5—H5A0.9700N3—O41.213 (3)
C5—H5B0.9700N3—O31.224 (3)
C6—N11.488 (3)N3—O21.246 (3)
C6—C71.519 (3)O1—Zn1i2.0057 (13)
O1i—Zn1—O174.53 (6)C6—C7—H7A109.4
O1i—Zn1—O2104.21 (8)N2—C7—H7B109.4
O1—Zn1—O2100.80 (8)C6—C7—H7B109.4
O1i—Zn1—N289.50 (6)H7A—C7—H7B108.0
O1—Zn1—N2144.15 (7)O1—C8—C10120.25 (18)
O2—Zn1—N2114.32 (8)O1—C8—C4118.52 (19)
O1i—Zn1—N1143.63 (7)C10—C8—C4121.23 (18)
O1—Zn1—N188.27 (6)C10—C9—C2121.9 (2)
O2—Zn1—N1110.44 (8)C10—C9—H9119.0
N2—Zn1—N186.19 (7)C2—C9—H9119.0
C2—C1—H1A109.5C9—C10—C8118.5 (2)
C2—C1—H1B109.5C9—C10—C11121.3 (2)
H1A—C1—H1B109.5C8—C10—C11120.12 (18)
C2—C1—H1C109.5N2i—C11—C10113.11 (18)
H1A—C1—H1C109.5N2i—C11—H11A109.0
H1B—C1—H1C109.5C10—C11—H11A109.0
C3—C2—C9118.26 (19)N2i—C11—H11B109.0
C3—C2—C1120.9 (2)C10—C11—H11B109.0
C9—C2—C1120.8 (2)H11A—C11—H11B107.8
C2—C3—C4122.0 (2)C6—N1—C5111.31 (17)
C2—C3—H3119.0C6—N1—Zn1103.15 (12)
C4—C3—H3119.0C5—N1—Zn1115.58 (12)
C3—C4—C8118.1 (2)C6—N1—H1N111 (4)
C3—C4—C5122.1 (2)C5—N1—H1N107 (4)
C8—C4—C5119.36 (18)Zn1—N1—H1N110 (4)
N1—C5—C4115.52 (18)C7—N2—C11i113.39 (18)
N1—C5—H5A108.4C7—N2—Zn1105.06 (13)
C4—C5—H5A108.4C11i—N2—Zn1111.88 (14)
N1—C5—H5B108.4C7—N2—H2N113 (4)
C4—C5—H5B108.4C11i—N2—H2N105 (4)
H5A—C5—H5B107.5Zn1—N2—H2N108 (3)
N1—C6—C7109.84 (18)O4—N3—O3121.7 (2)
N1—C6—H6A109.7O4—N3—O2118.1 (2)
C7—C6—H6A109.7O3—N3—O2120.1 (2)
N1—C6—H6B109.7C8—O1—Zn1i129.47 (12)
C7—C6—H6B109.7C8—O1—Zn1123.38 (12)
H6A—C6—H6B108.2Zn1i—O1—Zn1105.47 (6)
N2—C7—C6111.27 (17)N3—O2—Zn1118.45 (15)
N2—C7—H7A109.4
C9—C2—C3—C4−0.7 (3)O2—Zn1—N1—C5104.10 (15)
C1—C2—C3—C4176.62 (19)N2—Zn1—N1—C5−141.34 (15)
C2—C3—C4—C80.9 (3)C6—C7—N2—C11i−86.8 (2)
C2—C3—C4—C5−170.78 (18)C6—C7—N2—Zn135.7 (2)
C3—C4—C5—N1−129.7 (2)O1i—Zn1—N2—C7−152.22 (14)
C8—C4—C5—N158.7 (2)O1—Zn1—N2—C7−90.10 (16)
N1—C6—C7—N2−57.0 (2)O2—Zn1—N2—C7102.38 (15)
C3—C4—C8—O1−179.12 (17)N1—Zn1—N2—C7−8.36 (14)
C5—C4—C8—O1−7.2 (3)O1i—Zn1—N2—C11i−28.78 (14)
C3—C4—C8—C100.4 (3)O1—Zn1—N2—C11i33.3 (2)
C5—C4—C8—C10172.34 (17)O2—Zn1—N2—C11i−134.18 (14)
C3—C2—C9—C10−0.9 (3)N1—Zn1—N2—C11i115.08 (15)
C1—C2—C9—C10−178.2 (2)C10—C8—O1—Zn1i−32.2 (3)
C2—C9—C10—C82.1 (3)C4—C8—O1—Zn1i147.37 (15)
C2—C9—C10—C11−174.79 (19)C10—C8—O1—Zn1130.89 (16)
O1—C8—C10—C9177.62 (18)C4—C8—O1—Zn1−49.6 (2)
C4—C8—C10—C9−1.9 (3)O1i—Zn1—O1—C8−166.5 (2)
O1—C8—C10—C11−5.4 (3)O2—Zn1—O1—C8−64.57 (18)
C4—C8—C10—C11175.08 (18)N2—Zn1—O1—C8126.99 (17)
C9—C10—C11—N2i−125.4 (2)N1—Zn1—O1—C845.92 (17)
C8—C10—C11—N2i57.7 (3)O1i—Zn1—O1—Zn1i0.0
C7—C6—N1—C5169.00 (16)O2—Zn1—O1—Zn1i101.92 (9)
C7—C6—N1—Zn144.46 (18)N2—Zn1—O1—Zn1i−66.52 (14)
C4—C5—N1—C6−164.74 (17)N1—Zn1—O1—Zn1i−147.59 (8)
C4—C5—N1—Zn1−47.5 (2)O4—N3—O2—Zn1−10.1 (3)
O1i—Zn1—N1—C664.33 (16)O3—N3—O2—Zn1173.52 (17)
O1—Zn1—N1—C6124.92 (13)O1i—Zn1—O2—N3−128.41 (18)
O2—Zn1—N1—C6−134.20 (13)O1—Zn1—O2—N3155.00 (18)
N2—Zn1—N1—C6−19.64 (13)N2—Zn1—O2—N3−32.4 (2)
O1i—Zn1—N1—C5−57.37 (19)N1—Zn1—O2—N362.8 (2)
O1—Zn1—N1—C53.22 (14)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O1i2.0057 (13)Zn1—N22.1051 (19)
Zn1—O12.0068 (14)Zn1—N12.1216 (16)
Zn1—O22.0079 (18)O1—Zn1i2.0057 (13)
O1i—Zn1—O174.53 (6)O2—Zn1—N2114.32 (8)
O1i—Zn1—O2104.21 (8)O1i—Zn1—N1143.63 (7)
O1—Zn1—O2100.80 (8)O1—Zn1—N188.27 (6)
O1i—Zn1—N289.50 (6)O2—Zn1—N1110.44 (8)
O1—Zn1—N2144.15 (7)N2—Zn1—N186.19 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the National Natural Science Foundation of China (No. 20471014), Program for New Century Excellent Talents in Chinese University (NCET-05–0320), the Fok Ying Tung Education Foundation and the Analysis and Testing Foundation of Northeast Normal University for support.

references
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