Bis­(saccharinato-[kappa]N)zinc(II) com­plexes with N,N'-bidentate 2-amino­methyl­pyridine and 2-amino­ethylpyridine

The structures of trans-bis[2-(amino­methyl)­pyridine-[kappa]²N,N']­bis­(saccharinato-[kappa]N)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₆H₈N₂)₂], (I), and [2-(amino­ethyl)­pyridine-[kappa]²N,N']bis­(saccharinato-[kappa]N)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₇H₁₀N₂)], (II), exhibit octa- and tetrahedrally coordinated Zn^II atoms, respectively. The di­amine ligands behave as N,N'-bidentate ligands, while saccharinate (sac) is coordinated through the N atom. In (I), the complex lies about an inversion centre with the Zn atom disordered and displaced by 0.256 (2) Å from a centre of symmetry towards a sac N atom. The crystal structure of (I) is stabilized by N-H...O hydrogen bonds and the crystal packing of (II) is determined by hydrogen bonding as well as weak [pi]-[pi] stacking interactions between the sac ligands.

S1. Comment

Saccharin (3H-benzisothiazol-3-one 1,1-dioxide or o-benzosulfimide) is a well known artificial sweetener and is readily deprotonated to form the corresponding saccharinate anion (sac), which is a versatile polyfunctional ligand (Ager et al., 1998). Sac coordinates to metals both through the negatively charged N atom and through the carbonyl and sulfonyl O atoms as a mono- or bidentate ligand and, in some cases, also as a bridging ligand. This study forms part of our continuing research into the synthesis and spectral, thermal and structural characterization of a series of mixed-ligand complexes of sac with other co-ligands. In this work, we used two unsymmetrical diamine ligands, namely 2-aminomethylpyridine (ampy) and 2-aminoethylpyridine (aepy), as co-ligands, since metal complexes of both ligands are rare. This paper reports the structures of the title compounds, trans-[Zn(sac)₂(ampy)₂], (I), and [Zn(sac)₂(aepy)], (II). Both consist of neutral molecules.

In (I) (Fig. 1), the disordered zinc cation is displaced from a centre of symmetry towards a sac N atom [Zn1—N1 = 2.188 (2) Å] and forms? a very long Zn1—N1ⁱ (see Table 1 for symmetry codes) bond [2.700 (2) Å] to a symmetry- equivalent N-bonded sac ligand in the trans position. This strongly distorted octahedral coordination is completed by two ampy ligands, thus forming the equatorial plane of the coordination polyhedron. The neutral ampy ligand behaves as a bidentate donor to the Zn atom through the two amine N atoms, thus forming a five-membered chelate ring. An alternative model of the structure, which placed the Zn species at the (1/2, 1/2, 1/2) inversion centre, resulted in slightly higher residuals and identical Zn—N(sac) bond lengths [2.443 (2) Å]. However, the zinc anisotropic displacement parameters displayed gross anisotropy normal to the Zn(ampy)₂ plane and a PLATON (Spek, 2003) analysis indicated that the Zn1—N1(sac) bond failed the Hirshfeld (1976) rigid-bond test by over 100σ. The disorder in the Zn atom also results in non-equivalent Zn—N_ampy bond distances, as shown in Table 1.

In (II) (Fig. 2), the Zn atom exhibits a somewhat distorted tetrahedral coordination geometry, with a neutral bidendate aepy ligand and two anionic sac ligands, thus forming a ZnN₄ chromophore. The four Zn—N bond distances in (II) are practically identical (Table 3), but the N—Zn—N bond angle associated with the aepy grouping is significantly less than the nominal tetrahedral angle of 109.5°. The Zn—N_sac bond distance of (II) is similar to those observed in [Zn(sac)₂(py)₂] [1.977 (2) Å; py is pyridine; Quinzani et al., 1997] but considerably shorter than the corresponding values found in previously reported zinc(II) complexes with sac, viz. 2.200 (4) Å in [Zn(sac)₂(H₂O)₄]·2H₂O (Haider et al., 1984), 2.157 (5) Å in [Zn(sac)₂(bpy)₂]·H₂O (Johns et al., 2001), 2.2423 (9) Å in [Zn(sac)₂(mea)₂] (Yilmaz et al., 2001), 2.159 Å in [Zn(H₂O)(bpy)₂(sac)](sac) (Grupce et al., 2001) and 2.1167 (16) Å in [Zn(sac)₂(mpy)₂] (Yilmaz et al., 2002), where bpy, mea and mpy are 2,2'-bipyridine, monoethanolamine and 2-pyridylmethanol, respectively.

It seems that the difference in the coordination geometry of complexes (I) and (II) may be the consequence of the steric hindrance created by the chelate rings, so that the aepy ligand prevents the coordination of a second aepy ligand, resulting in a tetrahedral coordination. Large distortions in the coordination polyhedra of both complexes are clearly evident from the N—Zn—N bond angles, which deviate significantly from the ideal values. The highest deviations occur at the bite angles of the ampy and aepy ligands.

The sac ligands in both complexes are essentially planar. The r.m.s. deviations from the best planes for atoms C1–C7, N1, O3 and S1 in (I), atoms C1–C7, N1 O1 and S1 in (II), and atoms C8–C14, N2, O4 and S2 in (II) are 0.014, 0.024 and 0.030 Å, respectively. The pyridine rings of the ampy and aepy ligands are also planar, with r.m.s. deviations of 0.013 Å for atoms C8–C13 and N3 in (I), and 0.004 Å for atoms C15–C20 and N3 in (II), respectively. For (II), atoms C21 and N4 deviate from the pyridine plane by 1.135 (3) and 0.846 (3) Å, respectively. The ampy and sac ligands in (I) are almost perpendicular to one another, with a dihedral angle of 89.67 (7)°.

Packing diagrams of (I) and (II) are shown in Figs. 3 and 4, respectively. In (I), the amine H atoms of the ampy ligand form intramolecular hydrogen bonds with the carbonyl and sulfonyl O atoms of the sac ligands (Table 2). The individual molecules of (I) are connected by relatively weak intermolecular C—H···O interactions involving one of the py ring H atoms and the sulfonyl O atom of the sac ligand in a neighboring unit. The molecules of (II) are linked by a strong hydrogen bond between the amine H atom of the aepy ligand and the sulfonyl O atom of the sac ligand of an adjacent molecule (Table 4). Furthermore, weak π–π interactions between the sac rings in (II) [Cg···Cgⁱ = 3.690 Å; symmetry code: (i) 1/2 − x, 1/2 + y, 1/2 − z] contribute to the formation of a three-dimensional network.

S2. Experimental

Tetraaquabis(saccharinato)zinc(II) dihydrate, [Zn(H₂O)₄(sac)₂]·2H₂O, was prepared according to the method described by Haider et al. (1984). For the preparation of (I) and (II), an aqueous solution (25 ml) of [Zn(H₂O)₄(sac)₂]·2H₂O (0.27 g, 0.5 mmol) was mixed, at 333 K, with ampy (1 mmol) and aepy (1 mmol) ligands, respectively. The precipitated white polycrystalline solid was dissolved in a methanol–water mixture (1:2, v/v) and the resulting solution was left to stand at room temperature and allowed to evaporate slowly over a few days. Colourless crystals of (I) and (II) suitable for X-ray diffraction analyses were collected separately by suction filtration and dried in air.

S3. Refinement

All H atoms were placed in idealized positions and treated as riding. The U_iso(H) values were constrained to 1.2 U_eq(parent atom) in all cases.

Computing details

For both compounds, data collection: SMART (Bruker, 1999); 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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular view of (I), showing displacement ellipsoids at the 50% probability level. Symmetry codes are as given in Table 1. Atom Zn1 shows positional disorder, and the site occupation factor of atom Zn1 is 50%. Atom Zn1^i and H atoms bonded to C atoms have been omitted for clarity. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. Molecular view of (II), showing displacement ellipsoids at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 3. Packing diagram for (I). All H atoms have been omitted for clarity.
	Fig. 4. Packing diagram for (II). H atoms bonded to C atoms have been omitted for clarity. Hydrogen bonds are indicated by dashed lines.

(I) trans-bis(2-aminomethylpyridine-κ²N,N')bis(saccharinato-κN)zinc(II)

Crystal data

[Zn(C7H4NO3S)2(C6H8N2)2]	F(000) = 664
Mr = 646.00	Dx = 1.533 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4514 reflections
a = 7.4169 (4) Å	θ = 2.5–29.2°
b = 21.5662 (10) Å	µ = 1.08 mm^−1
c = 8.7502 (4) Å	T = 293 K
β = 90.257 (1)°	Block, colourless
V = 1399.62 (12) Å^3	0.46 × 0.41 × 0.20 mm
Z = 2

Data collection

Bruker SMART 1000 CCD diffractometer	4077 independent reflections
Radiation source: fine-focus sealed tube	2798 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
Tmin = 0.637, Tmax = 0.813	k = −30→30
14105 measured reflections	l = −12→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0612P)^2] where P = (Fo^2 + 2Fc^2)/3
4077 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.23 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.4884 (3)	0.49061 (7)	0.4850 (2)	0.0457 (3)	0.50
S1	0.16514 (6)	0.40402 (2)	0.32226 (6)	0.04488 (14)
O1	0.05939 (19)	0.40975 (7)	0.45979 (18)	0.0543 (4)
O2	0.1112 (2)	0.44440 (7)	0.2003 (2)	0.0658 (4)
O3	0.63285 (18)	0.35190 (7)	0.3461 (2)	0.0603 (4)
N1	0.3771 (2)	0.41073 (7)	0.3626 (2)	0.0461 (4)
C1	0.4689 (2)	0.35778 (9)	0.3295 (2)	0.0451 (4)
C2	0.3500 (3)	0.30783 (9)	0.2674 (2)	0.0458 (4)
C3	0.3957 (3)	0.24874 (11)	0.2201 (3)	0.0615 (6)
H3	0.5143	0.2350	0.2259	0.074*
C4	0.2624 (4)	0.21100 (11)	0.1647 (3)	0.0718 (7)
H4	0.2918	0.1712	0.1326	0.086*
C5	0.0856 (4)	0.23048 (12)	0.1550 (3)	0.0719 (7)
H5	−0.0015	0.2039	0.1151	0.086*
C6	0.0357 (3)	0.28933 (11)	0.2043 (3)	0.0612 (6)
H6	−0.0833	0.3028	0.2006	0.073*
C7	0.1717 (3)	0.32650 (9)	0.2588 (2)	0.0470 (4)
N2	0.4287 (2)	0.55675 (7)	0.30872 (19)	0.0434 (4)
N3	0.7280 (2)	0.48919 (8)	0.3702 (2)	0.0457 (4)
H1	0.8237	0.5026	0.4245	0.055*
H2	0.7440	0.4485	0.3518	0.055*
C8	0.2753 (3)	0.58870 (10)	0.2872 (3)	0.0565 (6)
H8	0.1916	0.5901	0.3659	0.068*
C9	0.2374 (4)	0.61923 (13)	0.1545 (3)	0.0695 (7)
H9	0.1280	0.6396	0.1409	0.083*
C10	0.3649 (4)	0.61901 (17)	0.0417 (3)	0.0938 (11)
H10	0.3457	0.6410	−0.0483	0.113*
C11	0.5204 (4)	0.58616 (16)	0.0627 (3)	0.0902 (10)
H11	0.6063	0.5846	−0.0142	0.108*
C12	0.5490 (3)	0.55561 (10)	0.1977 (2)	0.0498 (5)
C13	0.7235 (3)	0.52142 (15)	0.2265 (3)	0.0728 (8)
H13	0.7421	0.4918	0.1448	0.087*
H14	0.8223	0.5509	0.2239	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0329 (5)	0.0547 (9)	0.0495 (8)	0.0104 (5)	0.0128 (4)	0.0176 (5)
S1	0.0340 (2)	0.0448 (2)	0.0559 (3)	0.00780 (18)	0.0050 (2)	0.0036 (2)
O1	0.0370 (7)	0.0616 (8)	0.0643 (9)	0.0058 (6)	0.0121 (7)	−0.0064 (7)
O2	0.0573 (9)	0.0636 (9)	0.0764 (11)	0.0160 (8)	−0.0031 (9)	0.0187 (8)
O3	0.0371 (7)	0.0634 (9)	0.0804 (12)	0.0140 (6)	0.0054 (7)	−0.0027 (8)
N1	0.0329 (7)	0.0451 (8)	0.0605 (11)	0.0066 (6)	0.0087 (7)	0.0024 (7)
C1	0.0391 (9)	0.0487 (10)	0.0477 (11)	0.0095 (8)	0.0101 (8)	0.0045 (8)
C2	0.0455 (10)	0.0465 (10)	0.0455 (11)	0.0083 (8)	0.0090 (9)	0.0033 (8)
C3	0.0676 (14)	0.0533 (12)	0.0638 (14)	0.0156 (11)	0.0121 (12)	−0.0016 (10)
C4	0.096 (2)	0.0487 (12)	0.0705 (16)	0.0033 (13)	0.0151 (15)	−0.0117 (11)
C5	0.0815 (18)	0.0672 (15)	0.0670 (15)	−0.0176 (14)	0.0058 (14)	−0.0098 (12)
C6	0.0531 (13)	0.0657 (14)	0.0648 (15)	−0.0041 (11)	0.0009 (11)	−0.0029 (11)
C7	0.0455 (10)	0.0483 (10)	0.0472 (11)	0.0042 (8)	0.0061 (9)	0.0028 (8)
N2	0.0356 (7)	0.0473 (8)	0.0473 (9)	0.0061 (6)	0.0083 (7)	0.0092 (7)
N3	0.0349 (8)	0.0536 (9)	0.0485 (10)	0.0083 (7)	0.0050 (7)	−0.0007 (7)
C8	0.0472 (11)	0.0648 (13)	0.0577 (13)	0.0181 (10)	0.0150 (10)	0.0180 (10)
C9	0.0675 (15)	0.0801 (16)	0.0609 (15)	0.0323 (13)	0.0061 (12)	0.0176 (12)
C10	0.093 (2)	0.138 (3)	0.0502 (15)	0.051 (2)	0.0153 (14)	0.0369 (16)
C11	0.085 (2)	0.138 (3)	0.0485 (14)	0.0486 (18)	0.0254 (13)	0.0316 (16)
C12	0.0472 (10)	0.0611 (12)	0.0413 (11)	0.0109 (9)	0.0099 (9)	0.0031 (9)
C13	0.0535 (13)	0.112 (2)	0.0532 (14)	0.0335 (14)	0.0187 (11)	0.0213 (14)

Geometric parameters (Å, º)

Zn1—Zn1^i	0.512 (2)	C5—H5	0.9300
Zn1—N3	2.046 (3)	C6—C7	1.372 (3)
Zn1—N3^i	2.095 (3)	C6—H6	0.9300
Zn1—N2	2.146 (3)	N2—C12	1.322 (2)
Zn1—N2^i	2.161 (3)	N2—C8	1.343 (2)
Zn1—N1	2.188 (2)	N2—Zn1^i	2.161 (3)
Zn1—N1^i	2.700 (2)	N3—C13	1.437 (3)
S1—O2	1.4333 (16)	N3—Zn1^i	2.095 (3)
S1—O1	1.4447 (15)	N3—H1	0.9000
S1—N1	1.6163 (17)	N3—H2	0.9000
S1—C7	1.762 (2)	C8—C9	1.363 (3)
O3—C1	1.231 (2)	C8—H8	0.9300
N1—C1	1.361 (2)	C9—C10	1.370 (3)
C1—C2	1.493 (3)	C9—H9	0.9300
C2—C3	1.383 (3)	C10—C11	1.365 (4)
C2—C7	1.384 (3)	C10—H10	0.9300
C3—C4	1.368 (4)	C11—C12	1.368 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.379 (4)	C12—C13	1.510 (3)
C4—H4	0.9300	C13—H13	0.9700
C5—C6	1.391 (3)	C13—H14	0.9700
Zn1^i—Zn1—N3	88.4 (5)	C4—C5—C6	120.8 (2)
Zn1^i—Zn1—N3^i	77.5 (5)	C4—C5—H5	119.6
N3—Zn1—N3^i	165.85 (6)	C6—C5—H5	119.6
Zn1^i—Zn1—N2	84.9 (5)	C7—C6—C5	116.4 (2)
N3—Zn1—N2	80.43 (10)	C7—C6—H6	121.8
N3^i—Zn1—N2	98.07 (10)	C5—C6—H6	121.8
Zn1^i—Zn1—N2^i	81.5 (5)	C6—C7—C2	123.3 (2)
N3—Zn1—N2^i	99.11 (11)	C6—C7—S1	129.98 (17)
N3^i—Zn1—N2^i	79.00 (10)	C2—C7—S1	106.65 (15)
N2—Zn1—N2^i	166.35 (6)	C12—N2—C8	118.73 (17)
Zn1^i—Zn1—N1	177.4 (5)	C12—N2—Zn1	112.22 (13)
N3—Zn1—N1	94.26 (9)	C8—N2—Zn1	127.88 (14)
N3^i—Zn1—N1	99.89 (10)	C12—N2—Zn1^i	114.47 (14)
N2—Zn1—N1	95.47 (10)	C8—N2—Zn1^i	126.71 (14)
N2^i—Zn1—N1	98.17 (9)	C13—N3—Zn1	113.94 (15)
Zn1^i—Zn1—N1^i	2.1 (4)	C13—N3—Zn1^i	114.45 (14)
N3—Zn1—N1^i	86.24 (8)	C13—N3—H1	108.8
N3^i—Zn1—N1^i	79.62 (7)	Zn1—N3—H1	114.9
N2—Zn1—N1^i	84.59 (7)	Zn1^i—N3—H1	102.6
N2^i—Zn1—N1^i	81.76 (8)	C13—N3—H2	108.5
N1—Zn1—N1^i	179.50 (10)	Zn1—N3—H2	102.6
O2—S1—O1	114.69 (9)	Zn1^i—N3—H2	114.4
O2—S1—N1	112.10 (9)	H1—N3—H2	107.6
O1—S1—N1	109.98 (9)	N2—C8—C9	122.6 (2)
O2—S1—C7	110.48 (10)	N2—C8—H8	118.7
O1—S1—C7	111.06 (9)	C9—C8—H8	118.7
N1—S1—C7	97.22 (9)	C8—C9—C10	118.2 (2)
C1—N1—S1	111.41 (14)	C8—C9—H9	120.9
C1—N1—Zn1	125.23 (15)	C10—C9—H9	120.9
S1—N1—Zn1	122.80 (10)	C11—C10—C9	119.3 (2)
C1—N1—Zn1^i	125.61 (14)	C11—C10—H10	120.3
S1—N1—Zn1^i	122.38 (9)	C9—C10—H10	120.3
O3—C1—N1	123.79 (19)	C10—C11—C12	119.6 (2)
O3—C1—C2	123.38 (17)	C10—C11—H11	120.2
N1—C1—C2	112.82 (16)	C12—C11—H11	120.2
C3—C2—C7	119.2 (2)	N2—C12—C11	121.5 (2)
C3—C2—C1	128.97 (19)	N2—C12—C13	117.86 (18)
C7—C2—C1	111.86 (17)	C11—C12—C13	120.6 (2)
C4—C3—C2	118.5 (2)	N3—C13—C12	113.49 (18)
C4—C3—H3	120.8	N3—C13—H13	108.9
C2—C3—H3	120.8	C12—C13—H13	108.9
C3—C4—C5	121.7 (2)	N3—C13—H14	108.9
C3—C4—H4	119.1	C12—C13—H14	108.9
C5—C4—H4	119.1	H13—C13—H14	107.7
O2—S1—N1—C1	−114.11 (15)	Zn1^i—Zn1—N2—C12	102.4 (5)
O1—S1—N1—C1	117.05 (14)	N3—Zn1—N2—C12	13.16 (15)
C7—S1—N1—C1	1.49 (16)	N3^i—Zn1—N2—C12	178.93 (15)
O2—S1—N1—Zn1	74.04 (15)	N2^i—Zn1—N2—C12	102.4 (5)
O1—S1—N1—Zn1	−54.81 (15)	N1—Zn1—N2—C12	−80.25 (16)
C7—S1—N1—Zn1	−170.37 (13)	N1^i—Zn1—N2—C12	100.24 (15)
O2—S1—N1—Zn1^i	74.34 (14)	Zn1^i—Zn1—N2—C8	−90.3 (5)
O1—S1—N1—Zn1^i	−54.50 (13)	N3—Zn1—N2—C8	−179.5 (2)
C7—S1—N1—Zn1^i	−170.06 (12)	N3^i—Zn1—N2—C8	−13.8 (2)
N3—Zn1—N1—C1	42.97 (19)	N2^i—Zn1—N2—C8	−90.3 (5)
N3^i—Zn1—N1—C1	−137.05 (17)	N1—Zn1—N2—C8	87.0 (2)
N2—Zn1—N1—C1	123.75 (17)	N1^i—Zn1—N2—C8	−92.5 (2)
N2^i—Zn1—N1—C1	−56.88 (19)	N3—Zn1—N2—Zn1^i	−89.2 (5)
N3—Zn1—N1—S1	−146.32 (12)	N3^i—Zn1—N2—Zn1^i	76.6 (5)
N3^i—Zn1—N1—S1	33.65 (16)	N1—Zn1—N2—Zn1^i	177.4 (5)
N2—Zn1—N1—S1	−65.55 (14)	N1^i—Zn1—N2—Zn1^i	−2.1 (4)
N2^i—Zn1—N1—S1	113.83 (12)	Zn1^i—Zn1—N3—C13	−95.2 (6)
S1—N1—C1—O3	177.89 (17)	N3^i—Zn1—N3—C13	−95.2 (6)
Zn1—N1—C1—O3	−10.5 (3)	N2—Zn1—N3—C13	−10.18 (18)
Zn1^i—N1—C1—O3	−10.9 (3)	N2^i—Zn1—N3—C13	−176.35 (18)
S1—N1—C1—C2	−0.8 (2)	N1—Zn1—N3—C13	84.66 (19)
Zn1—N1—C1—C2	170.85 (15)	N1^i—Zn1—N3—C13	−95.32 (19)
Zn1^i—N1—C1—C2	170.45 (13)	N2—Zn1—N3—Zn1^i	85.1 (5)
O3—C1—C2—C3	0.5 (3)	N2^i—Zn1—N3—Zn1^i	−81.1 (5)
N1—C1—C2—C3	179.2 (2)	N1—Zn1—N3—Zn1^i	179.9 (6)
O3—C1—C2—C7	−179.29 (19)	N1^i—Zn1—N3—Zn1^i	−0.1 (5)
N1—C1—C2—C7	−0.6 (2)	C12—N2—C8—C9	1.0 (4)
C7—C2—C3—C4	0.7 (3)	Zn1—N2—C8—C9	−165.5 (2)
C1—C2—C3—C4	−179.1 (2)	Zn1^i—N2—C8—C9	177.4 (2)
C2—C3—C4—C5	0.0 (4)	N2—C8—C9—C10	−2.6 (4)
C3—C4—C5—C6	−1.1 (4)	C8—C9—C10—C11	3.1 (5)
C4—C5—C6—C7	1.4 (4)	C9—C10—C11—C12	−2.0 (6)
C5—C6—C7—C2	−0.6 (3)	C8—N2—C12—C11	0.1 (4)
C5—C6—C7—S1	176.67 (18)	Zn1—N2—C12—C11	168.7 (2)
C3—C2—C7—C6	−0.4 (3)	Zn1^i—N2—C12—C11	−176.7 (2)
C1—C2—C7—C6	179.4 (2)	C8—N2—C12—C13	177.8 (2)
C3—C2—C7—S1	−178.27 (17)	Zn1—N2—C12—C13	−13.7 (3)
C1—C2—C7—S1	1.6 (2)	Zn1^i—N2—C12—C13	1.0 (3)
O2—S1—C7—C6	−62.6 (2)	C10—C11—C12—N2	0.4 (5)
O1—S1—C7—C6	65.9 (2)	C10—C11—C12—C13	−177.2 (3)
N1—S1—C7—C6	−179.4 (2)	Zn1—N3—C13—C12	6.3 (3)
O2—S1—C7—C2	115.08 (15)	Zn1^i—N3—C13—C12	−9.2 (3)
O1—S1—C7—C2	−116.49 (15)	N2—C12—C13—N3	5.4 (4)
N1—S1—C7—C2	−1.80 (16)	C11—C12—C13—N3	−176.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1^i	0.90	2.31	3.071 (2)	142
N3—H2···O3	0.90	2.24	3.051 (2)	150
C8—H8···O1^ii	0.93	2.41	3.334 (3)	171

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

(II) (2-aminoethylpyridine-κ²N,N')bis(saccharinato-κN)zinc(II)

Crystal data

[Zn(C7H4NO3S)2(C7H10N2)]	F(000) = 1128
Mr = 551.88	Dx = 1.666 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5706 reflections
a = 9.1654 (4) Å	θ = 2.4–29.9°
b = 13.9784 (6) Å	µ = 1.35 mm^−1
c = 17.4679 (7) Å	T = 293 K
β = 100.522 (1)°	Chunk, colourless
V = 2200.31 (16) Å^3	0.44 × 0.33 × 0.11 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer	6434 independent reflections
Radiation source: fine-focus sealed tube	4512 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 30.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −11→12
Tmin = 0.586, Tmax = 0.866	k = −19→12
16660 measured reflections	l = −23→24

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0424P)^2] where P = (Fo^2 + 2Fc^2)/3
6434 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.33 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.32239 (2)	0.538171 (15)	0.289643 (12)	0.03199 (7)
S1	−0.01046 (6)	0.58938 (4)	0.19492 (3)	0.03958 (12)
O1	0.24893 (15)	0.40557 (10)	0.15034 (8)	0.0429 (3)
O2	−0.07643 (18)	0.57493 (12)	0.26231 (10)	0.0568 (4)
O3	0.00534 (18)	0.68646 (11)	0.17170 (11)	0.0628 (5)
N1	0.14761 (17)	0.53148 (11)	0.20494 (9)	0.0348 (4)
C1	0.1429 (2)	0.45752 (13)	0.15230 (11)	0.0329 (4)
C2	−0.0048 (2)	0.45082 (13)	0.09994 (11)	0.0334 (4)
C3	−0.0496 (2)	0.38642 (15)	0.03971 (12)	0.0414 (5)
H3	0.0135	0.3380	0.0293	0.050*
C4	−0.1903 (2)	0.39605 (17)	−0.00432 (13)	0.0485 (5)
H4	−0.2223	0.3536	−0.0449	0.058*
C5	−0.2836 (2)	0.46784 (18)	0.01126 (14)	0.0511 (6)
H5	−0.3771	0.4734	−0.0198	0.061*
C6	−0.2422 (2)	0.53192 (17)	0.07182 (13)	0.0465 (5)
H6	−0.3059	0.5798	0.0827	0.056*
C7	−0.1005 (2)	0.52090 (14)	0.11537 (11)	0.0352 (4)
S2	0.47285 (5)	0.70981 (4)	0.20797 (3)	0.03531 (11)
O4	0.64442 (18)	0.57233 (12)	0.37928 (10)	0.0578 (4)
O5	0.34243 (17)	0.76421 (12)	0.21268 (10)	0.0594 (5)
O6	0.48760 (18)	0.67848 (13)	0.13182 (8)	0.0562 (4)
N2	0.48779 (17)	0.62166 (11)	0.26959 (9)	0.0330 (3)
C8	0.6140 (2)	0.62947 (14)	0.32633 (12)	0.0370 (4)
C9	0.7011 (2)	0.71659 (14)	0.31581 (11)	0.0351 (4)
C10	0.8330 (2)	0.74771 (17)	0.36012 (14)	0.0475 (5)
H10	0.8809	0.7119	0.4022	0.057*
C11	0.8918 (3)	0.83278 (18)	0.34059 (15)	0.0534 (6)
H11	0.9812	0.8542	0.3695	0.064*
C12	0.8211 (3)	0.88708 (17)	0.27895 (15)	0.0526 (6)
H12	0.8621	0.9453	0.2680	0.063*
C13	0.6896 (2)	0.85645 (15)	0.23286 (13)	0.0442 (5)
H13	0.6417	0.8922	0.1908	0.053*
C14	0.6337 (2)	0.77015 (13)	0.25283 (11)	0.0333 (4)
N3	0.25687 (17)	0.59319 (11)	0.38658 (9)	0.0321 (3)
N4	0.39238 (19)	0.40864 (12)	0.33288 (10)	0.0382 (4)
H4A	0.3410	0.3631	0.3030	0.046*
H4B	0.4887	0.4017	0.3297	0.046*
C15	0.2517 (2)	0.68840 (14)	0.39606 (12)	0.0388 (4)
H15	0.2757	0.7277	0.3572	0.047*
C16	0.2127 (2)	0.73031 (15)	0.46021 (12)	0.0442 (5)
H16	0.2115	0.7965	0.4652	0.053*
C17	0.1754 (3)	0.67217 (16)	0.51706 (13)	0.0481 (5)
H17	0.1483	0.6986	0.5613	0.058*
C18	0.1785 (2)	0.57407 (16)	0.50783 (12)	0.0423 (5)
H18	0.1526	0.5339	0.5457	0.051*
C19	0.2203 (2)	0.53578 (13)	0.44196 (11)	0.0326 (4)
C20	0.2274 (2)	0.42965 (14)	0.42972 (13)	0.0431 (5)
H20A	0.1510	0.4121	0.3859	0.052*
H20B	0.2048	0.3976	0.4754	0.052*
C21	0.3755 (3)	0.39329 (15)	0.41479 (12)	0.0443 (5)
H21A	0.4549	0.4261	0.4491	0.053*
H21B	0.3840	0.3255	0.4267	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03876 (12)	0.02832 (12)	0.02931 (12)	−0.00321 (9)	0.00735 (9)	−0.00036 (9)
S1	0.0395 (3)	0.0316 (3)	0.0494 (3)	0.0029 (2)	0.0125 (2)	−0.0066 (2)
O1	0.0425 (8)	0.0422 (8)	0.0417 (8)	0.0129 (6)	0.0014 (6)	−0.0075 (6)
O2	0.0595 (10)	0.0625 (11)	0.0543 (10)	0.0002 (8)	0.0261 (8)	−0.0175 (8)
O3	0.0590 (10)	0.0286 (8)	0.1002 (14)	0.0024 (7)	0.0130 (10)	0.0011 (8)
N1	0.0373 (8)	0.0324 (9)	0.0343 (9)	0.0030 (7)	0.0053 (7)	−0.0069 (7)
C1	0.0387 (10)	0.0305 (10)	0.0293 (9)	0.0006 (8)	0.0062 (8)	0.0006 (7)
C2	0.0348 (9)	0.0339 (10)	0.0312 (10)	0.0002 (8)	0.0053 (8)	0.0041 (7)
C3	0.0470 (12)	0.0414 (12)	0.0348 (11)	−0.0007 (9)	0.0046 (9)	−0.0032 (9)
C4	0.0461 (12)	0.0572 (15)	0.0395 (12)	−0.0120 (11)	0.0009 (10)	−0.0013 (10)
C5	0.0345 (11)	0.0723 (17)	0.0438 (13)	−0.0061 (11)	−0.0001 (9)	0.0117 (12)
C6	0.0353 (10)	0.0532 (14)	0.0523 (13)	0.0041 (9)	0.0115 (9)	0.0107 (11)
C7	0.0359 (10)	0.0349 (11)	0.0361 (10)	−0.0017 (8)	0.0098 (8)	0.0033 (8)
S2	0.0362 (2)	0.0364 (3)	0.0333 (3)	−0.00100 (19)	0.00645 (19)	0.00789 (19)
O4	0.0555 (10)	0.0549 (10)	0.0550 (10)	−0.0082 (8)	−0.0113 (8)	0.0258 (8)
O5	0.0432 (8)	0.0545 (10)	0.0810 (13)	0.0149 (7)	0.0129 (8)	0.0249 (9)
O6	0.0674 (10)	0.0717 (12)	0.0294 (8)	−0.0193 (9)	0.0083 (7)	−0.0028 (7)
N2	0.0345 (8)	0.0304 (8)	0.0335 (9)	−0.0032 (6)	0.0042 (7)	0.0066 (6)
C8	0.0367 (10)	0.0352 (11)	0.0385 (11)	−0.0003 (8)	0.0049 (8)	0.0036 (8)
C9	0.0355 (10)	0.0324 (10)	0.0385 (11)	−0.0005 (8)	0.0099 (8)	−0.0022 (8)
C10	0.0403 (11)	0.0496 (14)	0.0511 (14)	−0.0055 (10)	0.0044 (10)	−0.0028 (10)
C11	0.0421 (12)	0.0511 (15)	0.0676 (17)	−0.0123 (10)	0.0114 (11)	−0.0169 (12)
C12	0.0588 (14)	0.0378 (12)	0.0683 (17)	−0.0143 (11)	0.0303 (13)	−0.0129 (11)
C13	0.0571 (13)	0.0353 (11)	0.0442 (12)	−0.0040 (10)	0.0200 (10)	0.0010 (9)
C14	0.0387 (10)	0.0291 (10)	0.0350 (10)	−0.0025 (8)	0.0142 (8)	−0.0039 (8)
N3	0.0407 (9)	0.0287 (8)	0.0272 (8)	−0.0037 (7)	0.0069 (7)	−0.0010 (6)
N4	0.0405 (9)	0.0311 (9)	0.0449 (10)	0.0001 (7)	0.0128 (8)	0.0016 (7)
C15	0.0512 (12)	0.0299 (10)	0.0370 (11)	−0.0022 (9)	0.0127 (9)	0.0017 (8)
C16	0.0582 (13)	0.0320 (11)	0.0430 (12)	0.0041 (9)	0.0111 (10)	−0.0039 (9)
C17	0.0668 (14)	0.0456 (13)	0.0346 (11)	0.0110 (11)	0.0166 (10)	−0.0038 (9)
C18	0.0546 (12)	0.0428 (12)	0.0323 (11)	0.0041 (10)	0.0151 (9)	0.0065 (9)
C19	0.0358 (9)	0.0317 (10)	0.0303 (10)	−0.0033 (8)	0.0056 (7)	0.0024 (8)
C20	0.0612 (13)	0.0298 (10)	0.0419 (12)	−0.0091 (9)	0.0196 (10)	0.0027 (8)
C21	0.0600 (13)	0.0304 (11)	0.0404 (12)	0.0045 (9)	0.0038 (10)	0.0066 (8)

Geometric parameters (Å, º)

Zn1—N1	1.9744 (16)	C9—C10	1.381 (3)
Zn1—N2	1.9942 (15)	C10—C11	1.374 (3)
Zn1—N4	2.0207 (16)	C10—H10	0.9300
Zn1—N3	2.0472 (15)	C11—C12	1.379 (3)
S1—O3	1.4312 (17)	C11—H11	0.9300
S1—O2	1.4326 (16)	C12—C13	1.389 (3)
S1—N1	1.6407 (16)	C12—H12	0.9300
S1—C7	1.763 (2)	C13—C14	1.380 (3)
O1—C1	1.219 (2)	C13—H13	0.9300
N1—C1	1.379 (2)	N3—C15	1.343 (2)
C1—C2	1.491 (3)	N3—C19	1.346 (2)
C2—C7	1.374 (3)	N4—C21	1.483 (2)
C2—C3	1.389 (3)	N4—H4A	0.9000
C3—C4	1.382 (3)	N4—H4B	0.9000
C3—H3	0.9300	C15—C16	1.369 (3)
C4—C5	1.378 (3)	C15—H15	0.9300
C4—H4	0.9300	C16—C17	1.374 (3)
C5—C6	1.385 (3)	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.382 (3)
C6—C7	1.388 (3)	C17—H17	0.9300
C6—H6	0.9300	C18—C19	1.385 (3)
S2—O6	1.4300 (15)	C18—H18	0.9300
S2—O5	1.4317 (15)	C19—C20	1.502 (3)
S2—N2	1.6253 (16)	C20—C21	1.516 (3)
S2—C14	1.7543 (19)	C20—H20A	0.9700
O4—C8	1.215 (2)	C20—H20B	0.9700
N2—C8	1.383 (2)	C21—H21A	0.9700
C8—C9	1.486 (3)	C21—H21B	0.9700
C9—C14	1.380 (3)
N1—Zn1—N2	115.77 (6)	C11—C10—C9	118.4 (2)
N1—Zn1—N4	113.35 (7)	C11—C10—H10	120.8
N2—Zn1—N4	112.98 (6)	C9—C10—H10	120.8
N1—Zn1—N3	108.50 (6)	C10—C11—C12	121.3 (2)
N2—Zn1—N3	105.82 (6)	C10—C11—H11	119.3
N4—Zn1—N3	98.54 (6)	C12—C11—H11	119.3
O3—S1—O2	116.50 (11)	C11—C12—C13	121.2 (2)
O3—S1—N1	111.40 (9)	C11—C12—H12	119.4
O2—S1—N1	109.86 (10)	C13—C12—H12	119.4
O3—S1—C7	110.39 (10)	C14—C13—C12	116.5 (2)
O2—S1—C7	111.34 (9)	C14—C13—H13	121.8
N1—S1—C7	95.36 (9)	C12—C13—H13	121.8
C1—N1—S1	112.27 (13)	C9—C14—C13	122.91 (19)
C1—N1—Zn1	117.23 (12)	C9—C14—S2	108.21 (14)
S1—N1—Zn1	129.52 (9)	C13—C14—S2	128.87 (16)
O1—C1—N1	122.50 (18)	C15—N3—C19	118.90 (16)
O1—C1—C2	125.75 (17)	C15—N3—Zn1	119.78 (13)
N1—C1—C2	111.74 (16)	C19—N3—Zn1	121.32 (13)
C7—C2—C3	119.96 (18)	C21—N4—Zn1	114.11 (12)
C7—C2—C1	112.05 (17)	C21—N4—H4A	108.7
C3—C2—C1	127.96 (18)	Zn1—N4—H4A	108.7
C4—C3—C2	118.4 (2)	C21—N4—H4B	108.7
C4—C3—H3	120.8	Zn1—N4—H4B	108.7
C2—C3—H3	120.8	H4A—N4—H4B	107.6
C5—C4—C3	120.7 (2)	N3—C15—C16	123.06 (18)
C5—C4—H4	119.6	N3—C15—H15	118.5
C3—C4—H4	119.6	C16—C15—H15	118.5
C4—C5—C6	121.9 (2)	C15—C16—C17	118.4 (2)
C4—C5—H5	119.0	C15—C16—H16	120.8
C6—C5—H5	119.0	C17—C16—H16	120.8
C5—C6—C7	116.4 (2)	C16—C17—C18	119.32 (19)
C5—C6—H6	121.8	C16—C17—H17	120.3
C7—C6—H6	121.8	C18—C17—H17	120.3
C2—C7—C6	122.58 (19)	C17—C18—C19	119.67 (19)
C2—C7—S1	108.51 (14)	C17—C18—H18	120.2
C6—C7—S1	128.90 (17)	C19—C18—H18	120.2
O6—S2—O5	115.96 (11)	N3—C19—C18	120.66 (18)
O6—S2—N2	111.90 (10)	N3—C19—C20	117.63 (16)
O5—S2—N2	109.57 (9)	C18—C19—C20	121.71 (17)
O6—S2—C14	110.38 (9)	C19—C20—C21	114.76 (17)
O5—S2—C14	111.19 (10)	C19—C20—H20A	108.6
N2—S2—C14	96.11 (9)	C21—C20—H20A	108.6
C8—N2—S2	111.90 (13)	C19—C20—H20B	108.6
C8—N2—Zn1	118.90 (12)	C21—C20—H20B	108.6
S2—N2—Zn1	125.81 (9)	H20A—C20—H20B	107.6
O4—C8—N2	122.64 (18)	N4—C21—C20	111.84 (17)
O4—C8—C9	125.36 (19)	N4—C21—H21A	109.2
N2—C8—C9	111.96 (16)	C20—C21—H21A	109.2
C14—C9—C10	119.63 (19)	N4—C21—H21B	109.2
C14—C9—C8	111.77 (17)	C20—C21—H21B	109.2
C10—C9—C8	128.60 (19)	H21A—C21—H21B	107.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O5^i	0.90	2.15	2.952 (2)	147

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.