metal-organic compounds
Bis[2-(2-pyridylmethylamino)ethanesulfonato-κ3N,N′,O]zinc(II)
aDepartment of Chemistry, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
*Correspondence e-mail: dzx6281@126.com
The title mononuclear complex, [Zn(C8H11N2O3S)2], is a zinc salt of 2-(2-pyridylmethylamino)ethanesulfonic acid (Hpmt). The ZnII ion is located on an inversion centre and is octahedrally surrounded by four N and two O atoms. The deprotonated pmt− anion coordinates in a facial arrangement through its two N atoms and one of the sulfonate O atoms. The crystal packing is determined by intermolecular N—H⋯O and C—H⋯O hydrogen bonds.
Related literature
For the structures of the Co(II) and Ni(II) analogues, see: Li et al. (2008); Liao et al. (2007). For the preparation of the Hpmt ligand, see: Li et al. (2006).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809019990/at2794sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809019990/at2794Isup2.hkl
The ligand Hpmt was prepared according to the method of Li et al., 2006. To the solution of Hpmt (2.0 mmol, 0.43 g) in water (25 ml), solid ZnCl2 (1 mmol, 0.14 g) was added. The resulting mixture was stirred at 333 K for 5 h, then cooled to room temperature. After filtration, the filtrate was left to stand at room temperature for slow evaporation. Colourless block-shaped crystals suitable for X-ray diffraction were obtained in a yield of 42%. Analysis, found: C 38.66, H 4.37, N 11.32, S 12.95%; C16H22N4O6S2Zn requires: C 38.72, H 4.44, N 11.29, S 12.90%. IR (KBr, ν, cm-1): 771.3 [γ(C=C—H)], 746.5(γCH2); 1190.3, 1151.4, 1038.8(ν SO3-); 1607.2, 1572.3(ν C=C + ν C=N); 3198.2(ν N—H).
H atoms bonded to C were positioned geometrically with C—H distance of 0.93–0.97 Å, and treated as riding atoms, with Uiso(H) =1.2Ueq(C). The N—H hydrogen atom was located in a difference Fourier map and refined isotropically.
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. Atoms with the suffix A are at the symmetry position (-x, -y, -z). | |
Fig. 2. The hydrogen bonding interactions in (I) (dashed lines) projected in bc plane. H atoms on C atoms have been omitted. |
[Zn(C8H11N2O3S)2] | F(000) = 512 |
Mr = 495.87 | Dx = 1.565 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4168 reflections |
a = 9.6288 (13) Å | θ = 2.8–28.2° |
b = 10.0047 (13) Å | µ = 1.41 mm−1 |
c = 11.3624 (15) Å | T = 291 K |
β = 105.965 (1)° | Block, colourless |
V = 1052.4 (2) Å3 | 0.50 × 0.39 × 0.29 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 2419 independent reflections |
Radiation source: fine-focus sealed tube | 2221 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→12 |
Tmin = 0.540, Tmax = 0.689 | k = −9→12 |
6318 measured reflections | l = −14→14 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0322P)2 + 0.3355P] where P = (Fo2 + 2Fc2)/3 |
2419 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
[Zn(C8H11N2O3S)2] | V = 1052.4 (2) Å3 |
Mr = 495.87 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6288 (13) Å | µ = 1.41 mm−1 |
b = 10.0047 (13) Å | T = 291 K |
c = 11.3624 (15) Å | 0.50 × 0.39 × 0.29 mm |
β = 105.965 (1)° |
Bruker APEXII CCD area-detector diffractometer | 2419 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2221 reflections with I > 2σ(I) |
Tmin = 0.540, Tmax = 0.689 | Rint = 0.012 |
6318 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.23 e Å−3 |
2419 reflections | Δρmin = −0.38 e Å−3 |
137 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.0000 | 0.5000 | 0.02437 (8) | |
S1 | 0.63235 (4) | 0.29294 (4) | 0.45567 (3) | 0.02858 (10) | |
O1 | 0.57188 (13) | 0.16226 (11) | 0.40792 (10) | 0.0375 (3) | |
O2 | 0.55332 (14) | 0.40018 (12) | 0.37950 (10) | 0.0428 (3) | |
O3 | 0.78676 (14) | 0.30037 (16) | 0.47547 (13) | 0.0573 (4) | |
N1 | 0.27433 (14) | 0.03618 (13) | 0.39160 (12) | 0.0309 (3) | |
N2 | 0.42452 (13) | 0.13247 (12) | 0.61609 (11) | 0.0274 (3) | |
C1 | 0.2143 (2) | 0.02195 (18) | 0.27020 (16) | 0.0412 (4) | |
H1 | 0.2677 | −0.0185 | 0.2232 | 0.049* | |
C2 | 0.0760 (2) | 0.0655 (3) | 0.2137 (2) | 0.0633 (6) | |
H2 | 0.0370 | 0.0549 | 0.1297 | 0.076* | |
C3 | −0.0031 (2) | 0.1249 (3) | 0.2834 (2) | 0.0746 (7) | |
H3 | −0.0961 | 0.1558 | 0.2468 | 0.090* | |
C4 | 0.05670 (19) | 0.1385 (2) | 0.4085 (2) | 0.0584 (5) | |
H4 | 0.0044 | 0.1775 | 0.4571 | 0.070* | |
C5 | 0.19633 (16) | 0.09248 (16) | 0.45981 (15) | 0.0350 (3) | |
C6 | 0.26892 (17) | 0.10136 (17) | 0.59524 (15) | 0.0360 (3) | |
H6A | 0.2233 | 0.1707 | 0.6313 | 0.043* | |
H6B | 0.2584 | 0.0171 | 0.6342 | 0.043* | |
C7 | 0.44409 (17) | 0.27835 (15) | 0.59923 (13) | 0.0303 (3) | |
H7A | 0.4184 | 0.3273 | 0.6639 | 0.036* | |
H7B | 0.3796 | 0.3066 | 0.5217 | 0.036* | |
C8 | 0.59850 (16) | 0.31189 (15) | 0.60131 (13) | 0.0292 (3) | |
H8A | 0.6637 | 0.2542 | 0.6599 | 0.035* | |
H8B | 0.6190 | 0.4034 | 0.6287 | 0.035* | |
H1N | 0.4634 (18) | 0.1133 (17) | 0.6913 (16) | 0.032 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02484 (13) | 0.02218 (13) | 0.02641 (12) | 0.00349 (8) | 0.00760 (9) | −0.00102 (8) |
S1 | 0.03239 (19) | 0.02599 (19) | 0.02848 (17) | 0.00050 (14) | 0.01027 (14) | 0.00143 (13) |
O1 | 0.0591 (7) | 0.0267 (6) | 0.0308 (5) | −0.0037 (5) | 0.0194 (5) | −0.0023 (4) |
O2 | 0.0672 (8) | 0.0301 (6) | 0.0319 (5) | 0.0094 (5) | 0.0148 (5) | 0.0068 (5) |
O3 | 0.0353 (7) | 0.0786 (11) | 0.0625 (8) | −0.0049 (6) | 0.0208 (6) | −0.0068 (7) |
N1 | 0.0272 (6) | 0.0305 (6) | 0.0330 (6) | 0.0024 (5) | 0.0051 (5) | 0.0010 (5) |
N2 | 0.0307 (6) | 0.0268 (6) | 0.0253 (6) | 0.0022 (5) | 0.0087 (5) | 0.0003 (5) |
C1 | 0.0404 (9) | 0.0424 (10) | 0.0366 (8) | −0.0027 (7) | 0.0035 (7) | 0.0020 (7) |
C2 | 0.0453 (11) | 0.0799 (16) | 0.0501 (11) | −0.0037 (11) | −0.0114 (9) | 0.0067 (11) |
C3 | 0.0310 (10) | 0.097 (2) | 0.0817 (16) | 0.0137 (11) | −0.0080 (10) | 0.0102 (15) |
C4 | 0.0270 (8) | 0.0691 (14) | 0.0786 (14) | 0.0112 (9) | 0.0137 (9) | 0.0001 (11) |
C5 | 0.0259 (7) | 0.0329 (8) | 0.0474 (9) | 0.0013 (6) | 0.0118 (6) | 0.0005 (7) |
C6 | 0.0327 (8) | 0.0387 (9) | 0.0430 (8) | 0.0013 (7) | 0.0210 (7) | −0.0030 (7) |
C7 | 0.0367 (8) | 0.0245 (7) | 0.0313 (7) | 0.0042 (6) | 0.0120 (6) | −0.0028 (6) |
C8 | 0.0348 (7) | 0.0268 (7) | 0.0241 (6) | −0.0009 (6) | 0.0048 (5) | −0.0029 (5) |
Zn1—N2 | 2.1336 (12) | C1—H1 | 0.9300 |
Zn1—N2i | 2.1336 (12) | C2—C3 | 1.376 (4) |
Zn1—O1 | 2.1465 (11) | C2—H2 | 0.9300 |
Zn1—O1i | 2.1465 (11) | C3—C4 | 1.386 (3) |
Zn1—N1i | 2.2130 (13) | C3—H3 | 0.9300 |
Zn1—N1 | 2.2130 (13) | C4—C5 | 1.388 (2) |
S1—O3 | 1.4431 (13) | C4—H4 | 0.9300 |
S1—O2 | 1.4549 (12) | C5—C6 | 1.508 (2) |
S1—O1 | 1.4727 (11) | C6—H6A | 0.9700 |
S1—C8 | 1.7825 (15) | C6—H6B | 0.9700 |
N1—C5 | 1.342 (2) | C7—C8 | 1.518 (2) |
N1—C1 | 1.349 (2) | C7—H7A | 0.9700 |
N2—C6 | 1.4841 (19) | C7—H7B | 0.9700 |
N2—C7 | 1.4908 (19) | C8—H8A | 0.9700 |
N2—H1N | 0.856 (17) | C8—H8B | 0.9700 |
C1—C2 | 1.380 (3) | ||
N2—Zn1—N2i | 180.0 | N1—C1—H1 | 119.0 |
N2—Zn1—O1 | 92.40 (5) | C2—C1—H1 | 119.0 |
N2i—Zn1—O1 | 87.60 (4) | C3—C2—C1 | 118.96 (19) |
N2—Zn1—O1i | 87.60 (5) | C3—C2—H2 | 120.5 |
N2i—Zn1—O1i | 92.40 (5) | C1—C2—H2 | 120.5 |
O1—Zn1—O1i | 180.0 | C2—C3—C4 | 119.55 (18) |
N2—Zn1—N1i | 101.93 (5) | C2—C3—H3 | 120.2 |
N2i—Zn1—N1i | 78.06 (5) | C4—C3—H3 | 120.2 |
O1—Zn1—N1i | 89.78 (5) | C3—C4—C5 | 118.7 (2) |
O1i—Zn1—N1i | 90.22 (5) | C3—C4—H4 | 120.7 |
N2—Zn1—N1 | 78.06 (5) | C5—C4—H4 | 120.7 |
N2i—Zn1—N1 | 101.94 (5) | N1—C5—C4 | 121.82 (16) |
O1—Zn1—N1 | 90.22 (5) | N1—C5—C6 | 115.98 (13) |
O1i—Zn1—N1 | 89.78 (5) | C4—C5—C6 | 122.19 (16) |
N1i—Zn1—N1 | 180.0 | N2—C6—C5 | 109.85 (12) |
O3—S1—O2 | 113.74 (9) | N2—C6—H6A | 109.7 |
O3—S1—O1 | 112.90 (8) | C5—C6—H6A | 109.7 |
O2—S1—O1 | 110.27 (7) | N2—C6—H6B | 109.7 |
O3—S1—C8 | 107.06 (8) | C5—C6—H6B | 109.7 |
O2—S1—C8 | 105.93 (7) | H6A—C6—H6B | 108.2 |
O1—S1—C8 | 106.36 (7) | N2—C7—C8 | 111.86 (12) |
S1—O1—Zn1 | 129.76 (6) | N2—C7—H7A | 109.2 |
C5—N1—C1 | 118.96 (14) | C8—C7—H7A | 109.2 |
C5—N1—Zn1 | 111.53 (10) | N2—C7—H7B | 109.2 |
C1—N1—Zn1 | 129.14 (12) | C8—C7—H7B | 109.2 |
C6—N2—C7 | 110.03 (12) | H7A—C7—H7B | 107.9 |
C6—N2—Zn1 | 105.77 (9) | C7—C8—S1 | 112.98 (10) |
C7—N2—Zn1 | 116.88 (9) | C7—C8—H8A | 109.0 |
C6—N2—H1N | 104.9 (12) | S1—C8—H8A | 109.0 |
C7—N2—H1N | 108.2 (12) | C7—C8—H8B | 109.0 |
Zn1—N2—H1N | 110.4 (11) | S1—C8—H8B | 109.0 |
N1—C1—C2 | 122.03 (19) | H8A—C8—H8B | 107.8 |
O3—S1—O1—Zn1 | 103.94 (10) | N1—Zn1—N2—C7 | −90.09 (10) |
O2—S1—O1—Zn1 | −127.61 (9) | C5—N1—C1—C2 | 1.1 (3) |
C8—S1—O1—Zn1 | −13.19 (11) | Zn1—N1—C1—C2 | −171.19 (16) |
N2—Zn1—O1—S1 | 33.74 (10) | N1—C1—C2—C3 | −0.2 (3) |
N2i—Zn1—O1—S1 | −146.26 (10) | C1—C2—C3—C4 | −0.7 (4) |
N1i—Zn1—O1—S1 | −68.19 (10) | C2—C3—C4—C5 | 0.7 (4) |
N1—Zn1—O1—S1 | 111.81 (10) | C1—N1—C5—C4 | −1.1 (3) |
N2—Zn1—N1—C5 | −14.41 (11) | Zn1—N1—C5—C4 | 172.45 (15) |
N2i—Zn1—N1—C5 | 165.59 (11) | C1—N1—C5—C6 | 178.25 (15) |
O1—Zn1—N1—C5 | −106.82 (11) | Zn1—N1—C5—C6 | −8.16 (17) |
O1i—Zn1—N1—C5 | 73.18 (11) | C3—C4—C5—N1 | 0.3 (3) |
N2—Zn1—N1—C1 | 158.35 (15) | C3—C4—C5—C6 | −179.1 (2) |
N2i—Zn1—N1—C1 | −21.65 (15) | C7—N2—C6—C5 | 80.21 (15) |
O1—Zn1—N1—C1 | 65.94 (14) | Zn1—N2—C6—C5 | −46.87 (14) |
O1i—Zn1—N1—C1 | −114.06 (14) | N1—C5—C6—N2 | 37.7 (2) |
O1—Zn1—N2—C6 | 122.46 (10) | C4—C5—C6—N2 | −142.93 (17) |
O1i—Zn1—N2—C6 | −57.54 (10) | C6—N2—C7—C8 | −171.67 (11) |
N1i—Zn1—N2—C6 | −147.26 (9) | Zn1—N2—C7—C8 | −51.08 (14) |
N1—Zn1—N2—C6 | 32.74 (9) | N2—C7—C8—S1 | 85.42 (13) |
O1—Zn1—N2—C7 | −0.37 (10) | O3—S1—C8—C7 | −168.32 (11) |
O1i—Zn1—N2—C7 | 179.63 (10) | O2—S1—C8—C7 | 69.97 (12) |
N1i—Zn1—N2—C7 | 89.91 (10) | O1—S1—C8—C7 | −47.37 (12) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O2ii | 0.855 (18) | 2.079 (18) | 2.9259 (17) | 170.6 (16) |
C1—H1···O2iii | 0.93 | 2.47 | 3.388 (2) | 169 |
C4—H4···O3iv | 0.93 | 2.49 | 3.324 (2) | 150 |
C6—H6B···O1i | 0.97 | 2.56 | 3.056 (2) | 112 |
C8—H8B···O2v | 0.97 | 2.56 | 3.265 (2) | 130 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C8H11N2O3S)2] |
Mr | 495.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 9.6288 (13), 10.0047 (13), 11.3624 (15) |
β (°) | 105.965 (1) |
V (Å3) | 1052.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.50 × 0.39 × 0.29 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.540, 0.689 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6318, 2419, 2221 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.062, 1.07 |
No. of reflections | 2419 |
No. of parameters | 137 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.38 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Zn1—N2 | 2.1336 (12) | Zn1—N1 | 2.2130 (13) |
Zn1—O1 | 2.1465 (11) | ||
N2—Zn1—O1 | 92.40 (5) | O1—Zn1—N1i | 89.78 (5) |
N2i—Zn1—O1 | 87.60 (4) | N2—Zn1—N1 | 78.06 (5) |
N2—Zn1—N1i | 101.93 (5) | O1—Zn1—N1 | 90.22 (5) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O2ii | 0.855 (18) | 2.079 (18) | 2.9259 (17) | 170.6 (16) |
C1—H1···O2iii | 0.9300 | 2.4700 | 3.388 (2) | 169.00 |
C4—H4···O3iv | 0.9300 | 2.4900 | 3.324 (2) | 150.00 |
C6—H6B···O1i | 0.9700 | 2.5600 | 3.056 (2) | 112.00 |
C8—H8B···O2v | 0.9700 | 2.5600 | 3.265 (2) | 130.00 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Acknowledgements
This work was supported financially by the National Natural Science Foundation of China (No. 20771054).
References
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, J.-X., Jiang, Y.-M. & Li, H.-Y. (2006). Acta Cryst. E62, m2984–m2986. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, J.-X., Jiang, Y.-M. & Lian, B.-R. (2008). J. Chem. Crystallogr. 38, 711–715. Web of Science CSD CrossRef CAS Google Scholar
Liao, B.-L., Li, J.-X. & Jiang, Y.-M. (2007). Acta Cryst. E63, m1974. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The complex (I) is isostructural with its analogues [Co(C8H11N2O3S)2] (Li et al., 2006), [Ni(C8H11N2O3S)2] (Liao et al., 2007) and [Cu(C8H11N2O3S)2].2H2O (Li et al., 2008), whose structures have been described in detail. The six-coordinate ZnII ion locates on a centre of symmetry with two deprotonated pmt- anions coordinate in a tridentate facial arrangement with its three donor atoms (Fig.1). The bond lengths and angles of (I) are in good agreement with its Co(II) and Ni(II) analogues (Table 1).
The N—H donor and S═O acceptor groups of the pmt ions are involved in hydrogen bonding interactions and forms a two-dimensional network in the bc plane (Table 2 and Fig. 2).