data reports Bis{2-[({[3-(dimethylazaniumyl)propyl]imino}- methyl)phenyl]sulfanido}nickel(ii) tetraphenylborate Structure description

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1 ISSN Bis{2-[({[3-(dimethylazaniumyl)propyl]imino}- methyl)phenyl]sulfanido}nickel(ii) tetraphenylborate Alexandra Meloccaro, Joshua R. Zimmerman and David M. Eichhorn* Received 25 June 2017 Accepted 19 July 2017 Edited by R. J. Butcher, Howard University, USA Keywords: crystal structure; nickel complex. Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS , USA. *Correspondence In the title compound, [Ni(C 12 H 18 N 2 S) 2 ](C 24 H 20 B) 2, the Ni II atom is coordinated by two ligands via the thiolate S and the imine N atoms. The amine N atoms are protonated and interact with the phenyl rings of the BPh 4 anions. CCDC reference: Structural data: full structural data are available from iucrdata.iucr.org Structure description We have previously published the reaction of 2,2 0 -dithiodibenzaldehyde with NiCl 2 and N,N-dimethylethylenediamine to produce a nickel complex of a tridentate ligand in which the Ni is coordinated by the three potential donor atoms (imine N, amine N, and thiolate S) of the ligand with the square-planar Ni coordination sphere completed by a Cl ligand. When Ni(BPh 4 ) 2 was used as the nickel source, a related species was isolated in which the fourth coordination site is occupied by a thiolate derived from the tridentate ligand. (Zimmerman, et al., 2011) In an analogous reaction using N,N-dimethylpropylenediamine, the title complex was isolated in which the potentially tridentate ligand utilizes only the imine N and thiolate S atoms to bind to Ni (Table 1). Two ligands coordinate to the Ni atom, related to each other by a crystallographic twofold rotation axis (Fig. 1). The coordination around Ni deviates somewhat from ideal square planar, with the chelate rings of the two ligands rotated by (9) with respect to each other. The amine N atoms are protonated, with each proton participating in a hydrogen bond with a phenyl ring of one BPh 4 anion (Fig. 2, Table 2). Synthesis and crystallization The title compound was synthesized and crystallized by layering a solution of 0.10 g (0.90 mmol) of N,N-dimethylpropylenediamine and g (1.0 mmol) of [Ni(BPh 4 ) 2 ]in 20 ml of ethyl acetate on top of a solution of g (0.45 mmol) of 2,2 0 -dithiodibenzaldehyde in 10 ml of dichloromethane. 1of3

2 Table 1 Selected geometric parameters (Å, ). Ni1 S (8) Ni1 N (2) S1 Ni1 S1 i (4) N1 Ni1 S (7) N1 Ni1 S1 i (7) N1 i Ni1 S1 i (7) N1 i Ni1 S (7) N1 i Ni1 N (13) Symmetry code: (i) x þ 1; y; z þ 3 2. Table 2 Hydrogen-bond geometry (Å, ). Cg is the centroid of the C25 C30 ring. D HA D H HA DA D HA N2 H2Cg (3) 171 Table 3 Experimental details. Figure 1 The molecular structure of the cation in the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. Refinement Crystal data, data collection and structure refinement details are summarized in Table 3. Acknowledgements JRZ acknowledges support from the Graduate Assistance in Areas of National Need program of the US Department of Crystal data Chemical formula [Ni(C 12 H 18 N 2 S) 2 ](C 24 H 20 B) 2 M r Crystal system, space group Monoclinic, C2/c Temperature (K) 150 a, b, c (Å) (2), (14), (5) ( ) (4) V (Å 3 ) (14) Z 4 Radiation type Mo K (mm 1 ) 0.45 Crystal size (mm) Data collection Diffractometer Bruker APEXII CCD Absorption correction Numerical (SADABS; Bruker, 2012) T min, T max 0.599, No. of measured, independent and 30373, 6401, 4454 observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.054, 0.109, 1.05 No. of reflections 6401 No. of parameters 368 H-atom treatment H-atom parameters constrained max, min (e Å 3 ) 0.30, 0.71 Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015), XL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009). Education. DME acknowledges support from the National Center for Research Resources NIH COBRE Award P20 RR Figure 2 Part of the crystal structure of the title compound showing interactions between the protonated amine groups on the cation and the BPh 4 anions, indicated by red lines connecting the N H hydrogen atom and the orange sphere representing the centroid of the phenyl ring. Funding information Funding for this research was provided by: Kansas IDeA Network of Biomedical Research Excellence. References Bruker (2012). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. 2of3 Meloccaro et al. [Ni(C 12 H 18 N 2 S) 2 ](C 24 H 20 B) 2

3 Bruker (2013). APEX and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, Sheldrick, G. M. (2008). Acta Cryst. A64, Sheldrick, G. M. (2015). Acta Cryst. A71, 3 8. Zimmerman, J. R., Smucker, B. W., Dain, R. P., Van Stipdonk, M. J. & Eichhorn, D. M. (2011). Inorg. Chim. Acta, 373, Meloccaro et al. [Ni(C 12 H 18 N 2 S) 2 ](C 24 H 20 B) 2 3of3

4 full crystallographic data [ Bis{2-[({[3-(dimethylazaniumyl)propyl]imino}methyl)phenyl]sulfanido}nickel(II) tetraphenylborate Alexandra Meloccaro, Joshua R. Zimmerman and David M. Eichhorn Bis{2-[({[3-(dimethylazaniumyl)propyl]imino}methyl)phenyl]sulfanido}nickel(II) tetraphenylborate Crystal data [Ni(C 12 H 18 N 2 S 2 ) 2 ](C 24 H 20 B) 2 M r = Monoclinic, C2/c a = (2) Å b = (14) Å c = (5) Å β = (4) V = (14) Å 3 Z = 4 F(000) = 2424 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 4652 reflections θ = µ = 0.45 mm 1 T = 150 K Block, violet mm Data collection Bruker APEXII CCD diffractometer Radiation source: sealed X-ray tube Graphite monochromator Detector resolution: 5.6 pixels mm -1 φ and ω scans Absorption correction: numerical (SADABS; Bruker, 2012) T min = 0.599, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 368 parameters 0 restraints Primary atom site location: dual measured reflections 6401 independent reflections 4454 reflections with I > 2σ(I) R int = θ max = 27.1, θ min = 3.1 h = k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.029P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.30 e Å 3 Δρ min = 0.71 e Å 3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. data-1

5 Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups, All N(H) groups At 1.5 times of: All C(H,H,H) groups 2.a Ternary CH refined with riding coordinates: N2(H2) 2.b Secondary CH2 refined with riding coordinates: C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B) 2.c Aromatic/amide H refined with riding coordinates: C18(H18), C3(H3), C17(H17), C15(H15), C1(H1), C16(H16), C14(H14), C6(H6), C32(H32), C5(H5), C4(H4), C33(H33), C34(H34), C36(H36), C35(H35), C24(H24), C26(H26), C23(H23), C20(H20), C21(H21), C30(H30), C22(H22), C29(H29), C27(H27), C28(H28) 2.d Idealised Me refined as rotating group: C11(H11A,H11B,H11C), C12(H12A,H12B,H12C) Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Ni (5) (13) S (4) (7) (2) (18) N (13) (2) (6) (5) N (14) (2) (6) (6) H * C (16) (3) (7) (6) H * C (17) (3) (8) (7) H * C (16) (3) (7) (6) C (18) (3) (8) (7) H * C (19) (3) (8) (7) H * C (17) (2) (7) (6) C (17) (3) (7) (6) H * C (16) (3) (7) (6) C (19) (3) (8) (6) H * C (17) (3) (8) (6) H * C (17) (3) (8) (7) H * C (16) (3) (7) (6) C (16) (3) (8) (6) H * C (18) (3) (8) (7) H * C (16) (3) (8) (6) data-2

6 C (17) (3) (7) (6) H8A * H8B * C (16) (3) (7) (6) C (17) (3) (8) (7) H * C (18) (3) (8) (7) H * C (18) (3) (8) (7) H * C (18) (3) (7) (6) H * C (18) (3) (8) (7) H * C (17) (3) (8) (6) H * C (17) (3) (8) (6) H * C (19) (3) (8) (7) H * C (17) (3) (7) (6) H * C (17) (3) (7) (6) H9A * H9B * C (18) (3) (8) (7) H * C (19) (3) (8) (7) H * C (2) (3) (8) (8) H * C (18) (3) (8) (7) H10A * H10B * C (2) (3) (10) (8) H * C (19) (3) (9) (8) H * C (2) (3) (9) (8) H * C (2) (3) (9) (8) H11A * H11B * H11C * C (2) (4) (10) (10) H12A * H12B * H12C * data-3

7 B (19) (3) (9) (7) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Ni (3) (2) (3) (2) S (4) (3) (4) (3) (3) (3) N (12) (11) (12) (9) (10) (9) N (14) (14) (14) (11) (11) (11) C (14) (13) (15) (11) (12) (12) C (15) (15) (17) (12) (13) (13) C (14) (13) (15) (11) (12) (11) C (17) (15) (16) (12) (14) (12) C (17) (14) (16) (13) (13) (13) C (15) (13) (15) (11) (12) (11) C (15) (13) (15) (11) (12) (12) C (14) (13) (14) (11) (11) (11) C (18) (14) (14) (14) (13) (12) C (16) (15) (16) (12) (13) (12) C (16) (15) (17) (12) (13) (13) C (14) (14) (14) (12) (11) (12) C (16) (15) (15) (12) (12) (12) C (16) (18) (16) (15) (13) (14) C (14) (14) (15) (11) (12) (12) C (16) (13) (15) (11) (12) (11) C (14) (14) (15) (11) (12) (11) C (16) (18) (16) (13) (13) (14) C (15) (16) (18) (13) (13) (14) C (16) (16) (17) (13) (13) (13) C (15) (14) (15) (12) (12) (12) C (18) (15) (16) (13) (14) (12) C (16) (15) (15) (12) (13) (12) C (16) (15) (16) (12) (13) (12) C (19) (17) (18) (14) (15) (14) C (15) (15) (15) (12) (12) (12) C (16) (15) (16) (12) (13) (12) C (17) (19) (16) (15) (13) (14) C (18) (16) (18) (14) (14) (14) C (18) (2) (18) (16) (15) (15) C (17) (16) (16) (13) (13) (13) C (2) (18) (2) (15) (16) (16) C (18) (15) (2) (13) (16) (14) C (19) (15) (2) (15) (17) (15) C (2) (18) (2) (16) (16) (15) C (2) (2) (2) (19) (17) (2) B (17) (15) (17) (13) (13) (13) data-4

8 Geometric parameters (Å, º) Ni1 S (8) C25 C (4) Ni1 S1 i (8) C25 B (4) Ni1 N1 i (2) C8 H8A Ni1 N (2) C8 H8B S1 C (3) C8 C (4) N1 C (3) C4 H N1 C (3) C33 H N2 H C33 C (4) N2 C (3) C34 H N2 C (4) C34 C (4) N2 C (4) C36 H C18 H C36 C (4) C18 C (4) C35 H C18 C (4) C24 H C3 H C24 C (4) C3 C (4) C26 H C3 C (4) C26 C (4) C2 C (4) C23 H C2 C (4) C23 C (4) C17 H C20 H C17 C (4) C20 C (4) C15 H C9 H9A C15 C (4) C9 H9B C15 C (4) C9 C (4) C13 C (4) C21 H C13 B (4) C21 C (4) C1 H C30 H C31 C (4) C30 C (4) C31 C (4) C22 H C31 B (4) C10 H10A C16 H C10 H10B C14 H C29 H C6 H C29 C (4) C6 C (4) C27 H C6 C (4) C27 C (4) C19 C (4) C28 H C19 C (4) C11 H11A C19 B (4) C11 H11B C32 H C11 H11C C32 C (4) C12 H12A C5 H C12 H12B C5 C (4) C12 H12C C25 C (4) S1 Ni1 S1 i (4) C32 C33 H N1 Ni1 S1 i (7) C34 C33 C (3) data-5

9 N1 i Ni1 S (7) C34 C33 H N1 Ni1 S (7) C33 C34 H N1 i Ni1 S1 i (7) C33 C34 C (3) N1 i Ni1 N (13) C35 C34 H C7 S1 Ni (9) C31 C36 H C1 N1 Ni (19) C35 C36 C (3) C1 N1 C (2) C35 C36 H C8 N1 Ni (16) C34 C35 C (3) C10 N2 H C34 C35 H C11 N2 H C36 C35 H C11 N2 C (2) C19 C24 H C12 N2 H C23 C24 C (3) C12 N2 C (2) C23 C24 H C12 N2 C (3) C25 C26 H C17 C18 H C27 C26 C (3) C17 C18 C (3) C27 C26 H C13 C18 H C24 C23 H C2 C3 H C24 C23 C (3) C4 C3 H C22 C23 H C4 C3 C (3) C19 C20 H C3 C2 C (2) C21 C20 C (3) C3 C2 C (2) C21 C20 H C7 C2 C (2) C8 C9 H9A C18 C17 H C8 C9 H9B C16 C17 C (3) H9A C9 H9B C16 C17 H C10 C9 C (2) C16 C15 H C10 C9 H9A C16 C15 C (3) C10 C9 H9B C14 C15 H C20 C21 H C18 C13 C (2) C22 C21 C (3) C18 C13 B (2) C22 C21 H C14 C13 B (2) C25 C30 H N1 C1 C (2) C29 C30 C (3) N1 C1 H C29 C30 H C2 C1 H C23 C22 H C32 C31 B (2) C21 C22 C (3) C36 C31 C (2) C21 C22 H C36 C31 B (2) N2 C10 C (2) C17 C16 H N2 C10 H10A C15 C16 C (3) N2 C10 H10B C15 C16 H C9 C10 H10A C15 C14 C (3) C9 C10 H10B C15 C14 H H10A C10 H10B C13 C14 H C30 C29 H C5 C6 H C28 C29 C (3) C5 C6 C (3) C28 C29 H C7 C6 H C26 C27 H C24 C19 B (2) C28 C27 C (3) data-6

10 C20 C19 C (2) C28 C27 H C20 C19 B (2) C29 C28 H C31 C32 H C27 C28 C (3) C33 C32 C (3) C27 C28 H C33 C32 H N2 C11 H11A C6 C5 H N2 C11 H11B C6 C5 C (3) N2 C11 H11C C4 C5 H H11A C11 H11B C26 C25 B (2) H11A C11 H11C C30 C25 C (2) H11B C11 H11C C30 C25 B (2) N2 C12 H12A N1 C8 H8A N2 C12 H12B N1 C8 H8B N2 C12 H12C N1 C8 C (2) H12A C12 H12B H8A C8 H8B H12A C12 H12C C9 C8 H8A H12B C12 H12C C9 C8 H8B C13 B1 C (2) C2 C7 S (2) C31 B1 C (2) C6 C7 S (2) C31 B1 C (2) C6 C7 C (2) C19 B1 C (2) C3 C4 C (3) C19 B1 C (2) C3 C4 H C19 B1 C (2) C5 C4 H Symmetry code: (i) x+1, y, z+3/2. Hydrogen-bond geometry (Å, º) Cg is the centroid of the C25 C30 ring. D H A D H H A D A D H A N2 H2 Cg (3) 171 data-7