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The title complex, (1RS,3SR,8SR,10RS-3,5,7,7,10,12,12,14-octa­methyl-1,4,8,11-tetraazacyclotetra­deca-4,11-diene-κ4N1,4,8,11)­nickel(II) bis­(thio­cyanate), [Ni(C18H36N4)](NCS)2, has a centrosymmetrical square-planar singlet ground state nickel(II) cation, with Ni—Namine = 1.940 (1) Å and Ni—Nimine = 1.921 (1) Å. The C-3 methyl substituent is axially oriented. The thio­cyanate N atom is hydrogen bonded to the NH group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680504078X/hg6270sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680504078X/hg6270Isup2.hkl
Contains datablock I

CCDC reference: 296567

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.023
  • wR factor = 0.061
  • Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N1 .. 5.88 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - N4 .. 6.59 su PLAT412_ALERT_2_C Short Intra XH3 .. XHn H3 .. H51A .. 1.87 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The azamacrocyle cations C-meso- and C-rac-(Me8[14]diene)nickel(II) (Me8[14]diene = 3,5,7,7,10,12,12,14-octamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene), formed by reaction of tris(rac-propane-1,2-diamine)nickel(II) compounds with acetone, were separated by fractional crystallization, see the Scheme (Blight & Curtis, 1962; Curtis, 1973). Compounds of the C-meso isomer can also be prepared from salts [H2(C-meso-Me8[14]diene)]X2, formed by reaction of mono-protonated salts [H(rac-propane-1,2-diamine)]X, X = ClO4, Br, NCS, etc, with acetone (Curtis, 1973).

The structure of yellow, singlet ground state, [Ni(C-meso-Me8[14]diene)](CNS)2, is reported here. It is comprised of a centrosymmetrical square-planar cation [Ni(C-meso-Me8[14]diene)]2+ with the thiocyanate ion located off the tetragonal axis (with closest approach Ni—NNCS = 4.054 Å) and hydrogen bonded to the N—H group. The closest axial approach to the nickel is by the imine methyl group of another cation with Ni···H51B = 3.68 Å.

The nickel(II) ion is coordinated by the four N-atoms of the macrocycle, with the Ni—N distance 0.029 (2) Å shorter for the imine than the secondary amine N atom, see Fig. 1 and Table 1. The propane-1,2-diamine residue methyl substituent is at ring position 3, adjacent to the imine N atom, axially oriented on the same side of the molecular plane as the N1—H atom, on the opposite side to the axial component of the gem dimethyl group, (C72). Displacements of atoms from the NiN4 plane are: C2, −0.476 (2); C3, 0.1503 (2); C31, 1.627 (2); C5, −0.068 (2); C51, −0.109 (3); C6, −0.059 (3); C7, 0.703 (2); C71, 0.612 (3); C72, 2.167 (2) Å.

The structurally characterized compound of the C-rac isomeric cation, [Ni(C-rac-Me8[14]diene)](ClO4)2, (Swann, et al., 1972) has approximate twofold symmetry, with the C3 and C10 methyl substituents axially oriented on the same side of the molecular plane, with the axially oriented components of the C7 and C14 gem-dimethyl groups oriented towards the other side of the plane, with mean distances Ni—Namine = 1.93 (1) and Ni—Nimine = 1.89 (1) Å.

The compound [Cu(C-meso-Me8[14]diene)](ClO4)2·2H2O (Hazari et al., 1999) has the same configuration and similar conformation of the macrocycle to the title compound, with Cu—Namine = 2.010 (2), Cu—Nimine = 1.985 (3) Å, with perchlorate oxygen atoms in approximate axial sites with Cu—O = 2.779 (3) Å.

The structures of thiocyanate complexes of (5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-5,11- diene)nickel(II), [Ni(Me6[14]diene)]2+, (Curtis & Curtis, 1966) have been determined. The structure of N-meso-[Ni(Me6[14]diene)](SCN)2 (Hanic & Miklos, 1972) is similar to that of the title complex, with mean distances Ni—Namine = 1.92 and Ni—Nimine = 1.88 Å, while N-rac-[Ni(Me6[14]diene)(NCS)]ClO4 (Shen et al., 1999) has an unusual singlet ground state five-coordinate structure with mean distances Ni—Namine = 2.045 (8), Ni—Nimine = 2.015 (8) and Ni—NNCS = 2.221 (5) Å.

The structure of trans-[Co(C-meso-Me8[14]diene)Cl2]ClO4 (Lu et al., 1992) and the space group and cell parameters of [Ni(C-meso-Me8[14]diene)](ClO4)2 (Curtis et al., 1969) have been reported.

Experimental top

Excess of NaCNS was added to a hot saturated aqueous solution of orange [Ni(C-meso-L)](ClO4)2. (What is L?) The yellow thiocyanate salt was filtered off from the cold solution and recrystallized from methanol.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.96 Å and were included in the least squares refinement as riding on their carrier atoms, with Uiso(H) = 1.2Ueq of the corresponding carrier atom.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3.2 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. [Ni(C-meso-Me8[14]diene))(NCS)2 drawn with displacement ellipsoids at 50% probability level, with H atoms shown as circles of arbitrary radii.
(1RS,3SR,8SR,10RS-3,5,7,7,10,12,12,14-octamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene-κ4N1,4,8,11)nickel(II) bis(thiocyanate) top
Crystal data top
[Ni(C18H36N4)](NCS)2Z = 1
Mr = 483.38F(000) = 258
Triclinic, P1Dx = 1.412 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3383 (6) ÅCell parameters from 2683 reflections
b = 8.0955 (6) Åθ = 2.8–28.3°
c = 10.2042 (8) ŵ = 1.06 mm1
α = 69.917 (1)°T = 273 K
β = 86.852 (1)°Block, yellow
γ = 88.965 (1)°0.40 × 0.20 × 0.18 mm
V = 568.48 (8) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2393 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.008
Graphite monochromatorθmax = 28.4°, θmin = 2.1°
ϕ and ω scansh = 99
3335 measured reflectionsk = 810
2472 independent reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0311P)2 + 0.291P]
where P = (Fo2 + 2Fc2)/3
2472 reflections(Δ/σ)max = 0.001
137 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Ni(C18H36N4)](NCS)2γ = 88.965 (1)°
Mr = 483.38V = 568.48 (8) Å3
Triclinic, P1Z = 1
a = 7.3383 (6) ÅMo Kα radiation
b = 8.0955 (6) ŵ = 1.06 mm1
c = 10.2042 (8) ÅT = 273 K
α = 69.917 (1)°0.40 × 0.20 × 0.18 mm
β = 86.852 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2393 reflections with I > 2σ(I)
3335 measured reflectionsRint = 0.008
2472 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.06Δρmax = 0.38 e Å3
2472 reflectionsΔρmin = 0.25 e Å3
137 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
xyzUiso*/Ueq
Ni10.50000.50000.50000.00971 (8)
N10.50725 (14)0.47718 (14)0.69517 (11)0.0120 (2)
H10.57790.56740.69710.014*
N40.27883 (15)0.63089 (14)0.49926 (11)0.0128 (2)
C50.16839 (17)0.69536 (17)0.40027 (14)0.0136 (2)
C60.20809 (18)0.68678 (18)0.25715 (14)0.0153 (3)
H6A0.14840.78580.19060.018*
H6B0.15260.58050.25380.018*
C20.32061 (18)0.51070 (18)0.74570 (14)0.0155 (3)
H2A0.32680.53750.83100.019*
H2B0.24480.40720.76540.019*
C70.40883 (18)0.68814 (17)0.20850 (13)0.0135 (3)
C510.00540 (18)0.79061 (19)0.41374 (14)0.0180 (3)
H51A0.05390.74610.50870.027*
H51B0.09260.77250.35320.027*
H51C0.01920.91410.38800.027*
C310.3210 (2)0.84069 (18)0.62284 (15)0.0192 (3)
H31A0.45140.83670.61020.029*
H31B0.28930.86490.70700.029*
H31C0.27310.93170.54450.029*
C720.5068 (2)0.85158 (18)0.21209 (15)0.0180 (3)
H72A0.51700.84410.30740.027*
H72B0.43850.95470.16360.027*
H72C0.62650.85850.16760.027*
C710.41348 (19)0.68588 (19)0.05837 (13)0.0172 (3)
H71A0.53730.69760.02080.026*
H71B0.34220.78180.00170.026*
H71C0.36390.57680.05880.026*
C30.24005 (18)0.66384 (17)0.63368 (13)0.0147 (3)
H30.10770.66600.65210.018*
N200.76296 (17)0.74108 (17)0.72386 (13)0.0221 (3)
C200.83366 (18)0.77659 (18)0.81043 (14)0.0164 (3)
S200.93355 (5)0.83066 (5)0.93031 (4)0.02264 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01007 (12)0.01126 (12)0.00886 (12)0.00289 (8)0.00114 (8)0.00484 (9)
N10.0118 (5)0.0135 (5)0.0116 (5)0.0027 (4)0.0011 (4)0.0054 (4)
N40.0131 (5)0.0148 (5)0.0115 (5)0.0025 (4)0.0003 (4)0.0060 (4)
C50.0132 (6)0.0133 (6)0.0147 (6)0.0012 (5)0.0004 (5)0.0054 (5)
C60.0143 (6)0.0197 (6)0.0130 (6)0.0059 (5)0.0037 (5)0.0069 (5)
C20.0134 (6)0.0207 (7)0.0128 (6)0.0037 (5)0.0006 (5)0.0067 (5)
C70.0152 (6)0.0152 (6)0.0102 (6)0.0039 (5)0.0023 (5)0.0044 (5)
C510.0152 (6)0.0232 (7)0.0153 (6)0.0071 (5)0.0023 (5)0.0065 (5)
C310.0221 (7)0.0176 (7)0.0213 (7)0.0045 (5)0.0029 (6)0.0108 (6)
C720.0221 (7)0.0141 (6)0.0173 (6)0.0009 (5)0.0006 (5)0.0047 (5)
C710.0198 (6)0.0212 (7)0.0105 (6)0.0049 (5)0.0018 (5)0.0052 (5)
C30.0145 (6)0.0177 (6)0.0133 (6)0.0031 (5)0.0008 (5)0.0075 (5)
N200.0209 (6)0.0253 (6)0.0234 (6)0.0027 (5)0.0022 (5)0.0127 (5)
C200.0136 (6)0.0151 (6)0.0186 (6)0.0012 (5)0.0033 (5)0.0043 (5)
S200.02041 (18)0.0299 (2)0.01789 (18)0.00037 (14)0.00455 (14)0.00796 (15)
Geometric parameters (Å, º) top
Ni1—N41.921 (1)C7—C721.5297 (18)
Ni1—N4i1.9212 (11)C7—C711.5368 (17)
Ni1—N11.940 (1)C51—H51A0.9600
Ni1—N1i1.9395 (11)C51—H51B0.9600
N1—C21.4901 (16)C51—H51C0.9600
N1—C7i1.5066 (16)C31—C31.5263 (19)
N1—H10.9100C31—H31A0.9600
N4—C51.289 (2)C31—H31B0.9600
N4—C31.4963 (16)C31—H31C0.9600
C5—C61.4983 (18)C72—H72A0.9600
C5—C511.5027 (18)C72—H72B0.9600
C6—C71.5275 (18)C72—H72C0.9600
C6—H6A0.9700C71—H71A0.9600
C6—H6B0.9700C71—H71B0.9600
C2—C31.5058 (18)C71—H71C0.9600
C2—H2A0.9700C3—H30.9800
C2—H2B0.9700N20—C201.167 (2)
C7—N1i1.5066 (16)C20—S201.644 (2)
N4—Ni1—N4i180.00 (7)C6—C7—C71106.91 (10)
N4—Ni1—N186.05 (5)C72—C7—C71110.20 (11)
N4i—Ni1—N193.95 (5)C5—C51—H51A109.5
N4—Ni1—N1i93.95 (5)C5—C51—H51B109.5
N4i—Ni1—N1i86.05 (5)H51A—C51—H51B109.5
N1—Ni1—N1i180.0C5—C51—H51C109.5
C2—N1—C7i112.68 (10)H51A—C51—H51C109.5
C2—N1—Ni1108.42 (8)H51B—C51—H51C109.5
C7i—N1—Ni1117.01 (8)C3—C31—H31A109.5
C2—N1—H1106.0C3—C31—H31B109.5
C7i—N1—H1106.0H31A—C31—H31B109.5
Ni1—N1—H1106.0C3—C31—H31C109.5
C5—N4—C3118.29 (11)H31A—C31—H31C109.5
C5—N4—Ni1129.2 (1)H31B—C31—H31C109.5
C3—N4—Ni1112.44 (8)C7—C72—H72A109.5
N4—C5—C6121.8 (1)C7—C72—H72B109.5
N4—C5—C51124.4 (1)H72A—C72—H72B109.5
C6—C5—C51113.72 (11)C7—C72—H72C109.5
C5—C6—C7116.80 (11)H72A—C72—H72C109.5
C5—C6—H6A108.1H72B—C72—H72C109.5
C7—C6—H6A108.1C7—C71—H71A109.5
C5—C6—H6B108.1C7—C71—H71B109.5
C7—C6—H6B108.1H71A—C71—H71B109.5
H6A—C6—H6B107.3C7—C71—H71C109.5
N1—C2—C3108.32 (10)H71A—C71—H71C109.5
N1—C2—H2A110.0H71B—C71—H71C109.5
C3—C2—H2A110.0N4—C3—C2106.12 (10)
N1—C2—H2B110.0N4—C3—C31109.63 (11)
C3—C2—H2B110.0C2—C3—C31113.20 (11)
H2A—C2—H2B108.4N4—C3—H3109.3
N1i—C7—C6106.76 (10)C2—C3—H3109.3
N1i—C7—C72110.97 (11)C31—C3—H3109.3
C6—C7—C72111.31 (11)N20—C20—S20178.9 (1)
N1i—C7—C71110.57 (10)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N200.912.072.968 (2)171

Experimental details

Crystal data
Chemical formula[Ni(C18H36N4)](NCS)2
Mr483.38
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)7.3383 (6), 8.0955 (6), 10.2042 (8)
α, β, γ (°)69.917 (1), 86.852 (1), 88.965 (1)
V3)568.48 (8)
Z1
Radiation typeMo Kα
µ (mm1)1.06
Crystal size (mm)0.40 × 0.20 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3335, 2472, 2393
Rint0.008
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.061, 1.06
No. of reflections2472
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.25

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3.2 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Ni1—N41.921 (1)N20—C201.167 (2)
Ni1—N11.940 (1)C20—S201.644 (2)
N4—C51.289 (2)
N4—Ni1—N186.05 (5)N4—C5—C6121.8 (1)
N4i—Ni1—N193.95 (5)N4—C5—C51124.4 (1)
C5—N4—Ni1129.2 (1)N20—C20—S20178.9 (1)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N200.912.072.968 (2)171
 

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