C meso (3,5,7,7,10,12,12,14 Octa­methyl 1,4,8,11 tetra­aza­cyclo­tetra­deca 4,11 diene)nickel(II) bis­­(thio­cyanate)

metal-organic papers

m80

18H36N4)](NCS)2 doi:10.1107/S160053680504078X Acta Cryst.(2006). E62, m80–m82

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

C

-

meso

-(3,5,7,7,10,12,12,14-Octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II)

bis(thio-cyanate)

Neil F. Curtis,a* Rebekah Pawleyband Ward T. Robinsonb

a

School of Chemical and Physical Sciences, Victoria University of Wellington, Box 600, Wellington, New Zealand, andb_Chemistry

Department, University of Canterbury, Christchurch, New Zealand

Correspondence e-mail: neil.curtis@vuw.ac.nz

Key indicators

Single-crystal X-ray study T= 273 K

Mean(C–C) = 0.002 A˚ Rfactor = 0.023 wRfactor = 0.061

Data-to-parameter ratio = 18.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography

Printed in Great Britain – all rights reserved

The title complex, (1RS,3SR,8SR,10RS -3,5,7,7,10,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene-4

N1,4,8,11 )-nickel(II) bis(thiocyanate), [Ni(C18H36N4)](NCS)2, has a

centrosymmetrical square-planar singlet ground state nick-el(II) cation, with Ni—Namine= 1.940 (1) A˚ and Ni—Nimine=

1.921 (1) A˚ . The C-3 methyl substituent is axially oriented. The thiocyanate N atom is hydrogen bonded to the NH group.

Comment

The azamacrocyle cations C-meso- and C-rac-(Me8

[14]-diene)nickel(II) (Me8[14]diene =

3,5,7,7,10,12,12,14-octa-methyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), formed by reaction of tris(rac-propane-1,2-diamine)nickel(II) complexes with acetone, were separated by fractional crystallization (see 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-proto-nated 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 consists of a

centrosymmetric 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 (1) A˚ ] 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 A˚ .

The nickel(II) ion is coordinated by the four N-atoms of the macrocycle, with the Ni—N distance 0.029 (2) A˚ 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 same side as 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) A˚ .

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, and 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) A˚ .

The compound [Cu(C-meso-Me8[14]diene)](ClO4)22H2O

(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)A˚ , with

perchlorate O atoms in approximate axial sites with Cu—O = 2.779 (3) A˚ .

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 A˚ , 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) A˚ .

The structure of trans-[Co(C-meso-Me8[14]diene)Cl2]ClO4

(Luet 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

Excess of NaCNS was added to a hot saturated aqueous solution of orange [Ni(C-meso-Me8[14]diene)](ClO4)2The yellow thiocyanate

salt was filtered off from the cold solution and recrystallized from methanol.

Crystal data

[Ni(C18H36N4)](NCS)2

Mr= 483.38

Triclinic,P1 a= 7.3383 (6) A˚ b= 8.0955 (6) A˚ c= 10.2042 (8) A˚

= 69.917 (1) = 86.852 (1) = 88.965 (1)

V= 568.48 (8) A˚3

Z= 1

Dx= 1.412 Mg m 3

MoKradiation Cell parameters from 2683

reflections

= 2.8–28.3 = 1.06 mm1

T= 273 (2) K Block, yellow 0.400.200.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: none 3335 measured reflections 2472 independent reflections

2393 reflections withI> 2(I) Rint= 0.008

max= 28.4

h=9!9 k=8!10 l=13!13

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.023 wR(F2_{) = 0.061}

S= 1.06 2472 reflections 137 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0311P)2

+ 0.291P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.38 e A˚

3

min=0.25 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Ni1—N4 1.921 (1) Ni1—N1 1.940 (1) N4—C5 1.289 (2)

N20—C20 1.167 (2) C20—S20 1.644 (2)

N4—Ni1—N1 86.05 (5) N4i

—Ni1—N1 93.95 (5) C5—N4—Ni1 129.2 (1)

N4—C5—C6 121.8 (1) N4—C5—C51 124.4 (1) N20—C20—S20 178.9 (1)

Symmetry code: (i)xþ1;yþ1;zþ1.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1 N20 0.91 2.07 2.968 (2) 171

All H atoms were placed in calculated positions, with C—H = 0.96 A˚ , and were included in the least squares refinement as riding on their carrier atoms, withUiso(H) = 1.2Ueqof the corresponding carrier

atom.

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.

References

Blight, M. M. & Curtis, N. F. (1962).J. Chem. Soc.pp. 1204–1207. Curtis, N. F. (1973).J. Chem. Soc. Dalton Trans.pp. 863–866. Curtis, N. F. & Curtis, Y. M. (1966).J. Chem. Soc. A, pp. 1653–1656. Curtis, N. F., Swann, D. A., Waters, T. N. & Maxwell, I. E. (1969).J. Am. Chem.

Soc.91, 4588–4589.

Farrugia, L. J. (1997).ORTEP3.2. J. Appl. Cryst.30, 565. Hanic, F. & Miklos, D. (1972).J. Cryst. Mol. Struct.2, 107–116.

metal-organic papers

Acta Cryst.(2006). E62, m80–m82 Curtiset al. _[Ni(C

18H36N4)](NCS)2

m81

[Ni(C-meso-Me8[14]diene))(NCS)2drawn with displacement ellipsoids at

Hazari, S. K. S., Roy, T. G., Dey, B. K., Chakrabarti, S. & Tiekink, E. R. T. (1999).Z. Kristallogr. New Cryst. Struct.214, 51–52.

Lu, T. H., Chen, B. H. & Chung, C. S. (1992).J. Chin. Chem. Soc. (Taipei),39, 343–345.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467–473.

Sheldrick, G. M. (1997).SHELXTL. University of Gottingen, Germany.

Shen, H.-Y., Liao, D.-Z., Jiang Z.-H. & Yan, S. P. (1999).Trans. Metal Chem.

24, 581–583.

Siemens (1995).SMARTandSAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Swann, D. A., Waters, T. N. & Curtis, N. F. (1972).J. Chem. Soc. Dalton Trans. pp. 1115–1120.

metal-organic papers

m82

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supporting information

Acta Cryst. (2006). E62, m80–m82 [doi:10.1107/S160053680504078X]

C-meso-(3,5,7,7,10,12,12,14-Octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis(thiocyanate)

Neil F. Curtis, Rebekah Pawley and Ward T. Robinson

S1. Comment

The azamacrocyle cations C-meso- and C-rac-(Me8[14]diene)nickel(II) (Me8[14]diene =

3,5,7,7,10,12,12,14-octa-methyl-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− _{= ClO}

4−, 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—

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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.

S2. Experimental

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.

S3. Refinement

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.

Figure 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-κ4_N1,4,8,11_{)nickel(II) bis(thiocyanate)}

Crystal data

[Ni(C18H36N4)](NCS)2

Mr = 483.38 Triclinic, P1 Hall symbol: -P 1

a = 7.3383 (6) Å

b = 8.0955 (6) Å

c = 10.2042 (8) Å

α = 69.917 (1)°

β = 86.852 (1)°

γ = 88.965 (1)°

V = 568.48 (8) Å3

Z = 1

F(000) = 258

Dx = 1.412 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2683 reflections

θ = 2.8–28.3°

µ = 1.06 mm−1

T = 273 K Block, yellow

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Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

3335 measured reflections 2472 independent reflections

2393 reflections with I > 2σ(I)

Rint = 0.008

θmax = 28.4°, θmin = 2.1°

h = −9→9

k = −8→10

l = −13→13

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.023}

wR(F2_{) = 0.061}

S = 1.06 2472 reflections 137 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0311P)2 + 0.291P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 0.38 e Å−3 Δρmin = −0.25 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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Ni1 0.5000 0.5000 0.5000 0.00971 (8)

N1 0.50725 (14) 0.47718 (14) 0.69517 (11) 0.0120 (2)

H1 0.5779 0.5674 0.6971 0.014*

N4 0.27883 (15) 0.63089 (14) 0.49926 (11) 0.0128 (2)

C5 0.16839 (17) 0.69536 (17) 0.40027 (14) 0.0136 (2)

C6 0.20809 (18) 0.68678 (18) 0.25715 (14) 0.0153 (3)

H6A 0.1484 0.7858 0.1906 0.018*

H6B 0.1526 0.5805 0.2538 0.018*

C2 0.32061 (18) 0.51070 (18) 0.74570 (14) 0.0155 (3)

H2A 0.3268 0.5375 0.8310 0.019*

H2B 0.2448 0.4072 0.7654 0.019*

C7 0.40883 (18) 0.68814 (17) 0.20850 (13) 0.0135 (3)

C51 −0.00540 (18) 0.79061 (19) 0.41374 (14) 0.0180 (3)

H51A −0.0539 0.7461 0.5087 0.027*

H51B −0.0926 0.7725 0.3532 0.027*

H51C 0.0192 0.9141 0.3880 0.027*

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H31A 0.4514 0.8367 0.6102 0.029*

H31B 0.2893 0.8649 0.7070 0.029*

H31C 0.2731 0.9317 0.5445 0.029*

C72 0.5068 (2) 0.85158 (18) 0.21209 (15) 0.0180 (3)

H72A 0.5170 0.8441 0.3074 0.027*

H72B 0.4385 0.9547 0.1636 0.027*

H72C 0.6265 0.8585 0.1676 0.027*

C71 0.41348 (19) 0.68588 (19) 0.05837 (13) 0.0172 (3)

H71A 0.5373 0.6976 0.0208 0.026*

H71B 0.3422 0.7818 0.0017 0.026*

H71C 0.3639 0.5768 0.0588 0.026*

C3 0.24005 (18) 0.66384 (17) 0.63368 (13) 0.0147 (3)

H3 0.1077 0.6660 0.6521 0.018*

N20 0.76296 (17) 0.74108 (17) 0.72386 (13) 0.0221 (3)

C20 0.83366 (18) 0.77659 (18) 0.81043 (14) 0.0164 (3)

S20 0.93355 (5) 0.83066 (5) 0.93031 (4) 0.02264 (10)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ni1 0.01007 (12) 0.01126 (12) 0.00886 (12) 0.00289 (8) −0.00114 (8) −0.00484 (9)

N1 0.0118 (5) 0.0135 (5) 0.0116 (5) 0.0027 (4) −0.0011 (4) −0.0054 (4)

N4 0.0131 (5) 0.0148 (5) 0.0115 (5) 0.0025 (4) −0.0003 (4) −0.0060 (4)

C5 0.0132 (6) 0.0133 (6) 0.0147 (6) 0.0012 (5) −0.0004 (5) −0.0054 (5)

C6 0.0143 (6) 0.0197 (6) 0.0130 (6) 0.0059 (5) −0.0037 (5) −0.0069 (5)

C2 0.0134 (6) 0.0207 (7) 0.0128 (6) 0.0037 (5) 0.0006 (5) −0.0067 (5)

C7 0.0152 (6) 0.0152 (6) 0.0102 (6) 0.0039 (5) −0.0023 (5) −0.0044 (5)

C51 0.0152 (6) 0.0232 (7) 0.0153 (6) 0.0071 (5) −0.0023 (5) −0.0065 (5)

C31 0.0221 (7) 0.0176 (7) 0.0213 (7) 0.0045 (5) −0.0029 (6) −0.0108 (6)

C72 0.0221 (7) 0.0141 (6) 0.0173 (6) 0.0009 (5) −0.0006 (5) −0.0047 (5)

C71 0.0198 (6) 0.0212 (7) 0.0105 (6) 0.0049 (5) −0.0018 (5) −0.0052 (5)

C3 0.0145 (6) 0.0177 (6) 0.0133 (6) 0.0031 (5) 0.0008 (5) −0.0075 (5)

N20 0.0209 (6) 0.0253 (6) 0.0234 (6) −0.0027 (5) 0.0022 (5) −0.0127 (5)

C20 0.0136 (6) 0.0151 (6) 0.0186 (6) 0.0012 (5) 0.0033 (5) −0.0043 (5)

S20 0.02041 (18) 0.0299 (2) 0.01789 (18) −0.00037 (14) −0.00455 (14) −0.00796 (15)

Geometric parameters (Å, º)

Ni1—N4 1.921 (1) C7—C72 1.5297 (18)

Ni1—N4i _{1.9212 (11) C7—C71 1.5368 (17)}

Ni1—N1 1.940 (1) C51—H51A 0.9600

Ni1—N1i _{1.9395 (11) C51—H51B 0.9600}

N1—C2 1.4901 (16) C51—H51C 0.9600

N1—C7i _{1.5066 (16) C31—C3 1.5263 (19)}

N1—H1 0.9100 C31—H31A 0.9600

N4—C5 1.289 (2) C31—H31B 0.9600

N4—C3 1.4963 (16) C31—H31C 0.9600

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C5—C51 1.5027 (18) C72—H72B 0.9600

C6—C7 1.5275 (18) C72—H72C 0.9600

C6—H6A 0.9700 C71—H71A 0.9600

C6—H6B 0.9700 C71—H71B 0.9600

C2—C3 1.5058 (18) C71—H71C 0.9600

C2—H2A 0.9700 C3—H3 0.9800

C2—H2B 0.9700 N20—C20 1.167 (2)

C7—N1i _{1.5066 (16) C20—S20 1.644 (2)}

N4—Ni1—N4i _{180.00 (7) C6—C7—C71 106.91 (10)}

N4—Ni1—N1 86.05 (5) C72—C7—C71 110.20 (11)

N4i_{—Ni1—N1 93.95 (5) C5—C51—H51A 109.5}

N4—Ni1—N1i _{93.95 (5) C5—C51—H51B 109.5}

N4i_—Ni1—N1i _{86.05 (5) H51A—C51—H51B 109.5}

N1—Ni1—N1i _{180.0 C5—C51—H51C 109.5}

C2—N1—C7i _{112.68 (10) H51A—C51—H51C 109.5}

C2—N1—Ni1 108.42 (8) H51B—C51—H51C 109.5

C7i_{—N1—Ni1 117.01 (8) C3—C31—H31A 109.5}

C2—N1—H1 106.0 C3—C31—H31B 109.5

C7i_{—N1—H1 106.0 H31A—C31—H31B 109.5}

Ni1—N1—H1 106.0 C3—C31—H31C 109.5

C5—N4—C3 118.29 (11) H31A—C31—H31C 109.5

C5—N4—Ni1 129.2 (1) H31B—C31—H31C 109.5

C3—N4—Ni1 112.44 (8) C7—C72—H72A 109.5

N4—C5—C6 121.8 (1) C7—C72—H72B 109.5

N4—C5—C51 124.4 (1) H72A—C72—H72B 109.5

C6—C5—C51 113.72 (11) C7—C72—H72C 109.5

C5—C6—C7 116.80 (11) H72A—C72—H72C 109.5

C5—C6—H6A 108.1 H72B—C72—H72C 109.5

C7—C6—H6A 108.1 C7—C71—H71A 109.5

C5—C6—H6B 108.1 C7—C71—H71B 109.5

C7—C6—H6B 108.1 H71A—C71—H71B 109.5

H6A—C6—H6B 107.3 C7—C71—H71C 109.5

N1—C2—C3 108.32 (10) H71A—C71—H71C 109.5

N1—C2—H2A 110.0 H71B—C71—H71C 109.5

C3—C2—H2A 110.0 N4—C3—C2 106.12 (10)

N1—C2—H2B 110.0 N4—C3—C31 109.63 (11)

C3—C2—H2B 110.0 C2—C3—C31 113.20 (11)

H2A—C2—H2B 108.4 N4—C3—H3 109.3

N1i_{—C7—C6 106.76 (10) C2—C3—H3 109.3}

N1i_{—C7—C72 110.97 (11) C31—C3—H3 109.3}

C6—C7—C72 111.31 (11) N20—C20—S20 178.9 (1)

N1i_{—C7—C71 110.57 (10)}

supporting information

sup-6

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A