[(1RS,4RS)-5,5,7,13,15,15-Hexa­methyl-1,4,8,12-tetra­aza­cyclo­pentadeca-7,12-diene-N1,N4,N8,N12]­nickel(II) diperchlorate

Curtis, N.F.; Waters, J.M.; Rickard, C.E.

doi:10.1107/S1600536800020559

[(1RS,4RS)-5,5,7,13,15,15-Hexamethyl-1,4,8,12-tetraazacyclopentadeca-7,12-diene-N¹,N⁴,N⁸,N¹²]nickel(II) diperchlorate

N. F. Curtis, J. M. Waters and C. E. Rickard

The title compound, [Ni(C₁₇H₃₄N₄)](ClO₄)₂, has singlet ground-state nickel(II) complex cations in tetrahedrally twisted square-planar coordination by the four N atoms of the 15-membered diamine diimine tetraazamacrocycle and disordered perchlorate anions, linked into molecular clusters by N—H

O hydrogen bonds and weak Ni

O interactions. The cation has approximate twofold symmetry, with bond lengths Ni—N_amine of 1.920 (2) and 1.924 (2) Å, and Ni—N_imine of 1.915 (2) and 1.929 (2) Å, and trans–N—Ni—N angles of 165.1 (1) and 163.4 (1)°, with the shortest Ni

O distance being 3.27 (3) Å.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020559/na6009sup1.cif Contains datablocks global, nfc10
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020559/na6009Isup2.hkl Contains datablock I

CCDC reference: 155850

checkCIF report

Key indicators

Single-crystal X-ray study
T = 203 K
Mean (C-C) = 0.005 Å
Disorder in solvent or counterion
R factor = 0.042
wR factor = 0.105
Data-to-parameter ratio = 16.0

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_302  Alert C Anion/Solvent disorder .......................      50.00 Perc.

PLAT_320  Alert C Check Hybridisation of  C(7)   in main residue          ?

PLAT_320  Alert C Check Hybridisation of  C(13)  in main residue          ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

Comment top

The preparations of hexamethyl–diamine–diimine macrocycle compounds of nickel(II) and copper(II) by reactions with acetone of the metal-ion compounds of diamines with varying chain length have been described (Curtis, 1968). Reaction of equimolar amounts of tris(ethane-1,2-diamine)- and tris(propane-1,3-diamine)nickel(II) perchlorates with acetone yields [Ni(trans-[15]diene)](ClO₄)₂·H₂O (trans-[15]diene 5,7,7,13,15,14-hexamethyl-1,5,8,12-tetraazacyclopentadeca-4,12-diene) (Curtis & House, 1967; Curtis & Gainsford, 1986), while reaction of 4,4,9,9-tetramethyl-5,8-diazoniumdodecane-2,11-dione diperchlorate [formed by reaction of ethane-1,2-diammonium perchlorate with acetone (Curtis, 1982)] with (propane-1,3-diamine)nickel(II) or -copper(II) perchlorates yields 5,5,7,13,15,15-hexamethyl-1,4,8,12-tetraazacyclopentadeca-7,12-diene (cis-[15]diene) complex cations (Curtis & Gainsford, 1986). The structures of N-rac-[Cu(cis-[15]diene)]₂Cl(ClO₄)₃ (Gladkikh & Curtis, 1996) and N-rac-[Ni(trans-[15]diene)](ClO₄)₂·H₂O (Curtis & Gainsford, 1986) have been reported.

The title compound, 1RS,4RS-[Ni(cis-[15]diene)](ClO₄)₂, (I), has discrete singlet ground-state nickel(II) square-planar complex cations and perchlorate anions, linked to form molecular clusters by N—H···O hydrogen bonding and weak Ni···O interactions (Fig. 1 and Table 1). The closest Ni···O contact, of 3.27 (3) Å, indicates no significant axial coordination. The distances C7—N8 and N12—C13 and the angles about these atoms confirm the locations of two imine functions.

The cation shows approximate twofold symmetry through C10, Ni and the midpoint of C2—C3 (configuration 1RS,4RS, N-rac). There is appreciable tetrahedral twisting of the coordination plane with displacements from the best N₄ plane of ±0.26 Å. The chelate ring conformations and displacements of atoms from the relevant NiN₂ planes (Å, s.u. < 0.003 Å) are: N1—Ni—N4, gauche, C2, 0.433; C3, -0.253; N4—Ni—N8, half chair, C5, -1.99 (C51, -2.465; C52, -1.249); C6, -1.016; C7, 0.748 (C71, 0.664); N8—Ni—N12, asym.-twist, C9, -0.828; C10, 0.123; C11, 0.694; N12—Ni—N1, half-chair, C13, 0.618 (C131, 0.462); C14, 0.781; C15, 1.094 (C151, 1.072; C152, 2.448). The intracyclic angles at the central C atoms C5—-C6–C7 and C13—C14—C15 of the trimethyl substituted chelate rings are, as usual, large (cf. angle C9—C10—C11).

The structure has weakly bound `molecules', [Ni(cis-[15]diene)](ClO₄)₂, with a perchlorate ion above each face of the macrocycle, with weak Ni···O interactions, shorter for the minor oxygen sites [Ni···O12, 3.47 (1); Ni···O18, 3.27 (3), Ni···O23, 3.74 (1); Ni···O26, 3.71 (3) Å] and weak N—H···O hydrogen bonds, shorter for the major oxygen sites. These `molecules' are linked by C—H···O interactions (Table 2).

The nickel(II) compound of a related 15-membered hexaaza macrocycle, which has the C⁹ and C¹¹ methylene groups of cis-[15]diene replaced by NH groups, has a similar structure, with the N-rac-configuration with approximate twofold symmetry, and with similar dimensions: Ni—N_amine 1.908 (4) and 1.913 (4) Å, Ni—N_imine 1.885 (4) and 1.902 (4) Å, and trans-N—Ni—N angles 167.9 (2) and 166.9 (2)° (Curtis et al., 1998). The isomeric cation present for N-rac-[Ni(trans-[15]diene)](ClO₄)₂·H₂O has similar coordination geometry with Ni—N_amine 1.882 (4) and 1.913 (4) Å, Ni—N_imine 1.924 (4) and 1.896 (4) Å, and trans-N—Ni—N angles of 169.4 (2) and 166.1 (2)°, although this cation is saddle shaped. The general conformation and tetrahedral twisting of the NiN₄ group is also similar for N-rac-[Cu(cis-[15]diene)]₂Cl(ClO₄)₃ with trans-N—Cu—N angles 168.3 (3) and 158.0 (3)°.

The Ni—N distances observed for N-rac-[Ni(cis-[15]diene)](ClO₄)₂ are within the range found for singlet ground state nickel compounds of related 14-membered macrocycles for which many structures have been reported (Donnelly & Zimmer, 1999; Cambridge Structural Database, 2000), including the fourteen-membered homologue N-rac-[Ni(cis-[14]diene)](ClO₄)₂ [Ni—N_amine 1.927 (6) and Ni—N_imine 1.891 (6) Å] (Kilbourn et al., 1969). N-rac-[Ni(cis-[15]diene)](ClO₄)₂ is unusual in that the Ni—N_imine distance Ni—N12 is longer than both Ni—N_amine distances, whereas bonds to imine nitrogen are more typically ca 0.03 Å shorter, as observed for N-rac-[Cu(cis-[15]diene)]₂Cl(ClO₄)₃.

The tetrahedral twisting of the N₄ plane for N-rac-[Ni(cis-[15]diene)](ClO₄)₂ is similar to that observed for other 15-membered tetraaza macrocyles coordinated to singlet ground-state nickel(II), and much greater than observed for related 14-membered macrocycle compounds, including N-rac-[Ni(cis-[14]diene)](ClO₄)₂, which has trans-N—Ni—N of 175.7 (3)°.

Experimental top

N-rac-[Ni(cis-[15]diene)](ClO₄)₂ was prepared as reported by Curtis & Gainsford (1986) and crystallized from water.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

Figures top

Fig. 1. View of the title compound.

[(1RS,4RS)-5,5,7,13,15,15-Hexamethyl-1,4,8,12-tetraazacyclopentadeca- 7,12-diene-N¹,N⁴,N⁸,N¹²]nickel(II) diperchlorate top

Crystal data top

[Ni(C₁₇H₃₄N₄)](ClO₄)₂	F(000) = 1160
M_r = 552.09	D_x = 1.529 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.3529 (1) Å	Cell parameters from 8197 reflections
b = 16.1128 (1) Å	θ = 1.9–27.5°
c = 15.0400 (1) Å	µ = 1.08 mm⁻¹
β = 107.025 (1)°	T = 203 K
V = 2398.94 (3) Å³	Prism, orange
Z = 4	0.25 × 0.17 × 0.16 mm

Data collection top

Siemens SMART CCD diffractometer	5243 independent reflections
Radiation source: fine-focus sealed tube	4531 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.002
area–detector ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (Blessing, 1995)	h = −13→12
T_min = 0.774, T_max = 0.879	k = 0→20
14323 measured reflections	l = 0→19

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	Only H-atom coordinates refined
S = 1.04	w = 1/[σ²(F_o²) + (0.048P)² + 3.2464P] where P = (F_o² + 2F_c²)/3
5243 reflections	(Δ/σ)_max = 0.001
327 parameters	Δρ_max = 0.70 e Å⁻³
40 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Ni(C₁₇H₃₄N₄)](ClO₄)₂	V = 2398.94 (3) Å³
M_r = 552.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.3529 (1) Å	µ = 1.08 mm⁻¹
b = 16.1128 (1) Å	T = 203 K
c = 15.0400 (1) Å	0.25 × 0.17 × 0.16 mm
β = 107.025 (1)°

Data collection top

Siemens SMART CCD diffractometer	5243 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	4531 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.879	R_int = 0.002
14323 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	40 restraints
wR(F²) = 0.105	Only H-atom coordinates refined
S = 1.04	Δρ_max = 0.70 e Å⁻³
5243 reflections	Δρ_min = −0.66 e Å⁻³
327 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni	0.48685 (3)	0.07048 (2)	0.22713 (2)	0.02468 (10)
N1	0.3671 (2)	−0.00883 (13)	0.25706 (15)	0.0295 (4)
H1	0.3292 (2)	0.01636 (13)	0.29833 (15)	0.050*
C2	0.4522 (3)	−0.0785 (2)	0.3073 (2)	0.0436 (7)
H2A	0.4780 (3)	−0.1150 (2)	0.2632 (2)	0.080*
H2B	0.4025 (3)	−0.1113 (2)	0.3413 (2)	0.080*
C3	0.5754 (3)	−0.0405 (2)	0.3736 (2)	0.0441 (7)
H3A	0.5510 (3)	−0.0111 (2)	0.4234 (2)	0.080*
H3B	0.6414 (3)	−0.0837 (2)	0.4016 (2)	0.080*
N4	0.6333 (2)	0.01842 (13)	0.3191 (2)	0.0310 (5)
H4	0.6817 (2)	−0.01217 (13)	0.2882 (2)	0.050*
C5	0.7283 (3)	0.0822 (2)	0.3781 (2)	0.0352 (6)
C51	0.6467 (3)	0.1436 (2)	0.4166 (2)	0.0428 (7)
H51A	0.6005 (3)	0.1143 (2)	0.4547 (2)	0.080*
H51B	0.5807 (3)	0.1708 (2)	0.3656 (2)	0.080*
H51C	0.7068 (3)	0.1848 (2)	0.4541 (2)	0.080*
C52	0.8342 (3)	0.0388 (2)	0.4572 (2)	0.0556 (9)
H52A	0.8852 (3)	0.0000 (2)	0.4314 (2)	0.080*
H52B	0.7896 (3)	0.0091 (2)	0.4960 (2)	0.080*
H52C	0.8951 (3)	0.0799 (2)	0.4944 (2)	0.080*
C6	0.8035 (3)	0.1250 (2)	0.3173 (2)	0.0409 (7)
H6A	0.8596 (3)	0.1685 (2)	0.3552 (2)	0.050*
H6B	0.8652 (3)	0.0840 (2)	0.3040 (2)	0.050*
C7	0.7276 (3)	0.1634 (2)	0.2272 (2)	0.0491 (8)
C71	0.8180 (3)	0.2065 (3)	0.1789 (3)	0.0630 (10)
H71A	0.7633 (3)	0.2303 (3)	0.1208 (3)	0.080*
H71B	0.8807 (3)	0.1667 (3)	0.1664 (3)	0.080*
H71C	0.8681 (3)	0.2503 (3)	0.2186 (3)	0.080*
N8	0.6126 (2)	0.1267 (2)	0.1768 (2)	0.0398 (6)
C9	0.5470 (3)	0.1537 (2)	0.0801 (2)	0.0395 (6)
H9A	0.4927 (3)	0.1080 (2)	0.0453 (2)	0.080*
H9B	0.6165 (3)	0.1675 (2)	0.0501 (2)	0.080*
C10	0.4574 (4)	0.2285 (2)	0.0773 (2)	0.0491 (8)
H10A	0.5123 (4)	0.2789 (2)	0.0847 (2)	0.080*
H10B	0.3894 (4)	0.2310 (2)	0.0163 (2)	0.080*
C11	0.3868 (3)	0.2262 (2)	0.1522 (2)	0.0377 (6)
H11A	0.4494 (3)	0.2452 (2)	0.2110 (2)	0.080*
H11B	0.3098 (3)	0.2644 (2)	0.1356 (2)	0.080*
N12	0.3382 (2)	0.1419 (2)	0.1652 (2)	0.0405 (6)
C13	0.2147 (3)	0.1171 (2)	0.1159 (2)	0.0459 (8)
C131	0.1055 (3)	0.1801 (2)	0.0762 (2)	0.0498 (8)
H13A	0.1455 (3)	0.2303 (2)	0.0602 (2)	0.080*
H13B	0.0592 (3)	0.1931 (2)	0.1220 (2)	0.080*
H13C	0.0414 (3)	0.1576 (2)	0.0209 (2)	0.080*
C14	0.1597 (3)	0.0386 (2)	0.1419 (2)	0.0376 (6)
H14A	0.0859 (3)	0.0208 (2)	0.0880 (2)	0.050*
H14B	0.1193 (3)	0.0519 (2)	0.1915 (2)	0.050*
C15	0.2523 (3)	−0.0362 (2)	0.1743 (2)	0.0339 (6)
C151	0.1699 (3)	−0.1040 (2)	0.2044 (3)	0.0477 (8)
H15A	0.1354 (3)	−0.0828 (2)	0.2534 (3)	0.080*
H15B	0.2272 (3)	−0.1517 (2)	0.2273 (3)	0.080*
H15C	0.0949 (3)	−0.1205 (2)	0.1517 (3)	0.080*
C152	0.3075 (3)	−0.0680 (2)	0.0975 (2)	0.0421 (7)
H15D	0.3658 (3)	−0.1153 (2)	0.1200 (2)	0.080*
H15E	0.3588 (3)	−0.0244 (2)	0.0790 (2)	0.080*
H15F	0.2331 (3)	−0.0846 (2)	0.0444 (2)	0.080*
Cl1	0.77772 (9)	−0.09388 (7)	0.15944 (7)	0.0601 (2)	0.877 (7)
O11	0.8237 (4)	−0.1649 (3)	0.1282 (4)	0.101 (2)	0.877 (7)
O12	0.6406 (5)	−0.0874 (6)	0.1386 (6)	0.189 (5)	0.877 (7)
O13	0.8290 (6)	−0.0227 (3)	0.1248 (4)	0.135 (2)	0.877 (7)
O14	0.8332 (4)	−0.0909 (3)	0.2582 (3)	0.094 (2)	0.877 (7)
Cl11	0.77772 (9)	−0.09388 (7)	0.15944 (7)	0.0601 (2)	0.123 (7)
O15	0.821 (2)	−0.1052 (17)	0.0771 (15)	0.073 (8)*	0.123 (7)
O16	0.849 (2)	−0.0370 (14)	0.2240 (15)	0.056 (6)*	0.123 (7)
O17	0.778 (5)	−0.176 (2)	0.203 (3)	0.35 (6)*	0.123 (7)
O18	0.631 (3)	−0.0703 (15)	0.1312 (19)	0.046 (6)*	0.123 (7)
Cl2	0.23467 (8)	0.16963 (5)	0.40219 (5)	0.0432 (2)	0.855 (8)
O21	0.3456 (4)	0.2205 (3)	0.4528 (3)	0.0865 (15)	0.855 (8)
O22	0.1775 (5)	0.2026 (3)	0.3119 (2)	0.0719 (11)	0.855 (8)
O23	0.2872 (5)	0.0877 (2)	0.3974 (2)	0.0690 (13)	0.855 (8)
O24	0.1387 (4)	0.1676 (3)	0.4535 (3)	0.0645 (10)	0.855 (8)
Cl21	0.23467 (8)	0.16963 (5)	0.40219 (5)	0.0432 (2)	0.145 (8)
O25	0.186 (2)	0.0849 (11)	0.3588 (14)	0.068 (6)*	0.145 (8)
O26	0.359 (2)	0.1822 (19)	0.400 (2)	0.118 (11)*	0.145 (8)
O27	0.189 (2)	0.1782 (13)	0.4747 (13)	0.048 (6)*	0.145 (8)
O28	0.143 (2)	0.2234 (14)	0.3266 (15)	0.058 (6)*	0.145 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0216 (2)	0.0245 (2)	0.0277 (2)	0.00088 (11)	0.00687 (12)	0.00188 (12)
N1	0.0321 (11)	0.0277 (11)	0.0294 (11)	−0.0039 (9)	0.0103 (9)	−0.0021 (8)
C2	0.048 (2)	0.0306 (14)	0.047 (2)	−0.0058 (12)	0.0049 (13)	0.0084 (12)
C3	0.049 (2)	0.0362 (15)	0.039 (2)	−0.0045 (13)	0.0007 (13)	0.0122 (12)
N4	0.0311 (11)	0.0269 (11)	0.0320 (11)	0.0026 (9)	0.0047 (9)	−0.0015 (9)
C5	0.0285 (13)	0.0380 (15)	0.0341 (14)	−0.0001 (11)	0.0013 (11)	−0.0015 (11)
C51	0.046 (2)	0.041 (2)	0.040 (2)	−0.0070 (13)	0.0123 (13)	−0.0118 (13)
C52	0.044 (2)	0.058 (2)	0.050 (2)	−0.001 (2)	−0.0107 (15)	0.009 (2)
C6	0.0238 (12)	0.049 (2)	0.048 (2)	−0.0034 (12)	0.0068 (12)	−0.0026 (13)
C7	0.0291 (14)	0.068 (2)	0.050 (2)	−0.0083 (14)	0.0111 (13)	0.014 (2)
C71	0.039 (2)	0.086 (3)	0.069 (2)	−0.017 (2)	0.023 (2)	0.013 (2)
N8	0.0291 (11)	0.0460 (14)	0.0414 (13)	−0.0053 (10)	0.0057 (10)	0.0123 (11)
C9	0.0396 (15)	0.048 (2)	0.0325 (14)	0.0025 (13)	0.0128 (12)	0.0060 (12)
C10	0.057 (2)	0.044 (2)	0.052 (2)	0.0111 (15)	0.025 (2)	0.0204 (14)
C11	0.0368 (14)	0.0295 (14)	0.048 (2)	0.0046 (11)	0.0139 (12)	0.0088 (12)
N12	0.0278 (11)	0.0349 (13)	0.054 (2)	0.0014 (10)	0.0045 (10)	0.0141 (11)
C13	0.0248 (13)	0.051 (2)	0.061 (2)	0.0048 (12)	0.0108 (13)	0.0187 (15)
C131	0.0300 (14)	0.063 (2)	0.057 (2)	0.0129 (14)	0.0142 (13)	0.023 (2)
C14	0.0243 (12)	0.048 (2)	0.041 (2)	−0.0033 (11)	0.0104 (11)	−0.0026 (12)
C15	0.0287 (13)	0.0368 (14)	0.0367 (14)	−0.0071 (11)	0.0103 (11)	−0.0063 (11)
C151	0.040 (2)	0.043 (2)	0.064 (2)	−0.0130 (13)	0.0211 (15)	−0.0061 (15)
C152	0.040 (2)	0.047 (2)	0.040 (2)	−0.0045 (13)	0.0131 (12)	−0.0139 (13)
Cl1	0.0452 (4)	0.0704 (6)	0.0663 (6)	0.0102 (4)	0.0185 (4)	−0.0217 (5)
O11	0.095 (3)	0.071 (3)	0.150 (4)	0.005 (2)	0.055 (3)	−0.055 (3)
O12	0.041 (2)	0.354 (12)	0.158 (6)	0.031 (4)	0.007 (3)	−0.147 (7)
O13	0.143 (5)	0.091 (4)	0.172 (6)	0.012 (3)	0.046 (4)	0.055 (3)
O14	0.094 (3)	0.114 (4)	0.067 (2)	0.029 (3)	0.014 (2)	−0.007 (2)
Cl11	0.0452 (4)	0.0704 (6)	0.0663 (6)	0.0102 (4)	0.0185 (4)	−0.0217 (5)
Cl2	0.0469 (4)	0.0430 (4)	0.0454 (4)	0.0013 (3)	0.0226 (3)	0.0007 (3)
O21	0.055 (2)	0.090 (3)	0.102 (3)	−0.024 (2)	0.003 (2)	−0.018 (2)
O22	0.103 (3)	0.072 (2)	0.040 (2)	0.015 (2)	0.021 (2)	0.005 (2)
O23	0.105 (3)	0.057 (2)	0.056 (2)	0.028 (2)	0.041 (2)	−0.0021 (14)
O24	0.049 (2)	0.089 (3)	0.065 (2)	0.001 (2)	0.033 (2)	−0.008 (2)
Cl21	0.0469 (4)	0.0430 (4)	0.0454 (4)	0.0013 (3)	0.0226 (3)	0.0007 (3)

Geometric parameters (Å, º) top

Ni—N8	1.915 (2)	C10—C11	1.513 (4)
Ni—N4	1.920 (2)	C10—H10A	0.98
Ni—N1	1.924 (2)	C10—H10B	0.98
Ni—N12	1.929 (2)	C11—N12	1.480 (4)
N1—C2	1.489 (4)	C11—H11A	0.98
N1—C15	1.513 (3)	C11—H11B	0.98
N1—O23	2.929 (3)	N12—C13	1.338 (4)
N1—O25	3.13 (2)	C13—C14	1.487 (4)
N1—H1	0.92	C13—C131	1.507 (4)
C2—C3	1.499 (4)	C131—H13A	0.97
C2—H2A	0.98	C131—H13B	0.97
C2—H2B	0.98	C131—H13C	0.97
C3—N4	1.491 (4)	C14—C15	1.528 (4)
C3—H3A	0.98	C14—H14A	0.98
C3—H3B	0.98	C14—H14B	0.98
N4—C5	1.516 (3)	C15—C152	1.521 (4)
N4—O14	3.054 (5)	C15—C151	1.535 (4)
N4—O16	3.11 (2)	C151—H15A	0.97
N4—H4	0.92	C151—H15B	0.97
C5—C51	1.521 (4)	C151—H15C	0.97
C5—C6	1.528 (4)	C152—H15D	0.97
C5—C52	1.531 (4)	C152—H15E	0.97
C51—H51A	0.97	C152—H15F	0.97
C51—H51B	0.97	Cl1—O12	1.365 (5)
C51—H51C	0.97	Cl1—O11	1.375 (3)
C52—H52A	0.97	Cl1—O13	1.425 (5)
C52—H52B	0.97	Cl1—O14	1.428 (4)
C52—H52C	0.97	Cl11—O16	1.38 (2)
C6—C7	1.489 (4)	Cl11—O15	1.44 (2)
C6—H6A	0.98	Cl11—O17	1.47 (3)
C6—H6B	0.98	Cl11—O18	1.50 (2)
C7—N8	1.346 (4)	Cl2—O22	1.416 (3)
C7—C71	1.511 (4)	Cl2—O24	1.426 (3)
C71—H71A	0.97	Cl2—O21	1.434 (3)
C71—H71B	0.97	Cl2—O23	1.438 (3)
C71—H71C	0.97	Cl21—O26	1.31 (2)
N8—C9	1.478 (4)	Cl21—O27	1.32 (2)
C9—C10	1.514 (4)	Cl21—O28	1.52 (2)
C9—H9A	0.98	Cl21—O25	1.53 (2)
C9—H9B	0.98

N8—Ni—N4	90.38 (10)	C10—C9—H9A	109.4 (2)
N8—Ni—N1	165.11 (11)	N8—C9—H9B	109.37 (14)
N4—Ni—N1	88.19 (9)	C10—C9—H9B	109.4 (2)
N8—Ni—N12	93.73 (10)	H9A—C9—H9B	108.0
N4—Ni—N12	163.43 (11)	C11—C10—C9	112.6 (2)
N1—Ni—N12	91.83 (10)	C11—C10—H10A	109.1 (2)
C2—N1—C15	113.8 (2)	C9—C10—H10A	109.1 (2)
C2—N1—Ni	107.0 (2)	C11—C10—H10B	109.1 (2)
C15—N1—Ni	114.0 (2)	C9—C10—H10B	109.1 (2)
C2—N1—O23	106.5 (2)	H10A—C10—H10B	107.8
C15—N1—O23	115.3 (2)	N12—C11—C10	112.2 (3)
Ni—N1—O23	98.82 (11)	N12—C11—H11A	109.2 (2)
C2—N1—O25	117.7 (4)	C10—C11—H11A	109.2 (2)
C15—N1—O25	96.0 (4)	N12—C11—H11B	109.17 (14)
Ni—N1—O25	108.2 (3)	C10—C11—H11B	109.2 (2)
C2—N1—H1	107.2 (2)	H11A—C11—H11B	107.9
C15—N1—H1	107.23 (13)	C13—N12—C11	120.5 (2)
Ni—N1—H1	107.23 (6)	C13—N12—Ni	126.0 (2)
O23—N1—H1	9.42 (10)	C11—N12—Ni	110.9 (2)
N1—C2—C3	107.0 (2)	N12—C13—C14	119.1 (3)
N1—C2—H2A	110.3 (2)	N12—C13—C131	120.2 (3)
C3—C2—H2A	110.3 (2)	C14—C13—C131	112.1 (2)
N1—C2—H2B	110.32 (15)	C13—C131—H13A	109.5 (2)
C3—C2—H2B	110.3 (2)	C13—C131—H13B	109.5 (2)
H2A—C2—H2B	108.6	H13A—C131—H13B	109.5
N4—C3—C2	107.1 (2)	C13—C131—H13C	109.5 (2)
N4—C3—H3A	110.3 (2)	H13A—C131—H13C	109.5
C2—C3—H3A	110.3 (2)	H13B—C131—H13C	109.5
N4—C3—H3B	110.29 (15)	C13—C14—C15	120.2 (2)
C2—C3—H3B	110.3 (2)	C13—C14—H14A	107.3 (2)
H3A—C3—H3B	108.5	C15—C14—H14A	107.28 (15)
C3—N4—C5	114.0 (2)	C13—C14—H14B	107.3 (2)
C3—N4—Ni	108.3 (2)	C15—C14—H14B	107.28 (15)
C5—N4—Ni	111.5 (2)	H14A—C14—H14B	106.9
C3—N4—O14	102.4 (2)	N1—C15—C152	110.1 (2)
C5—N4—O14	100.7 (2)	N1—C15—C14	107.5 (2)
Ni—N4—O14	119.82 (12)	C152—C15—C14	111.3 (2)
C3—N4—O16	121.9 (5)	N1—C15—C151	109.6 (2)
C5—N4—O16	91.9 (4)	C152—C15—C151	110.5 (2)
Ni—N4—O16	108.4 (4)	C14—C15—C151	107.7 (2)
C3—N4—H4	107.6 (2)	C15—C151—H15A	109.5 (2)
C5—N4—H4	107.61 (14)	C15—C151—H15B	109.5 (2)
Ni—N4—H4	107.61 (7)	H15A—C151—H15B	109.5
O14—N4—H4	12.22 (9)	C15—C151—H15C	109.5 (2)
N4—C5—C51	109.0 (2)	H15A—C151—H15C	109.5
N4—C5—C6	108.2 (2)	H15B—C151—H15C	109.5
C51—C5—C6	111.8 (2)	C15—C152—H15D	109.5 (2)
N4—C5—C52	109.9 (2)	C15—C152—H15E	109.5 (2)
C51—C5—C52	110.6 (3)	H15D—C152—H15E	109.5
C6—C5—C52	107.2 (2)	C15—C152—H15F	109.47 (15)
C5—C51—H51A	109.5 (2)	H15D—C152—H15F	109.5
C5—C51—H51B	109.5 (2)	H15E—C152—H15F	109.5
H51A—C51—H51B	109.5	O12—Cl1—O11	115.2 (4)
C5—C51—H51C	109.47 (15)	O12—Cl1—O13	109.2 (5)
H51A—C51—H51C	109.5	O11—Cl1—O13	110.0 (3)
H51B—C51—H51C	109.5	O12—Cl1—O14	108.1 (4)
C5—C52—H52A	109.5 (2)	O11—Cl1—O14	108.1 (3)
C5—C52—H52B	109.5 (2)	O13—Cl1—O14	105.9 (3)
H52A—C52—H52B	109.5	Cl1—O14—H4	98.2 (2)
C5—C52—H52C	109.5 (2)	Cl1—O14—N4	103.3 (2)
H52A—C52—H52C	109.5	O16—Cl11—O15	116.8 (12)
H52B—C52—H52C	109.5	O16—Cl11—O17	110.7 (18)
C7—C6—C5	120.5 (2)	O15—Cl11—O17	107.8 (18)
C7—C6—H6A	107.2 (2)	O16—Cl11—O18	108.6 (12)
C5—C6—H6A	107.2 (2)	O15—Cl11—O18	109.2 (12)
C7—C6—H6B	107.2 (2)	O17—Cl11—O18	102.9 (18)
C5—C6—H6B	107.2 (2)	Cl11—O16—N4	101.8 (10)
H6A—C6—H6B	106.8	O22—Cl2—O24	111.4 (3)
N8—C7—C6	118.3 (3)	O22—Cl2—O21	109.9 (3)
N8—C7—C71	120.1 (3)	O24—Cl2—O21	107.6 (3)
C6—C7—C71	113.1 (3)	O22—Cl2—O23	110.7 (2)
C7—C71—H71A	109.5 (2)	O24—Cl2—O23	109.9 (2)
C7—C71—H71B	109.5 (2)	O21—Cl2—O23	107.2 (2)
H71A—C71—H71B	109.5	Cl2—O23—H1	136.3 (2)
C7—C71—H71C	109.5 (2)	Cl2—O23—N1	135.6 (2)
H71A—C71—H71C	109.5	O26—Cl21—O27	126.6 (15)
H71B—C71—H71C	109.5	O26—Cl21—O28	107.2 (14)
C7—N8—C9	120.0 (2)	O27—Cl21—O28	105.2 (11)
C7—N8—Ni	125.2 (2)	O26—Cl21—O25	109.1 (14)
C9—N8—Ni	111.0 (2)	O27—Cl21—O25	107.1 (11)
N8—C9—C10	111.3 (2)	O28—Cl21—O25	97.7 (11)
N8—C9—H9A	109.4 (2)	Cl21—O25—N1	118.0 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O23	0.92	2.03	2.93 (1)	166
N1—H1···O25	0.92	2.24	3.13 (3)	163
N4—H4···O12	0.92	2.48	3.23 (1)	138
N4—H4···O14	0.92	2.17	3.06 (1)	163
N4—H4···O16	0.92	2.25	3.12 (2)	156
N4—H4···O18	0.92	2.45	3.16 (3)	134
C51—H51B···O26	0.97	2.51	2.98 (3)	110
C6—H6B···O16	0.98	2.27	3.07 (2)	137
C14—H14B···O25	0.98	2.46	3.28 (2)	140
C71—H71C···O17ⁱ	0.97	2.48	2.96 (5)	111
C131—H13C···O15ⁱⁱ	0.97	2.48	2.90 (5)	106

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₇H₃₄N₄)](ClO₄)₂
M_r	552.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	203
a, b, c (Å)	10.3529 (1), 16.1128 (1), 15.0400 (1)
β (°)	107.025 (1)
V (Å³)	2398.94 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.25 × 0.17 × 0.16

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.774, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	14323, 5243, 4531
R_int	0.002
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.105, 1.04
No. of reflections	5243
No. of parameters	327
No. of restraints	40
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.66

Computer programs: SMART (Siemens, 1995), SMART, SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Ni—N8	1.915 (2)	Ni—N12	1.929 (2)
Ni—N4	1.920 (2)	C7—N8	1.346 (4)
Ni—N1	1.924 (2)	N12—C13	1.338 (4)

N8—Ni—N4	90.38 (10)	C7—N8—Ni	125.2 (2)
N8—Ni—N1	165.11 (11)	C9—N8—Ni	111.0 (2)
N4—Ni—N1	88.19 (9)	C11—C10—C9	112.6 (2)
N8—Ni—N12	93.73 (10)	C13—N12—C11	120.5 (2)
N4—Ni—N12	163.43 (11)	C13—N12—Ni	126.0 (2)
N1—Ni—N12	91.83 (10)	C11—N12—Ni	110.9 (2)
C7—C6—C5	120.5 (2)	N12—C13—C14	119.1 (3)
N8—C7—C6	118.3 (3)	N12—C13—C131	120.2 (3)
N8—C7—C71	120.1 (3)	C14—C13—C131	112.1 (2)
C6—C7—C71	113.1 (3)	C13—C14—C15	120.2 (2)
C7—N8—C9	120.0 (2)