(C-rac-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)(nicotinato-O,O′)nickel(II) perchlorate

Basiuk, E.V.; Basiuk, V.A.; Hernández-Ortega, S.; Martínez-García, M.; Saniger-Blesa, J.-M.

doi:10.1107/S010827010100333X

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(C-rac-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)(nicotinato-O,O′)nickel(II) perchlorate

E. V. Basiuk, V. A. Basiuk, S. Hernández-Ortega, M. Martínez-García and J.-M. Saniger-Blesa

In the title compound, [Ni(C₆H₄NO₂)(C₁₆H₃₆N₄)]ClO₄, the macrocyclic unit adopts a folded conformation, allowing the two carboxyl O atoms to occupy two neighbouring coordination sites and thus form an additional four-membered chelate ring. The less crowded side of the macrocycle (that with the two asymmetric C—H groups) is directed towards the nicotinate anion and the asymmetric C—CH₃ groups are directed away from it. The macrocyclic NH groups neighbouring the C—CH₃ groups are also directed away from the nicotinate anion, while those NH groups which are near to the geminal methyl groups are directed towards the nicotinate anion. Although the complex does not include water molecules, three types of hydrogen bond were found, involving NH groups of the macrocyclic ligand, pyridine N atoms and O atoms of the perchlorate anions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010100333X/da1165sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S010827010100333X/da1165Isup2.hkl Contains datablock I

CCDC reference: 164640

Comment top

Many Ni^II complexes with saturated 12- to 16-membered tetraazamacrocyclic ligands are known to exist, both in a low-spin square-planar tetracoordinated form and in a high-spin octahedral hexacoordinated form (see, for example, Adam et al., 1994, 1996). We are especially interested in the more rarely studied (although known for more than three decades) `Curtis-type' complexes with the common saturated ligand rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (rac-Me₆[14]aneN₄) and carboxylic acids (Basiuk et al., 2000; Curtis, 1964, 1968; Whimp et al., 1970). In these complexes, the macrocyclic unit adopts a folded conformation, allowing the two carboxylic O atoms to occupy two neighbouring coordination sites and thus form a four-membered chelate ring. Until recently, the only known structurally characterized example of complexes of this type was [Ni^II(rac-Me₆[14]aneN₄)]-acetate monoperchlorate (Whimp et al., 1970); another example is a bridged complex, bis[Ni^II(rac-Me₆[14]aneN₄)]-2,5-pyridinedicarboxylate diperchlorate monohydrate, synthesized and characterized recently by us (Basiuk et al., 2000). In addition, we have undertaken the preparation and X-ray analysis of the 3,5-pyridinedicarboxylic analogue of the latter. However, although good quality single crystals have been obtained (after many unsuccessful attempts), they appeared to decay before the X-ray diffraction data collected were sufficient for structure solution.

In the present paper we report the preparation and X-ray structure determination of another high-spin complex of the above type, (nicotinato- O,O')(C-rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane- N,N',N'',N''')nickel(II) perchlorate, (I). As in its acetate and 2,5-pyridinedicarboxylate analogues, the less crowded side of the macrocycle (that with the two asymmetric C—H groups) is directed towards the nicotinate anion and the asymmetric C—CH₃ groups are directed away from it. The NH groups of the macrocycle neighbouring the C—CH₃ groups are also directed away from the nicotinate, while those NH groups which are near to the geminal methyl groups are directed towards the nicotinate anion.

The macrocyclic units are folded around N1—Ni1—N8 [172.24 (13)°], with an N4—Ni1—N11 angle of 103.21 (13)°. These values are very close to the corresponding parameters for the macrocyclic unit in the bridged complex bis[Ni^II(rac-Me₆[14]aneN₄)]-2,5-pyridinedicarboxylate diperchlorate monohydrate (ca 176 and 103°, respectively; Basiuk et al., 2000). A dissimilarity between the two complexes occurs with the Ni—O distances, which are almost equal in the nicotinate [2.153 (3) and 2.156 (3) Å], but noticeably different in the bridged complex [2.123 (12) and 2.255 (13) Å], apparently due to a steric hindrance created by the second macrocyclic moiety. The mean Ni—N distance in (I) is 2.12 Å, which is typical for an octahedral triplet ground-state Ni^II coordinated to secondary amino groups (Whimp et al., 1970).

Unlike the 2,5-pyridinedicarboxylate, and similar to [Ni^II(rac-Me₆[14]aneN₄)]-acetate monoperchlorate (Whimp et al., 1970), complex (I) does not include water molecules. Nevertheless, there are three types of hydrogen bonds involving NH groups of the macrocyclic ligand, pyridine N atoms and O atoms of the perchlorate anions (Fig. 2), namely N8—H8···N21, N4—H4···O4 and N11—H11···O4.

Related literature top

For related literature, see: Adam et al. (1994, 1996); Basiuk et al. (2000); Curtis (1964, 1968); Whimp et al. (1970).

Experimental top

Caution: perchlorate salts of metal complexes are potentially explosive and should be handled with care. Nicotinic acid (Aldrich) was used without further purification. [Ni^II(rac-Me₆[14]aneN₄)](ClO₄)₂ was synthesized by complexation of the free ligand with Ni^II acetate in methanol, followed by the addition of perchloric acid (Curtis, 1964). The title complex was synthesized in a manner similar to that used for the 2,5-pyridinedicarboxylic analogue (Basiuk et al., 2000), by dissolving [Ni^II(rac-Me₆[14]aneN₄)](ClO₄)₂ (0.54 g, 1 mmol) and nicotinic acid (0.25 g, 2 mmol) in water (100 ml) and adjusting the pH to ca 12 by adding NH₄OH. The solution was heated with stirring until the solvent was evaporated by half. Violet-blue crystals of the product were filtered after standing for 2 d at room temperature. Crystals of (I) suitable for X-ray analysis were obtained by recrystallization from methanol.

Computing details top

Data collection: XSCANS (Siemens 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick 1990); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I) drawn with 40% probability displacement ellipsoids. H atoms on C have been omitted; the remaining H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing diagram for (I).

(Nicotinato-O,O')(C-rac-5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane-N,N',N'',N''')nickel(II) perchlorate top

Crystal data top

[Ni(C₁₆H₃₆N₄)(C₆H₄NO₂)]·(ClO₄)	F(000) = 1200
M_r = 564.75	D_x = 1.336 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.474 (2) Å	Cell parameters from 50 reflections
b = 13.221 (2) Å	θ = 3.9–21.5°
c = 20.288 (3) Å	µ = 0.83 mm⁻¹
β = 91.33 (1)°	T = 293 K
V = 2808.7 (8) Å³	Prism, violet
Z = 4	0.36 × 0.24 × 0.16 mm

Data collection top

Siemens P4/PC diffractometer	2980 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 25°, θ_min = 1.8°
ω scans	h = 0→12
Absorption correction: ψ-scan (North et al., 1968)	k = 0→15
T_min = 0.755, T_max = 0.879	l = −24→24
5239 measured reflections	3 standard reflections every 97 reflections
4950 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	Calculated w = 1/[σ²(F_o²) + (0.025P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.009
4950 reflections	Δρ_max = 0.70 e Å⁻³
335 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00184 (16)

Crystal data top

[Ni(C₁₆H₃₆N₄)(C₆H₄NO₂)]·(ClO₄)	V = 2808.7 (8) Å³
M_r = 564.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.474 (2) Å	µ = 0.83 mm⁻¹
b = 13.221 (2) Å	T = 293 K
c = 20.288 (3) Å	0.36 × 0.24 × 0.16 mm
β = 91.33 (1)°

Data collection top

Siemens P4/PC diffractometer	2980 reflections with I > 2σ(I)
Absorption correction: ψ-scan (North et al., 1968)	R_int = 0.057
T_min = 0.755, T_max = 0.879	3 standard reflections every 97 reflections
5239 measured reflections	intensity decay: none
4950 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.70 e Å⁻³
4950 reflections	Δρ_min = −0.35 e Å⁻³
335 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

	x	y	z	U_iso*/U_eq
Ni1	0.21203 (5)	0.13469 (4)	0.15470 (2)	0.04081 (14)
Cl1	−0.13188 (12)	0.09815 (10)	0.31852 (6)	0.0676 (3)
O1	−0.2059 (5)	0.0300 (4)	0.3533 (3)	0.1272 (18)
O2	−0.2099 (5)	0.1608 (4)	0.2779 (3)	0.144 (2)
O3	−0.0746 (6)	0.1727 (5)	0.3596 (3)	0.171 (3)
O4	−0.0379 (6)	0.0523 (3)	0.2846 (3)	0.157 (3)
O5	0.3763 (3)	0.2229 (2)	0.12833 (14)	0.0574 (8)
O6	0.2942 (3)	0.1101 (2)	0.05975 (13)	0.0540 (7)
N1	0.1043 (3)	0.2693 (3)	0.13465 (17)	0.0511 (9)
H1	0.166 (4)	0.312 (3)	0.126 (2)	0.061*
C2	0.0618 (4)	0.3008 (3)	0.2013 (2)	0.0599 (12)
H2A	−0.0111	0.2605	0.2139	0.072*
H2B	0.0358	0.3713	0.2003	0.072*
C3	0.1687 (4)	0.2869 (3)	0.2506 (2)	0.0606 (12)
H3A	0.2419	0.3267	0.2379	0.073*
H3B	0.1424	0.3098	0.2937	0.073*
N4	0.2034 (3)	0.1797 (3)	0.25361 (16)	0.0489 (8)
H4	0.146 (4)	0.141 (4)	0.268 (2)	0.059*
C5	0.3197 (4)	0.1599 (4)	0.2958 (2)	0.0642 (13)
H5	0.3927	0.1943	0.2763	0.077*
C6	0.3483 (5)	0.0471 (4)	0.2997 (2)	0.0688 (13)
H6A	0.2707	0.0133	0.3128	0.083*
H6B	0.4109	0.0372	0.3351	0.083*
C7	0.3974 (4)	−0.0084 (4)	0.2386 (2)	0.0660 (13)
N8	0.2991 (3)	−0.0043 (3)	0.18354 (18)	0.0503 (9)
H8	0.333 (4)	−0.027 (4)	0.155 (2)	0.060*
C9	0.1894 (4)	−0.0739 (3)	0.1914 (2)	0.0596 (12)
H9A	0.1506	−0.0623	0.2337	0.072*
H9B	0.2188	−0.1435	0.1902	0.072*
C10	0.0931 (4)	−0.0564 (3)	0.1372 (2)	0.0576 (11)
H10A	0.1320	−0.0678	0.0949	0.069*
H10B	0.0228	−0.1035	0.1414	0.069*
N11	0.0449 (3)	0.0488 (3)	0.14071 (17)	0.0459 (8)
H11	0.001 (4)	0.053 (3)	0.176 (2)	0.055*
C12	−0.0431 (4)	0.0768 (4)	0.0851 (2)	0.0559 (11)
H12	0.0039	0.0706	0.0441	0.067*
C13	−0.0894 (4)	0.1848 (4)	0.0905 (3)	0.0652 (13)
H13A	−0.1260	0.1925	0.1337	0.078*
H13B	−0.1585	0.1935	0.0583	0.078*
C14	0.0039 (5)	0.2726 (4)	0.0813 (2)	0.0639 (12)
C15	0.3025 (7)	0.2001 (5)	0.3654 (3)	0.107 (2)
H15A	0.3741	0.1802	0.3928	0.129*
H15B	0.2255	0.1729	0.3831	0.129*
H15C	0.2971	0.2726	0.3642	0.129*
C16	0.5176 (4)	0.0410 (5)	0.2132 (3)	0.0878 (18)
H16A	0.4981	0.1084	0.1984	0.105*
H16B	0.5494	0.0021	0.1771	0.105*
H16C	0.5812	0.0437	0.2480	0.105*
C17	0.4284 (6)	−0.1187 (5)	0.2581 (3)	0.0956 (19)
H17A	0.4450	−0.1573	0.2191	0.115*
H17B	0.3570	−0.1475	0.2802	0.115*
H17C	0.5023	−0.1199	0.2869	0.115*
C18	−0.1597 (5)	0.0064 (4)	0.0801 (3)	0.0817 (16)
H18A	−0.1316	−0.0618	0.0732	0.098*
H18B	−0.2139	0.0270	0.0438	0.098*
H18C	−0.2063	0.0100	0.1202	0.098*
C19	0.0692 (6)	0.2662 (5)	0.0156 (2)	0.0842 (16)
H19A	0.1237	0.3239	0.0104	0.101*
H19B	0.0058	0.2652	−0.0194	0.101*
H19C	0.1193	0.2055	0.0140	0.101*
C20	−0.0720 (6)	0.3724 (5)	0.0831 (3)	0.0996 (19)
H20A	−0.0138	0.4284	0.0861	0.120*
H20B	−0.1260	0.3725	0.1207	0.120*
H20C	−0.1237	0.3785	0.0436	0.120*
N21	0.5854 (4)	0.1555 (4)	−0.0727 (2)	0.0855 (14)
C22	0.4987 (4)	0.1375 (4)	−0.0266 (2)	0.0636 (12)
H22	0.4534	0.0771	−0.0287	0.076*
C23	0.4732 (4)	0.2041 (3)	0.0238 (2)	0.0497 (10)
C24	0.5387 (4)	0.2940 (4)	0.0266 (2)	0.0664 (13)
H24	0.5252	0.3397	0.0605	0.080*
C25	0.6252 (5)	0.3154 (5)	−0.0221 (3)	0.0866 (17)
H25	0.6691	0.3766	−0.0225	0.104*
C26	0.6439 (6)	0.2441 (6)	−0.0691 (3)	0.0943 (19)
H26	0.7026	0.2588	−0.1014	0.113*
C27	0.3758 (4)	0.1772 (3)	0.07360 (19)	0.0482 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0394 (2)	0.0461 (3)	0.0374 (2)	−0.0069 (2)	0.00885 (17)	−0.0055 (3)
Cl1	0.0691 (7)	0.0683 (8)	0.0662 (7)	0.0022 (6)	0.0193 (6)	−0.0044 (6)
O1	0.111 (3)	0.133 (4)	0.141 (4)	0.002 (3)	0.074 (3)	0.043 (3)
O2	0.133 (4)	0.122 (4)	0.175 (5)	0.004 (3)	−0.035 (4)	0.037 (4)
O3	0.140 (5)	0.193 (6)	0.179 (6)	−0.003 (4)	−0.024 (4)	−0.099 (5)
O4	0.218 (6)	0.063 (3)	0.197 (5)	0.018 (3)	0.156 (5)	0.012 (3)
O5	0.0530 (16)	0.071 (2)	0.0488 (17)	−0.0168 (15)	0.0118 (13)	−0.0109 (15)
O6	0.0561 (16)	0.061 (2)	0.0456 (15)	−0.0154 (14)	0.0128 (13)	−0.0033 (13)
N1	0.053 (2)	0.051 (2)	0.049 (2)	−0.0046 (17)	0.0021 (16)	−0.0006 (17)
C2	0.070 (3)	0.046 (3)	0.065 (3)	0.005 (2)	0.011 (2)	−0.013 (2)
C3	0.073 (3)	0.058 (3)	0.051 (3)	−0.010 (2)	0.009 (2)	−0.019 (2)
N4	0.0502 (19)	0.052 (2)	0.0447 (19)	−0.0105 (16)	0.0066 (15)	−0.0063 (16)
C5	0.062 (3)	0.076 (4)	0.055 (3)	−0.009 (2)	−0.006 (2)	−0.012 (2)
C6	0.066 (3)	0.092 (4)	0.048 (3)	0.003 (3)	−0.005 (2)	0.004 (3)
C7	0.050 (2)	0.085 (4)	0.063 (3)	0.012 (2)	0.002 (2)	0.006 (3)
N8	0.0428 (18)	0.057 (2)	0.051 (2)	0.0016 (16)	0.0115 (16)	−0.0043 (17)
C9	0.059 (3)	0.051 (3)	0.070 (3)	−0.002 (2)	0.019 (2)	0.003 (2)
C10	0.060 (3)	0.046 (3)	0.068 (3)	−0.011 (2)	0.009 (2)	−0.008 (2)
N11	0.0425 (18)	0.054 (2)	0.0422 (19)	−0.0081 (15)	0.0098 (15)	−0.0095 (16)
C12	0.050 (2)	0.066 (3)	0.052 (2)	−0.009 (2)	0.003 (2)	−0.015 (2)
C13	0.050 (2)	0.077 (3)	0.068 (3)	0.007 (2)	−0.008 (2)	−0.007 (3)
C14	0.071 (3)	0.056 (3)	0.064 (3)	0.010 (2)	−0.013 (2)	0.000 (2)
C15	0.128 (5)	0.125 (6)	0.067 (4)	0.024 (4)	−0.033 (4)	−0.034 (4)
C16	0.045 (3)	0.131 (5)	0.087 (4)	0.006 (3)	0.000 (2)	−0.004 (4)
C17	0.096 (4)	0.098 (5)	0.093 (4)	0.042 (4)	−0.005 (3)	0.010 (4)
C18	0.061 (3)	0.096 (4)	0.087 (4)	−0.023 (3)	−0.012 (3)	−0.019 (3)
C19	0.110 (4)	0.089 (4)	0.053 (3)	−0.007 (3)	−0.009 (3)	0.017 (3)
C20	0.103 (4)	0.083 (4)	0.112 (5)	0.017 (4)	−0.026 (4)	−0.005 (4)
N21	0.092 (3)	0.087 (4)	0.080 (3)	0.006 (3)	0.047 (2)	0.006 (3)
C22	0.070 (3)	0.067 (3)	0.055 (2)	0.004 (3)	0.026 (2)	0.013 (3)
C23	0.044 (2)	0.063 (3)	0.043 (2)	−0.008 (2)	0.0065 (17)	0.004 (2)
C24	0.060 (3)	0.084 (4)	0.056 (3)	−0.021 (3)	0.007 (2)	−0.002 (2)
C25	0.067 (3)	0.104 (5)	0.089 (4)	−0.034 (3)	0.016 (3)	0.018 (4)
C26	0.084 (4)	0.119 (5)	0.081 (4)	−0.008 (4)	0.043 (3)	0.016 (4)
C27	0.041 (2)	0.063 (3)	0.041 (2)	−0.008 (2)	0.0102 (17)	0.004 (2)

Geometric parameters (Å, º) top

Ni1—N4	2.097 (3)	C10—H10B	0.9700
Ni1—N11	2.101 (3)	N11—C12	1.488 (6)
Ni1—N8	2.127 (4)	N11—H11	0.86 (4)
Ni1—N1	2.141 (4)	C12—C13	1.513 (6)
Ni1—O6	2.153 (3)	C12—C18	1.537 (6)
Ni1—O5	2.156 (3)	C12—H12	0.9800
Ni1—C27	2.469 (3)	C13—C14	1.531 (7)
Cl1—O4	1.358 (4)	C13—H13A	0.9700
Cl1—O1	1.391 (4)	C13—H13B	0.9700
Cl1—O2	1.415 (5)	C14—C19	1.516 (7)
Cl1—O3	1.416 (5)	C14—C20	1.541 (7)
O5—C27	1.264 (5)	C15—H15A	0.9600
O6—C27	1.259 (5)	C15—H15B	0.9600
N1—C14	1.492 (6)	C15—H15C	0.9600
N1—C2	1.493 (5)	C16—H16A	0.9600
N1—H1	0.87 (4)	C16—H16B	0.9600
C2—C3	1.496 (6)	C16—H16C	0.9600
C2—H2A	0.9700	C17—H17A	0.9600
C2—H2B	0.9700	C17—H17B	0.9600
C3—N4	1.464 (6)	C17—H17C	0.9600
C3—H3A	0.9700	C18—H18A	0.9600
C3—H3B	0.9700	C18—H18B	0.9600
N4—C5	1.495 (6)	C18—H18C	0.9600
N4—H4	0.84 (4)	C19—H19A	0.9600
C5—C6	1.523 (7)	C19—H19B	0.9600
C5—C15	1.525 (7)	C19—H19C	0.9600
C5—H5	0.9800	C20—H20A	0.9600
C6—C7	1.539 (7)	C20—H20B	0.9600
C6—H6A	0.9700	C20—H20C	0.9600
C6—H6B	0.9700	N21—C26	1.323 (8)
C7—N8	1.502 (6)	N21—C22	1.340 (5)
C7—C16	1.519 (7)	C22—C23	1.379 (6)
C7—C17	1.544 (8)	C22—H22	0.9300
N8—C9	1.484 (5)	C23—C24	1.373 (6)
N8—H8	0.75 (4)	C23—C27	1.496 (5)
C9—C10	1.492 (6)	C24—C25	1.385 (7)
C9—H9A	0.9700	C24—H24	0.9300
C9—H9B	0.9700	C25—C26	1.358 (8)
C10—N11	1.482 (6)	C25—H25	0.9300
C10—H10A	0.9700	C26—H26	0.9300

N4—Ni1—N11	103.21 (13)	N11—C10—H10B	109.7
N4—Ni1—N8	90.57 (14)	C9—C10—H10B	109.7
N11—Ni1—N8	85.45 (14)	H10A—C10—H10B	108.2
N4—Ni1—N1	84.92 (14)	C10—N11—C12	113.8 (3)
N11—Ni1—N1	89.43 (14)	C10—N11—Ni1	103.3 (2)
N8—Ni1—N1	172.24 (13)	C12—N11—Ni1	117.9 (3)
N4—Ni1—O6	157.85 (12)	C10—N11—H11	107 (3)
N11—Ni1—O6	98.42 (12)	C12—N11—H11	106 (3)
N8—Ni1—O6	86.42 (12)	Ni1—N11—H11	109 (3)
N1—Ni1—O6	100.11 (12)	N11—C12—C13	112.0 (4)
N4—Ni1—O5	97.84 (12)	N11—C12—C18	112.1 (4)
N11—Ni1—O5	157.86 (12)	C13—C12—C18	108.7 (4)
N8—Ni1—O5	101.28 (12)	N11—C12—H12	108.0
N1—Ni1—O5	85.62 (13)	C13—C12—H12	108.0
O6—Ni1—O5	61.43 (10)	C18—C12—H12	108.0
N4—Ni1—C27	128.25 (14)	C12—C13—C14	120.0 (4)
N11—Ni1—C27	128.51 (13)	C12—C13—H13A	107.3
N8—Ni1—C27	94.57 (13)	C14—C13—H13A	107.3
N1—Ni1—C27	93.17 (14)	C12—C13—H13B	107.3
O6—Ni1—C27	30.66 (12)	C14—C13—H13B	107.3
O5—Ni1—C27	30.78 (12)	H13A—C13—H13B	106.9
O4—Cl1—O1	112.8 (3)	N1—C14—C19	108.2 (4)
O4—Cl1—O2	112.5 (4)	N1—C14—C13	109.3 (4)
O1—Cl1—O2	110.7 (3)	C19—C14—C13	111.5 (4)
O4—Cl1—O3	108.0 (4)	N1—C14—C20	111.4 (4)
O1—Cl1—O3	112.7 (4)	C19—C14—C20	108.2 (5)
O2—Cl1—O3	99.5 (4)	C13—C14—C20	108.4 (4)
C27—O5—Ni1	88.4 (2)	C5—C15—H15A	109.5
C27—O6—Ni1	88.7 (2)	C5—C15—H15B	109.5
C14—N1—C2	115.3 (4)	H15A—C15—H15B	109.5
C14—N1—Ni1	121.5 (3)	C5—C15—H15C	109.5
C2—N1—Ni1	103.1 (3)	H15A—C15—H15C	109.5
C14—N1—H1	110 (3)	H15B—C15—H15C	109.5
C2—N1—H1	104 (3)	C7—C16—H16A	109.5
Ni1—N1—H1	101 (3)	C7—C16—H16B	109.5
N1—C2—C3	109.7 (4)	H16A—C16—H16B	109.5
N1—C2—H2A	109.7	C7—C16—H16C	109.5
C3—C2—H2A	109.7	H16A—C16—H16C	109.5
N1—C2—H2B	109.7	H16B—C16—H16C	109.5
C3—C2—H2B	109.7	C7—C17—H17A	109.5
H2A—C2—H2B	108.2	C7—C17—H17B	109.5
N4—C3—C2	109.1 (4)	H17A—C17—H17B	109.5
N4—C3—H3A	109.9	C7—C17—H17C	109.5
C2—C3—H3A	109.9	H17A—C17—H17C	109.5
N4—C3—H3B	109.9	H17B—C17—H17C	109.5
C2—C3—H3B	109.9	C12—C18—H18A	109.5
H3A—C3—H3B	108.3	C12—C18—H18B	109.5
C3—N4—C5	113.1 (4)	H18A—C18—H18B	109.5
C3—N4—Ni1	104.6 (3)	C12—C18—H18C	109.5
C5—N4—Ni1	116.4 (3)	H18A—C18—H18C	109.5
C3—N4—H4	115 (3)	H18B—C18—H18C	109.5
C5—N4—H4	106 (3)	C14—C19—H19A	109.5
Ni1—N4—H4	101 (3)	C14—C19—H19B	109.5
N4—C5—C6	111.0 (4)	H19A—C19—H19B	109.5
N4—C5—C15	110.9 (4)	C14—C19—H19C	109.5
C6—C5—C15	108.7 (5)	H19A—C19—H19C	109.5
N4—C5—H5	108.7	H19B—C19—H19C	109.5
C6—C5—H5	108.7	C14—C20—H20A	109.5
C15—C5—H5	108.7	C14—C20—H20B	109.5
C5—C6—C7	119.6 (4)	H20A—C20—H20B	109.5
C5—C6—H6A	107.4	C14—C20—H20C	109.5
C7—C6—H6A	107.4	H20A—C20—H20C	109.5
C5—C6—H6B	107.4	H20B—C20—H20C	109.5
C7—C6—H6B	107.4	C26—N21—C22	116.1 (5)
H6A—C6—H6B	107.0	N21—C22—C23	123.3 (5)
N8—C7—C16	106.9 (4)	N21—C22—H22	118.3
N8—C7—C6	110.3 (4)	C23—C22—H22	118.3
C16—C7—C6	111.3 (5)	C24—C23—C22	118.6 (4)
N8—C7—C17	111.1 (4)	C24—C23—C27	121.7 (4)
C16—C7—C17	108.8 (4)	C22—C23—C27	119.7 (4)
C6—C7—C17	108.4 (4)	C23—C24—C25	118.9 (5)
C9—N8—C7	114.6 (4)	C23—C24—H24	120.6
C9—N8—Ni1	103.7 (3)	C25—C24—H24	120.6
C7—N8—Ni1	121.2 (3)	C26—C25—C24	117.7 (5)
C9—N8—H8	102 (4)	C26—C25—H25	121.1
C7—N8—H8	103 (4)	C24—C25—H25	121.1
Ni1—N8—H8	110 (4)	N21—C26—C25	125.4 (5)
N8—C9—C10	109.6 (4)	N21—C26—H26	117.3
N8—C9—H9A	109.7	C25—C26—H26	117.3
C10—C9—H9A	109.7	O6—C27—O5	121.5 (3)
N8—C9—H9B	109.7	O6—C27—C23	119.1 (4)
C10—C9—H9B	109.7	O5—C27—C23	119.4 (4)
H9A—C9—H9B	108.2	O6—C27—Ni1	60.65 (18)
N11—C10—C9	109.6 (4)	O5—C27—Ni1	60.80 (18)
N11—C10—H10A	109.7	C23—C27—Ni1	179.0 (3)
C9—C10—H10A	109.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···N21ⁱ	0.75 (4)	2.54 (5)	3.263 (5)	161 (5)
N4—H4···O4	0.84 (4)	2.29 (5)	3.114 (6)	166 (4)
N11—H11···O4	0.86 (4)	2.26 (4)	3.064 (6)	157 (4)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₆H₃₆N₄)(C₆H₄NO₂)]·(ClO₄)
M_r	564.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.474 (2), 13.221 (2), 20.288 (3)
β (°)	91.33 (1)
V (Å³)	2808.7 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.36 × 0.24 × 0.16

Data collection
Diffractometer	Siemens P4/PC diffractometer
Absorption correction	ψ-scan (North et al., 1968)
T_min, T_max	0.755, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	5239, 4950, 2980
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.100, 0.96
No. of reflections	4950
No. of parameters	335
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.35

Computer programs: XSCANS (Siemens 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick 1990), SHELXL97.

Selected geometric parameters (Å, º) top

Ni1—N4	2.097 (3)	Ni1—N1	2.141 (4)
Ni1—N11	2.101 (3)	Ni1—O6	2.153 (3)
Ni1—N8	2.127 (4)	Ni1—O5	2.156 (3)

N4—Ni1—N11	103.21 (13)	N11—Ni1—O5	157.86 (12)
N4—Ni1—N8	90.57 (14)	N8—Ni1—O5	101.28 (12)
N11—Ni1—N8	85.45 (14)	N1—Ni1—O5	85.62 (13)
N4—Ni1—N1	84.92 (14)	O6—Ni1—O5	61.43 (10)
N11—Ni1—N1	89.43 (14)	N4—Ni1—C27	128.25 (14)
N8—Ni1—N1	172.24 (13)	N11—Ni1—C27	128.51 (13)
N4—Ni1—O6	157.85 (12)	N8—Ni1—C27	94.57 (13)
N11—Ni1—O6	98.42 (12)	N1—Ni1—C27	93.17 (14)
N8—Ni1—O6	86.42 (12)	O6—Ni1—C27	30.66 (12)
N1—Ni1—O6	100.11 (12)	O5—Ni1—C27	30.78 (12)
N4—Ni1—O5	97.84 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···N21ⁱ	0.75 (4)	2.54 (5)	3.263 (5)	161 (5)
N4—H4···O4	0.84 (4)	2.29 (5)	3.114 (6)	166 (4)
N11—H11···O4	0.86 (4)	2.26 (4)	3.064 (6)	157 (4)

Symmetry code: (i) −x+1, −y, −z.

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