Bis[(3-hydr­oxy-2-naphth­yl)(2-pyridyl­methyl­ene­hydrazono)­methano­lato]­nickel(II)

In the title complex, [Ni(C₁₇H₁₂N₃O₂)₂], the Ni^II ion is coordinated by two O [Ni—O = 2.066 (3) and 2.068 (3) Å] and four N [Ni—N = 1.982 (3)–2.120 (3)Å] atoms in a distorted octa­hedral geometry. Two intra­molecular O—H...N hydrogen bonds contribute to the mol­ecular conformation. Weak inter­molecular C—H...O hydrogen bonds stabilize the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.047
• wR factor = 0.148
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.69 mm
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            N5  -NI1 -N2  -C12   142.00  2.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            N5  -NI1 -N2  -N1    -35.00  2.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         25
            N2  -NI1 -N5  -C29   139.00  2.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            N2  -NI1 -N5  -N4    -40.00  2.00   1.555   1.555   1.555   1.555

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.23

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The chemistry of aroylhydrazones is widely studied due to their coordination abilities to metal ions (Beghidja et al., 2006) and their biological activities (Mostafa & Haifaa, 2007). Our group have reported the crystal structures of two aroylhydrazone complexes - [Cu(C₁₂H₁₂N₂O₃)(C₅H₅N)] (Liu et al., 2005a) and [Ni(C₁₈H₁₂N₂O₃)(C₅H₅N)] (Liu et al., 2005b). As an extension of our work on the structural characterization of aroylhydrazone derivatives, the title complex, (I), was synthesized and characterized.

In (I) (Fig. 1), the Ni ion is six-coordinated by four N atoms and two O atoms in a distorted octahedron geometry. Each ligand coordinate the Ni ion in a tridentate mode via N atom of the azomethine group, O atom of the the hydroxyl group and N atom of the pyridine ring. Each ligand forms two five-membered chelate rings Ni—N—N—C—O and Ni—N—C—C—N with the nickel atom. The atoms N3, N6, O3 and O1 constitute the equatorial plane, with the mean deviation from plane of 0.43 (6) Å. The angles O1—Ni1—N3 and O3—Ni1—N6 are 155.95 (12) and 155.93 (13)°, respectively. The axial positions are occupied by the atoms N5 and N2. The angle of N5—Ni1—N2 is 176.33 (14)°. There are two intramolecular O2—H2···N1 and O4—H4···N4 hydrogen bonds (Table 1 and Fig. 1).

In the crystal, the weak intermolecular C—H···O hydrogen bonds (Table 1) contribute to the crystal packing stabilization.

Related literature

For related crystal structures of Cu and Ni complexes with aroylhydrazone derivatives, see Liu et al. (2005a,b). For general background, see Beghidja et al. (2006), and for the specific biological activities of aroylhydrazones, see Mostafa & Haifaa (2007).

S2. Experimental

A dimethylformamide solution (10 ml) of H₂L (0.073 g, 0.25 mmol) and KOH (0.014 g, 0.25 mmol) was mixed with a pyridine solution (10 ml) of Ni(OAC)₂⁴H₂O (0.062 g, 0.25 mmol). The mixture was stirred for 4 h, filtered, and was left to stand. Two weeks later, red crystals were isolated from the solution (m.p. >573 K). Analysis, calculated for C₃₄H₂₄N₆NiO₄: C 63.88, H 3.78, N 13.15%; found: C 63.76, H 3.80, N 13.01%.

S3. Refinement

All H atoms were placed in geometrically idealized positions (O—H 0.82 and C—H 0.93 Å) and treated as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. The dashed lines denote hydrogen bonds. C-bound H atoms have been omitted for clarity.

Bis[(3-hydroxy-2-naphthyl)(2-pyridylmethylenehydrazono)methanolato]nickel(II)

Crystal data

[Ni(C17H12N3O2)2]	F(000) = 1320
Mr = 639.30	Dx = 1.437 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.257 (3) Å	Cell parameters from 3186 reflections
b = 11.653 (3) Å	θ = 2.4–22.9°
c = 11.938 (3) Å	µ = 0.71 mm^−1
β = 91.686 (3)°	T = 293 K
V = 2955.6 (10) Å^3	Plate, red
Z = 4	0.69 × 0.66 × 0.13 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5202 independent reflections
Radiation source: fine-focus sealed tube	3068 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→23
Tmin = 0.641, Tmax = 0.914	k = −13→9
14859 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.6517P] where P = (Fo^2 + 2Fc^2)/3
5202 reflections	(Δ/σ)max = 0.001
408 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.45 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 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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.24926 (2)	0.45673 (5)	1.00715 (4)	0.03962 (19)
N1	0.31082 (16)	0.5566 (3)	0.8193 (3)	0.0468 (9)
N2	0.26876 (15)	0.5813 (3)	0.9004 (3)	0.0433 (8)
N3	0.18729 (15)	0.5883 (3)	1.0576 (3)	0.0405 (8)
N4	0.19264 (15)	0.2411 (3)	1.0620 (3)	0.0444 (9)
N5	0.23030 (15)	0.3252 (3)	1.1058 (3)	0.0428 (8)
N6	0.30319 (16)	0.4982 (3)	1.1532 (3)	0.0480 (9)
O1	0.31986 (13)	0.3844 (3)	0.9151 (2)	0.0511 (8)
O2	0.37269 (18)	0.5822 (3)	0.6396 (3)	0.0745 (10)
H2	0.3465	0.5973	0.6865	0.112*
O3	0.18427 (12)	0.3650 (2)	0.9110 (2)	0.0435 (7)
O4	0.12798 (17)	0.0556 (2)	1.0564 (3)	0.0663 (9)
H4	0.1537	0.1029	1.0800	0.099*
C1	0.33299 (18)	0.4505 (4)	0.8363 (3)	0.0413 (10)
C2	0.4035 (2)	0.3014 (4)	0.7651 (3)	0.0512 (12)
H2A	0.3924	0.2582	0.8271	0.061*
C3	0.37842 (18)	0.4088 (4)	0.7523 (3)	0.0436 (10)
C4	0.3953 (2)	0.4740 (4)	0.6578 (3)	0.0541 (12)
C5	0.4366 (2)	0.4292 (5)	0.5824 (4)	0.0639 (14)
H5	0.4480	0.4735	0.5215	0.077*
C6	0.4619 (2)	0.3181 (5)	0.5953 (4)	0.0575 (13)
C7	0.44529 (19)	0.2531 (4)	0.6885 (4)	0.0533 (12)
C8	0.4700 (2)	0.1419 (5)	0.7015 (4)	0.0710 (15)
H8	0.4593	0.0984	0.7634	0.085*
C9	0.5087 (3)	0.0976 (6)	0.6261 (5)	0.0848 (18)
H9	0.5241	0.0235	0.6353	0.102*
C10	0.5258 (2)	0.1631 (6)	0.5335 (5)	0.0867 (19)
H10	0.5533	0.1324	0.4821	0.104*
C11	0.5032 (2)	0.2693 (6)	0.5180 (4)	0.0785 (17)
H11	0.5148	0.3114	0.4557	0.094*
C12	0.2399 (2)	0.6765 (4)	0.9079 (4)	0.0521 (12)
H12	0.2462	0.7362	0.8577	0.063*
C13	0.19617 (19)	0.6866 (4)	1.0007 (3)	0.0469 (11)
C14	0.1689 (2)	0.7886 (4)	1.0314 (4)	0.0656 (14)
H14	0.1760	0.8553	0.9909	0.079*
C15	0.1311 (2)	0.7901 (4)	1.1229 (4)	0.0689 (14)
H15	0.1126	0.8581	1.1457	0.083*
C16	0.1211 (2)	0.6909 (4)	1.1798 (4)	0.0604 (13)
H16	0.0954	0.6903	1.2416	0.072*
C17	0.14953 (19)	0.5914 (4)	1.1450 (3)	0.0508 (11)
H17	0.1421	0.5238	1.1839	0.061*
C18	0.17036 (18)	0.2725 (4)	0.9597 (3)	0.0388 (10)
C19	0.10074 (18)	0.2221 (3)	0.8001 (3)	0.0417 (10)
H19	0.1155	0.2878	0.7654	0.050*
C20	0.12551 (18)	0.1931 (3)	0.9040 (3)	0.0381 (10)
C21	0.1047 (2)	0.0897 (4)	0.9549 (4)	0.0485 (11)
C22	0.0590 (2)	0.0251 (4)	0.9018 (4)	0.0555 (12)
H22	0.0456	−0.0422	0.9354	0.067*
C23	0.0318 (2)	0.0575 (4)	0.7981 (4)	0.0479 (11)
C24	0.05415 (19)	0.1566 (3)	0.7443 (3)	0.0434 (10)
C25	0.0279 (2)	0.1874 (4)	0.6383 (4)	0.0554 (12)
H25	0.0428	0.2519	0.6017	0.066*
C26	−0.0189 (2)	0.1237 (5)	0.5895 (4)	0.0650 (14)
H26	−0.0357	0.1442	0.5195	0.078*
C27	−0.0418 (2)	0.0276 (5)	0.6446 (5)	0.0732 (15)
H27	−0.0746	−0.0142	0.6116	0.088*
C28	−0.0173 (2)	−0.0059 (4)	0.7443 (5)	0.0649 (14)
H28	−0.0327	−0.0715	0.7784	0.078*
C29	0.25446 (19)	0.3233 (4)	1.2053 (3)	0.0503 (12)
H29	0.2491	0.2617	1.2536	0.060*
C30	0.2909 (2)	0.4242 (4)	1.2374 (3)	0.0514 (12)
C31	0.3103 (2)	0.4486 (5)	1.3469 (4)	0.0744 (16)
H31	0.3017	0.3979	1.4046	0.089*
C32	0.3428 (3)	0.5496 (6)	1.3691 (5)	0.090 (2)
H32	0.3554	0.5680	1.4422	0.108*
C33	0.3562 (3)	0.6220 (5)	1.2828 (5)	0.0805 (17)
H33	0.3788	0.6893	1.2959	0.097*
C34	0.3356 (2)	0.5933 (5)	1.1769 (4)	0.0618 (13)
H34	0.3448	0.6427	1.1184	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0449 (3)	0.0372 (3)	0.0370 (3)	0.0009 (3)	0.0062 (2)	0.0018 (2)
N1	0.052 (2)	0.046 (2)	0.043 (2)	−0.0032 (19)	0.0177 (17)	0.0012 (17)
N2	0.047 (2)	0.042 (2)	0.0417 (19)	−0.0034 (19)	0.0059 (16)	−0.0001 (17)
N3	0.0388 (18)	0.039 (2)	0.0438 (19)	0.0003 (18)	0.0075 (15)	0.0060 (17)
N4	0.049 (2)	0.038 (2)	0.047 (2)	0.0005 (19)	0.0070 (16)	0.0088 (17)
N5	0.045 (2)	0.045 (2)	0.039 (2)	0.0068 (19)	0.0072 (16)	0.0055 (17)
N6	0.046 (2)	0.056 (2)	0.042 (2)	0.004 (2)	0.0039 (16)	−0.0093 (19)
O1	0.0570 (18)	0.0515 (19)	0.0453 (16)	0.0092 (16)	0.0111 (14)	0.0083 (15)
O2	0.101 (3)	0.071 (2)	0.054 (2)	0.018 (2)	0.0344 (18)	0.0169 (18)
O3	0.0544 (17)	0.0339 (16)	0.0422 (16)	−0.0044 (15)	0.0016 (13)	0.0072 (13)
O4	0.102 (3)	0.0379 (19)	0.059 (2)	−0.0121 (19)	0.0050 (18)	0.0136 (16)
C1	0.041 (2)	0.045 (3)	0.039 (2)	−0.001 (2)	0.0021 (18)	−0.002 (2)
C2	0.051 (3)	0.055 (3)	0.047 (3)	−0.001 (3)	0.005 (2)	−0.003 (2)
C3	0.041 (2)	0.054 (3)	0.036 (2)	−0.002 (2)	0.0038 (18)	−0.004 (2)
C4	0.061 (3)	0.061 (3)	0.041 (2)	0.007 (3)	0.011 (2)	0.003 (2)
C5	0.071 (3)	0.081 (4)	0.041 (3)	0.002 (3)	0.018 (2)	0.002 (3)
C6	0.046 (3)	0.081 (4)	0.046 (3)	0.006 (3)	0.006 (2)	−0.011 (3)
C7	0.041 (3)	0.068 (3)	0.051 (3)	0.007 (3)	0.002 (2)	−0.010 (3)
C8	0.072 (3)	0.074 (4)	0.068 (3)	0.023 (3)	0.003 (3)	−0.009 (3)
C9	0.074 (4)	0.090 (5)	0.090 (4)	0.031 (4)	−0.001 (3)	−0.022 (4)
C10	0.063 (3)	0.119 (6)	0.079 (4)	0.028 (4)	0.010 (3)	−0.035 (4)
C11	0.066 (3)	0.111 (5)	0.060 (3)	0.015 (4)	0.019 (3)	−0.014 (3)
C12	0.061 (3)	0.039 (3)	0.058 (3)	0.002 (3)	0.019 (2)	0.011 (2)
C13	0.047 (3)	0.042 (3)	0.052 (3)	0.006 (2)	0.009 (2)	0.002 (2)
C14	0.082 (4)	0.037 (3)	0.079 (3)	0.008 (3)	0.028 (3)	0.008 (3)
C15	0.079 (3)	0.048 (3)	0.081 (4)	0.018 (3)	0.028 (3)	−0.005 (3)
C16	0.063 (3)	0.060 (3)	0.060 (3)	0.009 (3)	0.022 (2)	−0.002 (3)
C17	0.054 (3)	0.044 (3)	0.055 (3)	−0.004 (2)	0.015 (2)	0.002 (2)
C18	0.044 (2)	0.033 (2)	0.040 (2)	0.009 (2)	0.0140 (19)	0.004 (2)
C19	0.044 (2)	0.030 (2)	0.052 (3)	−0.002 (2)	0.015 (2)	0.002 (2)
C20	0.043 (2)	0.026 (2)	0.046 (2)	0.000 (2)	0.0141 (19)	−0.0025 (19)
C21	0.065 (3)	0.028 (2)	0.052 (3)	0.000 (2)	0.019 (2)	0.004 (2)
C22	0.067 (3)	0.029 (3)	0.072 (3)	−0.015 (2)	0.025 (3)	−0.001 (2)
C23	0.049 (3)	0.034 (3)	0.061 (3)	−0.003 (2)	0.020 (2)	−0.012 (2)
C24	0.043 (2)	0.033 (2)	0.055 (3)	0.000 (2)	0.012 (2)	−0.010 (2)
C25	0.054 (3)	0.048 (3)	0.065 (3)	−0.006 (3)	0.004 (2)	−0.005 (2)
C26	0.063 (3)	0.064 (4)	0.067 (3)	0.002 (3)	−0.007 (3)	−0.012 (3)
C27	0.060 (3)	0.068 (4)	0.092 (4)	−0.015 (3)	0.007 (3)	−0.026 (3)
C28	0.065 (3)	0.046 (3)	0.085 (4)	−0.016 (3)	0.020 (3)	−0.012 (3)
C29	0.054 (3)	0.054 (3)	0.043 (3)	0.010 (3)	0.008 (2)	0.012 (2)
C30	0.050 (3)	0.065 (3)	0.039 (2)	0.014 (3)	0.003 (2)	0.003 (2)
C31	0.085 (4)	0.095 (5)	0.042 (3)	0.018 (4)	−0.010 (2)	0.000 (3)
C32	0.096 (4)	0.108 (5)	0.064 (4)	0.028 (4)	−0.033 (3)	−0.029 (4)
C33	0.085 (4)	0.077 (4)	0.078 (4)	0.009 (3)	−0.022 (3)	−0.026 (3)
C34	0.058 (3)	0.063 (3)	0.064 (3)	−0.001 (3)	−0.003 (2)	−0.012 (3)

Geometric parameters (Å, º)

Ni1—N5	1.982 (3)	C11—H11	0.9300
Ni1—N2	1.983 (3)	C12—C13	1.472 (5)
Ni1—O1	2.066 (3)	C12—H12	0.9300
Ni1—O3	2.068 (3)	C13—C14	1.376 (6)
Ni1—N6	2.114 (3)	C14—C15	1.376 (6)
Ni1—N3	2.120 (3)	C14—H14	0.9300
N1—C1	1.336 (5)	C15—C16	1.360 (6)
N1—N2	1.368 (4)	C15—H15	0.9300
N2—C12	1.272 (5)	C16—C17	1.377 (6)
N3—C17	1.336 (5)	C16—H16	0.9300
N3—C13	1.347 (5)	C17—H17	0.9300
N4—C18	1.349 (5)	C18—C20	1.473 (5)
N4—N5	1.360 (4)	C19—C20	1.375 (5)
N5—C29	1.280 (5)	C19—C24	1.403 (5)
N6—C34	1.331 (6)	C19—H19	0.9300
N6—C30	1.355 (5)	C20—C21	1.426 (5)
O1—C1	1.254 (5)	C21—C22	1.370 (6)
O2—C4	1.364 (5)	C22—C23	1.401 (6)
O2—H2	0.8200	C22—H22	0.9300
O3—C18	1.263 (4)	C23—C24	1.410 (6)
O4—C21	1.354 (5)	C23—C28	1.417 (6)
O4—H4	0.8200	C24—C25	1.413 (6)
C1—C3	1.494 (5)	C25—C26	1.360 (6)
C2—C3	1.367 (6)	C25—H25	0.9300
C2—C7	1.411 (6)	C26—C27	1.392 (7)
C2—H2A	0.9300	C26—H26	0.9300
C3—C4	1.415 (6)	C27—C28	1.343 (7)
C4—C5	1.378 (6)	C27—H27	0.9300
C5—C6	1.409 (6)	C28—H28	0.9300
C5—H5	0.9300	C29—C30	1.454 (6)
C6—C7	1.399 (6)	C29—H29	0.9300
C6—C11	1.412 (6)	C30—C31	1.389 (6)
C7—C8	1.405 (6)	C31—C32	1.385 (7)
C8—C9	1.340 (7)	C31—H31	0.9300
C8—H8	0.9300	C32—C33	1.368 (8)
C9—C10	1.401 (8)	C32—H32	0.9300
C9—H9	0.9300	C33—C34	1.367 (6)
C10—C11	1.339 (7)	C33—H33	0.9300
C10—H10	0.9300	C34—H34	0.9300
N5—Ni1—N2	176.33 (14)	C13—C12—H12	122.0
N5—Ni1—O1	99.45 (12)	N3—C13—C14	122.3 (4)
N2—Ni1—O1	77.76 (13)	N3—C13—C12	114.3 (4)
N5—Ni1—O3	77.62 (13)	C14—C13—C12	123.3 (4)
N2—Ni1—O3	99.83 (12)	C13—C14—C15	118.8 (4)
O1—Ni1—O3	88.73 (11)	C13—C14—H14	120.6
N5—Ni1—N6	78.55 (15)	C15—C14—H14	120.6
N2—Ni1—N6	104.12 (14)	C16—C15—C14	119.3 (5)
O1—Ni1—N6	98.46 (12)	C16—C15—H15	120.4
O3—Ni1—N6	155.94 (13)	C14—C15—H15	120.4
N5—Ni1—N3	104.59 (13)	C15—C16—C17	119.2 (4)
N2—Ni1—N3	78.25 (13)	C15—C16—H16	120.4
O1—Ni1—N3	155.95 (12)	C17—C16—H16	120.4
O3—Ni1—N3	96.94 (12)	N3—C17—C16	122.5 (4)
N6—Ni1—N3	85.81 (13)	N3—C17—H17	118.7
C1—N1—N2	108.8 (3)	C16—C17—H17	118.7
C12—N2—N1	124.0 (4)	O3—C18—N4	124.6 (4)
C12—N2—Ni1	118.9 (3)	O3—C18—C20	119.1 (4)
N1—N2—Ni1	117.0 (3)	N4—C18—C20	116.3 (4)
C17—N3—C13	117.8 (4)	C20—C19—C24	122.8 (4)
C17—N3—Ni1	129.3 (3)	C20—C19—H19	118.6
C13—N3—Ni1	112.0 (2)	C24—C19—H19	118.6
C18—N4—N5	109.8 (3)	C19—C20—C21	118.4 (4)
C29—N5—N4	124.0 (4)	C19—C20—C18	118.6 (4)
C29—N5—Ni1	118.8 (3)	C21—C20—C18	122.9 (4)
N4—N5—Ni1	117.2 (2)	O4—C21—C22	119.3 (4)
C34—N6—C30	118.8 (4)	O4—C21—C20	121.3 (4)
C34—N6—Ni1	129.1 (3)	C22—C21—C20	119.4 (4)
C30—N6—Ni1	110.8 (3)	C21—C22—C23	121.9 (4)
C1—O1—Ni1	109.2 (3)	C21—C22—H22	119.0
C4—O2—H2	109.5	C23—C22—H22	119.0
C18—O3—Ni1	110.3 (2)	C22—C23—C24	119.2 (4)
C21—O4—H4	109.5	C22—C23—C28	122.6 (4)
O1—C1—N1	126.7 (4)	C24—C23—C28	118.2 (4)
O1—C1—C3	117.8 (4)	C19—C24—C23	118.1 (4)
N1—C1—C3	115.6 (4)	C19—C24—C25	122.8 (4)
C3—C2—C7	122.8 (4)	C23—C24—C25	119.1 (4)
C3—C2—H2A	118.6	C26—C25—C24	120.6 (5)
C7—C2—H2A	118.6	C26—C25—H25	119.7
C2—C3—C4	118.3 (4)	C24—C25—H25	119.7
C2—C3—C1	118.7 (4)	C25—C26—C27	119.9 (5)
C4—C3—C1	123.0 (4)	C25—C26—H26	120.1
O2—C4—C5	118.3 (4)	C27—C26—H26	120.1
O2—C4—C3	121.8 (4)	C28—C27—C26	121.4 (5)
C5—C4—C3	120.0 (5)	C28—C27—H27	119.3
C4—C5—C6	121.7 (4)	C26—C27—H27	119.3
C4—C5—H5	119.2	C27—C28—C23	120.8 (5)
C6—C5—H5	119.2	C27—C28—H28	119.6
C7—C6—C5	118.7 (4)	C23—C28—H28	119.6
C7—C6—C11	118.6 (5)	N5—C29—C30	115.3 (4)
C5—C6—C11	122.8 (5)	N5—C29—H29	122.3
C6—C7—C8	119.0 (4)	C30—C29—H29	122.3
C6—C7—C2	118.6 (4)	N6—C30—C31	120.7 (5)
C8—C7—C2	122.4 (5)	N6—C30—C29	115.6 (4)
C9—C8—C7	121.0 (5)	C31—C30—C29	123.7 (5)
C9—C8—H8	119.5	C32—C31—C30	119.1 (5)
C7—C8—H8	119.5	C32—C31—H31	120.5
C8—C9—C10	120.0 (6)	C30—C31—H31	120.5
C8—C9—H9	120.0	C33—C32—C31	119.6 (5)
C10—C9—H9	120.0	C33—C32—H32	120.2
C11—C10—C9	120.7 (5)	C31—C32—H32	120.2
C11—C10—H10	119.6	C34—C33—C32	118.5 (6)
C9—C10—H10	119.6	C34—C33—H33	120.8
C10—C11—C6	120.7 (5)	C32—C33—H33	120.8
C10—C11—H11	119.7	N6—C34—C33	123.4 (5)
C6—C11—H11	119.7	N6—C34—H34	118.3
N2—C12—C13	116.1 (4)	C33—C34—H34	118.3
N2—C12—H12	122.0
C1—N1—N2—C12	179.2 (4)	C11—C6—C7—C8	−0.3 (7)
C1—N1—N2—Ni1	−4.0 (4)	C5—C6—C7—C2	0.6 (6)
N5—Ni1—N2—C12	142 (2)	C11—C6—C7—C2	−179.3 (4)
O1—Ni1—N2—C12	−177.3 (4)	C3—C2—C7—C6	0.0 (6)
O3—Ni1—N2—C12	96.1 (3)	C3—C2—C7—C8	−179.0 (4)
N6—Ni1—N2—C12	−81.6 (3)	C6—C7—C8—C9	−0.3 (7)
N3—Ni1—N2—C12	1.0 (3)	C2—C7—C8—C9	178.7 (5)
N5—Ni1—N2—N1	−35 (2)	C7—C8—C9—C10	1.0 (8)
O1—Ni1—N2—N1	5.7 (3)	C8—C9—C10—C11	−1.1 (9)
O3—Ni1—N2—N1	−80.9 (3)	C9—C10—C11—C6	0.5 (8)
N6—Ni1—N2—N1	101.4 (3)	C7—C6—C11—C10	0.2 (7)
N3—Ni1—N2—N1	−176.0 (3)	C5—C6—C11—C10	−179.7 (5)
N5—Ni1—N3—C17	8.4 (4)	N1—N2—C12—C13	179.6 (3)
N2—Ni1—N3—C17	−174.0 (4)	Ni1—N2—C12—C13	2.9 (5)
O1—Ni1—N3—C17	−170.1 (3)	C17—N3—C13—C14	1.4 (6)
O3—Ni1—N3—C17	87.3 (4)	Ni1—N3—C13—C14	−169.1 (4)
N6—Ni1—N3—C17	−68.7 (4)	C17—N3—C13—C12	178.2 (4)
N5—Ni1—N3—C13	177.5 (3)	Ni1—N3—C13—C12	7.7 (4)
N2—Ni1—N3—C13	−4.9 (3)	N2—C12—C13—N3	−7.3 (6)
O1—Ni1—N3—C13	−1.0 (5)	N2—C12—C13—C14	169.5 (4)
O3—Ni1—N3—C13	−103.6 (3)	N3—C13—C14—C15	−0.3 (7)
N6—Ni1—N3—C13	100.4 (3)	C12—C13—C14—C15	−176.8 (4)
C18—N4—N5—C29	174.7 (4)	C13—C14—C15—C16	−0.7 (8)
C18—N4—N5—Ni1	−6.3 (4)	C14—C15—C16—C17	0.5 (8)
N2—Ni1—N5—C29	139 (2)	C13—N3—C17—C16	−1.6 (6)
O1—Ni1—N5—C29	98.6 (3)	Ni1—N3—C17—C16	167.0 (3)
O3—Ni1—N5—C29	−174.8 (3)	C15—C16—C17—N3	0.7 (7)
N6—Ni1—N5—C29	1.8 (3)	Ni1—O3—C18—N4	2.8 (5)
N3—Ni1—N5—C29	−80.7 (3)	Ni1—O3—C18—C20	−178.8 (2)
N2—Ni1—N5—N4	−40 (2)	N5—N4—C18—O3	2.0 (5)
O1—Ni1—N5—N4	−80.5 (3)	N5—N4—C18—C20	−176.4 (3)
O3—Ni1—N5—N4	6.1 (2)	C24—C19—C20—C21	2.6 (6)
N6—Ni1—N5—N4	−177.3 (3)	C24—C19—C20—C18	−175.0 (3)
N3—Ni1—N5—N4	100.1 (3)	O3—C18—C20—C19	0.7 (5)
N5—Ni1—N6—C34	−173.5 (4)	N4—C18—C20—C19	179.1 (3)
N2—Ni1—N6—C34	9.1 (4)	O3—C18—C20—C21	−176.8 (4)
O1—Ni1—N6—C34	88.5 (4)	N4—C18—C20—C21	1.7 (5)
O3—Ni1—N6—C34	−165.3 (3)	C19—C20—C21—O4	179.0 (4)
N3—Ni1—N6—C34	−67.7 (4)	C18—C20—C21—O4	−3.6 (6)
N5—Ni1—N6—C30	−7.1 (3)	C19—C20—C21—C22	−2.8 (6)
N2—Ni1—N6—C30	175.4 (3)	C18—C20—C21—C22	174.6 (4)
O1—Ni1—N6—C30	−105.1 (3)	O4—C21—C22—C23	178.2 (4)
O3—Ni1—N6—C30	1.0 (5)	C20—C21—C22—C23	0.0 (6)
N3—Ni1—N6—C30	98.7 (3)	C21—C22—C23—C24	3.1 (6)
N5—Ni1—O1—C1	171.4 (3)	C21—C22—C23—C28	−177.4 (4)
N2—Ni1—O1—C1	−6.2 (3)	C20—C19—C24—C23	0.5 (6)
O3—Ni1—O1—C1	94.2 (3)	C20—C19—C24—C25	178.9 (4)
N6—Ni1—O1—C1	−108.9 (3)	C22—C23—C24—C19	−3.3 (6)
N3—Ni1—O1—C1	−10.1 (5)	C28—C23—C24—C19	177.2 (4)
N5—Ni1—O3—C18	−4.6 (2)	C22—C23—C24—C25	178.3 (4)
N2—Ni1—O3—C18	172.7 (2)	C28—C23—C24—C25	−1.3 (6)
O1—Ni1—O3—C18	95.4 (2)	C19—C24—C25—C26	−177.4 (4)
N6—Ni1—O3—C18	−12.8 (4)	C23—C24—C25—C26	1.0 (6)
N3—Ni1—O3—C18	−108.1 (2)	C24—C25—C26—C27	0.5 (7)
Ni1—O1—C1—N1	6.8 (5)	C25—C26—C27—C28	−1.9 (8)
Ni1—O1—C1—C3	−173.8 (3)	C26—C27—C28—C23	1.6 (8)
N2—N1—C1—O1	−2.3 (6)	C22—C23—C28—C27	−179.5 (5)
N2—N1—C1—C3	178.3 (3)	C24—C23—C28—C27	0.0 (6)
C7—C2—C3—C4	0.1 (6)	N4—N5—C29—C30	−177.3 (3)
C7—C2—C3—C1	178.1 (4)	Ni1—N5—C29—C30	3.7 (5)
O1—C1—C3—C2	0.0 (6)	C34—N6—C30—C31	1.8 (6)
N1—C1—C3—C2	179.4 (4)	Ni1—N6—C30—C31	−166.2 (3)
O1—C1—C3—C4	177.9 (4)	C34—N6—C30—C29	179.1 (4)
N1—C1—C3—C4	−2.7 (6)	Ni1—N6—C30—C29	11.1 (4)
C2—C3—C4—O2	−179.5 (4)	N5—C29—C30—N6	−10.3 (5)
C1—C3—C4—O2	2.6 (7)	N5—C29—C30—C31	167.0 (4)
C2—C3—C4—C5	−0.7 (7)	N6—C30—C31—C32	−0.3 (7)
C1—C3—C4—C5	−178.7 (4)	C29—C30—C31—C32	−177.4 (4)
O2—C4—C5—C6	−179.8 (4)	C30—C31—C32—C33	−1.3 (8)
C3—C4—C5—C6	1.3 (7)	C31—C32—C33—C34	1.5 (8)
C4—C5—C6—C7	−1.2 (7)	C30—N6—C34—C33	−1.6 (7)
C4—C5—C6—C11	178.7 (4)	Ni1—N6—C34—C33	163.8 (4)
C5—C6—C7—C8	179.6 (4)	C32—C33—C34—N6	0.0 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···N4	0.82	1.83	2.561 (4)	148
O2—H2···N1	0.82	1.84	2.567 (4)	147
C15—H15···O4^i	0.93	2.56	3.195 (6)	126
C32—H32···O2^ii	0.93	2.38	3.295 (6)	168

Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1.