A new nickel(II) complex with a [14]N4 macrocyclic ligand

Yu, M.; Yang, G.-M.

doi:10.1107/S1600536805034458

A new nickel(II) complex with a [14]N4 macrocyclic ligand

The title compound, (9,20-dichloro-12,17-diphenyl-2,4,13,16-tetraazatricyclo[16.4.0.0^6,11]docosa-6,8,10,12,16,18,20,22-octaene-3,4-dionato)nickel(II) methanol hemisolvate, [Ni(C₃₀H₂₀Cl₂N₄O₂)]·0.5CH₃OH, has a square-planar coordination geometry around the Ni^II ion. The two phenyl groups of the macrocyclic ligand are nearly perpendicular to the coordination plane. The solvent methanol molecule is disordered over two sites, near to a twofold axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805034458/xu6050sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805034458/xu6050Isup2.hkl Contains datablock I

CCDC reference: 289941

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.008 Å
H-atom completeness 91%
Disorder in solvent or counterion
R factor = 0.054
wR factor = 0.137
Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.53 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C30.5 H22 Cl2 N4 Ni1 O2.5
            Atom count from the _atom_site data:  C30.5 H20 Cl2 N4 Ni1 O2.5
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C30.5 H22 Cl2 N4 Ni O2.5
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        244.00    244.00    0.00
           H        176.00    160.00   16.00
           Cl        16.00     16.00    0.00
           N         32.00     32.00    0.00
           Ni         8.00      8.00    0.00
           O         20.00     20.00    0.00

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

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

Computing details top

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

(9,20-dichloro-12,17-diphenyl-2,4,13,16-tetraazatricyclo[16.4.0.0^6,11]docosa- 6,8,10,12,16,18,20,22-octaene-3,4-dionato)nickel(II) methanol hemisolvate top

Crystal data top

[Ni(C₃₀H₂₀Cl₂N₄O₂)]·0.5CH₄O	F(000) = 2516
M_r = 613.63	D_x = 1.552 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 833 reflections
a = 29.869 (9) Å	θ = 1.5–25.1°
b = 7.268 (2) Å	µ = 0.98 mm⁻¹
c = 26.307 (8) Å	T = 293 K
β = 113.126 (5)°	Plate, orange
V = 5252 (3) Å³	0.20 × 0.14 × 0.12 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	4676 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→33
T_min = 0.846, T_max = 0.890	k = −8→8
13262 measured reflections	l = −16→31

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0576P)²] where P = (F_o² + 2F_c²)/3
4676 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

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	Occ. (<1)
Ni1	0.52787 (2)	0.73712 (8)	0.55168 (2)	0.0355 (2)
Cl1	0.78058 (4)	0.5798 (2)	0.59734 (6)	0.0659 (4)
Cl2	0.26701 (5)	0.8916 (2)	0.44399 (6)	0.0647 (4)
O1	0.46172 (13)	0.7576 (6)	0.39090 (14)	0.0676 (11)
O2	0.55039 (12)	0.6183 (5)	0.41914 (14)	0.0532 (9)
N1	0.47544 (12)	0.7845 (5)	0.48394 (14)	0.0330 (9)
N2	0.56602 (13)	0.6874 (5)	0.51127 (15)	0.0337 (9)
N3	0.57808 (13)	0.6683 (5)	0.61875 (15)	0.0409 (10)
N4	0.49164 (13)	0.7961 (5)	0.59337 (15)	0.0400 (10)
C1	0.48681 (16)	0.7452 (7)	0.44028 (19)	0.0409 (11)
C2	0.53891 (16)	0.6753 (6)	0.4561 (2)	0.0387 (12)
C3	0.61669 (16)	0.6579 (6)	0.5316 (2)	0.0368 (11)
C4	0.64262 (17)	0.6702 (7)	0.4971 (2)	0.0458 (13)
H4	0.6256	0.6953	0.4597	0.055*
C5	0.69213 (17)	0.6463 (7)	0.5168 (2)	0.0495 (13)
H5	0.7082	0.6564	0.4930	0.059*
C6	0.71775 (17)	0.6075 (7)	0.5715 (2)	0.0469 (13)
C7	0.69437 (17)	0.5965 (7)	0.6068 (2)	0.0441 (12)
H7	0.7122	0.5698	0.6439	0.053*
C8	0.64375 (16)	0.6248 (6)	0.58819 (19)	0.0378 (11)
C9	0.62279 (16)	0.6201 (6)	0.62987 (19)	0.0397 (12)
C10	0.65505 (15)	0.5649 (7)	0.68744 (19)	0.0402 (12)
C11	0.68745 (18)	0.6859 (7)	0.7232 (2)	0.0529 (14)
H11	0.6899	0.8045	0.7113	0.064*
C12	0.71640 (18)	0.6345 (9)	0.7765 (2)	0.0616 (16)
H12	0.7380	0.7187	0.8003	0.074*
C13	0.71350 (18)	0.4612 (9)	0.7946 (2)	0.0601 (16)
H13	0.7334	0.4260	0.8304	0.072*
C14	0.68125 (19)	0.3397 (8)	0.7597 (2)	0.0571 (15)
H14	0.6790	0.2213	0.7718	0.069*
C15	0.65169 (18)	0.3910 (8)	0.7062 (2)	0.0521 (14)
H15	0.6295	0.3074	0.6829	0.062*
C16	0.55913 (18)	0.6557 (8)	0.6628 (2)	0.0556 (15)
H16A	0.5442	0.5365	0.6618	0.067*
H16B	0.5854	0.6712	0.6988	0.067*
C17	0.52299 (17)	0.8027 (8)	0.65272 (19)	0.0526 (15)
H17A	0.5390	0.9213	0.6624	0.063*
H17B	0.5038	0.7830	0.6747	0.063*
C18	0.44495 (17)	0.8181 (6)	0.57821 (19)	0.0386 (11)
C19	0.42346 (16)	0.8426 (8)	0.62058 (19)	0.0433 (13)
C20	0.42353 (19)	1.0136 (8)	0.6437 (2)	0.0548 (14)
H20	0.4370	1.1145	0.6330	0.066*
C21	0.4035 (2)	1.0338 (9)	0.6826 (2)	0.0665 (17)
H21	0.4033	1.1490	0.6979	0.080*
C22	0.3842 (2)	0.8872 (10)	0.6987 (3)	0.0721 (18)
H22	0.3712	0.9021	0.7253	0.086*
C23	0.3836 (2)	0.7194 (9)	0.6762 (3)	0.0691 (18)
H23	0.3700	0.6199	0.6873	0.083*
C24	0.40323 (19)	0.6944 (8)	0.6368 (2)	0.0563 (15)
H24	0.4027	0.5788	0.6214	0.068*
C25	0.41185 (16)	0.8277 (6)	0.51999 (19)	0.0353 (11)
C26	0.36203 (17)	0.8495 (6)	0.5087 (2)	0.0444 (12)
H26	0.3518	0.8453	0.5378	0.053*
C27	0.32838 (16)	0.8766 (7)	0.4564 (2)	0.0438 (13)
C28	0.34362 (18)	0.8963 (7)	0.4137 (2)	0.0503 (14)
H28	0.3212	0.9240	0.3784	0.060*
C29	0.39202 (17)	0.8751 (7)	0.4233 (2)	0.0466 (13)
H29	0.4018	0.8926	0.3942	0.056*
C30	0.42725 (16)	0.8280 (6)	0.47546 (18)	0.0358 (11)
O3	0.5239 (5)	0.298 (2)	0.7153 (6)	0.161 (6)	0.50
C31	0.5019 (18)	0.392 (3)	0.737 (2)	0.165 (14)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0322 (3)	0.0433 (4)	0.0267 (3)	−0.0036 (3)	0.0068 (2)	−0.0005 (3)
Cl1	0.0370 (7)	0.0939 (11)	0.0662 (10)	0.0049 (7)	0.0198 (7)	−0.0051 (9)
Cl2	0.0368 (7)	0.0828 (10)	0.0620 (10)	0.0067 (7)	0.0061 (6)	−0.0015 (8)
O1	0.053 (2)	0.114 (3)	0.027 (2)	0.011 (2)	0.0065 (17)	−0.001 (2)
O2	0.049 (2)	0.076 (3)	0.037 (2)	−0.0062 (18)	0.0178 (17)	−0.012 (2)
N1	0.032 (2)	0.038 (2)	0.025 (2)	−0.0031 (16)	0.0066 (16)	0.0003 (17)
N2	0.034 (2)	0.037 (2)	0.025 (2)	−0.0069 (16)	0.0058 (16)	−0.0011 (17)
N3	0.034 (2)	0.057 (3)	0.031 (2)	0.0009 (19)	0.0120 (18)	0.001 (2)
N4	0.038 (2)	0.052 (3)	0.024 (2)	−0.0018 (18)	0.0050 (17)	−0.0021 (18)
C1	0.039 (3)	0.047 (3)	0.028 (3)	−0.008 (2)	0.004 (2)	−0.005 (3)
C2	0.039 (3)	0.038 (3)	0.038 (3)	−0.009 (2)	0.013 (2)	−0.001 (2)
C3	0.039 (3)	0.031 (3)	0.041 (3)	−0.005 (2)	0.016 (2)	−0.002 (2)
C4	0.044 (3)	0.055 (3)	0.039 (3)	−0.009 (2)	0.016 (2)	−0.002 (3)
C5	0.044 (3)	0.063 (3)	0.047 (3)	−0.009 (3)	0.023 (3)	−0.005 (3)
C6	0.035 (3)	0.049 (3)	0.052 (3)	−0.001 (2)	0.012 (3)	−0.007 (3)
C7	0.040 (3)	0.053 (3)	0.035 (3)	0.000 (2)	0.011 (2)	0.002 (3)
C8	0.040 (3)	0.035 (3)	0.034 (3)	−0.006 (2)	0.010 (2)	0.000 (2)
C9	0.038 (3)	0.040 (3)	0.036 (3)	−0.001 (2)	0.009 (2)	0.001 (2)
C10	0.032 (3)	0.055 (3)	0.032 (3)	0.004 (2)	0.010 (2)	0.003 (2)
C11	0.045 (3)	0.062 (3)	0.046 (3)	−0.007 (3)	0.011 (3)	−0.002 (3)
C12	0.039 (3)	0.084 (5)	0.045 (4)	−0.007 (3)	−0.001 (3)	−0.012 (3)
C13	0.039 (3)	0.097 (5)	0.035 (3)	0.015 (3)	0.004 (2)	0.005 (3)
C14	0.055 (3)	0.066 (4)	0.045 (3)	0.009 (3)	0.016 (3)	0.009 (3)
C15	0.050 (3)	0.065 (4)	0.035 (3)	−0.002 (3)	0.011 (3)	−0.003 (3)
C16	0.042 (3)	0.092 (4)	0.030 (3)	0.008 (3)	0.010 (2)	0.005 (3)
C17	0.037 (3)	0.086 (4)	0.030 (3)	0.005 (3)	0.008 (2)	−0.003 (3)
C18	0.039 (3)	0.040 (3)	0.032 (3)	0.002 (2)	0.008 (2)	0.005 (2)
C19	0.030 (3)	0.064 (3)	0.030 (3)	0.010 (2)	0.005 (2)	0.009 (3)
C20	0.059 (3)	0.066 (4)	0.041 (3)	0.003 (3)	0.020 (3)	0.000 (3)
C21	0.072 (4)	0.078 (4)	0.055 (4)	0.019 (3)	0.030 (3)	0.001 (3)
C22	0.068 (4)	0.101 (5)	0.057 (4)	0.029 (4)	0.036 (3)	0.018 (4)
C23	0.067 (4)	0.078 (5)	0.077 (5)	0.007 (3)	0.045 (4)	0.022 (4)
C24	0.055 (3)	0.061 (4)	0.058 (4)	0.004 (3)	0.027 (3)	0.011 (3)
C25	0.032 (2)	0.034 (3)	0.030 (3)	0.000 (2)	0.003 (2)	0.000 (2)
C26	0.045 (3)	0.046 (3)	0.042 (3)	0.002 (2)	0.017 (3)	0.001 (3)
C27	0.034 (3)	0.045 (3)	0.041 (3)	0.005 (2)	0.002 (2)	−0.002 (3)
C28	0.047 (3)	0.054 (3)	0.031 (3)	0.005 (3)	−0.005 (2)	−0.001 (3)
C29	0.048 (3)	0.054 (3)	0.034 (3)	0.001 (3)	0.012 (2)	0.000 (3)
C30	0.041 (3)	0.032 (2)	0.027 (3)	−0.003 (2)	0.004 (2)	−0.002 (2)
O3	0.149 (12)	0.173 (14)	0.115 (10)	−0.008 (10)	0.002 (9)	0.041 (10)
C31	0.20 (2)	0.118 (13)	0.29 (5)	−0.01 (2)	0.21 (3)	−0.03 (2)

Geometric parameters (Å, º) top

Ni1—N1	1.885 (3)	C13—C14	1.362 (7)
Ni1—N2	1.874 (4)	C13—H13	0.9300
Ni1—N3	1.880 (4)	C14—C15	1.386 (7)
Ni1—N4	1.868 (4)	C14—H14	0.9300
Cl1—C6	1.739 (5)	C15—H15	0.9300
Cl2—C27	1.735 (5)	C16—C17	1.467 (7)
O1—C1	1.222 (5)	C16—H16A	0.9700
O2—C2	1.223 (5)	C16—H16B	0.9700
N1—C1	1.350 (6)	C17—H17A	0.9700
N1—C30	1.403 (6)	C17—H17B	0.9700
N2—C2	1.359 (6)	C18—C25	1.462 (6)
N2—C3	1.409 (5)	C18—C19	1.499 (7)
N3—C9	1.298 (5)	C19—C24	1.382 (7)
N3—C16	1.479 (6)	C19—C20	1.383 (7)
N4—C17	1.473 (6)	C20—C21	1.382 (7)
N4—C18	1.301 (6)	C20—H20	0.9300
C1—C2	1.531 (7)	C21—C22	1.356 (8)
C3—C8	1.408 (6)	C21—H21	0.9300
C3—C4	1.409 (6)	C22—C23	1.352 (8)
C4—C5	1.372 (6)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.390 (7)
C5—C6	1.368 (7)	C23—H23	0.9300
C5—H5	0.9300	C24—H24	0.9300
C6—C7	1.366 (6)	C25—C26	1.407 (6)
C7—C8	1.409 (6)	C25—C30	1.417 (6)
C7—H7	0.9300	C26—C27	1.362 (6)
C8—C9	1.461 (7)	C26—H26	0.9300
C9—C10	1.496 (6)	C27—C28	1.374 (7)
C10—C11	1.371 (6)	C28—C29	1.375 (7)
C10—C15	1.375 (7)	C28—H28	0.9300
C11—C12	1.379 (7)	C29—C30	1.404 (6)
C11—H11	0.9300	C29—H29	0.9300
C12—C13	1.361 (8)	O3—C31	1.23 (2)
C12—H12	0.9300

N4—Ni1—N2	177.35 (16)	C13—C14—C15	120.6 (6)
N4—Ni1—N3	86.70 (16)	C13—C14—H14	119.7
N2—Ni1—N3	92.43 (16)	C15—C14—H14	119.7
N4—Ni1—N1	93.17 (16)	C10—C15—C14	120.3 (5)
N2—Ni1—N1	87.91 (16)	C10—C15—H15	119.9
N3—Ni1—N1	174.91 (16)	C14—C15—H15	119.9
C1—N1—C30	119.8 (4)	C17—C16—N3	107.1 (4)
C1—N1—Ni1	111.9 (3)	C17—C16—H16A	110.3
C30—N1—Ni1	127.7 (3)	N3—C16—H16A	110.3
C2—N2—C3	119.7 (4)	C17—C16—H16B	110.3
C2—N2—Ni1	112.2 (3)	N3—C16—H16B	110.3
C3—N2—Ni1	128.0 (3)	H16A—C16—H16B	108.6
C9—N3—C16	118.9 (4)	C16—C17—N4	106.5 (4)
C9—N3—Ni1	130.9 (3)	C16—C17—H17A	110.4
C16—N3—Ni1	110.0 (3)	N4—C17—H17A	110.4
C18—N4—C17	118.7 (4)	C16—C17—H17B	110.4
C18—N4—Ni1	130.3 (3)	N4—C17—H17B	110.4
C17—N4—Ni1	110.9 (3)	H17A—C17—H17B	108.6
O1—C1—N1	129.4 (5)	N4—C18—C25	122.0 (4)
O1—C1—C2	116.5 (4)	N4—C18—C19	120.5 (4)
N1—C1—C2	114.1 (4)	C25—C18—C19	117.5 (4)
O2—C2—N2	129.4 (4)	C24—C19—C20	119.4 (5)
O2—C2—C1	118.0 (4)	C24—C19—C18	120.2 (5)
N2—C2—C1	112.6 (4)	C20—C19—C18	120.4 (5)
C8—C3—C4	117.4 (4)	C21—C20—C19	119.7 (6)
C8—C3—N2	120.8 (4)	C21—C20—H20	120.2
C4—C3—N2	121.7 (4)	C19—C20—H20	120.2
C5—C4—C3	122.1 (5)	C22—C21—C20	120.6 (6)
C5—C4—H4	119.0	C22—C21—H21	119.7
C3—C4—H4	119.0	C20—C21—H21	119.7
C6—C5—C4	119.9 (5)	C23—C22—C21	120.4 (6)
C6—C5—H5	120.0	C23—C22—H22	119.8
C4—C5—H5	120.0	C21—C22—H22	119.8
C7—C6—C5	120.2 (4)	C22—C23—C24	120.5 (6)
C7—C6—Cl1	119.3 (4)	C22—C23—H23	119.7
C5—C6—Cl1	120.4 (4)	C24—C23—H23	119.7
C6—C7—C8	121.3 (5)	C19—C24—C23	119.5 (6)
C6—C7—H7	119.3	C19—C24—H24	120.3
C8—C7—H7	119.3	C23—C24—H24	120.3
C3—C8—C7	119.0 (4)	C26—C25—C30	119.0 (4)
C3—C8—C9	124.1 (4)	C26—C25—C18	116.8 (4)
C7—C8—C9	116.9 (4)	C30—C25—C18	124.1 (4)
N3—C9—C8	122.0 (4)	C27—C26—C25	122.0 (5)
N3—C9—C10	119.8 (4)	C27—C26—H26	119.0
C8—C9—C10	118.1 (4)	C25—C26—H26	119.0
C11—C10—C15	118.3 (5)	C26—C27—C28	119.4 (5)
C11—C10—C9	121.5 (5)	C26—C27—Cl2	120.3 (4)
C15—C10—C9	120.1 (4)	C28—C27—Cl2	120.3 (4)
C10—C11—C12	121.1 (5)	C27—C28—C29	120.0 (4)
C10—C11—H11	119.5	C27—C28—H28	120.0
C12—C11—H11	119.5	C29—C28—H28	120.0
C13—C12—C11	120.3 (5)	C28—C29—C30	122.5 (5)
C13—C12—H12	119.8	C28—C29—H29	118.8
C11—C12—H12	119.8	C30—C29—H29	118.8
C12—C13—C14	119.3 (5)	N1—C30—C29	122.6 (4)
C12—C13—H13	120.3	N1—C30—C25	120.9 (4)
C14—C13—H13	120.3	C29—C30—C25	116.5 (4)

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