[(1RS,7RS,8RS,14RS)-5,12-Di­methyl-7,14-di­phenyl-1,4,8,11-tetra­aza­cyclo­tetradeca-4,11-diene-κ⁴N^1,4,8,11]­nickel(II) perchlorate

The title compound, [Ni(C₂₄H₃₂N₄)](ClO₄), has singlet ground-state nickel(II) complex cations with tetrahedrally twisted [0.013 (4) Å] square-planar coordination by four N atoms of the 14-membered di­amine–di­imine tetra­aza-macrocycle and perchlorate anions. A perchlorate O atom is sited near the tetragonal axis [Ni...O 2.694 (4) Å], with both N—H groups oriented towards the other side of the plane forming N—H...O hydrogen bonds to O atoms of different perchlorate ions, with no O atom near the nickel(II) tetragonal axis.

Key indicators

• Single-crystal X-ray study
• T = 158 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.041
• wR factor = 0.083
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      0.760

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.106

PLAT_420  Alert C D-H Without Acceptor       N(1)   -   H(1)              ?

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.30
         From the CIF: _reflns_number_total               4658
         Count of symmetry unique reflns         2997
         Completeness (_total/calc)            155.42%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1661
         Fraction of Friedel pairs measured     0.554
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 (Johnson, 1999); software used to prepare material for publication: PARST (Nardelli, 1995).

(1RS,7RS,8RS,14SR-5,12-Dimethyl-7,14-diphenyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene-N¹,N⁴,N⁸,N¹¹)nickel(II) Perchlorate

Crystal data

[Ni(C24H32N4)](ClO4)	F(000) = 5280
Mr = 634.13	Dx = 1.521 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 4795 reflections
a = 40.66 (2) Å	θ = 2.4–23.6°
b = 29.40 (1) Å	µ = 0.95 mm^−1
c = 9.267 (4) Å	T = 158 K
V = 11078 (8) Å^3	Needle, orange
Z = 16	0.85 × 0.13 × 0.07 mm

Data collection

Siemens CCD area-detector diffractometer	2435 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.106
Graphite monochromator	θmax = 26.3°, θmin = 2.4°
φ and ω scans	h = −50→50
34536 measured reflections	k = −36→36
4658 independent reflections	l = −6→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.76	(Δ/σ)max = 0.016
4658 reflections	Δρmax = 0.54 e Å^−3
356 parameters	Δρmin = −0.36 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1661 Friedel pairs [CHECK]
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.020 (18)

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 1.0 mm diameter collimator was used. Data was collected in space group C c and converted to F d d2. Friedel pairs were not merged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.079441 (15)	0.12187 (3)	0.76238 (8)	0.03021 (19)
N1	0.12421 (9)	0.13695 (16)	0.6958 (5)	0.0308 (12)
H1	0.1319	0.1608	0.7525	0.030 (15)*
N4	0.06453 (10)	0.16662 (14)	0.6265 (4)	0.0272 (12)
N8	0.03528 (10)	0.11016 (16)	0.8373 (5)	0.0320 (12)
H8	0.0315	0.1312	0.9105	0.09 (2)*
N11	0.09474 (11)	0.08148 (14)	0.9118 (4)	0.0319 (12)
C2	0.12061 (11)	0.15446 (19)	0.5442 (5)	0.0346 (15)
H2A	0.1156	0.1297	0.4784	0.041*
H2B	0.1407	0.1692	0.5128	0.041*
C3	0.09269 (13)	0.18810 (19)	0.5485 (6)	0.0427 (17)
H3A	0.0995	0.2156	0.5981	0.051*
H3B	0.0861	0.1962	0.4512	0.051*
C5	0.03572 (13)	0.18338 (19)	0.6093 (5)	0.0250 (14)
C6	0.00571 (12)	0.16329 (18)	0.6757 (5)	0.0327 (15)
H6A	−0.0118	0.1647	0.6049	0.039*
H6B	−0.0007	0.1825	0.7559	0.039*
C7	0.00772 (12)	0.1152 (2)	0.7300 (6)	0.0376 (16)
H7	0.0124	0.0953	0.6476	0.045*
C9	0.03633 (13)	0.06374 (19)	0.9064 (6)	0.0446 (17)
H9I	0.0374	0.0403	0.8330	0.054*
H9J	0.0168	0.0588	0.9643	0.054*
C10	0.06710 (12)	0.0624 (2)	1.0013 (6)	0.0408 (16)
H10G	0.0639	0.0806	1.0875	0.049*
H10H	0.0720	0.0314	1.0300	0.049*
C12	0.12456 (13)	0.07222 (19)	0.9530 (6)	0.0326 (15)
C13	0.15406 (12)	0.0887 (2)	0.8687 (6)	0.0355 (16)
H13A	0.1712	0.0659	0.8766	0.043*
H13B	0.1622	0.1162	0.9143	0.043*
C14	0.14862 (11)	0.09878 (19)	0.7076 (5)	0.0296 (14)
H14	0.1390	0.0717	0.6626	0.036*
C51	0.02968 (12)	0.22638 (17)	0.5170 (6)	0.0438 (16)
H51A	0.0437	0.2505	0.5501	0.066*
H51B	0.0071	0.2355	0.5260	0.066*
H51C	0.0345	0.2198	0.4178	0.066*
C71	−0.02574 (12)	0.0995 (2)	0.7994 (6)	0.0321 (15)
C72	−0.04301 (13)	0.06211 (18)	0.7456 (6)	0.0343 (14)
H72	−0.0342	0.0448	0.6710	0.041*
C73	−0.07393 (14)	0.0506 (2)	0.8046 (7)	0.0486 (18)
H73	−0.0857	0.0260	0.7684	0.058*
C74	−0.08654 (14)	0.0765 (2)	0.9182 (6)	0.0452 (18)
H74	−0.1071	0.0696	0.9568	0.054*
C76	−0.03882 (13)	0.1249 (2)	0.9149 (6)	0.0401 (16)
H76	−0.0275	0.1499	0.9517	0.048*
C75	−0.06877 (14)	0.1119 (2)	0.9722 (6)	0.0447 (18)
H75	−0.0771	0.1280	1.0506	0.054*
C121	0.13178 (13)	0.0452 (2)	1.0837 (6)	0.0511 (19)
H12C	0.1229	0.0151	1.0727	0.077*
H12D	0.1220	0.0595	1.1662	0.077*
H12E	0.1552	0.0433	1.0971	0.077*
C141	0.18149 (12)	0.1078 (2)	0.6373 (5)	0.0278 (14)
C142	0.19860 (14)	0.0714 (2)	0.5687 (5)	0.0357 (15)
H142	0.1883	0.0434	0.5562	0.043*
C143	0.23039 (14)	0.0778 (2)	0.5208 (6)	0.0425 (15)
H143	0.2416	0.0535	0.4797	0.051*
C144	0.24583 (13)	0.1193 (2)	0.5326 (6)	0.0396 (16)
H144	0.2671	0.1230	0.4979	0.047*
C145	0.22960 (14)	0.1553 (2)	0.5959 (6)	0.0415 (16)
H145	0.2399	0.1835	0.6043	0.050*
C146	0.19824 (13)	0.1494 (2)	0.6464 (5)	0.0328 (15)
H146	0.1876	0.1740	0.6886	0.039*
Cl1	0.06464 (4)	0.21000 (6)	0.07034 (17)	0.0469 (5)
O11	0.03803 (10)	0.20000 (14)	−0.0264 (5)	0.0681 (14)
O12	0.09267 (9)	0.22770 (15)	−0.0052 (5)	0.0732 (14)
O13	0.05259 (10)	0.24407 (15)	0.1690 (4)	0.0687 (14)
O14	0.07355 (10)	0.16875 (16)	0.1471 (6)	0.0847 (17)
Cl2	0.07278 (5)	0.03380 (7)	0.44805 (18)	0.0537 (5)
O21	0.07483 (17)	0.04772 (19)	0.5928 (5)	0.125 (2)
O22	0.04269 (14)	0.01419 (18)	0.4338 (10)	0.188 (4)
O23	0.09743 (13)	0.00110 (19)	0.4339 (7)	0.128 (2)
O24	0.07649 (15)	0.07442 (18)	0.3705 (6)	0.109 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0283 (3)	0.0379 (4)	0.0244 (3)	0.0042 (4)	−0.0007 (3)	0.0047 (4)
N1	0.026 (3)	0.036 (3)	0.030 (3)	0.004 (2)	−0.007 (2)	0.003 (3)
N4	0.015 (2)	0.034 (3)	0.032 (3)	0.004 (2)	0.006 (2)	0.001 (2)
N8	0.037 (3)	0.036 (3)	0.023 (3)	0.000 (2)	0.006 (2)	0.008 (3)
N11	0.040 (3)	0.031 (3)	0.024 (3)	0.000 (2)	0.008 (2)	0.003 (2)
C2	0.028 (3)	0.049 (4)	0.027 (3)	−0.003 (3)	−0.001 (3)	0.012 (3)
C3	0.045 (4)	0.039 (4)	0.044 (4)	0.005 (3)	−0.012 (3)	0.025 (3)
C5	0.032 (4)	0.031 (4)	0.012 (3)	0.003 (3)	−0.003 (2)	−0.002 (3)
C6	0.034 (4)	0.038 (4)	0.026 (3)	0.002 (3)	−0.011 (3)	0.002 (3)
C7	0.029 (3)	0.056 (5)	0.028 (4)	−0.003 (3)	0.004 (3)	0.002 (3)
C9	0.040 (4)	0.046 (4)	0.048 (4)	−0.003 (3)	0.009 (3)	0.010 (4)
C10	0.031 (3)	0.059 (4)	0.033 (4)	0.004 (3)	−0.002 (3)	0.009 (4)
C12	0.035 (4)	0.034 (4)	0.029 (3)	0.011 (3)	−0.006 (3)	0.000 (3)
C13	0.025 (3)	0.052 (5)	0.030 (3)	0.011 (3)	0.007 (3)	0.013 (3)
C14	0.023 (3)	0.033 (4)	0.033 (3)	0.006 (3)	−0.004 (3)	0.000 (3)
C51	0.042 (3)	0.040 (4)	0.049 (4)	0.004 (3)	0.001 (3)	0.009 (4)
C71	0.027 (3)	0.044 (4)	0.025 (3)	−0.008 (3)	−0.008 (3)	0.006 (3)
C72	0.041 (4)	0.037 (4)	0.024 (3)	0.001 (3)	0.001 (3)	0.003 (3)
C73	0.045 (4)	0.044 (4)	0.057 (5)	−0.011 (3)	−0.013 (3)	0.008 (4)
C74	0.029 (4)	0.069 (5)	0.038 (4)	−0.003 (4)	0.014 (3)	0.015 (4)
C76	0.043 (4)	0.051 (4)	0.025 (3)	−0.005 (3)	−0.002 (3)	0.000 (4)
C75	0.040 (4)	0.063 (5)	0.031 (4)	−0.011 (3)	0.009 (3)	−0.007 (3)
C121	0.042 (4)	0.066 (5)	0.045 (4)	0.008 (3)	−0.006 (3)	0.014 (4)
C141	0.024 (3)	0.040 (4)	0.019 (3)	0.003 (3)	−0.002 (2)	0.002 (3)
C142	0.040 (4)	0.035 (4)	0.033 (4)	0.003 (3)	−0.001 (3)	−0.001 (3)
C143	0.046 (4)	0.057 (5)	0.025 (3)	0.021 (4)	0.006 (3)	−0.007 (4)
C144	0.025 (3)	0.066 (5)	0.027 (3)	−0.005 (3)	0.006 (3)	0.014 (4)
C145	0.039 (4)	0.047 (4)	0.039 (4)	−0.006 (3)	0.003 (3)	−0.002 (4)
C146	0.028 (3)	0.047 (4)	0.024 (3)	0.007 (3)	0.006 (3)	−0.008 (3)
Cl1	0.0388 (10)	0.0481 (12)	0.0537 (11)	−0.0059 (9)	0.0022 (8)	0.0043 (10)
O11	0.055 (3)	0.080 (3)	0.070 (3)	0.008 (3)	−0.013 (3)	−0.030 (3)
O12	0.045 (3)	0.091 (4)	0.083 (4)	0.007 (3)	0.030 (3)	0.032 (3)
O13	0.090 (3)	0.067 (3)	0.049 (3)	−0.018 (3)	0.008 (3)	−0.017 (3)
O14	0.064 (3)	0.065 (4)	0.125 (5)	−0.001 (3)	−0.004 (3)	0.048 (4)
Cl2	0.0644 (12)	0.0518 (13)	0.0449 (11)	−0.0078 (11)	0.0028 (9)	−0.0017 (10)
O21	0.230 (7)	0.104 (5)	0.041 (3)	−0.005 (4)	0.029 (4)	−0.008 (3)
O22	0.119 (5)	0.071 (4)	0.374 (11)	−0.028 (4)	−0.151 (6)	0.053 (6)
O23	0.110 (4)	0.099 (4)	0.176 (6)	0.033 (4)	0.073 (4)	−0.034 (4)
O24	0.198 (6)	0.074 (5)	0.056 (3)	−0.032 (4)	0.017 (4)	0.005 (3)

Geometric parameters (Å, º)

Ni1—N4	1.919 (4)	C14—H14	0.980
Ni1—N11	1.927 (4)	C51—H51A	0.960
Ni1—N8	1.955 (4)	C51—H51B	0.960
Ni1—N1	1.972 (4)	C51—H51C	0.9600
N1—C14	1.502 (6)	C71—C72	1.396 (7)
N1—C2	1.504 (6)	C71—C76	1.410 (7)
N1—H1	0.930	C72—C73	1.412 (7)
N4—C5	1.281 (6)	C72—H72	0.930
N4—C3	1.494 (6)	C73—C74	1.397 (7)
N8—C7	1.505 (6)	C73—H73	0.930
N8—C9	1.508 (6)	C74—C75	1.362 (7)
N8—H8	0.9299	C74—H74	0.930
N11—C12	1.300 (6)	C76—C75	1.382 (7)
N11—C10	1.505 (6)	C76—H76	0.930
C2—C3	1.506 (6)	C75—H75	0.930
C2—H2A	0.970	C121—H12C	0.960
C2—H2B	0.970	C121—H12D	0.960
C3—H3A	0.970	C121—H12E	0.960
C3—H3B	0.970	C141—C146	1.402 (7)
C5—C6	1.489 (7)	C141—C142	1.426 (7)
C5—C51	1.545 (7)	C142—C143	1.379 (7)
C6—C7	1.504 (7)	C142—H142	0.930
C6—H6A	0.970	C143—C144	1.377 (7)
C6—H6B	0.970	C143—H143	0.930
C7—C71	1.574 (6)	C144—C145	1.380 (7)
C7—H7	0.980	C144—H144	0.930
C9—C10	1.529 (7)	C145—C146	1.369 (6)
C9—H9I	0.970	C145—H145	0.930
C9—H9J	0.970	C146—H146	0.930
C10—H10G	0.970	Cl1—O12	1.435 (4)
C10—H10H	0.970	Cl1—O11	1.436 (4)
C12—C121	1.478 (7)	Cl1—O13	1.442 (4)
C12—C13	1.511 (7)	Cl1—O14	1.452 (4)
C13—C14	1.538 (7)	Cl2—O22	1.359 (5)
C13—H13A	0.970	Cl2—O23	1.395 (5)
C13—H13B	0.970	Cl2—O24	1.402 (5)
C14—C141	1.510 (6)	Cl2—O21	1.405 (5)
N4—Ni1—N11	174.63 (19)	C12—C13—H13B	108.1
N4—Ni1—N8	93.64 (17)	C14—C13—H13B	108.1
N11—Ni1—N8	86.14 (19)	H13A—C13—H13B	107.3
N4—Ni1—N1	86.12 (17)	N1—C14—C141	115.0 (4)
N11—Ni1—N1	93.75 (17)	N1—C14—C13	108.0 (4)
N8—Ni1—N1	176.3 (2)	C141—C14—C13	109.0 (4)
C14—N1—C2	112.8 (4)	N1—C14—H14	108.2
C14—N1—Ni1	114.8 (3)	C141—C14—H14	108.2
C2—N1—Ni1	106.2 (3)	C13—C14—H14	108.2
C14—N1—H1	107.4	C5—C51—H51A	109.5
C2—N1—H1	107.6	C5—C51—H51B	109.5
Ni1—N1—H1	107.7	H51A—C51—H51B	109.5
C5—N4—C3	118.5 (4)	C5—C51—H51C	109.5
C5—N4—Ni1	129.4 (4)	H51A—C51—H51C	109.5
C3—N4—Ni1	111.4 (3)	H51B—C51—H51C	109.5
C7—N8—C9	113.0 (4)	C72—C71—C76	120.0 (5)
C7—N8—Ni1	115.6 (3)	C72—C71—C7	121.3 (5)
C9—N8—Ni1	106.5 (3)	C76—C71—C7	118.7 (5)
C7—N8—H8	107.2	C71—C72—C73	119.9 (5)
C9—N8—H8	107.2	C71—C72—H72	120.1
Ni1—N8—H8	107.0	C73—C72—H72	120.1
C12—N11—C10	117.2 (4)	C74—C73—C72	119.2 (5)
C12—N11—Ni1	129.9 (4)	C74—C73—H73	120.4
C10—N11—Ni1	112.6 (3)	C72—C73—H73	120.4
N1—C2—C3	105.9 (4)	C75—C74—C73	120.0 (5)
N1—C2—H2A	110.6	C75—C74—H74	120.0
C3—C2—H2A	110.6	C73—C74—H74	120.0
N1—C2—H2B	110.6	C75—C76—C71	118.5 (5)
C3—C2—H2B	110.6	C75—C76—H76	120.8
H2A—C2—H2B	108.7	C71—C76—H76	120.8
N4—C3—C2	108.2 (4)	C74—C75—C76	122.5 (5)
N4—C3—H3A	110.1	C74—C75—H75	118.7
C2—C3—H3A	110.1	C76—C75—H75	118.7
N4—C3—H3B	110.1	C12—C121—H12C	109.5
C2—C3—H3B	110.1	C12—C121—H12D	109.5
H3A—C3—H3B	108.4	H12C—C121—H12D	109.5
N4—C5—C6	123.0 (5)	C12—C121—H12E	109.5
N4—C5—C51	121.9 (5)	H12C—C121—H12E	109.5
C6—C5—C51	115.0 (4)	H12D—C121—H12E	109.5
C5—C6—C7	117.8 (4)	C146—C141—C142	116.3 (5)
C5—C6—H6A	107.8	C146—C141—C14	123.9 (5)
C7—C6—H6A	107.8	C142—C141—C14	119.5 (5)
C5—C6—H6B	107.8	C143—C142—C141	120.0 (5)
C7—C6—H6B	107.8	C143—C142—H142	120.0
H6A—C6—H6B	107.2	C141—C142—H142	120.0
C6—C7—N8	110.7 (4)	C144—C143—C142	121.5 (5)
C6—C7—C71	111.4 (4)	C144—C143—H143	119.3
N8—C7—C71	110.2 (4)	C142—C143—H143	119.3
C6—C7—H7	108.1	C143—C144—C145	119.8 (5)
N8—C7—H7	108.1	C143—C144—H144	120.1
C71—C7—H7	108.1	C145—C144—H144	120.1
N8—C9—C10	106.9 (4)	C146—C145—C144	119.5 (6)
N8—C9—H9I	110.3	C146—C145—H145	120.3
C10—C9—H9I	110.3	C144—C145—H145	120.3
N8—C9—H9J	110.3	C145—C146—C141	122.9 (5)
C10—C9—H9J	110.3	C145—C146—H146	118.5
H9I—C9—H9J	108.6	C141—C146—H146	118.5
N11—C10—C9	106.5 (4)	O12—Cl1—O11	111.6 (3)
N11—C10—H10G	110.4	O12—Cl1—O13	109.1 (3)
C9—C10—H10G	110.4	O11—Cl1—O13	106.4 (3)
N11—C10—H10H	110.4	O12—Cl1—O14	110.1 (3)
C9—C10—H10H	110.4	O11—Cl1—O14	108.9 (3)
H10G—C10—H10H	108.6	O13—Cl1—O14	110.7 (3)
N11—C12—C121	122.6 (5)	O22—Cl2—O23	110.2 (4)
N11—C12—C13	121.4 (5)	O22—Cl2—O24	114.1 (4)
C121—C12—C13	116.0 (5)	O23—Cl2—O24	117.5 (4)
C12—C13—C14	116.7 (4)	O22—Cl2—O21	105.6 (5)
C12—C13—H13A	108.1	O23—Cl2—O21	104.3 (4)
C14—C13—H13A	108.1	O24—Cl2—O21	103.6 (3)