The title compound, [Ni(C5H12N2)2](ClO4)2, consists of discrete [Ni(C5H12N2)2]2+ cations and perchlorate anions. The NiII atom is at the center of symmetry and is coordinated in a square-planar manner by the nitrogen donors of a pair of mesocyclic 1,4-diazacycloheptane (DACH) ligands. Both DACH rings adopt boat conformations in the trans form. The perchlorate O atoms are hydrogen bonded with the nitrogen donors of the DACH rings to form a macrocycle-like system.
Supporting information
CCDC reference: 170735
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.051
- wR factor = 0.141
- Data-to-parameter ratio = 13.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_737 Alert C D...A Calc 2.997(7), Rep 2.997(3) .... 2.33 s.u-Ratio
N1 -O3 1.555 2.645
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
A mixture of Ni(ClO4)2·6H2O (220 mg, 0.6 mmol) and
1,4-diazacycloheptane (120 mg, 1.2 mmol) was dissolved in methanol (15 ml) at
room temperature. A yellow powder precipitated immediately. The complex was
filtered off and washed several times with anhydrous ether. Yield: 253 mg
(92%). Yellow block-shaped single crystals of (I) were grown from
CH3COCH3/CH3OH (5:1). FT–IR data (KBr pellet, cm-1): 3268 (m),
3123 (m), 3083 (m), 2948 (w), 1635 (w), 1473 (m), 1122
(versus), 1109 (versus), 988 (m), 636 (s), 626
(s). Analysis calculated for (I): C 26.23, H 5.28, N 12.24%; found: C
26.41, H 5.40, N 12.13%.
The H atoms attached to C and N atoms were placed in geometrically calculated
positions and included in the final refinement as riding with displacement
parameters derived from the atoms to which they were bonded.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998).
Bis(1,4-diazacycloheptane-N,
N')nickel(II) diperchlorate
top
Crystal data top
[Ni(C5H12N2)2](ClO4)2 | F(000) = 476 |
Mr = 457.94 | Dx = 1.724 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7899 (17) Å | Cell parameters from 3489 reflections |
b = 8.071 (2) Å | θ = 2.5–25.0° |
c = 16.152 (4) Å | µ = 1.45 mm−1 |
β = 94.760 (5)° | T = 293 K |
V = 882.0 (4) Å3 | Prism, yellow |
Z = 2 | 0.20 × 0.20 × 0.15 mm |
Data collection top
Bruker SMART 1000 diffractometer | 968 reflections with I > 2σ(I) |
ω scans | Rint = 0.052 |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | θmax = 25.0° |
Tmin = 0.760, Tmax = 0.812 | h = −8→8 |
3544 measured reflections | k = −9→9 |
1557 independent reflections | l = −8→19 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.141 | (Δ/σ)max = 0.007 |
S = 0.98 | Δρmax = 0.65 e Å−3 |
1557 reflections | Δρmin = −0.41 e Å−3 |
115 parameters | |
Crystal data top
[Ni(C5H12N2)2](ClO4)2 | V = 882.0 (4) Å3 |
Mr = 457.94 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.7899 (17) Å | µ = 1.45 mm−1 |
b = 8.071 (2) Å | T = 293 K |
c = 16.152 (4) Å | 0.20 × 0.20 × 0.15 mm |
β = 94.760 (5)° | |
Data collection top
Bruker SMART 1000 diffractometer | 1557 independent reflections |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | 968 reflections with I > 2σ(I) |
Tmin = 0.760, Tmax = 0.812 | Rint = 0.052 |
3544 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 115 parameters |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.65 e Å−3 |
1557 reflections | Δρmin = −0.41 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. Single crystal X-ray diffraction measurements were carried out on a BRUKER
SMART 1000 CCD diffractometer. The structure was solved by direct and
difference Fourier methods and refined by full-matrix least-squares methods. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.0265 (3) | |
N1 | 0.1841 (6) | 0.0219 (5) | 0.0955 (3) | 0.0314 (11) | |
H1C | 0.2933 | −0.0403 | 0.0885 | 0.038* | |
N2 | −0.1095 (6) | 0.1921 (5) | 0.0486 (3) | 0.0325 (11) | |
H2C | −0.1973 | 0.2422 | 0.0110 | 0.039* | |
C1 | 0.0855 (9) | −0.0405 (7) | 0.1691 (4) | 0.0423 (16) | |
H1A | 0.1838 | −0.0559 | 0.2155 | 0.051* | |
H1B | 0.0247 | −0.1470 | 0.1558 | 0.051* | |
C2 | −0.0711 (9) | 0.0804 (8) | 0.1935 (4) | 0.0478 (16) | |
H2A | −0.1464 | 0.0280 | 0.2348 | 0.057* | |
H2B | −0.0056 | 0.1764 | 0.2193 | 0.057* | |
C3 | −0.2118 (8) | 0.1384 (8) | 0.1231 (4) | 0.0431 (15) | |
H3A | −0.2884 | 0.2304 | 0.1419 | 0.052* | |
H3B | −0.3030 | 0.0493 | 0.1069 | 0.052* | |
C4 | 0.0611 (8) | 0.3057 (7) | 0.0713 (4) | 0.0383 (15) | |
H4A | 0.0280 | 0.3816 | 0.1146 | 0.046* | |
H4B | 0.0914 | 0.3700 | 0.0233 | 0.046* | |
C5 | 0.2402 (8) | 0.1995 (7) | 0.1022 (4) | 0.0388 (15) | |
H5A | 0.3498 | 0.2215 | 0.0688 | 0.047* | |
H5B | 0.2814 | 0.2268 | 0.1595 | 0.047* | |
Cl1 | 0.4644 (2) | 0.15911 (19) | 0.37453 (10) | 0.0456 (5) | |
O1 | 0.4525 (13) | 0.2417 (11) | 0.2992 (4) | 0.160 (4) | |
O2 | 0.3003 (13) | 0.0729 (12) | 0.3883 (6) | 0.193 (5) | |
O3 | 0.4917 (9) | 0.2842 (7) | 0.4364 (4) | 0.098 (2) | |
O4 | 0.6346 (14) | 0.0742 (12) | 0.3836 (8) | 0.216 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0243 (5) | 0.0296 (5) | 0.0245 (5) | 0.0070 (4) | −0.0039 (4) | −0.0033 (5) |
N1 | 0.028 (2) | 0.038 (3) | 0.027 (2) | 0.011 (2) | −0.0032 (19) | −0.002 (2) |
N2 | 0.028 (3) | 0.037 (3) | 0.030 (3) | 0.010 (2) | −0.006 (2) | −0.001 (2) |
C1 | 0.051 (4) | 0.041 (4) | 0.033 (3) | −0.001 (3) | −0.004 (3) | 0.009 (3) |
C2 | 0.052 (4) | 0.056 (4) | 0.038 (4) | −0.001 (3) | 0.013 (3) | −0.007 (3) |
C3 | 0.027 (3) | 0.052 (4) | 0.051 (4) | 0.003 (3) | 0.009 (3) | −0.013 (3) |
C4 | 0.043 (4) | 0.026 (3) | 0.045 (4) | −0.004 (3) | −0.001 (3) | −0.005 (3) |
C5 | 0.027 (3) | 0.045 (3) | 0.043 (4) | −0.005 (3) | −0.001 (3) | 0.000 (3) |
Cl1 | 0.0425 (9) | 0.0430 (9) | 0.0504 (10) | −0.0030 (7) | −0.0009 (7) | −0.0046 (8) |
O1 | 0.193 (8) | 0.211 (9) | 0.068 (5) | −0.038 (7) | −0.035 (5) | 0.043 (5) |
O2 | 0.170 (8) | 0.237 (9) | 0.182 (8) | −0.174 (8) | 0.075 (7) | −0.097 (8) |
O3 | 0.112 (5) | 0.096 (4) | 0.088 (4) | −0.054 (4) | 0.021 (4) | −0.023 (4) |
O4 | 0.183 (9) | 0.150 (7) | 0.328 (15) | 0.108 (7) | 0.095 (10) | 0.065 (9) |
Geometric parameters (Å, º) top
Ni1—N1 | 1.911 (4) | C2—H2A | 0.9700 |
Ni1—N1i | 1.911 (4) | C2—H2B | 0.9700 |
Ni1—N2 | 1.915 (4) | C3—H3A | 0.9700 |
Ni1—N2i | 1.915 (4) | C3—H3B | 0.9700 |
N1—C5 | 1.484 (7) | C4—C5 | 1.537 (7) |
N1—C1 | 1.499 (7) | C4—H4A | 0.9700 |
N1—H1C | 0.9100 | C4—H4B | 0.9700 |
N2—C4 | 1.499 (6) | C5—H5A | 0.9700 |
N2—C3 | 1.502 (7) | C5—H5B | 0.9700 |
N2—H2C | 0.9100 | Cl1—O4 | 1.341 (8) |
C1—C2 | 1.519 (8) | Cl1—O2 | 1.348 (6) |
C1—H1A | 0.9700 | Cl1—O1 | 1.384 (7) |
C1—H1B | 0.9700 | Cl1—O3 | 1.421 (6) |
C2—C3 | 1.499 (8) | | |
| | | |
N1—Ni1—N1i | 180.0 (3) | C3—C2—H2B | 108.6 |
N1—Ni1—N2 | 81.06 (17) | C1—C2—H2B | 108.6 |
N1i—Ni1—N2 | 98.94 (17) | H2A—C2—H2B | 107.6 |
N1—Ni1—N2i | 98.94 (17) | C2—C3—N2 | 113.0 (4) |
N1i—Ni1—N2i | 81.06 (17) | C2—C3—H3A | 109.0 |
N2—Ni1—N2i | 180.0 (3) | N2—C3—H3A | 109.0 |
C5—N1—C1 | 113.3 (5) | C2—C3—H3B | 109.0 |
C5—N1—Ni1 | 107.2 (3) | N2—C3—H3B | 109.0 |
C1—N1—Ni1 | 107.7 (3) | H3A—C3—H3B | 107.8 |
C5—N1—H1C | 109.5 | N2—C4—C5 | 108.2 (4) |
C1—N1—H1C | 109.5 | N2—C4—H4A | 110.1 |
Ni1—N1—H1C | 109.5 | C5—C4—H4A | 110.1 |
C4—N2—C3 | 112.3 (4) | N2—C4—H4B | 110.1 |
C4—N2—Ni1 | 106.1 (3) | C5—C4—H4B | 110.1 |
C3—N2—Ni1 | 108.4 (3) | H4A—C4—H4B | 108.4 |
C4—N2—H2C | 110.0 | N1—C5—C4 | 108.9 (4) |
C3—N2—H2C | 110.0 | N1—C5—H5A | 109.9 |
Ni1—N2—H2C | 110.0 | C4—C5—H5A | 109.9 |
N1—C1—C2 | 111.0 (4) | N1—C5—H5B | 109.9 |
N1—C1—H1A | 109.4 | C4—C5—H5B | 109.9 |
C2—C1—H1A | 109.4 | H5A—C5—H5B | 108.3 |
N1—C1—H1B | 109.4 | O4—Cl1—O2 | 115.8 (7) |
C2—C1—H1B | 109.4 | O4—Cl1—O1 | 109.2 (7) |
H1A—C1—H1B | 108.0 | O2—Cl1—O1 | 113.9 (6) |
C3—C2—C1 | 114.8 (5) | O4—Cl1—O3 | 103.0 (7) |
C3—C2—H2A | 108.6 | O2—Cl1—O3 | 108.2 (4) |
C1—C2—H2A | 108.6 | O1—Cl1—O3 | 105.7 (5) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1c···O3ii | 0.91 | 2.10 | 2.997 (3) | 170 |
N2—H2c···O3iii | 0.91 | 2.35 | 3.137 (4) | 144 |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Ni(C5H12N2)2](ClO4)2 |
Mr | 457.94 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.7899 (17), 8.071 (2), 16.152 (4) |
β (°) | 94.760 (5) |
V (Å3) | 882.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] |
Tmin, Tmax | 0.760, 0.812 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3544, 1557, 968 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.141, 0.98 |
No. of reflections | 1557 |
No. of parameters | 115 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.41 |
Selected geometric parameters (Å, º) topNi1—N1 | 1.911 (4) | N2—C3 | 1.502 (7) |
Ni1—N2 | 1.915 (4) | C1—C2 | 1.519 (8) |
N1—C5 | 1.484 (7) | C2—C3 | 1.499 (8) |
N1—C1 | 1.499 (7) | C4—C5 | 1.537 (7) |
N2—C4 | 1.499 (6) | | |
| | | |
N1—Ni1—N2 | 81.06 (17) | C3—N2—Ni1 | 108.4 (3) |
N1i—Ni1—N2 | 98.94 (17) | N1—C1—C2 | 111.0 (4) |
C5—N1—C1 | 113.3 (5) | C3—C2—C1 | 114.8 (5) |
C5—N1—Ni1 | 107.2 (3) | C2—C3—N2 | 113.0 (4) |
C1—N1—Ni1 | 107.7 (3) | N2—C4—C5 | 108.2 (4) |
C4—N2—C3 | 112.3 (4) | N1—C5—C4 | 108.9 (4) |
C4—N2—Ni1 | 106.1 (3) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1c···O3ii | .91 | 2.10 | 2.997 (3) | 170 |
N2—H2c···O3iii | .91 | 2.35 | 3.137 (4) | 144 |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, −y+1/2, z−1/2. |
Mesocyclic ligands (molecules contain seven- to ten-membered rings) occupy an important place between acyclic and macrocyclic ligands due to offer several attractive features as a framework for ligand development with exceptionally strong ligand fields, unique conformational requirements and the potential for further functionalization (Musker, 1992; Grapperhaus & Darensbourg, 1998; Bu et al., 2000). 1,5-Diazacyclooctane (DACO) and 1,4-diazacycloheptane (DACH) are the most typical examples of the diazamesocyclic ligands. However, comparison of the widely investigation of DACO, structural studies on DACH are still quite rare (Musker, 1992; Allen et al., 1996). As part of our effort to further develop this interesting system, we report herein the synthesis and X-ray crystal structure of a NiII complex of DACH, namely the title compound, (I).
In the complex cation, the NiII center is four-coordinated, forming an exact plane, with the Ni1 atom at the center of symmetry (Fig. 1). The Ni—N1 and Ni—N2 bond distances are 1.911 (4) and 1.915 (4) Å, respectively, and are nearly equivalent. The chelate N1—Ni1—N2 angle is 81.06 (17)°, and slightly smaller than the non-chelate N1—Ni1—N2i angle [symmetry code: (i) -x, -y, -z]. The C—C bond distances in the methylene groups of DACH are in the range 1.499 (8)–1.537 (7) Å, which are normal aliphatic C—C bonds with sp3 hybridization. Both DACH moieties in the complex adopt the boat conformation in a trans form due to the central symmetry, which is similar to the structure of [Ni(DACH)2]Cl2·2H2O (Hussain, 1983). The perchlorate ions have no close contacts to the NiII centers, since the shortest axial distance for Ni···O is 3.925 (3) Å.
The [Ni(DACH)2]2+ unit carries two perchlorate ions which are hydrogen bonded to the nitrogen donors of DACH (Fig. 2). These hydrogen bonds form a macrocycle-like ring system including a pair of N—-H···O···N–H bridges, which is similar to the structure of [Ni(DACO)2]Br2 (Du et al., 2000).