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In the crystal structure of the title complex, [Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2 or [Ni(dmaeoxd)Ni(dmbp)2](ClO4)2 {H2dmaeoxd is N,N'-bis­[2-(dimethyl­amino)ethyl]oxamide and dmbp is 4,4'-dimethyl-2,2'-bipyridine}, the deprotonated dmaeoxd2- ligand is in a cis conformation and bridges two NiII atoms, one of which is located in a slightly distorted square-planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd2- ligands inter­act with each other via C-H...O hydrogen bonds and [pi]-[pi] inter­actions, which results in an extended chain along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010700282X/sk3088sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010700282X/sk3088Isup2.hkl
Contains datablock I

CCDC reference: 641789

Comment top

There has been a great interest in the crystal engineering of self-assembled supramolecular architectures formed through relatively weak C—H···O and ππ stacking interactions (Blake et al., 1999; Lin et al., 2003). Considerable attention has been devoted to metal polypyridyl complexes (Kalyanasundaram & Grätzel 1998; Ye et al., 1998), in which the hydrophilic groups are linked via hydrogen bonds while the hydrophobic groups are stacked via ππ interactions. N,N'-Disubstituted oxamidates are well known as versatile bridging ligands, which can afford symmetric and asymmetric oxamidate bridges by the cistrans conformational change (Ruiz et al., 1999). Four crystal structures of dinuclear oxamidate-bridged NiII complexes with the Ni atoms in different coordination geometries have been reported to date, namely [Ni(obbz)Ni(H2O)4]·2H2O, (II) (Reference?), Ni(aeox)Ni(en)(SCN)2, (III) (Chen et al., 1994), [Ni(aeox)Ni(phen)2](ClO4)2·3H2O, (IV) (Wei et al., 1995), and [Ni(apox)Ni(phen)2](ClO4)2·CH3OH·2H2O, (V) (Jiu et al., 2000) [obbz is deprotonated N,N'-bis(2-aminobenzoato)oxamide, aeox is deprotonated N,N'-bis(2-aminoethyl)oxamide, en is ethylenediamine, phen is 1,10-phenanthroline and apox is deprotonated N,N'-bis(3-aminopropyl)oxamide]. In these complexes, however, the types of hydrogen-bond interactions were not discussed in detail and the ππ stacking was not studied at all. In order to study the supramolecular architecture of this kind of complex, we chose H2dmaeoxd as a polydentate ligand to synthesize the title binuclear NiII complex, (I), formulated as [Ni(dmaeoxd)Ni(dmbp)2](ClO4)2, and report its crystal structure here.

Compound (I) consists of an [Ni(dmaeoxd)Ni(dmbp)2]2+ cation and two uncoordinated ClO4- anions. A view of the compound is depicted in Fig. 1, and selected bond lengths and angles are listed in Table 1. The deprotonated dmaeoxd2- ligand exhibits a cisoid conformation and bridges two NiII atoms, with an Ni···Ni distance of 5.2955 (18) Å. A crystallographic twofold axis passes through this Ni···Ni vector and the middle of the C5—C5i bond [symmetry code: (i) 1 - x, y, 1/2 - z]. Within the bridging oxamide fragment, the C—O and C—N bonds have partial double-bond character [N2—C5 = 1.299 (4) Å and C5—O1 = 1.255 (4) Å], while the C5—C5i bond of 1.521 (6) Å is identical to the standard value of a single bond (Standard reference?). These bonds are similar to those in many other oxamidate complexes (Lloret et al., 1989; Real et al., 1993).

Atom Ni1 is coordinated by four N atoms of dmaeoxd, with the maximum deviation from the coordinated plane being 0.023 (3) Å for atom N2. The Ni1—N2 bond length of 1.853 (3) Å is comparable with the distances between the Ni and amide N atoms in compounds (II)–(V) (1.837–1.895 Å). The Ni1—N1 distance [1.976 (3) Å] is longer than the corresponding distance in compounds (III)–(V), which is perhaps due to the steric hindrance between the two pairs of methyl groups on atom N1. The bridging ligand coordinates atom Ni1 by forming three five-membered chelate rings. Those formed by the ethylene diamine fragment adopt a twist form, with puckering parameters (Cremer & Pople, 1975) of Q = 0.418 (4) Å and ϕ = 62.4 (5)°.

Atom Ni2 is coordinated by four N donors of two dmbp molecules and two O atoms of the dmaeoxd ligand. Due to the rigidity of the three bidentate ligands, the hexacoordinated atom Ni2 has a distorted octahedral geometry. Atom N4 and its symmetry-related atom N4i are axially coordinated, with an approximately linear N—Ni—N angle. The equatorial plane is defined by the other four atoms and the mean displacement from this plane is 0.173 Å. Atom Ni2 lies exactly in the plane. The terminal dmbp ligands are present in the usual chelating bidentate mode, except for the envelope form of the chelate ring on Ni2. The torsion angles Ni2—N3—C10—C11 and Ni2—N4—C11—C10 are -11.2 (4) and 15.5 (4)°, respectively.

As shown in Fig. 2, the binuclear cation complexes and perchlorate anions are connected through a non-classical hydrogen bond, C6—H6···O13 (Table 2), which gives rise to an ion triplet, [Ni(dmaeoxd)Ni(dmbp)2]2+·2ClO4-. These triplets are linked into a one-dimensional ribbon along the c axis by a combination of a C12—H12···O1ii [symmetry code: (ii) x, 1 - y, 1/2 + z] interaction and a ππ stacking interaction between the dmbp ligand and that generated by the symmetry operation (1 - x, 1 - y, 1 - z), with separations of 3.505 (4) [atom C9 at (1 - x, 1 - y, 1 - z)] and 3.526 (4) Å [atom C13 at (1 - x, 1 - y, 1 - z)].

Related literature top

For related literature, see: Blake et al. (1999); Chen et al. (1994); Cremer & Pople (1975); Jiu et al. (2000); Kalyanasundaram & Grätzel (1998); Lin et al. (2003); Lloret et al. (1989); Ojima & Yamada (1970); Real et al. (1993); Ruiz et al. (1999); Wei et al. (1995); Ye et al. (1998).

Experimental top

All reagents were of AR grade and were used without further purification. The H2dmaeoxd ligand was synthesized according to the method of Ojima & Yamada (1970). [Ni(dmaeoxd)Ni(dmbp)2](ClO4)2 was obtained as follows. To a solution of H2dmaeoxd (0.0230 g, 0.1 mmol) in methanol (10 ml) was added successively piperidine (0.2 mmol) and a solution of Ni(ClO4)2·6H2O (0.0731 g, 0.2 mmol) in methanol (5 ml). After stirring for 20 min, dmbp (0.0368 g, 0.2 mmol) in methanol (5 ml) was added. The reaction mixture was stirred at 333 K for a further 2 h. Orange crystals of the title compound suitable for X-ray analysis were obtained from the solution by slow evaporation at room temperature on the second day (yield 67%). Spectroscopic analysis: IR (KBr pellet, γ, cm-1): 1649 (vs), 1615 (vs), 1487 (m), 1471 (s), 1088 (vs), 833 (m), 623 (s).

Refinement top

All H atoms were placed in calculated positions, with C—H distances of 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and refined in riding mode, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The CH3 groups bound to the pyridine rings were allowed to rotate freely around the C—C bond.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) 1 - x, y, 1/2 - z.]
[Figure 2] Fig. 2. A view showing the ribbon extending along [001], formed by C—H···O hydrogen bonds (dashed lines) and π-π stacking interactions. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (ii) x, 1 - y, 1/2 + z; (iii) x, 1 - y, z - 1/2.]
µ-{N,N'-Bis[2-(dimethylamino)ethyl]oxamidato(2-)}- 1κ2O,O':2κ4N,N',N'',N'''-bis(4,4'-dimethyl-2,2'-bipyridine- 1κ2N,N')dinickel(II) bis(perchlorate) top
Crystal data top
[Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2F(000) = 1896
Mr = 913.05Dx = 1.538 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2683 reflections
a = 19.068 (6) Åθ = 2.3–25.5°
b = 13.431 (4) ŵ = 1.16 mm1
c = 15.920 (5) ÅT = 298 K
β = 104.744 (4)°Block, orange
V = 3943 (2) Å30.45 × 0.38 × 0.29 mm
Z = 4
Data collection top
Bruker APEX CCD area-detector
diffractometer
3470 independent reflections
Radiation source: fine-focus sealed tube2338 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 2222
Tmin = 0.612, Tmax = 0.716k = 1015
10149 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0464P)2 + 5.2848P]
where P = (Fo2 + 2Fc2)/3
3470 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2V = 3943 (2) Å3
Mr = 913.05Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.068 (6) ŵ = 1.16 mm1
b = 13.431 (4) ÅT = 298 K
c = 15.920 (5) Å0.45 × 0.38 × 0.29 mm
β = 104.744 (4)°
Data collection top
Bruker APEX CCD area-detector
diffractometer
3470 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2338 reflections with I > 2σ(I)
Tmin = 0.612, Tmax = 0.716Rint = 0.036
10149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.02Δρmax = 0.50 e Å3
3470 reflectionsΔρmin = 0.28 e Å3
256 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
xyzUiso*/Ueq
Ni10.50000.15403 (5)0.25000.0409 (2)
O10.44689 (13)0.42838 (18)0.17369 (14)0.0390 (6)
N10.43379 (19)0.0663 (3)0.1663 (2)0.0578 (9)
N20.44962 (16)0.2568 (2)0.18333 (19)0.0426 (8)
C10.4666 (3)0.0381 (4)0.0955 (3)0.0979 (19)
H1A0.50670.00590.11750.147*
H1B0.48330.09670.07210.147*
H1C0.43100.00490.05050.147*
C20.4060 (3)0.0225 (4)0.2016 (4)0.0957 (19)
H2A0.36730.05140.15760.144*
H2B0.38810.00370.25050.144*
H2C0.44430.07020.21970.144*
C30.3676 (3)0.1308 (4)0.1305 (3)0.0742 (15)
H3A0.33740.10010.07860.089*
H3B0.33940.13580.17310.089*
C40.3892 (2)0.2315 (3)0.1092 (3)0.0574 (11)
H4A0.40460.23100.05560.069*
H4B0.34960.27840.10350.069*
C50.46976 (18)0.3467 (3)0.2083 (2)0.0349 (8)
Ni20.50000.54830 (5)0.25000.0371 (2)
N30.54611 (16)0.6452 (2)0.34900 (19)0.0389 (7)
N40.42297 (16)0.5480 (2)0.31922 (18)0.0400 (7)
C60.6064 (2)0.6995 (3)0.3574 (3)0.0499 (10)
H60.62690.70420.31040.060*
C70.6392 (2)0.7489 (3)0.4333 (3)0.0520 (10)
H70.68110.78570.43670.062*
C80.6101 (2)0.7440 (3)0.5045 (3)0.0478 (10)
C90.5466 (2)0.6893 (3)0.4946 (2)0.0417 (9)
H90.52480.68460.54050.050*
C100.51560 (18)0.6418 (3)0.4167 (2)0.0360 (8)
C110.44678 (18)0.5847 (3)0.4008 (2)0.0339 (8)
C120.40814 (18)0.5704 (3)0.4616 (2)0.0384 (8)
H120.42680.59380.51790.046*
C130.34184 (19)0.5219 (3)0.4411 (2)0.0393 (9)
C140.31761 (19)0.4863 (3)0.3566 (2)0.0454 (10)
H140.27360.45270.33940.055*
C150.3592 (2)0.5014 (3)0.2988 (2)0.0477 (10)
H150.34190.47780.24240.057*
C160.6453 (2)0.7946 (4)0.5892 (3)0.0702 (14)
H16A0.69110.76350.61480.105*
H16B0.61440.78880.62810.105*
H16C0.65280.86370.57880.105*
C170.2994 (2)0.5077 (3)0.5076 (2)0.0550 (11)
H17A0.33100.48390.56080.083*
H17B0.26140.46010.48670.083*
H17C0.27850.57020.51810.083*
Cl10.67672 (6)0.83632 (9)0.14899 (7)0.0614 (3)
O110.7066 (2)0.7814 (3)0.0902 (2)0.1060 (13)
O120.6018 (2)0.8186 (3)0.1303 (3)0.1304 (18)
O130.7061 (3)0.8090 (4)0.2356 (3)0.1341 (17)
O140.6898 (3)0.9380 (3)0.1419 (3)0.1299 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0449 (4)0.0382 (4)0.0376 (4)0.0000.0069 (3)0.000
O10.0501 (15)0.0394 (15)0.0239 (12)0.0035 (12)0.0029 (10)0.0019 (11)
N10.071 (2)0.044 (2)0.055 (2)0.0173 (18)0.0083 (18)0.0053 (17)
N20.0452 (18)0.0393 (19)0.0366 (17)0.0020 (15)0.0019 (14)0.0016 (14)
C10.120 (5)0.104 (5)0.071 (4)0.015 (4)0.026 (3)0.042 (3)
C20.102 (4)0.064 (3)0.113 (5)0.038 (3)0.012 (4)0.009 (3)
C30.062 (3)0.073 (3)0.074 (3)0.014 (3)0.008 (2)0.008 (3)
C40.058 (3)0.052 (3)0.051 (2)0.008 (2)0.009 (2)0.004 (2)
C50.0375 (19)0.042 (2)0.0243 (17)0.0011 (18)0.0064 (14)0.0003 (17)
Ni20.0450 (4)0.0405 (4)0.0256 (3)0.0000.0086 (3)0.000
N30.0436 (17)0.0373 (17)0.0362 (17)0.0007 (15)0.0108 (13)0.0011 (14)
N40.0430 (17)0.0465 (19)0.0291 (16)0.0042 (15)0.0065 (13)0.0066 (14)
C60.053 (2)0.050 (2)0.051 (2)0.010 (2)0.021 (2)0.001 (2)
C70.044 (2)0.045 (2)0.065 (3)0.0109 (19)0.010 (2)0.002 (2)
C80.047 (2)0.041 (2)0.049 (2)0.0015 (19)0.0024 (19)0.0075 (19)
C90.046 (2)0.048 (2)0.029 (2)0.0001 (18)0.0066 (16)0.0062 (17)
C100.0373 (19)0.035 (2)0.0339 (19)0.0032 (16)0.0061 (15)0.0002 (16)
C110.0371 (19)0.036 (2)0.0264 (18)0.0014 (16)0.0047 (15)0.0000 (15)
C120.042 (2)0.042 (2)0.0283 (18)0.0008 (17)0.0021 (15)0.0036 (16)
C130.039 (2)0.043 (2)0.036 (2)0.0062 (17)0.0106 (16)0.0033 (17)
C140.033 (2)0.062 (3)0.038 (2)0.0096 (18)0.0046 (17)0.0061 (19)
C150.046 (2)0.059 (3)0.034 (2)0.005 (2)0.0034 (17)0.0114 (19)
C160.062 (3)0.076 (3)0.067 (3)0.013 (3)0.006 (2)0.028 (3)
C170.051 (2)0.075 (3)0.041 (2)0.005 (2)0.0146 (19)0.002 (2)
Cl10.0631 (7)0.0709 (8)0.0513 (6)0.0170 (6)0.0161 (5)0.0119 (6)
O110.101 (3)0.132 (4)0.091 (3)0.007 (3)0.036 (2)0.036 (3)
O120.072 (3)0.134 (4)0.188 (5)0.029 (3)0.039 (3)0.066 (3)
O130.166 (4)0.159 (4)0.064 (3)0.017 (4)0.006 (3)0.018 (3)
O140.181 (4)0.073 (3)0.160 (4)0.039 (3)0.088 (4)0.007 (3)
Geometric parameters (Å, º) top
Ni1—N11.976 (3)C5—O11.255 (4)
Ni1—N1i1.976 (3)C5—C5i1.521 (6)
Ni1—N21.853 (3)C6—C71.381 (5)
Ni1—N2i1.853 (3)C6—H60.9300
Ni2—N32.060 (3)C7—C81.383 (5)
Ni2—N3i2.060 (3)C7—H70.9300
Ni2—N42.048 (3)C8—C91.390 (5)
Ni2—N4i2.048 (3)C8—C161.508 (5)
Ni2—O12.114 (2)C9—C101.385 (5)
Ni2—O1i2.114 (2)C9—H90.9300
N1—C11.471 (6)C10—C111.485 (5)
N1—C21.473 (5)C11—C121.372 (5)
N1—C31.517 (6)C12—C131.386 (5)
N2—C51.299 (4)C12—H120.9300
N2—C41.464 (4)C13—C141.391 (5)
N3—C61.339 (5)C13—C171.500 (5)
N3—C101.350 (4)C14—C151.373 (5)
N4—C151.333 (4)C14—H140.9300
N4—C111.355 (4)C15—H150.9300
C1—H1A0.9600C16—H16A0.9600
C1—H1B0.9600C16—H16B0.9600
C1—H1C0.9600C16—H16C0.9600
C2—H2A0.9600C17—H17A0.9600
C2—H2B0.9600C17—H17B0.9600
C2—H2C0.9600C17—H17C0.9600
C3—C41.478 (6)Cl1—O131.398 (4)
C3—H3A0.9700Cl1—O141.398 (4)
C3—H3B0.9700Cl1—O121.404 (4)
C4—H4A0.9700Cl1—O111.420 (4)
C4—H4B0.9700
N1—Ni1—N1i106.7 (2)N2—C5—C5i111.51 (19)
N1—Ni1—N284.78 (14)C5—O1—Ni2110.6 (2)
N2i—Ni1—N1168.43 (14)C6—N3—C10118.2 (3)
N2i—Ni1—N283.74 (18)C6—N3—Ni2127.5 (3)
N2i—Ni1—N1i84.78 (14)C10—N3—Ni2113.8 (2)
N2—Ni1—N1i168.43 (14)C15—N4—C11117.8 (3)
O1—Ni2—O1i80.74 (13)C15—N4—Ni2127.2 (2)
N3—Ni2—O1165.81 (10)C11—N4—Ni2113.8 (2)
N3—Ni2—O1i89.60 (10)N3—C6—C7122.3 (4)
N4—Ni2—O190.20 (10)N3—C6—H6118.8
N4—Ni2—O1i89.63 (11)C7—C6—H6118.8
N4—Ni2—N379.31 (11)C6—C7—C8120.5 (4)
N4—Ni2—N3i100.83 (12)C6—C7—H7119.8
N4i—Ni2—N4179.78 (17)C8—C7—H7119.8
N4i—Ni2—N3100.83 (12)C7—C8—C9116.8 (3)
N4i—Ni2—N3i79.31 (11)C7—C8—C16122.1 (4)
N3—Ni2—N3i101.66 (16)C9—C8—C16121.1 (4)
N4i—Ni2—O189.63 (11)C10—C9—C8120.4 (4)
N3i—Ni2—O189.60 (10)C10—C9—H9119.8
N4i—Ni2—O1i90.20 (10)C8—C9—H9119.8
N3i—Ni2—O1i165.81 (10)N3—C10—C9121.8 (3)
C1—N1—C2110.4 (4)N3—C10—C11115.0 (3)
C1—N1—C3109.5 (4)C9—C10—C11123.2 (3)
C2—N1—C3105.1 (4)N4—C11—C12121.1 (3)
C1—N1—Ni1110.3 (3)N4—C11—C10114.7 (3)
C2—N1—Ni1117.1 (3)C12—C11—C10124.2 (3)
C3—N1—Ni1103.9 (3)C11—C12—C13121.4 (3)
C5—N2—C4125.0 (3)C11—C12—H12119.3
C5—N2—Ni1116.6 (2)C13—C12—H12119.3
C4—N2—Ni1118.4 (2)C12—C13—C14116.6 (3)
N1—C1—H1A109.5C12—C13—C17121.1 (3)
N1—C1—H1B109.5C14—C13—C17122.2 (3)
H1A—C1—H1B109.5C15—C14—C13119.4 (3)
N1—C1—H1C109.5C15—C14—H14120.3
H1A—C1—H1C109.5C13—C14—H14120.3
H1B—C1—H1C109.5N4—C15—C14123.5 (3)
N1—C2—H2A109.5N4—C15—H15118.2
N1—C2—H2B109.5C14—C15—H15118.2
H2A—C2—H2B109.5C8—C16—H16A109.5
N1—C2—H2C109.5C8—C16—H16B109.5
H2A—C2—H2C109.5H16A—C16—H16B109.5
H2B—C2—H2C109.5C8—C16—H16C109.5
C4—C3—N1110.8 (4)H16A—C16—H16C109.5
C4—C3—H3A109.5H16B—C16—H16C109.5
N1—C3—H3A109.5C13—C17—H17A109.5
C4—C3—H3B109.5C13—C17—H17B109.5
N1—C3—H3B109.5H17A—C17—H17B109.5
H3A—C3—H3B108.1C13—C17—H17C109.5
N2—C4—C3103.6 (3)H17A—C17—H17C109.5
N2—C4—H4A111.0H17B—C17—H17C109.5
C3—C4—H4A111.0O13—Cl1—O14107.5 (3)
N2—C4—H4B111.0O13—Cl1—O12107.2 (3)
C3—C4—H4B111.0O14—Cl1—O12110.0 (3)
H4A—C4—H4B109.0O13—Cl1—O11112.7 (3)
O1—C5—N2129.5 (3)O14—Cl1—O11110.2 (3)
O1—C5—C5i119.01 (18)O12—Cl1—O11109.3 (3)
N2i—Ni1—N1—C199.4 (8)O1—Ni2—N3—C1027.9 (6)
N2—Ni1—N1—C192.7 (3)O1i—Ni2—N3—C1074.7 (2)
N1i—Ni1—N1—C186.2 (3)N3—Ni2—N4—C15176.0 (3)
N2i—Ni1—N1—C2133.1 (7)N3i—Ni2—N4—C1576.0 (3)
N2—Ni1—N1—C2139.9 (4)O1—Ni2—N4—C1513.6 (3)
N1i—Ni1—N1—C241.2 (3)O1i—Ni2—N4—C1594.3 (3)
N2i—Ni1—N1—C317.8 (8)N3—Ni2—N4—C1116.5 (2)
N2—Ni1—N1—C324.6 (3)N3i—Ni2—N4—C11116.5 (2)
N1i—Ni1—N1—C3156.5 (3)O1—Ni2—N4—C11153.9 (2)
N2i—Ni1—N2—C50.98 (19)O1i—Ni2—N4—C1173.1 (2)
N1—Ni1—N2—C5179.6 (3)C10—N3—C6—C72.2 (6)
N1i—Ni1—N2—C55.8 (9)Ni2—N3—C6—C7168.6 (3)
N2i—Ni1—N2—C4176.9 (4)N3—C6—C7—C80.2 (6)
N1—Ni1—N2—C41.7 (3)C6—C7—C8—C91.2 (6)
N1i—Ni1—N2—C4176.3 (6)C6—C7—C8—C16178.4 (4)
C1—N1—C3—C473.1 (5)C7—C8—C9—C100.7 (5)
C2—N1—C3—C4168.3 (4)C16—C8—C9—C10178.9 (4)
Ni1—N1—C3—C444.8 (4)C6—N3—C10—C92.7 (5)
C5—N2—C4—C3155.4 (4)Ni2—N3—C10—C9169.4 (3)
Ni1—N2—C4—C322.4 (4)C6—N3—C10—C11176.8 (3)
N1—C3—C4—N243.2 (5)Ni2—N3—C10—C1111.2 (4)
C4—N2—C5—O15.0 (6)C8—C9—C10—N31.2 (5)
Ni1—N2—C5—O1177.2 (3)C8—C9—C10—C11178.2 (3)
C4—N2—C5—C5i175.4 (4)C15—N4—C11—C122.9 (5)
Ni1—N2—C5—C5i2.4 (5)Ni2—N4—C11—C12165.8 (3)
N2—C5—O1—Ni2177.8 (3)C15—N4—C11—C10175.8 (3)
C5i—C5—O1—Ni22.6 (5)Ni2—N4—C11—C1015.5 (4)
C5—O1—Ni2—N4i91.2 (2)N3—C10—C11—N42.8 (4)
C5—O1—Ni2—N488.6 (2)C9—C10—C11—N4176.6 (3)
C5—O1—Ni2—N346.6 (5)N3—C10—C11—C12178.5 (3)
C5—O1—Ni2—N3i170.6 (2)C9—C10—C11—C122.1 (5)
C5—O1—Ni2—O1i0.98 (18)N4—C11—C12—C132.9 (5)
N4i—Ni2—N3—C66.3 (3)C10—C11—C12—C13175.8 (3)
N4—Ni2—N3—C6173.9 (3)C11—C12—C13—C141.6 (5)
N3i—Ni2—N3—C674.9 (3)C11—C12—C13—C17179.1 (3)
O1—Ni2—N3—C6143.2 (4)C12—C13—C14—C150.5 (5)
O1i—Ni2—N3—C696.4 (3)C17—C13—C14—C15179.8 (4)
N4i—Ni2—N3—C10164.9 (2)C11—N4—C15—C141.9 (6)
N4—Ni2—N3—C1015.0 (2)Ni2—N4—C15—C14165.1 (3)
N3i—Ni2—N3—C10114.0 (3)C13—C14—C15—N40.7 (6)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O130.932.573.379 (6)146
C12—H12···O1ii0.932.433.267 (4)150
Symmetry code: (ii) x, y+1, z+1/2.

Experimental details

Crystal data
Chemical formula[Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2
Mr913.05
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)19.068 (6), 13.431 (4), 15.920 (5)
β (°) 104.744 (4)
V3)3943 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.16
Crystal size (mm)0.45 × 0.38 × 0.29
Data collection
DiffractometerBruker APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.612, 0.716
No. of measured, independent and
observed [I > 2σ(I)] reflections
10149, 3470, 2338
Rint0.036
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.113, 1.02
No. of reflections3470
No. of parameters256
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.28

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Ni1—N11.976 (3)Ni2—O12.114 (2)
Ni1—N21.853 (3)N2—C51.299 (4)
Ni2—N32.060 (3)C5—O11.255 (4)
Ni2—N42.048 (3)C5—C5i1.521 (6)
N1—Ni1—N1i106.7 (2)N3—Ni2—O1i89.60 (10)
N1—Ni1—N284.78 (14)N4—Ni2—O190.20 (10)
N2i—Ni1—N1168.43 (14)N4—Ni2—O1i89.63 (11)
N2i—Ni1—N283.74 (18)N4—Ni2—N379.31 (11)
O1—Ni2—O1i80.74 (13)N4—Ni2—N3i100.83 (12)
N3—Ni2—O1165.81 (10)N4i—Ni2—N4179.78 (17)
Ni2—N3—C10—C1111.2 (4)Ni2—N4—C11—C1015.5 (4)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O130.932.573.379 (6)145.8
C12—H12···O1ii0.932.433.267 (4)149.7
Symmetry code: (ii) x, y+1, z+1/2.
 

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