[mu]-1,4-Benzenedicarboxylato-bis[trans-aqua(1,4,8,11-tetraazacyclotetradecane)nickel(II)] diperchlorate forms a three-dimensional hydrogen-bonded framework

The title compound, [Ni₂(C₈H₄O₄)(C₁₀H₂₄N₄)₂(H₂O)₂](ClO₄)₂, contains two independent octahedral Ni^II centres with trans-NiN₄O₂ chromophores. The bridging benzene­dicarboxyl­ate ligand is bonded to the two Ni atoms, each via one O atom of each carboxyl­ate, while the other O atom participates in an intramolecular N-H...O hydrogen bond, forming an S(6) motif. The cations are linked to the perchlorate anions via O-H...O and N-H...O hydrogen bonds [O...O 2.904 (6) and 2.898 (6) Å; O-H...O 158 (6) and 165 (6)°; N...O 3.175 (7) and 3.116 (7) Å; N-H...O 168 and 166°] to form molecular ladders. These ladders are linked by further O-H...O and N-H...O hydrogen bonds [O...O 2.717 (6) and 2.730 (5) Å; O-H...O 170 (4) and 163 (6)°; N...O 3.373 (7) and 3.253 (7) Å; N-H...O 163 and 167°] to form a continuous three-dimensional framework. The perchlorate anions both participate in three hydrogen bonds, and both are thus fully ordered.

S1. Comment

The [Ni(cyclam)]²⁺ cation [(1,4,8,11-tetraazacyclotetradecane)nickel(II)], [Ni(C₁₀H₂₄N₄)]²⁺, reacts readily with two equivalents of the 4-hydroxybenzoate anion to yield a neutral complex containing a trans octahedral NiN₄O₂ chromophore (Glidewell et al., 2000). In this complex, [(HOC₆H₄COO)₂Ni(cyclam)], the square-planar [Ni(cyclam)] fragment has two axial sites available for coordination, in this case by the hydroxybenzoate ligands, and a well defined array of axial N—H bonds, two on each face of the nearly-planar macrocycle, available for hydrogen-bond formation. The [Ni(cyclam)]²⁺ cation is thus an attractive building block for the construction of pre-designed coordination polymer networks, using, for example, polycarboxylate anions as the axial ligands. It is reasonable to envisage that growth of coordination polymer networks proceeds in a stepwise fashion via low- and medium-molecularity intermediates. By use of the 1,4-benzenedicarboxylate (terephthalate) anion, [C₆H₄(COO)₂]^2-, we have now isolated the title anion-bridged dinuclear complex, (I), and its structure is presented here. \sch

In the cation of (I) (Fig. 1), the bridging dianionic ligand utilizes one O atom of each carboxylate group to coordinate to the Ni, while the other O atom in each group accepts a hydrogen bond, forming an S(6) motif, precisely as observed in the 4-hydroxybenzoate complex (Glidewell et al., 2000). This coordination mode, with direct Ni—O bonds to the carboxylate anion, differs from that observed with 1,3,5-benzenetricarboxylate, where the anions are simply hydrogen-bonded to trans [Ni(cyclam)(H₂O)₂]²⁺ cations (Choi et al., 1999). Each Ni atom is also coordinated by four N atoms from the cyclam ligand, which occupy the equatorial sites of an axially elongated octahedron. A water molecule occupies the second axial site of each Ni.

The cyclam ligands adopt the usual trans-III conformation (Barefield, Bianchi et al., 1986), with all torsion angles in the ring within 15° of either 180° (antiperiplanar) or ±60° (synclinal) (Table 1). The Ni—N distances are closely similar, ranging only from 2.049 (5) to 2.089 (5) Å; these distances are typical of those observed in octahedral Ni^II complexes of cyclam and its C-methyl derivatives (Whimp et al., 1970; Curtis et al., 1973; Hay et al., 1982; Ito et al., 1984; Barefield, Bianchi et al., 1986; Barefield, Freeman & Van Derveer, 1986; Hambley, 1986; Mochizuki & Kondo, 1995; Choi et al., 1999; Glidewell et al., 2000), although they are significantly shorter than those observed in the square-planar systems (Prasad & McAuley, 1983; Barefield, Bianchi et al., 1986; Adam et al., 1991). The mean value of the Ni—O distances, 2.161 (4) Å, is virtually identical with those observed in salts of trans [Ni(cyclam)(H₂O)₂]²⁺ cations (Mochizuki & Kondo, 1995; Choi et al., 1999). On the other hand, the C—N distances exhibit a much wider range, from 1.431 (9) to 1.524 (9) Å.

Although the two [Ni(cyclam)] fragments in the cation are fully eclipsed with respect to the Ni···Ni vector, the detailed differences in the C—N distances and in the magnitudes of the torsion angles involving corresponding sets of atoms in the two [Ni(cyclam)] fragments prevent the cation from attaining a centrosymmetric configuration. Nonetheless, the O—Ni(N₄)-benzenedicarboxylato-Ni(N₄)-O unit (i.e. the entire cation except for the C atoms of the cyclam ligands) is very close to being centrosymmetric. In the bridging ligand, the carboxylate groups based on C7 and C8 are rotated out of the plane of the aryl ring by 38.0 (2)° and 35.2 (2)°, respectively, with the sense of the rotations mimicking centrosymmetry (Fig. 1).

The two perchlorate anions are both fully ordered. Each participates in three hydrogen bonds (Table 2), and it is these which prevent the almost free rotation often observed with this anion. Within the selected asymmetric unit (Fig. 1), N111 and N211 act as hydrogen-bond donors to O14 and O24, respectively (Table 2).

Apart from the formation of the four N—H···O hydrogen bonds within the selected asymmetric unit, the cation of (I) has four N—H and four O—H bonds available for the formation of hydrogen bonds to other aggregates. Four of the resulting hydrogen bonds (entries 5–8 in Table 2) link the three-ion aggregates into chains running parallel to the [100] direction, while the other four (entries 9–12 in Table 2) link each [100] to four of its neighbours, so generating a continuous three-dimensional framework. Atom N14 in the cation at (x, y, z) acts as a donor to perchlorate atom O13 at (1 + x, y, z), while atom O5 at (x, y, z) acts as a donor, via H52, to O11 in the same perchlorate at (1 + x, y, z). In an entirely similar manner, atoms N24 and O6 at (x, y, z) act as donors to O23 and O21, respectively, at (-1 + x, y, z), so forming a molecular ladder parallel to [100] in which each upright is a C(8) C(8)[R₂²(8)] chain of rings, while the Ni-(benzenedicarboxylato)-Ni units form the rungs (Fig. 2). This ladder runs approximately along the line (x, 1/2, 1/4) and a second similar ladder runs approximately along the line (x, 0, 3/4). Each ladder is directly linked to four neighbouring ladders: atoms N18 and O5 at (x, y, z), which are components of the ladder along (x, 1/2, 1/4), both act as hydrogen-bond donors to O4 at (1 - x, 1/2 + y, 1 - z), which is a component of the ladder along (x, 1, 3/4). Similarly, atoms N28 and O6 at (x, y, z) both act as donors to O2 at (-x, y - 1/2, -z), which is a component of the ladder along (x, 0, -1/4). In this manner, the ladder along (x, 1/2, 1/4) is directly linked to the four ladders along (x, 0, 3/4), (x, 0, -1/4), (x, 1, 3/4) and (x, 1, -1/4) (Fig. 3), and propagation of these hydrogen bonds by the space group links all of the [100] ladders into a three-dimensional framework.

In addition to the O—H···O and N—H···O hydrogen bonds, there are also four significant C—H···O hydrogen bonds. Two of these (entries 13 and 14 in Table 2) reinforce the [100] chains, while the other two reinforce the links between these chains.

For the two intracation N—H···O hydrogen bonds, the short N···O distances are probably largely determined by the adjacent Ni—O coordination. The remainder of the N—H···O hydrogen bonds fall into two clear groups (Table 2): those having perchlorate O as acceptor have significantly shorter N···O distances than those having carboxylate O as acceptor. By contrast, the O—H···O hydrogen bonds with perchlorate O as acceptor have significantly longer O···O distances than those with carboxylate O acceptors. The D—H···A angles for the hard interion hydrogen bonds are all closely clustered around the mean value of 166°. Hence, the pattern of the H···A distances closely follows that of the D···A distances.

Related literature

For related literature, see: Adam et al. (1991); Barefield, Bianchi, Billo, Connolly, Paoletti, Summers & Van Derveer (1986); Barefield, Freeman & Van Derveer (1986); Choi et al. (1999); Curtis et al. (1973); Flack (1983); Glidewell et al. (2000); Hambley (1986); Hay et al. (1982); Ito et al. (1984); Mochizuki & Kondo (1995); Prasad & McAuley (1983); Sheldrick (1997); Whimp et al. (1970).

S2. Experimental

A sample of compound (I) was isolated as a purple microcrystalline solid from the reaction between [Ni(cyclam)]²⁺·2ClO₄^- and the disodium salt of terephthalic acid in aqueous methanol. Crystals of (I) suitable for single-crystal X-ray diffraction were grown from solution in water.

S3. Refinement

Compound (I) crystallized in the monoclinic system, space group P2₁ or P2₁/m from the systematic absences. P2₁ was assumed and confirmed by the analysis. H atoms were treated as riding, with C—H = 0.95 (aromatic) and 0.99 Å (aliphatic CH₂), and N—H = 0.93 Å. Water H atoms were clearly visible in difference maps and were initially refined isotropically using a DFIX command (SHELXL97; Sheldrick, 1997), with a free variable for the common O—H distance and a free variable for the overall U_iso value. The final refinement had the water O—H distance set to 0.85 Å. Refinement of the Flack parameter (Flack, 1983) using 3083 Friedel-related reflections suggested that the data should be treated as a racemic twin, using the TWIN and BASF commands in SHELXL97. The structure of (I) approximates closely to a centrosymmetric one, with the terephthalate moiety lying about an inversion centre in space group P2₁/n. There is an almost perfect fit of atoms, except for all the C and H atoms of the cyclam residues. Inspection of the reflection data shows clearly that the h0l glide reflections (h+l = 2n+1), which would be absent in P2₁/n, are clearly present, although many are weak.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The asymmetric unit of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity, except those on N atoms and in water molecules, which are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a molecular ladder parallel to [100]. H atoms bonded to C have been omitted for clarity.
	Fig. 3. Part of the crystal structure of (I) showing the linking of the [100] molecular ladders into a three-dimensional framework. H atoms bonded to C have been omitted for clarity.

µ-1,4-Benzenedicarboxylato-bis[trans-aqua(1,4,8,11-tetraazacyclotetradecane) nickel(II)] diperchlorate

Crystal data

[Ni2(C10H24N4)2(H2O)2(C8H4O4)](ClO4)2	F(000) = 964
Mr = 917.09	Dx = 1.557 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.2842 (3) Å	Cell parameters from 7654 reflections
b = 14.9172 (4) Å	θ = 2.8–27.5°
c = 13.0621 (4) Å	µ = 1.17 mm^−1
β = 102.5220 (11)°	T = 150 K
V = 1956.21 (10) Å^3	Plate, purple
Z = 2	0.18 × 0.18 × 0.07 mm

Data collection

Kappa-CCD diffractometer	7654 independent reflections
Radiation source: fine-focus sealed X-ray tube	5458 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −13→13
Tmin = 0.817, Tmax = 0.922	k = −19→17
13566 measured reflections	l = −16→16

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 atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.019P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
7654 reflections	Δρmax = 0.70 e Å^−3
501 parameters	Δρmin = −0.44 e Å^−3
5 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.38 (3)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 6.7013 (0.0061) x + 9.5657 (0.0090) y - 3.3217 (0.0164) z = 2.2537 (0.0081)

* -0.0064 (0.0046) C1 * -0.0089 (0.0046) C2 * 0.0004 (0.0049) C3 * 0.0155 (0.0047) C4 * 0.0070 (0.0047) C5 * -0.0157 (0.0048) C6 * 0.0131 (0.0047) C7 * -0.0050 (0.0049) C8

Rms deviation of fitted atoms = 0.0103

- 7.1702 (0.0237) x + 10.0577 (0.0356) y + 5.0802 (0.0341) z = 4.4222 (0.0322)

Angle to previous plane (with approximate e.s.d.) = 38.0 (2)

* 0.0009 (0.0013) C1 * -0.0031 (0.0048) C7 * 0.0011 (0.0017) O1 * 0.0011 (0.0017) O2

Rms deviation of fitted atoms = 0.0018

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- 6.7013 (0.0061) x + 9.5657 (0.0090) y - 3.3217 (0.0164) z = 2.2537 (0.0081)

* -0.0064 (0.0046) C1 * -0.0089 (0.0046) C2 * 0.0004 (0.0049) C3 * 0.0155 (0.0047) C4 * 0.0070 (0.0047) C5 * -0.0157 (0.0048) C6 * 0.0131 (0.0047) C7 * -0.0050 (0.0049) C8

Rms deviation of fitted atoms = 0.0103

- 7.1482 (0.0235) x + 10.3230 (0.0344) y + 4.4540 (0.0350) z = 4.4624 (0.0134)

Angle to previous plane (with approximate e.s.d.) = 35.2 (2)

* 0.0013 (0.0014) C4 * -0.0048 (0.0050) C8 * 0.0017 (0.0018) O3 * 0.0017 (0.0018) O4

Rms deviation of fitted atoms = 0.0028

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

	x	y	z	Uiso*/Ueq
Ni1	0.68641 (7)	0.74680 (4)	0.38396 (6)	0.01733 (16)
O5	0.8430 (4)	0.8439 (3)	0.4538 (3)	0.0245 (11)
N11	0.6599 (5)	0.8093 (4)	0.2392 (4)	0.0250 (12)
N14	0.8279 (5)	0.6711 (4)	0.3318 (4)	0.0303 (12)
N18	0.7122 (5)	0.6837 (4)	0.5287 (4)	0.0350 (15)
N111	0.5483 (5)	0.8251 (4)	0.4356 (4)	0.0269 (12)
C12	0.7696 (6)	0.7819 (4)	0.1918 (5)	0.0360 (17)
C13	0.8000 (7)	0.6839 (5)	0.2156 (5)	0.0387 (17)
C15	0.8343 (6)	0.5766 (4)	0.3604 (5)	0.0384 (16)
C16	0.8602 (6)	0.5638 (4)	0.4780 (5)	0.0428 (17)
C17	0.7421 (6)	0.5838 (4)	0.5264 (5)	0.0405 (18)
C19	0.5928 (7)	0.7062 (5)	0.5678 (5)	0.045 (2)
C110	0.5683 (6)	0.8045 (5)	0.5502 (4)	0.0395 (19)
C112	0.5455 (7)	0.9189 (4)	0.4087 (6)	0.0434 (18)
C113	0.5234 (6)	0.9330 (4)	0.2916 (5)	0.0457 (19)
C114	0.6387 (7)	0.9069 (4)	0.2415 (5)	0.0390 (18)
Ni2	−0.18413 (7)	0.25284 (4)	0.11557 (6)	0.01788 (16)
O6	−0.3443 (4)	0.1574 (3)	0.0511 (3)	0.0213 (10)
N21	−0.1797 (5)	0.2092 (3)	0.2650 (4)	0.0279 (12)
N24	−0.3223 (5)	0.3445 (4)	0.1457 (4)	0.0289 (13)
N28	−0.1939 (5)	0.2965 (4)	−0.0378 (4)	0.0343 (14)
N211	−0.0487 (5)	0.1595 (4)	0.0875 (4)	0.0355 (14)
C22	−0.2953 (5)	0.2507 (4)	0.2989 (4)	0.0290 (14)
C23	−0.3099 (7)	0.3447 (5)	0.2595 (5)	0.0391 (17)
C25	−0.3157 (7)	0.4349 (4)	0.0983 (5)	0.0413 (18)
C26	−0.3261 (7)	0.4280 (4)	−0.0201 (5)	0.049 (2)
C27	−0.2042 (7)	0.3913 (4)	−0.0539 (5)	0.0459 (19)
C29	−0.0725 (6)	0.2532 (6)	−0.0663 (4)	0.049 (2)
C210	−0.0596 (6)	0.1571 (5)	−0.0282 (5)	0.0425 (18)
C213	−0.0479 (7)	0.0740 (4)	0.2502 (5)	0.0476 (19)
C212	−0.0564 (6)	0.0687 (5)	0.1331 (5)	0.047 (2)
C214	−0.1676 (6)	0.1124 (4)	0.2832 (5)	0.0382 (17)
O1	0.5332 (4)	0.6538 (3)	0.3288 (3)	0.0210 (10)
O2	0.4479 (4)	0.6792 (3)	0.1583 (3)	0.0239 (11)
O3	−0.0244 (4)	0.3442 (3)	0.1653 (3)	0.0236 (10)
O4	0.0527 (4)	0.3232 (3)	0.3379 (3)	0.0269 (11)
C1	0.3491 (6)	0.5647 (4)	0.2454 (4)	0.0180 (13)
C2	0.3097 (6)	0.5075 (4)	0.1610 (4)	0.0208 (14)
C3	0.2136 (6)	0.4419 (4)	0.1630 (5)	0.0226 (15)
C4	0.1556 (6)	0.4327 (4)	0.2490 (4)	0.0191 (14)
C5	0.1970 (6)	0.4907 (4)	0.3350 (5)	0.0235 (14)
C6	0.2927 (6)	0.5546 (4)	0.3330 (5)	0.0221 (15)
C7	0.4518 (6)	0.6382 (4)	0.2440 (4)	0.0182 (13)
C8	0.0547 (6)	0.3610 (4)	0.2521 (5)	0.0212 (14)
Cl1	0.17207 (15)	0.80653 (12)	0.39094 (11)	0.0262 (4)
O11	0.0568 (4)	0.8591 (4)	0.3416 (4)	0.0396 (13)
O12	0.2517 (4)	0.8581 (3)	0.4746 (3)	0.0361 (11)
O13	0.1263 (4)	0.7258 (3)	0.4336 (4)	0.0412 (13)
O14	0.2506 (4)	0.7836 (3)	0.3155 (3)	0.0372 (12)
Cl2	0.33011 (15)	0.19328 (12)	0.11237 (11)	0.0280 (4)
O21	0.4401 (4)	0.1345 (4)	0.1595 (4)	0.0345 (12)
O22	0.2529 (4)	0.1515 (4)	0.0206 (3)	0.0411 (12)
O23	0.3851 (4)	0.2758 (3)	0.0830 (4)	0.0483 (14)
O24	0.2479 (4)	0.2099 (4)	0.1864 (3)	0.0481 (15)
H11	0.5828	0.7851	0.1978	0.030*
H14	0.9109	0.6962	0.3595	0.036*
H18	0.7845	0.7108	0.5732	0.042*
H111	0.4651	0.8023	0.4041	0.032*
H12A	0.8494	0.8186	0.2203	0.043*
H12B	0.7449	0.7911	0.1149	0.043*
H13A	0.7230	0.6466	0.1817	0.046*
H13B	0.8782	0.6654	0.1880	0.046*
H15A	0.9063	0.5473	0.3331	0.046*
H15B	0.7492	0.5472	0.3275	0.046*
H16A	0.9351	0.6031	0.5112	0.051*
H16B	0.8883	0.5010	0.4945	0.051*
H17A	0.7604	0.5602	0.5990	0.049*
H17B	0.6627	0.5524	0.4859	0.049*
H19A	0.6069	0.6920	0.6435	0.054*
H19B	0.5154	0.6713	0.5297	0.054*
H11A	0.6452	0.8388	0.5899	0.047*
H11B	0.4882	0.8224	0.5758	0.047*
H11C	0.6310	0.9469	0.4435	0.052*
H11D	0.4733	0.9488	0.4351	0.052*
H11E	0.5029	0.9971	0.2766	0.055*
H11F	0.4440	0.8981	0.2573	0.055*
H11G	0.6211	0.9302	0.1689	0.047*
H11H	0.7212	0.9357	0.2810	0.047*
H21	−0.1040	0.2346	0.3070	0.033*
H24	−0.4060	0.3212	0.1164	0.035*
H28	−0.2690	0.2705	−0.0800	0.041*
H211	0.0354	0.1820	0.1170	0.043*
H22A	−0.3775	0.2164	0.2701	0.035*
H22B	−0.2803	0.2502	0.3764	0.035*
H23A	−0.3899	0.3723	0.2768	0.047*
H23B	−0.2311	0.3803	0.2935	0.047*
H25A	−0.2306	0.4642	0.1314	0.050*
H25B	−0.3894	0.4726	0.1120	0.050*
H26A	−0.4031	0.3893	−0.0501	0.059*
H26B	−0.3452	0.4885	−0.0509	0.059*
H27A	−0.2105	0.4049	−0.1290	0.055*
H27B	−0.1232	0.4209	−0.0130	0.055*
H29A	−0.0817	0.2547	−0.1433	0.059*
H29B	0.0086	0.2872	−0.0337	0.059*
H21A	−0.1386	0.1219	−0.0627	0.051*
H21B	0.0207	0.1290	−0.0446	0.051*
H21C	−0.0322	0.0129	0.2797	0.057*
H21D	0.0306	0.1108	0.2818	0.057*
H21E	0.0175	0.0312	0.1195	0.057*
H21F	−0.1414	0.0398	0.0987	0.057*
H21G	−0.2489	0.0824	0.2436	0.046*
H21H	−0.1606	0.1002	0.3587	0.046*
H2	0.3482	0.5130	0.1014	0.025*
H3	0.1875	0.4029	0.1046	0.027*
H5	0.1587	0.4856	0.3947	0.028*
H6	0.3209	0.5926	0.3920	0.027*
H51	0.869 (6)	0.832 (4)	0.5187 (12)	0.042 (7)*
H52	0.904 (4)	0.863 (4)	0.425 (4)	0.042 (7)*
H61	−0.373 (6)	0.153 (4)	−0.0148 (12)	0.042 (7)*
H62	−0.414 (3)	0.159 (4)	0.076 (4)	0.042 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0159 (3)	0.0199 (4)	0.0154 (3)	−0.0029 (3)	0.0015 (3)	0.0011 (3)
O5	0.023 (2)	0.028 (3)	0.021 (2)	−0.003 (2)	0.0018 (19)	−0.002 (2)
N11	0.023 (2)	0.033 (3)	0.016 (2)	−0.016 (2)	−0.0024 (18)	0.004 (2)
N14	0.023 (2)	0.031 (3)	0.036 (3)	−0.007 (2)	0.003 (2)	−0.014 (2)
N18	0.026 (3)	0.053 (4)	0.020 (2)	−0.018 (2)	−0.007 (2)	0.007 (2)
N111	0.013 (2)	0.036 (3)	0.028 (3)	−0.004 (2)	−0.0019 (19)	−0.012 (2)
C12	0.036 (3)	0.053 (4)	0.021 (3)	−0.021 (3)	0.009 (2)	−0.004 (3)
C13	0.030 (3)	0.062 (5)	0.028 (3)	−0.012 (3)	0.014 (2)	−0.020 (3)
C15	0.025 (3)	0.028 (3)	0.057 (4)	0.000 (2)	−0.004 (3)	−0.011 (3)
C16	0.035 (3)	0.025 (3)	0.058 (4)	0.005 (2)	−0.013 (3)	0.014 (3)
C17	0.042 (4)	0.030 (3)	0.039 (4)	−0.013 (3)	−0.017 (3)	0.023 (3)
C19	0.038 (4)	0.079 (5)	0.016 (3)	−0.029 (3)	0.004 (2)	0.002 (3)
C110	0.022 (3)	0.077 (5)	0.022 (3)	−0.007 (4)	0.010 (2)	−0.020 (4)
C112	0.026 (3)	0.027 (3)	0.071 (5)	0.009 (3)	−0.002 (3)	−0.019 (3)
C113	0.033 (3)	0.028 (3)	0.062 (4)	0.004 (3)	−0.021 (3)	0.001 (3)
C114	0.040 (4)	0.023 (3)	0.044 (4)	−0.012 (3)	−0.014 (3)	0.017 (3)
Ni2	0.0163 (3)	0.0205 (4)	0.0158 (3)	−0.0026 (3)	0.0011 (3)	−0.0002 (3)
O6	0.013 (2)	0.031 (3)	0.018 (2)	−0.003 (2)	−0.0009 (17)	−0.002 (2)
N21	0.029 (3)	0.026 (2)	0.024 (2)	−0.011 (2)	−0.008 (2)	0.0069 (19)
N24	0.019 (2)	0.028 (3)	0.036 (3)	0.001 (2)	−0.0023 (19)	−0.008 (2)
N28	0.027 (3)	0.052 (3)	0.020 (2)	−0.022 (2)	−0.004 (2)	0.004 (2)
N211	0.021 (2)	0.049 (4)	0.036 (3)	0.002 (2)	0.005 (2)	−0.016 (2)
C22	0.023 (3)	0.050 (4)	0.017 (2)	−0.012 (3)	0.0091 (19)	−0.008 (3)
C23	0.030 (3)	0.051 (4)	0.037 (4)	−0.002 (3)	0.009 (3)	−0.015 (3)
C25	0.045 (4)	0.016 (3)	0.056 (5)	0.007 (3)	−0.004 (3)	0.006 (3)
C26	0.051 (5)	0.032 (4)	0.049 (4)	−0.006 (3)	−0.021 (3)	0.013 (3)
C27	0.048 (4)	0.044 (4)	0.036 (4)	−0.019 (3)	−0.011 (3)	0.021 (3)
C29	0.026 (3)	0.105 (6)	0.018 (3)	−0.023 (5)	0.008 (2)	−0.001 (5)
C210	0.024 (3)	0.065 (5)	0.038 (4)	−0.005 (3)	0.005 (2)	−0.020 (3)
C213	0.054 (4)	0.018 (3)	0.057 (4)	0.004 (3)	−0.018 (3)	0.011 (3)
C212	0.025 (3)	0.025 (3)	0.086 (6)	0.005 (2)	0.000 (4)	−0.014 (4)
C214	0.033 (3)	0.038 (4)	0.036 (3)	−0.014 (3)	−0.011 (3)	0.013 (3)
O1	0.017 (2)	0.027 (3)	0.016 (2)	−0.0088 (19)	−0.0052 (16)	0.0041 (19)
O2	0.025 (2)	0.028 (3)	0.0166 (19)	−0.0109 (19)	−0.0006 (16)	0.003 (2)
O3	0.021 (2)	0.027 (3)	0.020 (2)	−0.007 (2)	−0.0001 (18)	−0.0007 (19)
O4	0.028 (2)	0.028 (3)	0.021 (2)	−0.010 (2)	−0.0011 (17)	0.004 (2)
C1	0.014 (3)	0.022 (3)	0.015 (3)	0.000 (3)	−0.006 (2)	0.006 (3)
C2	0.024 (3)	0.022 (3)	0.014 (3)	−0.006 (3)	0.000 (2)	0.002 (2)
C3	0.029 (3)	0.019 (3)	0.019 (3)	−0.005 (3)	0.002 (3)	−0.003 (3)
C4	0.019 (3)	0.012 (3)	0.024 (3)	−0.002 (3)	0.001 (2)	−0.002 (3)
C5	0.024 (3)	0.026 (4)	0.020 (3)	−0.001 (3)	0.005 (3)	0.001 (3)
C6	0.016 (3)	0.021 (4)	0.026 (3)	−0.004 (3)	−0.004 (3)	−0.002 (3)
C7	0.016 (3)	0.016 (3)	0.022 (3)	0.000 (3)	0.003 (2)	0.002 (3)
C8	0.016 (3)	0.024 (4)	0.022 (3)	−0.001 (3)	0.001 (3)	−0.002 (3)
Cl1	0.0179 (8)	0.0302 (9)	0.0287 (8)	0.0001 (7)	0.0010 (7)	0.0013 (7)
O11	0.021 (2)	0.055 (3)	0.039 (2)	0.012 (2)	−0.001 (2)	0.016 (3)
O12	0.034 (2)	0.038 (2)	0.033 (2)	−0.006 (2)	0.000 (2)	−0.007 (2)
O13	0.033 (2)	0.040 (3)	0.050 (3)	−0.005 (2)	0.007 (2)	0.008 (2)
O14	0.025 (2)	0.051 (3)	0.038 (3)	0.004 (2)	0.013 (2)	−0.007 (2)
Cl2	0.0200 (8)	0.0349 (10)	0.0271 (8)	−0.0026 (8)	0.0005 (7)	−0.0010 (7)
O21	0.026 (3)	0.041 (3)	0.033 (2)	0.004 (2)	−0.001 (2)	0.004 (2)
O22	0.033 (2)	0.059 (3)	0.026 (2)	−0.009 (2)	−0.0068 (19)	−0.004 (2)
O23	0.031 (3)	0.029 (3)	0.082 (3)	−0.004 (2)	0.005 (2)	0.013 (2)
O24	0.025 (2)	0.089 (4)	0.030 (3)	0.003 (3)	0.005 (2)	−0.008 (3)

Geometric parameters (Å, º)

Ni1—N11	2.072 (5)	N24—C25	1.493 (8)
Ni1—N14	2.071 (5)	N24—H24	0.93
Ni1—N18	2.077 (5)	N28—C27	1.431 (9)
Ni1—N111	2.062 (5)	N28—C29	1.521 (9)
Ni1—O1	2.106 (4)	N28—H28	0.93
Ni1—O5	2.211 (4)	N211—C210	1.491 (7)
O5—H51	0.85 (2)	N211—C212	1.490 (9)
O5—H52	0.85 (5)	N211—H211	0.93
N11—C114	1.474 (8)	C22—C23	1.489 (8)
N11—C12	1.459 (8)	C22—H22A	0.99
N11—H11	0.93	C22—H22B	0.99
N14—C13	1.494 (8)	C23—H23A	0.99
N14—C15	1.457 (8)	C23—H23B	0.99
N14—H14	0.9300	C25—C26	1.530 (8)
N18—C17	1.524 (9)	C25—H25A	0.99
N18—C19	1.467 (9)	C25—H25B	0.99
N18—H18	0.93	C26—C27	1.519 (9)
N111—C110	1.499 (7)	C26—H26A	0.99
N111—C112	1.441 (8)	C26—H26B	0.99
N111—H111	0.93	C27—H27A	0.99
C12—C13	1.512 (9)	C27—H27B	0.99
C12—H12A	0.99	C29—C210	1.514 (10)
C12—H12B	0.99	C29—H29A	0.99
C13—H13A	0.99	C29—H29B	0.99
C13—H13B	0.99	C210—H21A	0.99
C15—C16	1.513 (8)	C210—H21B	0.99
C15—H15A	0.99	C213—C214	1.503 (9)
C15—H15B	0.99	C213—C212	1.515 (8)
C16—C17	1.515 (9)	C213—H21C	0.99
C16—H16A	0.99	C213—H21D	0.99
C16—H16B	0.99	C212—H21E	0.99
C17—H17A	0.99	C212—H21F	0.99
C17—H17B	0.99	C214—H21G	0.99
C19—C110	1.497 (10)	C214—H21H	0.99
C19—H19A	0.99	O1—C7	1.257 (6)
C19—H19B	0.99	O2—C7	1.269 (6)
C110—H11A	0.99	O3—C8	1.268 (6)
C110—H11B	0.99	O4—C8	1.259 (7)
C112—C113	1.511 (9)	C1—C2	1.384 (7)
C112—H11C	0.99	C1—C6	1.399 (8)
C112—H11D	0.99	C1—C7	1.524 (8)
C113—C114	1.524 (9)	C2—C3	1.395 (8)
C113—H11E	0.99	C2—H2	0.95
C113—H11F	0.99	C3—C4	1.389 (8)
C114—H11G	0.99	C3—H3	0.95
C114—H11H	0.99	C4—C5	1.409 (7)
Ni2—N21	2.049 (5)	C4—C8	1.496 (8)
Ni2—N24	2.070 (5)	C5—C6	1.374 (8)
Ni2—N28	2.089 (5)	C5—H5	0.95
Ni2—N211	2.057 (6)	C6—H6	0.95
Ni2—O3	2.125 (4)	Cl1—O12	1.438 (4)
Ni2—O6	2.202 (4)	Cl1—O14	1.443 (5)
O6—H61	0.85 (2)	Cl1—O13	1.448 (5)
O6—H62	0.85 (4)	Cl1—O11	1.451 (5)
N21—C214	1.464 (8)	Cl2—O22	1.429 (4)
N21—C22	1.491 (7)	Cl2—O24	1.437 (5)
N21—H21	0.93	Cl2—O23	1.441 (5)
N24—C23	1.463 (8)	Cl2—O21	1.459 (5)
N111—Ni1—N14	178.5 (3)	C214—N21—Ni2	116.8 (4)
N111—Ni1—N11	94.6 (2)	C22—N21—Ni2	107.2 (3)
N14—Ni1—N11	84.7 (2)	C214—N21—H21	106.0
N111—Ni1—N18	85.4 (2)	C22—N21—H21	106.0
N14—Ni1—N18	95.3 (2)	Ni2—N21—H21	106.0
N11—Ni1—N18	179.7 (2)	C23—N24—C25	114.7 (5)
N111—Ni1—O1	88.14 (19)	C23—N24—Ni2	106.4 (4)
N14—Ni1—O1	93.19 (19)	C25—N24—Ni2	115.0 (4)
N11—Ni1—O1	92.51 (17)	C23—N24—H24	106.7
N18—Ni1—O1	87.21 (19)	C25—N24—H24	106.7
N111—Ni1—O5	89.17 (18)	Ni2—N24—H24	106.7
N14—Ni1—O5	89.54 (19)	C27—N28—C29	115.0 (6)
N11—Ni1—O5	91.24 (18)	C27—N28—Ni2	115.8 (5)
N18—Ni1—O5	89.04 (19)	C29—N28—Ni2	103.4 (4)
O1—Ni1—O5	175.55 (17)	C27—N28—H28	107.4
Ni1—O5—H51	109 (4)	C29—N28—H28	107.4
Ni1—O5—H52	126 (4)	Ni2—N28—H28	107.4
H51—O5—H52	114 (6)	C212—N211—C210	112.6 (5)
C12—N11—C114	114.7 (5)	C212—N211—Ni2	116.6 (4)
C12—N11—Ni1	107.5 (4)	C210—N211—Ni2	107.0 (4)
C114—N11—Ni1	114.6 (4)	C212—N211—H211	106.7
C12—N11—H11	106.5	C210—N211—H211	106.7
C114—N11—H11	106.5	Ni2—N211—H211	106.7
Ni1—N11—H11	106.5	C23—C22—N21	108.4 (5)
C15—N14—C13	111.9 (5)	C23—C22—H22A	110.0
C15—N14—Ni1	116.0 (4)	N21—C22—H22A	110.0
C13—N14—Ni1	105.7 (4)	C23—C22—H22B	110.0
C15—N14—H14	107.6	N21—C22—H22B	110.0
C13—N14—H14	107.6	H22A—C22—H22B	108.4
Ni1—N14—H14	107.6	N24—C23—C22	109.2 (5)
C19—N18—C17	114.7 (6)	N24—C23—H23A	109.8
C19—N18—Ni1	105.2 (4)	C22—C23—H23A	109.8
C17—N18—Ni1	114.3 (4)	N24—C23—H23B	109.8
C19—N18—H18	107.4	C22—C23—H23B	109.8
C17—N18—H18	107.4	H23A—C23—H23B	108.3
Ni1—N18—H18	107.4	N24—C25—C26	111.1 (5)
C112—N111—C110	115.7 (5)	N24—C25—H25A	109.4
C112—N111—Ni1	116.7 (5)	C26—C25—H25A	109.4
C110—N111—Ni1	104.8 (4)	N24—C25—H25B	109.4
C112—N111—H111	106.3	C26—C25—H25B	109.4
C110—N111—H111	106.3	H25A—C25—H25B	108.0
Ni1—N111—H111	106.3	C27—C26—C25	115.9 (5)
N11—C12—C13	109.1 (5)	C27—C26—H26A	108.3
N11—C12—H12A	109.9	C25—C26—H26A	108.3
C13—C12—H12A	109.9	C27—C26—H26B	108.3
N11—C12—H12B	109.9	C25—C26—H26B	108.3
C13—C12—H12B	109.9	H26A—C26—H26B	107.4
H12A—C12—H12B	108.3	N28—C27—C26	110.7 (6)
N14—C13—C12	108.5 (6)	N28—C27—H27A	109.5
N14—C13—H13A	110.0	C26—C27—H27A	109.5
C12—C13—H13A	110.0	N28—C27—H27B	109.5
N14—C13—H13B	110.0	C26—C27—H27B	109.5
C12—C13—H13B	110.0	H27A—C27—H27B	108.1
H13A—C13—H13B	108.4	C210—C29—N28	109.9 (5)
N14—C15—C16	111.8 (5)	C210—C29—H29A	109.7
N14—C15—H15A	109.3	N28—C29—H29A	109.7
C16—C15—H15A	109.3	C210—C29—H29B	109.7
N14—C15—H15B	109.3	N28—C29—H29B	109.7
C16—C15—H15B	109.3	H29A—C29—H29B	108.2
H15A—C15—H15B	107.9	N211—C210—C29	107.0 (6)
C15—C16—C17	114.7 (5)	N211—C210—H21A	110.3
C15—C16—H16A	108.6	C29—C210—H21A	110.3
C17—C16—H16A	108.6	N211—C210—H21B	110.3
C15—C16—H16B	108.6	C29—C210—H21B	110.3
C17—C16—H16B	108.6	H21A—C210—H21B	108.6
H16A—C16—H16B	107.6	C214—C213—C212	116.0 (5)
C16—C17—N18	112.6 (5)	C214—C213—H21C	108.3
C16—C17—H17A	109.1	C212—C213—H21C	108.3
N18—C17—H17A	109.1	C214—C213—H21D	108.3
C16—C17—H17B	109.1	C212—C213—H21D	108.3
N18—C17—H17B	109.1	H21C—C213—H21D	107.4
H17A—C17—H17B	107.8	N211—C212—C213	111.1 (6)
N18—C19—C110	107.2 (6)	N211—C212—H21E	109.4
N18—C19—H19A	110.3	C213—C212—H21E	109.4
C110—C19—H19A	110.3	N211—C212—H21F	109.4
N18—C19—H19B	110.3	C213—C212—H21F	109.4
C110—C19—H19B	110.3	H21E—C212—H21F	108.0
H19A—C19—H19B	108.5	N21—C214—C213	112.1 (6)
C19—C110—N111	109.7 (6)	N21—C214—H21G	109.2
C19—C110—H11A	109.7	C213—C214—H21G	109.2
N111—C110—H11A	109.7	N21—C214—H21H	109.2
C19—C110—H11B	109.7	C213—C214—H21H	109.2
N111—C110—H11B	109.7	H21G—C214—H21H	107.9
H11A—C110—H11B	108.2	C7—O1—Ni1	136.8 (4)
N111—C112—C113	111.8 (5)	C8—O3—Ni2	134.7 (4)
N111—C112—H11C	109.2	C2—C1—C6	118.9 (5)
C113—C112—H11C	109.2	C2—C1—C7	121.2 (5)
N111—C112—H11D	109.2	C6—C1—C7	119.9 (5)
C113—C112—H11D	109.2	C1—C2—C3	120.3 (5)
H11C—C112—H11D	107.9	C1—C2—H2	119.9
C112—C113—C114	116.0 (5)	C3—C2—H2	119.9
C112—C113—H11E	108.3	C4—C3—C2	121.0 (6)
C114—C113—H11E	108.3	C4—C3—H3	119.5
C112—C113—H11F	108.3	C2—C3—H3	119.5
C114—C113—H11F	108.3	C3—C4—C5	118.4 (5)
H11E—C113—H11F	107.4	C3—C4—C8	120.9 (5)
N11—C114—C113	113.2 (6)	C5—C4—C8	120.6 (5)
N11—C114—H11G	108.9	C6—C5—C4	120.3 (6)
C113—C114—H11G	108.9	C6—C5—H5	119.8
N11—C114—H11H	108.9	C4—C5—H5	119.8
C113—C114—H11H	108.9	C5—C6—C1	121.1 (6)
H11G—C114—H11H	107.8	C5—C6—H6	119.5
N21—Ni2—N211	94.5 (2)	C1—C6—H6	119.5
N21—Ni2—N24	84.4 (2)	O1—C7—O2	125.2 (5)
N211—Ni2—N24	178.7 (3)	O1—C7—C1	116.9 (5)
N21—Ni2—N28	178.5 (2)	O2—C7—C1	117.9 (5)
N211—Ni2—N28	86.2 (2)	O4—C8—O3	125.2 (5)
N24—Ni2—N28	94.9 (2)	O4—C8—C4	119.3 (5)
N21—Ni2—O3	93.23 (17)	O3—C8—C4	115.6 (5)
N211—Ni2—O3	88.9 (2)	O12—Cl1—O14	109.5 (3)
N24—Ni2—O3	92.03 (19)	O12—Cl1—O13	109.3 (3)
N28—Ni2—O3	88.09 (19)	O14—Cl1—O13	110.0 (3)
N21—Ni2—O6	91.10 (17)	O12—Cl1—O11	108.9 (3)
N211—Ni2—O6	88.5 (2)	O14—Cl1—O11	110.4 (3)
N24—Ni2—O6	90.69 (18)	O13—Cl1—O11	108.6 (3)
N28—Ni2—O6	87.60 (18)	O22—Cl2—O24	109.8 (3)
O3—Ni2—O6	175.09 (16)	O22—Cl2—O23	109.1 (3)
Ni2—O6—H61	120 (4)	O24—Cl2—O23	110.7 (4)
Ni2—O6—H62	117 (4)	O22—Cl2—O21	109.3 (3)
H61—O6—H62	105 (5)	O24—Cl2—O21	109.6 (3)
C214—N21—C22	114.0 (6)	O23—Cl2—O21	108.3 (3)
N11—C12—C13—N14	−55.8 (7)	C210—N211—C212—C213	−178.8 (5)
C12—C13—N14—C15	169.6 (5)	N211—C212—C213—C214	71.1 (8)
C13—N14—C15—C16	−179.0 (5)	C212—C213—C214—N21	−71.7 (8)
N14—C15—C16—C17	73.8 (7)	C213—C214—N21—C22	−178.7 (4)
C15—C16—C17—N18	−72.2 (7)	C214—N21—C22—C23	−170.3 (5)
C16—C17—N18—C19	175.7 (5)	C6—C1—C2—C3	1.0 (7)
C17—N18—C19—C110	−172.1 (5)	C7—C1—C2—C3	−178.7 (5)
N18—C19—C110—N111	59.5 (7)	C1—C2—C3—C4	0.2 (8)
C19—C110—N111—C112	−170.1 (6)	C2—C3—C4—C5	−0.7 (8)
C110—N111—C112—C113	−179.3 (5)	C2—C3—C4—C8	−178.6 (5)
N111—C112—C113—C114	−70.2 (8)	C3—C4—C5—C6	0.0 (7)
C112—C113—C114—N11	70.2 (7)	C8—C4—C5—C6	178.0 (5)
C113—C114—N11—C12	180.0 (5)	C4—C5—C6—C1	1.2 (8)
C114—N11—C12—C13	167.6 (5)	C2—C1—C6—C5	−1.7 (8)
N21—C22—C23—N24	55.6 (6)	C7—C1—C6—C5	178.0 (5)
C22—C23—N24—C25	−170.7 (5)	C2—C1—C7—O1	−142.6 (6)
C23—N24—C25—C26	178.6 (5)	C6—C1—C7—O1	37.7 (8)
N24—C25—C26—C27	−72.8 (7)	C2—C1—C7—O2	38.0 (8)
C25—C26—C27—N28	74.6 (7)	C6—C1—C7—O2	−141.7 (6)
C26—C27—N28—C29	−178.3 (5)	C3—C4—C8—O4	144.1 (6)
C27—N28—C29—C210	170.0 (5)	C5—C4—C8—O4	−33.8 (8)
N28—C29—C210—N211	−58.3 (6)	C3—C4—C8—O3	−36.8 (8)
C29—C210—N211—C212	171.1 (5)	C5—C4—C8—O3	145.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O2	0.93	2.09	2.939 (6)	151
N21—H21···O4	0.93	2.06	2.920 (7)	154
N111—H111···O14	0.93	2.27	3.183 (7)	165
N211—H211···O24	0.93	2.22	3.135 (7)	170
N14—H14···O13^i	0.93	2.26	3.175 (7)	168
O5—H52···O11^i	0.85 (5)	2.10 (5)	2.904 (6)	158 (6)
N24—H24···O23^ii	0.93	2.20	3.116 (7)	166
O6—H62···O21^ii	0.85 (4)	2.07 (4)	2.898 (6)	165 (6)
N18—H18···O4^iii	0.93	2.47	3.373 (7)	163
O5—H51···O4^iii	0.85 (2)	1.88 (2)	2.717 (6)	170 (4)
N28—H28···O2^iv	0.93	2.34	3.253 (7)	167
O6—H61···O2^iv	0.85 (2)	1.91 (2)	2.730 (5)	163 (6)
C12—H12A···O11^i	0.99	2.44	3.372 (8)	157
C22—H22A···O21^ii	0.99	2.43	3.402 (7)	166
C19—H19A···O24^iii	0.99	2.41	3.273 (8)	146
C29—H29A···O14^iv	0.99	2.56	3.402 (7)	142

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z.