Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614008134/uk3094sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614008134/uk3094Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614008134/uk3094IIsup3.hkl |
CCDC references: 996690; 996691
Projects on transition metal (TM) complexes surveying organic carboxylates (OC) (and eventually including some ancillary ligand) have proven throughout the years an almost inexhaustible resource of crystal structures of varied complexity (zero- to three-dimensional), and many of them, initally generated out of a pure academic interest ended up generating materials of practical interest (Zheng et al., 2014, and references therein). Regarding magnetism (our main line of interest), some regularities linking structure and magnetic behaviour have been relatively well established over the years. For instance, syn–syn OC coordination modes frequently appear to lead to strong antiferromagnetism, while syn–anti and anti–anti modes tend to favour ferro- or antiferromagnetic coupling. In pursuit of our interest on TM—OC systems with potentially interesting magnetic properties, we present herein two new NiII complexes involving the ancillary ligand bis[(pyridin-2-yl)methyl]amine (bpma) and two different carboxylates, i.e. homophthalate (hph) and benzene-1,2,4,5-tetracarboxylate (btc), namely [Ni(hph)(bpma)(H2O)]n, (I), and [Ni2(btc)(bpma)2(H2O)2].[Ni(bpma)(H2O)3]2(btc).6H2O, (II).
Complexes (I) and (II) were synthesized by similar methods. The corresponding carboxylic acid [homophthalic acid for (I) and benzene-1,2,4,5-tetracarboxylic for (II)] (1 mmol) was added slowly to an aqueous solution (20 ml) of NaOH (4 mmol or 2 mmol, respectively). Nickel acetate tetrahydrate (2 mmol) was dissolved in water (100 ml) and added to the above solution. The resulting mixture was stirred for 15 min, followed by the addition of a methanolic solution (20 ml) of bis[(pyridin-2-yl)methyl]amine (2 mmol) and the resulting solution was maintained under reflux for 4 h. Good single crystals suitable for X-ray diffraction could be picked from the precipitates obtained after slow evaporation at room temperature.
All H atoms were originally found in a difference Fourier but were treated differently in the refinement. H atoms attached to C atoms were repositioned in their expected positions according to the corresponding collection temperatures [150 (2) K for (I) and 298 (2) K for (II)] and thereafter allowed to ride, with Uiso(H) = xUeq(host); C—H = 0.93/0.95 Å and x = 1.2 for aromatic H atoms, and C—H = 0.97/0.99 Å and x = 1.5 for methyl H atoms. H atoms attached to N and O atoms were refined with restrained X—H distances of 0.85 (1) Å and Uiso(H) = 1.2Ueq(N,O). In (I), atoms H21N is not involved in any conventional hydrogen bond; however, it makes two rather short N21—H21N···O intermolecular contacts to O32 [2.62 (3) Å and 143 (3)°] and O22(-x+1/2, y+1/2, -z+1/2) [2.74 (3) Å and 118 (4)°], which could be considered as frustrated hydrogen bonds, inhibited by geometrical hindrance. In structure (II), an anti-bumpping restraint was imposed between atoms H3WB and H7WA in order to preclude an unrealistic closeness.
The structure of (I), [Ni(hph)(bpma)(H2O)]n, presents its NiII cations octahedrally coordinated by one aqua ligand, an N,N',N''-tridentate bpma ligand bent in its usual `butterfly' fashion, and a µ2-O:O hph ligand which bridges neighbouring metal centres into one-dimensional polymeric structures parallel to the unique b axis (Fig. 1). N/O—Ni coordination distances (Table 2) are similar, spanning the rather tight range 2.0674 (18)–2.104 (2)Å. Departures from regularity are more noticeable in the coordination angles [cis angles = 79.39 (9)–94.94 (7)° and trans angles = 170.36 (8)–172.97 (8)°]. The symmetry operation leading to the chain construction is the 21 screw along [010], through an Ni—O32i [(i) -x+1/2, y-1/2, -z+1/2.] bond, and the repetition step in the chain is thus the length of the short b axis, 10.4511 (14)Å. Even if not novel, the "modest" µ2κ2 bridging mode displayed by hph in (I) is rather unfrequent: it is found in less than 10% of the reported structures, the ligand usually preferring more significant involvement in cation coordination; in this context µ2 (κ3 and κ4), µ3 (κ2 to κ5) and µ4 (κ4) modes are more usual.
There are eight relevant hydrogen-bonding interactions in the structure of (I) (Table 3), six of which are internal to the chains; among these, entries 1–3 in Table 3 are internal to a single Ni coordination polyhedron, while entries 4–6 provide for the linkage of neighbouring polyhedra within chains (Fig. 1). The compact one-dimensional arrays thus formed are disposed in a parallel fashion (Fig. 2) and interact with each other via two centrosymmetric hydrogen-bonding loops involving the last two hydrogen bonds in Table 3, that involving atom H22 (loop `A' in Fig. 2) linking chains along the [100] direction and that involving atom H52 (loop `B' in Fig. 2) linking chains along [001].
In contrast to the formally simple structure of (I), the structure of compound (II) appears more complex. An inspection of Scheme 1 discloses the most outstanding feature of the structure, viz. the neutral coordination complex {[NiII(bpma)(H2O)]2(btc)} (hereinafter denoted C, leftmost part of Scheme 1), co-existing with a salt formulated as [NiII(bpma)(H2O)3]2(btc) (hereinafter denoted S, rightmost part of Scheme 1), the whole group being stabilized by six solvent water molecules. Substructures C and S are both centrosymmetric, with their central btc anion lying on a centre of inversion. Fig. 3(a) shows a view of substructure C, expanded through application of the 1 operation, while Fig. 3(b) shows an equivalent view for substructure S.
In the case of substructure C, the NiII cation is octahedrally coordinated by one aqua ligand, three N atoms from a bpma ligand and two O atoms from different carboxylate groups of a btc ligand, which serves as a bridge in the binuclear complex molecule. The case of substructure Sis similar, the difference being that the btc bonds to NiII are absent, being replaced by two aqua ligands, thus generating a three-membered [NiII(bpma)(H2O)3]2(btc) group of ions.
As for the hph ligand in (I), the bridging mode displayed by the btc ligand in substructures C of (II) is rare; a search of the Cambridge Structural Database (CSD, Version 5.34 and updates; Allen, 2002) revealed that out of ca 500 complexes with coordinated btc ligands, only three report the anion in a µ2,κ4-mode (all O atoms from different carboxylate groups), two with Cu [CSD refcodes GECNIL (Chaudhuri et al., 1988) and SALTIJ (Shi et al., 2004)] and one with Co (GEFGAA; Xia et al., 2006).
From a metrical point of view, there are no substantial differences between the Ni1 (in substructure C) and Ni2 (in substructure S) coordination polyhedra (Table 4), or with that in (I), with ranges of coordination lengths and angles (listed for substructures C and S, respectively) as follows: N/O—Ni = 2.0437 (12)–2.1241 (13) and 2.0448 (13)–2.0995 (15) Å; cis angles = 80.95 (6)–95.65 (6) and 80.70 (6)–96.25 (6)°; trans angles = 168.58 (6)–176.24 (6) and 170.22 (6)–176.31 (6)°. The fundamental difference with (I) concerns the packing scheme, due to the large number of hydrogen-bonding donors/acceptors. Even if somewhat arbitrarily, we shall describe the interactions in a stepwise fashion, looking firstly to those interactions internal to the C substructures, secondly to those internal to S substructures, and finally those hydrogen bonds linking them into a three-dimensional supramolecular structure. At this stage, it is pertinent to state that each of the substructures has one hydration water molecule (O5W for C and O7W for S) fulfilling a thoroughly `internal' role, in that they make and receive all their interactions to O atoms (and from H atoms) in the corresponding substructure, with no direct interactions with the other. As we shall see, only O6W acts as a bridge between both subunits.
According to this, substructure C can be considered as formed by atom Ni1, bpma(1), btc(4), O1W and O5W, while substructure S would be composed of atom Ni2, bpma(2), btc(3), O2W, O3W, O4W and O7W, where parenthesis refer to the trailing numbers characterizing atoms labels in each ligand. Again here the µ2,κ4-O1,O2:O4,O5 bridging mode of the anion (with all O atoms from different carboxylate groups) is rather unusual and only three further examples are found in the CSD, out of ca 500 complexes reporting the anion in a coordinating mode.
Table 5 presents the hydrogen bonds in (II), sorted into three blocks. The upper block (entries 1–7) contains only interactions internal to substructure C, which give rise to two-dimensional structures (Fig. 4a) parallel to (001) at z ~0.50 (Fig. 4b). The outstanding role of atom O5W (highlighted with a circle) is apparent. The second block (entries 8–18) contains in turn the interaction internal to substructure S, also generating two-dimensional structures (Fig. 5a) parallel to (001), this time at z ~0.00, 1.00 (Fig. 5b). Also here, hydration water molecule O7W (circled) is relevant for the group stability. Finally, the third block (entries 19–20) presents the only two significant bridging hydrogen-bond interactions, a bifurcated one pivoted by atom O6W and the weak nonconventional C72—H72B···O5W hydrogen bond. Fig. 6 presents a complete [100] view of the structure, with the bridging interactions circled for clear identification.
The magnetic characterization of both compounds is in progress.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
The asymmetric unit of (I), suggesting the way in which [010] chains are
formed. Broken lines represent hydrogen bonds. [Symmetry code: (i)
-x+1/2, y-1/2, -z+1/2.] A packing view of (I), showing in projection the interaction between columns. Broken lines represent hydrogen bonds Molecular views of (II), showing (a) substructure C and (b) substructure S (both views expanded after application of the 1 operation through the inversion centre at the btc mid-point). Displacement ellipsoids are drawn at the 40% probability level and the independent part of both substructures is shown with full bonds. [Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+2, -z.] Partial packing views of (II), showing details of the C two-dimensional substructure, (a) projected down c and showing the internal hydrogen-bonding network, and (b) in a rotated view of the same atomic disposition now projected down a. Broken lines represent hydrogen bonds. Partial packing views of (II), showing details of the S two-dimensional substructure (a) projected down c and showing the internal hydrogen-bonding network, and (b) in a rotated view of the same atomic disposition now projected down a. Broken lines represent hydrogen bonds. The environment of water atom O7W is highlighted with a circle. A full packing view of (II) projected down a and showing the interaction between the C and S substructures. Broken lines represent hydrogen bonds. The bridging ligands (see text for details) are highlighted. |
[Ni(C9H6O4)(C12H13N3)(H2O)] | F(000) = 1888 |
Mr = 454.12 | Dx = 1.517 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2835 reflections |
a = 18.233 (3) Å | θ = 2.2–26.8° |
b = 10.4511 (14) Å | µ = 1.02 mm−1 |
c = 20.898 (3) Å | T = 150 K |
β = 93.081 (2)° | Block, blue |
V = 3976.3 (9) Å3 | 0.39 × 0.13 × 0.12 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 4399 independent reflections |
Radiation source: fine-focus sealed tube | 3562 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
CCD rotation images, thin slices scans | θmax = 27.8°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −23→22 |
Tmin = 0.86, Tmax = 0.88 | k = −13→13 |
15811 measured reflections | l = −27→27 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.43 | w = 1/[σ2(Fo2) + (0.0538P)2 + 2.6787P] where P = (Fo2 + 2Fc2)/3 |
4399 reflections | (Δ/σ)max = 0.002 |
280 parameters | Δρmax = 0.72 e Å−3 |
4 restraints | Δρmin = −0.37 e Å−3 |
[Ni(C9H6O4)(C12H13N3)(H2O)] | V = 3976.3 (9) Å3 |
Mr = 454.12 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.233 (3) Å | µ = 1.02 mm−1 |
b = 10.4511 (14) Å | T = 150 K |
c = 20.898 (3) Å | 0.39 × 0.13 × 0.12 mm |
β = 93.081 (2)° |
Bruker SMART CCD area-detector diffractometer | 4399 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 3562 reflections with I > 2σ(I) |
Tmin = 0.86, Tmax = 0.88 | Rint = 0.028 |
15811 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 4 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.43 | Δρmax = 0.72 e Å−3 |
4399 reflections | Δρmin = −0.37 e Å−3 |
280 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.268905 (17) | 0.54699 (3) | 0.182666 (15) | 0.01720 (13) | |
N11 | 0.32496 (12) | 0.5816 (2) | 0.09987 (10) | 0.0220 (5) | |
N21 | 0.28959 (13) | 0.7444 (2) | 0.19247 (10) | 0.0222 (5) | |
H21N | 0.2611 (14) | 0.785 (3) | 0.2153 (12) | 0.027* | |
N31 | 0.36272 (12) | 0.5344 (2) | 0.24201 (10) | 0.0205 (5) | |
C11 | 0.35626 (14) | 0.4973 (3) | 0.06188 (13) | 0.0245 (6) | |
H1A | 0.3570 | 0.4098 | 0.0742 | 0.029* | |
C21 | 0.38752 (19) | 0.5306 (3) | 0.00586 (15) | 0.0391 (8) | |
H21 | 0.4081 | 0.4675 | −0.0205 | 0.047* | |
C31 | 0.3881 (2) | 0.6591 (4) | −0.01100 (16) | 0.0495 (10) | |
H31 | 0.4104 | 0.6858 | −0.0488 | 0.059* | |
C41 | 0.3559 (2) | 0.7475 (3) | 0.02769 (14) | 0.0430 (9) | |
H41 | 0.3549 | 0.8356 | 0.0164 | 0.052* | |
C51 | 0.32516 (16) | 0.7061 (3) | 0.08312 (13) | 0.0260 (6) | |
C61 | 0.28692 (17) | 0.7966 (3) | 0.12672 (13) | 0.0294 (6) | |
H61A | 0.3113 | 0.8813 | 0.1267 | 0.035* | |
H61B | 0.2352 | 0.8081 | 0.1109 | 0.035* | |
C71 | 0.36221 (15) | 0.7644 (3) | 0.22740 (13) | 0.0238 (6) | |
H71A | 0.3986 | 0.7900 | 0.1963 | 0.029* | |
H71B | 0.3579 | 0.8355 | 0.2583 | 0.029* | |
C81 | 0.38960 (14) | 0.6485 (3) | 0.26261 (12) | 0.0210 (5) | |
C91 | 0.44319 (15) | 0.6562 (3) | 0.31322 (13) | 0.0284 (6) | |
H91 | 0.4603 | 0.7371 | 0.3285 | 0.034* | |
C101 | 0.47052 (16) | 0.5456 (3) | 0.34028 (14) | 0.0336 (7) | |
H101 | 0.5066 | 0.5490 | 0.3748 | 0.040* | |
C111 | 0.44528 (17) | 0.4286 (3) | 0.31707 (14) | 0.0323 (7) | |
H111 | 0.4652 | 0.3508 | 0.3340 | 0.039* | |
C121 | 0.39053 (15) | 0.4277 (3) | 0.26882 (13) | 0.0248 (6) | |
H121 | 0.3718 | 0.3476 | 0.2540 | 0.030* | |
O12 | 0.10542 (10) | 0.6298 (2) | 0.23059 (9) | 0.0275 (4) | |
O22 | 0.21205 (10) | 0.54161 (17) | 0.26559 (9) | 0.0215 (4) | |
O32 | 0.23373 (10) | 0.85118 (19) | 0.33165 (9) | 0.0254 (4) | |
O42 | 0.33763 (11) | 0.83428 (19) | 0.39241 (9) | 0.0287 (4) | |
C12 | 0.12750 (14) | 0.6080 (2) | 0.34231 (12) | 0.0187 (5) | |
C22 | 0.05291 (15) | 0.5936 (3) | 0.35230 (14) | 0.0247 (6) | |
H22 | 0.0194 | 0.5791 | 0.3166 | 0.030* | |
C32 | 0.02663 (16) | 0.5999 (3) | 0.41350 (14) | 0.0310 (7) | |
H32 | −0.0242 | 0.5889 | 0.4197 | 0.037* | |
C42 | 0.07535 (17) | 0.6224 (3) | 0.46512 (14) | 0.0308 (7) | |
H42 | 0.0583 | 0.6260 | 0.5072 | 0.037* | |
C52 | 0.14927 (16) | 0.6398 (3) | 0.45535 (13) | 0.0271 (6) | |
H52 | 0.1820 | 0.6574 | 0.4912 | 0.033* | |
C62 | 0.17708 (14) | 0.6323 (2) | 0.39446 (12) | 0.0188 (5) | |
C72 | 0.15014 (14) | 0.5928 (2) | 0.27372 (12) | 0.0202 (5) | |
C82 | 0.25815 (15) | 0.6559 (2) | 0.38849 (12) | 0.0215 (5) | |
H82A | 0.2762 | 0.5963 | 0.3561 | 0.026* | |
H82B | 0.2842 | 0.6354 | 0.4300 | 0.026* | |
C92 | 0.27836 (14) | 0.7920 (2) | 0.36970 (11) | 0.0176 (5) | |
O1W | 0.17249 (11) | 0.58304 (19) | 0.12623 (9) | 0.0250 (4) | |
H1WA | 0.1641 (16) | 0.5069 (14) | 0.1137 (14) | 0.030* | |
H1WB | 0.1416 (13) | 0.598 (3) | 0.1542 (11) | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01567 (19) | 0.01819 (19) | 0.01774 (19) | 0.00132 (12) | 0.00081 (12) | 0.00055 (12) |
N11 | 0.0223 (12) | 0.0215 (11) | 0.0223 (11) | −0.0072 (9) | 0.0019 (9) | −0.0051 (9) |
N21 | 0.0249 (12) | 0.0198 (11) | 0.0221 (11) | 0.0041 (9) | 0.0041 (9) | −0.0016 (9) |
N31 | 0.0170 (11) | 0.0245 (11) | 0.0203 (11) | 0.0000 (9) | 0.0030 (9) | −0.0024 (9) |
C11 | 0.0183 (13) | 0.0299 (14) | 0.0254 (14) | −0.0108 (12) | 0.0005 (11) | −0.0017 (11) |
C21 | 0.0360 (18) | 0.052 (2) | 0.0292 (16) | −0.0164 (15) | 0.0055 (13) | −0.0166 (14) |
C31 | 0.059 (2) | 0.060 (2) | 0.0305 (17) | −0.0253 (19) | 0.0113 (16) | −0.0021 (16) |
C41 | 0.071 (3) | 0.0316 (17) | 0.0268 (16) | −0.0200 (17) | 0.0048 (15) | 0.0074 (13) |
C51 | 0.0303 (16) | 0.0269 (14) | 0.0204 (13) | −0.0110 (12) | −0.0034 (11) | 0.0006 (11) |
C61 | 0.0386 (18) | 0.0196 (13) | 0.0294 (15) | −0.0030 (12) | −0.0043 (12) | 0.0046 (11) |
C71 | 0.0174 (13) | 0.0233 (13) | 0.0308 (14) | −0.0020 (11) | 0.0023 (11) | −0.0056 (11) |
C81 | 0.0129 (12) | 0.0328 (15) | 0.0176 (12) | 0.0005 (11) | 0.0035 (9) | 0.0000 (10) |
C91 | 0.0183 (14) | 0.0399 (17) | 0.0271 (14) | −0.0057 (12) | 0.0038 (11) | −0.0029 (12) |
C101 | 0.0200 (14) | 0.059 (2) | 0.0217 (14) | 0.0035 (14) | −0.0024 (11) | 0.0050 (13) |
C111 | 0.0303 (16) | 0.0373 (17) | 0.0292 (15) | 0.0102 (13) | 0.0008 (12) | 0.0097 (13) |
C121 | 0.0212 (14) | 0.0262 (14) | 0.0275 (14) | 0.0044 (11) | 0.0047 (11) | 0.0049 (11) |
O12 | 0.0228 (10) | 0.0375 (11) | 0.0218 (9) | 0.0083 (9) | −0.0041 (8) | −0.0021 (8) |
O22 | 0.0184 (9) | 0.0241 (10) | 0.0222 (9) | 0.0039 (7) | 0.0037 (7) | 0.0034 (7) |
O32 | 0.0262 (10) | 0.0287 (10) | 0.0206 (9) | −0.0021 (8) | −0.0042 (8) | 0.0018 (8) |
O42 | 0.0264 (11) | 0.0305 (11) | 0.0285 (10) | −0.0070 (8) | −0.0040 (8) | 0.0061 (8) |
C12 | 0.0225 (14) | 0.0119 (11) | 0.0221 (12) | −0.0005 (10) | 0.0053 (10) | 0.0012 (9) |
C22 | 0.0181 (14) | 0.0212 (13) | 0.0349 (15) | 0.0022 (11) | 0.0030 (11) | −0.0015 (11) |
C32 | 0.0196 (14) | 0.0358 (16) | 0.0387 (16) | 0.0018 (12) | 0.0111 (12) | 0.0023 (13) |
C42 | 0.0415 (18) | 0.0273 (15) | 0.0248 (14) | 0.0027 (13) | 0.0125 (13) | 0.0034 (11) |
C52 | 0.0355 (16) | 0.0239 (14) | 0.0217 (13) | 0.0000 (12) | 0.0001 (12) | 0.0000 (11) |
C62 | 0.0218 (13) | 0.0124 (11) | 0.0222 (12) | 0.0032 (10) | 0.0011 (10) | 0.0001 (9) |
C72 | 0.0206 (14) | 0.0171 (12) | 0.0228 (13) | −0.0013 (10) | 0.0013 (10) | −0.0031 (10) |
C82 | 0.0282 (15) | 0.0204 (13) | 0.0160 (12) | 0.0015 (11) | 0.0005 (10) | 0.0008 (10) |
C92 | 0.0155 (13) | 0.0241 (13) | 0.0134 (11) | 0.0012 (10) | 0.0013 (9) | −0.0029 (9) |
O1W | 0.0272 (11) | 0.0256 (10) | 0.0224 (10) | 0.0036 (9) | 0.0040 (8) | −0.0014 (8) |
Ni1—N31 | 2.062 (2) | C91—C101 | 1.369 (4) |
Ni1—O22 | 2.0674 (18) | C91—H91 | 0.9500 |
Ni1—O32i | 2.068 (2) | C101—C111 | 1.385 (5) |
Ni1—N11 | 2.088 (2) | C101—H101 | 0.9500 |
Ni1—O1W | 2.098 (2) | C111—C121 | 1.380 (4) |
Ni1—N21 | 2.106 (2) | C111—H111 | 0.9500 |
N11—C11 | 1.334 (4) | C121—H121 | 0.9500 |
N11—C51 | 1.347 (4) | O12—C72 | 1.244 (3) |
N21—C61 | 1.477 (3) | O22—C72 | 1.269 (3) |
N21—C71 | 1.492 (4) | O32—C92 | 1.268 (3) |
N21—H21N | 0.841 (10) | O42—C92 | 1.238 (3) |
N31—C121 | 1.335 (3) | C12—C22 | 1.395 (4) |
N31—C81 | 1.351 (3) | C12—C62 | 1.401 (4) |
C11—C21 | 1.374 (4) | C12—C72 | 1.521 (3) |
C11—H1A | 0.9500 | C22—C32 | 1.391 (4) |
C21—C31 | 1.388 (5) | C22—H22 | 0.9500 |
C21—H21 | 0.9500 | C32—C42 | 1.380 (4) |
C31—C41 | 1.379 (5) | C32—H32 | 0.9500 |
C31—H31 | 0.9500 | C42—C52 | 1.386 (4) |
C41—C51 | 1.383 (4) | C42—H42 | 0.9500 |
C41—H41 | 0.9500 | C52—C62 | 1.397 (4) |
C51—C61 | 1.510 (4) | C52—H52 | 0.9500 |
C61—H61A | 0.9900 | C62—C82 | 1.510 (4) |
C61—H61B | 0.9900 | C82—C92 | 1.525 (4) |
C71—C81 | 1.490 (4) | C82—H82A | 0.9900 |
C71—H71A | 0.9900 | C82—H82B | 0.9900 |
C71—H71B | 0.9900 | O1W—H1WA | 0.849 (10) |
C81—C91 | 1.403 (4) | O1W—H1WB | 0.848 (10) |
N31—Ni1—O22 | 86.06 (8) | N21—C71—H71B | 109.0 |
N31—Ni1—O32i | 92.06 (8) | H71A—C71—H71B | 107.8 |
O22—Ni1—O32i | 94.91 (7) | N31—C81—C91 | 121.1 (3) |
N31—Ni1—N11 | 94.72 (9) | N31—C81—C71 | 117.0 (2) |
O22—Ni1—N11 | 171.57 (8) | C91—C81—C71 | 121.8 (3) |
O32i—Ni1—N11 | 93.45 (8) | C101—C91—C81 | 119.1 (3) |
N31—Ni1—O1W | 172.97 (8) | C101—C91—H91 | 120.5 |
O22—Ni1—O1W | 91.91 (7) | C81—C91—H91 | 120.5 |
O32i—Ni1—O1W | 94.83 (7) | C91—C101—C111 | 119.6 (3) |
N11—Ni1—O1W | 86.32 (8) | C91—C101—H101 | 120.2 |
N31—Ni1—N21 | 82.28 (9) | C111—C101—H101 | 120.2 |
O22—Ni1—N21 | 92.31 (8) | C121—C111—C101 | 118.4 (3) |
O32i—Ni1—N21 | 170.50 (8) | C121—C111—H111 | 120.8 |
N11—Ni1—N21 | 79.50 (9) | C101—C111—H111 | 120.8 |
O1W—Ni1—N21 | 91.09 (9) | N31—C121—C111 | 123.0 (3) |
C11—N11—C51 | 118.4 (2) | N31—C121—H121 | 118.5 |
C11—N11—Ni1 | 128.51 (19) | C111—C121—H121 | 118.5 |
C51—N11—Ni1 | 113.01 (18) | C72—O22—Ni1 | 126.19 (17) |
C61—N21—C71 | 112.8 (2) | C92—O32—Ni1ii | 125.65 (17) |
C61—N21—Ni1 | 105.95 (16) | C22—C12—C62 | 119.8 (2) |
C71—N21—Ni1 | 109.55 (16) | C22—C12—C72 | 116.5 (2) |
C61—N21—H21N | 110 (2) | C62—C12—C72 | 123.7 (2) |
C71—N21—H21N | 102 (2) | C32—C22—C12 | 121.3 (3) |
Ni1—N21—H21N | 116 (2) | C32—C22—H22 | 119.4 |
C121—N31—C81 | 118.7 (2) | C12—C22—H22 | 119.4 |
C121—N31—Ni1 | 126.13 (19) | C42—C32—C22 | 119.2 (3) |
C81—N31—Ni1 | 114.23 (17) | C42—C32—H32 | 120.4 |
N11—C11—C21 | 123.4 (3) | C22—C32—H32 | 120.4 |
N11—C11—H1A | 118.3 | C32—C42—C52 | 119.8 (3) |
C21—C11—H1A | 118.3 | C32—C42—H42 | 120.1 |
C11—C21—C31 | 118.0 (3) | C52—C42—H42 | 120.1 |
C11—C21—H21 | 121.0 | C42—C52—C62 | 122.0 (3) |
C31—C21—H21 | 121.0 | C42—C52—H52 | 119.0 |
C41—C31—C21 | 119.3 (3) | C62—C52—H52 | 119.0 |
C41—C31—H31 | 120.3 | C52—C62—C12 | 117.9 (2) |
C21—C31—H31 | 120.3 | C52—C62—C82 | 118.1 (2) |
C31—C41—C51 | 119.1 (3) | C12—C62—C82 | 124.0 (2) |
C31—C41—H41 | 120.5 | O12—C72—O22 | 126.0 (2) |
C51—C41—H41 | 120.5 | O12—C72—C12 | 116.7 (2) |
N11—C51—C41 | 121.8 (3) | O22—C72—C12 | 117.3 (2) |
N11—C51—C61 | 116.1 (2) | C62—C82—C92 | 115.1 (2) |
C41—C51—C61 | 122.0 (3) | C62—C82—H82A | 108.5 |
N21—C61—C51 | 109.7 (2) | C92—C82—H82A | 108.5 |
N21—C61—H61A | 109.7 | C62—C82—H82B | 108.5 |
C51—C61—H61A | 109.7 | C92—C82—H82B | 108.5 |
N21—C61—H61B | 109.7 | H82A—C82—H82B | 107.5 |
C51—C61—H61B | 109.7 | O42—C92—O32 | 125.7 (2) |
H61A—C61—H61B | 108.2 | O42—C92—C82 | 116.9 (2) |
C81—C71—N21 | 113.1 (2) | O32—C92—C82 | 117.4 (2) |
C81—C71—H71A | 109.0 | Ni1—O1W—H1WA | 98 (2) |
N21—C71—H71A | 109.0 | Ni1—O1W—H1WB | 102 (2) |
C81—C71—H71B | 109.0 | H1WA—O1W—H1WB | 105.7 (15) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O12 | 0.84 (2) | 1.79 (2) | 2.603 (3) | 162 (2) |
C82—H82A···O22 | 0.99 | 2.24 | 2.916 (3) | 124 |
C121—H121···O32i | 0.95 | 2.55 | 3.110 (4) | 118 |
O1W—H1WA···O42i | 0.84 (2) | 1.81 (2) | 2.632 (3) | 163 (3) |
C71—H71B···O22ii | 0.99 | 2.54 | 3.205 (4) | 125 |
C121—H121···O12i | 0.95 | 2.33 | 3.114 (4) | 139 |
C22—H22···O12iii | 0.95 | 2.49 | 3.309 (3) | 144 |
C52—H52···O42iv | 0.95 | 2.48 | 3.191 (3) | 131 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+3/2, −z+1. |
[Ni2(C10H2O8)(C12H13N3)2(H2O)2]·[Ni(C12H13N3)(H2O)3]2(C10H2O8)·6H2O' | Z = 1 |
Mr = 1784.32 | F(000) = 928 |
Triclinic, P1 | Dx = 1.598 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8485 (6) Å | Cell parameters from 6234 reflections |
b = 10.7208 (6) Å | θ = 2.3–26.1° |
c = 19.4924 (11) Å | µ = 1.10 mm−1 |
α = 85.008 (1)° | T = 298 K |
β = 82.823 (1)° | Plate, blue |
γ = 65.2930 (8)° | 0.41 × 0.37 × 0.07 mm |
V = 1853.65 (19) Å3 |
Bruker SMART CCD area-detector diffractometer | 7916 independent reflections |
Radiation source: fine-focus sealed tube | 6969 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
CCD rotation images, thin slices scans | θmax = 27.9°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −12→12 |
Tmin = 0.65, Tmax = 0.93 | k = −13→13 |
15507 measured reflections | l = −25→24 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0481P)2 + 0.4178P] where P = (Fo2 + 2Fc2)/3 |
7916 reflections | (Δ/σ)max = 0.001 |
562 parameters | Δρmax = 0.60 e Å−3 |
24 restraints | Δρmin = −0.31 e Å−3 |
[Ni2(C10H2O8)(C12H13N3)2(H2O)2]·[Ni(C12H13N3)(H2O)3]2(C10H2O8)·6H2O' | γ = 65.2930 (8)° |
Mr = 1784.32 | V = 1853.65 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.8485 (6) Å | Mo Kα radiation |
b = 10.7208 (6) Å | µ = 1.10 mm−1 |
c = 19.4924 (11) Å | T = 298 K |
α = 85.008 (1)° | 0.41 × 0.37 × 0.07 mm |
β = 82.823 (1)° |
Bruker SMART CCD area-detector diffractometer | 7916 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 6969 reflections with I > 2σ(I) |
Tmin = 0.65, Tmax = 0.93 | Rint = 0.015 |
15507 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 24 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.60 e Å−3 |
7916 reflections | Δρmin = −0.31 e Å−3 |
562 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.86938 (2) | 0.65317 (2) | 0.387961 (11) | 0.02431 (7) | |
Ni2 | 0.73509 (2) | 0.30305 (2) | 0.105617 (11) | 0.02524 (7) | |
N11 | 0.89448 (17) | 0.83613 (15) | 0.39166 (8) | 0.0292 (3) | |
N21 | 1.09898 (17) | 0.57239 (17) | 0.39571 (8) | 0.0327 (3) | |
H21N | 1.117 (2) | 0.5022 (16) | 0.4229 (10) | 0.039* | |
N31 | 0.93585 (17) | 0.65210 (15) | 0.28392 (8) | 0.0297 (3) | |
C11 | 0.7954 (2) | 0.9644 (2) | 0.37731 (11) | 0.0382 (4) | |
H11 | 0.7041 | 0.9769 | 0.3626 | 0.046* | |
C21 | 0.8235 (3) | 1.0778 (2) | 0.38356 (12) | 0.0518 (6) | |
H21 | 0.7519 | 1.1656 | 0.3741 | 0.062* | |
C31 | 0.9595 (4) | 1.0592 (3) | 0.40408 (14) | 0.0619 (7) | |
H31 | 0.9812 | 1.1342 | 0.4091 | 0.074* | |
C41 | 1.0623 (3) | 0.9284 (3) | 0.41701 (13) | 0.0551 (6) | |
H41 | 1.1555 | 0.9137 | 0.4303 | 0.066* | |
C51 | 1.0275 (2) | 0.8184 (2) | 0.41032 (10) | 0.0365 (4) | |
C61 | 1.1339 (2) | 0.6735 (2) | 0.42659 (13) | 0.0473 (5) | |
H61A | 1.2354 | 0.6614 | 0.4097 | 0.057* | |
H61B | 1.1301 | 0.6573 | 0.4764 | 0.057* | |
C71 | 1.1790 (2) | 0.5274 (3) | 0.32723 (12) | 0.0512 (6) | |
H71A | 1.2140 | 0.4284 | 0.3260 | 0.061* | |
H71B | 1.2666 | 0.5483 | 0.3209 | 0.061* | |
C81 | 1.0852 (2) | 0.5931 (2) | 0.26809 (11) | 0.0376 (4) | |
C91 | 1.1482 (3) | 0.5879 (3) | 0.20003 (12) | 0.0556 (6) | |
H91 | 1.2518 | 0.5455 | 0.1897 | 0.067* | |
C101 | 1.0558 (3) | 0.6462 (3) | 0.14788 (12) | 0.0571 (6) | |
H101 | 1.0963 | 0.6438 | 0.1020 | 0.068* | |
C111 | 0.9027 (3) | 0.7082 (2) | 0.16443 (11) | 0.0483 (5) | |
H111 | 0.8381 | 0.7485 | 0.1301 | 0.058* | |
C121 | 0.8475 (2) | 0.7092 (2) | 0.23289 (10) | 0.0368 (4) | |
H121 | 0.7442 | 0.7515 | 0.2442 | 0.044* | |
N12 | 0.92631 (17) | 0.17616 (15) | 0.15501 (8) | 0.0292 (3) | |
N22 | 0.70576 (19) | 0.42348 (16) | 0.18884 (9) | 0.0336 (4) | |
H22N | 0.666 (2) | 0.5074 (11) | 0.1768 (11) | 0.040* | |
N32 | 0.62005 (17) | 0.21498 (16) | 0.17317 (8) | 0.0311 (3) | |
C12 | 1.0065 (2) | 0.0405 (2) | 0.15041 (10) | 0.0349 (4) | |
H12 | 0.9860 | −0.0049 | 0.1173 | 0.042* | |
C22 | 1.1178 (2) | −0.0348 (2) | 0.19231 (11) | 0.0407 (5) | |
H22 | 1.1706 | −0.1291 | 0.1878 | 0.049* | |
C32 | 1.1496 (2) | 0.0323 (2) | 0.24112 (11) | 0.0453 (5) | |
H32 | 1.2257 | −0.0159 | 0.2696 | 0.054* | |
C42 | 1.0669 (2) | 0.1719 (2) | 0.24712 (12) | 0.0451 (5) | |
H42 | 1.0861 | 0.2190 | 0.2798 | 0.054* | |
C52 | 0.9548 (2) | 0.2409 (2) | 0.20384 (10) | 0.0344 (4) | |
C62 | 0.8572 (2) | 0.3926 (2) | 0.20759 (12) | 0.0426 (5) | |
H62A | 0.8501 | 0.4217 | 0.2541 | 0.051* | |
H62B | 0.9024 | 0.4432 | 0.1763 | 0.051* | |
C72 | 0.6044 (3) | 0.3974 (2) | 0.24439 (12) | 0.0466 (5) | |
H72A | 0.5092 | 0.4775 | 0.2474 | 0.056* | |
H72B | 0.6470 | 0.3859 | 0.2880 | 0.056* | |
C82 | 0.5750 (2) | 0.2728 (2) | 0.23503 (10) | 0.0342 (4) | |
C92 | 0.5004 (2) | 0.2221 (2) | 0.28741 (11) | 0.0448 (5) | |
H92 | 0.4718 | 0.2618 | 0.3304 | 0.054* | |
C102 | 0.4694 (3) | 0.1133 (3) | 0.27522 (13) | 0.0523 (6) | |
H102 | 0.4171 | 0.0801 | 0.3095 | 0.063* | |
C112 | 0.5162 (3) | 0.0529 (3) | 0.21160 (13) | 0.0490 (6) | |
H112 | 0.4975 | −0.0218 | 0.2024 | 0.059* | |
C122 | 0.5915 (2) | 0.1072 (2) | 0.16249 (11) | 0.0390 (5) | |
H122 | 0.6241 | 0.0669 | 0.1197 | 0.047* | |
O13 | 0.38940 (14) | 0.72407 (13) | 0.07835 (7) | 0.0322 (3) | |
O23 | 0.56320 (17) | 0.73292 (15) | 0.13791 (7) | 0.0423 (3) | |
O33 | 0.68113 (15) | 0.62855 (13) | −0.02583 (8) | 0.0366 (3) | |
O43 | 0.85608 (15) | 0.70986 (15) | −0.03987 (10) | 0.0522 (4) | |
C13 | 0.38596 (19) | 1.02223 (17) | 0.05253 (9) | 0.0266 (4) | |
H13 | 0.3084 | 1.0380 | 0.0878 | 0.032* | |
C23 | 0.49120 (18) | 0.88841 (17) | 0.04133 (9) | 0.0237 (3) | |
C33 | 0.60597 (18) | 0.86647 (17) | −0.01208 (9) | 0.0245 (3) | |
C43 | 0.48171 (19) | 0.77153 (17) | 0.08953 (9) | 0.0265 (4) | |
C53 | 0.72385 (19) | 0.72304 (17) | −0.02725 (10) | 0.0280 (4) | |
O14 | 0.46858 (16) | 0.69176 (14) | 0.45087 (8) | 0.0393 (3) | |
O24 | 0.64556 (13) | 0.72099 (13) | 0.37746 (6) | 0.0294 (3) | |
O34 | 0.81310 (14) | 0.65154 (12) | 0.49520 (6) | 0.0298 (3) | |
O44 | 0.82825 (16) | 0.75958 (14) | 0.58413 (7) | 0.0406 (3) | |
C14 | 0.40566 (19) | 0.99632 (18) | 0.45498 (9) | 0.0246 (3) | |
H14 | 0.3419 | 0.9937 | 0.4243 | 0.030* | |
C24 | 0.53018 (18) | 0.87609 (17) | 0.46901 (9) | 0.0231 (3) | |
C34 | 0.62721 (18) | 0.87996 (17) | 0.51503 (9) | 0.0229 (3) | |
C44 | 0.55201 (18) | 0.75083 (17) | 0.43124 (9) | 0.0250 (3) | |
C54 | 0.76667 (19) | 0.75516 (17) | 0.53266 (9) | 0.0255 (3) | |
O1W | 0.89054 (16) | 0.44803 (13) | 0.38595 (7) | 0.0355 (3) | |
H1WA | 0.9691 (13) | 0.3815 (17) | 0.3980 (11) | 0.043* | |
H1WB | 0.8181 (14) | 0.427 (2) | 0.4012 (11) | 0.043* | |
O2W | 0.52974 (16) | 0.43747 (14) | 0.07384 (9) | 0.0416 (4) | |
H2WA | 0.471 (2) | 0.410 (2) | 0.0592 (12) | 0.050* | |
H2WB | 0.489 (2) | 0.5225 (10) | 0.0753 (13) | 0.050* | |
O3W | 0.77663 (15) | 0.17377 (13) | 0.02531 (7) | 0.0309 (3) | |
H3WA | 0.7214 (17) | 0.206 (2) | −0.0069 (8) | 0.037* | |
H3WB | 0.8619 (11) | 0.1694 (16) | 0.0105 (10) | 0.037* | |
O4W | 0.84376 (16) | 0.40591 (15) | 0.04555 (9) | 0.0445 (4) | |
H4WA | 0.798 (2) | 0.4736 (18) | 0.0202 (11) | 0.053* | |
H4WB | 0.9340 (12) | 0.392 (2) | 0.0418 (12) | 0.053* | |
O5W | 0.62544 (19) | 0.41145 (16) | 0.42080 (8) | 0.0485 (4) | |
H5WA | 0.572 (2) | 0.4963 (10) | 0.4270 (12) | 0.058* | |
H5WB | 0.602 (3) | 0.3695 (19) | 0.4556 (9) | 0.058* | |
O6W | 0.4270 (2) | 0.7324 (2) | 0.27846 (10) | 0.0684 (5) | |
H6WA | 0.464 (3) | 0.742 (3) | 0.2376 (6) | 0.082* | |
H6WB | 0.499 (2) | 0.708 (3) | 0.3036 (11) | 0.082* | |
O7W | 0.92981 (16) | 0.88579 (15) | 0.02230 (8) | 0.0403 (3) | |
H7WA | 0.8597 (17) | 0.9619 (10) | 0.0243 (12) | 0.048* | |
H7WB | 0.907 (2) | 0.8344 (17) | 0.0004 (11) | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02213 (12) | 0.02136 (12) | 0.02693 (13) | −0.00661 (9) | −0.00231 (9) | −0.00046 (9) |
Ni2 | 0.02518 (12) | 0.02285 (12) | 0.02769 (13) | −0.00958 (9) | −0.00516 (9) | 0.00117 (9) |
N11 | 0.0310 (8) | 0.0272 (8) | 0.0304 (8) | −0.0134 (7) | −0.0018 (6) | 0.0002 (6) |
N21 | 0.0271 (8) | 0.0314 (9) | 0.0338 (9) | −0.0072 (7) | −0.0058 (7) | 0.0062 (7) |
N31 | 0.0297 (8) | 0.0268 (8) | 0.0300 (8) | −0.0098 (6) | −0.0010 (6) | 0.0003 (6) |
C11 | 0.0406 (11) | 0.0301 (10) | 0.0405 (11) | −0.0124 (9) | −0.0022 (9) | 0.0026 (8) |
C21 | 0.0727 (17) | 0.0290 (11) | 0.0500 (13) | −0.0191 (11) | −0.0010 (12) | 0.0005 (9) |
C31 | 0.097 (2) | 0.0496 (15) | 0.0613 (16) | −0.0513 (16) | −0.0092 (15) | −0.0011 (12) |
C41 | 0.0644 (16) | 0.0653 (17) | 0.0583 (15) | −0.0474 (14) | −0.0157 (12) | 0.0029 (12) |
C51 | 0.0399 (11) | 0.0415 (11) | 0.0344 (10) | −0.0231 (9) | −0.0053 (8) | 0.0021 (8) |
C61 | 0.0366 (11) | 0.0508 (13) | 0.0588 (14) | −0.0194 (10) | −0.0206 (10) | 0.0066 (11) |
C71 | 0.0279 (10) | 0.0614 (15) | 0.0439 (12) | 0.0003 (10) | 0.0001 (9) | 0.0002 (11) |
C81 | 0.0327 (10) | 0.0352 (11) | 0.0376 (11) | −0.0088 (9) | 0.0024 (8) | −0.0005 (8) |
C91 | 0.0420 (13) | 0.0657 (16) | 0.0452 (13) | −0.0129 (12) | 0.0128 (10) | −0.0034 (12) |
C101 | 0.0656 (17) | 0.0691 (17) | 0.0309 (12) | −0.0259 (14) | 0.0069 (11) | 0.0001 (11) |
C111 | 0.0587 (14) | 0.0528 (14) | 0.0345 (11) | −0.0250 (12) | −0.0087 (10) | 0.0093 (10) |
C121 | 0.0385 (11) | 0.0343 (10) | 0.0359 (10) | −0.0136 (9) | −0.0071 (8) | 0.0045 (8) |
N12 | 0.0299 (8) | 0.0273 (8) | 0.0310 (8) | −0.0120 (6) | −0.0063 (6) | 0.0016 (6) |
N22 | 0.0387 (9) | 0.0221 (8) | 0.0371 (9) | −0.0083 (7) | −0.0084 (7) | −0.0021 (7) |
N32 | 0.0295 (8) | 0.0302 (8) | 0.0315 (8) | −0.0106 (7) | −0.0045 (6) | 0.0026 (6) |
C12 | 0.0358 (10) | 0.0310 (10) | 0.0347 (10) | −0.0106 (8) | −0.0036 (8) | −0.0008 (8) |
C22 | 0.0338 (10) | 0.0341 (11) | 0.0442 (12) | −0.0057 (9) | −0.0028 (9) | 0.0047 (9) |
C32 | 0.0334 (10) | 0.0536 (14) | 0.0415 (12) | −0.0093 (10) | −0.0143 (9) | 0.0074 (10) |
C42 | 0.0417 (12) | 0.0544 (14) | 0.0423 (12) | −0.0192 (11) | −0.0163 (10) | −0.0026 (10) |
C52 | 0.0339 (10) | 0.0344 (10) | 0.0378 (10) | −0.0157 (8) | −0.0078 (8) | −0.0012 (8) |
C62 | 0.0483 (12) | 0.0344 (11) | 0.0503 (13) | −0.0177 (10) | −0.0179 (10) | −0.0065 (9) |
C72 | 0.0544 (14) | 0.0396 (12) | 0.0405 (12) | −0.0148 (10) | 0.0049 (10) | −0.0124 (9) |
C82 | 0.0288 (9) | 0.0320 (10) | 0.0328 (10) | −0.0046 (8) | −0.0017 (8) | 0.0019 (8) |
C92 | 0.0370 (11) | 0.0519 (13) | 0.0341 (11) | −0.0096 (10) | 0.0012 (9) | 0.0046 (9) |
C102 | 0.0456 (13) | 0.0656 (16) | 0.0481 (14) | −0.0295 (12) | −0.0046 (10) | 0.0206 (12) |
C112 | 0.0519 (13) | 0.0531 (14) | 0.0531 (14) | −0.0337 (12) | −0.0106 (11) | 0.0129 (11) |
C122 | 0.0431 (11) | 0.0409 (11) | 0.0385 (11) | −0.0226 (10) | −0.0069 (9) | 0.0031 (9) |
O13 | 0.0347 (7) | 0.0292 (7) | 0.0381 (7) | −0.0186 (6) | −0.0081 (6) | 0.0060 (5) |
O23 | 0.0504 (9) | 0.0413 (8) | 0.0423 (8) | −0.0238 (7) | −0.0234 (7) | 0.0157 (6) |
O33 | 0.0299 (7) | 0.0215 (6) | 0.0593 (9) | −0.0103 (5) | −0.0099 (6) | 0.0004 (6) |
O43 | 0.0217 (7) | 0.0294 (8) | 0.1024 (14) | −0.0077 (6) | 0.0034 (8) | −0.0149 (8) |
C13 | 0.0226 (8) | 0.0248 (9) | 0.0318 (9) | −0.0097 (7) | −0.0009 (7) | −0.0011 (7) |
C23 | 0.0226 (8) | 0.0213 (8) | 0.0288 (9) | −0.0104 (7) | −0.0058 (7) | 0.0025 (7) |
C33 | 0.0202 (8) | 0.0203 (8) | 0.0329 (9) | −0.0076 (7) | −0.0058 (7) | 0.0003 (7) |
C43 | 0.0274 (9) | 0.0213 (8) | 0.0283 (9) | −0.0081 (7) | −0.0018 (7) | 0.0006 (7) |
C53 | 0.0247 (9) | 0.0216 (8) | 0.0358 (10) | −0.0074 (7) | −0.0050 (7) | 0.0002 (7) |
O14 | 0.0398 (8) | 0.0343 (7) | 0.0493 (8) | −0.0221 (6) | 0.0054 (6) | −0.0079 (6) |
O24 | 0.0229 (6) | 0.0324 (7) | 0.0296 (7) | −0.0075 (5) | −0.0013 (5) | −0.0059 (5) |
O34 | 0.0325 (7) | 0.0212 (6) | 0.0277 (6) | −0.0028 (5) | −0.0039 (5) | −0.0008 (5) |
O44 | 0.0393 (8) | 0.0311 (7) | 0.0415 (8) | 0.0002 (6) | −0.0194 (6) | −0.0053 (6) |
C14 | 0.0232 (8) | 0.0262 (9) | 0.0246 (8) | −0.0101 (7) | −0.0048 (6) | 0.0004 (7) |
C24 | 0.0204 (8) | 0.0206 (8) | 0.0252 (8) | −0.0064 (6) | 0.0010 (6) | −0.0009 (6) |
C34 | 0.0201 (8) | 0.0207 (8) | 0.0247 (8) | −0.0056 (6) | −0.0018 (6) | 0.0000 (6) |
C44 | 0.0209 (8) | 0.0212 (8) | 0.0296 (9) | −0.0045 (7) | −0.0064 (7) | −0.0001 (7) |
C54 | 0.0237 (8) | 0.0223 (8) | 0.0268 (9) | −0.0063 (7) | −0.0028 (7) | 0.0017 (7) |
O1W | 0.0334 (7) | 0.0256 (7) | 0.0435 (8) | −0.0085 (6) | −0.0046 (6) | 0.0010 (6) |
O2W | 0.0345 (8) | 0.0258 (7) | 0.0665 (10) | −0.0102 (6) | −0.0232 (7) | 0.0028 (7) |
O3W | 0.0305 (7) | 0.0307 (7) | 0.0309 (7) | −0.0112 (6) | −0.0068 (5) | 0.0000 (5) |
O4W | 0.0260 (7) | 0.0390 (8) | 0.0642 (10) | −0.0131 (6) | −0.0082 (7) | 0.0239 (7) |
O5W | 0.0579 (10) | 0.0347 (8) | 0.0489 (9) | −0.0187 (8) | 0.0117 (8) | −0.0067 (7) |
O6W | 0.0612 (12) | 0.0782 (14) | 0.0539 (11) | −0.0149 (11) | −0.0140 (9) | −0.0025 (10) |
O7W | 0.0400 (8) | 0.0335 (8) | 0.0486 (9) | −0.0154 (6) | −0.0061 (7) | −0.0041 (7) |
Ni1—O24 | 2.0437 (12) | C32—H32 | 0.9300 |
Ni1—N31 | 2.0512 (15) | C42—C52 | 1.385 (3) |
Ni1—N21 | 2.0764 (16) | C42—H42 | 0.9300 |
Ni1—N11 | 2.0852 (15) | C52—C62 | 1.507 (3) |
Ni1—O34 | 2.0950 (13) | C62—H62A | 0.9700 |
Ni1—O1W | 2.1241 (13) | C62—H62B | 0.9700 |
Ni2—O4W | 2.0448 (13) | C72—C82 | 1.510 (3) |
Ni2—N32 | 2.0528 (16) | C72—H72A | 0.9700 |
Ni2—O2W | 2.0668 (13) | C72—H72B | 0.9700 |
Ni2—O3W | 2.0695 (13) | C82—C92 | 1.388 (3) |
Ni2—N22 | 2.0778 (16) | C92—C102 | 1.370 (3) |
Ni2—N12 | 2.0995 (15) | C92—H92 | 0.9300 |
N11—C51 | 1.335 (2) | C102—C112 | 1.385 (4) |
N11—C11 | 1.342 (2) | C102—H102 | 0.9300 |
N21—C61 | 1.460 (3) | C112—C122 | 1.375 (3) |
N21—C71 | 1.472 (3) | C112—H112 | 0.9300 |
N21—H21N | 0.850 (9) | C122—H122 | 0.9300 |
N31—C121 | 1.336 (2) | O13—C43 | 1.260 (2) |
N31—C81 | 1.342 (2) | O23—C43 | 1.244 (2) |
C11—C21 | 1.373 (3) | O33—C53 | 1.246 (2) |
C11—H11 | 0.9300 | O43—C53 | 1.244 (2) |
C21—C31 | 1.375 (4) | C13—C23 | 1.391 (2) |
C21—H21 | 0.9300 | C13—C33i | 1.397 (2) |
C31—C41 | 1.367 (4) | C13—H13 | 0.9300 |
C31—H31 | 0.9300 | C23—C33 | 1.394 (2) |
C41—C51 | 1.379 (3) | C23—C43 | 1.527 (2) |
C41—H41 | 0.9300 | C33—C13i | 1.397 (2) |
C51—C61 | 1.500 (3) | C33—C53 | 1.517 (2) |
C61—H61A | 0.9700 | O14—C44 | 1.240 (2) |
C61—H61B | 0.9700 | O24—C44 | 1.273 (2) |
C71—C81 | 1.503 (3) | O34—C54 | 1.269 (2) |
C71—H71A | 0.9700 | O44—C54 | 1.249 (2) |
C71—H71B | 0.9700 | C14—C34ii | 1.391 (2) |
C81—C91 | 1.388 (3) | C14—C24 | 1.393 (2) |
C91—C101 | 1.378 (4) | C14—H14 | 0.9300 |
C91—H91 | 0.9300 | C24—C34 | 1.405 (2) |
C101—C111 | 1.378 (3) | C24—C44 | 1.511 (2) |
C101—H101 | 0.9300 | C34—C14ii | 1.391 (2) |
C111—C121 | 1.376 (3) | C34—C54 | 1.515 (2) |
C111—H111 | 0.9300 | O1W—H1WA | 0.847 (9) |
C121—H121 | 0.9300 | O1W—H1WB | 0.845 (9) |
N12—C12 | 1.338 (2) | O2W—H2WA | 0.835 (9) |
N12—C52 | 1.346 (2) | O2W—H2WB | 0.830 (9) |
N22—C72 | 1.469 (3) | O3W—H3WA | 0.836 (9) |
N22—C62 | 1.473 (3) | O3W—H3WB | 0.837 (9) |
N22—H22N | 0.842 (9) | O4W—H4WA | 0.833 (9) |
N32—C122 | 1.337 (3) | O4W—H4WB | 0.833 (9) |
N32—C82 | 1.342 (2) | O5W—H5WA | 0.850 (9) |
C12—C22 | 1.375 (3) | O5W—H5WB | 0.843 (9) |
C12—H12 | 0.9300 | O6W—H6WA | 0.849 (10) |
C22—C32 | 1.379 (3) | O6W—H6WB | 0.846 (10) |
C22—H22 | 0.9300 | O7W—H7WA | 0.820 (9) |
C32—C42 | 1.380 (3) | O7W—H7WB | 0.837 (9) |
O24—Ni1—N31 | 95.65 (6) | C122—N32—C82 | 118.79 (17) |
O24—Ni1—N21 | 176.24 (6) | C122—N32—Ni2 | 127.29 (14) |
N31—Ni1—N21 | 82.88 (6) | C82—N32—Ni2 | 113.88 (13) |
O24—Ni1—N11 | 102.50 (6) | N12—C12—C22 | 123.12 (19) |
N31—Ni1—N11 | 88.32 (6) | N12—C12—H12 | 118.4 |
N21—Ni1—N11 | 80.95 (6) | C22—C12—H12 | 118.4 |
O24—Ni1—O34 | 87.32 (5) | C12—C22—C32 | 118.7 (2) |
N31—Ni1—O34 | 177.01 (5) | C12—C22—H22 | 120.6 |
N21—Ni1—O34 | 94.17 (6) | C32—C22—H22 | 120.6 |
N11—Ni1—O34 | 90.80 (5) | C22—C32—C42 | 118.95 (19) |
O24—Ni1—O1W | 88.92 (5) | C22—C32—H32 | 120.5 |
N31—Ni1—O1W | 90.39 (6) | C42—C32—H32 | 120.5 |
N21—Ni1—O1W | 87.62 (6) | C32—C42—C52 | 119.2 (2) |
N11—Ni1—O1W | 168.58 (6) | C32—C42—H42 | 120.4 |
O34—Ni1—O1W | 89.92 (5) | C52—C42—H42 | 120.4 |
O4W—Ni2—N32 | 174.15 (7) | N12—C52—C42 | 121.82 (19) |
O4W—Ni2—O2W | 91.77 (6) | N12—C52—C62 | 115.34 (17) |
N32—Ni2—O2W | 87.28 (6) | C42—C52—C62 | 122.84 (18) |
O4W—Ni2—O3W | 89.55 (6) | N22—C62—C52 | 110.56 (15) |
N32—Ni2—O3W | 96.25 (6) | N22—C62—H62A | 109.5 |
O2W—Ni2—O3W | 92.61 (6) | C52—C62—H62A | 109.5 |
O4W—Ni2—N22 | 90.77 (7) | N22—C62—H62B | 109.5 |
N32—Ni2—N22 | 83.48 (7) | C52—C62—H62B | 109.5 |
O2W—Ni2—N22 | 91.06 (6) | H62A—C62—H62B | 108.1 |
O3W—Ni2—N22 | 176.31 (6) | N22—C72—C82 | 114.44 (16) |
O4W—Ni2—N12 | 93.58 (6) | N22—C72—H72A | 108.6 |
N32—Ni2—N12 | 86.57 (6) | C82—C72—H72A | 108.6 |
O2W—Ni2—N12 | 170.22 (6) | N22—C72—H72B | 108.6 |
O3W—Ni2—N12 | 95.61 (6) | C82—C72—H72B | 108.6 |
N22—Ni2—N12 | 80.70 (6) | H72A—C72—H72B | 107.6 |
C51—N11—C11 | 118.44 (17) | N32—C82—C92 | 121.1 (2) |
C51—N11—Ni1 | 113.61 (13) | N32—C82—C72 | 117.32 (17) |
C11—N11—Ni1 | 127.95 (14) | C92—C82—C72 | 121.54 (19) |
C61—N21—C71 | 115.25 (19) | C102—C92—C82 | 119.4 (2) |
C61—N21—Ni1 | 108.77 (12) | C102—C92—H92 | 120.3 |
C71—N21—Ni1 | 108.88 (12) | C82—C92—H92 | 120.3 |
C61—N21—H21N | 109.8 (15) | C92—C102—C112 | 119.7 (2) |
C71—N21—H21N | 108.7 (15) | C92—C102—H102 | 120.1 |
Ni1—N21—H21N | 104.9 (15) | C112—C102—H102 | 120.1 |
C121—N31—C81 | 118.80 (17) | C122—C112—C102 | 117.7 (2) |
C121—N31—Ni1 | 126.87 (13) | C122—C112—H112 | 121.1 |
C81—N31—Ni1 | 114.23 (13) | C102—C112—H112 | 121.1 |
N11—C11—C21 | 122.5 (2) | N32—C122—C112 | 123.3 (2) |
N11—C11—H11 | 118.7 | N32—C122—H122 | 118.4 |
C21—C11—H11 | 118.7 | C112—C122—H122 | 118.4 |
C11—C21—C31 | 118.8 (2) | C23—C13—C33i | 121.54 (16) |
C11—C21—H21 | 120.6 | C23—C13—H13 | 119.2 |
C31—C21—H21 | 120.6 | C33i—C13—H13 | 119.2 |
C41—C31—C21 | 118.9 (2) | C13—C23—C33 | 118.50 (15) |
C41—C31—H31 | 120.6 | C13—C23—C43 | 119.30 (15) |
C21—C31—H31 | 120.6 | C33—C23—C43 | 122.14 (15) |
C31—C41—C51 | 119.8 (2) | C23—C33—C13i | 119.95 (15) |
C31—C41—H41 | 120.1 | C23—C33—C53 | 121.16 (15) |
C51—C41—H41 | 120.1 | C13i—C33—C53 | 118.89 (15) |
N11—C51—C41 | 121.5 (2) | O23—C43—O13 | 125.05 (17) |
N11—C51—C61 | 116.53 (17) | O23—C43—C23 | 117.32 (15) |
C41—C51—C61 | 121.9 (2) | O13—C43—C23 | 117.60 (15) |
N21—C61—C51 | 112.56 (16) | O43—C53—O33 | 125.45 (17) |
N21—C61—H61A | 109.1 | O43—C53—C33 | 116.74 (15) |
C51—C61—H61A | 109.1 | O33—C53—C33 | 117.81 (15) |
N21—C61—H61B | 109.1 | C44—O24—Ni1 | 119.20 (11) |
C51—C61—H61B | 109.1 | C54—O34—Ni1 | 125.34 (11) |
H61A—C61—H61B | 107.8 | C34ii—C14—C24 | 122.74 (16) |
N21—C71—C81 | 113.87 (16) | C34ii—C14—H14 | 118.6 |
N21—C71—H71A | 108.8 | C24—C14—H14 | 118.6 |
C81—C71—H71A | 108.8 | C14—C24—C34 | 118.73 (15) |
N21—C71—H71B | 108.8 | C14—C24—C44 | 116.35 (15) |
C81—C71—H71B | 108.8 | C34—C24—C44 | 124.91 (15) |
H71A—C71—H71B | 107.7 | C14ii—C34—C24 | 118.54 (15) |
N31—C81—C91 | 121.2 (2) | C14ii—C34—C54 | 118.87 (15) |
N31—C81—C71 | 116.60 (18) | C24—C34—C54 | 122.59 (15) |
C91—C81—C71 | 122.08 (19) | O14—C44—O24 | 124.36 (16) |
C101—C91—C81 | 119.3 (2) | O14—C44—C24 | 117.95 (15) |
C101—C91—H91 | 120.3 | O24—C44—C24 | 117.36 (15) |
C81—C91—H91 | 120.3 | O44—C54—O34 | 123.66 (16) |
C91—C101—C111 | 119.2 (2) | O44—C54—C34 | 117.88 (15) |
C91—C101—H101 | 120.4 | O34—C54—C34 | 118.45 (15) |
C111—C101—H101 | 120.4 | Ni1—O1W—H1WA | 120.3 (14) |
C121—C111—C101 | 118.5 (2) | Ni1—O1W—H1WB | 120.8 (14) |
C121—C111—H111 | 120.8 | H1WA—O1W—H1WB | 106.1 (13) |
C101—C111—H111 | 120.8 | Ni2—O2W—H2WA | 122.1 (14) |
N31—C121—C111 | 122.9 (2) | Ni2—O2W—H2WB | 128.8 (15) |
N31—C121—H121 | 118.5 | H2WA—O2W—H2WB | 109.0 (14) |
C111—C121—H121 | 118.5 | Ni2—O3W—H3WA | 116.2 (15) |
C12—N12—C52 | 118.14 (16) | Ni2—O3W—H3WB | 97.6 (13) |
C12—N12—Ni2 | 128.48 (13) | H3WA—O3W—H3WB | 107.7 (13) |
C52—N12—Ni2 | 112.71 (12) | Ni2—O4W—H4WA | 121.5 (15) |
C72—N22—C62 | 115.19 (17) | Ni2—O4W—H4WB | 129.7 (15) |
C72—N22—Ni2 | 109.51 (12) | H4WA—O4W—H4WB | 108.7 (15) |
C62—N22—Ni2 | 106.37 (12) | H5WA—O5W—H5WB | 105.7 (14) |
C72—N22—H22N | 107.9 (16) | H6WA—O6W—H6WB | 105.7 (15) |
C62—N22—H22N | 107.6 (16) | H7WA—O7W—H7WB | 109.3 (14) |
Ni2—N22—H22N | 110.3 (16) | ||
O24—Ni1—N11—C51 | 169.15 (13) | N12—Ni2—N32—C122 | −94.24 (17) |
N31—Ni1—N11—C51 | −95.43 (13) | O2W—Ni2—N32—C82 | −88.96 (13) |
N21—Ni1—N11—C51 | −12.38 (13) | O3W—Ni2—N32—C82 | 178.71 (13) |
O34—Ni1—N11—C51 | 81.72 (13) | N22—Ni2—N32—C82 | 2.42 (13) |
O1W—Ni1—N11—C51 | −11.8 (4) | N12—Ni2—N32—C82 | 83.44 (13) |
O24—Ni1—N11—C11 | −11.38 (17) | C52—N12—C12—C22 | −1.1 (3) |
N31—Ni1—N11—C11 | 84.03 (17) | Ni2—N12—C12—C22 | −170.96 (15) |
N21—Ni1—N11—C11 | 167.09 (17) | N12—C12—C22—C32 | −0.6 (3) |
O34—Ni1—N11—C11 | −98.82 (16) | C12—C22—C32—C42 | 1.3 (3) |
O1W—Ni1—N11—C11 | 167.6 (3) | C22—C32—C42—C52 | −0.3 (3) |
N31—Ni1—N21—C61 | 112.18 (14) | C12—N12—C52—C42 | 2.1 (3) |
N11—Ni1—N21—C61 | 22.76 (13) | Ni2—N12—C52—C42 | 173.49 (16) |
O34—Ni1—N21—C61 | −67.39 (14) | C12—N12—C52—C62 | −178.17 (18) |
O1W—Ni1—N21—C61 | −157.13 (14) | Ni2—N12—C52—C62 | −6.8 (2) |
N31—Ni1—N21—C71 | −14.15 (15) | C32—C42—C52—N12 | −1.4 (3) |
N11—Ni1—N21—C71 | −103.57 (15) | C32—C42—C52—C62 | 178.9 (2) |
O34—Ni1—N21—C71 | 166.28 (15) | C72—N22—C62—C52 | 80.8 (2) |
O1W—Ni1—N21—C71 | 76.54 (15) | Ni2—N22—C62—C52 | −40.7 (2) |
O24—Ni1—N31—C121 | 12.69 (16) | N12—C52—C62—N22 | 32.6 (3) |
N21—Ni1—N31—C121 | −170.79 (17) | C42—C52—C62—N22 | −147.7 (2) |
N11—Ni1—N31—C121 | −89.70 (16) | C62—N22—C72—C82 | −107.2 (2) |
O1W—Ni1—N31—C121 | 101.65 (16) | Ni2—N22—C72—C82 | 12.6 (2) |
O24—Ni1—N31—C81 | −171.06 (14) | C122—N32—C82—C92 | 0.2 (3) |
N21—Ni1—N31—C81 | 5.45 (14) | Ni2—N32—C82—C92 | −177.70 (15) |
N11—Ni1—N31—C81 | 86.54 (14) | C122—N32—C82—C72 | −177.90 (18) |
O1W—Ni1—N31—C81 | −82.11 (14) | Ni2—N32—C82—C72 | 4.2 (2) |
C51—N11—C11—C21 | −2.4 (3) | N22—C72—C82—N32 | −11.7 (3) |
Ni1—N11—C11—C21 | 178.11 (16) | N22—C72—C82—C92 | 170.26 (19) |
N11—C11—C21—C31 | 1.2 (3) | N32—C82—C92—C102 | −1.4 (3) |
C11—C21—C31—C41 | 0.5 (4) | C72—C82—C92—C102 | 176.6 (2) |
C21—C31—C41—C51 | −0.9 (4) | C82—C92—C102—C112 | 1.7 (3) |
C11—N11—C51—C41 | 2.0 (3) | C92—C102—C112—C122 | −0.8 (3) |
Ni1—N11—C51—C41 | −178.51 (18) | C82—N32—C122—C112 | 0.8 (3) |
C11—N11—C51—C61 | 179.36 (18) | Ni2—N32—C122—C112 | 178.38 (16) |
Ni1—N11—C51—C61 | −1.1 (2) | C102—C112—C122—N32 | −0.5 (3) |
C31—C41—C51—N11 | −0.3 (4) | C33i—C13—C23—C33 | −0.6 (3) |
C31—C41—C51—C61 | −177.6 (2) | C33i—C13—C23—C43 | 176.80 (15) |
C71—N21—C61—C51 | 92.9 (2) | C13—C23—C33—C13i | 0.5 (3) |
Ni1—N21—C61—C51 | −29.7 (2) | C43—C23—C33—C13i | −176.73 (15) |
N11—C51—C61—N21 | 21.2 (3) | C13—C23—C33—C53 | −179.70 (16) |
C41—C51—C61—N21 | −161.5 (2) | C43—C23—C33—C53 | 3.0 (2) |
C61—N21—C71—C81 | −102.0 (2) | C13—C23—C43—O23 | −96.9 (2) |
Ni1—N21—C71—C81 | 20.5 (2) | C33—C23—C43—O23 | 80.4 (2) |
C121—N31—C81—C91 | −1.5 (3) | C13—C23—C43—O13 | 81.3 (2) |
Ni1—N31—C81—C91 | −178.03 (18) | C33—C23—C43—O13 | −101.4 (2) |
C121—N31—C81—C71 | −178.55 (19) | C23—C33—C53—O43 | −137.43 (19) |
Ni1—N31—C81—C71 | 4.9 (2) | C13i—C33—C53—O43 | 42.3 (2) |
N21—C71—C81—N31 | −17.5 (3) | C23—C33—C53—O33 | 42.3 (2) |
N21—C71—C81—C91 | 165.4 (2) | C13i—C33—C53—O33 | −137.96 (18) |
N31—C81—C91—C101 | 0.9 (4) | N31—Ni1—O24—C44 | −173.47 (13) |
C71—C81—C91—C101 | 177.9 (2) | N11—Ni1—O24—C44 | −83.95 (13) |
C81—C91—C101—C111 | −0.1 (4) | O34—Ni1—O24—C44 | 6.28 (13) |
C91—C101—C111—C121 | −0.2 (4) | O1W—Ni1—O24—C44 | 96.25 (13) |
C81—N31—C121—C111 | 1.2 (3) | O24—Ni1—O34—C54 | −82.65 (14) |
Ni1—N31—C121—C111 | 177.28 (16) | N21—Ni1—O34—C54 | 100.82 (14) |
C101—C111—C121—N31 | −0.4 (3) | N11—Ni1—O34—C54 | 19.83 (14) |
O4W—Ni2—N12—C12 | −112.57 (17) | O1W—Ni1—O34—C54 | −171.57 (14) |
N32—Ni2—N12—C12 | 73.28 (16) | C34ii—C14—C24—C34 | −0.4 (3) |
O3W—Ni2—N12—C12 | −22.67 (17) | C34ii—C14—C24—C44 | −178.86 (16) |
N22—Ni2—N12—C12 | 157.23 (17) | C14—C24—C34—C14ii | 0.4 (3) |
O4W—Ni2—N12—C52 | 77.12 (14) | C44—C24—C34—C14ii | 178.70 (16) |
N32—Ni2—N12—C52 | −97.02 (14) | C14—C24—C34—C54 | −179.04 (15) |
O3W—Ni2—N12—C52 | 167.02 (13) | C44—C24—C34—C54 | −0.7 (3) |
N22—Ni2—N12—C52 | −13.07 (13) | Ni1—O24—C44—O14 | −118.09 (17) |
O4W—Ni2—N22—C72 | 170.62 (14) | Ni1—O24—C44—C24 | 68.69 (17) |
N32—Ni2—N22—C72 | −8.30 (14) | C14—C24—C44—O14 | −74.9 (2) |
O2W—Ni2—N22—C72 | 78.84 (14) | C34—C24—C44—O14 | 106.7 (2) |
N12—Ni2—N22—C72 | −95.87 (14) | C14—C24—C44—O24 | 98.72 (18) |
O4W—Ni2—N22—C62 | −64.30 (13) | C34—C24—C44—O24 | −79.6 (2) |
N32—Ni2—N22—C62 | 116.78 (13) | Ni1—O34—C54—O44 | −124.30 (17) |
O2W—Ni2—N22—C62 | −156.09 (13) | Ni1—O34—C54—C34 | 56.8 (2) |
N12—Ni2—N22—C62 | 29.21 (13) | C14ii—C34—C54—O44 | 15.3 (2) |
O2W—Ni2—N32—C122 | 93.37 (17) | C24—C34—C54—O44 | −165.23 (17) |
O3W—Ni2—N32—C122 | 1.04 (17) | C14ii—C34—C54—O34 | −165.70 (16) |
N22—Ni2—N32—C122 | −175.25 (17) | C24—C34—C54—O34 | 13.7 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21N···O34iii | 0.85 (2) | 2.15 (2) | 2.978 (2) | 166 (2) |
O1W—H1WA···O44iii | 0.85 (2) | 1.99 (2) | 2.827 (2) | 170 (2) |
O1W—H1WB···O5W | 0.85 (2) | 1.96 (2) | 2.793 (3) | 167 (2) |
O5W—H5WA···O14 | 0.85 (1) | 1.98 (1) | 2.821 (2) | 172 (2) |
O5W—H5WB···O14iv | 0.84 (2) | 2.02 (2) | 2.852 (2) | 167 (2) |
C21—H21···O5Wv | 0.93 | 2.59 | 3.375 (3) | 142 |
C31—H31···O44vi | 0.93 | 2.59 | 3.435 (4) | 151 |
N22—H22N···O23 | 0.84 (2) | 2.30 (1) | 3.139 (2) | 177 (3) |
O2W—H2WA···O33vii | 0.84 (2) | 1.91 (2) | 2.742 (2) | 173 (2) |
O2W—H2WB···O13 | 0.83 (1) | 1.97 (1) | 2.797 (2) | 179 (3) |
O3W—H3WA···O13vii | 0.84 (2) | 1.79 (2) | 2.627 (2) | 177 (2) |
O3W—H3WB···O7Wviii | 0.84 (1) | 1.92 (1) | 2.742 (2) | 167 (2) |
O4W—H4WA···O33 | 0.83 (2) | 1.81 (2) | 2.642 (2) | 173 (2) |
O4W—H4WB···O43viii | 0.83 (2) | 1.89 (2) | 2.677 (2) | 158 (2) |
O6W—H6WA···O23 | 0.85 (2) | 2.05 (2) | 2.896 (2) | 171 (3) |
O7W—H7WA···O3Wv | 0.82 (1) | 2.07 (1) | 2.816 (2) | 151 (2) |
O7W—H7WB···O43 | 0.84 (2) | 1.87 (2) | 2.705 (2) | 174 (2) |
C12—H12···O7Wix | 0.93 | 2.51 | 3.435 (3) | 176 |
O6W—H6WB···O24 | 0.85 (2) | 2.21 (2) | 3.025 (2) | 160 (3) |
C72—H72B···O5W | 0.97 | 2.60 | 3.490 (3) | 153 |
Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z; (vi) −x+2, −y+2, −z+1; (vii) −x+1, −y+1, −z; (viii) −x+2, −y+1, −z; (ix) x, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ni(C9H6O4)(C12H13N3)(H2O)] | [Ni2(C10H2O8)(C12H13N3)2(H2O)2]·[Ni(C12H13N3)(H2O)3]2(C10H2O8)·6H2O' |
Mr | 454.12 | 1784.32 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 150 | 298 |
a, b, c (Å) | 18.233 (3), 10.4511 (14), 20.898 (3) | 9.8485 (6), 10.7208 (6), 19.4924 (11) |
α, β, γ (°) | 90, 93.081 (2), 90 | 85.008 (1), 82.823 (1), 65.2930 (8) |
V (Å3) | 3976.3 (9) | 1853.65 (19) |
Z | 8 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.02 | 1.10 |
Crystal size (mm) | 0.39 × 0.13 × 0.12 | 0.41 × 0.37 × 0.07 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) |
Tmin, Tmax | 0.86, 0.88 | 0.65, 0.93 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15811, 4399, 3562 | 15507, 7916, 6969 |
Rint | 0.028 | 0.015 |
(sin θ/λ)max (Å−1) | 0.656 | 0.659 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.125, 1.43 | 0.032, 0.087, 1.09 |
No. of reflections | 4399 | 7916 |
No. of parameters | 280 | 562 |
No. of restraints | 4 | 24 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.72, −0.37 | 0.60, −0.31 |
Computer programs: SMART (Bruker, 2001), SAINT-NT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Ni1—N31 | 2.062 (2) | Ni1—N11 | 2.088 (2) |
Ni1—O22 | 2.0674 (18) | Ni1—O1W | 2.098 (2) |
Ni1—O32i | 2.068 (2) | Ni1—N21 | 2.106 (2) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O12 | 0.84 (2) | 1.79 (2) | 2.603 (3) | 162 (2) |
C82—H82A···O22 | 0.99 | 2.24 | 2.916 (3) | 124 |
C121—H121···O32i | 0.95 | 2.55 | 3.110 (4) | 118 |
O1W—H1WA···O42i | 0.84 (2) | 1.814 (15) | 2.632 (3) | 163 (3) |
C71—H71B···O22ii | 0.99 | 2.54 | 3.205 (4) | 125 |
C121—H121···O12i | 0.95 | 2.33 | 3.114 (4) | 139 |
C22—H22···O12iii | 0.95 | 2.49 | 3.309 (3) | 144 |
C52—H52···O42iv | 0.95 | 2.48 | 3.191 (3) | 131 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+3/2, −z+1. |
Ni1—O24 | 2.0437 (12) | Ni2—O4W | 2.0448 (13) |
Ni1—N31 | 2.0512 (15) | Ni2—N32 | 2.0528 (16) |
Ni1—N21 | 2.0764 (16) | Ni2—O2W | 2.0668 (13) |
Ni1—N11 | 2.0852 (15) | Ni2—O3W | 2.0695 (13) |
Ni1—O34 | 2.0950 (13) | Ni2—N22 | 2.0778 (16) |
Ni1—O1W | 2.1241 (13) | Ni2—N12 | 2.0995 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21N···O34i | 0.85 (2) | 2.147 (17) | 2.978 (2) | 166 (2) |
O1W—H1WA···O44i | 0.847 (17) | 1.988 (16) | 2.827 (2) | 170.4 (18) |
O1W—H1WB···O5W | 0.846 (18) | 1.962 (18) | 2.793 (3) | 166.6 (19) |
O5W—H5WA···O14 | 0.850 (11) | 1.978 (11) | 2.821 (2) | 171.8 (19) |
O5W—H5WB···O14ii | 0.84 (2) | 2.02 (2) | 2.852 (2) | 167.4 (17) |
C21—H21···O5Wiii | 0.93 | 2.59 | 3.375 (3) | 142 |
C31—H31···O44iv | 0.93 | 2.59 | 3.435 (4) | 151 |
N22—H22N···O23 | 0.84 (2) | 2.296 (12) | 3.139 (2) | 177 (3) |
O2W—H2WA···O33v | 0.84 (2) | 1.91 (2) | 2.742 (2) | 173 (2) |
O2W—H2WB···O13 | 0.830 (10) | 1.968 (10) | 2.797 (2) | 179 (3) |
O3W—H3WA···O13v | 0.835 (17) | 1.792 (17) | 2.627 (2) | 177.1 (19) |
O3W—H3WB···O7Wvi | 0.837 (14) | 1.921 (14) | 2.742 (2) | 166.7 (15) |
O4W—H4WA···O33 | 0.833 (19) | 1.814 (19) | 2.642 (2) | 173 (2) |
O4W—H4WB···O43vi | 0.832 (15) | 1.889 (17) | 2.677 (2) | 157.6 (19) |
O6W—H6WA···O23 | 0.850 (17) | 2.054 (16) | 2.896 (2) | 171 (3) |
O7W—H7WA···O3Wiii | 0.820 (12) | 2.069 (10) | 2.816 (2) | 151.2 (16) |
O7W—H7WB···O43 | 0.840 (19) | 1.87 (2) | 2.705 (2) | 174 (2) |
C12—H12···O7Wvii | 0.93 | 2.51 | 3.435 (3) | 176 |
O6W—H6WB···O24 | 0.85 (2) | 2.21 (2) | 3.025 (2) | 160 (3) |
C72—H72B···O5W | 0.97 | 2.60 | 3.490 (3) | 153 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+2, −y+2, −z+1; (v) −x+1, −y+1, −z; (vi) −x+2, −y+1, −z; (vii) x, y−1, z. |