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The title compound, [Ni(C28H30N3O2PS)], crystallizes with two independent mol­ecules in the asymmetric unit. The NiII atoms are in significantly deformed square-planar environments formed by an ONNP donor set from a thio­semi­carbazide-based tetra­dentate ligand. The NiII atom and the ONN donor atoms are nearly coplanar, while the P atom deviates from their mean planes by 0.278 (4) and 0.202 (4) Å for the two independent mol­ecules. The P-containing chelate rings are remarkably non-planar, adopting a boat conformation, which is unusual for chelate rings in transition metal complexes with thio­semicarbazide-based tetra­dentate ligands. The orientation of the eth­oxy group bonded to this chelate ring is caused by an intra­molecular C—H...π inter­action with the opposing phenyl ring. There are no hydrogen bonds; instead, numerous inter­molecular C—H...π inter­actions dominate in the crystal packing.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106018932/av3009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106018932/av3009Isup2.hkl
Contains datablock I

CCDC reference: 616124

Comment top

Transition metal complexes with thiosemicarbazide-based ligands have been very extensively investigated because of their interesting structural properties and biological activities (Campbell, 1975; Padhye & Kauffman, 1985; West et al., 1991; Casas et al., 2000; Beraldo & Gambino, 2004). This work is a part of our systematic study of transition metal complexes containing thiosemicarbazide-based ligands, aimed at investigating their structural properties and the influence of the thiosemicarbazide substituents on the properties of the complexes (Leovac et al., 2000; Bogdanović et al., 2001; Leovac et al., 2002).

Among the more than 150 crystal structures of metal complexes with isothiosemicarbazide-based ligands (ITSC), the title compound, [NiL1], (I), represents a rare example of a transition metal complex involving a P atom in its coordination sphere. Only one other metal complex, [NiL2], [Ni(C30H28N3O2PS)], (II), with an ITSC ligand possessing a P atom as one of ligator atoms, has hitherto been reported (Bogdanović et al., 1998).

The asymmetric unit of the [NiL1] complex (Fig. 1) contains two crystallographically independent molecules, [NiL1]a and [NiL1]b. These molecules are of the same composition but have slightly different conformations. The mutual orientation of the molecules is shown in Fig. 2, from which it can be seen that the angle between the coordination plane of molecules [NiL1]a and [NiL1]b is 56.4 (1)°. The square-planar coordination geometry of the Ni atom is significantly deformed. Atoms Ni1, O1, N1 and N3 are nearly coplanar, but atoms P1 deviate from the mean plane by 0.278 (4), 0.203 (4) and 0.280 (3) Å for the molecules [NiL1]a, [NiL1]b and [NiL2], respectively. The L1 ligands are coordinated to the Ni atom through four atoms (O1, N1, P1 and N3), forming three fused chelate rings (Fig. 1), one being five-membered (ring A; Ni1/N1/N2/C1/N3), and two six-membered, ring B (Ni1/N1/C4–C6/O1) and ring C (Ni1/N3/C10/C12/C11/P1). Rings A and B are nearly planar, with delocalized π bonds (Table 1). However, ring C is non-planar, adopting a boat conformation with atoms Ni1, N3, C11 and C12 approximately coplanar. The conformational parameters (Cremer & Pople, 1975) of all three complex molecules, [NiL1]a, [NiL1]b and [NiL2] (Table 2), are very similar. This non-planar form of a six-membered chelate ring in metal complexes with ITSC ligands is unusual and could be caused by (a) the addition of EtOH across the azomethine N3C10 bonds and/or (b) the presence of P atoms, which tends to decrease the Ni1—P1—C11 angles, as described by Brčeski et al. (2003).

The conformation of ring C in similar square-planar metal complexes [(III) in the scheme above] that possess a triphenylphosphine fragment and two condensed chelate rings were also analyzed. In almost all of the 29 examples fiund in the Cambridge Structural Database (version of April 2005; Allen, 2002), the six-membered rings were more or less non-planar, with an average value of 22.3° for the largest C—P—M—N torsion angle (C1—P—M—N). On the other hand, the most planar part of the rings was the P—C1—C2—C3 fragment, (III), with a mean P—C1—C2—C3 torsion angle of 5.7°. As shown in Fig. 3, a direct relation exists between the values of the C1—P—M—N torsion angle and the displacement of the P atom (ΔP) from the mean plane of the chelate ring. The rings are the most puckered when the N—C3 and C3—C2 bonds are single bonds, which enables additional rotation around them. For this reason, four of the six highest ΔP values are found for [NiL1], described in this work, and the previously published [NiL2] (Bogdanović et al., 1998) and [PtL3]CHCl3, [Pt(C44H32N2O2P2)](CCl3H) (Burger et al., 2003), all of which are labeled by circles in Fig. 3.

It was considered worthwhile to analyze the orientation of the ethoxy –O2—C9H2—C8H3 group. Although the rotation around the O2—C9 and C9—C8 single bonds is not restricted, the orientation of the ethoxy group is very similar in all of the three compared molecules [NiL1]a, [NiL1]b and [NiL2]. An explanation for this structural behavior can be found in intramolecular C—H···π interactions between the C8 methyl group and the Ph2 phenyl ring (Fig. 2), which was not observed in the previously published crystal structure of [NiL2] (Bogdanović et al., 1998). The geometrical parameters of this interaction for the [NiL1]a, [NiL1]b and [NiL2] complexes are listed in Table 3.

There are no intermolecular hydrogen bonds or significant ππ interactions with participation of the phenyl rings from the triphenylphosphine fragment in the crystal of the [NiL1] complex. However, numerous intermolecular C—H···π interactions are found in the crystal packing. The geometrical parameters listed in Table 3 were calculated for normalized C—H distances (1.08 Å) as is usual for the analysis of C—H···π interactions (Desiraju & Steiner, 1999). Four interactions have a H···Ω distance (where Ω is the midpoint of the ring) shorter than 2.70 Å. It is known that chelate rings with π delocalized bonds are able to participate in C—H···π interactions as π acceptors (Bogdanović et al., 2002), which was here observed in the case of rings A and B in [NiL1]b. The [NiL1]b molecule forms as many as seven intermolecular interactions (four as C—H donor and three as π acceptor). Generally speaking, it can be concluded that C—H···π interactions play a dominant role in the crystal packing.

The existence of C—H···π interactions in (III), as well as the mutual position of the three phenyl rings bonded to one P atom, was also analyzed. Almost all of the 29 structures lack significant intermolecular hydrogen bonds (25 in total) but form C—H···π interactions with phenyl or chelate rings acting as π acceptors. Comparing the angle between the mean planes of the phenyl rings bonded to the P atom and taking into account their position relative to the coordination plane, it was found that the conformations of the triphenylphosphine structural part in all 29 crystal structures, including the structures presented in this work, are very similar. Such a mutual position of the phenyl rings avoids short and destabilizing H···H contacts of their H atoms in the ortho positions. Nevertheless, it is interesting to note the existence of three short H···C contacts between an H atom in the ortho position and a C atom bonded to the P atom from a neighboring phenyl group. These H···C distances range from 2.5 to 2.8 Å, with C—H···C angles of about 110°. A similar orientation of the phenyl rings exists in uncoordinated triphenylphosphine and its derivatives (Daly, 1964; Dunne & Orpen, 1991; Chekhlov, 1993; Bruckmann et al., 1995; Kooijman et al., 1998; Ziemer et al., 2000), suggesting the presented mutual orientation of phenyl rings is the most stable.

Experimental top

The title complex was obtained by the reaction between a warm (about 313 K) ethanol solution containing 0.5 mmol of each of [Ni(L)NH3]·2H2O (L, dianion 2,4-pentandione S-methylisothiosemicarbazone) (Leovac et al., 1993) and 2-(diphenyl-phosphino)benzaldehyde.

Refinement top

All H atoms are found in a difference Fourier map, but they were placed at geometrically calculated positions and refined using a riding model. H atoms from methyl groups are treated with HFIX 137 instruction. Isotropic displacement parameters are equal to 1.2 (or 1.5 for methyl groups) times the equivalent isotropic displacement parameter of the parent atom.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. ORTEPIII (Burnett & Johnson, 1996) drawing of [NiL1], with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. View of the mutual orientation of the [NiL1]a and [NiL1]b molecules. Displacement ellipsoids are drawn at the 30% probability level. Some H atoms have been omitted for clarity. Π is the plane defined by atoms Ni1, N1, N3 and O1. Intramolecular C—H···π interactions are represented by dotted lines.
[Figure 3] Fig. 3. Relation between the values of the C1—P—M—N torsion angle and the displacement of the P atom from the mean plane of the chelate ring. Crystal structures are represented by squares, except those that possess the N—C3 and C3—C2 single bonds (represented by circles).
[4-(2-diphenylphosphino-α-ethoxybenzyl-κP)-S-methyl-1-(4-oxo-2- pentyl-κO)thiosemicarbazido-κ2N1,N4]nickel(II) top
Crystal data top
[Ni(C28H30N3O2PS)]Z = 4
Mr = 562.29F(000) = 1176
Triclinic, P1Dx = 1.350 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 11.974 (3) ÅCell parameters from 25 reflections
b = 12.531 (2) Åθ = 12.0–15.9°
c = 20.827 (7) ŵ = 0.86 mm1
α = 89.81 (2)°T = 293 K
β = 73.56 (2)°Prism, black
γ = 68.26 (2)°0.36 × 0.30 × 0.26 mm
V = 2765.9 (12) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.025
ω/2θ scansθmax = 26.0°, θmin = 1.0°
Absorption correction: gaussian
(PLATON; Spek, 2003)
h = 014
Tmin = 0.756, Tmax = 0.820k = 1315
11363 measured reflectionsl = 2425
10824 independent reflections3 standard reflections every 60 min
6782 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.0452P)2 + 0.729P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.117(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.43 e Å3
10824 reflectionsΔρmin = 0.28 e Å3
657 parameters
Crystal data top
[Ni(C28H30N3O2PS)]γ = 68.26 (2)°
Mr = 562.29V = 2765.9 (12) Å3
Triclinic, P1Z = 4
a = 11.974 (3) ÅMo Kα radiation
b = 12.531 (2) ŵ = 0.86 mm1
c = 20.827 (7) ÅT = 293 K
α = 89.81 (2)°0.36 × 0.30 × 0.26 mm
β = 73.56 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
6782 reflections with I > 2σ(I)
Absorption correction: gaussian
(PLATON; Spek, 2003)
Rint = 0.025
Tmin = 0.756, Tmax = 0.8203 standard reflections every 60 min
11363 measured reflections intensity decay: none
10824 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.01Δρmax = 0.43 e Å3
10824 reflectionsΔρmin = 0.28 e Å3
657 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni1a0.18357 (4)0.26223 (4)0.11535 (2)0.04047 (12)
P1a0.31500 (8)0.34566 (7)0.06963 (5)0.0404 (2)
S1a0.08343 (12)0.28575 (12)0.33548 (6)0.0770 (3)
O1a0.1816 (2)0.2243 (2)0.03069 (12)0.0544 (6)
O2a0.4019 (2)0.2517 (2)0.18981 (13)0.0523 (6)
N1a0.0596 (3)0.2092 (2)0.16089 (15)0.0476 (7)
N2a0.0294 (3)0.2197 (3)0.23164 (16)0.0545 (8)
N3a0.1861 (3)0.2932 (2)0.20187 (14)0.0453 (7)
C1a0.1014 (3)0.2635 (3)0.24861 (18)0.0487 (9)
C2a0.0456 (5)0.2431 (5)0.3729 (2)0.1071 (19)
H72a0.12100.29740.36590.161*
H82a0.05720.24140.42040.161*
H92a0.02750.16750.35270.161*
C3a0.1043 (4)0.1309 (4)0.1803 (3)0.0874 (15)
H73a0.06640.06960.20460.131*
H83a0.14550.10510.15400.131*
H93a0.16500.19650.21160.131*
C4a0.0031 (3)0.1650 (3)0.1341 (2)0.0562 (10)
C5a0.0207 (4)0.1508 (3)0.0645 (2)0.0597 (10)
H5a0.02670.11880.04890.072*
C6a0.1063 (4)0.1793 (3)0.0175 (2)0.0575 (10)
C7a0.1237 (5)0.1626 (5)0.0567 (2)0.0913 (16)
H77a0.10980.23550.07460.137*
H87a0.06440.13260.06350.137*
H97a0.20800.10910.07920.137*
C8a0.5649 (4)0.0689 (4)0.1812 (3)0.0984 (18)
H78a0.59310.06410.13290.148*
H88a0.58340.00760.19460.148*
H98a0.60750.10640.19980.148*
C9a0.4277 (4)0.1361 (4)0.2061 (2)0.0769 (13)
H79a0.38450.10120.18540.092*
H89a0.39750.13620.25450.092*
C10a0.2752 (3)0.3299 (3)0.22051 (18)0.0469 (8)
H10a0.25700.33450.26960.056*
C11a0.2951 (3)0.4617 (3)0.12956 (17)0.0424 (8)
C12a0.2708 (3)0.4458 (3)0.19806 (18)0.0441 (8)
C13a0.2467 (4)0.5355 (3)0.24436 (19)0.0559 (10)
H13a0.22990.52530.28990.067*
C14a0.2471 (4)0.6410 (3)0.2243 (2)0.0613 (11)
H14a0.23010.70120.25620.074*
C15a0.2726 (4)0.6566 (3)0.1571 (2)0.0564 (10)
H15a0.27430.72690.14360.068*
C16a0.2957 (3)0.5681 (3)0.10981 (19)0.0475 (9)
H16a0.31170.57940.06450.057*
C17a0.4827 (3)0.2564 (3)0.03803 (17)0.0445 (8)
C18a0.5731 (3)0.2924 (3)0.0487 (2)0.0580 (10)
H18a0.54830.36120.07560.070*
C19a0.7001 (4)0.2261 (4)0.0194 (2)0.0744 (13)
H19a0.76060.25080.02630.089*
C20a0.7362 (4)0.1255 (4)0.0192 (3)0.0829 (15)
H20a0.82170.08130.03870.099*
C21a0.6483 (4)0.0876 (3)0.0300 (2)0.0775 (14)
H21a0.67450.01820.05670.093*
C22a0.5202 (4)0.1526 (3)0.0011 (2)0.0608 (10)
H22a0.46040.12700.00800.073*
C23a0.2844 (3)0.4195 (3)0.00269 (17)0.0441 (8)
C24a0.3805 (4)0.4111 (3)0.06106 (19)0.0581 (10)
H24a0.46330.36350.06460.070*
C25a0.3545 (5)0.4726 (4)0.1139 (2)0.0768 (13)
H25a0.42010.46740.15220.092*
C26a0.2329 (5)0.5411 (4)0.1101 (2)0.0780 (14)
H26a0.21550.58150.14600.094*
C27a0.1369 (4)0.5497 (4)0.0531 (3)0.0774 (14)
H27a0.05430.59650.05040.093*
C28a0.1616 (4)0.4895 (3)0.0005 (2)0.0624 (11)
H28a0.09550.49600.03880.075*
Ni1b0.47224 (4)0.22627 (4)0.55006 (2)0.04287 (12)
P1b0.44638 (8)0.31256 (8)0.64687 (5)0.0410 (2)
S1b0.86028 (9)0.00663 (9)0.44389 (6)0.0647 (3)
O1b0.3025 (2)0.3056 (2)0.56445 (13)0.0584 (7)
O2b0.7068 (2)0.2921 (2)0.55316 (13)0.0529 (6)
N1b0.5004 (3)0.1400 (2)0.47082 (14)0.0462 (7)
N2b0.6262 (3)0.0644 (3)0.43833 (15)0.0514 (7)
N3b0.6450 (2)0.1468 (2)0.53222 (15)0.0464 (7)
C1b0.6958 (3)0.0765 (3)0.47384 (18)0.0457 (8)
C2b0.8721 (5)0.0792 (4)0.3670 (2)0.0952 (16)
H72b0.84810.02330.33660.143*
H82b0.81700.12050.37620.143*
H92b0.95750.13250.34670.143*
C3b0.4549 (4)0.0583 (4)0.3800 (2)0.0722 (13)
H73b0.49190.02000.38930.108*
H83b0.51570.07530.34500.108*
H93b0.38260.06780.36570.108*
C4b0.4152 (4)0.1390 (3)0.44241 (19)0.0525 (9)
C5b0.2877 (4)0.2136 (4)0.4708 (2)0.0606 (11)
H5b0.23180.21010.44850.073*
C6b0.2380 (4)0.2895 (4)0.5272 (2)0.0589 (10)
C7b0.0991 (4)0.3631 (4)0.5535 (2)0.0817 (14)
H77b0.08740.44300.55890.123*
H87b0.06370.34110.59630.123*
H97b0.05780.35220.52230.123*
C8b0.7661 (4)0.4513 (3)0.5540 (2)0.0684 (12)
H78b0.67910.50100.57400.103*
H88b0.78690.44840.50580.103*
H98b0.81860.48100.56920.103*
C9b0.7874 (4)0.3313 (3)0.5742 (2)0.0616 (11)
H79b0.87450.27990.55310.074*
H89b0.76960.33300.62260.074*
C10b0.7229 (3)0.1750 (3)0.56487 (18)0.0477 (9)
H10b0.81130.12420.54330.057*
C11b0.5674 (3)0.2242 (3)0.68338 (17)0.0414 (8)
C12b0.6884 (3)0.1611 (3)0.63893 (19)0.0454 (8)
C13b0.7785 (4)0.0831 (3)0.6648 (2)0.0551 (10)
H13b0.85890.04100.63600.066*
C14b0.7503 (4)0.0673 (3)0.7322 (2)0.0624 (11)
H14b0.81100.01360.74820.075*
C15b0.6326 (4)0.1308 (3)0.7759 (2)0.0608 (11)
H15b0.61440.12160.82150.073*
C16b0.5405 (4)0.2090 (3)0.75158 (19)0.0508 (9)
H16b0.46070.25120.78100.061*
C17b0.4437 (3)0.4584 (3)0.64893 (17)0.0438 (8)
C18b0.4721 (3)0.5054 (3)0.69862 (19)0.0515 (9)
H18b0.49920.46020.73090.062*
C19b0.4605 (4)0.6202 (3)0.7010 (2)0.0650 (11)
H19b0.47960.65180.73480.078*
C20b0.4203 (4)0.6865 (3)0.6526 (2)0.0687 (12)
H20b0.41050.76370.65440.082*
C21b0.3951 (4)0.6394 (3)0.6023 (2)0.0648 (11)
H21b0.37050.68410.56920.078*
C22b0.4059 (3)0.5259 (3)0.6000 (2)0.0559 (10)
H22b0.38780.49450.56570.067*
C23b0.2961 (3)0.3270 (3)0.70847 (17)0.0438 (8)
C24b0.2011 (3)0.4324 (3)0.7349 (2)0.0589 (10)
H24b0.21390.49970.72360.071*
C25b0.0861 (4)0.4396 (4)0.7782 (2)0.0746 (13)
H25b0.02270.51150.79640.089*
C26b0.0659 (4)0.3408 (4)0.7944 (2)0.0718 (12)
H26b0.01140.34550.82320.086*
C27b0.1601 (4)0.2348 (4)0.7679 (2)0.0698 (12)
H27b0.14680.16760.77890.084*
C28b0.2750 (4)0.2278 (3)0.7247 (2)0.0616 (11)
H28b0.33830.15580.70660.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni1a0.0369 (2)0.0392 (2)0.0457 (3)0.01682 (19)0.01027 (19)0.00625 (19)
P1a0.0357 (4)0.0391 (5)0.0444 (5)0.0154 (4)0.0080 (4)0.0066 (4)
S1a0.0872 (8)0.1019 (9)0.0473 (6)0.0501 (7)0.0102 (6)0.0166 (6)
O1a0.0564 (16)0.0553 (15)0.0548 (16)0.0253 (13)0.0169 (13)0.0036 (12)
O2a0.0477 (14)0.0541 (15)0.0643 (17)0.0242 (12)0.0245 (13)0.0233 (13)
N1a0.0389 (16)0.0434 (16)0.063 (2)0.0199 (13)0.0132 (15)0.0100 (14)
N2a0.0526 (19)0.061 (2)0.054 (2)0.0322 (16)0.0089 (15)0.0134 (16)
N3a0.0451 (16)0.0520 (17)0.0435 (17)0.0252 (14)0.0119 (13)0.0106 (14)
C1a0.045 (2)0.046 (2)0.051 (2)0.0167 (17)0.0094 (17)0.0126 (17)
C2a0.104 (4)0.143 (5)0.069 (3)0.069 (4)0.011 (3)0.021 (3)
C3a0.071 (3)0.106 (4)0.106 (4)0.062 (3)0.020 (3)0.018 (3)
C4a0.043 (2)0.042 (2)0.083 (3)0.0165 (17)0.019 (2)0.004 (2)
C5a0.053 (2)0.050 (2)0.083 (3)0.0223 (19)0.028 (2)0.002 (2)
C6a0.059 (2)0.046 (2)0.069 (3)0.0128 (19)0.030 (2)0.0046 (19)
C7a0.106 (4)0.107 (4)0.070 (3)0.044 (3)0.035 (3)0.010 (3)
C8a0.070 (3)0.078 (3)0.122 (5)0.009 (3)0.018 (3)0.043 (3)
C9a0.070 (3)0.064 (3)0.097 (4)0.024 (2)0.028 (3)0.039 (3)
C10a0.050 (2)0.053 (2)0.044 (2)0.0240 (18)0.0186 (17)0.0111 (17)
C11a0.0357 (17)0.0445 (19)0.048 (2)0.0191 (15)0.0092 (15)0.0039 (16)
C12a0.0435 (19)0.0443 (19)0.053 (2)0.0228 (16)0.0194 (17)0.0090 (16)
C13a0.065 (3)0.065 (3)0.047 (2)0.034 (2)0.0192 (19)0.0058 (19)
C14a0.068 (3)0.052 (2)0.070 (3)0.031 (2)0.020 (2)0.005 (2)
C15a0.062 (2)0.046 (2)0.071 (3)0.0299 (19)0.021 (2)0.0107 (19)
C16a0.046 (2)0.047 (2)0.050 (2)0.0220 (17)0.0093 (17)0.0078 (17)
C17a0.0368 (18)0.0423 (19)0.048 (2)0.0112 (15)0.0095 (16)0.0145 (16)
C18a0.046 (2)0.052 (2)0.073 (3)0.0166 (18)0.018 (2)0.013 (2)
C19a0.041 (2)0.068 (3)0.108 (4)0.017 (2)0.019 (2)0.031 (3)
C20a0.046 (3)0.067 (3)0.105 (4)0.004 (2)0.002 (3)0.025 (3)
C21a0.072 (3)0.041 (2)0.088 (3)0.002 (2)0.004 (3)0.001 (2)
C22a0.056 (2)0.046 (2)0.069 (3)0.0146 (19)0.009 (2)0.006 (2)
C23a0.0448 (19)0.0360 (18)0.050 (2)0.0139 (15)0.0142 (17)0.0061 (15)
C24a0.057 (2)0.058 (2)0.048 (2)0.0133 (19)0.0102 (19)0.0120 (19)
C25a0.096 (4)0.072 (3)0.046 (2)0.021 (3)0.013 (2)0.011 (2)
C26a0.112 (4)0.065 (3)0.074 (3)0.036 (3)0.051 (3)0.028 (2)
C27a0.067 (3)0.061 (3)0.118 (4)0.022 (2)0.052 (3)0.035 (3)
C28a0.048 (2)0.054 (2)0.081 (3)0.0176 (19)0.017 (2)0.020 (2)
Ni1b0.0356 (2)0.0517 (3)0.0456 (3)0.0203 (2)0.0142 (2)0.0087 (2)
P1b0.0355 (5)0.0431 (5)0.0455 (5)0.0160 (4)0.0128 (4)0.0093 (4)
S1b0.0444 (5)0.0672 (7)0.0716 (7)0.0217 (5)0.0009 (5)0.0073 (5)
O1b0.0367 (13)0.0740 (18)0.0647 (17)0.0190 (13)0.0188 (13)0.0083 (14)
O2b0.0446 (14)0.0579 (15)0.0652 (17)0.0283 (12)0.0184 (12)0.0124 (13)
N1b0.0523 (18)0.0511 (17)0.0444 (17)0.0296 (15)0.0156 (14)0.0133 (14)
N2b0.0557 (19)0.0546 (18)0.0475 (18)0.0286 (16)0.0115 (15)0.0071 (14)
N3b0.0342 (15)0.0548 (18)0.0507 (18)0.0179 (13)0.0126 (13)0.0017 (15)
C1b0.045 (2)0.043 (2)0.048 (2)0.0230 (16)0.0047 (17)0.0084 (16)
C2b0.077 (3)0.095 (4)0.086 (4)0.021 (3)0.001 (3)0.030 (3)
C3b0.099 (4)0.087 (3)0.062 (3)0.062 (3)0.036 (3)0.016 (2)
C4b0.069 (3)0.057 (2)0.053 (2)0.040 (2)0.029 (2)0.0223 (19)
C5b0.061 (3)0.074 (3)0.072 (3)0.041 (2)0.039 (2)0.027 (2)
C6b0.049 (2)0.065 (3)0.077 (3)0.030 (2)0.030 (2)0.027 (2)
C7b0.045 (2)0.099 (4)0.110 (4)0.032 (2)0.033 (3)0.029 (3)
C8b0.056 (2)0.071 (3)0.088 (3)0.039 (2)0.017 (2)0.015 (2)
C9b0.060 (2)0.069 (3)0.068 (3)0.037 (2)0.020 (2)0.009 (2)
C10b0.0339 (18)0.050 (2)0.055 (2)0.0136 (16)0.0106 (16)0.0024 (17)
C11b0.0422 (18)0.0392 (18)0.050 (2)0.0203 (15)0.0182 (16)0.0090 (15)
C12b0.0405 (19)0.0410 (19)0.063 (2)0.0184 (16)0.0243 (18)0.0044 (17)
C13b0.048 (2)0.050 (2)0.076 (3)0.0196 (18)0.030 (2)0.011 (2)
C14b0.068 (3)0.049 (2)0.088 (3)0.024 (2)0.049 (3)0.025 (2)
C15b0.083 (3)0.061 (3)0.063 (3)0.042 (2)0.041 (2)0.025 (2)
C16b0.056 (2)0.046 (2)0.059 (2)0.0268 (18)0.0225 (19)0.0103 (18)
C17b0.0368 (18)0.047 (2)0.049 (2)0.0185 (16)0.0119 (16)0.0118 (16)
C18b0.054 (2)0.052 (2)0.050 (2)0.0225 (18)0.0145 (18)0.0118 (18)
C19b0.076 (3)0.059 (3)0.070 (3)0.039 (2)0.019 (2)0.006 (2)
C20b0.067 (3)0.048 (2)0.090 (3)0.029 (2)0.012 (2)0.015 (2)
C21b0.062 (3)0.057 (3)0.081 (3)0.028 (2)0.024 (2)0.032 (2)
C22b0.052 (2)0.064 (3)0.062 (3)0.0273 (19)0.027 (2)0.023 (2)
C23b0.0370 (18)0.053 (2)0.043 (2)0.0188 (16)0.0120 (15)0.0067 (16)
C24b0.041 (2)0.054 (2)0.072 (3)0.0120 (18)0.0118 (19)0.012 (2)
C25b0.041 (2)0.078 (3)0.083 (3)0.008 (2)0.005 (2)0.013 (3)
C26b0.046 (2)0.102 (4)0.064 (3)0.033 (3)0.006 (2)0.008 (3)
C27b0.069 (3)0.079 (3)0.067 (3)0.047 (3)0.006 (2)0.004 (2)
C28b0.054 (2)0.056 (2)0.066 (3)0.024 (2)0.000 (2)0.004 (2)
Geometric parameters (Å, º) top
Ni1a—O1a1.836 (3)Ni1b—O1b1.835 (2)
Ni1a—N3a1.856 (3)Ni1b—N1b1.852 (3)
Ni1a—N1a1.864 (3)Ni1b—N3b1.857 (3)
Ni1a—P1a2.2001 (10)Ni1b—P1b2.1780 (12)
P1a—C23a1.819 (4)P1b—C17b1.816 (3)
P1a—C17a1.820 (3)P1b—C11b1.826 (3)
P1a—C11a1.821 (3)P1b—C23b1.836 (3)
S1a—C1a1.771 (4)S1b—C1b1.773 (4)
S1a—C2a1.791 (5)S1b—C2b1.789 (5)
O1a—C6a1.314 (4)O1b—C6b1.303 (4)
O2a—C10a1.423 (4)O2b—C9b1.399 (4)
O2a—C9a1.427 (4)O2b—C10b1.437 (4)
N1a—C4a1.315 (4)N1b—C4b1.320 (4)
N1a—N2a1.408 (4)N1b—N2b1.412 (4)
N2a—C1a1.302 (4)N2b—C1b1.307 (4)
N3a—C1a1.354 (4)N3b—C1b1.347 (4)
N3a—C10a1.450 (4)N3b—C10b1.437 (4)
C2a—H72a0.9600C2b—H72b0.9600
C2a—H82a0.9600C2b—H82b0.9600
C2a—H92a0.9600C2b—H92b0.9600
C3a—C4a1.515 (5)C3b—C4b1.497 (5)
C3a—H73a0.9600C3b—H73b0.9600
C3a—H83a0.9600C3b—H83b0.9600
C3a—H93a0.9600C3b—H93b0.9600
C4a—C5a1.394 (5)C4b—C5b1.411 (5)
C5a—C6a1.355 (5)C5b—C6b1.353 (6)
C5a—H5a0.9300C5b—H5b0.9300
C6a—C7a1.503 (5)C6b—C7b1.506 (5)
C7a—H77a0.9600C7b—H77b0.9600
C7a—H87a0.9600C7b—H87b0.9600
C7a—H97a0.9600C7b—H97b0.9600
C8a—C9a1.474 (6)C8b—C9b1.508 (5)
C8a—H78a0.9600C8b—H78b0.9600
C8a—H88a0.9600C8b—H88b0.9600
C8a—H98a0.9600C8b—H98b0.9600
C9a—H79a0.9700C9b—H79b0.9700
C9a—H89a0.9700C9b—H89b0.9700
C10a—C12a1.511 (5)C10b—C12b1.507 (5)
C10a—H10a0.9800C10b—H10b0.9800
C11a—C16a1.395 (4)C11b—C16b1.394 (5)
C11a—C12a1.402 (5)C11b—C12b1.407 (5)
C12a—C13a1.374 (5)C12b—C13b1.397 (5)
C13a—C14a1.387 (5)C13b—C14b1.381 (5)
C13a—H13a0.9300C13b—H13b0.9300
C14a—C15a1.374 (5)C14b—C15b1.377 (6)
C14a—H14a0.9300C14b—H14b0.9300
C15a—C16a1.380 (5)C15b—C16b1.394 (5)
C15a—H15a0.9300C15b—H15b0.9300
C16a—H16a0.9300C16b—H16b0.9300
C17a—C18a1.386 (5)C17b—C18b1.373 (5)
C17a—C22a1.387 (5)C17b—C22b1.389 (5)
C18a—C19a1.385 (5)C18b—C19b1.393 (5)
C18a—H18a0.9300C18b—H18b0.9300
C19a—C20a1.353 (6)C19b—C20b1.383 (6)
C19a—H19a0.9300C19b—H19b0.9300
C20a—C21a1.375 (6)C20b—C21b1.361 (6)
C20a—H20a0.9300C20b—H20b0.9300
C21a—C22a1.391 (5)C21b—C22b1.380 (5)
C21a—H21a0.9300C21b—H21b0.9300
C22a—H22a0.9300C22b—H22b0.9300
C23a—C28a1.388 (5)C23b—C24b1.370 (5)
C23a—C24a1.390 (5)C23b—C28b1.381 (5)
C24a—C25a1.382 (5)C24b—C25b1.387 (5)
C24a—H24a0.9300C24b—H24b0.9300
C25a—C26a1.369 (6)C25b—C26b1.370 (6)
C25a—H25a0.9300C25b—H25b0.9300
C26a—C27a1.371 (6)C26b—C27b1.373 (6)
C26a—H26a0.9300C26b—H26b0.9300
C27a—C28a1.385 (6)C27b—C28b1.385 (5)
C27a—H27a0.9300C27b—H27b0.9300
C28a—H28a0.9300C28b—H28b0.9300
O1a—Ni1a—N3a177.14 (12)O1b—Ni1b—N1b95.85 (13)
O1a—Ni1a—N1a95.34 (13)O1b—Ni1b—N3b177.92 (12)
N3a—Ni1a—N1a82.79 (13)N1b—Ni1b—N3b82.64 (13)
O1a—Ni1a—P1a88.92 (8)O1b—Ni1b—P1b87.09 (9)
N3a—Ni1a—P1a93.17 (9)N1b—Ni1b—P1b174.70 (9)
N1a—Ni1a—P1a172.77 (9)N3b—Ni1b—P1b94.53 (10)
C23a—P1a—C17a102.62 (16)C17b—P1b—C11b108.06 (15)
C23a—P1a—C11a103.22 (16)C17b—P1b—C23b103.91 (16)
C17a—P1a—C11a107.56 (16)C11b—P1b—C23b104.93 (16)
C23a—P1a—Ni1a114.21 (12)C17b—P1b—Ni1b117.72 (12)
C17a—P1a—Ni1a118.51 (11)C11b—P1b—Ni1b109.86 (12)
C11a—P1a—Ni1a109.42 (11)C23b—P1b—Ni1b111.48 (12)
C1a—S1a—C2a101.6 (2)C1b—S1b—C2b100.8 (2)
C6a—O1a—Ni1a125.3 (3)C6b—O1b—Ni1b125.3 (3)
C10a—O2a—C9a114.3 (3)C9b—O2b—C10b114.4 (3)
C4a—N1a—N2a117.1 (3)C4b—N1b—N2b116.4 (3)
C4a—N1a—Ni1a127.0 (3)C4b—N1b—Ni1b127.1 (3)
N2a—N1a—Ni1a115.9 (2)N2b—N1b—Ni1b116.5 (2)
C1a—N2a—N1a108.3 (3)C1b—N2b—N1b107.5 (3)
C1a—N3a—C10a121.1 (3)C1b—N3b—C10b121.2 (3)
C1a—N3a—Ni1a111.5 (2)C1b—N3b—Ni1b111.5 (2)
C10a—N3a—Ni1a127.0 (2)C10b—N3b—Ni1b125.5 (2)
N2a—C1a—N3a121.6 (3)N2b—C1b—N3b121.7 (3)
N2a—C1a—S1a117.8 (3)N2b—C1b—S1b117.6 (3)
N3a—C1a—S1a120.6 (3)N3b—C1b—S1b120.7 (3)
S1a—C2a—H72a109.5S1b—C2b—H72b109.5
S1a—C2a—H82a109.5S1b—C2b—H82b109.5
H72a—C2a—H82a109.5H72b—C2b—H82b109.5
S1a—C2a—H92a109.5S1b—C2b—H92b109.5
H72a—C2a—H92a109.5H72b—C2b—H92b109.5
H82a—C2a—H92a109.5H82b—C2b—H92b109.5
C4a—C3a—H73a109.5C4b—C3b—H73b109.5
C4a—C3a—H83a109.5C4b—C3b—H83b109.5
H73a—C3a—H83a109.5H73b—C3b—H83b109.5
C4a—C3a—H93a109.5C4b—C3b—H93b109.5
H73a—C3a—H93a109.5H73b—C3b—H93b109.5
H83a—C3a—H93a109.5H83b—C3b—H93b109.5
N1a—C4a—C5a121.2 (4)N1b—C4b—C5b120.1 (4)
N1a—C4a—C3a118.9 (4)N1b—C4b—C3b119.5 (4)
C5a—C4a—C3a120.0 (4)C5b—C4b—C3b120.4 (4)
C6a—C5a—C4a126.3 (4)C6b—C5b—C4b126.9 (4)
C6a—C5a—H5a116.8C6b—C5b—H5b116.5
C4a—C5a—H5a116.8C4b—C5b—H5b116.5
O1a—C6a—C5a124.8 (4)O1b—C6b—C5b124.6 (4)
O1a—C6a—C7a112.7 (4)O1b—C6b—C7b113.3 (4)
C5a—C6a—C7a122.5 (4)C5b—C6b—C7b122.1 (4)
C6a—C7a—H77a109.5C6b—C7b—H77b109.5
C6a—C7a—H87a109.5C6b—C7b—H87b109.5
H77a—C7a—H87a109.5H77b—C7b—H87b109.5
C6a—C7a—H97a109.5C6b—C7b—H97b109.5
H77a—C7a—H97a109.5H77b—C7b—H97b109.5
H87a—C7a—H97a109.5H87b—C7b—H97b109.5
C9a—C8a—H78a109.5C9b—C8b—H78b109.5
C9a—C8a—H88a109.5C9b—C8b—H88b109.5
H78a—C8a—H88a109.5H78b—C8b—H88b109.5
C9a—C8a—H98a109.5C9b—C8b—H98b109.5
H78a—C8a—H98a109.5H78b—C8b—H98b109.5
H88a—C8a—H98a109.5H88b—C8b—H98b109.5
O2a—C9a—C8a109.1 (3)O2b—C9b—C8b108.1 (3)
O2a—C9a—H79a109.9O2b—C9b—H79b110.1
C8a—C9a—H79a109.9C8b—C9b—H79b110.1
O2a—C9a—H89a109.9O2b—C9b—H89b110.1
C8a—C9a—H89a109.9C8b—C9b—H89b110.1
H79a—C9a—H89a108.3H79b—C9b—H89b108.4
O2a—C10a—N3a111.7 (3)N3b—C10b—O2b105.6 (3)
O2a—C10a—C12a105.1 (3)N3b—C10b—C12b112.2 (3)
N3a—C10a—C12a112.8 (3)O2b—C10b—C12b112.0 (3)
O2a—C10a—H10a109.0N3b—C10b—H10b109.0
N3a—C10a—H10a109.0O2b—C10b—H10b109.0
C12a—C10a—H10a109.0C12b—C10b—H10b109.0
C16a—C11a—C12a119.3 (3)C16b—C11b—C12b119.8 (3)
C16a—C11a—P1a121.9 (3)C16b—C11b—P1b122.4 (3)
C12a—C11a—P1a118.7 (2)C12b—C11b—P1b117.5 (3)
C13a—C12a—C11a119.3 (3)C13b—C12b—C11b118.4 (4)
C13a—C12a—C10a120.3 (3)C13b—C12b—C10b119.5 (3)
C11a—C12a—C10a120.3 (3)C11b—C12b—C10b122.0 (3)
C12a—C13a—C14a121.0 (4)C14b—C13b—C12b121.3 (4)
C12a—C13a—H13a119.5C14b—C13b—H13b119.3
C14a—C13a—H13a119.5C12b—C13b—H13b119.3
C15a—C14a—C13a119.9 (4)C15b—C14b—C13b120.1 (4)
C15a—C14a—H14a120.1C15b—C14b—H14b119.9
C13a—C14a—H14a120.1C13b—C14b—H14b119.9
C14a—C15a—C16a120.1 (3)C14b—C15b—C16b119.9 (4)
C14a—C15a—H15a119.9C14b—C15b—H15b120.1
C16a—C15a—H15a119.9C16b—C15b—H15b120.1
C15a—C16a—C11a120.4 (3)C11b—C16b—C15b120.4 (4)
C15a—C16a—H16a119.8C11b—C16b—H16b119.8
C11a—C16a—H16a119.8C15b—C16b—H16b119.8
C18a—C17a—C22a119.7 (3)C18b—C17b—C22b119.2 (3)
C18a—C17a—P1a121.9 (3)C18b—C17b—P1b122.3 (3)
C22a—C17a—P1a118.3 (3)C22b—C17b—P1b118.4 (3)
C19a—C18a—C17a120.1 (4)C17b—C18b—C19b120.6 (4)
C19a—C18a—H18a119.9C17b—C18b—H18b119.7
C17a—C18a—H18a119.9C19b—C18b—H18b119.7
C20a—C19a—C18a120.0 (4)C20b—C19b—C18b119.2 (4)
C20a—C19a—H19a120.0C20b—C19b—H19b120.4
C18a—C19a—H19a120.0C18b—C19b—H19b120.4
C19a—C20a—C21a120.9 (4)C21b—C20b—C19b120.4 (4)
C19a—C20a—H20a119.6C21b—C20b—H20b119.8
C21a—C20a—H20a119.6C19b—C20b—H20b119.8
C20a—C21a—C22a120.2 (4)C20b—C21b—C22b120.5 (4)
C20a—C21a—H21a119.9C20b—C21b—H21b119.8
C22a—C21a—H21a119.9C22b—C21b—H21b119.8
C17a—C22a—C21a119.1 (4)C21b—C22b—C17b120.1 (4)
C17a—C22a—H22a120.5C21b—C22b—H22b119.9
C21a—C22a—H22a120.5C17b—C22b—H22b119.9
C28a—C23a—C24a118.1 (3)C24b—C23b—C28b119.0 (3)
C28a—C23a—P1a119.5 (3)C24b—C23b—P1b122.4 (3)
C24a—C23a—P1a122.4 (3)C28b—C23b—P1b118.4 (3)
C25a—C24a—C23a120.9 (4)C23b—C24b—C25b120.6 (4)
C25a—C24a—H24a119.6C23b—C24b—H24b119.7
C23a—C24a—H24a119.6C25b—C24b—H24b119.7
C26a—C25a—C24a120.4 (4)C26b—C25b—C24b120.1 (4)
C26a—C25a—H25a119.8C26b—C25b—H25b120.0
C24a—C25a—H25a119.8C24b—C25b—H25b120.0
C25a—C26a—C27a119.5 (4)C25b—C26b—C27b119.7 (4)
C25a—C26a—H26a120.3C25b—C26b—H26b120.1
C27a—C26a—H26a120.3C27b—C26b—H26b120.1
C26a—C27a—C28a120.8 (4)C26b—C27b—C28b120.1 (4)
C26a—C27a—H27a119.6C26b—C27b—H27b119.9
C28a—C27a—H27a119.6C28b—C27b—H27b119.9
C27a—C28a—C23a120.4 (4)C23b—C28b—C27b120.4 (4)
C27a—C28a—H28a119.8C23b—C28b—H28b119.8
C23a—C28a—H28a119.8C27b—C28b—H28b119.8
O1a—Ni1a—P1a—C23a36.62 (14)O1b—Ni1b—P1b—C17b82.10 (15)
N3a—Ni1a—P1a—C23a145.34 (15)N3b—Ni1b—P1b—C17b96.59 (15)
O1a—Ni1a—P1a—C17a84.50 (16)O1b—Ni1b—P1b—C11b153.70 (14)
N3a—Ni1a—P1a—C17a93.54 (16)N3b—Ni1b—P1b—C11b27.61 (15)
O1a—Ni1a—P1a—C11a151.74 (14)O1b—Ni1b—P1b—C23b37.82 (15)
N3a—Ni1a—P1a—C11a30.22 (15)N3b—Ni1b—P1b—C23b143.49 (15)
N1a—Ni1a—O1a—C6a2.3 (3)N1b—Ni1b—O1b—C6b3.3 (3)
P1a—Ni1a—O1a—C6a171.8 (3)P1b—Ni1b—O1b—C6b172.3 (3)
O1a—Ni1a—N1a—C4a2.0 (3)O1b—Ni1b—N1b—C4b4.1 (3)
N3a—Ni1a—N1a—C4a179.8 (3)N3b—Ni1b—N1b—C4b177.4 (3)
O1a—Ni1a—N1a—N2a179.0 (2)O1b—Ni1b—N1b—N2b178.1 (2)
N3a—Ni1a—N1a—N2a1.2 (2)N3b—Ni1b—N1b—N2b0.5 (2)
C4a—N1a—N2a—C1a179.3 (3)C4b—N1b—N2b—C1b179.3 (3)
Ni1a—N1a—N2a—C1a1.6 (4)Ni1b—N1b—N2b—C1b1.2 (3)
N1a—Ni1a—N3a—C1a0.5 (2)N1b—Ni1b—N3b—C1b2.0 (2)
P1a—Ni1a—N3a—C1a173.5 (2)P1b—Ni1b—N3b—C1b177.5 (2)
N1a—Ni1a—N3a—C10a171.8 (3)N1b—Ni1b—N3b—C10b166.8 (3)
P1a—Ni1a—N3a—C10a14.3 (3)P1b—Ni1b—N3b—C10b17.7 (3)
N1a—N2a—C1a—N3a1.2 (5)N1b—N2b—C1b—N3b3.2 (4)
N1a—N2a—C1a—S1a179.8 (2)N1b—N2b—C1b—S1b178.8 (2)
C10a—N3a—C1a—N2a173.1 (3)C10b—N3b—C1b—N2b169.2 (3)
Ni1a—N3a—C1a—N2a0.3 (4)Ni1b—N3b—C1b—N2b3.7 (4)
C10a—N3a—C1a—S1a7.9 (4)C10b—N3b—C1b—S1b12.9 (4)
Ni1a—N3a—C1a—S1a179.29 (18)Ni1b—N3b—C1b—S1b178.37 (17)
C2a—S1a—C1a—N2a3.3 (4)C2b—S1b—C1b—N2b2.4 (3)
C2a—S1a—C1a—N3a175.7 (3)C2b—S1b—C1b—N3b179.6 (3)
N2a—N1a—C4a—C5a179.7 (3)N2b—N1b—C4b—C5b178.8 (3)
Ni1a—N1a—C4a—C5a1.3 (5)Ni1b—N1b—C4b—C5b3.4 (5)
N2a—N1a—C4a—C3a1.3 (5)N2b—N1b—C4b—C3b1.3 (5)
Ni1a—N1a—C4a—C3a177.7 (3)Ni1b—N1b—C4b—C3b176.5 (3)
N1a—C4a—C5a—C6a0.3 (6)N1b—C4b—C5b—C6b0.9 (6)
C3a—C4a—C5a—C6a178.7 (4)C3b—C4b—C5b—C6b179.1 (4)
Ni1a—O1a—C6a—C5a2.0 (5)Ni1b—O1b—C6b—C5b2.0 (5)
Ni1a—O1a—C6a—C7a177.6 (3)Ni1b—O1b—C6b—C7b176.9 (3)
C4a—C5a—C6a—O1a0.7 (6)C4b—C5b—C6b—O1b0.2 (7)
C4a—C5a—C6a—C7a178.9 (4)C4b—C5b—C6b—C7b178.7 (4)
C10a—O2a—C9a—C8a170.4 (4)C10b—O2b—C9b—C8b175.9 (3)
C9a—O2a—C10a—N3a58.8 (4)C1b—N3b—C10b—O2b105.6 (3)
C9a—O2a—C10a—C12a178.5 (3)Ni1b—N3b—C10b—O2b57.8 (4)
C1a—N3a—C10a—O2a116.0 (3)C1b—N3b—C10b—C12b132.1 (3)
Ni1a—N3a—C10a—O2a55.6 (4)Ni1b—N3b—C10b—C12b64.5 (4)
C1a—N3a—C10a—C12a125.8 (3)C9b—O2b—C10b—N3b172.6 (3)
Ni1a—N3a—C10a—C12a62.6 (4)C9b—O2b—C10b—C12b65.0 (4)
C23a—P1a—C11a—C16a16.7 (3)C17b—P1b—C11b—C16b92.3 (3)
C17a—P1a—C11a—C16a91.4 (3)C23b—P1b—C11b—C16b18.1 (3)
Ni1a—P1a—C11a—C16a138.7 (3)Ni1b—P1b—C11b—C16b138.1 (3)
C23a—P1a—C11a—C12a159.4 (3)C17b—P1b—C11b—C12b94.1 (3)
C17a—P1a—C11a—C12a92.6 (3)C23b—P1b—C11b—C12b155.4 (3)
Ni1a—P1a—C11a—C12a37.4 (3)Ni1b—P1b—C11b—C12b35.5 (3)
C16a—C11a—C12a—C13a0.7 (5)C16b—C11b—C12b—C13b0.8 (5)
P1a—C11a—C12a—C13a175.4 (3)P1b—C11b—C12b—C13b172.9 (2)
C16a—C11a—C12a—C10a177.3 (3)C16b—C11b—C12b—C10b179.5 (3)
P1a—C11a—C12a—C10a6.5 (4)P1b—C11b—C12b—C10b6.8 (4)
O2a—C10a—C12a—C13a115.5 (4)N3b—C10b—C12b—C13b119.8 (3)
N3a—C10a—C12a—C13a122.5 (4)O2b—C10b—C12b—C13b121.6 (3)
O2a—C10a—C12a—C11a62.6 (4)N3b—C10b—C12b—C11b59.9 (4)
N3a—C10a—C12a—C11a59.4 (4)O2b—C10b—C12b—C11b58.7 (4)
C11a—C12a—C13a—C14a0.5 (6)C11b—C12b—C13b—C14b0.2 (5)
C10a—C12a—C13a—C14a177.5 (3)C10b—C12b—C13b—C14b179.5 (3)
C12a—C13a—C14a—C15a0.4 (6)C12b—C13b—C14b—C15b1.5 (6)
C13a—C14a—C15a—C16a1.1 (6)C13b—C14b—C15b—C16b1.7 (6)
C14a—C15a—C16a—C11a0.9 (6)C12b—C11b—C16b—C15b0.6 (5)
C12a—C11a—C16a—C15a0.0 (5)P1b—C11b—C16b—C15b172.8 (3)
P1a—C11a—C16a—C15a176.0 (3)C14b—C15b—C16b—C11b0.7 (5)
C23a—P1a—C17a—C18a95.5 (3)C11b—P1b—C17b—C18b31.6 (3)
C11a—P1a—C17a—C18a13.0 (3)C23b—P1b—C17b—C18b79.5 (3)
Ni1a—P1a—C17a—C18a137.7 (3)Ni1b—P1b—C17b—C18b156.7 (3)
C23a—P1a—C17a—C22a80.7 (3)C11b—P1b—C17b—C22b151.4 (3)
C11a—P1a—C17a—C22a170.8 (3)C23b—P1b—C17b—C22b97.5 (3)
Ni1a—P1a—C17a—C22a46.2 (3)Ni1b—P1b—C17b—C22b26.3 (3)
C22a—C17a—C18a—C19a1.1 (6)C22b—C17b—C18b—C19b1.4 (5)
P1a—C17a—C18a—C19a174.9 (3)P1b—C17b—C18b—C19b175.6 (3)
C17a—C18a—C19a—C20a0.6 (6)C17b—C18b—C19b—C20b0.2 (6)
C18a—C19a—C20a—C21a0.1 (7)C18b—C19b—C20b—C21b1.5 (6)
C19a—C20a—C21a—C22a0.0 (7)C19b—C20b—C21b—C22b1.8 (6)
C18a—C17a—C22a—C21a1.1 (6)C20b—C21b—C22b—C17b0.5 (6)
P1a—C17a—C22a—C21a175.1 (3)C18b—C17b—C22b—C21b1.1 (5)
C20a—C21a—C22a—C17a0.6 (6)P1b—C17b—C22b—C21b176.0 (3)
C17a—P1a—C23a—C28a174.6 (3)C17b—P1b—C23b—C24b12.3 (4)
C11a—P1a—C23a—C28a73.6 (3)C11b—P1b—C23b—C24b125.6 (3)
Ni1a—P1a—C23a—C28a45.1 (3)Ni1b—P1b—C23b—C24b115.5 (3)
C17a—P1a—C23a—C24a7.2 (3)C17b—P1b—C23b—C28b172.7 (3)
C11a—P1a—C23a—C24a104.6 (3)C11b—P1b—C23b—C28b59.3 (3)
Ni1a—P1a—C23a—C24a136.8 (3)Ni1b—P1b—C23b—C28b59.5 (3)
C28a—C23a—C24a—C25a1.2 (6)C28b—C23b—C24b—C25b1.1 (6)
P1a—C23a—C24a—C25a177.0 (3)P1b—C23b—C24b—C25b176.1 (3)
C23a—C24a—C25a—C26a1.4 (7)C23b—C24b—C25b—C26b0.9 (7)
C24a—C25a—C26a—C27a1.0 (7)C24b—C25b—C26b—C27b0.5 (7)
C25a—C26a—C27a—C28a0.3 (7)C25b—C26b—C27b—C28b0.3 (7)
C26a—C27a—C28a—C23a0.2 (7)C24b—C23b—C28b—C27b0.9 (6)
C24a—C23a—C28a—C27a0.6 (6)P1b—C23b—C28b—C27b176.1 (3)
P1a—C23a—C28a—C27a177.6 (3)C26b—C27b—C28b—C23b0.5 (7)

Experimental details

Crystal data
Chemical formula[Ni(C28H30N3O2PS)]
Mr562.29
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)11.974 (3), 12.531 (2), 20.827 (7)
α, β, γ (°)89.81 (2), 73.56 (2), 68.26 (2)
V3)2765.9 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.86
Crystal size (mm)0.36 × 0.30 × 0.26
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionGaussian
(PLATON; Spek, 2003)
Tmin, Tmax0.756, 0.820
No. of measured, independent and
observed [I > 2σ(I)] reflections
11363, 10824, 6782
Rint0.025
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.117, 1.01
No. of reflections10824
No. of parameters657
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Ni1a—O1a1.836 (3)Ni1b—O1b1.835 (2)
Ni1a—N3a1.856 (3)Ni1b—N1b1.852 (3)
Ni1a—N1a1.864 (3)Ni1b—N3b1.857 (3)
Ni1a—P1a2.2001 (10)Ni1b—P1b2.1780 (12)
O1a—C6a1.314 (4)O1b—C6b1.303 (4)
N1a—C4a1.315 (4)N1b—C4b1.320 (4)
N1a—N2a1.408 (4)N1b—N2b1.412 (4)
N2a—C1a1.302 (4)N2b—C1b1.307 (4)
N3a—C1a1.354 (4)N3b—C1b1.347 (4)
C4a—C5a1.394 (5)C4b—C5b1.411 (5)
C5a—C6a1.355 (5)C5b—C6b1.353 (6)
O1a—Ni1a—N1a95.34 (13)O1b—Ni1b—N1b95.85 (13)
N3a—Ni1a—N1a82.79 (13)N1b—Ni1b—N3b82.64 (13)
O1a—Ni1a—P1a88.92 (8)O1b—Ni1b—P1b87.09 (9)
N3a—Ni1a—P1a93.17 (9)N3b—Ni1b—P1b94.53 (10)
The puckering parameters for the P1—C11—C12—C10—N3—Ni1 sequence top
Qq2q3θϕ
[NiL1]a0.714 (4)0.714 (4)-0.005 (3)90.4 (2)178.7 (3)
[NiL1]b0.696 (4)0.696 (4)0.018 (3)88.5 (2)-178.7 (3)
[NiL2]0.700.70-0.0392.3179.4
Geometrical parameters (Å,°) for selected C—H···π interactions top
Ω is the mid-point of an aromatic ring; β is the angle between the line connecting the H atom and Ω and the normal to the ring.
C—H···ΩH···ΩC···ΩβC—H···ΩΩ symmetry code
[NiL1]aC8a—H78a···Ω1a2.913.854.2146x,y,z
C14a—H14a···Ω2 b2.793.6710.11401 − x,1 − y,1 − z
C21a—H21a···Ω3a2.903.6913.51301 − x,-y,-z
C27a—H27a···Ω3a2.653.5519.3141-x,1 − y,-z
[NiL1]bC3b—H73b···Ω4 b2.843.6024.01281 − x,-y,1 − z
C8b—H78b···Ω1 b2.613.640.4159x,y,z
C21b—H21b···Ω4 b2.683.527.01351 − x,1 − y,1 − z
C25b—H25b···Ω4a2.663.6715.3157-x,1 − y,1 − z
C26b—H26b···Ω2a2.793.6110.6133-x,1 − y,1 − z
[NiL2]C8c—H78c···Ω1c3.064.0026.2146x,y,z
C9c—H79c···Ω5c3.013.8725.3137-1 + x,y,z
C19c—H19c···Ω2c3.003.9511.51471 − x,1 − y,1 − z
C21c—H21c···Ω6c2.973.7916.9134-x,-y,1 − z
Ω1a is the centroid of the C17a–C22a ring; (Ω2a), the C11a–C16a ring; (Ω3a), ring B; (Ω4a), ring A; (Ω1 b), the C17b—C22b ring; (Ω2 b), the C11b–C16b ring; (Ω4 b), ring A; (Ω1c), the C17c–C22c ring; (Ω2c), the C11c–C16c ring; (Ω5c), the C23c–C28c ring; (Ω6c), the C5c–C31c ring.
 

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