Bis{methyl [1-(6-acetyl-2-pyrid­yl)ethyl­idene]hydrazinecarbodithio­ato}nickel(II)

The title compound, [Ni(C₁₁H₁₂N₃OS₂)₂], is a six-coordinate Ni^II complex that is similar to other bis-tridentate N,N',S-coordinated Schiff bases, but in this case an acetyl substituent adjacent to the coordinated pyridyl N atom elongates the Ni-N bond by more than 0.06 Å relative to the complex where no substituent is present. A related 6-methyl-substituted Ni complex also shows a similar Ni-N bond elongation.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.027
• wR factor = 0.075
• Data-to-parameter ratio = 8.2

checkCIF/PLATON results

No syntax errors found





Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.97 Deg.

Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.75 Ratio
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C4A
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C4B
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety       C11B
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         12

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           24.97
           From the CIF: _reflns_number_total               2601
           Count of symmetry unique reflns         2601
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.02

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The potentially pentadendate Schiff base ligand (I) and its close relatives have been shown to favour pentagonal bipyramidal structures when complexed with metals such Sn(IV) (Akbar Ali et al., 2004), Zn(II) and Cd(II) (Akbar Ali, Mirza, Voo et al., 2003). In the synthesis of (I) it has been reported that the intermediate one-armed analogue (II) is also a product of the condensation reaction between 2,6-diacetylpyridine and S-methyldithiocarbate (Akbar Ali, Mirza, Keng & Butcher, 2003). The Pd(II) complex of (II) was structurally characterized. Herein we report the crystal structure of the bis-ligated six-coordinate Ni^II complex (III).

The structure of (III) reveals a distorted octahedral coordination geometry (Fig. 1). Each ligand deprotonates at N1a/b and the C1a/b-N1/a/b bonds approach double bond order due to the preferred ene-thiolate form of the coordinated monoanionic ligand (Table 2). The ligands each bind as a tridentate N,N,S chelate and the planar nature of the ligand enforces a meridional coordination mode. The shortest bond lengths are the central Ni—N bonds as expected. A point of interest is the rather long Ni—N3a/b bonds in comparison with the homologous complex (IV) (av. 2.12 Å) which lacks any substituents on the 6-positions of its pyridyl rings (Su et al., 1998). In this case the Ni—N bond lengths are more than 0.06 Å longer than found in the structure of (IV). Steric interactions between the non-coordinating acetyl groups and the adjacent ligand result in this bond elongation. The structure of the 6-methyl substituted analog (V) also exhibits a similar lengthening of the Ni—N_pyr coordinate bonds (Akbar Ali et al., 1997). It is also notable that these coordinate bond distortions are localized at the pyridyl groups as the remaining Ni—N and Ni—S coordinate bonds are the same within experimental error as those reported for (IV).

In conclusion, the absence of a second chelating arm in the ligand (II) leads to a preferred bis-tridentate coordination mode in complex with Ni^II and the 6-acetyl substituents on the pyridyl rings play a role in lengthening the Ni—N_pyr bonds substantially.

Related literature

For related literature, see: Akbar Ali, Mahbub-ul-Haque Majumder, Butcher, Jasinski & Jasinski (1997); Akbar Ali, Mirza, Keng & Butcher (2003); Akbar Ali, Mirza, Tan, Wei & Bernhardt (2004); Akbar Ali, Mirza, Voo, Tan & Bernhardt (2003); Su et al. (1998).

S2. Experimental

To a solution of nickel(II) chloride hexahydrate (0.03 g; 1.25 x 10 ^-4 mol) in boiling methanol (20 ml), conc. HCl (ca 0.3 ml) was added. The solution was mixed with a hot solution of the Schiff base, 2,6-diacetylpyridinebis(S-methyldithiocarbazonate, (I)) (0.09 g; 2.5 x 10 ^-4 mol) in methanol (50 ml) and the mixture was heated on a water bath for about one minute. On standing, the reaction mixture deposited crystals of the complex which were filtered off, washed with methanol and dried in a desiccator over anhydrous silica gel. Hydrolysis of (I) to (II) during the reaction was confirmed by isolation of its Ni^II complex (III).

S3. Refinement

All H atoms were treated as riding with C—H distances ranging from 0.93 to 0.96 Å and U_iso(H) values equal to 1.5 (methyl H atoms) or 1.2 (all other atoms) times U_eq of the parent atom. Only a unique (octant) data set was measured for the orthorhombic system so the R_int value is undetermined. Also the Flack parameter is only nominal given the lack of Friedel pairs in the data set.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; 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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Version 1.64.02; Farrugia, 1999).

Figures

	Fig. 1. ORTEP-3 plot of (III) (30% probability ellipsoids). H-atoms have been omitted for clarity. Atom labelling on ligand B follows that shown on ligand A.
	Fig. 2. The structures of compounds (I)–(V).

Bis{methyl [1-(6-acetyl-2-pyridyl)ethylidene]hydrazinecarbodithioato}nickel(II)

Crystal data

[Ni(C11H12N3OS2)2]	F(000) = 1224
Mr = 591.42	Dx = 1.51 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 10.6343 (8) Å	θ = 11.5–13.5°
b = 10.8217 (7) Å	µ = 1.10 mm^−1
c = 22.603 (2) Å	T = 293 K
V = 2601.2 (3) Å^3	Prism, brown
Z = 4	0.6 × 0.6 × 0.3 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2197 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
non–profiled ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.558, Tmax = 0.734	l = 0→26
2601 measured reflections	3 standard reflections every 120 min
2601 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.1306P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2601 reflections	Δρmax = 0.36 e Å^−3
316 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.032 (17)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni1	0.73584 (4)	0.93441 (4)	0.12063 (2)	0.03305 (14)
C1A	0.7000 (4)	0.7464 (4)	0.21782 (18)	0.0388 (9)
C1B	0.5642 (4)	0.9426 (4)	0.01415 (17)	0.0409 (9)
C2A	0.6984 (6)	0.6758 (5)	0.33646 (19)	0.0660 (15)
H2A1	0.6993	0.6094	0.3646	0.099*
H2A2	0.6235	0.7241	0.3417	0.099*
H2A3	0.7709	0.7273	0.3424	0.099*
C2B	0.5101 (5)	0.9472 (6)	−0.10626 (19)	0.0710 (15)
H2B1	0.447	0.9499	−0.1366	0.107*
H2B2	0.5595	0.8735	−0.1107	0.107*
H2B3	0.5636	1.0183	−0.1096	0.107*
C3A	0.6694 (4)	1.0590 (4)	0.22846 (16)	0.0376 (9)
C3B	0.8810 (4)	0.9067 (4)	0.01403 (19)	0.0424 (10)
C4A	0.6422 (5)	1.0822 (4)	0.29212 (17)	0.0531 (11)
H4A1	0.6389	1.0049	0.3129	0.08*
H4A2	0.5629	1.1237	0.2958	0.08*
H4A3	0.7074	1.1329	0.3087	0.08*
C4B	0.9165 (5)	0.8986 (5)	−0.05007 (18)	0.0612 (14)
H4B1	0.8424	0.9058	−0.074	0.092*
H4B2	0.9563	0.8205	−0.0576	0.092*
H4B3	0.9737	0.9643	−0.0596	0.092*
C5A	0.6787 (4)	1.1619 (4)	0.18649 (19)	0.0380 (9)
C5B	0.9791 (4)	0.8978 (4)	0.06058 (19)	0.0400 (10)
C6A	0.6311 (4)	1.2788 (4)	0.1985 (2)	0.0475 (11)
H6A	0.5937	1.2954	0.2349	0.057*
C6B	1.1035 (4)	0.8744 (5)	0.0466 (2)	0.0545 (12)
H6B	1.1279	0.8658	0.0073	0.065*
C7A	0.6397 (5)	1.3698 (4)	0.1562 (2)	0.0573 (12)
H7A	0.6052	1.4474	0.1631	0.069*
C7B	1.1902 (4)	0.8640 (5)	0.0910 (2)	0.0605 (13)
H7B	1.2741	0.8479	0.0825	0.073*
C8A	0.6995 (5)	1.3451 (4)	0.1041 (2)	0.0542 (12)
H8A	0.7058	1.4055	0.0749	0.065*
C8B	1.1505 (4)	0.8780 (4)	0.1483 (2)	0.0578 (13)
H8B	1.2074	0.8697	0.1793	0.069*
C9A	0.7504 (4)	1.2290 (4)	0.09532 (18)	0.0442 (9)
C9B	1.0268 (4)	0.9041 (4)	0.15966 (19)	0.0432 (10)
C10A	0.8309 (6)	1.2056 (4)	0.0410 (2)	0.0630 (14)
C10B	0.9866 (4)	0.9276 (4)	0.22341 (19)	0.0481 (10)
C11A	0.7768 (8)	1.2393 (6)	−0.0167 (2)	0.103 (3)
H11D	0.8364	1.2215	−0.0475	0.155*
H11E	0.7571	1.3258	−0.017	0.155*
H11F	0.7014	1.1924	−0.0233	0.155*
C11B	1.0123 (6)	0.8259 (5)	0.2656 (2)	0.0741 (16)
H11A	0.9843	0.8494	0.3044	0.111*
H11B	1.101	0.8094	0.2666	0.111*
H11C	0.9683	0.7529	0.2532	0.111*
N1A	0.6847 (3)	0.8516 (3)	0.24452 (15)	0.0412 (8)
N1B	0.6739 (3)	0.9282 (3)	−0.00883 (13)	0.0403 (7)
N2A	0.6903 (3)	0.9504 (3)	0.20621 (13)	0.0355 (7)
N2B	0.7690 (3)	0.9214 (3)	0.03321 (13)	0.0361 (7)
N3A	0.7383 (3)	1.1368 (3)	0.13456 (13)	0.0353 (7)
N3B	0.9405 (3)	0.9159 (3)	0.11689 (15)	0.0378 (7)
S1A	0.71898 (12)	0.71710 (10)	0.14389 (5)	0.0465 (3)
S1B	0.52284 (9)	0.95535 (12)	0.08710 (4)	0.0471 (3)
S2A	0.70145 (14)	0.61389 (11)	0.26300 (5)	0.0592 (3)
S2B	0.43594 (11)	0.94696 (14)	−0.03511 (5)	0.0573 (3)
O1A	0.9365 (4)	1.1685 (4)	0.04757 (19)	0.0833 (13)
O1B	0.9389 (3)	1.0233 (3)	0.23694 (15)	0.0592 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0334 (2)	0.0345 (2)	0.0312 (2)	−0.0014 (2)	0.0013 (2)	−0.0021 (2)
C1A	0.036 (2)	0.037 (2)	0.044 (2)	−0.0014 (18)	−0.0042 (18)	0.0084 (18)
C1B	0.046 (2)	0.033 (2)	0.044 (2)	0.001 (2)	−0.0068 (18)	−0.003 (2)
C2A	0.092 (4)	0.063 (3)	0.043 (3)	−0.003 (3)	0.003 (3)	0.012 (2)
C2B	0.075 (3)	0.096 (4)	0.042 (2)	−0.009 (3)	−0.010 (2)	0.009 (3)
C3A	0.0350 (19)	0.040 (2)	0.0376 (19)	−0.003 (2)	0.0012 (16)	−0.0049 (19)
C3B	0.046 (2)	0.038 (2)	0.044 (2)	−0.0020 (19)	0.0095 (19)	−0.0023 (19)
C4A	0.068 (3)	0.052 (3)	0.039 (2)	−0.004 (3)	0.007 (2)	−0.007 (2)
C4B	0.057 (3)	0.084 (4)	0.043 (2)	0.004 (3)	0.015 (2)	−0.004 (2)
C5A	0.035 (2)	0.034 (2)	0.045 (2)	−0.0054 (17)	−0.006 (2)	−0.0063 (18)
C5B	0.038 (2)	0.033 (2)	0.049 (2)	−0.0027 (17)	0.0031 (19)	−0.0017 (18)
C6A	0.049 (3)	0.039 (2)	0.054 (3)	0.002 (2)	0.006 (2)	−0.013 (2)
C6B	0.037 (2)	0.053 (3)	0.073 (3)	−0.004 (2)	0.012 (2)	−0.006 (3)
C7A	0.061 (3)	0.032 (2)	0.079 (3)	0.005 (2)	0.002 (3)	−0.004 (2)
C7B	0.028 (2)	0.058 (3)	0.095 (4)	0.002 (2)	0.004 (2)	−0.011 (3)
C8A	0.062 (3)	0.033 (2)	0.067 (3)	0.000 (2)	0.005 (2)	0.010 (2)
C8B	0.034 (2)	0.053 (3)	0.086 (3)	0.002 (2)	−0.016 (2)	−0.010 (3)
C9A	0.045 (2)	0.040 (2)	0.048 (2)	−0.005 (2)	−0.001 (2)	0.0049 (18)
C9B	0.038 (2)	0.034 (2)	0.058 (3)	−0.0058 (18)	−0.006 (2)	−0.0061 (19)
C10A	0.097 (4)	0.033 (2)	0.060 (3)	−0.009 (3)	0.023 (3)	0.007 (2)
C10B	0.039 (2)	0.051 (3)	0.054 (2)	−0.004 (2)	−0.0140 (19)	−0.011 (2)
C11A	0.172 (8)	0.086 (4)	0.052 (3)	−0.007 (5)	0.020 (4)	0.009 (3)
C11B	0.083 (4)	0.074 (4)	0.065 (4)	0.011 (3)	−0.013 (3)	0.006 (3)
N1A	0.0463 (19)	0.0378 (19)	0.0394 (18)	−0.0045 (16)	0.0008 (16)	0.0074 (16)
N1B	0.0421 (18)	0.0453 (19)	0.0336 (16)	0.0015 (18)	−0.0038 (14)	0.0003 (17)
N2A	0.0364 (17)	0.0354 (18)	0.0347 (16)	−0.0019 (15)	−0.0012 (13)	0.0003 (14)
N2B	0.0364 (16)	0.0369 (17)	0.0351 (15)	0.0005 (17)	0.0048 (15)	−0.0003 (14)
N3A	0.0354 (17)	0.0336 (16)	0.0367 (17)	0.0007 (15)	0.0030 (15)	0.0003 (13)
N3B	0.0317 (15)	0.0347 (18)	0.0470 (18)	−0.0014 (14)	−0.0029 (15)	−0.0028 (17)
S1A	0.0627 (7)	0.0349 (5)	0.0417 (5)	−0.0032 (5)	0.0036 (5)	−0.0027 (4)
S1B	0.0327 (5)	0.0656 (8)	0.0428 (5)	−0.0014 (5)	0.0003 (4)	−0.0091 (6)
S2A	0.0878 (9)	0.0398 (6)	0.0500 (7)	−0.0036 (6)	−0.0048 (6)	0.0104 (5)
S2B	0.0481 (6)	0.0739 (9)	0.0499 (6)	0.0051 (7)	−0.0147 (5)	−0.0001 (7)
O1A	0.086 (3)	0.065 (3)	0.098 (3)	0.009 (2)	0.048 (3)	0.013 (2)
O1B	0.058 (2)	0.0513 (19)	0.069 (2)	0.0038 (17)	−0.0120 (17)	−0.0159 (17)

Geometric parameters (Å, º)

Ni1—N2A	2.002 (3)	C5A—N3A	1.361 (5)
Ni1—N2B	2.012 (3)	C5A—C6A	1.390 (6)
Ni1—N3B	2.188 (3)	C5B—N3B	1.351 (5)
Ni1—N3A	2.213 (3)	C5B—C6B	1.383 (6)
Ni1—S1B	2.399 (1)	C6A—C7A	1.375 (6)
Ni1—S1A	2.416 (1)	C6A—H6A	0.93
C1A—N1A	1.299 (5)	C6B—C7B	1.368 (7)
C1A—S1A	1.713 (4)	C6B—H6B	0.93
C1A—S2A	1.760 (4)	C7A—C8A	1.366 (6)
C1B—N1B	1.286 (5)	C7A—H7A	0.93
C1B—S1B	1.712 (4)	C7B—C8B	1.370 (7)
C1B—S2B	1.761 (4)	C7B—H7B	0.93
C2A—S2A	1.791 (5)	C8A—C9A	1.382 (6)
C2A—H2A1	0.96	C8A—H8A	0.93
C2A—H2A2	0.96	C8B—C9B	1.371 (6)
C2A—H2A3	0.96	C8B—H8B	0.93
C2B—S2B	1.791 (5)	C9A—N3A	1.342 (5)
C2B—H2B1	0.96	C9A—C10A	1.518 (7)
C2B—H2B2	0.96	C9B—N3B	1.338 (5)
C2B—H2B3	0.96	C9B—C10B	1.524 (6)
C3A—N2A	1.297 (5)	C10A—O1A	1.201 (7)
C3A—C5A	1.466 (6)	C10A—C11A	1.473 (8)
C3A—C4A	1.489 (5)	C10B—O1B	1.193 (5)
C3B—N2B	1.277 (5)	C10B—C11B	1.482 (6)
C3B—C5B	1.485 (6)	C11A—H11D	0.96
C3B—C4B	1.500 (5)	C11A—H11E	0.96
C4A—H4A1	0.96	C11A—H11F	0.96
C4A—H4A2	0.96	C11B—H11A	0.96
C4A—H4A3	0.96	C11B—H11B	0.96
C4B—H4B1	0.96	C11B—H11C	0.96
C4B—H4B2	0.96	N1A—N2A	1.377 (4)
C4B—H4B3	0.96	N1B—N2B	1.390 (4)
N2A—Ni1—N2B	176.0 (1)	C5A—C6A—H6A	120.3
N2A—Ni1—N3B	106.6 (1)	C7B—C6B—C5B	119.4 (5)
N2B—Ni1—N3B	77.4 (1)	C7B—C6B—H6B	120.3
N2A—Ni1—N3A	77.3 (1)	C5B—C6B—H6B	120.3
N2B—Ni1—N3A	102.0 (1)	C8A—C7A—C6A	119.4 (4)
N3B—Ni1—N3A	94.8 (1)	C8A—C7A—H7A	120.3
N2A—Ni1—S1B	93.92 (9)	C6A—C7A—H7A	120.3
N2B—Ni1—S1B	82.07 (9)	C6B—C7B—C8B	118.5 (4)
N3B—Ni1—S1B	159.4 (1)	C6B—C7B—H7B	120.7
N3A—Ni1—S1B	87.85 (9)	C8B—C7B—H7B	120.7
N2A—Ni1—S1A	81.7 (1)	C7A—C8A—C9A	118.9 (4)
N2B—Ni1—S1A	99.12 (9)	C7A—C8A—H8A	120.5
N3B—Ni1—S1A	89.61 (9)	C9A—C8A—H8A	120.5
N3A—Ni1—S1A	158.93 (8)	C7B—C8B—C9B	119.7 (4)
S1B—Ni1—S1A	95.20 (5)	C7B—C8B—H8B	120.2
N1A—C1A—S1A	129.0 (3)	C9B—C8B—H8B	120.2
N1A—C1A—S2A	116.5 (3)	N3A—C9A—C8A	123.0 (4)
S1A—C1A—S2A	114.5 (2)	N3A—C9A—C10A	117.7 (4)
N1B—C1B—S1B	129.2 (3)	C8A—C9A—C10A	119.3 (4)
N1B—C1B—S2B	116.8 (3)	N3B—C9B—C8B	122.8 (4)
S1B—C1B—S2B	114.1 (2)	N3B—C9B—C10B	118.4 (3)
S2A—C2A—H2A1	109.5	C8B—C9B—C10B	118.7 (4)
S2A—C2A—H2A2	109.5	O1A—C10A—C11A	123.9 (6)
H2A1—C2A—H2A2	109.5	O1A—C10A—C9A	118.9 (5)
S2A—C2A—H2A3	109.5	C11A—C10A—C9A	117.0 (5)
H2A1—C2A—H2A3	109.5	O1B—C10B—C11B	123.9 (4)
H2A2—C2A—H2A3	109.5	O1B—C10B—C9B	120.4 (4)
S2B—C2B—H2B1	109.5	C11B—C10B—C9B	115.7 (4)
S2B—C2B—H2B2	109.5	C10A—C11A—H11D	109.5
H2B1—C2B—H2B2	109.5	C10A—C11A—H11E	109.5
S2B—C2B—H2B3	109.5	H11D—C11A—H11E	109.5
H2B1—C2B—H2B3	109.5	C10A—C11A—H11F	109.5
H2B2—C2B—H2B3	109.5	H11D—C11A—H11F	109.5
N2A—C3A—C5A	115.2 (3)	H11E—C11A—H11F	109.5
N2A—C3A—C4A	124.1 (4)	C10B—C11B—H11A	109.5
C5A—C3A—C4A	120.7 (4)	C10B—C11B—H11B	109.5
N2B—C3B—C5B	115.0 (4)	H11A—C11B—H11B	109.5
N2B—C3B—C4B	124.8 (4)	C10B—C11B—H11C	109.5
C5B—C3B—C4B	120.2 (4)	H11A—C11B—H11C	109.5
C3A—C4A—H4A1	109.5	H11B—C11B—H11C	109.5
C3A—C4A—H4A2	109.5	C1A—N1A—N2A	112.5 (3)
H4A1—C4A—H4A2	109.5	C1B—N1B—N2B	113.0 (3)
C3A—C4A—H4A3	109.5	C3A—N2A—N1A	116.9 (3)
H4A1—C4A—H4A3	109.5	C3A—N2A—Ni1	119.6 (3)
H4A2—C4A—H4A3	109.5	N1A—N2A—Ni1	123.4 (2)
C3B—C4B—H4B1	109.5	C3B—N2B—N1B	117.0 (3)
C3B—C4B—H4B2	109.5	C3B—N2B—Ni1	120.4 (3)
H4B1—C4B—H4B2	109.5	N1B—N2B—Ni1	122.7 (2)
C3B—C4B—H4B3	109.5	C9A—N3A—C5A	117.8 (3)
H4B1—C4B—H4B3	109.5	C9A—N3A—Ni1	130.1 (3)
H4B2—C4B—H4B3	109.5	C5A—N3A—Ni1	108.4 (2)
N3A—C5A—C6A	121.3 (4)	C9B—N3B—C5B	117.3 (3)
N3A—C5A—C3A	115.9 (3)	C9B—N3B—Ni1	131.5 (3)
C6A—C5A—C3A	122.7 (4)	C5B—N3B—Ni1	110.6 (3)
N3B—C5B—C6B	122.2 (4)	C1A—S1A—Ni1	92.36 (14)
N3B—C5B—C3B	116.4 (3)	C1B—S1B—Ni1	93.10 (14)
C6B—C5B—C3B	121.4 (4)	C1A—S2A—C2A	103.5 (2)
C7A—C6A—C5A	119.4 (4)	C1B—S2B—C2B	103.1 (2)
C7A—C6A—H6A	120.3