Tetra­kis[tris­(2,2′-bi-1H-benzimidazole)nickel(II)] bis­(phosphate) sulfate

Ling, C.-S.; Yan, L.

doi:10.1107/S1600536808032571

Tetrakis[tris(2,2′-bi-1H-benzimidazole)nickel(II)] bis(phosphate) sulfate

The title compound, [Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄), consists of [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations (.3. symmetry) and disordered anions ( ${\overline 4}$ symmetry) with occupancy factors of two-thirds for PO₄³⁻ and one-third for SO₄²⁻. The Ni²⁺ centre is chelated by three bidentate 2,2′-bi-1H-benzimidazole molecules in a distorted octahedral coordination. N—H

O hydrogen bonds consolidate the building units into a framework structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808032571/at2642sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808032571/at2642Isup2.hkl Contains datablock I

CCDC reference: 709514

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.006 Å
Disorder in solvent or counterion
R factor = 0.038
wR factor = 0.098
Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   296.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.02
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         O1
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N3  -NI1 -N1  -C7     41.70  0.70   7.564   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            N3  -NI1 -N1  -C1   -138.60  0.60   7.564   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N1  -NI1 -N3  -C14    49.90  0.70  10.655   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -NI1 -N3  -C8   -126.70  0.60  10.655   1.555   1.555   1.555

Alert level G
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: check formula stoichiometry or atom site occupancies.
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C168 H120 N48 Ni4 O12 P2 S
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        672.00    672.00    0.00
           H        480.00    480.00    0.00
           N        192.00    192.00    0.00
           Ni        16.00     16.00    0.00
           O         48.00     48.00    0.00
           P          8.00      8.04   -0.04
           S          4.00      3.96    0.04
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               2551
           From the CIF: _diffrn_reflns_limit_ max hkl   11.   29.   20.
           From the CIF: _diffrn_reflns_limit_ min hkl  -30.  -30.  -21.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   30.   30.   30.
           Calculated minimum hkl  -30.  -30.  -30.
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               2551
           Count of symmetry unique reflns         1369
           Completeness (_total/calc)            186.34%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1182
           Fraction of Friedel pairs measured     0.863
           Are heavy atom types Z>Si present        yes
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      17.00 Perc.

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

   4 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
   0 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

More attentions have been paid to metal-organic coordination compounds (MOCCs) because of their potential applications in gas absorption and separation, catalysis, nonlinear optics, luminescence and magnetism (Kitagawa & Matsuda 2007, Maspoch et al. 2007). In the field of coordination chemistry, the N,N-bidentate ligands, such as 2,2'-bipyridine, 1,10-phenanthroline and their derivatives act as versatile ligands owing to the stable coordination configuration in the bidentate N-donors chelating manner. Herein, we report the title compound (I).

The title compound (I) consists of four [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations, one [SO₄]^2- and two [PO₄]^3- anions. In the mlecular structure, the Ni²⁺ centre is coordinated by six N atoms from three bidentate 1H,1'H-2,2'-bi-1H-benzimidazole molecules (Fig.1). The 1H,1'H-2,2'-bi-1H-benzimidazole ligand was prepared in situ and coordinated to the Ni²⁺ cations in hydrothermal reaction. Additionally, the [SO₄]^2- and [PO₄]^3- anions statistically distribute in one position with 1/3 probability for S and 2/3 probability for P atoms. The environment of the Ni²⁺ caion is in a distorted octahedral geometry with the Ni—N distances ranging from 2.088 (3) to 2.122 (3) Å (Table 1).

In addition, the [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations, [SO₄]^2- and [PO₄]^3- anions in the complexes are linked together via many N—H···O hydrogen bonds resulting in a three-dimensional structural frameworks (Fig.2 and Table 2).

Related literature top

For the potential applications of metal–organic coordination compounds in gas absorption and separation, catalysis, nonlinear optics, luminescence and magnetism, see: Kitagawa & Matsuda (2007); Maspoch et al. (2007).

Experimental top

All reagents were commercially available and of analytical grade. The mixture of NiSO₄.6H₂O, H₃PO₄, oxalic acid, and 1,2-diaminobenzene in the mole ratio of 1: 1.5: 6: 6 was dissolved in 25 ml H₂O, which was heated in a Teflon-lined steel autoclave inside a programmable electric furnace at 393 K for five days. After cooling the autoclave to room temperature, green block crystals of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
	Fig. 2. Three-dimensional structure of (I). Displacement ellipsoids are drawn at the 50% probability level. For clarity, H atoms not involved in hydrogen bonds are omitted.

Tetrakis[tris(2,2'-bi-1H-benzimidazole)nickel(II)] bis(phosphate) sulfate top

Crystal data top

[Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄)	D_x = 1.423 Mg m⁻³
M_r = 3331.96	Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d	Cell parameters from 3375 reflections
Hall symbol: I -4bd 2c 3	θ = 2.3–19.2°
a = 24.964 (7) Å	µ = 0.59 mm⁻¹
V = 15558 (8) Å³	T = 296 K
Z = 4	Block, green
F(000) = 6872	0.32 × 0.27 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2551 independent reflections
Radiation source: fine-focus sealed tube	1782 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −30→11
T_min = 0.834, T_max = 0.876	k = −30→29
20222 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0528P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
2551 reflections	Δρ_max = 0.61 e Å⁻³
177 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1182 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Crystal data top

[Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄)	Z = 4
M_r = 3331.96	Mo Kα radiation
Cubic, I43d	µ = 0.59 mm⁻¹
a = 24.964 (7) Å	T = 296 K
V = 15558 (8) Å³	0.32 × 0.27 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2551 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1782 reflections with I > 2σ(I)
T_min = 0.834, T_max = 0.876	R_int = 0.066
20222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.098	Δρ_max = 0.61 e Å⁻³
S = 1.01	Δρ_min = −0.20 e Å⁻³
2551 reflections	Absolute structure: Flack (1983), 1182 Friedel pairs
177 parameters	Absolute structure parameter: −0.02 (2)
0 restraints

Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.564621 (16)	0.435379 (16)	−0.064621 (16)	0.0428 (2)
P1	0.7500	0.6250	1.0000	0.0427 (4)	0.67
S1	0.7500	0.6250	1.0000	0.0427 (4)	0.33
N1	0.64773 (10)	0.44469 (11)	−0.06574 (11)	0.0443 (6)
N2	0.71668 (10)	0.50117 (12)	−0.06248 (11)	0.0498 (7)
H2B	0.7340	0.5309	−0.0604	0.060*
N3	0.56297 (10)	0.42828 (11)	0.02009 (10)	0.0444 (6)
N4	0.55652 (11)	0.37290 (12)	0.08942 (11)	0.0502 (7)
H4B	0.5538	0.3435	0.1072	0.060*
C1	0.69498 (13)	0.41559 (13)	−0.06917 (13)	0.0462 (8)
C2	0.70405 (15)	0.36114 (16)	−0.07434 (15)	0.0594 (9)
H2	0.6758	0.3370	−0.0763	0.071*
C3	0.75637 (17)	0.34409 (18)	−0.07642 (16)	0.0744 (13)
H3	0.7638	0.3077	−0.0797	0.089*
C4	0.79858 (16)	0.3808 (2)	−0.07359 (16)	0.0707 (12)
H4	0.8335	0.3679	−0.0750	0.085*
C5	0.79104 (13)	0.43383 (18)	−0.06895 (15)	0.0627 (10)
H5	0.8197	0.4576	−0.0670	0.075*
C6	0.73810 (12)	0.45147 (14)	−0.06724 (14)	0.0473 (8)
C7	0.66286 (13)	0.49523 (14)	−0.06164 (13)	0.0443 (8)
C8	0.56226 (15)	0.45873 (13)	0.06673 (14)	0.0487 (9)
C9	0.56566 (17)	0.51278 (15)	0.07424 (15)	0.0645 (11)
H9	0.5681	0.5363	0.0455	0.077*
C10	0.5653 (2)	0.53090 (18)	0.12671 (19)	0.0848 (13)
H10	0.5672	0.5675	0.1333	0.102*
C11	0.5623 (2)	0.49628 (19)	0.16920 (17)	0.0863 (14)
H11	0.5627	0.5102	0.2037	0.104*
C12	0.55859 (18)	0.44183 (18)	0.16272 (14)	0.0698 (11)
H12	0.5562	0.4186	0.1917	0.084*
C13	0.55865 (13)	0.42369 (14)	0.11042 (13)	0.0489 (8)
C14	0.55946 (13)	0.37792 (14)	0.03571 (13)	0.0443 (8)
O1	0.77314 (11)	0.59036 (9)	0.95604 (10)	0.0629 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0428 (2)	0.0428 (2)	0.0428 (2)	−0.00140 (19)	−0.00140 (19)	0.00140 (19)
P1	0.0469 (6)	0.0341 (9)	0.0469 (6)	0.000	0.000	0.000
S1	0.0469 (6)	0.0341 (9)	0.0469 (6)	0.000	0.000	0.000
N1	0.0386 (14)	0.0485 (17)	0.0458 (16)	0.0000 (13)	−0.0006 (13)	0.0019 (15)
N2	0.0447 (17)	0.0543 (18)	0.0503 (17)	−0.0083 (14)	−0.0009 (14)	−0.0019 (15)
N3	0.0432 (16)	0.0445 (16)	0.0456 (15)	0.0006 (15)	−0.0046 (13)	−0.0007 (13)
N4	0.0552 (19)	0.0518 (18)	0.0436 (17)	−0.0046 (14)	−0.0034 (14)	0.0093 (14)
C1	0.049 (2)	0.0486 (19)	0.0411 (18)	0.0030 (16)	−0.0031 (17)	−0.0036 (15)
C2	0.054 (2)	0.060 (2)	0.065 (2)	0.0073 (18)	−0.0023 (19)	−0.0042 (19)
C3	0.064 (3)	0.076 (3)	0.084 (3)	0.024 (2)	−0.003 (2)	−0.009 (2)
C4	0.045 (2)	0.097 (4)	0.070 (3)	0.021 (2)	−0.002 (2)	−0.014 (2)
C5	0.0439 (19)	0.083 (3)	0.061 (3)	0.000 (2)	−0.0050 (18)	−0.016 (3)
C6	0.0417 (19)	0.064 (2)	0.0366 (18)	0.0018 (16)	−0.0048 (16)	−0.0077 (17)
C7	0.044 (2)	0.048 (2)	0.0410 (19)	−0.0065 (15)	−0.0027 (15)	−0.0012 (16)
C8	0.049 (2)	0.052 (2)	0.0449 (19)	0.0051 (16)	−0.0042 (18)	−0.0057 (16)
C9	0.092 (3)	0.050 (2)	0.051 (2)	−0.002 (2)	−0.009 (2)	−0.0036 (17)
C10	0.124 (4)	0.065 (3)	0.066 (3)	0.006 (3)	−0.010 (3)	−0.013 (2)
C11	0.133 (4)	0.077 (3)	0.049 (3)	0.001 (3)	−0.013 (3)	−0.017 (2)
C12	0.093 (3)	0.074 (3)	0.042 (2)	−0.006 (3)	−0.005 (2)	0.001 (2)
C13	0.050 (2)	0.055 (2)	0.0423 (19)	−0.0009 (18)	−0.0050 (16)	−0.0006 (16)
C14	0.0315 (18)	0.053 (2)	0.049 (2)	−0.0032 (16)	−0.0021 (15)	0.0045 (17)
O1	0.0818 (18)	0.0455 (15)	0.0616 (17)	−0.0077 (13)	0.0150 (14)	−0.0033 (12)

Geometric parameters (Å, º) top

Ni1—N1	2.088 (3)	C1—C6	1.401 (5)
Ni1—N1ⁱ	2.088 (3)	C2—C3	1.375 (5)
Ni1—N1ⁱⁱ	2.088 (3)	C2—H2	0.9300
Ni1—N3ⁱⁱ	2.122 (3)	C3—C4	1.398 (6)
Ni1—N3	2.122 (3)	C3—H3	0.9300
Ni1—N3ⁱ	2.122 (3)	C4—C5	1.342 (6)
P1—O1ⁱⁱⁱ	1.512 (3)	C4—H4	0.9300
P1—O1^iv	1.512 (3)	C5—C6	1.394 (4)
P1—O1	1.512 (3)	C5—H5	0.9300
P1—O1^v	1.512 (3)	C7—C14ⁱⁱ	1.435 (5)
N1—C7	1.321 (4)	C8—C9	1.365 (5)
N1—C1	1.388 (4)	C8—C13	1.401 (5)
N2—C7	1.352 (4)	C9—C10	1.386 (6)
N2—C6	1.356 (4)	C9—H9	0.9300
N2—H2B	0.8600	C10—C11	1.370 (6)
N3—C14	1.319 (4)	C10—H10	0.9300
N3—C8	1.391 (4)	C11—C12	1.372 (6)
N4—C14	1.349 (4)	C11—H11	0.9300
N4—C13	1.373 (4)	C12—C13	1.382 (5)
N4—H4B	0.8600	C12—H12	0.9300
C1—C2	1.384 (5)	C14—C7ⁱ	1.435 (5)

N1—Ni1—N1ⁱ	95.67 (10)	C1—C2—H2	121.2
N1—Ni1—N1ⁱⁱ	95.67 (10)	C2—C3—C4	120.7 (4)
N1ⁱ—Ni1—N1ⁱⁱ	95.67 (10)	C2—C3—H3	119.6
N1—Ni1—N3ⁱⁱ	78.84 (10)	C4—C3—H3	119.6
N1ⁱ—Ni1—N3ⁱⁱ	170.67 (9)	C5—C4—C3	123.0 (4)
N1ⁱⁱ—Ni1—N3ⁱⁱ	92.40 (9)	C5—C4—H4	118.5
N1—Ni1—N3	92.40 (9)	C3—C4—H4	118.5
N1ⁱ—Ni1—N3	78.84 (10)	C4—C5—C6	116.6 (4)
N1ⁱⁱ—Ni1—N3	170.67 (9)	C4—C5—H5	121.7
N3ⁱⁱ—Ni1—N3	93.75 (9)	C6—C5—H5	121.7
N1—Ni1—N3ⁱ	170.67 (9)	N2—C6—C5	131.7 (3)
N1ⁱ—Ni1—N3ⁱ	92.40 (9)	N2—C6—C1	106.6 (3)
N1ⁱⁱ—Ni1—N3ⁱ	78.84 (10)	C5—C6—C1	121.7 (3)
N3ⁱⁱ—Ni1—N3ⁱ	93.75 (9)	N1—C7—N2	112.8 (3)
N3—Ni1—N3ⁱ	93.75 (9)	N1—C7—C14ⁱⁱ	118.2 (3)
O1ⁱⁱⁱ—P1—O1^iv	110.22 (17)	N2—C7—C14ⁱⁱ	128.9 (3)
O1ⁱⁱⁱ—P1—O1	109.10 (9)	C9—C8—N3	130.9 (3)
O1^iv—P1—O1	109.10 (9)	C9—C8—C13	121.0 (3)
O1ⁱⁱⁱ—P1—O1^v	109.10 (9)	N3—C8—C13	108.1 (3)
O1^iv—P1—O1^v	109.10 (9)	C8—C9—C10	116.9 (4)
O1—P1—O1^v	110.22 (17)	C8—C9—H9	121.6
C7—N1—C1	105.2 (3)	C10—C9—H9	121.6
C7—N1—Ni1	112.9 (2)	C11—C10—C9	121.7 (4)
C1—N1—Ni1	141.9 (2)	C11—C10—H10	119.1
C7—N2—C6	107.0 (3)	C9—C10—H10	119.1
C7—N2—H2B	126.5	C10—C11—C12	122.5 (4)
C6—N2—H2B	126.5	C10—C11—H11	118.7
C14—N3—C8	105.8 (3)	C12—C11—H11	118.7
C14—N3—Ni1	112.0 (2)	C11—C12—C13	115.8 (4)
C8—N3—Ni1	142.1 (2)	C11—C12—H12	122.1
C14—N4—C13	107.0 (3)	C13—C12—H12	122.1
C14—N4—H4B	126.5	N4—C13—C12	131.5 (3)
C13—N4—H4B	126.5	N4—C13—C8	106.4 (3)
C2—C1—N1	131.2 (3)	C12—C13—C8	122.1 (3)
C2—C1—C6	120.4 (3)	N3—C14—N4	112.7 (3)
N1—C1—C6	108.4 (3)	N3—C14—C7ⁱ	117.7 (3)
C3—C2—C1	117.6 (4)	N4—C14—C7ⁱ	129.5 (3)
C3—C2—H2	121.2

N1ⁱ—Ni1—N1—C7	−168.5 (2)	C2—C1—C6—N2	179.6 (3)
N1ⁱⁱ—Ni1—N1—C7	95.2 (3)	N1—C1—C6—N2	0.3 (4)
N3ⁱⁱ—Ni1—N1—C7	3.9 (2)	C2—C1—C6—C5	−1.8 (5)
N3—Ni1—N1—C7	−89.5 (3)	N1—C1—C6—C5	178.9 (3)
N3ⁱ—Ni1—N1—C7	41.7 (7)	C1—N1—C7—N2	0.4 (4)
N1ⁱ—Ni1—N1—C1	11.1 (4)	Ni1—N1—C7—N2	−179.9 (2)
N1ⁱⁱ—Ni1—N1—C1	−85.2 (3)	C1—N1—C7—C14ⁱⁱ	177.6 (3)
N3ⁱⁱ—Ni1—N1—C1	−176.5 (4)	Ni1—N1—C7—C14ⁱⁱ	−2.6 (4)
N3—Ni1—N1—C1	90.1 (4)	C6—N2—C7—N1	−0.2 (4)
N3ⁱ—Ni1—N1—C1	−138.6 (6)	C6—N2—C7—C14ⁱⁱ	−177.1 (3)
N1—Ni1—N3—C14	−100.0 (2)	C14—N3—C8—C9	178.8 (4)
N1ⁱ—Ni1—N3—C14	−4.7 (2)	Ni1—N3—C8—C9	−4.5 (7)
N1ⁱⁱ—Ni1—N3—C14	49.9 (7)	C14—N3—C8—C13	0.5 (4)
N3ⁱⁱ—Ni1—N3—C14	−178.9 (2)	Ni1—N3—C8—C13	177.2 (3)
N3ⁱ—Ni1—N3—C14	87.1 (3)	N3—C8—C9—C10	−178.2 (4)
N1—Ni1—N3—C8	83.5 (4)	C13—C8—C9—C10	0.0 (6)
N1ⁱ—Ni1—N3—C8	178.8 (4)	C8—C9—C10—C11	0.7 (7)
N1ⁱⁱ—Ni1—N3—C8	−126.7 (6)	C9—C10—C11—C12	−1.0 (8)
N3ⁱⁱ—Ni1—N3—C8	4.5 (4)	C10—C11—C12—C13	0.6 (8)
N3ⁱ—Ni1—N3—C8	−89.5 (3)	C14—N4—C13—C12	−178.1 (4)
C7—N1—C1—C2	−179.6 (4)	C14—N4—C13—C8	0.8 (4)
Ni1—N1—C1—C2	0.7 (7)	C11—C12—C13—N4	178.7 (4)
C7—N1—C1—C6	−0.4 (4)	C11—C12—C13—C8	0.0 (6)
Ni1—N1—C1—C6	180.0 (3)	C9—C8—C13—N4	−179.3 (3)
N1—C1—C2—C3	−179.6 (3)	N3—C8—C13—N4	−0.8 (4)
C6—C1—C2—C3	1.2 (5)	C9—C8—C13—C12	−0.3 (6)
C1—C2—C3—C4	−0.3 (6)	N3—C8—C13—C12	178.2 (4)
C2—C3—C4—C5	−0.2 (6)	C8—N3—C14—N4	0.0 (4)
C3—C4—C5—C6	−0.3 (6)	Ni1—N3—C14—N4	−177.9 (2)
C7—N2—C6—C5	−178.5 (4)	C8—N3—C14—C7ⁱ	−177.4 (3)
C7—N2—C6—C1	0.0 (4)	Ni1—N3—C14—C7ⁱ	4.8 (3)
C4—C5—C6—N2	179.5 (4)	C13—N4—C14—N3	−0.5 (4)
C4—C5—C6—C1	1.3 (6)	C13—N4—C14—C7ⁱ	176.5 (3)

Symmetry codes: (i) −z+1/2, −x+1, y−1/2; (ii) −y+1, z+1/2, −x+1/2; (iii) −z+7/4, −y+5/4, x+1/4; (iv) z−1/4, −y+5/4, −x+7/4; (v) −x+3/2, y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1^vi	0.86	1.96	2.766 (4)	156
N2—H2B···O1^vii	0.86	1.82	2.675 (4)	170

Symmetry codes: (vi) x−1/4, −z+5/4, −y+3/4; (vii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄)
M_r	3331.96
Crystal system, space group	Cubic, I43d
Temperature (K)	296
a (Å)	24.964 (7)
V (Å³)	15558 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.32 × 0.27 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.834, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	20222, 2551, 1782
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.01
No. of reflections	2551
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.20
Absolute structure	Flack (1983), 1182 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).