Crystal engineering on superpolyhedral building blocks in metal–organic frameworks applied in gas adsorption

Two metal–organic frameworks [PCN-426(Ni) and PCN-427(Cu)] have been designed and synthesized to investigate the structure predictability using a SBB (supermolecular building blocks) approach. Tetratopic ligands featuring 120° angular carboxylate moieties were coordinated with a [Ni₃(μ₃-O)] cluster and a [Cu₂O₂] unit, respectively. As topologically predicted, 4-connected networks with square coordination adopted the nbo net for the Ni-MOF and ssb net for the Cu-MOF. PCN-426(Ni) was augmented with 12-connected octahedral SBBs, while PCN-427(Cu) was constructed with tetragonal open channels. After a CO₂ supercritical drying procedure, the PCN-426(Ni) possessed a Brunauer–Emmett–Teller (BET) surface area as high as 3935 m² g⁻¹ and impressively high N₂ uptake of 1500 cm³ g⁻¹. This work demonstrates the generalization of the SBB strategy, finding an alternative to inconvenient synthetic processes to achieve the desired structural features.

Computing details

For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT+ ver. (Bruker, 2001); data reduction: SAINT+ ver. (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL12 (Sheldrick, 2012); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(Cu3344_sq)

Crystal data

(Cu2O2)(C32H22O8)	Dx = 0.726 Mg m^−3
Mr = 693.58	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/mnm	Cell parameters from 9993 reflections
a = 18.7570 (5) Å	θ = 2.2–21.4°
c = 36.092 (2) Å	µ = 0.70 mm^−1
V = 12698.2 (9) Å^3	T = 110 K
Z = 8	Block, blue
F(000) = 2816	0.1 × 0.1 × 0.1 mm

Data collection

Bruker SMART APEX II CCD area detector diffractometer	6634 independent reflections
Radiation source: fine-focus sealed tube	4986 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
phi and ω scans	θmax = 26.0°, θmin = 1.2°
Absorption correction: multi-scan SADABS (Sheldrick, 2008)	h = −23→23
Tmin = 0.934, Tmax = 0.934	k = −23→23
131327 measured reflections	l = −44→44

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.030P)^2 + 40.P] where P = (Fo^2 + 2Fc^2)/3
6634 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cu1	0.20137 (3)	0.79863 (3)	0.226367 (18)	0.0439 (2)
Cu2	0.26578 (3)	0.73422 (3)	0.282786 (17)	0.04118 (19)
O1	0.29616 (16)	0.80305 (18)	0.20531 (8)	0.0617 (8)
O1S	0.14899 (17)	0.85101 (17)	0.18114 (11)	0.0692 (13)
O2	0.35305 (14)	0.75031 (16)	0.25339 (7)	0.0516 (7)
O2S	0.31721 (17)	0.68279 (17)	0.32821 (11)	0.0644 (12)
O3	0.61530 (15)	0.71982 (17)	0.24486 (8)	0.0574 (8)
O4	0.66978 (14)	0.77253 (16)	0.19638 (7)	0.0514 (7)
C1	0.48273 (10)	0.76427 (11)	0.21648 (4)	0.0476 (10)
H1A	0.4849	0.7580	0.2426	0.057*
C2	0.41742 (9)	0.77588 (10)	0.19931 (5)	0.0513 (11)
C3	0.41419 (10)	0.78502 (14)	0.16113 (5)	0.0542 (11)
H3A	0.3696	0.7930	0.1494	0.065*
C4	0.47625 (11)	0.78255 (17)	0.14012 (4)	0.0568 (12)
C5	0.54155 (10)	0.77094 (15)	0.15730 (5)	0.0618 (13)
H5A	0.5840	0.7693	0.1429	0.074*
C6	0.54479 (9)	0.76180 (12)	0.19548 (5)	0.0474 (10)
C7	0.35035 (10)	0.77848 (17)	0.22116 (7)	0.0492 (10)
C8	0.61517 (10)	0.75215 (19)	0.21357 (7)	0.0585 (12)
C11	0.4721 (2)	0.78201 (17)	0.09829 (6)	0.0561 (12)
C12	0.4646 (2)	0.84633 (15)	0.07957 (7)	0.1635 (17)
C13	0.4621 (2)	0.84724 (17)	0.04108 (7)	0.1635 (17)
H13A	0.4569	0.8912	0.0283	0.196*
C14	0.4671 (2)	0.7838 (2)	0.02132 (6)	0.0689 (15)
C15	0.4747 (3)	0.71953 (17)	0.04004 (9)	0.1635 (17)
H15A	0.4782	0.6762	0.0265	0.196*
C16	0.4772 (3)	0.71861 (15)	0.07853 (9)	0.1635 (17)
C17	0.4454 (4)	0.91830 (18)	0.10045 (11)	0.1635 (17)
H17A	0.4489	0.9109	0.1273	0.245*
H17B	0.3967	0.9326	0.0941	0.245*
H17C	0.4787	0.9558	0.0929	0.245*
C18	0.4989 (6)	0.6508 (4)	0.09884 (16)	0.1635 (17)
H18A	0.5010	0.6111	0.0812	0.245*
H18B	0.4638	0.6401	0.1182	0.245*
H18C	0.5459	0.6576	0.1102	0.245*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0483 (3)	0.0483 (3)	0.0350 (3)	0.0115 (3)	−0.0039 (2)	0.0039 (2)
Cu2	0.0445 (3)	0.0445 (3)	0.0344 (3)	0.0084 (3)	−0.0034 (2)	0.0034 (2)
O1	0.0488 (18)	0.085 (2)	0.0509 (16)	0.0025 (16)	0.0021 (15)	0.0138 (17)
O1S	0.080 (2)	0.080 (2)	0.048 (2)	0.021 (3)	−0.0123 (16)	0.0123 (16)
O2	0.0432 (17)	0.071 (2)	0.0402 (15)	−0.0025 (14)	0.0026 (13)	0.0009 (14)
O2S	0.0709 (19)	0.0709 (19)	0.051 (2)	0.003 (2)	−0.0102 (16)	0.0102 (16)
O3	0.0498 (18)	0.073 (2)	0.0494 (16)	−0.0100 (15)	−0.0009 (14)	0.0128 (15)
O4	0.0402 (16)	0.070 (2)	0.0443 (15)	−0.0117 (14)	0.0003 (13)	0.0021 (14)
C1	0.049 (2)	0.046 (2)	0.048 (2)	−0.0068 (19)	0.0046 (19)	0.002 (2)
C2	0.053 (3)	0.060 (3)	0.041 (2)	−0.015 (2)	−0.0052 (19)	0.002 (2)
C3	0.047 (3)	0.073 (3)	0.043 (2)	−0.006 (2)	0.0017 (19)	0.002 (2)
C4	0.041 (2)	0.079 (4)	0.050 (2)	−0.012 (2)	−0.002 (2)	0.010 (2)
C5	0.039 (2)	0.103 (4)	0.044 (2)	−0.006 (2)	0.0064 (19)	0.007 (2)
C6	0.036 (2)	0.060 (3)	0.046 (2)	−0.0097 (19)	−0.0013 (18)	−0.003 (2)
C7	0.055 (3)	0.046 (2)	0.047 (2)	−0.004 (2)	0.005 (2)	−0.0067 (19)
C8	0.044 (2)	0.086 (4)	0.046 (2)	−0.012 (2)	0.008 (2)	−0.006 (2)
C11	0.052 (3)	0.067 (3)	0.050 (2)	−0.015 (2)	0.001 (2)	−0.003 (2)
C12	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)
C13	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)
C14	0.053 (3)	0.109 (4)	0.045 (2)	−0.010 (3)	−0.002 (2)	−0.001 (3)
C15	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)
C16	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)
C17	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)
C18	0.342 (6)	0.094 (2)	0.0537 (14)	0.016 (3)	−0.011 (2)	0.0005 (15)

Geometric parameters (Å, º)

Cu1—O1^i	1.935 (3)	C3—H3A	0.9500
Cu1—O1	1.935 (3)	C4—C5	1.3900
Cu1—O3^ii	1.951 (3)	C4—C11	1.512 (3)
Cu1—O3^iii	1.951 (3)	C5—C6	1.3900
Cu1—O1S	2.144 (4)	C5—H5A	0.9500
Cu1—Cu2	2.6582 (9)	C6—C8	1.4837
Cu2—O4^ii	1.956 (3)	C11—C12	1.3900
Cu2—O4^iii	1.956 (3)	C11—C16	1.3900
Cu2—O2^i	1.974 (3)	C12—C13	1.3900
Cu2—O2	1.974 (3)	C12—C17	1.5874
Cu2—O2S	2.133 (4)	C13—C14	1.3900
O1—C7	1.254 (4)	C13—H13A	0.9500
O2—C7	1.278 (4)	C14—C15	1.3900
O3—C8	1.282 (4)	C14—C14^v	1.539 (4)
O3—Cu1^iv	1.951 (3)	C15—C16	1.3900
O4—C8	1.257 (3)	C15—H15A	0.9500
O4—Cu2^iv	1.956 (3)	C16—C18	1.523 (7)
C1—C2	1.3900	C17—H17A	0.9800
C1—C6	1.3900	C17—H17B	0.9800
C1—H1A	0.9500	C17—H17C	0.9800
C2—C3	1.3900	C18—H18A	0.9800
C2—C7	1.4858	C18—H18B	0.9800
C3—C4	1.3900	C18—H18C	0.9800
O1^i—Cu1—O1	85.7 (2)	C5—C4—C11	119.32 (19)
O1^i—Cu1—O3^ii	167.70 (13)	C3—C4—C11	120.12 (19)
O1—Cu1—O3^ii	90.61 (14)	C4—C5—C6	120.0
O1^i—Cu1—O3^iii	90.61 (14)	C4—C5—H5A	120.0
O1—Cu1—O3^iii	167.70 (13)	C6—C5—H5A	120.0
O3^ii—Cu1—O3^iii	90.58 (19)	C5—C6—C1	120.0
O1^i—Cu1—O1S	95.87 (13)	C5—C6—C8	119.3
O1—Cu1—O1S	95.88 (13)	C1—C6—C8	120.6
O3^ii—Cu1—O1S	96.16 (12)	O1—C7—O2	126.8 (2)
O3^iii—Cu1—O1S	96.16 (12)	O1—C7—C2	117.13 (18)
O1^i—Cu1—Cu2	84.42 (9)	O2—C7—C2	115.85 (17)
O1—Cu1—Cu2	84.42 (9)	O4—C8—O3	125.3 (2)
O3^ii—Cu1—Cu2	83.55 (8)	O4—C8—C6	118.08 (18)
O3^iii—Cu1—Cu2	83.55 (8)	O3—C8—C6	116.55 (18)
O1S—Cu1—Cu2	179.59 (14)	C12—C11—C16	120.0
O4^ii—Cu2—O4^iii	88.35 (18)	C12—C11—C4	119.0 (2)
O4^ii—Cu2—O2^i	168.59 (12)	C16—C11—C4	121.0 (2)
O4^iii—Cu2—O2^i	90.70 (12)	C11—C12—C13	120.0
O4^ii—Cu2—O2	90.70 (12)	C11—C12—C17	122.0
O4^iii—Cu2—O2	168.59 (12)	C13—C12—C17	117.2
O2^i—Cu2—O2	87.97 (17)	C14—C13—C12	120.0
O4^ii—Cu2—O2S	95.25 (12)	C14—C13—H13A	120.0
O4^iii—Cu2—O2S	95.25 (12)	C12—C13—H13A	120.0
O2^i—Cu2—O2S	96.16 (12)	C13—C14—C15	120.0
O2—Cu2—O2S	96.16 (12)	C13—C14—C14^v	120.9
O4^ii—Cu2—Cu1	84.58 (8)	C15—C14—C14^v	119.1
O4^iii—Cu2—Cu1	84.58 (8)	C16—C15—C14	120.0
O2^i—Cu2—Cu1	84.01 (8)	C16—C15—H15A	120.0
O2—Cu2—Cu1	84.01 (8)	C14—C15—H15A	120.0
O2S—Cu2—Cu1	179.77 (15)	C15—C16—C11	120.0
C7—O1—Cu1	123.3 (2)	C15—C16—C18	120.0 (3)
C7—O2—Cu2	121.3 (2)	C11—C16—C18	119.0 (3)
C8—O3—Cu1^iv	123.7 (2)	C12—C17—H17A	109.5
C8—O4—Cu2^iv	122.7 (2)	C12—C17—H17B	109.5
C2—C1—C6	120.0	H17A—C17—H17B	109.5
C2—C1—H1A	120.0	C12—C17—H17C	109.5
C6—C1—H1A	120.0	H17A—C17—H17C	109.5
C1—C2—C3	120.0	H17B—C17—H17C	109.5
C1—C2—C7	121.0	C16—C18—H18A	109.5
C3—C2—C7	119.0	C16—C18—H18B	109.5
C2—C3—C4	120.0	H18A—C18—H18B	109.5
C2—C3—H3A	120.0	C16—C18—H18C	109.5
C4—C3—H3A	120.0	H18A—C18—H18C	109.5
C5—C4—C3	120.0	H18B—C18—H18C	109.5
O1^i—Cu1—Cu2—O4^ii	178.66 (14)	C11—C4—C5—C6	−171.4 (3)
O1—Cu1—Cu2—O4^ii	92.48 (13)	C4—C5—C6—C1	0.0
O3^ii—Cu1—Cu2—O4^ii	1.23 (13)	C4—C5—C6—C8	−177.7
O3^iii—Cu1—Cu2—O4^ii	−90.09 (13)	C2—C1—C6—C5	0.0
O1S—Cu1—Cu2—O4^ii	−44.43 (10)	C2—C1—C6—C8	177.7
O1^i—Cu1—Cu2—O4^iii	−92.48 (13)	Cu1—O1—C7—O2	−3.3 (5)
O1—Cu1—Cu2—O4^iii	−178.67 (14)	Cu1—O1—C7—C2	171.00 (15)
O3^ii—Cu1—Cu2—O4^iii	90.09 (13)	Cu2—O2—C7—O1	4.9 (5)
O3^iii—Cu1—Cu2—O4^iii	−1.23 (13)	Cu2—O2—C7—C2	−169.49 (13)
O1S—Cu1—Cu2—O4^iii	44.42 (10)	C1—C2—C7—O1	166.0 (3)
O1^i—Cu1—Cu2—O2^i	−1.20 (13)	C3—C2—C7—O1	−14.2 (3)
O1—Cu1—Cu2—O2^i	−87.39 (14)	C1—C2—C7—O2	−19.0 (3)
O3^ii—Cu1—Cu2—O2^i	−178.63 (13)	C3—C2—C7—O2	160.8 (3)
O3^iii—Cu1—Cu2—O2^i	90.05 (13)	Cu2^iv—O4—C8—O3	−5.9 (5)
O1S—Cu1—Cu2—O2^i	135.71 (10)	Cu2^iv—O4—C8—C6	178.23 (13)
O1^i—Cu1—Cu2—O2	87.38 (14)	Cu1^iv—O3—C8—O4	4.2 (5)
O1—Cu1—Cu2—O2	1.20 (13)	Cu1^iv—O3—C8—C6	−179.86 (15)
O3^ii—Cu1—Cu2—O2	−90.05 (13)	C5—C6—C8—O4	20.2 (3)
O3^iii—Cu1—Cu2—O2	178.63 (13)	C1—C6—C8—O4	−157.5 (3)
O1S—Cu1—Cu2—O2	−135.71 (10)	C5—C6—C8—O3	−156.1 (3)
O1^i—Cu1—Cu2—O2S	−14E1 (4)	C1—C6—C8—O3	26.2 (3)
O1—Cu1—Cu2—O2S	14E1 (4)	C5—C4—C11—C12	−105.6 (3)
O3^ii—Cu1—Cu2—O2S	46 (13)	C3—C4—C11—C12	83.0 (3)
O3^iii—Cu1—Cu2—O2S	−46 (12)	C5—C4—C11—C16	73.1 (3)
O1S—Cu1—Cu2—O2S	0 (12)	C3—C4—C11—C16	−98.3 (2)
O1^i—Cu1—O1—C7	−84.3 (3)	C16—C11—C12—C13	0.0
O3^ii—Cu1—O1—C7	83.9 (3)	C4—C11—C12—C13	178.7 (3)
O3^iii—Cu1—O1—C7	−11.6 (9)	C16—C11—C12—C17	169.4
O1S—Cu1—O1—C7	−179.8 (3)	C4—C11—C12—C17	−11.9 (3)
Cu2—Cu1—O1—C7	0.5 (3)	C11—C12—C13—C14	0.0
O4^ii—Cu2—O2—C7	−87.7 (3)	C17—C12—C13—C14	−169.9
O4^iii—Cu2—O2—C7	−2.5 (8)	C12—C13—C14—C15	0.0
O2^i—Cu2—O2—C7	81.0 (3)	C12—C13—C14—C14^v	−177.9
O2S—Cu2—O2—C7	177.0 (3)	C13—C14—C15—C16	0.0
Cu1—Cu2—O2—C7	−3.2 (3)	C14^v—C14—C15—C16	177.9
C6—C1—C2—C3	0.0	C14—C15—C16—C11	0.0
C6—C1—C2—C7	179.8	C14—C15—C16—C18	−168.8 (6)
C1—C2—C3—C4	0.0	C12—C11—C16—C15	0.0
C7—C2—C3—C4	−179.8	C4—C11—C16—C15	−178.7 (3)
C2—C3—C4—C5	0.0	C12—C11—C16—C18	168.9 (6)
C2—C3—C4—C11	171.4 (3)	C4—C11—C16—C18	−9.8 (6)
C3—C4—C5—C6	0.0

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

(Ni3344_sq)

Crystal data

(Ni3O8)(C32H22O8)Ni0.17	Mo Kα radiation, λ = 0.71073 Å
Mr = 848.41	Cell parameters from 9951 reflections
Cubic, Fm3m	θ = 2.2–20.3°
a = 40.9779 (8) Å	µ = 0.54 mm^−1
V = 68810 (2) Å^3	T = 110 K
Z = 24	Block, green
F(000) = 10336	0.10 × 0.10 × 0.10 mm
Dx = 0.491 Mg m^−3

Data collection

Bruker SMART APEX II CCD area detector diffractometer	2998 independent reflections
Radiation source: fine-focus sealed tube	1863 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.117
phi and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan SADABS (Sheldrick, 2008)	h = −48→48
Tmin = 0.948, Tmax = 0.948	k = −48→48
168914 measured reflections	l = −48→48

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.091	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.239	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.065P)^2 + 570.P] where P = (Fo^2 + 2Fc^2)/3
2998 reflections	(Δ/σ)max < 0.001
78 parameters	Δρmax = 0.71 e Å^−3
17 restraints	Δρmin = −0.63 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Ni1	0.13785 (3)	0.5000	0.0000	0.0505 (4)
O3	0.18840 (16)	0.5000	0.0000	0.074 (2)
O2	0.18638 (13)	0.43533 (15)	0.0103 (3)	0.116 (6)	0.50
O1	0.13550 (9)	0.44979 (9)	0.0000	0.0722 (11)
O5	0.08623 (18)	0.5000	0.0000	0.078 (2)
C3	0.17144 (6)	0.37011 (6)	0.0000	0.103 (3)
H3A	0.1938	0.3761	0.0000	0.123*
C2	0.14746 (6)	0.39410 (6)	0.0000	0.0759 (18)
C1	0.15693 (15)	0.42959 (16)	0.0000	0.082 (2)
C4	0.16267 (6)	0.33733 (6)	0.0000	0.099 (3)
C5	0.11468 (6)	0.38532 (6)	0.0000	0.067 (2)
H5A	0.0983	0.4017	0.0000	0.080*
C6	0.18881 (9)	0.31119 (9)	0.0000	0.169 (2)
C9	0.23679 (9)	0.26321 (9)	0.0000	0.169 (2)
C7	0.20081 (9)	0.29919 (9)	0.029380 (12)	0.169 (2)
C8	0.22480 (9)	0.27520 (9)	0.029379 (11)	0.169 (2)
H8A	0.2330	0.2670	0.0495	0.203*
C11	0.18689 (13)	0.31311 (13)	0.0618 (2)	0.169 (2)
H11A	0.1704	0.3297	0.0569	0.253*
H11B	0.2046	0.3230	0.0744	0.253*	0.50
H11C	0.1770	0.2954	0.0744	0.253*	0.50
Ni2	0.21488 (7)	0.47337 (6)	0.02663 (6)	0.1616 (13)	0.50
Ni3S	0.0000	0.5000	0.0000	0.188 (4)
O11	0.2384 (4)	0.4405 (2)	0.0595 (2)	0.258 (7)	0.50
O12	0.2468 (2)	0.4893 (4)	0.0394 (3)	0.258 (7)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0286 (7)	0.0615 (6)	0.0615 (6)	0.000	0.000	0.000
O3	0.022 (4)	0.100 (4)	0.100 (4)	0.000	0.000	0.000
O2	0.057 (3)	0.085 (4)	0.205 (19)	0.007 (3)	−0.018 (5)	−0.013 (5)
O1	0.059 (3)	0.057 (2)	0.100 (3)	0.004 (2)	0.000	0.000
O5	0.050 (5)	0.092 (4)	0.092 (4)	0.000	0.000	0.000
C3	0.056 (4)	0.071 (4)	0.182 (8)	0.016 (3)	0.000	0.000
C2	0.056 (4)	0.067 (4)	0.105 (5)	0.014 (3)	0.000	0.000
C1	0.048 (4)	0.070 (4)	0.128 (6)	0.004 (3)	0.000	0.000
C4	0.073 (4)	0.073 (4)	0.151 (11)	0.028 (5)	0.000	0.000
C5	0.057 (3)	0.057 (3)	0.087 (6)	0.020 (4)	0.000	0.000
C6	0.160 (3)	0.160 (3)	0.186 (6)	0.102 (4)	0.000	0.000
C9	0.160 (3)	0.160 (3)	0.186 (6)	0.102 (4)	0.000	0.000
C7	0.160 (3)	0.160 (3)	0.186 (6)	0.102 (4)	0.000	0.000
C8	0.160 (3)	0.160 (3)	0.186 (6)	0.102 (4)	0.000	0.000
C11	0.160 (3)	0.160 (3)	0.186 (6)	0.102 (4)	0.000	0.000
Ni2	0.0916 (17)	0.1966 (19)	0.1966 (19)	0.0159 (13)	−0.0159 (13)	−0.002 (2)
Ni3S	0.188 (4)	0.188 (4)	0.188 (4)	0.000	0.000	0.000
O11	0.127 (6)	0.323 (10)	0.323 (10)	0.041 (7)	−0.041 (7)	−0.063 (14)
O12	0.127 (6)	0.323 (10)	0.323 (10)	0.041 (7)	−0.041 (7)	−0.063 (14)

Geometric parameters (Å, º)

Ni1—O1	2.060 (4)	C5—H5A	0.9500
Ni1—O1^i	2.060 (4)	C6—C7^v	1.3901 (7)
Ni1—O1^ii	2.060 (4)	C6—C7	1.3901 (7)
Ni1—O1^iii	2.060 (4)	C9—C8^v	1.3901 (6)
Ni1—O3	2.071 (7)	C9—C8	1.3901 (6)
Ni1—O5	2.115 (8)	C9—C9^vi	1.531 (10)
O3—Ni2	1.887 (5)	C7—C8	1.3903 (9)
O3—Ni2^iii	1.887 (5)	C7—C11	1.553 (9)
O3—Ni2^iv	1.887 (5)	C8—H8A	0.9500
O3—Ni2^ii	1.887 (5)	C11—H11A	0.9800
O2—O2^iv	0.85 (3)	C11—H11B	0.9800
O2—C1	1.301 (9)	C11—H11C	0.9800
O2—Ni2	2.059 (8)	Ni2—O12	1.554 (12)
O1—C1	1.207 (7)	Ni2—O12^vii	1.554 (12)
C3—C4	1.3903 (6)	Ni2—O2^vii	2.059 (8)
C3—C2	1.3900 (9)	Ni2—O12^viii	2.081 (14)
C3—H3A	0.9500	Ni2—O12^i	2.081 (14)
C2—C5	1.3904 (7)	Ni2—O11	2.133 (9)
C2—C1	1.505 (7)	Ni2—Ni2^iii	2.183 (5)
C1—O2^iv	1.301 (9)	Ni2—Ni2^iv	2.183 (5)
C4—C3^v	1.3903 (6)	O12—O12^viii	0.88 (4)
C4—C6	1.515 (6)	O12—O12^vii	1.66 (3)
C5—C2^v	1.3904 (7)	O12—Ni2^iii	2.081 (14)
O1—Ni1—O1^i	89.875 (11)	C7—C8—H8A	120.0
O1—Ni1—O1^ii	174.6 (2)	C7—C11—H11A	109.5
O1^i—Ni1—O1^ii	89.875 (11)	C7—C11—H11B	109.5
O1—Ni1—O1^iii	89.875 (11)	H11A—C11—H11B	109.5
O1^i—Ni1—O1^iii	174.6 (2)	C7—C11—H11C	109.5
O1^ii—Ni1—O1^iii	89.875 (11)	H11A—C11—H11C	109.5
O1—Ni1—O3	92.68 (11)	H11B—C11—H11C	109.5
O1^i—Ni1—O3	92.68 (11)	O12—Ni2—O12^vii	64.8 (10)
O1^ii—Ni1—O3	92.68 (11)	O12—Ni2—O3	115.9 (6)
O1^iii—Ni1—O3	92.68 (11)	O12^vii—Ni2—O3	115.9 (6)
O1—Ni1—O5	87.32 (11)	O12—Ni2—O2	154.9 (6)
O1^i—Ni1—O5	87.32 (11)	O12^vii—Ni2—O2	94.9 (5)
O1^ii—Ni1—O5	87.32 (11)	O3—Ni2—O2	85.7 (3)
O1^iii—Ni1—O5	87.32 (11)	O12—Ni2—O2^vii	95.0 (5)
O3—Ni1—O5	180.0	O12^vii—Ni2—O2^vii	154.9 (6)
Ni2—O3—Ni2^iii	70.69 (19)	O3—Ni2—O2^vii	85.7 (3)
Ni2—O3—Ni2^iv	70.69 (19)	O2—Ni2—O2^vii	99.7 (6)
Ni2^iii—O3—Ni2^iv	109.8 (4)	O12—Ni2—O12^viii	22.5 (9)
Ni2—O3—Ni2^ii	109.8 (4)	O12^vii—Ni2—O12^viii	79.8 (7)
Ni2^iii—O3—Ni2^ii	70.69 (19)	O3—Ni2—O12^viii	94.7 (4)
Ni2^iv—O3—Ni2^ii	70.69 (19)	O2—Ni2—O12^viii	174.4 (5)
Ni2—O3—Ni1	125.11 (19)	O2^vii—Ni2—O12^viii	85.9 (5)
Ni2^iii—O3—Ni1	125.10 (19)	O12—Ni2—O12^i	79.8 (7)
Ni2^iv—O3—Ni1	125.10 (19)	O12^vii—Ni2—O12^i	22.5 (9)
Ni2^ii—O3—Ni1	125.10 (19)	O3—Ni2—O12^i	94.7 (4)
O2^iv—O2—C1	71.0 (6)	O2—Ni2—O12^i	85.9 (5)
O2^iv—O2—Ni2	108.9 (4)	O2^vii—Ni2—O12^i	174.4 (5)
C1—O2—Ni2	140.2 (5)	O12^viii—Ni2—O12^i	88.5 (7)
C1—O1—Ni1	130.6 (4)	O12—Ni2—O11	70.8 (7)
C4—C3—C2	120.01 (5)	O12^vii—Ni2—O11	70.8 (7)
C4—C3—H3A	120.0	O3—Ni2—O11	171.8 (5)
C2—C3—H3A	120.0	O2—Ni2—O11	89.1 (4)
C5—C2—C3	120.01 (6)	O2^vii—Ni2—O11	89.1 (4)
C5—C2—C1	119.9 (3)	O12^viii—Ni2—O11	91.2 (5)
C3—C2—C1	120.1 (3)	O12^i—Ni2—O11	91.2 (5)
O1—C1—O2^iv	123.5 (6)	O12—Ni2—Ni2^iii	65.2 (6)
O1—C1—O2	123.5 (6)	O12^vii—Ni2—Ni2^iii	109.7 (5)
O2^iv—C1—O2	38.0 (12)	O3—Ni2—Ni2^iii	54.66 (9)
O1—C1—C2	118.4 (5)	O2—Ni2—Ni2^iii	139.2 (2)
O2^iv—C1—C2	114.4 (5)	O2^vii—Ni2—Ni2^iii	71.1 (4)
O2—C1—C2	114.5 (5)	O12^viii—Ni2—Ni2^iii	42.7 (4)
C3^v—C4—C3	119.98 (9)	O12^i—Ni2—Ni2^iii	104.6 (4)
C3^v—C4—C6	120.01 (4)	O11—Ni2—Ni2^iii	129.1 (2)
C3—C4—C6	120.01 (4)	O12—Ni2—Ni2^iv	109.7 (5)
C2^v—C5—C2	119.98 (10)	O12^vii—Ni2—Ni2^iv	65.2 (6)
C2^v—C5—H5A	120.0	O3—Ni2—Ni2^iv	54.66 (9)
C2—C5—H5A	120.0	O2—Ni2—Ni2^iv	71.1 (4)
C7^v—C6—C7	120.01 (10)	O2^vii—Ni2—Ni2^iv	139.2 (2)
C7^v—C6—C4	120.00 (5)	O12^viii—Ni2—Ni2^iv	104.6 (4)
C7—C6—C4	120.00 (5)	O12^i—Ni2—Ni2^iv	42.7 (4)
C8^v—C9—C8	120.00 (9)	O11—Ni2—Ni2^iv	129.1 (2)
C8^v—C9—C9^vi	120.00 (4)	Ni2^iii—Ni2—Ni2^iv	90.0
C8—C9—C9^vi	120.00 (4)	O12^viii—O12—Ni2	114.8 (6)
C6—C7—C8	119.99 (6)	O12^viii—O12—O12^vii	135.012 (15)
C6—C7—C11	118.7 (4)	Ni2—O12—O12^vii	57.6 (5)
C8—C7—C11	121.3 (4)	O12^viii—O12—Ni2^iii	42.7 (4)
C9—C8—C7	120.00 (5)	Ni2—O12—Ni2^iii	72.2 (4)
C9—C8—H8A	120.0	O12^vii—O12—Ni2^iii	110.0 (4)
O1—Ni1—O3—Ni2	−45.0	Ni2^ii—O3—Ni2—O2	−129.9 (3)
O1^i—Ni1—O3—Ni2	−135.0	Ni1—O3—Ni2—O2	50.1 (3)
O1^ii—Ni1—O3—Ni2	135.0	Ni2^iii—O3—Ni2—O2^vii	69.8 (3)
O1^iii—Ni1—O3—Ni2	45.0	Ni2^iv—O3—Ni2—O2^vii	−170.0 (3)
O5—Ni1—O3—Ni2	0.0	Ni2^ii—O3—Ni2—O2^vii	129.9 (3)
O1—Ni1—O3—Ni2^iii	−135.0	Ni1—O3—Ni2—O2^vii	−50.1 (3)
O1^i—Ni1—O3—Ni2^iii	135.0	Ni2^iii—O3—Ni2—O12^viii	−15.6 (4)
O1^ii—Ni1—O3—Ni2^iii	45.0	Ni2^iv—O3—Ni2—O12^viii	104.6 (4)
O1^iii—Ni1—O3—Ni2^iii	−45.0	Ni2^ii—O3—Ni2—O12^viii	44.5 (4)
O5—Ni1—O3—Ni2^iii	0.0	Ni1—O3—Ni2—O12^viii	−135.5 (4)
O1—Ni1—O3—Ni2^iv	45.0	Ni2^iii—O3—Ni2—O12^i	−104.6 (4)
O1^i—Ni1—O3—Ni2^iv	−45.0	Ni2^iv—O3—Ni2—O12^i	15.6 (4)
O1^ii—Ni1—O3—Ni2^iv	−135.0	Ni2^ii—O3—Ni2—O12^i	−44.5 (4)
O1^iii—Ni1—O3—Ni2^iv	135.0	Ni1—O3—Ni2—O12^i	135.5 (4)
O5—Ni1—O3—Ni2^iv	0.0	Ni2^iii—O3—Ni2—O11	119.90 (12)
O1—Ni1—O3—Ni2^ii	135.0	Ni2^iv—O3—Ni2—O11	−119.90 (12)
O1^i—Ni1—O3—Ni2^ii	45.0	Ni2^ii—O3—Ni2—O11	180.00 (4)
O1^ii—Ni1—O3—Ni2^ii	−45.0	Ni1—O3—Ni2—O11	0.0000 (10)
O1^iii—Ni1—O3—Ni2^ii	−135.0	Ni2^iv—O3—Ni2—Ni2^iii	120.2 (2)
O5—Ni1—O3—Ni2^ii	0.0	Ni2^ii—O3—Ni2—Ni2^iii	60.10 (12)
O1^i—Ni1—O1—C1	92.68 (11)	Ni1—O3—Ni2—Ni2^iii	−119.90 (12)
O1^ii—Ni1—O1—C1	180.0	Ni2^iii—O3—Ni2—Ni2^iv	−120.2 (2)
O1^iii—Ni1—O1—C1	−92.68 (11)	Ni2^ii—O3—Ni2—Ni2^iv	−60.10 (12)
O3—Ni1—O1—C1	0.0	Ni1—O3—Ni2—Ni2^iv	119.90 (12)
O5—Ni1—O1—C1	180.0	O2^iv—O2—Ni2—O12	−96.2 (15)
C4—C3—C2—C5	0.0	C1—O2—Ni2—O12	−18E1 (9)
C4—C3—C2—C1	180.0	O2^iv—O2—Ni2—O12^vii	−61.6 (6)
Ni1—O1—C1—O2^iv	−23.0 (7)	C1—O2—Ni2—O12^vii	−144.3 (14)
Ni1—O1—C1—O2	23.0 (7)	O2^iv—O2—Ni2—O3	54.04 (15)
Ni1—O1—C1—C2	180.0	C1—O2—Ni2—O3	−28.7 (13)
O2^iv—O2—C1—O1	−103.2 (5)	O2^iv—O2—Ni2—O2^vii	138.9 (3)
Ni2—O2—C1—O1	−6.2 (17)	C1—O2—Ni2—O2^vii	56.2 (16)
Ni2—O2—C1—O2^iv	97.0 (13)	O2^iv—O2—Ni2—O12^viii	−40 (5)
O2^iv—O2—C1—C2	99.0 (4)	C1—O2—Ni2—O12^viii	−123 (5)
Ni2—O2—C1—C2	−164.0 (10)	O2^iv—O2—Ni2—O12^i	−41.0 (4)
C5—C2—C1—O1	0.0	C1—O2—Ni2—O12^i	−123.7 (14)
C3—C2—C1—O1	180.0	O2^iv—O2—Ni2—O11	−132.2 (4)
C5—C2—C1—O2^iv	−159.0 (6)	C1—O2—Ni2—O11	145.0 (14)
C3—C2—C1—O2^iv	21.0 (6)	O2^iv—O2—Ni2—Ni2^iii	66.6 (4)
C5—C2—C1—O2	159.0 (6)	C1—O2—Ni2—Ni2^iii	−16.1 (17)
C3—C2—C1—O2	−21.0 (6)	O2^iv—O2—Ni2—Ni2^iv	0.004 (2)
C2—C3—C4—C3^v	0.0	C1—O2—Ni2—Ni2^iv	−82.7 (13)
C2—C3—C4—C6	180.0	O12^vii—Ni2—O12—O12^viii	129.0 (3)
C3—C2—C5—C2^v	0.0	O3—Ni2—O12—O12^viii	21.1 (5)
C1—C2—C5—C2^v	180.0	O2—Ni2—O12—O12^viii	167.7 (13)
C3^v—C4—C6—C7^v	90.0	O2^vii—Ni2—O12—O12^viii	−66.5 (4)
C3—C4—C6—C7^v	−90.0	O12^i—Ni2—O12—O12^viii	111.4 (4)
C3^v—C4—C6—C7	−90.0	O11—Ni2—O12—O12^viii	−153.8 (5)
C3—C4—C6—C7	90.0	Ni2^iii—Ni2—O12—O12^viii	0.003 (4)
C7^v—C6—C7—C8	0.0	Ni2^iv—Ni2—O12—O12^viii	80.5 (3)
C4—C6—C7—C8	180.0	O3—Ni2—O12—O12^vii	−107.9 (5)
C7^v—C6—C7—C11	180.0000 (10)	O2—Ni2—O12—O12^vii	38.7 (12)
C4—C6—C7—C11	0.0	O2^vii—Ni2—O12—O12^vii	164.5 (6)
C8^v—C9—C8—C7	0.0000 (10)	O12^viii—Ni2—O12—O12^vii	−129.0 (3)
C9^vi—C9—C8—C7	180.0	O12^i—Ni2—O12—O12^vii	−17.6 (6)
C6—C7—C8—C9	0.0000 (10)	O11—Ni2—O12—O12^vii	77.2 (5)
C11—C7—C8—C9	180.000 (2)	Ni2^iii—Ni2—O12—O12^vii	−129.0 (3)
Ni2^iii—O3—Ni2—O12	−23.6 (6)	Ni2^iv—Ni2—O12—O12^vii	−48.5 (2)
Ni2^iv—O3—Ni2—O12	96.6 (5)	O12^vii—Ni2—O12—Ni2^iii	129.0 (3)
Ni2^ii—O3—Ni2—O12	36.5 (5)	O3—Ni2—O12—Ni2^iii	21.1 (5)
Ni1—O3—Ni2—O12	−143.5 (5)	O2—Ni2—O12—Ni2^iii	167.7 (13)
Ni2^iii—O3—Ni2—O12^vii	−96.6 (5)	O2^vii—Ni2—O12—Ni2^iii	−66.5 (4)
Ni2^iv—O3—Ni2—O12^vii	23.6 (6)	O12^viii—Ni2—O12—Ni2^iii	−0.003 (4)
Ni2^ii—O3—Ni2—O12^vii	−36.5 (5)	O12^i—Ni2—O12—Ni2^iii	111.4 (4)
Ni1—O3—Ni2—O12^vii	143.5 (5)	O11—Ni2—O12—Ni2^iii	−153.8 (5)
Ni2^iii—O3—Ni2—O2	170.0 (3)	Ni2^iv—Ni2—O12—Ni2^iii	80.5 (3)
Ni2^iv—O3—Ni2—O2	−69.8 (3)

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