Poly[diaqua­(μ₂-1,3-di-4-pyridylpropane-κ²N:N′)(μ₂-thio­phene-2,5-dicarboxyl­ato-κ²O:O′)nickel(II)]: a two-dimensional bilayered coordination polymer

The hydro­thermally prepared title compound, [Ni(C₆H₂O₄S)(C₁₃H₁₄N₂)(H₂O)₂]_n, is an Ni polymer based on thio­phene-2,5-dicarboxyl­ate dianions (tda²⁻) and 1,3-di-4-pyridylpropane (bpp) ligands. Each Ni atom is coordinated by two carboxyl­ate O atoms from two independent tda²⁻ groups along the a direction, two N atoms from two bpp ligands along the b direction, and two aqua O atoms, in a distorted octa­hedral geometry. This leads to a two-dimensional grid-type bilayer assembly running parallel to the (001) plane, in which the bilayer is formed through inter­molecular O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.042
• wR factor = 0.096
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O2     -   H2A    ...          ?

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

   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

As an important structural unit, linear bipyridyl ligands such as 4,4'-bipyridine (Wang et al., 2005; Chen et al., 2006; Lou et al., 2006) and 4,4'-bipyridyl with rigid or flexible spacers (Plater et al., 2000; Biradha et al., 2002; Fu et al., 2003; Wu et al., 2005) have been extensively employed to construct novel metal–organic coordination polymers with intriguing structural topologies and unexpected properties with potential applications as functional materials. The compound 1,3-di-4-pyridylpropane (bpp) is a bipyridine-type ligand with a flexible –CH₂CH₂CH₂– spacer, and a number of metal–bpp coordination polymers have been reported (Carlucci et al., 2000, 2002; Pan et al., 2001; Luan et al., 2005). Thiophene-2,5-dicarboxylic acid (H₂tda), which is similar to other dicarboxylic acids, such as benzene-1,3-dicarboxylic acid (Bourne et al., 2001; Zhang et al., 2003; Konar et al., 2004), shows diverse coordination modes and can act as a mono-, bi-, tri- or tetradentate ligand (Chen et al., 1998, 1999; Eddaoudi et al., 2002; Zhang et al., 2006; Deng et al., 2006). However, metal coordination polymers based on mixed bpp and thiophene-2,5-dicarboxylate dianions (tda^2-) ligands, to our knowledge, have not been reported to date. We report here the title new nickel(II) polymeric compound, [Ni(tda)(bpp)(H₂O)₂]_n, (I), with a two-dimensional grid-type bilayer structure, obtained via hydrothermal synthesis.

The Ni atom of (I) has a distorted octahedral geometry (Fig. 1) defined by two O atoms from two carboxylate groups of two independent tda ligands along the a direction, two N atoms from two bpp ligands along the b direction, and two aqua O atoms (Table 1). Both carboxylate groups of the tda ligand coordinate to Ni in a monodentate syn fashion, with an angle of 11.54 (11)° between the carboxylate planes. The C—O bond distances in both carboxylate groups are almost equivalent, consistent with its delocalized state. The shortest Ni···Ni distance bridged by a tda ligand is 11.024 (4) Å. The bpp ligand is in a trans–gauche conformation and acts as a µ₂-bridge linking two Ni centres, with an Ni···Ni separation of 11.828 (5) Å. The angle between the two pyridyl planes is 72.83 (16)°. The twist in the bpp ligand occurs at C7; the C3—C6—C7—C8 torsion angle is 73.2 (4)°. Two water molecules coordinate to the Ni atom in a cis fashion, with O1—Ni1—O2 = 82.05 (11)°.

As shown in Figs. 2 and 3, the Ni atoms are interlinked into a one-dimensional chain by the tda ligands along the a direction and this chain is propagated along the b direction by coordination between the Ni atoms and the flexible bpp ligands, to generate a two-dimensional grid-type layer 1 running parallel to the (001) plane. Two tda and two bpp ligands link four Ni atoms forming an Ni₄ grid with dimensions of 11.024 × 11.828 Ų, which is the basic building unit for the whole two-dimensional network of (I) (Fig. 4). Based on layer 1, layers 2, 3 and 4 can also be produced via symmetry operations (-x, 1/2 + y, 1/2 - z), (-x, -y, -z) and (x, 1/2 - y, 1/2 + z), respectively (Fig. 2). As shown in Fig. 3, all Ni atoms in the same layer are coplanar, and the respective distances between planes 1 and 2, planes 2 and 3, and planes 3 and 4 are 1.570 (2), 6.098 (1), and 1.570 (2) Å, respectively.

In the structure of (I), there are two types of hydrogen bonds (Table 2), namely intramolecular O1—H1A···O4 and O1—H1B···O5ⁱ hydrogen bonds [symmetry code: (i) -1 + x, y, z], and intermolecular hydrogen bonds between the O2 atoms of the coordinated water molecules and the uncoordinated carboxylate O4ⁱⁱ atoms, O2—H2B···O4ⁱⁱ (Fig. 3) [symmetry code: (ii) 1 - x, 1/2 + y, 1/2 - z], leading to a two-dimensional hydrogen-bonding bilayer architecture between polymeric layers 1 and 2. The bilayer structure is also parallel to the (001) plane. There seems to be no obvious interaction between the bilayer structures, but the grid bilayers stack closely in an offset way. Additionally, there is a contact between O2—H2A and π ring (N2/C11/C10/C9/C13/C12)ⁱⁱⁱ [symmetry code: (iii) 1 - x, -1/2 + y, 1/2 - z], and the distance between atom H2A and the centroid of the π ring is 2.97 (5) Å.

Related literature

For related literature, see: Biradha et al. (2002); Bourne et al. (2001); Carlucci et al. (2000, 2002); Chen et al. (2006, 1999, 1998); Deng et al. (2006); Eddaoudi et al. (2002); Fu et al. (2003); Konar et al. (2004); Lou et al. (2006); Luan et al. (2005); Pan et al. (2001); Plater et al. (2000); Spek (2003); Wang et al. (2005); Wu et al. (2005); Zhang et al. (2006, 2003).

S2. Experimental

A mixture of NiCl₂.6H₂O (0.060 g, 0.25 mmol) with Na₂tda (0.108 g, 0.5 mmol) and bpp (0.050 g, 0.25 mmol), in the molar ratio 1:2:1, and water (4 ml) was placed in a Parr Teflon-lined stainless steel vessel (25 ml). The sealed vessel was heated and held at 423 K for 24 h before the reaction mixture was cooled to room temperature at a rate of 2.5 K h^-1. The reaction yielded light-green crystals of (I) in a yield of ca 35% based on bpp. IR spectroscopic analysis (solid KBr disc, ν, cm^-1): 3430.3 (m), 1714.5 (s), 1611.3 (s), 1551.2 (m), 1529.0 (m), 1375.4 (vs), 1272.0 (w), 1221.3 (s), 1068.7 (w), 1019.4 (w), 835.0 (w), 772.2 (s), 523.2 (w), 474.8 (m).

S3. Refinement

H atoms attached to O atoms were located in a difference Fourier map and refined with a global U_iso(H) value. The O—H distances are in the range 0.82 (4)–0.89 (5) Å. H atoms attached to C atoms were placed in geometrically idealized positions, with C_sp3—H = 0.97 Å and C_sp2—H = 0.93 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of a fragment of the title compound, showing 50% probability displacement ellipsoids. [Symmetry codes: (A) -1 + x, y, z; (B) x, -1 + y, z; (C) 1 + x, y, z; (D) x, 1 + y, z.]
	Fig. 2. The bilayer structure in (I), showing Ni atoms (green balls) linked by tda ligands along the a axis. H atoms attached to C atoms have been omitted.
	Fig. 3. The crystal packing of complex (I), showing hydrogen-bonding interactions between the nearest layers along the b axis. Hydrogen bonds are shown as blue dotted lines, and H atoms attached to C atoms have been omitted. O atoms involved in hydrogen bonds are shown as balls and their colours are consistent with the corresponding colour of the layer.
	Fig. 4. A view of the two-dimensional network with grids.

Poly[diaqua(µ₂-1,3-di-4-pyridylpropane-κ²N:N')(µ₂-thiophene- 2,5-dicarboxylato-κ²O:O')nickel(II)]

Crystal data

[Ni(C6H2O4S)(C13H14N2)(H2O)2]	F(000) = 960
Mr = 463.14	Dx = 1.538 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7838 reflections
a = 11.024 (2) Å	θ = 2.0–27.3°
b = 11.828 (2) Å	µ = 1.11 mm^−1
c = 16.780 (6) Å	T = 298 K
β = 113.94 (2)°	Prism, light green
V = 1999.7 (9) Å^3	0.30 × 0.25 × 0.18 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer	3211 reflections with I > 2σ(I)
ω scans	Rint = 0.033
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	θmax = 27.3°, θmin = 2.0°
Tmin = 0.731, Tmax = 0.825	h = −14→14
7838 measured reflections	k = −14→15
4504 independent reflections	l = −21→21

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0469P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.71 e Å^−3
4504 reflections	Δρmin = −0.38 e Å^−3
278 parameters

Special details

Experimental. IR spectroscopic analysis (solid KBr disc, ν, cm^-1): 3430.3 (m), 1714.5 (s), 1611.3 (s), 1551.2 (m), 1529.0 (m), 1375.4 (versus), 1272.0 (w), 1221.3 (s), 1068.7 (w), 1019.4 (w), 835.0 (w), 772.2 (s), 523.2 (w), 474.8 (m).

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.33294 (3)	−0.02984 (3)	0.19881 (2)	0.02540 (11)
S1	0.87336 (6)	−0.15078 (6)	0.26664 (5)	0.03019 (17)
O1	0.4077 (2)	−0.1171 (2)	0.31908 (14)	0.0365 (5)
O2	0.3718 (3)	0.1130 (2)	0.28245 (18)	0.0454 (6)
O3	0.52232 (16)	−0.01725 (17)	0.20610 (13)	0.0341 (5)
O4	0.61008 (19)	−0.17787 (18)	0.27715 (15)	0.0416 (5)
O5	1.15763 (19)	−0.17305 (19)	0.29222 (14)	0.0411 (5)
O6	1.14822 (17)	−0.03662 (19)	0.19681 (14)	0.0387 (5)
N1	0.2659 (2)	0.0805 (2)	0.09064 (16)	0.0332 (5)
N2	0.3041 (2)	0.8199 (2)	0.12500 (16)	0.0315 (5)
C1	0.3449 (3)	0.1259 (3)	0.0563 (2)	0.0435 (8)
H1	0.4321	0.1004	0.0766	0.052*
C2	0.3053 (3)	0.2080 (3)	−0.0070 (2)	0.0449 (8)
H2	0.3647	0.235	−0.0291	0.054*
C3	0.1783 (3)	0.2508 (2)	−0.03801 (18)	0.0342 (6)
C4	0.0960 (3)	0.2019 (3)	−0.0040 (2)	0.0554 (10)
H4	0.0082	0.2257	−0.0236	0.066*
C5	0.1413 (3)	0.1193 (3)	0.0581 (2)	0.0515 (9)
H5	0.0821	0.0883	0.0788	0.062*
C6	0.1313 (3)	0.3476 (3)	−0.1018 (2)	0.0428 (8)
H6A	0.0398	0.3347	−0.1417	0.051*
H6B	0.1846	0.3509	−0.1357	0.051*
C7	0.1418 (3)	0.4603 (3)	−0.0545 (2)	0.0396 (7)
H7A	0.0905	0.5168	−0.0966	0.048*
H7B	0.1029	0.4516	−0.0123	0.048*
C8	0.2833 (3)	0.5023 (3)	−0.0078 (2)	0.0446 (8)
H8A	0.3347	0.4464	0.0349	0.054*
H8B	0.3227	0.5108	−0.0497	0.054*
C9	0.2906 (3)	0.6137 (3)	0.0375 (2)	0.0371 (7)
C10	0.3346 (4)	0.7122 (3)	0.0135 (2)	0.0550 (10)
H10	0.3604	0.7116	−0.0328	0.066*
C11	0.3402 (4)	0.8112 (3)	0.0580 (2)	0.0492 (9)
H11	0.3709	0.8758	0.0406	0.059*
C12	0.2606 (3)	0.7246 (3)	0.14740 (19)	0.0371 (7)
H12	0.2343	0.7273	0.1935	0.045*
C13	0.2526 (3)	0.6234 (3)	0.1061 (2)	0.0389 (7)
H13	0.2211	0.5601	0.1246	0.047*
C14	0.6135 (2)	−0.0898 (2)	0.23658 (18)	0.0284 (6)
C15	0.7364 (2)	−0.0646 (2)	0.22304 (18)	0.0287 (6)
C16	0.7592 (3)	0.0253 (3)	0.1796 (2)	0.0380 (7)
H16	0.6972	0.0817	0.1528	0.046*
C17	0.8873 (3)	0.0227 (3)	0.1801 (2)	0.0386 (7)
H17	0.9186	0.0768	0.1529	0.046*
C18	0.9606 (2)	−0.0676 (2)	0.22476 (18)	0.0286 (6)
C19	1.1005 (2)	−0.0961 (3)	0.23969 (19)	0.0303 (6)
H1A	0.464 (4)	−0.161 (3)	0.317 (2)	0.059 (12)*
H1B	0.343 (4)	−0.144 (3)	0.324 (3)	0.069 (13)*
H2A	0.445 (5)	0.102 (4)	0.322 (3)	0.083 (16)*
H2B	0.382 (4)	0.183 (4)	0.266 (3)	0.085 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01988 (15)	0.02479 (19)	0.0348 (2)	−0.000 (14)	0.01443 (13)	0.00044 (16)
S1	0.0226 (3)	0.0324 (4)	0.0402 (4)	0.0004 (3)	0.0174 (3)	0.0007 (3)
O1	0.0275 (10)	0.0439 (13)	0.0416 (13)	0.0040 (10)	0.0175 (9)	0.0014 (10)
O2	0.0494 (14)	0.0348 (14)	0.0545 (16)	−0.0002 (12)	0.0237 (13)	−0.0069 (12)
O3	0.0218 (9)	0.0324 (11)	0.0518 (13)	0.0034 (8)	0.0187 (9)	0.0045 (9)
O4	0.0337 (10)	0.0354 (13)	0.0658 (15)	0.0067 (9)	0.0305 (11)	0.0123 (11)
O5	0.0303 (10)	0.0478 (14)	0.0504 (14)	0.0064 (10)	0.0216 (10)	0.0138 (11)
O6	0.0249 (9)	0.0482 (13)	0.0495 (13)	0.0020 (9)	0.0217 (9)	0.0123 (11)
N1	0.0315 (11)	0.0295 (13)	0.0415 (15)	−0.0009 (10)	0.0177 (11)	0.0032 (11)
N2	0.0318 (11)	0.0296 (14)	0.0341 (14)	−0.0034 (10)	0.0144 (10)	−0.0005 (10)
C1	0.0363 (15)	0.0387 (19)	0.063 (2)	0.0085 (14)	0.0278 (15)	0.0157 (16)
C2	0.0488 (17)	0.043 (2)	0.054 (2)	0.0008 (15)	0.0321 (16)	0.0083 (16)
C3	0.0424 (15)	0.0281 (16)	0.0284 (15)	−0.0014 (13)	0.0106 (13)	−0.0032 (12)
C4	0.0341 (16)	0.070 (3)	0.060 (2)	0.0114 (17)	0.0172 (16)	0.028 (2)
C5	0.0314 (15)	0.065 (2)	0.060 (2)	0.0019 (16)	0.0203 (15)	0.0244 (18)
C6	0.0574 (19)	0.0341 (18)	0.0304 (17)	−0.0026 (15)	0.0112 (14)	0.0007 (13)
C7	0.0492 (17)	0.0321 (17)	0.0312 (16)	0.0029 (14)	0.0098 (13)	−0.0008 (13)
C8	0.0506 (18)	0.0352 (19)	0.048 (2)	−0.0007 (14)	0.0202 (16)	−0.0095 (14)
C9	0.0383 (15)	0.0342 (17)	0.0359 (17)	−0.0013 (14)	0.0120 (13)	−0.0066 (14)
C10	0.086 (3)	0.046 (2)	0.052 (2)	−0.019 (2)	0.048 (2)	−0.0150 (18)
C11	0.075 (2)	0.0388 (19)	0.046 (2)	−0.0162 (18)	0.0363 (18)	−0.0032 (15)
C12	0.0421 (15)	0.0378 (18)	0.0349 (17)	−0.0024 (14)	0.0191 (13)	−0.0014 (14)
C13	0.0506 (17)	0.0303 (17)	0.0365 (17)	−0.0059 (14)	0.0186 (14)	0.0003 (13)
C14	0.0230 (12)	0.0306 (16)	0.0357 (16)	−0.0003 (12)	0.0160 (11)	−0.0054 (13)
C15	0.0208 (12)	0.0329 (16)	0.0347 (15)	−0.0005 (11)	0.0138 (11)	−0.0045 (12)
C16	0.0288 (13)	0.0400 (18)	0.0499 (19)	0.0076 (14)	0.0208 (13)	0.0091 (16)
C17	0.0296 (13)	0.0420 (18)	0.0512 (19)	0.0005 (14)	0.0238 (13)	0.0111 (16)
C18	0.0225 (11)	0.0329 (15)	0.0341 (15)	−0.0056 (11)	0.0153 (11)	−0.0052 (12)
C19	0.0238 (12)	0.0373 (17)	0.0345 (16)	−0.0035 (12)	0.0168 (11)	−0.0062 (13)

Geometric parameters (Å, º)

Ni1—O6^i	2.0245 (18)	C4—C5	1.366 (5)
Ni1—O3	2.0466 (17)	C4—H4	0.9300
Ni1—N1	2.111 (3)	C5—H5	0.9300
Ni1—O1	2.114 (2)	C6—C7	1.532 (4)
Ni1—N2^ii	2.115 (2)	C6—H6A	0.9700
Ni1—O2	2.126 (2)	C6—H6B	0.9700
S1—C18	1.713 (3)	C7—C8	1.518 (4)
S1—C15	1.720 (3)	C7—H7A	0.9700
O1—H1A	0.83 (4)	C7—H7B	0.9700
O1—H1B	0.82 (4)	C8—C9	1.506 (4)
O2—H2A	0.83 (5)	C8—H8A	0.9700
O2—H2B	0.89 (5)	C8—H8B	0.9700
O3—C14	1.262 (3)	C9—C13	1.381 (4)
O4—C14	1.253 (3)	C9—C10	1.384 (4)
O5—C19	1.246 (4)	C10—C11	1.377 (5)
O6—C19	1.264 (3)	C10—H10	0.9300
O6—Ni1^iii	2.0245 (18)	C11—H11	0.9300
N1—C5	1.337 (4)	C12—C13	1.368 (4)
N1—C1	1.337 (4)	C12—H12	0.9300
N2—C12	1.337 (4)	C13—H13	0.9300
N2—C11	1.340 (4)	C14—C15	1.492 (3)
N2—Ni1^iv	2.115 (2)	C15—C16	1.369 (4)
C1—C2	1.374 (4)	C16—C17	1.409 (4)
C1—H1	0.9300	C16—H16	0.9300
C2—C3	1.376 (4)	C17—C18	1.366 (4)
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.380 (4)	C18—C19	1.497 (3)
C3—C6	1.508 (4)
O6^i—Ni1—O3	177.04 (9)	C3—C6—H6B	109.4
O6^i—Ni1—N1	90.64 (8)	C7—C6—H6B	109.4
O3—Ni1—N1	89.96 (8)	H6A—C6—H6B	108.0
O6^i—Ni1—O1	89.80 (9)	C8—C7—C6	113.5 (3)
O3—Ni1—O1	89.15 (9)	C8—C7—H7A	108.9
N1—Ni1—O1	171.03 (9)	C6—C7—H7A	108.9
O6^i—Ni1—N2^ii	92.62 (9)	C8—C7—H7B	108.9
O3—Ni1—N2^ii	90.20 (8)	C6—C7—H7B	108.9
N1—Ni1—N2^ii	95.69 (10)	H7A—C7—H7B	107.7
O1—Ni1—N2^ii	93.23 (9)	C9—C8—C7	112.4 (3)
O6^i—Ni1—O2	88.53 (9)	C9—C8—H8A	109.1
O3—Ni1—O2	88.59 (9)	C7—C8—H8A	109.1
N1—Ni1—O2	89.01 (11)	C9—C8—H8B	109.1
O1—Ni1—O2	82.05 (11)	C7—C8—H8B	109.1
N2^ii—Ni1—O2	175.15 (11)	H8A—C8—H8B	107.9
C18—S1—C15	91.57 (13)	C13—C9—C10	115.7 (3)
Ni1—O1—H1A	106 (3)	C13—C9—C8	121.4 (3)
Ni1—O1—H1B	106 (3)	C10—C9—C8	122.9 (3)
H1A—O1—H1B	118 (4)	C11—C10—C9	120.1 (3)
Ni1—O2—H2A	106 (3)	C11—C10—H10	119.9
Ni1—O2—H2B	124 (3)	C9—C10—H10	119.9
H2A—O2—H2B	101 (4)	N2—C11—C10	123.9 (3)
C14—O3—Ni1	126.91 (18)	N2—C11—H11	118.1
C19—O6—Ni1^iii	131.38 (19)	C10—C11—H11	118.1
C5—N1—C1	115.3 (3)	N2—C12—C13	123.5 (3)
C5—N1—Ni1	120.5 (2)	N2—C12—H12	118.2
C1—N1—Ni1	123.8 (2)	C13—C12—H12	118.2
C12—N2—C11	115.7 (3)	C12—C13—C9	121.1 (3)
C12—N2—Ni1^iv	122.0 (2)	C12—C13—H13	119.5
C11—N2—Ni1^iv	122.1 (2)	C9—C13—H13	119.5
N1—C1—C2	124.0 (3)	O4—C14—O3	126.2 (2)
N1—C1—H1	118.0	O4—C14—C15	118.6 (2)
C2—C1—H1	118.0	O3—C14—C15	115.2 (2)
C1—C2—C3	120.5 (3)	C16—C15—C14	127.7 (2)
C1—C2—H2	119.7	C16—C15—S1	111.56 (19)
C3—C2—H2	119.7	C14—C15—S1	120.8 (2)
C2—C3—C4	115.4 (3)	C15—C16—C17	112.4 (3)
C2—C3—C6	123.4 (3)	C15—C16—H16	123.8
C4—C3—C6	121.2 (3)	C17—C16—H16	123.8
C5—C4—C3	121.1 (3)	C18—C17—C16	112.8 (3)
C5—C4—H4	119.4	C18—C17—H17	123.6
C3—C4—H4	119.4	C16—C17—H17	123.6
N1—C5—C4	123.6 (3)	C17—C18—C19	127.4 (3)
N1—C5—H5	118.2	C17—C18—S1	111.65 (19)
C4—C5—H5	118.2	C19—C18—S1	120.9 (2)
C3—C6—C7	111.2 (2)	O5—C19—O6	127.0 (2)
C3—C6—H6A	109.4	O5—C19—C18	118.3 (2)
C7—C6—H6A	109.4	O6—C19—C18	114.7 (3)
N1—Ni1—O3—C14	−153.1 (2)	C12—N2—C11—C10	−0.1 (5)
O1—Ni1—O3—C14	35.8 (2)	Ni1^iv—N2—C11—C10	173.7 (3)
N2^ii—Ni1—O3—C14	−57.4 (2)	C9—C10—C11—N2	−0.5 (6)
O2—Ni1—O3—C14	117.9 (2)	C11—N2—C12—C13	0.2 (4)
O6^i—Ni1—N1—C5	4.9 (3)	Ni1^iv—N2—C12—C13	−173.6 (2)
O3—Ni1—N1—C5	−172.2 (3)	N2—C12—C13—C9	0.3 (5)
N2^ii—Ni1—N1—C5	97.6 (3)	C10—C9—C13—C12	−0.8 (5)
O2—Ni1—N1—C5	−83.6 (3)	C8—C9—C13—C12	179.5 (3)
O6^i—Ni1—N1—C1	177.3 (3)	Ni1—O3—C14—O4	−8.7 (4)
O3—Ni1—N1—C1	0.2 (3)	Ni1—O3—C14—C15	172.38 (17)
N2^ii—Ni1—N1—C1	−90.0 (3)	O4—C14—C15—C16	178.8 (3)
O2—Ni1—N1—C1	88.8 (3)	O3—C14—C15—C16	−2.2 (4)
C5—N1—C1—C2	1.0 (5)	O4—C14—C15—S1	−3.1 (4)
Ni1—N1—C1—C2	−171.8 (3)	O3—C14—C15—S1	175.9 (2)
N1—C1—C2—C3	1.4 (6)	C18—S1—C15—C16	−1.1 (2)
C1—C2—C3—C4	−2.8 (5)	C18—S1—C15—C14	−179.5 (2)
C1—C2—C3—C6	174.7 (3)	C14—C15—C16—C17	179.6 (3)
C2—C3—C4—C5	1.8 (5)	S1—C15—C16—C17	1.4 (4)
C6—C3—C4—C5	−175.7 (3)	C15—C16—C17—C18	−0.9 (4)
C1—N1—C5—C4	−2.0 (6)	C16—C17—C18—C19	−179.0 (3)
Ni1—N1—C5—C4	171.1 (3)	C16—C17—C18—S1	0.1 (4)
C3—C4—C5—N1	0.6 (6)	C15—S1—C18—C17	0.6 (2)
C2—C3—C6—C7	−95.4 (4)	C15—S1—C18—C19	179.7 (2)
C4—C3—C6—C7	81.8 (4)	Ni1^iii—O6—C19—O5	−4.8 (5)
C3—C6—C7—C8	73.2 (4)	Ni1^iii—O6—C19—C18	174.45 (18)
C6—C7—C8—C9	179.5 (3)	C17—C18—C19—O5	170.1 (3)
C7—C8—C9—C13	64.8 (4)	S1—C18—C19—O5	−8.9 (4)
C7—C8—C9—C10	−114.9 (4)	C17—C18—C19—O6	−9.3 (4)
C13—C9—C10—C11	0.9 (5)	S1—C18—C19—O6	171.7 (2)
C8—C9—C10—C11	−179.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.83 (4)	1.98 (4)	2.695 (3)	144 (3)
O1—H1B···O5^i	0.82 (4)	1.92 (4)	2.690 (3)	156 (4)
O2—H2B···O4^v	0.89 (5)	1.81 (5)	2.706 (3)	174 (4)

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