[Ni(cyclam)(OCOR)₂], a finite molecular complex: hydrogen-bonded supramolecular aggregation in one, two and three dimensions, and coordination polymers in one and two dimensions

In the complexes [Ni(cyclam)(OCOR)₂] (cyclam = 1,4,8,11-tetraazacyclotetradecane), where (RCOO)⁻ is 2-naphtho-ate [bis-(2-naphthoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (I), monoclinic P2₁/c, Z′ = 0.5], 3,5-dinitrobenzoate [bis-(3,5-dinitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (II), triclinic P, Z′ = 0.5], 4-nitrobenzoate [bis-(4-nitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (III), monoclinic P2₁/n, Z′ = 0.5], 3-hydroxybenzoate [bis-(3-hydroxybenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (IV), monoclinic P2₁/c, Z′ = 0.5] and 4-aminobenzo-ate [bis-(4-aminobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II), (V), monoclinic C2/c, Z′ = 0.5], the Ni lies on a centre of inversion with monodentate carboxylato ligands occupying trans sites. Compound (I) consists of isolated molecules. In (II) and (III), N—H...O hydrogen bonds link the complexes into chains. Compounds (IV) and (III) form two- and three-dimensional structures generated entirely by hard hydrogen bonds. The 5-hydroxyisophthalate(2−) anion forms a hydrated complex, [Ni(cyclam)(5-hydroxyisophthalate)(H₂O)]·4H₂O {[aqua-(5-hydroxyisophthalato)-1,4,8,11-tetraazacyclotetradecanenickel(II)] tetrahydrate, (VI), monoclinic Cc, Z′ = 1}, in which the monodentate carboxylato ligand and a water molecule occupy trans sites at Ni: extensive hydrogen bonding links the molecular aggregates into a three-dimensional framework. The terephthalate(2−) anion forms a hydrated linear coordination polymer {catena-poly[terephthalato-1,4,8,11-tetraazacyclotetradecanenickel(II)] monohydrate, (VII), monoclinic C2/c, Z′ = 0.5}. In 1,2,4,5-benzenecarboxylate tris[1,4,8,11-tetraazacyclotetradecanenickel(II)] diperchlorate hydrate (VIII), [Ni(cyclam)]₃·[1,2,4,5-benzenetetracarboxylate(4−)]·[ClO₄]₂·-[H₂O]₃, there are two distinct Ni sites: [Ni(cyclam)]²⁺ and centrosymmetric [C₁₀H₂O₈]⁴⁻ units form a two-dimensional coordination polymer, whose sheets are linked by centrosymmetric [Ni(cyclam)(H₂O)₂]²⁺ cations.

Computing details

Data collection: Kappa-CCD server software (Nonius, 1997) for (I), (II), (IV), (V), (VI), (VII), (VIII); Kappa-CCD server softare (Nonius, 1997) for (III). For all compounds, cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b). Molecular graphics: PLATON (Spek, 20001) for (I); PLATON (Spek, 2001) for (II), (III), (IV), (V), (VI), (VII), (VIII). For all compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b) and PRPKAPPA (Ferguson, 1999).

(I) Bis-(2-naphthoato)-1,4,8,11-tetraazacyclotetradecanenickel(II)

Crystal data

C32H38N4NiO4	F(000) = 636
Mr = 601.37	Dx = 1.366 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4970 (4) Å	Cell parameters from 3144 reflections
b = 10.6563 (4) Å	θ = 2.6–27.5°
c = 11.9407 (4) Å	µ = 0.71 mm^−1
β = 92.2080 (17)°	T = 150 K
V = 1461.83 (9) Å^3	Block, purple
Z = 2	0.36 × 0.26 × 0.18 mm

Data collection

Kappa-CCD diffractometer	3328 independent reflections
Radiation source: fine-focus sealed X-ray tube	2895 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→14
Tmin = 0.785, Tmax = 0.883	k = 0→13
9394 measured reflections	l = −15→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0155P)^2 + 0.7435P] where P = (Fo^2 + 2Fc^2)/3
3328 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01919 (9)
O1	0.39898 (9)	0.34617 (10)	0.54652 (8)	0.0268 (2)
O2	0.39786 (11)	0.22396 (11)	0.39435 (10)	0.0384 (3)
C11	0.24257 (12)	0.19082 (13)	0.64991 (12)	0.0217 (3)
C12	0.27874 (12)	0.16666 (13)	0.54398 (12)	0.0210 (3)
C13	0.23432 (13)	0.06007 (14)	0.48509 (13)	0.0270 (3)
C14	0.15576 (14)	−0.01766 (15)	0.53301 (14)	0.0308 (3)
C15	0.11721 (13)	0.00529 (14)	0.64248 (14)	0.0275 (3)
C16	0.03531 (15)	−0.07267 (17)	0.69482 (16)	0.0396 (4)
C17	−0.00158 (16)	−0.0457 (2)	0.79955 (17)	0.0442 (5)
C18	0.04227 (15)	0.05950 (18)	0.85834 (15)	0.0383 (4)
C19	0.12280 (13)	0.13622 (15)	0.81110 (13)	0.0290 (3)
C110	0.16119 (12)	0.11186 (14)	0.70172 (12)	0.0232 (3)
C111	0.36627 (12)	0.25133 (13)	0.48961 (12)	0.0220 (3)
N1	0.60752 (11)	0.39074 (12)	0.40417 (10)	0.0245 (3)
C2	0.71607 (14)	0.37508 (17)	0.47247 (14)	0.0325 (4)
C3	0.68618 (14)	0.35421 (17)	0.59425 (14)	0.0334 (4)
N4	0.61582 (11)	0.46044 (13)	0.63234 (10)	0.0263 (3)
C5	0.56383 (14)	0.43833 (16)	0.74220 (12)	0.0302 (3)
C6	0.48728 (14)	0.54690 (16)	0.77773 (12)	0.0312 (3)
C7	0.37303 (14)	0.56273 (15)	0.71011 (12)	0.0286 (3)
H11	0.2726	0.2619	0.6894	0.026*
H13	0.2594	0.0427	0.4118	0.032*
H14	0.1265	−0.0882	0.4923	0.037*
H16	0.0057	−0.1447	0.6565	0.048*
H17	−0.0572	−0.0984	0.8329	0.053*
H18	0.0161	0.0776	0.9311	0.046*
H19	0.1531	0.2062	0.8520	0.035*
H1	0.5731	0.3120	0.3970	0.029*
H2A	0.7652	0.4509	0.4664	0.039*
H2B	0.7603	0.3023	0.4450	0.039*
H3A	0.6420	0.2750	0.6011	0.040*
H3B	0.7586	0.3474	0.6415	0.040*
H4	0.6654	0.5290	0.6408	0.032*
H5A	0.6270	0.4255	0.7998	0.036*
H5B	0.5166	0.3607	0.7380	0.036*
H6A	0.5324	0.6256	0.7724	0.037*
H6B	0.4693	0.5350	0.8574	0.037*
H7A	0.3322	0.4810	0.7053	0.034*
H7B	0.3226	0.6226	0.7491	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02131 (14)	0.01902 (14)	0.01737 (13)	−0.00436 (10)	0.00246 (9)	0.00057 (9)
O1	0.0335 (6)	0.0237 (5)	0.0235 (5)	−0.0114 (4)	0.0066 (4)	−0.0022 (4)
O2	0.0501 (7)	0.0347 (6)	0.0319 (6)	−0.0172 (5)	0.0192 (5)	−0.0103 (5)
C11	0.0203 (7)	0.0188 (7)	0.0259 (7)	−0.0012 (5)	0.0000 (5)	0.0024 (5)
C12	0.0201 (6)	0.0180 (6)	0.0249 (7)	−0.0012 (5)	−0.0001 (5)	0.0024 (5)
C13	0.0299 (8)	0.0249 (8)	0.0261 (7)	−0.0042 (6)	0.0000 (6)	−0.0008 (6)
C14	0.0322 (8)	0.0249 (8)	0.0350 (8)	−0.0093 (6)	−0.0039 (7)	−0.0004 (6)
C15	0.0234 (7)	0.0249 (8)	0.0339 (8)	−0.0054 (6)	−0.0016 (6)	0.0075 (6)
C16	0.0348 (9)	0.0353 (9)	0.0485 (10)	−0.0150 (7)	−0.0018 (8)	0.0108 (8)
C17	0.0329 (9)	0.0484 (11)	0.0519 (11)	−0.0128 (8)	0.0085 (8)	0.0194 (9)
C18	0.0339 (9)	0.0443 (10)	0.0375 (9)	0.0009 (8)	0.0124 (7)	0.0153 (8)
C19	0.0265 (7)	0.0288 (8)	0.0321 (8)	0.0027 (6)	0.0050 (6)	0.0069 (6)
C110	0.0186 (6)	0.0225 (7)	0.0284 (7)	0.0008 (5)	0.0011 (5)	0.0067 (6)
C111	0.0237 (7)	0.0202 (7)	0.0222 (7)	−0.0026 (6)	0.0025 (5)	0.0013 (5)
N1	0.0266 (6)	0.0222 (6)	0.0250 (6)	−0.0048 (5)	0.0046 (5)	0.0000 (5)
C2	0.0256 (8)	0.0372 (9)	0.0351 (8)	0.0034 (7)	0.0054 (6)	0.0020 (7)
C3	0.0293 (8)	0.0364 (9)	0.0343 (8)	0.0038 (7)	−0.0007 (7)	0.0082 (7)
N4	0.0272 (6)	0.0288 (7)	0.0228 (6)	−0.0071 (5)	0.0009 (5)	0.0035 (5)
C5	0.0344 (8)	0.0354 (9)	0.0206 (7)	−0.0081 (7)	−0.0009 (6)	0.0059 (6)
C6	0.0393 (9)	0.0330 (8)	0.0215 (7)	−0.0115 (7)	0.0038 (6)	−0.0014 (6)
C7	0.0342 (8)	0.0283 (8)	0.0239 (7)	−0.0081 (7)	0.0099 (6)	−0.0039 (6)

Geometric parameters (Å, º)

Ni1—N4^i	2.070 (2)	C18—H18	0.95
Ni1—N4	2.070 (2)	C19—C110	1.419 (2)
Ni1—N1^i	2.074 (2)	C19—H19	0.95
Ni1—N1	2.074 (2)	N1—C2	1.474 (2)
Ni1—O1^i	2.096 (2)	N1—C7^i	1.477 (2)
Ni1—O1	2.096 (2)	N1—H1	0.93
O1—C111	1.267 (2)	C2—C3	1.523 (2)
O2—C111	1.242 (2)	C2—H2A	0.99
C11—C12	1.371 (2)	C2—H2B	0.99
C11—C110	1.418 (2)	C3—N4	1.473 (2)
C11—H11	0.95	C3—H3A	0.99
C12—C13	1.420 (2)	C3—H3B	0.99
C12—C111	1.516 (2)	N4—C5	1.481 (2)
C13—C14	1.367 (2)	N4—H4	0.93
C13—H13	0.95	C5—C6	1.524 (2)
C14—C15	1.418 (2)	C5—H5A	0.99
C14—H14	0.95	C5—H5B	0.99
C15—C16	1.419 (2)	C6—C7	1.524 (2)
C15—C110	1.421 (2)	C6—H6A	0.99
C16—C17	1.367 (3)	C6—H6B	0.99
C16—H16	0.95	C7—N1^i	1.477 (2)
C17—C18	1.406 (3)	C7—H7A	0.99
C17—H17	0.95	C7—H7B	0.99
C18—C19	1.373 (2)
N4^i—Ni1—N4	180.0	O2—C111—O1	126.0 (12)
N4^i—Ni1—N1^i	85.83 (5)	O2—C111—C12	118.3 (2)
N4—Ni1—N1^i	94.17 (5)	O1—C111—C12	115.7 (2)
N4^i—Ni1—N1	94.17 (5)	C2—N1—C7^i	113.2 (2)
N4—Ni1—N1	85.83 (5)	C2—N1—Ni1	105.56 (9)
N1^i—Ni1—N1	180.0	C7^i—N1—Ni1	115.8 (2)
N4^i—Ni1—O1^i	89.15 (5)	C2—N1—H1	107.3
N4—Ni1—O1^i	90.85 (5)	C7^i—N1—H1	107.3
N1^i—Ni1—O1^i	93.17 (4)	Ni1—N1—H1	107.3
N1—Ni1—O1^i	86.83 (4)	N1—C2—C3	109.1 (2)
N4^i—Ni1—O1	90.85 (5)	N1—C2—H2A	109.9
N4—Ni1—O1	89.15 (5)	C3—C2—H2A	109.9
N1^i—Ni1—O1	86.83 (4)	N1—C2—H2B	109.9
N1—Ni1—O1	93.17 (4)	C3—C2—H2B	109.9
O1^i—Ni1—O1	180.0	H2A—C2—H2B	108.3
C111—O1—Ni1	129.63 (9)	N4—C3—C2	109.2 (2)
C12—C11—C110	121.3 (2)	N4—C3—H3A	109.8
C12—C11—H11	119.3	C2—C3—H3A	109.8
C110—C11—H11	119.3	N4—C3—H3B	109.8
C11—C12—C13	119.4 (2)	C2—C3—H3B	109.8
C11—C12—C111	120.9 (2)	H3A—C3—H3B	108.3
C13—C12—C111	119.7 (2)	C3—N4—C5	113.4 (2)
C14—C13—C12	120.5 (2)	C3—N4—Ni1	105.41 (9)
C14—C13—H13	119.7	C5—N4—Ni1	116.02 (9)
C12—C13—H13	119.7	C3—N4—H4	107.2
C13—C14—C15	121.1 (2)	C5—N4—H4	107.2
C13—C14—H14	119.5	Ni1—N4—H4	107.2
C15—C14—H14	119.5	N4—C5—C6	112.5 (2)
C14—C15—C16	122.8 (2)	N4—C5—H5A	109.1
C14—C15—C110	118.6 (2)	C6—C5—H5A	109.1
C16—C15—C110	118.6 (2)	N4—C5—H5B	109.1
C17—C16—C15	121.0 (2)	C6—C5—H5B	109.1
C17—C16—H16	119.5	H5A—C5—H5B	107.8
C15—C16—H16	119.5	C5—C6—C7	115.6 (2)
C16—C17—C18	120.5 (2)	C5—C6—H6A	108.4
C16—C17—H17	119.8	C7—C6—H6A	108.4
C18—C17—H17	119.8	C5—C6—H6B	108.4
C19—C18—C17	120.3 (2)	C7—C6—H6B	108.4
C19—C18—H18	119.9	H6A—C6—H6B	107.4
C17—C18—H18	119.9	N1^i—C7—C6	111.6 (2)
C18—C19—C110	120.5 (2)	N1^i—C7—H7A	109.3
C18—C19—H19	119.7	C6—C7—H7A	109.3
C110—C19—H19	119.7	N1^i—C7—H7B	109.3
C11—C110—C19	121.8 (2)	C6—C7—H7B	109.3
C11—C110—C15	119.0 (2)	H7A—C7—H7B	108.0
C19—C110—C15	119.2 (2)
N4^i—Ni1—O1—C111	56.5 (2)	C11—C12—C111—O1	−2.5 (2)
N4—Ni1—O1—C111	−123.5 (2)	C13—C12—C111—O1	178.1 (2)
N1^i—Ni1—O1—C111	142.3 (3)	N4^i—Ni1—N1—C2	165.9 (2)
N1—Ni1—O1—C111	−37.7 (2)	N4—Ni1—N1—C2	−14.1 (2)
C110—C11—C12—C13	−0.3 (2)	O1^i—Ni1—N1—C2	77.03 (9)
C110—C11—C12—C111	−179.7 (2)	O1—Ni1—N1—C2	−103.0 (2)
C11—C12—C13—C14	0.3 (2)	N4^i—Ni1—N1—C7^i	39.8 (2)
C111—C12—C13—C14	179.7 (2)	N4—Ni1—N1—C7^i	−140.2 (2)
C12—C13—C14—C15	−0.4 (2)	O1^i—Ni1—N1—C7^i	−49.1 (2)
C13—C14—C15—C16	179.6 (2)	O1—Ni1—N1—C7^i	130.9 (2)
C13—C14—C15—C110	0.5 (2)	C7^i—N1—C2—C3	168.1 (2)
C14—C15—C16—C17	−178.5 (2)	Ni1—N1—C2—C3	40.4 (2)
C110—C15—C16—C17	0.6 (3)	N1—C2—C3—N4	−56.9 (2)
C15—C16—C17—C18	−0.8 (3)	C2—C3—N4—C5	169.2 (2)
C16—C17—C18—C19	−0.1 (3)	C2—C3—N4—Ni1	41.3 (2)
C17—C18—C19—C110	1.2 (2)	N1^i—Ni1—N4—C3	164.86 (9)
C12—C11—C110—C19	−179.7 (2)	N1—Ni1—N4—C3	−15.14 (9)
C12—C11—C110—C15	0.4 (2)	O1^i—Ni1—N4—C3	−101.90 (9)
C18—C19—C110—C11	178.8 (2)	O1—Ni1—N4—C3	78.10 (9)
C18—C19—C110—C15	−1.4 (2)	N1^i—Ni1—N4—C5	38.9 (2)
C14—C15—C110—C11	−0.5 (2)	N1—Ni1—N4—C5	−141.4 (2)
C16—C15—C110—C11	−179.6 (2)	O1^i—Ni1—N4—C5	131.8 (2)
C14—C15—C110—C19	179.7 (2)	O1—Ni1—N4—C5	−48.2 (2)
C16—C15—C110—C19	0.5 (2)	C3—N4—C5—C6	−177.6 (2)
Ni1—O1—C111—O2	7.4 (2)	Ni1—N4—C5—C6	−55.4 (2)
Ni1—O1—C111—C12	−171.29 (9)	N4—C5—C6—C7	70.1 (2)
C11—C12—C111—O2	178.6 (2)	C5—C6—C7—N1^i	−71.1 (2)
C13—C12—C111—O2	−0.7 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.93	2.22	2.994 (2)	140

(II) Bis-(3,5-dinitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II)

Crystal data

C24H30N8NiO12	Z = 1
Mr = 681.27	F(000) = 354
Triclinic, P1	Dx = 1.564 Mg m^−3
a = 7.7663 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7845 (6) Å	Cell parameters from 5718 reflections
c = 10.4026 (7) Å	θ = 2.8–27.2°
α = 99.826 (2)°	µ = 0.75 mm^−1
β = 97.966 (2)°	T = 293 K
γ = 108.388 (2)°	Plate, colourless
V = 723.30 (7) Å^3	0.30 × 0.24 × 0.02 mm

Data collection

Kappa-CCD diffractometer	3135 independent reflections
Radiation source: fine-focus sealed X-ray tube	2560 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
φ scans, and ω scans with κ offsets	θmax = 27.2°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→9
Tmin = 0.807, Tmax = 0.985	k = −12→11
17662 measured reflections	l = −13→13

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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2)P)^2 + 0.3293P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3135 reflections	Δρmax = 0.29 e Å^−3
206 parameters	Δρmin = −0.43 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (3)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891]which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.03420 (15)
N1	0.2732 (3)	0.5215 (2)	0.57420 (19)	0.0407 (5)
C2	0.2156 (4)	0.4009 (3)	0.6446 (3)	0.0529 (7)
C3	0.2281 (4)	0.2618 (3)	0.5626 (3)	0.0538 (7)
N4	0.4181 (3)	0.2920 (2)	0.5391 (2)	0.0415 (5)
C5	0.4378 (4)	0.1739 (3)	0.4400 (3)	0.0469 (6)
C6	0.6350 (4)	0.2085 (3)	0.4189 (3)	0.0494 (6)
C7	0.7033 (4)	0.3306 (3)	0.3461 (3)	0.0484 (6)
O11	0.3435 (2)	0.40263 (19)	0.30221 (16)	0.0456 (4)
O12	0.1530 (2)	0.5311 (2)	0.28440 (18)	0.0547 (5)
O32	0.0894 (3)	−0.0360 (3)	−0.2587 (2)	0.0800 (7)
O31	0.2989 (3)	0.0153 (2)	−0.0804 (2)	0.0681 (6)
O51	−0.3909 (3)	0.3286 (3)	−0.0794 (2)	0.0696 (6)
O52	−0.4066 (3)	0.1585 (2)	−0.2464 (2)	0.0704 (6)
N3	0.1675 (4)	0.0330 (2)	−0.1442 (2)	0.0537 (6)
N5	−0.3274 (3)	0.2430 (3)	−0.1391 (2)	0.0520 (6)
C11	0.1133 (3)	0.3314 (2)	0.1059 (2)	0.0362 (5)
C12	0.1873 (3)	0.2326 (3)	0.0429 (2)	0.0402 (5)
C13	0.0918 (3)	0.1419 (3)	−0.0800 (2)	0.0422 (6)
C14	−0.0744 (4)	0.1447 (3)	−0.1438 (2)	0.0454 (6)
C15	−0.1450 (3)	0.2432 (3)	−0.0773 (2)	0.0406 (5)
C16	−0.0543 (3)	0.3368 (3)	0.0452 (2)	0.0387 (5)
C17	0.2114 (3)	0.4321 (3)	0.2431 (2)	0.0373 (5)
H1	0.1802	0.5011	0.5024	0.049*
H2A	0.0894	0.3839	0.6563	0.063*
H2B	0.2958	0.4277	0.7319	0.063*
H3A	0.1973	0.1828	0.6097	0.065*
H3B	0.1406	0.2307	0.4781	0.065*
H4	0.4912	0.2983	0.6178	0.050*
H5A	0.3560	0.1601	0.3558	0.056*
H5B	0.3999	0.0820	0.4694	0.056*
H6A	0.6451	0.1189	0.3693	0.059*
H6B	0.7172	0.2355	0.5054	0.059*
H7A	0.8211	0.3316	0.3244	0.058*
H7B	0.6156	0.3098	0.2631	0.058*
H12	0.2993	0.2276	0.0829	0.048*
H14	−0.1359	0.0836	−0.2272	0.055*
H16	−0.1049	0.4026	0.0865	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0336 (2)	0.0363 (2)	0.0305 (2)	0.01418 (18)	0.00215 (16)	0.00157 (16)
N1	0.0408 (11)	0.0437 (11)	0.0369 (11)	0.0181 (9)	0.0050 (8)	0.0031 (9)
C2	0.0536 (15)	0.0572 (16)	0.0560 (16)	0.0230 (13)	0.0247 (13)	0.0161 (13)
C3	0.0516 (15)	0.0466 (15)	0.0645 (18)	0.0142 (12)	0.0205 (13)	0.0148 (13)
N4	0.0432 (11)	0.0433 (11)	0.0371 (11)	0.0181 (9)	0.0043 (9)	0.0045 (9)
C5	0.0559 (15)	0.0361 (13)	0.0458 (14)	0.0180 (11)	0.0060 (12)	0.0017 (11)
C6	0.0545 (15)	0.0464 (14)	0.0495 (15)	0.0274 (12)	0.0077 (12)	0.0009 (12)
C7	0.0502 (14)	0.0512 (15)	0.0445 (14)	0.0244 (12)	0.0112 (11)	−0.0014 (11)
O11	0.0459 (10)	0.0510 (10)	0.0361 (9)	0.0235 (8)	−0.0060 (7)	−0.0013 (8)
O12	0.0540 (11)	0.0602 (12)	0.0452 (10)	0.0309 (9)	−0.0064 (8)	−0.0082 (9)
O32	0.0983 (17)	0.0786 (15)	0.0522 (13)	0.0348 (13)	0.0104 (12)	−0.0174 (11)
O31	0.0765 (15)	0.0683 (14)	0.0687 (14)	0.0402 (12)	0.0159 (12)	0.0097 (11)
O51	0.0534 (12)	0.0792 (15)	0.0716 (14)	0.0291 (11)	−0.0048 (10)	0.0081 (12)
O52	0.0660 (13)	0.0622 (13)	0.0571 (13)	0.0111 (10)	−0.0284 (10)	0.0001 (10)
N3	0.0663 (15)	0.0442 (13)	0.0481 (14)	0.0169 (11)	0.0188 (12)	0.0028 (10)
N5	0.0462 (12)	0.0511 (13)	0.0490 (13)	0.0116 (11)	−0.0077 (10)	0.0104 (11)
C11	0.0376 (12)	0.0355 (12)	0.0307 (11)	0.0090 (9)	0.0014 (9)	0.0064 (9)
C12	0.0413 (13)	0.0410 (13)	0.0363 (12)	0.0142 (10)	0.0036 (10)	0.0070 (10)
C13	0.0503 (14)	0.0383 (13)	0.0363 (13)	0.0149 (11)	0.0091 (11)	0.0043 (10)
C14	0.0537 (15)	0.0414 (14)	0.0310 (12)	0.0088 (11)	0.0000 (11)	0.0035 (10)
C15	0.0385 (12)	0.0406 (13)	0.0352 (12)	0.0074 (10)	−0.0032 (10)	0.0100 (10)
C16	0.0402 (12)	0.0383 (12)	0.0348 (12)	0.0130 (10)	0.0031 (10)	0.0065 (10)
C17	0.0338 (11)	0.0399 (12)	0.0332 (12)	0.0119 (10)	0.0005 (9)	0.0019 (10)

Geometric parameters (Å, º)

Ni1—N1	2.073 (2)	C6—H6B	0.97
Ni1—N1^i	2.073 (2)	C7—N1^i	1.482 (3)
Ni1—N4	2.062 (2)	C7—H7A	0.97
Ni1—N4^i	2.062 (2)	C7—H7B	0.97
Ni1—O11^i	2.127 (2)	O11—C17	1.259 (3)
Ni1—O11	2.127 (2)	O12—C17	1.233 (3)
N1—C2	1.477 (3)	O31—N3	1.214 (3)
N1—C7^i	1.482 (3)	O32—N3	1.229 (3)
N1—H1	0.91	O51—N5	1.224 (3)
C2—C3	1.516 (4)	O52—N5	1.218 (3)
C2—H2A	0.97	N3—C13	1.479 (3)
C2—H2B	0.97	N5—C15	1.472 (3)
C3—N4	1.474 (3)	C11—C12	1.391 (3)
C3—H3A	0.97	C11—C16	1.386 (3)
C3—H3B	0.97	C11—C17	1.527 (3)
N4—C5	1.473 (3)	C12—C13	1.381 (3)
N4—H4	0.91	C12—H12	0.93
C5—C6	1.516 (4)	C13—C14	1.377 (4)
C5—H5A	0.97	C14—C15	1.386 (4)
C5—H5B	0.97	C14—H14	0.93
C6—C7	1.517 (4)	C15—C16	1.380 (3)
C6—H6A	0.97	C16—H16	0.93
N4—Ni1—N4^i	180.0	C6—C5—H5B	109.1
N4—Ni1—N1	85.46 (8)	H5A—C5—H5B	107.9
N4^i—Ni1—N1	94.54 (8)	C5—C6—C7	116.2 (2)
N4—Ni1—N1^i	94.54 (8)	C5—C6—H6A	108.2
N4^i—Ni1—N1^i	85.46 (8)	C7—C6—H6A	108.2
N1—Ni1—N1^i	180.0	C5—C6—H6B	108.2
N4—Ni1—O11^i	91.86 (7)	C7—C6—H6B	108.2
N4^i—Ni1—O11^i	88.14 (7)	H6A—C6—H6B	107.4
N1—Ni1—O11^i	86.49 (7)	N1^i—C7—C6	112.6 (2)
N1^i—Ni1—O11^i	93.51 (7)	N1^i—C7—H7A	109.1
N4—Ni1—O11	88.14 (7)	C6—C7—H7A	109.1
N4^i—Ni1—O11	91.86 (7)	N1^i—C7—H7B	109.1
N1—Ni1—O11	93.51 (7)	C6—C7—H7B	109.1
N1^i—Ni1—O11	86.49 (7)	H7A—C7—H7B	107.8
O11^i—Ni1—O11	180	C17—O11—Ni1	127.9 (2)
C2—N1—C7^i	114.0 (2)	O31—N3—O32	124.4 (3)
C2—N1—Ni1	105.8 (2)	O31—N3—C13	118.5 (2)
C7^i—N1—Ni1	116.7 (2)	O32—N3—C13	117.0 (3)
C2—N1—H1	106.6	O52—N5—O51	123.7 (2)
C7^i—N1—H1	106.6	O52—N5—C15	118.5 (2)
Ni1—N1—H1	106.6	O51—N5—C15	117.9 (2)
N1—C2—C3	108.7 (2)	C16—C11—C12	119.8 (2)
N1—C2—H2A	109.9	C16—C11—C17	119.2 (2)
C3—C2—H2A	109.9	C12—C11—C17	121.0 (2)
N1—C2—H2B	109.9	C13—C12—C11	118.9 (2)
C3—C2—H2B	109.9	C13—C12—H12	120.6
H2A—C2—H2B	108.3	C11—C12—H12	120.6
N4—C3—C2	109.3 (2)	C14—C13—C12	123.0 (2)
N4—C3—H3A	109.8	C14—C13—N3	118.3 (2)
C2—C3—H3A	109.8	C12—C13—N3	118.6 (2)
N4—C3—H3B	109.8	C13—C14—C15	116.5 (2)
C2—C3—H3B	109.8	C13—C14—H14	121.8
H3A—C3—H3B	108.3	C15—C14—H14	121.8
C5—N4—C3	113.9 (2)	C16—C15—C14	122.8 (2)
C5—N4—Ni1	115.8 (2)	C16—C15—N5	119.3 (2)
C3—N4—Ni1	106.1 (2)	C14—C15—N5	117.9 (2)
C5—N4—H4	106.8	C15—C16—C11	119.1 (2)
C3—N4—H4	106.8	C15—C16—H16	120.5
Ni1—N4—H4	106.8	C11—C16—H16	120.5
N4—C5—C6	112.4 (2)	O12—C17—O11	127.2 (2)
N4—C5—H5A	109.1	O12—C17—C11	117.4 (2)
C6—C5—H5A	109.1	O11—C17—C11	115.4 (2)
N4—C5—H5B	109.1
N4—Ni1—N1—C2	15.0 (2)	N1^i—Ni1—O11—C17	−144.0 (2)
N4^i—Ni1—N1—C2	−165.0 (2)	C16—C11—C12—C13	0.4 (3)
O11^i—Ni1—N1—C2	−77.1 (2)	C17—C11—C12—C13	178.8 (2)
O11—Ni1—N1—C2	102.9 (2)	C11—C12—C13—C14	0.0 (4)
N4—Ni1—N1—C7^i	143.0 (2)	C11—C12—C13—N3	−177.7 (2)
N4^i—Ni1—N1—C7^i	−37.0 (2)	O31—N3—C13—C14	−169.6 (2)
O11^i—Ni1—N1—C7^i	50.9 (2)	O32—N3—C13—C14	9.0 (3)
O11—Ni1—N1—C7^i	−129.2 (2)	O31—N3—C13—C12	8.2 (3)
C7^i—N1—C2—C3	−170.5 (2)	O32—N3—C13—C12	−173.2 (2)
Ni1—N1—C2—C3	−41.0 (2)	C12—C13—C14—C15	−0.9 (4)
N1—C2—C3—N4	56.4 (3)	N3—C13—C14—C15	176.9 (2)
C2—C3—N4—C5	−169.1 (2)	C13—C14—C15—C16	1.3 (4)
C2—C3—N4—Ni1	−40.5 (2)	C13—C14—C15—N5	−176.6 (2)
N1—Ni1—N4—C5	141.5 (12)	O52—N5—C15—C16	−179.1 (2)
N1^i—Ni1—N4—C5	−38.5 (2)	O51—N5—C15—C16	1.0 (3)
O11^i—Ni1—N4—C5	−132.1 (2)	O52—N5—C15—C14	−1.1 (3)
O11—Ni1—N4—C5	47.9 (2)	O51—N5—C15—C14	179.0 (2)
N1—Ni1—N4—C3	14.1 (2)	C14—C15—C16—C11	−0.9 (4)
N1^i—Ni1—N4—C3	−165.9 (2)	N5—C15—C16—C11	177.0 (2)
O11^i—Ni1—N4—C3	100.4 (2)	C12—C11—C16—C15	0.0 (3)
O11—Ni1—N4—C3	−79.6 (2)	C17—C11—C16—C15	−178.4 (2)
C3—N4—C5—C6	−179.8 (2)	Ni1—O11—C17—O12	5.5 (4)
Ni1—N4—C5—C6	56.8 (3)	Ni1—O11—C17—C11	−173.8 (2)
N4—C5—C6—C7	−71.0 (3)	C16—C11—C17—O12	−11.8 (3)
C5—C6—C7—N1^i	68.7 (3)	C12—C11—C17—O12	169.8 (2)
N4—Ni1—O11—C17	121.4 (2)	C16—C11—C17—O11	167.5 (2)
N4^i—Ni1—O11—C17	−58.6 (2)	C12—C11—C17—O11	−10.9 (3)
N1—Ni1—O11—C17	36.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.91	2.33	3.056 (3)	137
N4—H4···O52^ii	0.91	2.35	3.132 (3)	144
C2—H2A···O12^iii	0.97	2.40	3.287 (4)	152

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

(III) Bis-(4-nitrobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II)

Crystal data

C24H32N6NiO8	F(000) = 620
Mr = 591.27	Dx = 1.555 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.8106 (3) Å	Cell parameters from 2781 reflections
b = 8.4187 (2) Å	θ = 2.9–27.8°
c = 12.8397 (4) Å	µ = 0.83 mm^−1
β = 114.2543 (10)°	T = 150 K
V = 1262.51 (6) Å^3	Block, colourless
Z = 2	0.26 × 0.24 × 0.22 mm

Data collection

Kappa-CCD diffractometer	2894 independent reflections
Radiation source: fine-focus sealed X-ray tube	2456 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ scans, and ω scans with κ offsets	θmax = 27.8°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→16
Tmin = 0.813, Tmax = 0.838	k = 0→10
8828 measured reflections	l = −16→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 0.5307P] where P = (Fo^2 + 2Fc^2)/3
2894 reflections	(Δ/σ)max = 0.001
178 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01595 (11)
N1	0.57282 (10)	0.33040 (15)	0.62464 (11)	0.0193 (3)
C2	0.62427 (13)	0.21138 (19)	0.57574 (14)	0.0228 (3)
C3	0.54312 (13)	0.18189 (19)	0.45225 (14)	0.0226 (3)
N4	0.52317 (10)	0.33495 (16)	0.39076 (11)	0.0195 (3)
C5	0.43331 (14)	0.3272 (2)	0.27367 (14)	0.0238 (3)
C6	0.40728 (14)	0.48956 (19)	0.21559 (14)	0.0236 (3)
C7	0.34781 (13)	0.6063 (2)	0.26408 (13)	0.0217 (3)
O11	0.33036 (9)	0.42120 (13)	0.46359 (10)	0.0218 (3)
O12	0.34942 (10)	0.22940 (17)	0.59137 (12)	0.0410 (4)
O41	−0.23591 (12)	0.2008 (2)	0.40490 (17)	0.0595 (5)
O42	−0.25454 (10)	0.41423 (19)	0.30553 (12)	0.0423 (4)
N14	−0.19596 (12)	0.3093 (2)	0.36853 (14)	0.0343 (4)
C11	0.16301 (13)	0.32350 (19)	0.47697 (13)	0.0195 (3)
C12	0.09284 (14)	0.4217 (2)	0.38919 (14)	0.0239 (3)
C13	−0.02574 (14)	0.4187 (2)	0.35172 (15)	0.0262 (4)
C14	−0.07089 (13)	0.3137 (2)	0.40536 (14)	0.0250 (4)
C15	−0.00398 (14)	0.2141 (2)	0.49259 (15)	0.0271 (4)
C16	0.11389 (14)	0.2198 (2)	0.52871 (14)	0.0245 (4)
C17	0.29251 (13)	0.32381 (19)	0.51547 (14)	0.0210 (3)
H1	0.5135	0.2805	0.6359	0.023*
H2A	0.6378	0.1112	0.6197	0.027*
H2B	0.6987	0.2506	0.5798	0.027*
H3A	0.5771	0.1043	0.4171	0.027*
H3B	0.4698	0.1382	0.4482	0.027*
H4	0.5910	0.3615	0.3848	0.023*
H5A	0.3625	0.2836	0.2760	0.029*
H5B	0.4580	0.2538	0.2279	0.029*
H6A	0.4801	0.5376	0.2217	0.028*
H6B	0.3584	0.4740	0.1334	0.028*
H7A	0.3159	0.6952	0.2098	0.026*
H7B	0.2834	0.5521	0.2730	0.026*
H12	0.1264	0.4923	0.3540	0.029*
H13	−0.0737	0.4861	0.2918	0.031*
H15	−0.0380	0.1431	0.5272	0.032*
H16	0.1614	0.1527	0.5890	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01204 (15)	0.01563 (16)	0.01780 (16)	−0.00064 (10)	0.00373 (11)	0.00118 (10)
N1	0.0137 (6)	0.0196 (6)	0.0219 (7)	−0.0007 (5)	0.0046 (5)	0.0025 (5)
C2	0.0186 (7)	0.0188 (8)	0.0283 (9)	0.0026 (6)	0.0068 (6)	0.0035 (7)
C3	0.0206 (7)	0.0172 (8)	0.0285 (9)	0.0003 (6)	0.0085 (7)	−0.0004 (6)
N4	0.0139 (6)	0.0207 (6)	0.0219 (7)	−0.0022 (5)	0.0054 (5)	−0.0004 (5)
C5	0.0219 (8)	0.0263 (8)	0.0208 (8)	−0.0036 (7)	0.0063 (6)	−0.0036 (7)
C6	0.0206 (8)	0.0294 (9)	0.0190 (8)	−0.0025 (7)	0.0062 (6)	0.0013 (7)
C7	0.0161 (7)	0.0273 (8)	0.0180 (8)	−0.0023 (6)	0.0031 (6)	0.0033 (6)
O11	0.0147 (5)	0.0245 (6)	0.0244 (6)	−0.0033 (4)	0.0062 (4)	0.0030 (5)
O12	0.0183 (6)	0.0473 (8)	0.0505 (9)	0.0006 (6)	0.0071 (6)	0.0282 (7)
O41	0.0273 (7)	0.0675 (11)	0.0894 (13)	−0.0090 (7)	0.0297 (8)	0.0087 (10)
O42	0.0186 (6)	0.0622 (10)	0.0403 (8)	0.0062 (6)	0.0061 (6)	−0.0062 (7)
N14	0.0184 (7)	0.0482 (10)	0.0376 (9)	−0.0038 (7)	0.0128 (7)	−0.0118 (8)
C11	0.0167 (7)	0.0206 (8)	0.0208 (8)	−0.0021 (6)	0.0073 (6)	−0.0028 (6)
C12	0.0193 (8)	0.0258 (9)	0.0267 (9)	−0.0018 (6)	0.0094 (6)	0.0008 (7)
C13	0.0197 (8)	0.0313 (10)	0.0253 (9)	0.0021 (7)	0.0068 (6)	−0.0015 (7)
C14	0.0148 (7)	0.0332 (9)	0.0280 (9)	−0.0030 (6)	0.0097 (6)	−0.0103 (7)
C15	0.0239 (8)	0.0316 (9)	0.0312 (9)	−0.0054 (7)	0.0169 (7)	−0.0025 (7)
C16	0.0222 (8)	0.0276 (9)	0.0245 (8)	−0.0025 (7)	0.0104 (7)	0.0004 (7)
C17	0.0168 (7)	0.0214 (8)	0.0239 (8)	−0.0029 (6)	0.0073 (6)	0.0003 (6)

Geometric parameters (Å, º)

Ni1—N1^i	2.060 (2)	C6—H6A	0.99
Ni1—N1	2.060 (2)	C6—H6B	0.99
Ni1—N4^i	2.080 (2)	C7—N1^i	1.472 (2)
Ni1—N4	2.080 (2)	C7—H7A	0.99
Ni1—O11^i	2.132 (2)	C7—H7B	0.99
Ni1—O11	2.132 (2)	O11—C17	1.271 (2)
N1—C7^i	1.472 (2)	O12—C17	1.237 (2)
N1—C2	1.474 (2)	O41—N14	1.229 (2)
N1—H1	0.93	O42—N14	1.224 (2)
C2—C3	1.517 (2)	N14—C14	1.473 (2)
C2—H2A	0.99	C11—C12	1.389 (2)
C2—H2B	0.99	C11—C16	1.394 (2)
C3—N4	1.478 (2)	C11—C17	1.524 (2)
C3—H3A	0.99	C12—C13	1.393 (2)
C3—H3B	0.99	C12—H12	0.95
N4—C5	1.472 (2)	C13—C14	1.385 (2)
N4—H4	0.93	C13—H13	0.95
C5—C6	1.527 (2)	C14—C15	1.380 (3)
C5—H5A	0.99	C15—C16	1.386 (2)
C5—H5B	0.99	C15—H15	0.95
C6—C7	1.524 (2)	C16—H16	0.95
N1^i—Ni1—N1	180.0	C6—C5—H5A	109.1
N1^i—Ni1—N4^i	85.20 (5)	N4—C5—H5B	109.1
N1—Ni1—N4^i	94.80 (5)	C6—C5—H5B	109.1
N1^i—Ni1—N4	94.80 (5)	H5A—C5—H5B	107.9
N1—Ni1—N4	85.20 (5)	C7—C6—C5	115.04 (13)
N4^i—Ni1—N4	180.0	C7—C6—H6A	108.5
N1^i—Ni1—O11^i	92.88 (5)	C5—C6—H6A	108.5
N1—Ni1—O11^i	87.12 (5)	C7—C6—H6B	108.5
N4^i—Ni1—O11^i	93.39 (5)	C5—C6—H6B	108.5
N4—Ni1—O11^i	86.61 (5)	H6A—C6—H6B	107.5
N1^i—Ni1—O11	87.12 (5)	N1^i—C7—C6	111.6 (2)
N1—Ni1—O11	92.88 (5)	N1^i—C7—H7A	109.3
N4^i—Ni1—O11	86.61 (5)	C6—C7—H7A	109.3
N4—Ni1—O11	93.39 (5)	N1^i—C7—H7B	109.3
O11^i—Ni1—O11	180.0	C6—C7—H7B	109.3
C7^i—N1—C2	114.1 (2)	H7A—C7—H7B	108.0
C7^i—N1—Ni1	114.5 (2)	C17—O11—Ni1	131.3 (2)
C2—N1—Ni1	106.2 (2)	O42—N14—O41	123.3 (2)
C7^i—N1—H1	107.2	O42—N14—C14	119.0 (2)
C2—N1—H1	107.2	O41—N14—C14	117.7 (2)
Ni1—N1—H1	107.2	C12—C11—C16	119.4 (2)
N1—C2—C3	108.8 (2)	C12—C11—C17	121.2 (2)
N1—C2—H2A	109.9	C16—C11—C17	119.4 (2)
C3—C2—H2A	109.9	C11—C12—C13	121.3 (2)
N1—C2—H2B	109.9	C11—C12—H12	119.3
C3—C2—H2B	109.9	C13—C12—H12	119.3
H2A—C2—H2B	108.3	C14—C13—C12	117.3 (2)
N4—C3—C2	108.0 (2)	C14—C13—H13	121.3
N4—C3—H3A	110.1	C12—C13—H13	121.3
C2—C3—H3A	110.1	C15—C14—C13	123.0 (2)
N4—C3—H3B	110.1	C15—C14—N14	118.5 (2)
C2—C3—H3B	110.1	C13—C14—N14	118.5 (2)
H3A—C3—H3B	108.4	C14—C15—C16	118.6 (2)
C5—N4—C3	113.5 (2)	C14—C15—H15	120.7
C5—N4—Ni1	116.7 (2)	C16—C15—H15	120.7
C3—N4—Ni1	105.28 (9)	C15—C16—C11	120.4 (2)
C5—N4—H4	106.9	C15—C16—H16	119.8
C3—N4—H4	106.9	C11—C16—H16	119.8
Ni1—N4—H4	106.9	O12—C17—O11	126.8 (2)
N4—C5—C6	112.4 (2)	O12—C17—C11	117.7 (2)
N4—C5—H5A	109.1	O11—C17—C11	115.5 (2)
N4^i—Ni1—N1—C7^i	−39.6 (12)	N1^i—Ni1—O11—C17	−169.7 (2)
N4—Ni1—N1—C7^i	140.4 (2)	N1—Ni1—O11—C17	10.3 (12)
O11^i—Ni1—N1—C7^i	53.5 (2)	N4^i—Ni1—O11—C17	−84.3 (2)
O11—Ni1—N1—C7^i	−126.5 (2)	N4—Ni1—O11—C17	95.7 (2)
N4^i—Ni1—N1—C2	−166.51 (9)	C16—C11—C12—C13	0.0 (2)
N4—Ni1—N1—C2	13.49 (9)	C17—C11—C12—C13	178.3 (2)
O11^i—Ni1—N1—C2	−73.34 (9)	C11—C12—C13—C14	−0.1 (2)
O11—Ni1—N1—C2	106.66 (9)	C12—C13—C14—C15	0.0 (3)
C7^i—N1—C2—C3	−168.2 (2)	C12—C13—C14—N14	179.2 (2)
Ni1—N1—C2—C3	−41.1 (2)	O42—N14—C14—C15	167.8 (2)
N1—C2—C3—N4	58.2 (11)	O41—N14—C14—C15	−10.9 (2)
C2—C3—N4—C5	−172.0 (2)	O42—N14—C14—C13	−11.5 (2)
C2—C3—N4—Ni1	−43.2 (2)	O41—N14—C14—C13	169.8 (2)
N1^i—Ni1—N4—C5	−36.6 (2)	C13—C14—C15—C16	0.3 (3)
N1—Ni1—N4—C5	143.4 (2)	N14—C14—C15—C16	−178.9 (2)
O11^i—Ni1—N4—C5	−129.2 (2)	C14—C15—C16—C11	−0.5 (3)
O11—Ni1—N4—C5	50.8 (2)	C12—C11—C16—C15	0.3 (2)
N1^i—Ni1—N4—C3	−163.41 (9)	C17—C11—C16—C15	−178.0 (2)
N1—Ni1—N4—C3	16.59 (9)	Ni1—O11—C17—O12	−13.3 (3)
O11^i—Ni1—N4—C3	103.98 (9)	Ni1—O11—C17—C11	167.9 (2)
O11—Ni1—N4—C3	−76.02 (9)	C12—C11—C17—O12	−177.5 (2)
C3—N4—C5—C6	175.1 (2)	C16—C11—C17—O12	0.8 (2)
Ni1—N4—C5—C6	52.5 (2)	C12—C11—C17—O11	1.4 (2)
N4—C5—C6—C7	−69.4 (2)	C16—C11—C17—O11	179.6 (2)
C5—C6—C7—N1^i	74.1 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.93	1.99	2.845 (2)	153
N4—H4···O41^ii	0.93	2.52	3.221 (2)	132
C16—H16···O42^iii	0.95	2.60	3.439 (2)	148

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

(IV) Bis-(3-hydroxybenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II)

Crystal data

C24H34N4NiO6	F(000) = 564
Mr = 533.26	Dx = 1.485 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5180 (3) Å	Cell parameters from 2748 reflections
b = 13.2496 (5) Å	θ = 2.9–27.5°
c = 10.7720 (4) Å	µ = 0.86 mm^−1
β = 101.161 (2)°	T = 150 K
V = 1192.74 (8) Å^3	Needle, colourless
Z = 2	0.40 × 0.28 × 0.22 mm

Data collection

Kappa-CCD diffractometer	2721 independent reflections
Radiation source: fine-focus sealed X-ray tube	2194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→11
Tmin = 0.724, Tmax = 0.833	k = 0→17
9996 measured reflections	l = −13→13

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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0232P)^2 + 0.6219P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2721 reflections	Δρmax = 0.33 e Å^−3
162 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0036 (10)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01498 (11)
N1	0.43833 (18)	0.62473 (11)	0.38455 (13)	0.0188 (3)
C2	0.3062 (2)	0.59176 (15)	0.28307 (18)	0.0254 (4)
C3	0.3435 (2)	0.48667 (14)	0.24034 (17)	0.0255 (4)
N4	0.36826 (19)	0.41851 (11)	0.35181 (14)	0.0205 (3)
C5	0.4336 (2)	0.31855 (14)	0.32804 (18)	0.0249 (4)
C6	0.4585 (2)	0.25182 (14)	0.44562 (18)	0.0267 (4)
C7	0.5968 (2)	0.28196 (13)	0.55099 (18)	0.0236 (4)
O11	0.71243 (15)	0.47431 (9)	0.43020 (12)	0.0211 (3)
O12	0.74555 (16)	0.60133 (9)	0.30107 (13)	0.0256 (3)
O13	1.07609 (17)	0.20467 (10)	0.32970 (12)	0.0275 (3)
C11	0.8565 (2)	0.44052 (13)	0.26869 (16)	0.0184 (4)
C12	0.9286 (2)	0.35489 (14)	0.32983 (17)	0.0200 (4)
C13	1.0080 (2)	0.28633 (14)	0.26516 (17)	0.0197 (4)
C14	1.0144 (2)	0.30365 (14)	0.13851 (17)	0.0219 (4)
C15	0.9400 (2)	0.38830 (14)	0.07732 (17)	0.0226 (4)
C16	0.8619 (2)	0.45748 (14)	0.14164 (17)	0.0213 (4)
C17	0.7665 (2)	0.51106 (13)	0.33895 (16)	0.0180 (4)
H1	0.5252	0.6387	0.3466	0.023*
H2A	0.2942	0.6393	0.2109	0.030*
H2B	0.2046	0.5908	0.3148	0.030*
H3A	0.2537	0.4618	0.1750	0.031*
H3B	0.4411	0.4884	0.2033	0.031*
H4	0.2682	0.4073	0.3717	0.025*
H5A	0.5371	0.3276	0.3006	0.030*
H5B	0.3591	0.2846	0.2586	0.030*
H6A	0.3588	0.2523	0.4800	0.032*
H6B	0.4764	0.1817	0.4199	0.032*
H7A	0.6187	0.2265	0.6136	0.028*
H7B	0.6941	0.2923	0.5150	0.028*
H3	1.1246	0.1706	0.2831	0.041*
H12	0.9237	0.3431	0.4160	0.024*
H14	1.0695	0.2578	0.0942	0.026*
H15	0.9423	0.3991	−0.0095	0.027*
H16	0.8127	0.5157	0.0994	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01602 (17)	0.01348 (17)	0.01663 (16)	0.00086 (13)	0.00607 (11)	0.00009 (12)
N1	0.0184 (8)	0.0183 (8)	0.0217 (8)	0.0016 (6)	0.0087 (6)	0.0025 (6)
C2	0.0224 (10)	0.0275 (10)	0.0253 (10)	0.0009 (8)	0.0022 (8)	0.0063 (8)
C3	0.0260 (10)	0.0296 (11)	0.0199 (9)	−0.0043 (8)	0.0017 (7)	0.0000 (8)
N4	0.0206 (8)	0.0194 (8)	0.0227 (8)	−0.0019 (6)	0.0067 (6)	−0.0013 (6)
C5	0.0306 (11)	0.0195 (10)	0.0261 (10)	−0.0043 (8)	0.0096 (8)	−0.0086 (8)
C6	0.0346 (11)	0.0166 (9)	0.0317 (11)	−0.0015 (8)	0.0134 (9)	−0.0034 (8)
C7	0.0285 (10)	0.0161 (9)	0.0292 (10)	0.0081 (8)	0.0127 (8)	0.0041 (7)
O11	0.0215 (7)	0.0213 (7)	0.0235 (6)	0.0037 (5)	0.0121 (5)	0.0048 (5)
O12	0.0286 (7)	0.0158 (6)	0.0372 (8)	0.0029 (6)	0.0181 (6)	0.0042 (6)
O13	0.0321 (8)	0.0241 (7)	0.0294 (7)	0.0091 (6)	0.0137 (6)	0.0024 (6)
C11	0.0175 (9)	0.0175 (9)	0.0216 (9)	−0.0023 (7)	0.0072 (7)	0.0002 (7)
C12	0.0203 (9)	0.0205 (9)	0.0208 (9)	−0.0001 (7)	0.0082 (7)	0.0016 (7)
C13	0.0183 (9)	0.0164 (8)	0.0254 (9)	−0.0010 (7)	0.0067 (7)	0.0004 (7)
C14	0.0215 (9)	0.0219 (9)	0.0237 (9)	−0.0030 (8)	0.0080 (7)	−0.0063 (8)
C15	0.0244 (10)	0.0250 (10)	0.0194 (9)	−0.0026 (8)	0.0070 (7)	−0.0011 (7)
C16	0.0221 (9)	0.0188 (9)	0.0238 (9)	−0.0010 (8)	0.0062 (7)	0.0024 (7)
C17	0.0164 (8)	0.0176 (9)	0.0207 (8)	0.0000 (7)	0.0054 (7)	0.0006 (7)

Geometric parameters (Å, º)

Ni1—N4	2.069 (2)	C6—H6A	0.99
Ni1—N4^i	2.069 (2)	C6—H6B	0.99
Ni1—N1	2.074 (2)	C7—N1^i	1.477 (2)
Ni1—N1^i	2.074 (2)	C7—H7A	0.99
Ni1—O11^i	2.117 (2)	C7—H7B	0.99
Ni1—O11	2.117 (2)	O11—C17	1.261 (2)
N1—C2	1.475 (2)	O12—C17	1.265 (2)
N1—C7^i	1.477 (2)	O13—C13	1.354 (2)
N1—H1	0.93	O13—H3	0.84
C2—C3	1.519 (3)	C11—C12	1.393 (3)
C2—H2A	0.99	C11—C16	1.396 (2)
C2—H2B	0.99	C11—C17	1.503 (2)
C3—N4	1.485 (2)	C12—C13	1.397 (2)
C3—H3A	0.99	C12—H12	0.95
C3—H3B	0.99	C13—C14	1.395 (2)
N4—C5	1.478 (2)	C14—C15	1.390 (3)
N4—H4	0.93	C14—H14	0.95
C5—C6	1.525 (3)	C15—C16	1.393 (3)
C5—H5A	0.99	C15—H15	0.95
C5—H5B	0.99	C16—H16	0.95
C6—C7	1.523 (3)
N4—Ni1—N4^i	180.0	N4—C5—H5A	109.2
N4—Ni1—N1	85.22 (6)	C6—C5—H5A	109.2
N4^i—Ni1—N1	94.78 (6)	N4—C5—H5B	109.2
N4—Ni1—N1^i	94.78 (6)	C6—C5—H5B	109.2
N4^i—Ni1—N1^i	85.22 (6)	H5A—C5—H5B	107.9
N1—Ni1—N1^i	180.0	C7—C6—C5	115.5 (2)
N4—Ni1—O11^i	89.12 (6)	C7—C6—H6A	108.4
N4^i—Ni1—O11^i	90.88 (6)	C5—C6—H6A	108.4
N1—Ni1—O11^i	87.14 (5)	C7—C6—H6B	108.4
N1^i—Ni1—O11^i	92.86 (5)	C5—C6—H6B	108.4
N4—Ni1—O11	90.88 (6)	H6A—C6—H6B	107.5
N4^i—Ni1—O11	89.12 (6)	N1^i—C7—C6	111.8 (2)
N1—Ni1—O11	92.86 (5)	N1^i—C7—H7A	109.2
N1^i—Ni1—O11	87.14 (5)	C6—C7—H7A	109.2
O11^i—Ni1—O11	180.0	N1^i—C7—H7B	109.2
C2—N1—C7^i	113.7 (2)	C6—C7—H7B	109.2
C2—N1—Ni1	106.1 (2)	H7A—C7—H7B	107.9
C7^i—N1—Ni1	115.9 (2)	C17—O11—Ni1	132.9 (2)
C2—N1—H1	106.9	C13—O13—H3	109.5
C7^i—N1—H1	106.9	C12—C11—C16	120.0 (2)
Ni1—N1—H1	106.9	C12—C11—C17	119.3 (2)
N1—C2—C3	108.8 (2)	C16—C11—C17	120.7 (12)
N1—C2—H2A	109.9	C11—C12—C13	120.4 (2)
C3—C2—H2A	109.9	C11—C12—H12	119.8
N1—C2—H2B	109.9	C13—C12—H12	119.8
C3—C2—H2B	109.9	O13—C13—C14	122.7 (2)
H2A—C2—H2B	108.3	O13—C13—C12	117.7 (2)
N4—C3—C2	108.5 (2)	C14—C13—C12	119.7 (2)
N4—C3—H3A	110.0	C15—C14—C13	119.7 (2)
C2—C3—H3A	110.0	C15—C14—H14	120.1
N4—C3—H3B	110.0	C13—C14—H14	120.1
C2—C3—H3B	110.0	C14—C15—C16	120.9 (2)
H3A—C3—H3B	108.4	C14—C15—H15	119.6
C5—N4—C3	113.9 (2)	C16—C15—H15	119.6
C5—N4—Ni1	115.8 (2)	C15—C16—C11	119.4 (2)
C3—N4—Ni1	106.1 (2)	C15—C16—H16	120.3
C5—N4—H4	106.9	C11—C16—H16	120.3
C3—N4—H4	106.9	O11—C17—O12	124.5 (2)
Ni1—N4—H4	106.9	O11—C17—C11	116.8 (2)
N4—C5—C6	111.8 (2)	O12—C17—C11	118.6 (2)
N4—Ni1—N1—C2	14.9 (2)	N4—C5—C6—C7	−71.9 (2)
N4^i—Ni1—N1—C2	−165.1 (2)	C5—C6—C7—N1^i	71.7 (2)
O11^i—Ni1—N1—C2	−74.4 (2)	N4—Ni1—O11—C17	75.4 (2)
O11—Ni1—N1—C2	105.6 (2)	N4^i—Ni1—O11—C17	−104.6 (2)
N4—Ni1—N1—C7^i	142.1 (2)	N1—Ni1—O11—C17	−9.9 (2)
N4^i—Ni1—N1—C7^i	−38.0 (2)	N1^i—Ni1—O11—C17	170.1 (2)
O11^i—Ni1—N1—C7^i	52.7 (2)	C16—C11—C12—C13	0.8 (3)
O11—Ni1—N1—C7^i	−127.3 (2)	C17—C11—C12—C13	177.7 (2)
C7^i—N1—C2—C3	−167.0 (2)	C11—C12—C13—O13	179.8 (2)
Ni1—N1—C2—C3	−41.5 (2)	C11—C12—C13—C14	−0.3 (3)
N1—C2—C3—N4	56.9 (2)	O13—C13—C14—C15	179.1 (2)
C2—C3—N4—C5	−169.7 (2)	C12—C13—C14—C15	−0.8 (3)
C2—C3—N4—Ni1	−41.1 (2)	C13—C14—C15—C16	1.5 (3)
N1—Ni1—N4—C5	142.0 (2)	C14—C15—C16—C11	−1.0 (3)
N1^i—Ni1—N4—C5	−38.0 (2)	C12—C11—C16—C15	−0.1 (3)
O11^i—Ni1—N4—C5	−130.832)	C17—C11—C16—C15	−177.0 (2)
O11—Ni1—N4—C5	49.2 (2)	Ni1—O11—C17—O12	34.1 (3)
N1—Ni1—N4—C3	14.6 (2)	Ni1—O11—C17—C11	−143.6 (2)
N1^i—Ni1—N4—C3	−165.4 (2)	C12—C11—C17—O11	−24.2 (2)
O11^i—Ni1—N4—C3	101.8 (2)	C16—C11—C17—O11	152.7 (2)
O11—Ni1—N4—C3	−78.2 (2)	C12—C11—C17—O12	157.9 (2)
C3—N4—C5—C6	179.4 (2)	C16—C11—C17—O12	−25.1 (3)
Ni1—N4—C5—C6	56.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.93	2.09	2.943 (2)	152
O13—H3···O12^ii	0.84	1.81	2.645 (2)	172

Symmetry code: (ii) −x+2, y−1/2, −z+1/2.

(V) Bis-(4-aminobenzoato)-1,4,8,11-tetraazacyclotetradecanenickel(II)

Crystal data

C24H36N6NiO4	F(000) = 1128
Mr = 531.30	Dx = 1.420 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.4430 (4) Å	Cell parameters from 2913 reflections
b = 8.4149 (2) Å	θ = 2.8–27.5°
c = 16.8262 (4) Å	µ = 0.82 mm^−1
β = 107.8774 (14)°	T = 150 K
V = 2485.27 (10) Å^3	Block, colourless
Z = 4	0.42 × 0.40 × 0.38 mm

Data collection

Kappa-CCD diffractometer	2823 independent reflections
Radiation source: fine-focus sealed X-ray tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→23
Tmin = 0.724, Tmax = 0.745	k = 0→10
12342 measured reflections	l = −21→20

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)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0282P)^2 + 2.6861P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2823 reflections	Δρmax = 0.32 e Å^−3
161 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (3)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01544 (10)
N1	0.55981 (7)	0.42978 (16)	0.42106 (8)	0.0203 (3)
C2	0.50599 (10)	0.3387 (2)	0.35408 (10)	0.0266 (4)
C3	0.45702 (11)	0.2348 (2)	0.39085 (11)	0.0294 (4)
N4	0.41827 (8)	0.33600 (16)	0.43749 (8)	0.0238 (3)
C5	0.38198 (10)	0.2450 (2)	0.49033 (12)	0.0316 (4)
C6	0.34463 (10)	0.3531 (2)	0.53936 (12)	0.0323 (4)
C7	0.39919 (10)	0.4466 (2)	0.60996 (11)	0.0270 (4)
O11	0.55427 (6)	0.32521 (13)	0.58986 (7)	0.0219 (2)
O12	0.64821 (6)	0.21858 (14)	0.54774 (7)	0.0231 (3)
N14	0.69692 (8)	−0.14447 (18)	0.89459 (9)	0.0283 (3)
C11	0.63534 (8)	0.13716 (17)	0.67784 (9)	0.0165 (3)
C12	0.59138 (9)	0.13522 (18)	0.73217 (9)	0.0186 (3)
C13	0.61119 (9)	0.04265 (19)	0.80356 (10)	0.0206 (3)
C14	0.67787 (9)	−0.04965 (19)	0.82489 (10)	0.0201 (3)
C15	0.72308 (9)	−0.0451 (2)	0.77074 (10)	0.0224 (3)
C16	0.70153 (9)	0.04533 (19)	0.69872 (10)	0.0201 (3)
C17	0.61086 (8)	0.23363 (18)	0.59906 (9)	0.0170 (3)
H1	0.5964	0.3580	0.4509	0.024*
H2A	0.5343	0.2714	0.3255	0.032*
H2B	0.4732	0.4123	0.3125	0.032*
H3A	0.4187	0.1778	0.3456	0.035*
H3B	0.4893	0.1550	0.4289	0.035*
H4	0.3800	0.3916	0.3984	0.029*
H5A	0.4210	0.1784	0.5299	0.038*
H5B	0.3429	0.1732	0.4545	0.038*
H6A	0.3112	0.4293	0.4999	0.039*
H6B	0.3118	0.2871	0.5630	0.039*
H7A	0.3702	0.4970	0.6439	0.032*
H7B	0.4366	0.3727	0.6465	0.032*
H14A	0.6672	−0.1481	0.9267	0.034*
H14B	0.7389	−0.2017	0.9072	0.034*
H12	0.5468	0.1990	0.7198	0.022*
H13	0.5794	0.0415	0.8385	0.025*
H15	0.7689	−0.1050	0.7840	0.027*
H16	0.7324	0.0450	0.6627	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01769 (15)	0.01486 (15)	0.01392 (14)	−0.00007 (10)	0.00506 (10)	0.00034 (10)
N1	0.0242 (7)	0.0204 (7)	0.0174 (6)	0.0045 (5)	0.0080 (5)	0.0032 (5)
C2	0.0369 (10)	0.0260 (9)	0.0164 (7)	0.0046 (7)	0.0074 (7)	−0.0014 (6)
C3	0.0401 (10)	0.0217 (8)	0.0235 (8)	−0.0040 (7)	0.0056 (7)	−0.0069 (7)
N4	0.0257 (7)	0.0216 (7)	0.0216 (7)	−0.0041 (5)	0.0036 (6)	0.0004 (5)
C5	0.0318 (9)	0.0281 (9)	0.0341 (9)	−0.0107 (7)	0.0090 (8)	0.0034 (8)
C6	0.0232 (8)	0.0365 (10)	0.0382 (10)	−0.0031 (7)	0.0110 (7)	0.0109 (8)
C7	0.0266 (8)	0.0328 (9)	0.0264 (8)	0.0052 (7)	0.0152 (7)	0.0088 (7)
O11	0.0231 (6)	0.0230 (6)	0.0207 (5)	0.0071 (4)	0.0083 (4)	0.0062 (4)
O12	0.0229 (6)	0.0303 (6)	0.0183 (5)	0.0043 (5)	0.0098 (4)	0.0039 (5)
N14	0.0264 (7)	0.0360 (8)	0.0248 (7)	0.0096 (6)	0.0113 (6)	0.0143 (6)
C11	0.0174 (7)	0.0156 (7)	0.0163 (7)	−0.0017 (5)	0.0047 (6)	−0.0010 (6)
C12	0.0191 (7)	0.0176 (7)	0.0199 (7)	0.0019 (6)	0.0070 (6)	−0.0009 (6)
C13	0.0229 (8)	0.0221 (8)	0.0192 (7)	0.0007 (6)	0.0100 (6)	−0.0001 (6)
C14	0.0218 (8)	0.0187 (7)	0.0191 (7)	−0.0005 (6)	0.0053 (6)	0.0021 (6)
C15	0.0186 (7)	0.0245 (8)	0.0243 (8)	0.0048 (6)	0.0069 (6)	0.0052 (6)
C16	0.0187 (7)	0.0223 (8)	0.0215 (8)	0.0002 (6)	0.0093 (6)	0.0014 (6)
C17	0.0173 (7)	0.0159 (7)	0.0166 (7)	−0.0016 (6)	0.0034 (5)	−0.0005 (6)

Geometric parameters (Å, º)

Ni1—N1^i	2.057 (2)	C6—H6A	0.99
Ni1—N1	2.057 (2)	C6—H6B	0.99
Ni1—N4^i	2.076 (2)	C7—N1^i	1.473 (2)
Ni1—N4	2.076 (2)	C7—H7A	0.99
Ni1—O11^i	2.127 (2)	C7—H7B	0.99
Ni1—O11	2.127 (2)	O11—C17	1.268 (2)
N1—C2	1.468 (2)	O12—C17	1.266 (2)
N1—C7^i	1.473 (2)	N14—C14	1.372 (2)
N1—H1	0.93	N14—H14A	0.88
C2—C3	1.518 (2)	N14—H14B	0.88
C2—H2A	0.99	C11—C16	1.395 (2)
C2—H2B	0.99	C11—C12	1.396 (2)
C3—N4	1.482 (2)	C11—C17	1.501 (2)
C3—H3A	0.99	C12—C13	1.383 (2)
C3—H3B	0.99	C12—H12	0.95
N4—C5	1.480 (2)	C13—C14	1.405 (2)
N4—H4	0.93	C13—H13	0.95
C5—C6	1.527 (3)	C14—C15	1.412 (2)
C5—H5A	0.99	C15—C16	1.382 (2)
C5—H5B	0.99	C15—H15	0.95
C6—C7	1.519 (3)	C16—H16	0.95
N1^i—Ni1—N1	180.0	C6—C5—H5A	109.2
N1^i—Ni1—N4^i	86.08 (5)	N4—C5—H5B	109.2
N1—Ni1—N4^i	93.92 (5)	C6—C5—H5B	109.2
N1^i—Ni1—N4	93.92 (5)	H5A—C5—H5B	107.9
N1—Ni1—N4	86.08 (5)	C7—C6—C5	115.5 (2)
N4^i—Ni1—N4	180.0	C7—C6—H6A	108.4
N1^i—Ni1—O11^i	91.83 (5)	C5—C6—H6A	108.4
N1—Ni1—O11^i	88.18 (5)	C7—C6—H6B	108.4
N4^i—Ni1—O11^i	90.60 (5)	C5—C6—H6B	108.4
N4—Ni1—O11^i	89.40 (5)	H6A—C6—H6B	107.5
N1^i—Ni1—O11	88.18 (5)	N1^i—C7—C6	112.2 (2)
N1—Ni1—O11	91.82 (5)	N1^i—C7—H7A	109.2
N4^i—Ni1—O11	89.40 (5)	C6—C7—H7A	109.2
N4—Ni1—O11	90.60 (5)	N1^i—C7—H7B	109.2
O11^i—Ni1—O11	180.0	C6—C7—H7B	109.2
C2—N1—C7^i	113.4 (2)	H7A—C7—H7B	107.9
C2—N1—Ni1	106.0 (2)	C17—O11—Ni1	134.2 (2)
C7^i—N1—Ni1	117.5 (2)	C14—N14—H14A	120.0
C2—N1—H1	106.4	C14—N14—H14B	120.0
C7^i—N1—H1	106.4	H14A—N14—H14B	120.0
Ni1—N1—H1	106.4	C16—C11—C12	117.9 (12)
N1—C2—C3	109.5 (2)	C16—C11—C17	121.7 (2)
N1—C2—H2A	109.8	C12—C11—C17	120.45 (2)
C3—C2—H2A	109.8	C13—C12—C11	121.6 (2)
N1—C2—H2B	109.8	C13—C12—H12	119.2
C3—C2—H2B	109.8	C11—C12—H12	119.2
H2A—C2—H2B	108.2	C12—C13—C14	120.7 (2)
N4—C3—C2	109.2 (2)	C12—C13—H13	119.7
N4—C3—H3A	109.8	C14—C13—H13	119.7
C2—C3—H3A	109.8	N14—C14—C13	120.9 (2)
N4—C3—H3B	109.8	N14—C14—C15	121.4 (2)
C2—C3—H3B	109.8	C13—C14—C15	117.7 (2)
H3A—C3—H3B	108.3	C16—C15—C14	120.9 (2)
C5—N4—C3	113.7 (2)	C16—C15—H15	119.6
C5—N4—Ni1	115.6 (2)	C14—C15—H15	119.6
C3—N4—Ni1	104.9 (2)	C15—C16—C11	121.3 (2)
C5—N4—H4	107.4	C15—C16—H16	119.3
C3—N4—H4	107.4	C11—C16—H16	119.3
Ni1—N4—H4	107.4	O12—C17—O11	125.3 (2)
N4—C5—C6	112.2 (2)	O12—C17—C11	118.0 (2)
N4—C5—H5A	109.2	O11—C17—C11	116.7 (2)
N4^i—Ni1—N1—C2	−166.3 (2)	N4—C5—C6—C7	−70.8 (2)
N4—Ni1—N1—C2	13.7 (2)	C5—C6—C7—N1^i	69.0 (2)
O11^i—Ni1—N1—C2	−75.8 (2)	N1^i—Ni1—O11—C17	−168.7 (2)
O11—Ni1—N1—C2	104.2 (2)	N1—Ni1—O11—C17	11.4 (2)
N4^i—Ni1—N1—C7^i	−38.4 (2)	N4^i—Ni1—O11—C17	−82.6 (2)
N4—Ni1—N1—C7^i	141.6 (2)	N4—Ni1—O11—C17	97.5 (2)
O11^i—Ni1—N1—C7^i	52.1 (2)	C16—C11—C12—C13	−1.6 (2)
O11—Ni1—N1—C7^i	−127.9 (2)	C17—C11—C12—C13	177.5 (2)
C7^i—N1—C2—C3	−170.3 (2)	C11—C12—C13—C14	1.8 (2)
Ni1—N1—C2—C3	−40.0 (2)	C12—C13—C14—N14	−178.5 (2)
N1—C2—C3—N4	56.3 (2)	C12—C13—C14—C15	−0.5 (2)
C2—C3—N4—C5	−168.0 (2)	N14—C14—C15—C16	177.1 (2)
C2—C3—N4—Ni1	−40.8 (2)	C13—C14—C15—C16	−1.0 (2)
N1^i—Ni1—N4—C5	−39.0 (2)	C14—C15—C16—C11	1.1 (3)
N1—Ni1—N4—C5	141.1 (1)	C12—C11—C16—C15	0.1 (2)
O11^i—Ni1—N4—C5	−130.7 (2)	C17—C11—C16—C15	−179.0 (2)
O11—Ni1—N4—C5	49.3 (2)	Ni1—O11—C17—O12	−5.3 (2)
N1^i—Ni1—N4—C3	−164.9 (2)	Ni1—O11—C17—C11	174.1 (2)
N1—Ni1—N4—C3	15.1 (2)	C16—C11—C17—O12	6.3 (2)
O11^i—Ni1—N4—C3	103.3 (2)	C12—C11—C17—O12	−172.8 (2)
O11—Ni1—N4—C3	−76.7 (2)	C16—C11—C17—O11	−173.1 (2)
C3—N4—C5—C6	178.3 (2)	C12—C11—C17—O11	7.8 (2)
Ni1—N4—C5—C6	57.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.93	2.00	2.868 (2)	155
N14—H14A···O12^ii	0.88	2.25	3.043 (2)	150
N14—H14B···O12^iii	0.88	2.10	2.954 (2)	165

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

(VI) [Aqua-(5-hydroxyisophthalato)-1,4,8,11- tetraazacyclotetradecanenickel(II)] tetrahydrate

Crystal data

C18H30N4NiO6·4(H2O)	F(000) = 1128
Mr = 529.23	Dx = 1.474 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 18.4057 (8) Å	Cell parameters from 2739 reflections
b = 9.6927 (4) Å	θ = 2.8–27.5°
c = 13.4648 (5) Å	µ = 0.87 mm^−1
β = 96.724 (2)°	T = 150 K
V = 2385.61 (17) Å^3	Plate, purple
Z = 4	0.36 × 0.34 × 0.04 mm

Data collection

Kappa-CCD diffractometer	5106 independent reflections
Radiation source: fine-focus sealed X-ray tube	4757 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −23→23
Tmin = 0.744, Tmax = 0.966	k = −12→12
9912 measured reflections	l = −17→17

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2)P)^2 + 2.7841P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.082	(Δ/σ)max = 0.009
S = 1.03	Δρmax = 0.35 e Å^−3
5106 reflections	Δρmin = −0.36 e Å^−3
342 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
12 restraints	Extinction coefficient: 0.0014 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2357 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.434 (11)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.500367 (18)	0.19694 (3)	0.50001 (2)	0.01553 (9)
N1	0.51041 (13)	0.0522 (2)	0.38875 (16)	0.0181 (5)
C2	0.57352 (16)	0.0933 (4)	0.3380 (2)	0.0239 (6)
C3	0.57334 (16)	0.2497 (4)	0.3287 (2)	0.0221 (6)
N4	0.57657 (13)	0.3102 (2)	0.43020 (16)	0.0204 (5)
C5	0.56531 (18)	0.4616 (3)	0.4298 (2)	0.0267 (6)
C6	0.56375 (18)	0.5197 (3)	0.5343 (2)	0.0279 (6)
C7	0.49540 (17)	0.4861 (3)	0.5834 (2)	0.0240 (6)
N8	0.49288 (13)	0.3398 (2)	0.61357 (16)	0.0192 (5)
C9	0.42410 (18)	0.3013 (3)	0.6536 (2)	0.0243 (7)
C10	0.42015 (17)	0.1450 (4)	0.6640 (2)	0.0248 (7)
N11	0.42452 (13)	0.0827 (2)	0.56478 (16)	0.0187 (5)
C12	0.43508 (17)	−0.0686 (3)	0.5693 (2)	0.0249 (6)
C13	0.44081 (17)	−0.1301 (3)	0.4667 (2)	0.0240 (6)
C14	0.51042 (16)	−0.0937 (3)	0.4208 (2)	0.0226 (6)
O1	0.41696 (11)	0.3069 (2)	0.41743 (13)	0.0200 (4)
O2	0.37648 (11)	0.1701 (2)	0.28844 (14)	0.0227 (4)
O3	0.25257 (12)	0.7176 (2)	0.47024 (14)	0.0234 (4)
O4	0.24784 (12)	0.8581 (2)	0.34041 (14)	0.0239 (4)
O5	0.22645 (11)	0.5052 (2)	0.05556 (13)	0.0194 (4)
C21	0.33005 (14)	0.3993 (3)	0.29374 (19)	0.0173 (5)
C22	0.31571 (15)	0.5105 (3)	0.35362 (18)	0.0169 (5)
C23	0.27343 (14)	0.6215 (3)	0.31330 (18)	0.0156 (5)
C24	0.24506 (15)	0.6192 (3)	0.2125 (2)	0.0171 (5)
C25	0.25802 (14)	0.5062 (3)	0.15356 (18)	0.0151 (5)
C26	0.30025 (14)	0.3959 (3)	0.19354 (18)	0.0164 (5)
C27	0.37760 (15)	0.2817 (3)	0.33636 (18)	0.0168 (5)
C28	0.25685 (14)	0.7408 (3)	0.37872 (18)	0.0164 (5)
O6	0.58776 (11)	0.0983 (2)	0.59862 (14)	0.0214 (4)
O7	0.63580 (12)	0.2779 (2)	0.74172 (16)	0.0275 (5)
O8	0.67775 (13)	0.2377 (2)	0.93999 (15)	0.0287 (5)
O9	0.76311 (12)	0.4569 (2)	1.00127 (16)	0.0254 (4)
O10	0.75061 (12)	0.5538 (2)	1.19632 (14)	0.0247 (4)
H1	0.4694	0.0630	0.3421	0.022*
H2A	0.5701	0.0506	0.2708	0.029*
H2B	0.6195	0.0620	0.3770	0.029*
H3A	0.6161	0.2804	0.2962	0.027*
H3B	0.5283	0.2806	0.2872	0.027*
H4	0.6227	0.2922	0.4636	0.025*
H5A	0.5185	0.4836	0.3888	0.032*
H5B	0.6052	0.5066	0.3984	0.032*
H6C	0.5687	0.6212	0.5311	0.034*
H6D	0.6069	0.4841	0.5776	0.034*
H7C	0.4941	0.5453	0.6431	0.029*
H7D	0.4516	0.5074	0.5360	0.029*
H8	0.5315	0.3241	0.6633	0.023*
H9C	0.3817	0.3346	0.6079	0.029*
H9D	0.4224	0.3452	0.7197	0.029*
H10C	0.4612	0.1118	0.7122	0.030*
H10D	0.3736	0.1185	0.6890	0.030*
H11	0.3796	0.0983	0.5272	0.022*
H12A	0.3934	−0.1116	0.5980	0.030*
H12B	0.4802	−0.0899	0.6141	0.030*
H13A	0.3982	−0.0989	0.4205	0.029*
H13B	0.4377	−0.2318	0.4718	0.029*
H14A	0.5535	−0.1108	0.4706	0.027*
H14B	0.5146	−0.1541	0.3625	0.027*
H5	0.2404	0.4350	0.0265	0.029*
H22	0.3347	0.5113	0.4223	0.020*
H24	0.2169	0.6948	0.1843	0.020*
H26	0.3087	0.3189	0.1529	0.020*
H6A	0.609 (2)	0.143 (4)	0.653 (3)	0.052 (13)*
H6B	0.6248 (18)	0.050 (4)	0.577 (3)	0.040 (11)*
H7A	0.641 (2)	0.259 (4)	0.804 (2)	0.038 (11)*
H7B	0.670 (2)	0.334 (4)	0.722 (3)	0.040 (11)*
H8A	0.710 (2)	0.301 (4)	0.960 (3)	0.050 (13)*
H8B	0.697 (3)	0.163 (4)	0.968 (4)	0.068 (15)*
H9A	0.758 (2)	0.489 (4)	1.059 (2)	0.035 (10)*
H9B	0.758 (2)	0.520 (3)	0.954 (2)	0.030 (10)*
H10A	0.7918 (17)	0.602 (3)	1.222 (2)	0.026 (8)*
H10B	0.752 (4)	0.489 (5)	1.240 (4)	0.11 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01649 (15)	0.01509 (14)	0.01473 (14)	0.00102 (14)	0.00067 (10)	0.00032 (14)
N1	0.0179 (11)	0.0185 (12)	0.0174 (10)	0.0016 (9)	−0.0008 (8)	−0.0020 (9)
C2	0.0197 (14)	0.0314 (17)	0.0206 (13)	0.0033 (13)	0.0029 (11)	−0.0047 (12)
C3	0.0221 (15)	0.0310 (18)	0.0138 (13)	0.0012 (14)	0.0049 (11)	0.0006 (12)
N4	0.0203 (12)	0.0200 (12)	0.0207 (11)	−0.0014 (10)	0.0011 (9)	0.0013 (9)
C5	0.0324 (17)	0.0196 (15)	0.0278 (15)	−0.0018 (13)	0.0025 (12)	0.0042 (11)
C6	0.0303 (16)	0.0212 (15)	0.0312 (15)	−0.0039 (13)	−0.0011 (12)	0.0016 (12)
C7	0.0285 (16)	0.0176 (14)	0.0249 (14)	0.0008 (12)	−0.0012 (11)	−0.0039 (11)
N8	0.0187 (11)	0.0195 (12)	0.0188 (11)	0.0027 (9)	−0.0006 (9)	−0.0015 (9)
C9	0.0240 (15)	0.0294 (18)	0.0202 (14)	0.0042 (13)	0.0055 (11)	−0.0042 (12)
C10	0.0236 (15)	0.0304 (18)	0.0219 (14)	−0.0018 (14)	0.0084 (11)	0.0021 (13)
N11	0.0191 (11)	0.0182 (11)	0.0184 (10)	−0.0001 (10)	0.0005 (8)	0.0020 (9)
C12	0.0271 (15)	0.0189 (14)	0.0288 (14)	−0.0017 (12)	0.0034 (12)	0.0064 (11)
C13	0.0272 (15)	0.0155 (13)	0.0282 (14)	0.0011 (12)	−0.0016 (12)	−0.0001 (11)
C14	0.0256 (15)	0.0170 (13)	0.0246 (13)	0.0068 (12)	0.0008 (11)	−0.0045 (10)
O1	0.0212 (10)	0.0193 (10)	0.0182 (9)	0.0048 (8)	−0.0033 (7)	−0.0008 (7)
O2	0.0263 (11)	0.0176 (10)	0.0225 (9)	0.0052 (8)	−0.0042 (8)	−0.0041 (7)
O3	0.0386 (12)	0.0173 (10)	0.0150 (9)	0.0015 (9)	0.0063 (8)	−0.0002 (7)
O4	0.0375 (12)	0.0139 (9)	0.0206 (9)	0.0014 (9)	0.0042 (8)	0.0013 (8)
O5	0.0260 (10)	0.0182 (10)	0.0132 (8)	0.0029 (8)	−0.0005 (7)	0.0003 (7)
C21	0.0152 (12)	0.0197 (13)	0.0165 (12)	0.0000 (10)	−0.0002 (9)	0.0019 (10)
C22	0.0193 (12)	0.0173 (13)	0.0132 (11)	−0.0002 (10)	−0.0013 (9)	0.0014 (9)
C23	0.0166 (12)	0.0131 (12)	0.0175 (12)	−0.0006 (10)	0.0042 (10)	−0.0008 (9)
C24	0.0205 (13)	0.0122 (12)	0.0181 (12)	0.0003 (10)	0.0006 (10)	0.0020 (9)
C25	0.0159 (12)	0.0166 (12)	0.0130 (11)	−0.0015 (10)	0.0022 (9)	0.0021 (9)
C26	0.0181 (12)	0.0175 (12)	0.0135 (11)	−0.0014 (10)	0.0017 (9)	−0.0004 (9)
C27	0.0163 (12)	0.0205 (14)	0.0138 (11)	0.0006 (10)	0.0021 (9)	0.0012 (9)
C28	0.0183 (13)	0.0142 (12)	0.0167 (11)	0.0017 (10)	0.0022 (9)	0.0003 (9)
O6	0.0209 (10)	0.0246 (11)	0.0175 (9)	0.0040 (9)	−0.0023 (7)	0.0010 (8)
O7	0.0246 (11)	0.0326 (12)	0.0236 (11)	−0.0030 (10)	−0.0046 (9)	−0.0012 (9)
O8	0.0346 (12)	0.0190 (11)	0.0296 (11)	−0.0034 (10)	−0.0081 (9)	0.0044 (9)
O9	0.0323 (12)	0.0202 (10)	0.0229 (10)	−0.0020 (9)	−0.0007 (9)	0.0037 (8)
O10	0.0296 (11)	0.0222 (10)	0.0214 (10)	−0.0020 (9)	−0.0011 (8)	0.0043 (8)

Geometric parameters (Å, º)

Ni1—N11	2.054 (2)	C12—C13	1.519 (4)
Ni1—N1	2.077 (2)	C12—H12A	0.9900
Ni1—N8	2.079 (2)	C12—H12B	0.9900
Ni1—O1	2.081 (2)	C13—C14	1.527 (4)
Ni1—N4	2.089 (2)	C13—H13A	0.9900
Ni1—O6	2.183 (2)	C13—H13B	0.9900
N1—C2	1.470 (4)	C14—H14A	0.9900
N1—C14	1.479 (4)	C14—H14B	0.9900
N1—H1	0.9300	O1—C27	1.261 (3)
C2—C3	1.521 (5)	O2—C27	1.258 (3)
C2—H2A	0.9900	O3—C28	1.264 (3)
C2—H2B	0.9900	O4—C28	1.252 (3)
C3—N4	1.481 (4)	O5—C25	1.378 (3)
C3—H3A	0.9900	O5—H5	0.8400
C3—H3B	0.9900	C21—C22	1.390 (4)
N4—C5	1.482 (4)	C21—C26	1.396 (3)
N4—H4	0.9300	C21—C27	1.509 (4)
C5—C6	1.520 (4)	C22—C23	1.399 (4)
C5—H5A	0.9900	C22—H22	0.9500
C5—H5B	0.9900	C23—C24	1.396 (3)
C6—C7	1.523 (5)	C23—C28	1.507 (4)
C6—H6C	0.9900	C24—C25	1.390 (4)
C6—H6D	0.9900	C24—H24	0.9500
C7—N8	1.477 (4)	C25—C26	1.392 (4)
C7—H7C	0.9900	C26—H26	0.9500
C7—H7D	0.9900	O6—H6A	0.90 (3)
N8—C9	1.481 (4)	O6—H6B	0.90 (3)
N8—H8	0.9300	O7—H7A	0.86 (3)
C9—C10	1.524 (4)	O7—H7B	0.89 (3)
C9—H9C	0.9900	O8—H8A	0.88 (3)
C9—H9D	0.9900	O8—H8B	0.87 (3)
C10—N11	1.477 (4)	O9—H9A	0.85 (3)
C10—H10C	0.9900	O9—H9B	0.88 (3)
C10—H10D	0.9900	O10—H10A	0.92 (3)
N11—C12	1.480 (4)	O10—H10B	0.87 (3)
N11—H11	0.9300
N11—Ni1—N1	93.70 (9)	N8—C9—H9D	109.7
N11—Ni1—N8	86.6 (2)	C10—C9—H9D	109.7
N1—Ni1—N8	178.5 (2)	H9C—C9—H9D	108.2
N11—Ni1—O1	90.42 (9)	N11—C10—C9	108.4 (2)
N1—Ni1—O1	94.76 (8)	N11—C10—H10C	110.0
N8—Ni1—O1	86.77 (8)	C9—C10—H10C	110.0
N11—Ni1—N4	178.34 (9)	N11—C10—H10D	110.0
N1—Ni1—N4	84.80 (9)	C9—C10—H10D	110.0
N8—Ni1—N4	94.97 (9)	H10C—C10—H10D	108.4
O1—Ni1—N4	89.01 (9)	C10—N11—C12	112.9 (2)
N11—Ni1—O6	89.69 (8)	C10—N11—Ni1	106.0 (2)
N1—Ni1—O6	91.22 (8)	C12—N11—Ni1	117.3 (2)
N8—Ni1—O6	87.25 (8)	C10—N11—H11	106.7
O1—Ni1—O6	174.00 (8)	C12—N11—H11	106.7
N4—Ni1—O6	91.04 (8)	Ni1—N11—H11	106.7
C2—N1—C14	115.0 (2)	N11—C12—C13	112.0 (2)
C2—N1—Ni1	107.1 (2)	N11—C12—H12A	109.2
C14—N1—Ni1	115.6 (2)	C13—C12—H12A	109.2
C2—N1—H1	106.1	N11—C12—H12B	109.2
C14—N1—H1	106.1	C13—C12—H12B	109.2
Ni1—N1—H1	106.1	H12A—C12—H12B	107.9
N1—C2—C3	108.3 (2)	C12—C13—C14	115.3 (2)
N1—C2—H2A	110.0	C12—C13—H13A	108.4
C3—C2—H2A	110.0	C14—C13—H13A	108.4
N1—C2—H2B	110.0	C12—C13—H13B	108.4
C3—C2—H2B	110.0	C14—C13—H13B	108.4
H2A—C2—H2B	108.4	H13A—C13—H13B	107.5
N4—C3—C2	108.6 (2)	N1—C14—C13	111.6 (2)
N4—C3—H3A	110.0	N1—C14—H14A	109.3
C2—C3—H3A	110.0	C13—C14—H14A	109.3
N4—C3—H3B	110.0	N1—C14—H14B	109.3
C2—C3—H3B	110.0	C13—C14—H14B	109.3
H3A—C3—H3B	108.3	H14A—C14—H14B	108.0
C3—N4—C5	113.4 (2)	C27—O1—Ni1	132.6 (2)
C3—N4—Ni1	104.5 (2)	C25—O5—H5	109.5
C5—N4—Ni1	114.9 (2)	C22—C21—C26	119.9 (2)
C3—N4—H4	107.9	C22—C21—C27	120.4 (2)
C5—N4—H4	107.9	C26—C21—C27	119.6 (2)
Ni1—N4—H4	107.9	C21—C22—C23	120.4 (2)
N4—C5—C6	112.4 (2)	C21—C22—H22	119.8
N4—C5—H5A	109.1	C23—C22—H22	119.8
C6—C5—H5A	109.1	C24—C23—C22	119.6 (2)
N4—C5—H5B	109.1	C24—C23—C28	120.1 (2)
C6—C5—H5B	109.1	C22—C23—C28	120.3 (2)
H5A—C5—H5B	107.9	C25—C24—C23	119.9 (2)
C5—C6—C7	115.4 (3)	C25—C24—H24	120.1
C5—C6—H6C	108.4	C23—C24—H24	120.1
C7—C6—H6C	108.4	O5—C25—C24	118.1 (2)
C5—C6—H6D	108.4	O5—C25—C26	121.2 (2)
C7—C6—H6D	108.4	C24—C25—C26	120.6 (2)
H6C—C6—H6D	107.5	C25—C26—C21	119.6 (2)
N8—C7—C6	112.2 (2)	C25—C26—H26	120.2
N8—C7—H7C	109.2	C21—C26—H26	120.2
C6—C7—H7C	109.2	O2—C27—O1	125.7 (2)
N8—C7—H7D	109.2	O2—C27—C21	118.7 (2)
C6—C7—H7D	109.2	O1—C27—C21	115.6 (2)
H7C—C7—H7D	107.9	O4—C28—O3	122.9 (2)
C7—N8—C9	113.4 (2)	O4—C28—C23	118.9 (2)
C7—N8—Ni1	115.5 (2)	O3—C28—C23	118.2 (2)
C9—N8—Ni1	103.5 (2)	Ni1—O6—H6A	120 (3)
C7—N8—H8	108.0	Ni1—O6—H6B	124 (2)
C9—N8—H8	108.0	H6A—O6—H6B	103 (4)
Ni1—N8—H8	108.0	H7A—O7—H7B	115 (4)
N8—C9—C10	109.6 (2)	H8A—O8—H8B	103 (4)
N8—C9—H9C	109.7	H9A—O9—H9B	113 (4)
C10—C9—H9C	109.7	H10A—O10—H10B	99 (5)
N11—Ni1—N1—C2	−169.5 (2)	N1—Ni1—N11—C10	165.8 (2)
O1—Ni1—N1—C2	99.8 (2)	N8—Ni1—N11—C10	−12.7 (2)
N4—Ni1—N1—C2	11.2 (2)	O1—Ni1—N11—C10	−99.4 (2)
O6—Ni1—N1—C2	−79.7 (12)	O6—Ni1—N11—C10	74.6 (2)
N11—Ni1—N1—C14	−39.9 (2)	N1—Ni1—N11—C12	38.7 (2)
O1—Ni1—N1—C14	−130.6 (2)	N8—Ni1—N11—C12	−139.8 (2)
N4—Ni1—N1—C14	140.8 (2)	O1—Ni1—N11—C12	133.5 (2)
O6—Ni1—N1—C14	49.9 (2)	O6—Ni1—N11—C12	−52.5 (2)
C14—N1—C2—C3	−168.8 (2)	C10—N11—C12—C13	−179.0 (2)
Ni1—N1—C2—C3	−38.9 (2)	Ni1—N11—C12—C13	−55.3 (3)
N1—C2—C3—N4	58.3 (3)	N11—C12—C13—C14	69.5 (3)
C2—C3—N4—C5	−171.2 (2)	C2—N1—C14—C13	−176.3 (2)
C2—C3—N4—Ni1	−45.3 (2)	Ni1—N1—C14—C13	58.0 (3)
N1—Ni1—N4—C3	18.8 (2)	C12—C13—C14—N1	−71.6 (3)
N8—Ni1—N4—C3	−162.7 (2)	N11—Ni1—O1—C27	−82.8 (3)
O1—Ni1—N4—C3	−76.1 (2)	N1—Ni1—O1—C27	10.9 (3)
O6—Ni1—N4—C3	110.0 (2)	N8—Ni1—O1—C27	−169.4 (3)
N1—Ni1—N4—C5	143.8 (2)	N4—Ni1—O1—C27	95.6 (3)
N8—Ni1—N4—C5	−37.8 (2)	C26—C21—C22—C23	−2.0 (4)
O1—Ni1—N4—C5	48.9 (2)	C27—C21—C22—C23	178.1 (2)
O6—Ni1—N4—C5	−125.1 (2)	C21—C22—C23—C24	0.6 (4)
C3—N4—C5—C6	176.1 (2)	C21—C22—C23—C28	178.9 (2)
Ni1—N4—C5—C6	56.0 (3)	C22—C23—C24—C25	1.0 (4)
N4—C5—C6—C7	−72.3 (3)	C28—C23—C24—C25	−177.3 (3)
C5—C6—C7—N8	72.0 (3)	C23—C24—C25—O5	177.2 (2)
C6—C7—N8—C9	−175.1 (2)	C23—C24—C25—C26	−1.2 (4)
C6—C7—N8—Ni1	−55.9 (3)	O5—C25—C26—C21	−178.6 (2)
N11—Ni1—N8—C7	−141.4 (2)	C24—C25—C26—C21	−0.2 (4)
O1—Ni1—N8—C7	−50.8 (2)	C22—C21—C26—C25	1.8 (4)
N4—Ni1—N8—C7	37.9 (2)	C27—C21—C26—C25	−178.3 (2)
O6—Ni1—N8—C7	128.7 (2)	Ni1—O1—C27—O2	6.7 (4)
N11—Ni1—N8—C9	−16.9 (2)	Ni1—O1—C27—C21	−171.4 (2)
O1—Ni1—N8—C9	73.7 (2)	C22—C21—C27—O2	164.3 (3)
N4—Ni1—N8—C9	162.5 (2)	C26—C21—C27—O2	−15.6 (4)
O6—Ni1—N8—C9	−106.8 (2)	C22—C21—C27—O1	−17.5 (4)
C7—N8—C9—C10	169.3 (2)	C26—C21—C27—O1	162.7 (2)
Ni1—N8—C9—C10	43.5 (2)	C24—C23—C28—O4	−31.6 (4)
N8—C9—C10—N11	−58.1 (3)	C22—C23—C28—O4	150.1 (3)
C9—C10—N11—C12	169.3 (2)	C24—C23—C28—O3	148.3 (3)
C9—C10—N11—Ni1	39.5 (3)	C22—C23—C28—O3	−30.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.93	2.06	2.903 (3)	150
N4—H4···O3^i	0.93	2.49	3.344 (3)	153
N8—H8···O7	0.93	2.13	3.032 (3)	164
N11—H11···O9^ii	0.93	2.20	3.018 (3)	147
O5—H5···O3^iii	0.84	1.69	2.519 (3)	169
O6—H6A···O7	0.90 (3)	1.80 (3)	2.670 (3)	161 (4)
O6—H6B···O5^iv	0.90 (3)	2.00 (3)	2.864 (3)	160 (4)
O7—H7A···O8	0.86 (3)	1.88 (3)	2.719 (3)	164 (4)
O7—H7B···O10^iii	0.89 (3)	1.91 (3)	2.793 (3)	172 (4)
O8—H8A···O9	0.88 (3)	1.84 (3)	2.712 (3)	169 (4)
O8—H8B···O5^v	0.87 (3)	1.97 (3)	2.824 (3)	167 (5)
O9—H9A···O10	0.85 (3)	1.97 (3)	2.824 (3)	176 (4)
O9—H9B···O4^vi	0.88 (3)	1.93 (3)	2.801 (3)	174 (4)
O10—H10A···O2^vii	0.92 (3)	1.83 (3)	2.739 (3)	169 (3)
O10—H10B···O4^v	0.87 (3)	1.85 (3)	2.718 (3)	174 (8)

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

(VII) catena-poly[terephthalato-1,4,8,11- -tetraazacyclotetradecanenickel(II)] monohydrate

Crystal data

C18H28N4NiO4·H2O	F(000) = 936
Mr = 441.17	Dx = 1.441 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.2155 (4) Å	Cell parameters from 2402 reflections
b = 16.0404 (6) Å	θ = 2.6–27.5°
c = 8.8937 (3) Å	µ = 0.99 mm^−1
β = 118.4900 (16)°	T = 150 K
V = 2033.14 (11) Å^3	Block, purple
Z = 4	0.18 × 0.16 × 0.16 mm

Data collection

Kappa-CCD diffractometer	2333 independent reflections
Radiation source: fine-focus sealed X-ray tube	1622 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→20
Tmin = 0.842, Tmax = 0.858	k = 0→20
12978 measured reflections	l = −11→10

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)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0754P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2333 reflections	Δρmax = 0.83 e Å^−3
134 parameters	Δρmin = −0.85 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0193 (17)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Ni1	0.2500	0.2500	0.0000	0.0247 (2)
N1	0.17290 (19)	0.34829 (15)	0.0202 (3)	0.0269 (6)
C2	0.2208 (2)	0.3725 (2)	0.2020 (4)	0.0333 (8)
C3	0.2515 (2)	0.2942 (2)	0.3125 (4)	0.0326 (8)
N4	0.31102 (19)	0.24304 (15)	0.2643 (3)	0.0267 (6)
C5	0.3266 (2)	0.1572 (2)	0.3344 (4)	0.0334 (8)
C6	0.3900 (2)	0.1077 (2)	0.2841 (4)	0.0350 (8)
C7	0.3461 (2)	0.08048 (19)	0.0968 (4)	0.0333 (8)
O1	0.14783 (15)	0.16226 (13)	−0.0325 (3)	0.0301 (5)
O2	0.03070 (16)	0.22725 (14)	−0.0099 (3)	0.0338 (6)
C11	0.0346 (2)	0.07824 (19)	−0.0107 (4)	0.0270 (7)
C12	0.0720 (2)	0.0063 (2)	−0.0410 (4)	0.0304 (7)
C13	−0.0374 (2)	0.07130 (19)	0.0316 (4)	0.0288 (7)
C14	0.0733 (2)	0.16271 (19)	−0.0194 (4)	0.0268 (7)
O3	0.0000	0.3041 (3)	0.2500	0.0708 (14)
H1	0.1149	0.3266	−0.0026	0.032*
H2A	0.1778	0.4056	0.2284	0.040*
H2B	0.2763	0.4073	0.2266	0.040*
H3A	0.2871	0.3098	0.4348	0.039*
H3B	0.1957	0.2618	0.2953	0.039*
H4	0.3693	0.2689	0.3091	0.032*
H5A	0.2655	0.1284	0.2910	0.040*
H5B	0.3557	0.1598	0.4607	0.040*
H6A	0.4117	0.0573	0.3568	0.042*
H6B	0.4461	0.1419	0.3104	0.042*
H7A	0.3891	0.0412	0.0830	0.040*
H7B	0.2866	0.0507	0.0656	0.040*
H12	0.1218	0.0104	−0.0684	0.037*
H13	−0.0629	0.1201	0.0541	0.035*
H3	0.008 (6)	0.266 (3)	0.190 (8)	0.11 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0270 (4)	0.0229 (3)	0.0269 (3)	−0.0040 (2)	0.0151 (3)	0.0000 (2)
N1	0.0280 (14)	0.0243 (14)	0.0320 (14)	−0.0029 (11)	0.0172 (12)	0.0008 (11)
C2	0.0375 (18)	0.0323 (18)	0.0349 (18)	−0.0015 (15)	0.0211 (15)	−0.0062 (14)
C3	0.0362 (19)	0.036 (2)	0.0298 (17)	−0.0042 (15)	0.0192 (15)	−0.0021 (14)
N4	0.0276 (14)	0.0258 (14)	0.0274 (13)	−0.0035 (11)	0.0137 (11)	0.0009 (11)
C5	0.0346 (18)	0.0344 (19)	0.0300 (17)	−0.0040 (15)	0.0145 (15)	0.0068 (14)
C6	0.0358 (19)	0.0306 (18)	0.0353 (18)	0.0008 (15)	0.0143 (15)	0.0076 (14)
C7	0.0320 (17)	0.0245 (16)	0.0445 (19)	−0.0025 (14)	0.0192 (16)	0.0020 (14)
O1	0.0306 (12)	0.0257 (12)	0.0394 (12)	−0.0067 (10)	0.0210 (10)	−0.0021 (10)
O2	0.0329 (13)	0.0280 (12)	0.0438 (14)	−0.0021 (10)	0.0211 (11)	0.0024 (10)
C11	0.0264 (16)	0.0257 (16)	0.0277 (16)	−0.0025 (13)	0.0119 (13)	0.0049 (13)
C12	0.0258 (16)	0.0329 (19)	0.0352 (18)	−0.0029 (13)	0.0166 (14)	0.0023 (14)
C13	0.0291 (17)	0.0241 (16)	0.0355 (17)	−0.0034 (13)	0.0173 (14)	0.0020 (13)
C14	0.0267 (17)	0.0262 (17)	0.0268 (16)	−0.0044 (13)	0.0121 (13)	0.0027 (13)
O3	0.101 (4)	0.065 (3)	0.053 (3)	0.000	0.042 (3)	0.000

Geometric parameters (Å, º)

Ni1—N1^i	2.072 (3)	C5—H5A	0.99
Ni1—N1	2.072 (3)	C5—H5B	0.99
Ni1—N4	2.073 (3)	C6—C7	1.530 (4)
Ni1—N4^i	2.073 (3)	C6—H6A	0.99
Ni1—O1	2.086 (2)	C6—H6B	0.99
Ni1—O1^i	2.086 (2)	C7—N1^i	1.476 (4)
N1—C2	1.473 (4)	C7—H7A	0.99
N1—C7^i	1.476 (4)	C7—H7B	0.99
N1—H1	0.93	O1—C14	1.269 (3)
C2—C3	1.524 (4)	O2—C14	1.269 (4)
C2—H2A	0.99	C11—C12	1.388 (4)
C2—H2B	0.99	C11—C13	1.392 (4)
C3—N4	1.477 (4)	C11—C14	1.510 (4)
C3—H3A	0.99	C12—C13^ii	1.385 (4)
C3—H3B	0.99	C12—H12	0.95
N4—C5	1.482 (4)	C13—C12^ii	1.385 (4)
N4—H4	0.93	C13—H13	0.95
C5—C6	1.525 (5)	O3—H3	0.86 (7)
N1^i—Ni1—N1	180	C5—N4—Ni1	114.9 (2)
N1^i—Ni1—N4	94.4 (2)	C3—N4—H4	107.4
N1—Ni1—N4	85.7 (2)	C5—N4—H4	107.4
N1^i—Ni1—N4^i	85.7 (2)	Ni1—N4—H4	107.4
N1—Ni1—N4^i	94.4 (2)	N4—C5—C6	111.4 (3)
N4—Ni1—N4^i	180	N4—C5—H5A	109.4
N1^i—Ni1—O1	87.0 (2)	C6—C5—H5A	109.4
N1—Ni1—O1	93.1 (2)	N4—C5—H5B	109.4
N4—Ni1—O1	92.22 (9)	C6—C5—H5B	109.4
N4^i—Ni1—O1	87.78 (9)	H5A—C5—H5B	108.0
N1^i—Ni1—O1^i	93.1 (2)	C5—C6—C7	116.1 (3)
N1—Ni1—O1^i	87.0 (2)	C5—C6—H6A	108.3
N4—Ni1—O1^i	87.78 (9)	C7—C6—H6A	108.3
N4^i—Ni1—O1^i	92.22 (9)	C5—C6—H6B	108.3
O1—Ni1—O1^i	180	C7—C6—H6B	108.3
C2—N1—C7^i	113.2 (2)	H6A—C6—H6B	107.4
C2—N1—Ni1	105.7 (2)	N1^i—C7—C6	112.3 (3)
C7^i—N1—Ni1	117.4 (2)	N1^i—C7—H7A	109.2
C2—N1—H1	106.6	C6—C7—H7A	109.2
C7^i—N1—H1	106.6	N1^i—C7—H7B	109.2
Ni1—N1—H1	106.6	C6—C7—H7B	109.2
N1—C2—C3	109.3 (3)	H7A—C7—H7B	107.9
N1—C2—H2A	109.8	C14—O1—Ni1	135.4 (2)
C3—C2—H2A	109.8	C12—C11—C13	119.1 (3)
N1—C2—H2B	109.8	C12—C11—C14	120.4 (3)
C3—C2—H2B	109.8	C13—C11—C14	120.5 (3)
H2A—C2—H2B	108.3	C13^ii—C12—C11	120.5 (3)
N4—C3—C2	109.1 (2)	C13^ii—C12—H12	119.7
N4—C3—H3A	109.9	C11—C12—H12	119.7
C2—C3—H3A	109.9	C12^ii—C13—C11	120.3 (3)
N4—C3—H3B	109.9	C12^ii—C13—H13	119.8
C2—C3—H3B	109.9	C11—C13—H13	119.8
H3A—C3—H3B	108.3	O1—C14—O2	125.7 (3)
C3—N4—C5	113.4 (2)	O1—C14—C11	115.9 (3)
C3—N4—Ni1	105.9 (2)	O2—C14—C11	118.4 (3)
N4—Ni1—N1—C2	15.2 (2)	O1^i—Ni1—N4—C5	−133.1 (2)
N4^i—Ni1—N1—C2	−164.8 (2)	C3—N4—C5—C6	−178.8 (2)
O1—Ni1—N1—C2	107.2 (2)	Ni1—N4—C5—C6	59.1 (3)
O1^i—Ni1—N1—C2	−72.8 (2)	N4—C5—C6—C7	−72.6 (4)
N4—Ni1—N1—C7^i	142.5 (2)	C5—C6—C7—N1^i	68.4 (4)
N4^i—Ni1—N1—C7^i	−37.5 (2)	N1^i—Ni1—O1—C14	170.1 (3)
O1—Ni1—N1—C7^i	−125.5 (2)	N1—Ni1—O1—C14	−9.9 (3)
O1^i—Ni1—N1—C7^i	54.5 (2)	N4—Ni1—O1—C14	75.9 (3)
C7^i—N1—C2—C3	−170.9 (3)	N4^i—Ni1—O1—C14	−104.1 (3)
Ni1—N1—C2—C3	−41.1 (3)	C13—C11—C12—C13^ii	0.9 (5)
N1—C2—C3—N4	56.1 (3)	C14—C11—C12—C13^ii	179.4 (3)
C2—C3—N4—C5	−166.7 (3)	C12—C11—C13—C12^ii	−0.9 (5)
C2—C3—N4—Ni1	−39.8 (3)	C14—C11—C13—C12^ii	−179.4 (3)
N1^i—Ni1—N4—C3	−166.2 (2)	Ni1—O1—C14—O2	14.0 (5)
N1—Ni1—N4—C3	13.8 (2)	Ni1—O1—C14—C11	−164.5 (2)
O1—Ni1—N4—C3	−79.1 (2)	C12—C11—C14—O1	−9.0 (4)
O1^i—Ni1—N4—C3	100.9 (2)	C13—C11—C14—O1	169.5 (3)
N1^i—Ni1—N4—C5	−40.2 (2)	C12—C11—C14—O2	172.3 (3)
N1—Ni1—N4—C5	139.8 (2)	C13—C11—C14—O2	−9.2 (4)
O1—Ni1—N4—C5	46.9 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.93	2.08	2.927 (4)	151
N4—H4···O2^iii	0.93	2.33	3.182 (3)	152
O3—H3···O2	0.86 (7)	2.09 (4)	2.865 (3)	152 (5)

Symmetry code: (iii) x+1/2, −y+1/2, z+1/2.

(VIII)

Crystal data

2(C15H25N4NiO4)·C10H28N4NiO2·2(ClO4)·0.86(H2O)	F(000) = 1345
Mr = 1277.62	Dx = 1.550 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8295 (3) Å	Cell parameters from 6029 reflections
b = 16.9416 (5) Å	θ = 2.6–27.5°
c = 14.9596 (5) Å	µ = 1.20 mm^−1
β = 93.6260 (13)°	T = 150 K
V = 2739.13 (14) Å^3	Plate, purple
Z = 2	0.40 × 0.36 × 0.12 mm

Data collection

Kappa-CCD diffractometer	6277 independent reflections
Radiation source: fine-focus sealed X-ray tube	5362 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→14
Tmin = 0.646, Tmax = 0.869	k = 0→21
20675 measured reflections	l = −19→19

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)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0347P)^2 + 1.8839P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
6277 reflections	Δρmax = 0.45 e Å^−3
377 parameters	Δρmin = −0.62 e Å^−3
12 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (6)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.5000	0.5000	0.5000	0.02030 (10)
O1	0.38485 (14)	0.60422 (9)	0.51792 (10)	0.0259 (3)
N1	0.39309 (15)	0.43568 (10)	0.58281 (11)	0.0236 (3)
N4	0.37720 (15)	0.46280 (10)	0.39646 (11)	0.0237 (3)
C2	0.27679 (19)	0.41805 (12)	0.52933 (14)	0.0272 (4)
C3	0.30689 (19)	0.39725 (12)	0.43400 (14)	0.0274 (4)
C5	0.4313 (2)	0.44231 (13)	0.31113 (14)	0.0302 (5)
C6	0.5073 (2)	0.50998 (14)	0.27584 (14)	0.0330 (5)
C7	0.6280 (2)	0.52759 (14)	0.32990 (14)	0.0302 (5)
Ni2	0.05830 (2)	0.726187 (13)	0.219586 (15)	0.01786 (9)
N21	0.24350 (16)	0.74376 (10)	0.25471 (11)	0.0243 (3)
N24	0.11892 (16)	0.65442 (9)	0.11953 (10)	0.0229 (3)
N28	−0.12864 (16)	0.70977 (10)	0.18166 (11)	0.0232 (3)
N211	−0.00371 (16)	0.79631 (9)	0.32214 (10)	0.0229 (3)
C22	0.3101 (2)	0.71693 (13)	0.17691 (15)	0.0309 (5)
C23	0.2520 (2)	0.64054 (13)	0.14163 (14)	0.0293 (4)
C25	0.0468 (2)	0.58163 (12)	0.10260 (14)	0.0290 (4)
C26	−0.0892 (2)	0.59926 (13)	0.07795 (14)	0.0312 (5)
C27	−0.1634 (2)	0.62875 (13)	0.15456 (14)	0.0286 (4)
C29	−0.1968 (2)	0.73968 (14)	0.25759 (14)	0.0302 (4)
C210	−0.1339 (2)	0.81369 (12)	0.29573 (14)	0.0286 (4)
C212	0.0701 (2)	0.86785 (12)	0.34468 (13)	0.0295 (5)
C213	0.2064 (2)	0.84962 (13)	0.36452 (14)	0.0332 (5)
C214	0.2767 (2)	0.82481 (13)	0.28417 (14)	0.0307 (5)
O31	0.22188 (12)	0.61039 (8)	0.37722 (9)	0.0241 (3)
O32	0.03561 (12)	0.63084 (8)	0.30767 (8)	0.0203 (3)
O33	0.05499 (14)	0.67231 (8)	0.64061 (8)	0.0238 (3)
O34	0.06560 (15)	0.71343 (8)	0.49881 (9)	0.0294 (3)
C31	0.04684 (16)	0.55333 (10)	0.43868 (11)	0.0159 (3)
C32	0.03135 (16)	0.57742 (10)	0.52690 (11)	0.0163 (3)
C33	0.01418 (16)	0.47667 (10)	0.41329 (11)	0.0170 (3)
C37	0.10573 (17)	0.60403 (10)	0.37045 (11)	0.0175 (3)
C38	0.05380 (17)	0.66177 (10)	0.55700 (11)	0.0180 (4)
O2	0.6171 (6)	1.0018 (3)	0.5361 (5)	0.080 (3)	0.430 (9)
Cl1	0.56740 (10)	0.78843 (7)	0.45060 (7)	0.0347 (2)	0.914 (4)
O3	0.4901 (2)	0.76585 (13)	0.52103 (15)	0.0531 (7)	0.914 (4)
O4	0.5410 (2)	0.73697 (12)	0.37519 (14)	0.0498 (6)	0.914 (4)
O5	0.5434 (3)	0.86856 (12)	0.42446 (17)	0.0570 (7)	0.914 (4)
O6	0.6948 (3)	0.7793 (2)	0.4816 (3)	0.0500 (7)	0.914 (4)
Cl21	0.5838 (12)	0.8020 (8)	0.4670 (9)	0.0347 (2)	0.086 (4)
O23	0.540 (2)	0.8302 (13)	0.5482 (13)	0.052 (5)*	0.086 (4)
O24	0.502 (2)	0.7348 (12)	0.4352 (15)	0.052 (5)*	0.086 (4)
O25	0.569 (3)	0.8595 (15)	0.3952 (15)	0.052 (5)*	0.086 (4)
O26	0.708 (3)	0.773 (2)	0.477 (3)	0.052 (5)*	0.086 (4)
H1A	0.415 (3)	0.6503 (16)	0.5209 (19)	0.050 (6)*
H1B	0.328 (3)	0.6076 (18)	0.4750 (18)	0.050 (6)*
H11	0.4333	0.3879	0.5944	0.028*
H4	0.3217	0.5039	0.3844	0.028*
H2A	0.2214	0.4646	0.5286	0.033*
H2B	0.2338	0.3733	0.5564	0.033*
H3A	0.3565	0.3482	0.4342	0.033*
H3B	0.2294	0.3883	0.3967	0.033*
H5A	0.3640	0.4287	0.2659	0.036*
H5B	0.4849	0.3953	0.3204	0.036*
H6A	0.5265	0.4976	0.2136	0.040*
H6B	0.4558	0.5583	0.2739	0.040*
H7A	0.6748	0.4778	0.3401	0.036*
H7B	0.6789	0.5635	0.2951	0.036*
H21	0.2651	0.7100	0.3021	0.029*
H24	0.1127	0.6837	0.0668	0.027*
H28	−0.1479	0.7425	0.1329	0.028*
H211	−0.0026	0.7652	0.3734	0.027*
H22A	0.3985	0.7082	0.1951	0.037*
H22B	0.3046	0.7577	0.1294	0.037*
H23A	0.2926	0.6232	0.0875	0.035*
H23B	0.2629	0.5986	0.1875	0.035*
H25A	0.0534	0.5480	0.1569	0.035*
H25B	0.0819	0.5519	0.0532	0.035*
H26A	−0.0940	0.6394	0.0298	0.037*
H26B	−0.1289	0.5506	0.0533	0.037*
H27A	−0.2527	0.6273	0.1357	0.034*
H27B	−0.1494	0.5930	0.2066	0.034*
H29A	−0.1983	0.6987	0.3047	0.036*
H29B	−0.2833	0.7519	0.2368	0.036*
H10A	−0.1386	0.8561	0.2502	0.034*
H10B	−0.1766	0.8321	0.3484	0.034*
H12A	0.0372	0.8936	0.3976	0.035*
H12B	0.0611	0.9054	0.2940	0.035*
H13A	0.2136	0.8069	0.4097	0.040*
H13B	0.2469	0.8970	0.3916	0.040*
H14A	0.2578	0.8620	0.2341	0.037*
H14B	0.3668	0.8274	0.3002	0.037*
H33	0.0233	0.4607	0.3532	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01959 (18)	0.02151 (18)	0.01963 (17)	0.00139 (13)	−0.00010 (13)	−0.00117 (13)
O1	0.0260 (7)	0.0237 (7)	0.0277 (7)	0.0037 (6)	−0.0020 (6)	−0.0016 (6)
N1	0.0234 (8)	0.0237 (8)	0.0237 (8)	0.0016 (6)	0.0010 (6)	0.0001 (7)
N4	0.0235 (8)	0.0243 (8)	0.0231 (8)	0.0019 (6)	−0.0010 (6)	−0.0020 (7)
C2	0.0241 (10)	0.0266 (10)	0.0309 (10)	−0.0013 (8)	0.0018 (8)	−0.0004 (8)
C3	0.0243 (10)	0.0262 (10)	0.0312 (10)	−0.0007 (8)	−0.0016 (8)	−0.0017 (8)
C5	0.0333 (11)	0.0340 (12)	0.0229 (10)	0.0001 (9)	−0.0006 (8)	−0.0060 (9)
C6	0.0377 (12)	0.0393 (12)	0.0221 (10)	−0.0013 (10)	0.0023 (9)	0.0010 (9)
C7	0.0324 (11)	0.0345 (11)	0.0245 (10)	−0.0008 (9)	0.0080 (8)	−0.0001 (9)
Ni2	0.02472 (15)	0.01504 (13)	0.01393 (13)	0.00146 (9)	0.00205 (9)	0.00220 (8)
N21	0.0288 (9)	0.0223 (8)	0.0221 (8)	−0.0018 (7)	0.0029 (7)	0.0061 (7)
N24	0.0338 (9)	0.0179 (8)	0.0173 (7)	0.0045 (7)	0.0046 (6)	0.0026 (6)
N28	0.0281 (9)	0.0235 (8)	0.0179 (7)	0.0023 (7)	0.0001 (6)	0.0021 (6)
N211	0.0338 (9)	0.0192 (8)	0.0158 (7)	0.0022 (7)	0.0032 (6)	0.0015 (6)
C22	0.0294 (11)	0.0345 (12)	0.0296 (11)	0.0022 (9)	0.0084 (9)	0.0079 (9)
C23	0.0334 (11)	0.0285 (11)	0.0269 (10)	0.0093 (9)	0.0085 (8)	0.0044 (8)
C25	0.0469 (13)	0.0177 (9)	0.0226 (9)	0.0012 (9)	0.0028 (9)	−0.0016 (8)
C26	0.0438 (13)	0.0265 (10)	0.0224 (10)	−0.0043 (9)	−0.0041 (9)	−0.0048 (8)
C27	0.0312 (11)	0.0296 (11)	0.0245 (10)	−0.0061 (8)	−0.0027 (8)	0.0009 (8)
C29	0.0277 (11)	0.0365 (12)	0.0270 (10)	0.0052 (9)	0.0060 (8)	0.0011 (9)
C210	0.0357 (11)	0.0276 (10)	0.0231 (9)	0.0098 (9)	0.0060 (8)	0.0007 (8)
C212	0.0494 (13)	0.0185 (9)	0.0207 (9)	−0.0004 (9)	0.0026 (9)	−0.0016 (8)
C213	0.0465 (13)	0.0269 (11)	0.0253 (10)	−0.0099 (9)	−0.0052 (9)	−0.0005 (9)
C214	0.0346 (11)	0.0262 (10)	0.0307 (11)	−0.0091 (9)	−0.0022 (9)	0.0050 (9)
O31	0.0213 (7)	0.0254 (7)	0.0255 (7)	−0.0008 (5)	0.0009 (5)	0.0090 (6)
O32	0.0264 (7)	0.0186 (6)	0.0156 (6)	−0.0007 (5)	−0.0010 (5)	0.0054 (5)
O33	0.0409 (8)	0.0170 (6)	0.0138 (6)	−0.0047 (6)	0.0035 (5)	−0.0035 (5)
O34	0.0554 (10)	0.0157 (6)	0.0169 (6)	−0.0056 (6)	0.0015 (6)	0.0006 (5)
C31	0.0187 (8)	0.0137 (8)	0.0152 (8)	0.0009 (6)	−0.0005 (6)	0.0010 (6)
C32	0.0189 (8)	0.0151 (8)	0.0148 (8)	−0.0003 (6)	−0.0003 (6)	−0.0003 (6)
C33	0.0226 (9)	0.0157 (8)	0.0128 (7)	0.0003 (7)	0.0005 (6)	−0.0002 (6)
C37	0.0259 (9)	0.0129 (8)	0.0138 (8)	0.0003 (7)	0.0014 (7)	−0.0012 (6)
C38	0.0225 (9)	0.0163 (8)	0.0151 (8)	−0.0008 (7)	0.0006 (7)	−0.0006 (7)
O2	0.081 (4)	0.051 (3)	0.104 (5)	0.005 (3)	−0.023 (3)	−0.027 (3)
Cl1	0.0388 (4)	0.0278 (5)	0.0379 (5)	−0.0003 (3)	0.0054 (3)	−0.0003 (3)
O3	0.0557 (14)	0.0475 (13)	0.0596 (14)	−0.0008 (10)	0.0309 (11)	−0.0035 (10)
O4	0.0691 (15)	0.0357 (11)	0.0438 (12)	0.0074 (10)	−0.0038 (10)	−0.0073 (9)
O5	0.086 (2)	0.0241 (10)	0.0598 (16)	0.0048 (10)	−0.0016 (13)	0.0006 (10)
O6	0.0388 (13)	0.0518 (15)	0.0589 (15)	−0.0083 (10)	−0.0002 (11)	0.0090 (11)
Cl21	0.0388 (4)	0.0278 (5)	0.0379 (5)	−0.0003 (3)	0.0054 (3)	−0.0003 (3)

Geometric parameters (Å, º)

Ni1—N1^i	2.060 (2)	C22—C23	1.519 (3)
Ni1—N1	2.060 (2)	C22—H22A	0.99
Ni1—N4	2.075 (2)	C22—H22B	0.99
Ni1—N4^i	2.075 (2)	C23—H23A	0.99
Ni1—O1^i	2.188 (2)	C23—H23B	0.99
Ni1—O1	2.188 (2)	C25—C26	1.525 (3)
O1—H1A	0.85 (3)	C25—H25A	0.99
O1—H1B	0.86 (3)	C25—H25B	0.99
N1—C7^i	1.477 (3)	C26—C27	1.525 (3)
N1—C2	1.479 (3)	C26—H26A	0.99
N1—H11	0.93	C26—H26B	0.99
N4—C3	1.477 (3)	C27—H27A	0.99
N4—C5	1.479 (3)	C27—H27B	0.99
N4—H4	0.93	C29—C210	1.521 (3)
C2—C3	1.524 (3)	C29—H29A	0.99
C2—H2A	0.99	C29—H29B	0.99
C2—H2B	0.99	C210—H10A	0.99
C3—H3A	0.99	C210—H10B	0.99
C3—H3B	0.99	C212—C213	1.519 (3)
C5—C6	1.525 (3)	C212—H12A	0.99
C5—H5A	0.99	C212—H12B	0.99
C5—H5B	0.99	C213—C214	1.523 (3)
C6—C7	1.523 (3)	C213—H13A	0.99
C6—H6A	0.99	C213—H13B	0.99
C6—H6B	0.99	C214—H14A	0.99
C7—N1^i	1.477 (3)	C214—H14B	0.99
C7—H7A	0.99	O31—C37	1.260 (2)
C7—H7B	0.99	O32—C37	1.255 (2)
Ni2—N21	2.063 (2)	O33—C38	1.263 (2)
Ni2—N24	2.067 (2)	O33—Ni2^iii	2.086 (2)
Ni2—N211	2.085 (2)	O34—C38	1.247 (2)
Ni2—O33^ii	2.085 (2)	C31—C33	1.393 (2)
Ni2—N28	2.086 (2)	C31—C32	1.401 (2)
Ni2—O32	2.109 (2)	C31—C37	1.506 (2)
N21—C22	1.479 (3)	C32—C33^iv	1.393 (2)
N21—C214	1.480 (3)	C32—C38	1.513 (2)
N21—H21	0.93	C33—C32^iv	1.393 (2)
N24—C25	1.473 (3)	C33—H33	0.95
N24—C23	1.477 (3)	Cl1—O5	1.432 (2)
N24—H24	0.93	Cl1—O6	1.436 (3)
N28—C27	1.474 (3)	Cl1—O3	1.438 (2)
N28—C29	1.482 (3)	Cl1—O4	1.440 (2)
N28—H28	0.93	Cl21—O23	1.42 (2)
N211—C210	1.469 (3)	Cl21—O26	1.43 (2)
N211—C212	1.479 (3)	Cl21—O25	1.45 (2)
N211—H211	0.93	Cl21—O24	1.50 (2)
N1^i—Ni1—N1	180	C210—N211—Ni2	105.3 (2)
N1^i—Ni1—N4	94.00 (6)	C212—N211—Ni2	116.1 (2)
N1—Ni1—N4	86.00 (6)	C210—N211—H211	107.3
N1^i—Ni1—N4^i	85.99 (6)	C212—N211—H211	107.3
N1—Ni1—N4^i	94.01 (6)	Ni2—N211—H211	107.3
N4—Ni1—N4^i	180	N21—C22—C23	108.9 (2)
N1^i—Ni1—O1^i	90.39 (6)	N21—C22—H22A	109.9
N1—Ni1—O1^i	89.60 (6)	C23—C22—H22A	109.9
N4—Ni1—O1^i	90.39 (6)	N21—C22—H22B	109.9
N4^i—Ni1—O1^i	89.61 (6)	C23—C22—H22B	109.9
N1^i—Ni1—O1	89.61 (6)	H22A—C22—H22B	108.3
N1—Ni1—O1	90.40 (6)	N24—C23—C22	108.6 (2)
N4—Ni1—O1	89.61 (6)	N24—C23—H23A	110.0
N4^i—Ni1—O1	90.39 (6)	C22—C23—H23A	110.0
O1^i—Ni1—O1	180	N24—C23—H23B	110.0
Ni1—O1—H1A	122 (2)	C22—C23—H23B	110.0
Ni1—O1—H1B	110 (2)	H23A—C23—H23B	108.4
H1A—O1—H1B	103 (3)	N24—C25—C26	111.8 (2)
C7^i—N1—C2	112.9 (2)	N24—C25—H25A	109.3
C7^i—N1—Ni1	115.7 (2)	C26—C25—H25A	109.3
C2—N1—Ni1	105.9 (2)	N24—C25—H25B	109.3
C7^i—N1—H11	107.3	C26—C25—H25B	109.3
C2—N1—H11	107.3	H25A—C25—H25B	107.9
Ni1—N1—H11	107.3	C27—C26—C25	115.4 (2)
C3—N4—C5	113.2 (2)	C27—C26—H26A	108.4
C3—N4—Ni1	105.4 (2)	C25—C26—H26A	108.4
C5—N4—Ni1	116.4 (2)	C27—C26—H26B	108.4
C3—N4—H4	107.1	C25—C26—H26B	108.4
C5—N4—H4	107.1	H26A—C26—H26B	107.5
Ni1—N4—H4	107.1	N28—C27—C26	112.0 (2)
N1—C2—C3	109.12 (16)	N28—C27—H27A	109.2
N1—C2—H2A	109.9	C26—C27—H27A	109.2
C3—C2—H2A	109.9	N28—C27—H27B	109.2
N1—C2—H2B	109.9	C26—C27—H27B	109.2
C3—C2—H2B	109.9	H27A—C27—H27B	107.9
H2A—C2—H2B	108.3	N28—C29—C210	109.7 (2)
N4—C3—C2	109.1 (2)	N28—C29—H29A	109.7
N4—C3—H3A	109.9	C210—C29—H29A	109.7
C2—C3—H3A	109.9	N28—C29—H29B	109.7
N4—C3—H3B	109.9	C210—C29—H29B	109.7
C2—C3—H3B	109.9	H29A—C29—H29B	108.2
H3A—C3—H3B	108.3	N211—C210—C29	109.6 (2)
N4—C5—C6	112.0 (2)	N211—C210—H10A	109.8
N4—C5—H5A	109.2	C29—C210—H10A	109.8
C6—C5—H5A	109.2	N211—C210—H10B	109.8
N4—C5—H5B	109.2	C29—C210—H10B	109.8
C6—C5—H5B	109.2	H10A—C210—H10B	108.2
H5A—C5—H5B	107.9	N211—C212—C213	112.5 (2)
C7—C6—C5	115.3 (2)	N211—C212—H12A	109.1
C7—C6—H6A	108.4	C213—C212—H12A	109.1
C5—C6—H6A	108.4	N211—C212—H12B	109.1
C7—C6—H6B	108.4	C213—C212—H12B	109.1
C5—C6—H6B	108.4	H12A—C212—H12B	107.8
H6A—C6—H6B	107.5	C212—C213—C214	115.5 (2)
N1^i—C7—C6	112.1 (2)	C212—C213—H13A	108.4
N1^i—C7—H7A	109.2	C214—C213—H13A	108.4
C6—C7—H7A	109.2	C212—C213—H13B	108.4
N1^i—C7—H7B	109.2	C214—C213—H13B	108.4
C6—C7—H7B	109.2	H13A—C213—H13B	107.5
H7A—C7—H7B	107.9	N21—C214—C213	111.5 (2)
N21—Ni2—N24	85.48 (7)	N21—C214—H14A	109.3
N21—Ni2—N211	94.80 (7)	C213—C214—H14A	109.3
N24—Ni2—N211	178.71 (6)	N21—C214—H14B	109.3
N21—Ni2—O33^ii	90.39 (6)	C213—C214—H14B	109.3
N24—Ni2—O33^ii	93.99 (6)	H14A—C214—H14B	108.0
N211—Ni2—O33^ii	87.26 (6)	C37—O32—Ni2	131.0 (2)
N21—Ni2—N28	178.82 (6)	C38—O33—Ni2^iii	132.6 (2)
N24—Ni2—N28	94.12 (7)	C33—C31—C32	119.0 (2)
N211—Ni2—N28	85.63 (7)	C33—C31—C37	117.3 (2)
O33^ii—Ni2—N28	88.53 (6)	C32—C31—C37	123.6 (2)
N21—Ni2—O32	95.81 (6)	C33^iv—C32—C31	118.8 (2)
N24—Ni2—O32	93.26 (6)	C33^iv—C32—C38	119.1 (2)
N211—Ni2—O32	85.47 (6)	C31—C32—C38	121.9 (2)
O33^ii—Ni2—O32	170.81 (5)	C31—C33—C32^iv	122.2 (2)
N28—Ni2—O32	85.32 (6)	C31—C33—H33	118.9
C22—N21—C214	113.5 (2)	C32^iv—C33—H33	118.9
C22—N21—Ni2	105.7 (2)	O32—C37—O31	125.7 (2)
C214—N21—Ni2	115.1 (2)	O32—C37—C31	116.8 (2)
C22—N21—H21	107.4	O31—C37—C31	117.2 (2)
C214—N21—H21	107.4	O34—C38—O33	126.7 (2)
Ni2—N21—H21	107.4	O34—C38—C32	118.5 (2)
C25—N24—C23	113.9 (2)	O33—C38—C32	114.8 (2)
C25—N24—Ni2	115.3 (2)	O5—Cl1—O6	110.1 (2)
C23—N24—Ni2	106.4 (2)	O5—Cl1—O3	110.4 (2)
C25—N24—H24	106.9	O6—Cl1—O3	109.1 (2)
C23—N24—H24	106.9	O5—Cl1—O4	109.7 (2)
Ni2—N24—H24	106.9	O6—Cl1—O4	109.1 (2)
C27—N28—C29	113.5 (2)	O3—Cl1—O4	108.5 (2)
C27—N28—Ni2	115.2 (2)	O23—Cl21—O26	113 (2)
C29—N28—Ni2	105.5 (2)	O23—Cl21—O25	113 (2)
C27—N28—H28	107.4	O26—Cl21—O25	111 (2)
C29—N28—H28	107.4	O23—Cl21—O24	108 (2)
Ni2—N28—H28	107.4	O26—Cl21—O24	108 (2)
C210—N211—C212	113.1 (2)	O25—Cl21—O24	104 (2)
N4—Ni1—N1—C7^i	−140.2 (2)	N28—Ni2—N211—C210	−16.1 (2)
N4^i—Ni1—N1—C7^i	39.9 (2)	O32—Ni2—N211—C210	−101.7 (2)
O1^i—Ni1—N1—C7^i	129.4 (2)	N21—Ni2—N211—C212	36.9 (2)
O1—Ni1—N1—C7^i	−50.6 (2)	O33^ii—Ni2—N211—C212	−53.3 (2)
N4—Ni1—N1—C2	−14.3 (2)	N28—Ni2—N211—C212	−142.0 (2)
N4^i—Ni1—N1—C2	165.7 (2)	O32—Ni2—N211—C212	132.3 (2)
O1^i—Ni1—N1—C2	−104.8 (2)	C214—N21—C22—C23	−169.4 (2)
O1—Ni1—N1—C2	75.2 (2)	Ni2—N21—C22—C23	−42.4 (2)
N1^i—Ni1—N4—C3	165.4 (2)	C25—N24—C23—C22	−167.9 (2)
N1—Ni1—N4—C3	−14.6 (2)	Ni2—N24—C23—C22	−39.8 (2)
O1^i—Ni1—N4—C3	74.9 (2)	N21—C22—C23—N24	56.6 (2)
O1—Ni1—N4—C3	−105.1 (2)	C23—N24—C25—C26	−178.6 (2)
N1^i—Ni1—N4—C5	39.0 (2)	Ni2—N24—C25—C26	58.0 (2)
N1—Ni1—N4—C5	−141.0 (2)	N24—C25—C26—C27	−71.7 (2)
O1^i—Ni1—N4—C5	−51.4 (2)	C29—N28—C27—C26	−178.6 (2)
O1—Ni1—N4—C5	128.6 (2)	Ni2—N28—C27—C26	−56.8 (2)
C7^i—N1—C2—C3	1678.0 (2)	C25—C26—C27—N28	71.1 (2)
Ni1—N1—C2—C3	40.5 (2)	C27—N28—C29—C210	166.0 (2)
C5—N4—C3—C2	169.0 (2)	Ni2—N28—C29—C210	38.9 (2)
Ni1—N4—C3—C2	40.642)	C212—N211—C210—C29	169.7 (2)
N1—C2—C3—N4	−56.3 (2)	Ni2—N211—C210—C29	41.8 (2)
C3—N4—C5—C6	−177.89 (2)	N28—C29—C210—N211	−56.4 (2)
Ni1—N4—C5—C6	−55.4 (2)	C210—N211—C212—C213	−175.4 (2)
N4—C5—C6—C7	69.7 (2)	Ni2—N211—C212—C213	−53.4 (2)
C5—C6—C7—N1^i	−71.4 (2)	N211—C212—C213—C214	70.3 (2)
N24—Ni2—N21—C22	16.1 (2)	C22—N21—C214—C213	−179.8 (2)
N211—Ni2—N21—C22	−165.1 (2)	Ni2—N21—C214—C213	58.4 (2)
O33^ii—Ni2—N21—C22	−77.9 (2)	C212—C213—C214—N21	−73.2 (2)
O32—Ni2—N21—C22	108.9 (2)	N21—Ni2—O32—C37	10.84 (16)
N24—Ni2—N21—C214	142.1 (2)	N24—Ni2—O32—C37	96.62 (16)
N211—Ni2—N21—C214	−39.2 (2)	N211—Ni2—O32—C37	−83.5 (2)
O33^ii—Ni2—N21—C214	48.1 (2)	N28—Ni2—O32—C37	−169.5 (2)
O32—Ni2—N21—C214	−125.1 (2)	C33—C31—C32—C33^iv	1.1 (3)
N21—Ni2—N24—C25	140.5 (2)	C37—C31—C32—C33^iv	−174.3 (2)
O33^ii—Ni2—N24—C25	−129.5 (2)	C33—C31—C32—C38	−174.4 (2)
N28—Ni2—N24—C25	−40.7 (2)	C37—C31—C32—C38	10.2 (3)
O32—Ni2—N24—C25	44.9 (2)	C32—C31—C33—C32^iv	−1.2 (3)
N21—Ni2—N24—C23	13.2 (2)	C37—C31—C33—C32^iv	174.6 (2)
O33^ii—Ni2—N24—C23	103.3 (2)	Ni2—O32—C37—O31	−25.6 (3)
N28—Ni2—N24—C23	−167.9 (2)	Ni2—O32—C37—C31	160.6 (2)
O32—Ni2—N24—C23	−82.4 (2)	C33—C31—C37—O32	75.1 (2)
N24—Ni2—N28—C27	40.1 (2)	C32—C31—C37—O32	−109.4 (2)
N211—Ni2—N28—C27	−138.6 (2)	C33—C31—C37—O31	−99.3 (2)
O33^ii—Ni2—N28—C27	134.0 (2)	C32—C31—C37—O31	76.3 (2)
O32—Ni2—N28—C27	−52.8 (2)	Ni2^iii—O33—C38—O34	7.0 (3)
N24—Ni2—N28—C29	166.1 (2)	Ni2^iii—O33—C38—C32	−170.9 (2)
N211—Ni2—N28—C29	−12.7 (2)	C33^iv—C32—C38—O34	−163.1 (2)
O33^ii—Ni2—N28—C29	−100.0 (2)	C31—C32—C38—O34	12.4 (3)
O32—Ni2—N28—C29	73.2 (2)	C33^iv—C32—C38—O33	15.0 (2)
N21—Ni2—N211—C210	162.9 (2)	C31—C32—C38—O33	−169.6 (2)
O33^ii—Ni2—N211—C210	72.7 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.85 (3)	2.12 (3)	2.965 (3)	177 (3)
O1—H1A···O24	0.85 (3)	2.17 (4)	2.87 (2)	139 (3)
O1—H1B···O31	0.86 (3)	1.80 (3)	2.662 (2)	173 (3)
N1—H11···O4^i	0.93	2.18	3.066 (3)	159
N1—H11···O24^i	0.93	2.25	3.12 (2)	156
N4—H4···O31	0.93	2.10	3.017 (2)	167
N21—H21···O31	0.93	2.10	2.928 (2)	148
N24—H24···O34^ii	0.93	2.07	2.911 (2)	150
N211—H211···O34	0.93	2.16	3.045 (2)	159

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