cis-(Acetato-κ(2)O,O')(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N,N',N'',N''')nickel(II) perchlorate monohydrate.

The complete cation in the title hydrated mol-ecular salt, [Ni(CH(3)CO(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, is generated by the application of crystallographic twofold symmetry; the perchlorate anion and water mol-ecule are each disordered around a twofold axis. The Ni(II) atom exists within a cis-N(4)O(2) donor set based on a strongly distorted octa-hedron and defined by the four N atoms of the macrocyclic ligand and two O atoms of a symmetrically coordinating acetate ligand. In the crystal, hydrogen bonding (water-acetate/perchlorate O-H⋯O and amine-perchlorate N-H⋯O) leads to layers in the ab plane. The layers stack along the c axis, being connected by C-H⋯O(water) inter-actions. The crystal studied was found to be a non-merohedral twin; the minor component refined to 15.9 (6)%.

Related literature

For background to macrocyclic complexes, see: Hazari et al. (2010 ▶). For a related structure, see: Roy et al. (2012 ▶). For the treatment of data from twinned crystals, see: Spek (2009 ▶).

Experimental

Crystal data

[Ni(C2H3n class="Chemical">O2)(C16H36N4)]ClO4·H2O

M = 519.71

Monoclinic,

a = 9.4041 (2) Å

b = 15.9593 (4) Å

c = 16.0721 (6) Å

β = 96.534 (3)°

V = 2396.48 (12) Å3

Z = 4

Cu Kα radiation

μ = 2.58 mm−1

T = 100 K

0.25 × 0.20 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.850, T max = 1.000

5502 measured reflections

2480 independent reflections

2286 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.162

S = 1.09

2480 reflections

171 parameters

45 restraints

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.62 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812013232/hb6703sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013232/hb6703Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C2H3O2)(C16H36N4]ClO4·H2O	F(000) = 1112
Mr = 519.71	Dx = 1.440 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 3218 reflections
a = 9.4041 (2) Å	θ = 5.5–76.4°
b = 15.9593 (4) Å	µ = 2.58 mm−1
c = 16.0721 (6) Å	T = 100 K
β = 96.534 (3)°	Prism, light-purple
V = 2396.48 (12) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	2480 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2286 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
Detector resolution: 10.4041 pixels mm-1	θmax = 76.6°, θmin = 5.5°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −18→19
Tmin = 0.850, Tmax = 1.000	l = −3→20
5502 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0529P)2 + 9.9029P] where P = (Fo2 + 2Fc2)/3
2480 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.60 e Å−3
45 restraints	Δρmin = −0.62 e Å−3

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni	0.5000	0.56446 (4)	0.7500	0.0300 (3)
Cl1	0.4637 (3)	0.86782 (11)	0.71627 (15)	0.0559 (6)	0.50
O2	0.6083 (10)	0.8409 (9)	0.7174 (9)	0.197 (12)	0.50
O3	0.4105 (13)	0.8372 (5)	0.7910 (6)	0.111 (5)	0.50
O4	0.4585 (9)	0.9554 (3)	0.7181 (5)	0.085 (3)	0.50
O5	0.3800 (9)	0.8336 (6)	0.6466 (5)	0.111 (3)	0.50
O1W	0.7196 (13)	0.8995 (10)	0.8864 (7)	0.147 (6)	0.50
H1W1	0.7967	0.9187	0.8726	0.220*	0.50
H1W2	0.6729	0.8794	0.8433	0.220*	0.50
O1	0.4508 (2)	0.45087 (14)	0.80858 (16)	0.0318 (5)
N1	0.5584 (4)	0.64503 (18)	0.6573 (2)	0.0459 (9)
H1	0.5406	0.6967	0.6721	0.069*
N2	0.2798 (3)	0.5692 (2)	0.6999 (2)	0.0412 (8)
H2	0.2413	0.5227	0.7164	0.062*
C1	0.5402 (7)	0.6902 (4)	0.5067 (4)	0.085 (2)
H1A	0.6439	0.6833	0.5075	0.128*
H1B	0.5188	0.7483	0.5206	0.128*
H1C	0.4930	0.6766	0.4508	0.128*
C2	0.4854 (5)	0.6312 (3)	0.5713 (3)	0.0546 (12)
H2A	0.5042	0.5722	0.5546	0.066*
C3	0.3231 (5)	0.6426 (3)	0.5688 (4)	0.0681 (16)
H3A	0.2832	0.6489	0.5095	0.082*
H3B	0.3059	0.6961	0.5973	0.082*
C4	0.2374 (5)	0.5741 (3)	0.6076 (3)	0.0535 (12)
C5	0.2620 (5)	0.4882 (3)	0.5708 (3)	0.0554 (11)
H5A	0.3634	0.4733	0.5823	0.083*
H5B	0.2345	0.4895	0.5102	0.083*
H5C	0.2039	0.4465	0.5963	0.083*
C6	0.0754 (5)	0.5945 (4)	0.5877 (4)	0.0749 (17)
H6A	0.0558	0.6499	0.6102	0.112*
H6B	0.0190	0.5521	0.6134	0.112*
H6C	0.0493	0.5944	0.5269	0.112*
C7	0.2205 (4)	0.6372 (3)	0.7477 (3)	0.0534 (12)
H7A	0.1153	0.6310	0.7446	0.064*
H7B	0.2415	0.6920	0.7229	0.064*
C8	0.2843 (4)	0.6345 (3)	0.8372 (3)	0.0514 (11)
H8A	0.2428	0.6799	0.8689	0.062*
H8B	0.2614	0.5803	0.8624	0.062*
C9	0.5000	0.4119 (3)	0.7500	0.0312 (10)
C10	0.5000	0.3177 (3)	0.7500	0.0555 (16)
H10A	0.4629	0.2973	0.8008	0.083*	0.50
H10B	0.5979	0.2973	0.7486	0.083*	0.50
H10C	0.4392	0.2973	0.7006	0.083*	0.50

	U11	U22	U33	U12	U13	U23
Ni	0.0253 (4)	0.0131 (4)	0.0551 (6)	0.000	0.0195 (4)	0.000
Cl1	0.0651 (14)	0.0221 (8)	0.0840 (16)	0.0086 (8)	0.0232 (11)	−0.0024 (8)
O2	0.201 (15)	0.173 (14)	0.218 (15)	0.025 (9)	0.034 (10)	−0.029 (9)
O3	0.150 (9)	0.049 (5)	0.131 (8)	−0.031 (5)	0.013 (6)	0.048 (5)
O4	0.104 (7)	0.022 (3)	0.141 (8)	0.003 (3)	0.063 (5)	−0.004 (3)
O5	0.117 (7)	0.117 (7)	0.093 (6)	0.022 (6)	−0.005 (5)	−0.035 (5)
O1W	0.122 (9)	0.232 (15)	0.087 (7)	−0.090 (10)	0.017 (6)	−0.022 (8)
O1	0.0294 (12)	0.0186 (11)	0.0479 (14)	−0.0039 (9)	0.0068 (10)	0.0020 (9)
N1	0.0461 (19)	0.0204 (14)	0.079 (2)	0.0067 (13)	0.0404 (18)	0.0113 (14)
N2	0.0320 (15)	0.0318 (16)	0.063 (2)	0.0107 (13)	0.0194 (14)	0.0140 (14)
C1	0.090 (4)	0.070 (4)	0.106 (5)	0.023 (3)	0.058 (4)	0.052 (3)
C2	0.059 (3)	0.044 (2)	0.067 (3)	0.018 (2)	0.034 (2)	0.026 (2)
C3	0.061 (3)	0.065 (3)	0.083 (3)	0.034 (2)	0.029 (3)	0.044 (3)
C4	0.038 (2)	0.058 (3)	0.066 (3)	0.0198 (19)	0.0136 (19)	0.024 (2)
C5	0.041 (2)	0.070 (3)	0.054 (2)	0.014 (2)	0.0018 (19)	0.010 (2)
C6	0.044 (3)	0.094 (4)	0.087 (4)	0.032 (3)	0.010 (3)	0.031 (3)
C7	0.038 (2)	0.038 (2)	0.090 (3)	0.0211 (17)	0.033 (2)	0.014 (2)
C8	0.042 (2)	0.034 (2)	0.086 (3)	0.0081 (17)	0.042 (2)	0.002 (2)
C9	0.024 (2)	0.019 (2)	0.050 (3)	0.000	−0.001 (2)	0.000
C10	0.074 (4)	0.017 (2)	0.076 (4)	0.000	0.010 (3)	0.000

Ni—O1	2.118 (2)	C2—H2A	1.0000
Ni—N1i	2.089 (3)	C3—C4	1.532 (7)
Ni—N1	2.089 (3)	C3—H3A	0.9900
Ni—O1i	2.118 (2)	C3—H3B	0.9900
Ni—N2	2.136 (3)	C4—C5	1.521 (7)
Ni—N2i	2.136 (3)	C4—C6	1.556 (6)
Cl1—O4	1.400 (5)	C5—H5A	0.9800
Cl1—O5	1.404 (6)	C5—H5B	0.9800
Cl1—O2	1.424 (8)	C5—H5C	0.9800
Cl1—O3	1.439 (7)	C6—H6A	0.9800
O1W—H1W1	0.8400	C6—H6B	0.9800
O1W—H1W2	0.8399	C6—H6C	0.9800
O1—C9	1.259 (3)	C7—C8	1.495 (7)
N1—C8i	1.481 (5)	C7—H7A	0.9900
N1—C2	1.488 (6)	C7—H7B	0.9900
N1—H1	0.8800	C8—N1i	1.481 (5)
N2—C7	1.475 (5)	C8—H8A	0.9900
N2—C4	1.493 (6)	C8—H8B	0.9900
N2—H2	0.8800	C9—O1i	1.259 (3)
C1—C2	1.534 (6)	C9—C10	1.503 (7)
C1—H1A	0.9800	C10—H10A	0.9800
C1—H1B	0.9800	C10—H10B	0.9800
C1—H1C	0.9800	C10—H10C	0.9800
C2—C3	1.532 (6)
N1i—Ni—N1	104.01 (18)	C3—C2—H2A	108.2
N1i—Ni—O1i	158.84 (12)	C1—C2—H2A	108.2
N1—Ni—O1i	96.96 (11)	C2—C3—C4	118.2 (3)
N1i—Ni—O1	96.96 (11)	C2—C3—H3A	107.8
N1—Ni—O1	158.84 (12)	C4—C3—H3A	107.8
O1i—Ni—O1	62.28 (13)	C2—C3—H3B	107.8
N1i—Ni—N2	85.68 (14)	C4—C3—H3B	107.8
N1—Ni—N2	91.80 (13)	H3A—C3—H3B	107.1
O1i—Ni—N2	96.56 (11)	N2—C4—C5	107.7 (3)
O1—Ni—N2	86.94 (11)	N2—C4—C3	110.4 (4)
N1i—Ni—N2i	91.80 (13)	C5—C4—C3	112.0 (4)
N1—Ni—N2i	85.68 (14)	N2—C4—C6	111.1 (4)
O1i—Ni—N2i	86.94 (11)	C5—C4—C6	107.3 (5)
O1—Ni—N2i	96.56 (11)	C3—C4—C6	108.4 (4)
N2—Ni—N2i	175.92 (17)	C4—C5—H5A	109.5
O4—Cl1—O5	112.8 (5)	C4—C5—H5B	109.5
O4—Cl1—O2	109.7 (5)	H5A—C5—H5B	109.5
O5—Cl1—O2	109.9 (5)	C4—C5—H5C	109.5
O4—Cl1—O3	107.8 (4)	H5A—C5—H5C	109.5
O5—Cl1—O3	108.5 (5)	H5B—C5—H5C	109.5
O2—Cl1—O3	108.0 (5)	C4—C6—H6A	109.5
H1W1—O1W—H1W2	107.9	C4—C6—H6B	109.5
C9—O1—Ni	88.4 (2)	H6A—C6—H6B	109.5
C8i—N1—C2	113.0 (3)	C4—C6—H6C	109.5
C8i—N1—Ni	103.3 (3)	H6A—C6—H6C	109.5
C2—N1—Ni	116.1 (2)	H6B—C6—H6C	109.5
C8i—N1—H1	108.0	N2—C7—C8	110.3 (3)
C2—N1—H1	108.0	N2—C7—H7A	109.6
Ni—N1—H1	108.0	C8—C7—H7A	109.6
C7—N2—C4	113.9 (3)	N2—C7—H7B	109.6
C7—N2—Ni	103.7 (3)	C8—C7—H7B	109.6
C4—N2—Ni	120.9 (2)	H7A—C7—H7B	108.1
C7—N2—H2	105.7	N1i—C8—C7	110.0 (3)
C4—N2—H2	105.7	N1i—C8—H8A	109.7
Ni—N2—H2	105.7	C7—C8—H8A	109.7
C2—C1—H1A	109.5	N1i—C8—H8B	109.7
C2—C1—H1B	109.5	C7—C8—H8B	109.7
H1A—C1—H1B	109.5	H8A—C8—H8B	108.2
C2—C1—H1C	109.5	O1i—C9—O1	120.9 (4)
H1A—C1—H1C	109.5	O1i—C9—C10	119.6 (2)
H1B—C1—H1C	109.5	O1—C9—C10	119.6 (2)
N1—C2—C3	111.1 (4)	C9—C10—H10A	109.5
N1—C2—C1	112.4 (5)	C9—C10—H10B	109.5
C3—C2—C1	108.6 (4)	C9—C10—H10C	109.5
N1—C2—H2A	108.2
N1i—Ni—O1—C9	−175.68 (14)	O1—Ni—N2—C4	−123.0 (3)
N1—Ni—O1—C9	11.9 (4)	C8i—N1—C2—C3	180.0 (3)
O1i—Ni—O1—C9	0.0	Ni—N1—C2—C3	60.9 (4)
N2—Ni—O1—C9	99.05 (14)	C8i—N1—C2—C1	−58.0 (4)
N2i—Ni—O1—C9	−83.05 (14)	Ni—N1—C2—C1	−177.1 (3)
N1i—Ni—N1—C8i	109.4 (3)	N1—C2—C3—C4	−73.5 (6)
O1i—Ni—N1—C8i	−67.8 (3)	C1—C2—C3—C4	162.3 (5)
O1—Ni—N1—C8i	−78.4 (5)	C7—N2—C4—C5	−161.4 (3)
N2—Ni—N1—C8i	−164.6 (3)	Ni—N2—C4—C5	74.0 (4)
N2i—Ni—N1—C8i	18.6 (3)	C7—N2—C4—C3	76.1 (4)
N1i—Ni—N1—C2	−126.3 (3)	Ni—N2—C4—C3	−48.5 (4)
O1i—Ni—N1—C2	56.5 (3)	C7—N2—C4—C6	−44.2 (5)
O1—Ni—N1—C2	45.9 (5)	Ni—N2—C4—C6	−168.8 (3)
N2—Ni—N1—C2	−40.3 (3)	C2—C3—C4—N2	65.0 (6)
N2i—Ni—N1—C2	142.9 (3)	C2—C3—C4—C5	−55.0 (7)
N1i—Ni—N2—C7	10.5 (2)	C2—C3—C4—C6	−173.1 (5)
N1—Ni—N2—C7	−93.4 (2)	C4—N2—C7—C8	−172.0 (3)
O1i—Ni—N2—C7	169.4 (2)	Ni—N2—C7—C8	−38.6 (4)
O1—Ni—N2—C7	107.7 (2)	N2—C7—C8—N1i	60.1 (4)
N1i—Ni—N2—C4	139.7 (3)	Ni—O1—C9—O1i	0.0
N1—Ni—N2—C4	35.8 (3)	Ni—O1—C9—C10	180.000 (1)
O1i—Ni—N2—C4	−61.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88	2.47	3.289 (14)	154
N1—H1···O3i	0.88	2.35	3.181 (9)	158
N2—H2···O4ii	0.88	2.50	3.276 (8)	148
O1w—H1w1···O1iii	0.84	1.94	2.754 (11)	163
O1w—H1w2···O2	0.84	2.14	2.950 (18)	163
C3—H3A···O1Wiv	0.99	2.14	3.057 (13)	153

Ni—O1	2.118 (2)
Ni—N1	2.089 (3)
Ni—N2	2.136 (3)

O1i—Ni—O1

62.28 (13)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.88	2.47	3.289 (14)	154
N1—H1⋯O3i	0.88	2.35	3.181 (9)	158
N2—H2⋯O4ii	0.88	2.50	3.276 (8)	148
O1w—H1w1⋯O1iii	0.84	1.94	2.754 (11)	163
O1w—H1w2⋯O2	0.84	2.14	2.950 (18)	163
C3—H3A⋯O1Wiv	0.99	2.14	3.057 (13)	153

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .