metal-organic compounds
(2-Aminobenzoato-κ2O,O′)(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate
aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
In the title salt, [Ni(C7H6NO2)(C16H36N4)]ClO4·H2O, the NiII cation is O,O′-chelated by the benzoate anion and N,N′,N′′,N′′′-chelated by the macrocycle ligand, confering a distorted octahedral geometry on the metal atom. The complex cations, perchlorate anions and uncoordinated water molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network. The perchlorate ion is disordered over two positions in a 0.554 (8):0.446 (8) ratio.
Experimental
Crystal data
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Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536810037116/xu5028sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810037116/xu5028Isup2.hkl
Anthranilic acid (0.27 g, 2 mmol) and sodium hydroxide (0.08 g, 2 mmol) were dissolved in water (15 ml). To this solution was added (rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel diperchlorate (0.11 g, 2 mmol) dissolved in acetonitrile (10 ml). The solution was set aside for the growth of violet crystals after a few days.
Carbon-bound H-atoms were placed in calculated positions (C–H 0.95–1.00 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2–1.5U(C).The water and amino H atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01 Å and N–H 0.86±0.01 Å. For the water molecule, the H···H distance was restrained to 1.37±0.01 Å. The temperature factors were tied to those of the parent atoms by a factor of 1.2–1.5 times.
The perchlorate is disordered over two positions in a 0.554 (8):0.446 (8) ratio. All Cl–O distances were restrained to within 0.01 Å of each other as were the O···O distances. The anisotropic temperature factors of the O atoms were restrained to be nearly isotropic.
Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [Ni(C16H36N4)(C7H6NO2)][ClO4].H2O at the 50% probability level; hydrogen atoms are shown as spheres of arbitrary radius. The disorder in the perchlorate is not shown. |
[Ni(C7H6NO2)(C16H36N4)]ClO4·H2O | F(000) = 1272 |
Mr = 596.79 | Dx = 1.413 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 5267 reflections |
a = 9.6452 (5) Å | θ = 2.3–27.0° |
b = 21.5350 (11) Å | µ = 0.84 mm−1 |
c = 13.5083 (7) Å | T = 110 K |
β = 90.784 (1)° | Prism, violet |
V = 2805.5 (3) Å3 | 0.45 × 0.20 × 0.10 mm |
Z = 4 |
Bruker SMART APEX diffractometer | 3832 independent reflections |
Radiation source: fine-focus sealed tube | 3667 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 27.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→12 |
Tmin = 0.818, Tmax = 1.000 | k = −26→26 |
6638 measured reflections | l = −8→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.1275P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3832 reflections | Δρmax = 0.25 e Å−3 |
410 parameters | Δρmin = −0.21 e Å−3 |
142 restraints | Absolute structure: Flack (1983), 874 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.012 (9) |
[Ni(C7H6NO2)(C16H36N4)]ClO4·H2O | V = 2805.5 (3) Å3 |
Mr = 596.79 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 9.6452 (5) Å | µ = 0.84 mm−1 |
b = 21.5350 (11) Å | T = 110 K |
c = 13.5083 (7) Å | 0.45 × 0.20 × 0.10 mm |
β = 90.784 (1)° |
Bruker SMART APEX diffractometer | 3832 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3667 reflections with I > 2σ(I) |
Tmin = 0.818, Tmax = 1.000 | Rint = 0.016 |
6638 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.064 | Δρmax = 0.25 e Å−3 |
S = 1.08 | Δρmin = −0.21 e Å−3 |
3832 reflections | Absolute structure: Flack (1983), 874 Friedel pairs |
410 parameters | Absolute structure parameter: −0.012 (9) |
142 restraints |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.50011 (3) | 0.399116 (12) | 0.49992 (3) | 0.01859 (8) | |
O1 | 0.58175 (16) | 0.44546 (8) | 0.37089 (12) | 0.0219 (4) | |
O2 | 0.66792 (16) | 0.46225 (7) | 0.51979 (12) | 0.0201 (3) | |
Cl1 | 0.6956 (5) | 0.2675 (2) | 0.1539 (3) | 0.0295 (7) | 0.554 (8) |
O3 | 0.5575 (5) | 0.2886 (4) | 0.1347 (6) | 0.0444 (19) | 0.554 (8) |
O4 | 0.7620 (5) | 0.3111 (2) | 0.2197 (4) | 0.0581 (17) | 0.554 (8) |
O5 | 0.6945 (9) | 0.2080 (2) | 0.2001 (5) | 0.0439 (19) | 0.554 (8) |
O6 | 0.7708 (7) | 0.2650 (3) | 0.0641 (4) | 0.070 (2) | 0.554 (8) |
Cl1' | 0.6956 (6) | 0.2641 (3) | 0.1262 (4) | 0.0311 (10) | 0.446 (8) |
O3' | 0.5794 (8) | 0.2974 (4) | 0.1623 (6) | 0.042 (2) | 0.446 (8) |
O4' | 0.8213 (6) | 0.2957 (3) | 0.1496 (6) | 0.060 (3) | 0.446 (8) |
O5' | 0.6992 (12) | 0.2028 (3) | 0.1656 (9) | 0.057 (3) | 0.446 (8) |
O6' | 0.6838 (8) | 0.2577 (3) | 0.0218 (4) | 0.058 (2) | 0.446 (8) |
O1W | 0.5173 (2) | 0.42855 (9) | 0.17034 (14) | 0.0296 (4) | |
H11 | 0.545 (3) | 0.4343 (13) | 0.2291 (11) | 0.044* | |
H12 | 0.537 (4) | 0.3925 (8) | 0.153 (2) | 0.044* | |
N1 | 0.3714 (2) | 0.46844 (10) | 0.56243 (16) | 0.0190 (4) | |
H1 | 0.423 (2) | 0.4982 (10) | 0.585 (2) | 0.023* | |
N2 | 0.4909 (2) | 0.35763 (9) | 0.63905 (16) | 0.0211 (4) | |
H2 | 0.428 (2) | 0.3296 (10) | 0.636 (2) | 0.025* | |
N3 | 0.6127 (2) | 0.32080 (10) | 0.44631 (17) | 0.0243 (4) | |
H3 | 0.652 (3) | 0.3351 (13) | 0.3944 (14) | 0.029* | |
N4 | 0.3296 (2) | 0.36063 (10) | 0.42555 (16) | 0.0242 (4) | |
H4 | 0.280 (3) | 0.3380 (12) | 0.4632 (19) | 0.029* | |
N5 | 0.7978 (2) | 0.57537 (11) | 0.53966 (18) | 0.0289 (5) | |
H51 | 0.739 (3) | 0.5514 (12) | 0.567 (2) | 0.035* | |
H52 | 0.814 (3) | 0.6115 (8) | 0.563 (2) | 0.035* | |
C1 | 0.3207 (3) | 0.44029 (12) | 0.65532 (18) | 0.0245 (5) | |
H1A | 0.2438 | 0.4112 | 0.6402 | 0.029* | |
H1B | 0.2852 | 0.4732 | 0.6995 | 0.029* | |
C2 | 0.4374 (3) | 0.40601 (11) | 0.70620 (19) | 0.0253 (5) | |
H2A | 0.5126 | 0.4354 | 0.7241 | 0.030* | |
H2B | 0.4037 | 0.3866 | 0.7678 | 0.030* | |
C3 | 0.6234 (3) | 0.33020 (13) | 0.6779 (2) | 0.0282 (6) | |
H3a | 0.6968 | 0.3629 | 0.6751 | 0.034* | |
C4 | 0.6109 (3) | 0.30893 (15) | 0.7856 (2) | 0.0378 (7) | |
H4A | 0.5814 | 0.3440 | 0.8265 | 0.057* | |
H4B | 0.7011 | 0.2937 | 0.8096 | 0.057* | |
H4C | 0.5423 | 0.2755 | 0.7895 | 0.057* | |
C5 | 0.6684 (3) | 0.27612 (12) | 0.6133 (2) | 0.0293 (6) | |
H5A | 0.5883 | 0.2477 | 0.6059 | 0.035* | |
H5B | 0.7418 | 0.2532 | 0.6499 | 0.035* | |
C6 | 0.7230 (3) | 0.28992 (12) | 0.5088 (2) | 0.0298 (6) | |
C7 | 0.8464 (3) | 0.33447 (13) | 0.5146 (2) | 0.0353 (7) | |
H7A | 0.8832 | 0.3409 | 0.4481 | 0.053* | |
H7B | 0.9188 | 0.3167 | 0.5575 | 0.053* | |
H7C | 0.8162 | 0.3743 | 0.5418 | 0.053* | |
C8 | 0.7727 (3) | 0.22831 (14) | 0.4626 (3) | 0.0393 (7) | |
H8A | 0.7921 | 0.2348 | 0.3923 | 0.059* | |
H8B | 0.7003 | 0.1967 | 0.4692 | 0.059* | |
H8C | 0.8573 | 0.2143 | 0.4969 | 0.059* | |
C9 | 0.5037 (3) | 0.27846 (12) | 0.4086 (2) | 0.0297 (6) | |
H9A | 0.4632 | 0.2551 | 0.4643 | 0.036* | |
H9B | 0.5444 | 0.2483 | 0.3620 | 0.036* | |
C10 | 0.3920 (3) | 0.31573 (13) | 0.3564 (2) | 0.0288 (6) | |
H10A | 0.4324 | 0.3383 | 0.2998 | 0.035* | |
H10B | 0.3194 | 0.2874 | 0.3304 | 0.035* | |
C11 | 0.2384 (3) | 0.40671 (11) | 0.37461 (19) | 0.0241 (5) | |
H11A | 0.2979 | 0.4328 | 0.3310 | 0.029* | |
C12 | 0.1271 (3) | 0.37581 (15) | 0.3090 (2) | 0.0335 (6) | |
H12A | 0.1719 | 0.3517 | 0.2568 | 0.050* | |
H12B | 0.0680 | 0.4078 | 0.2788 | 0.050* | |
H12C | 0.0704 | 0.3481 | 0.3494 | 0.050* | |
C13 | 0.1684 (2) | 0.45014 (12) | 0.44934 (19) | 0.0238 (5) | |
H13A | 0.1253 | 0.4240 | 0.5007 | 0.029* | |
H13B | 0.0923 | 0.4722 | 0.4142 | 0.029* | |
C14 | 0.2594 (2) | 0.49930 (12) | 0.50235 (18) | 0.0217 (5) | |
C15 | 0.3297 (3) | 0.54169 (12) | 0.42814 (19) | 0.0237 (5) | |
H15A | 0.3819 | 0.5740 | 0.4637 | 0.036* | |
H15B | 0.2592 | 0.5611 | 0.3853 | 0.036* | |
H15C | 0.3932 | 0.5173 | 0.3876 | 0.036* | |
C16 | 0.1671 (3) | 0.54025 (13) | 0.5675 (2) | 0.0259 (6) | |
H16A | 0.2256 | 0.5678 | 0.6079 | 0.039* | |
H16B | 0.1117 | 0.5138 | 0.6109 | 0.039* | |
H16C | 0.1053 | 0.5652 | 0.5253 | 0.039* | |
C17 | 0.6690 (2) | 0.47306 (11) | 0.42754 (19) | 0.0186 (5) | |
C18 | 0.7701 (2) | 0.51743 (11) | 0.38477 (18) | 0.0198 (5) | |
C19 | 0.8068 (2) | 0.51078 (12) | 0.28554 (19) | 0.0234 (5) | |
H19 | 0.7678 | 0.4777 | 0.2479 | 0.028* | |
C20 | 0.8984 (3) | 0.55104 (13) | 0.2407 (2) | 0.0292 (6) | |
H20 | 0.9247 | 0.5450 | 0.1739 | 0.035* | |
C21 | 0.9514 (3) | 0.60087 (12) | 0.2959 (2) | 0.0301 (6) | |
H21 | 1.0125 | 0.6296 | 0.2657 | 0.036* | |
C22 | 0.9161 (3) | 0.60871 (12) | 0.3934 (2) | 0.0276 (6) | |
H22 | 0.9532 | 0.6430 | 0.4292 | 0.033* | |
C23 | 0.8259 (2) | 0.56699 (12) | 0.4417 (2) | 0.0219 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01972 (13) | 0.01555 (14) | 0.02064 (13) | −0.00292 (12) | 0.00605 (9) | −0.00109 (13) |
O1 | 0.0225 (8) | 0.0217 (9) | 0.0217 (8) | −0.0068 (7) | 0.0050 (7) | −0.0017 (7) |
O2 | 0.0227 (8) | 0.0171 (9) | 0.0207 (8) | −0.0015 (6) | 0.0043 (7) | −0.0002 (7) |
Cl1 | 0.0273 (9) | 0.0245 (10) | 0.0371 (17) | 0.0031 (6) | 0.0107 (11) | 0.0046 (11) |
O3 | 0.036 (2) | 0.035 (3) | 0.062 (4) | 0.005 (2) | −0.007 (2) | −0.016 (3) |
O4 | 0.053 (3) | 0.045 (3) | 0.075 (4) | −0.004 (2) | −0.017 (3) | −0.008 (2) |
O5 | 0.055 (3) | 0.015 (2) | 0.062 (4) | 0.000 (2) | 0.014 (3) | 0.010 (2) |
O6 | 0.071 (4) | 0.077 (4) | 0.065 (4) | 0.031 (3) | 0.052 (4) | 0.012 (3) |
Cl1' | 0.0308 (12) | 0.0213 (12) | 0.041 (3) | 0.0025 (8) | 0.0045 (16) | 0.0042 (15) |
O3' | 0.048 (4) | 0.033 (4) | 0.047 (4) | 0.016 (3) | 0.024 (3) | 0.001 (3) |
O4' | 0.055 (3) | 0.038 (3) | 0.087 (6) | −0.014 (3) | −0.021 (3) | 0.020 (3) |
O5' | 0.051 (4) | 0.027 (4) | 0.094 (7) | 0.008 (3) | 0.017 (5) | 0.010 (4) |
O6' | 0.055 (4) | 0.079 (4) | 0.041 (3) | 0.016 (3) | 0.009 (3) | −0.017 (3) |
O1W | 0.0405 (11) | 0.0243 (10) | 0.0239 (9) | 0.0039 (8) | −0.0026 (8) | 0.0000 (7) |
N1 | 0.0222 (10) | 0.0145 (10) | 0.0205 (10) | −0.0003 (8) | 0.0027 (8) | 0.0008 (8) |
N2 | 0.0208 (10) | 0.0180 (10) | 0.0248 (10) | 0.0008 (8) | 0.0057 (8) | 0.0009 (8) |
N3 | 0.0254 (10) | 0.0186 (11) | 0.0291 (11) | −0.0042 (8) | 0.0107 (9) | −0.0014 (9) |
N4 | 0.0258 (10) | 0.0228 (11) | 0.0242 (10) | −0.0061 (8) | 0.0086 (8) | −0.0022 (9) |
N5 | 0.0337 (12) | 0.0215 (11) | 0.0315 (12) | −0.0095 (9) | 0.0063 (9) | −0.0075 (9) |
C1 | 0.0287 (12) | 0.0262 (13) | 0.0187 (11) | 0.0058 (10) | 0.0078 (10) | 0.0013 (10) |
C2 | 0.0314 (13) | 0.0246 (13) | 0.0202 (11) | 0.0062 (10) | 0.0056 (10) | 0.0018 (10) |
C3 | 0.0250 (12) | 0.0240 (14) | 0.0356 (15) | 0.0034 (10) | 0.0030 (11) | 0.0032 (11) |
C4 | 0.0416 (16) | 0.0366 (16) | 0.0353 (15) | 0.0169 (13) | 0.0014 (13) | 0.0070 (13) |
C5 | 0.0295 (13) | 0.0180 (12) | 0.0406 (15) | 0.0043 (10) | 0.0081 (11) | 0.0038 (11) |
C6 | 0.0245 (13) | 0.0232 (14) | 0.0420 (16) | 0.0016 (10) | 0.0122 (11) | −0.0024 (12) |
C7 | 0.0229 (13) | 0.0326 (16) | 0.0507 (17) | 0.0009 (11) | 0.0090 (12) | −0.0002 (13) |
C8 | 0.0370 (16) | 0.0235 (15) | 0.058 (2) | 0.0074 (12) | 0.0127 (15) | −0.0063 (14) |
C9 | 0.0347 (13) | 0.0181 (13) | 0.0368 (14) | −0.0057 (10) | 0.0146 (11) | −0.0073 (11) |
C10 | 0.0315 (14) | 0.0250 (14) | 0.0301 (14) | −0.0081 (10) | 0.0079 (11) | −0.0125 (11) |
C11 | 0.0247 (12) | 0.0247 (13) | 0.0232 (12) | −0.0063 (9) | 0.0049 (10) | −0.0010 (10) |
C12 | 0.0295 (13) | 0.0429 (17) | 0.0282 (13) | −0.0081 (12) | 0.0010 (11) | −0.0065 (12) |
C13 | 0.0193 (11) | 0.0276 (13) | 0.0245 (12) | −0.0013 (9) | 0.0031 (10) | 0.0017 (10) |
C14 | 0.0229 (11) | 0.0224 (12) | 0.0200 (11) | 0.0015 (9) | 0.0040 (9) | 0.0031 (10) |
C15 | 0.0278 (12) | 0.0222 (12) | 0.0212 (11) | 0.0021 (9) | 0.0048 (10) | 0.0034 (10) |
C16 | 0.0263 (13) | 0.0259 (15) | 0.0256 (13) | 0.0059 (10) | 0.0062 (10) | 0.0040 (11) |
C17 | 0.0197 (11) | 0.0140 (11) | 0.0222 (12) | 0.0024 (9) | 0.0045 (9) | −0.0008 (9) |
C18 | 0.0190 (11) | 0.0170 (12) | 0.0236 (12) | 0.0000 (8) | 0.0017 (9) | 0.0014 (9) |
C19 | 0.0210 (12) | 0.0238 (13) | 0.0255 (12) | −0.0011 (9) | 0.0037 (10) | 0.0014 (10) |
C20 | 0.0253 (12) | 0.0355 (15) | 0.0269 (13) | 0.0006 (10) | 0.0083 (10) | 0.0080 (11) |
C21 | 0.0210 (12) | 0.0288 (14) | 0.0405 (15) | −0.0034 (9) | 0.0045 (11) | 0.0131 (12) |
C22 | 0.0249 (12) | 0.0199 (13) | 0.0378 (15) | −0.0048 (9) | −0.0005 (11) | 0.0034 (11) |
C23 | 0.0194 (11) | 0.0193 (12) | 0.0269 (12) | 0.0015 (9) | 0.0022 (10) | 0.0017 (10) |
Ni1—N1 | 2.124 (2) | C5—C6 | 1.541 (4) |
Ni1—N2 | 2.084 (2) | C5—H5A | 0.9900 |
Ni1—N3 | 2.138 (2) | C5—H5B | 0.9900 |
Ni1—N4 | 2.087 (2) | C6—C7 | 1.530 (4) |
Ni1—O1 | 2.1659 (17) | C6—C8 | 1.546 (4) |
Ni1—O2 | 2.1280 (16) | C7—H7A | 0.9800 |
O1—C17 | 1.276 (3) | C7—H7B | 0.9800 |
O2—C17 | 1.268 (3) | C7—H7C | 0.9800 |
Cl1—O6 | 1.423 (4) | C8—H8A | 0.9800 |
Cl1—O5 | 1.425 (5) | C8—H8B | 0.9800 |
Cl1—O3 | 1.427 (5) | C8—H8C | 0.9800 |
Cl1—O4 | 1.437 (5) | C9—C10 | 1.510 (4) |
Cl1'—O6' | 1.421 (5) | C9—H9A | 0.9900 |
Cl1'—O5' | 1.423 (6) | C9—H9B | 0.9900 |
Cl1'—O3' | 1.422 (5) | C10—H10A | 0.9900 |
Cl1'—O4' | 1.422 (6) | C10—H10B | 0.9900 |
O1W—H11 | 0.843 (10) | C11—C12 | 1.534 (4) |
O1W—H12 | 0.833 (10) | C11—C13 | 1.539 (3) |
N1—C1 | 1.482 (3) | C11—H11A | 1.0000 |
N1—C14 | 1.498 (3) | C12—H12A | 0.9800 |
N1—H1 | 0.861 (10) | C12—H12B | 0.9800 |
N2—C2 | 1.479 (3) | C12—H12C | 0.9800 |
N2—C3 | 1.496 (3) | C13—C14 | 1.545 (3) |
N2—H2 | 0.858 (10) | C13—H13A | 0.9900 |
N3—C9 | 1.477 (3) | C13—H13B | 0.9900 |
N3—C6 | 1.504 (4) | C14—C15 | 1.522 (3) |
N3—H3 | 0.860 (10) | C14—C16 | 1.538 (3) |
N4—C10 | 1.478 (3) | C15—H15A | 0.9800 |
N4—C11 | 1.489 (3) | C15—H15B | 0.9800 |
N4—H4 | 0.86 (3) | C15—H15C | 0.9800 |
N5—C23 | 1.366 (3) | C16—H16A | 0.9800 |
N5—H51 | 0.86 (3) | C16—H16B | 0.9800 |
N5—H52 | 0.854 (10) | C16—H16C | 0.9800 |
C1—C2 | 1.504 (3) | C17—C18 | 1.487 (3) |
C1—H1A | 0.9900 | C18—C19 | 1.399 (3) |
C1—H1B | 0.9900 | C18—C23 | 1.418 (3) |
C2—H2A | 0.9900 | C19—C20 | 1.383 (3) |
C2—H2B | 0.9900 | C19—H19 | 0.9500 |
C3—C5 | 1.522 (4) | C20—C21 | 1.400 (4) |
C3—C4 | 1.532 (4) | C20—H20 | 0.9500 |
C3—H3a | 1.0000 | C21—C22 | 1.375 (4) |
C4—H4A | 0.9800 | C21—H21 | 0.9500 |
C4—H4B | 0.9800 | C22—C23 | 1.416 (4) |
C4—H4C | 0.9800 | C22—H22 | 0.9500 |
N2—Ni1—N4 | 102.76 (8) | N3—C6—C7 | 107.2 (2) |
N2—Ni1—N1 | 84.86 (8) | N3—C6—C5 | 110.60 (19) |
N4—Ni1—N1 | 90.54 (8) | C7—C6—C5 | 110.5 (2) |
N2—Ni1—O2 | 101.64 (7) | N3—C6—C8 | 111.9 (2) |
N4—Ni1—O2 | 155.16 (8) | C7—C6—C8 | 108.2 (2) |
N1—Ni1—O2 | 87.05 (7) | C5—C6—C8 | 108.4 (2) |
N2—Ni1—N3 | 89.73 (8) | C6—C7—H7A | 109.5 |
N4—Ni1—N3 | 85.66 (8) | C6—C7—H7B | 109.5 |
N1—Ni1—N3 | 172.56 (8) | H7A—C7—H7B | 109.5 |
O2—Ni1—N3 | 99.07 (7) | C6—C7—H7C | 109.5 |
N2—Ni1—O1 | 160.67 (7) | H7A—C7—H7C | 109.5 |
N4—Ni1—O1 | 95.07 (7) | H7B—C7—H7C | 109.5 |
N1—Ni1—O1 | 102.53 (7) | C6—C8—H8A | 109.5 |
O2—Ni1—O1 | 61.50 (6) | C6—C8—H8B | 109.5 |
N3—Ni1—O1 | 84.20 (7) | H8A—C8—H8B | 109.5 |
C17—O1—Ni1 | 88.63 (14) | C6—C8—H8C | 109.5 |
C17—O2—Ni1 | 90.56 (14) | H8A—C8—H8C | 109.5 |
O6—Cl1—O5 | 110.2 (4) | H8B—C8—H8C | 109.5 |
O6—Cl1—O3 | 110.1 (4) | N3—C9—C10 | 109.4 (2) |
O5—Cl1—O3 | 110.7 (4) | N3—C9—H9A | 109.8 |
O6—Cl1—O4 | 108.9 (4) | C10—C9—H9A | 109.8 |
O5—Cl1—O4 | 108.8 (4) | N3—C9—H9B | 109.8 |
O3—Cl1—O4 | 108.1 (4) | C10—C9—H9B | 109.8 |
O6'—Cl1'—O5' | 106.4 (7) | H9A—C9—H9B | 108.2 |
O6'—Cl1'—O3' | 109.6 (5) | N4—C10—C9 | 110.3 (2) |
O5'—Cl1'—O3' | 110.8 (5) | N4—C10—H10A | 109.6 |
O6'—Cl1'—O4' | 108.9 (5) | C9—C10—H10A | 109.6 |
O5'—Cl1'—O4' | 110.2 (5) | N4—C10—H10B | 109.6 |
O3'—Cl1'—O4' | 110.8 (5) | C9—C10—H10B | 109.6 |
H11—O1W—H12 | 109.4 (17) | H10A—C10—H10B | 108.1 |
C1—N1—C14 | 113.35 (19) | N4—C11—C12 | 112.5 (2) |
C1—N1—Ni1 | 104.50 (15) | N4—C11—C13 | 111.3 (2) |
C14—N1—Ni1 | 121.17 (16) | C12—C11—C13 | 109.5 (2) |
C1—N1—H1 | 101.7 (19) | N4—C11—H11A | 107.8 |
C14—N1—H1 | 105.3 (19) | C12—C11—H11A | 107.8 |
Ni1—N1—H1 | 109.1 (18) | C13—C11—H11A | 107.8 |
C2—N2—C3 | 111.5 (2) | C11—C12—H12A | 109.5 |
C2—N2—Ni1 | 105.70 (15) | C11—C12—H12B | 109.5 |
C3—N2—Ni1 | 116.01 (15) | H12A—C12—H12B | 109.5 |
C2—N2—H2 | 106 (2) | C11—C12—H12C | 109.5 |
C3—N2—H2 | 110 (2) | H12A—C12—H12C | 109.5 |
Ni1—N2—H2 | 107 (2) | H12B—C12—H12C | 109.5 |
C9—N3—C6 | 114.5 (2) | C11—C13—C14 | 117.97 (19) |
C9—N3—Ni1 | 103.96 (15) | C11—C13—H13A | 107.8 |
C6—N3—Ni1 | 121.14 (16) | C14—C13—H13A | 107.8 |
C9—N3—H3 | 105 (2) | C11—C13—H13B | 107.8 |
C6—N3—H3 | 107 (2) | C14—C13—H13B | 107.8 |
Ni1—N3—H3 | 103 (2) | H13A—C13—H13B | 107.2 |
C10—N4—C11 | 112.8 (2) | N1—C14—C15 | 107.37 (19) |
C10—N4—Ni1 | 103.81 (15) | N1—C14—C16 | 111.3 (2) |
C11—N4—Ni1 | 114.50 (15) | C15—C14—C16 | 107.4 (2) |
C10—N4—H4 | 104 (2) | N1—C14—C13 | 110.4 (2) |
C11—N4—H4 | 109 (2) | C15—C14—C13 | 111.2 (2) |
Ni1—N4—H4 | 113 (2) | C16—C14—C13 | 109.19 (19) |
C23—N5—H51 | 119 (2) | C14—C15—H15A | 109.5 |
C23—N5—H52 | 116 (2) | C14—C15—H15B | 109.5 |
H51—N5—H52 | 121 (3) | H15A—C15—H15B | 109.5 |
N1—C1—C2 | 109.5 (2) | C14—C15—H15C | 109.5 |
N1—C1—H1A | 109.8 | H15A—C15—H15C | 109.5 |
C2—C1—H1A | 109.8 | H15B—C15—H15C | 109.5 |
N1—C1—H1B | 109.8 | C14—C16—H16A | 109.5 |
C2—C1—H1B | 109.8 | C14—C16—H16B | 109.5 |
H1A—C1—H1B | 108.2 | H16A—C16—H16B | 109.5 |
N2—C2—C1 | 109.3 (2) | C14—C16—H16C | 109.5 |
N2—C2—H2A | 109.8 | H16A—C16—H16C | 109.5 |
C1—C2—H2A | 109.8 | H16B—C16—H16C | 109.5 |
N2—C2—H2B | 109.8 | O2—C17—O1 | 119.3 (2) |
C1—C2—H2B | 109.8 | O2—C17—C18 | 120.9 (2) |
H2A—C2—H2B | 108.3 | O1—C17—C18 | 119.8 (2) |
N2—C3—C5 | 110.5 (2) | C19—C18—C23 | 119.9 (2) |
N2—C3—C4 | 111.9 (2) | C19—C18—C17 | 118.9 (2) |
C5—C3—C4 | 110.0 (2) | C23—C18—C17 | 121.3 (2) |
N2—C3—H3a | 108.1 | C20—C19—C18 | 121.8 (2) |
C5—C3—H3a | 108.1 | C20—C19—H19 | 119.1 |
C4—C3—H3a | 108.1 | C18—C19—H19 | 119.1 |
C3—C4—H4A | 109.5 | C19—C20—C21 | 118.6 (2) |
C3—C4—H4B | 109.5 | C19—C20—H20 | 120.7 |
H4A—C4—H4B | 109.5 | C21—C20—H20 | 120.7 |
C3—C4—H4C | 109.5 | C22—C21—C20 | 120.7 (2) |
H4A—C4—H4C | 109.5 | C22—C21—H21 | 119.6 |
H4B—C4—H4C | 109.5 | C20—C21—H21 | 119.6 |
C3—C5—C6 | 118.7 (2) | C21—C22—C23 | 121.7 (3) |
C3—C5—H5A | 107.6 | C21—C22—H22 | 119.1 |
C6—C5—H5A | 107.6 | C23—C22—H22 | 119.1 |
C3—C5—H5B | 107.6 | N5—C23—C18 | 123.1 (2) |
C6—C5—H5B | 107.6 | N5—C23—C22 | 119.6 (2) |
H5A—C5—H5B | 107.1 | C18—C23—C22 | 117.3 (2) |
N2—Ni1—O1—C17 | −31.3 (3) | C2—N2—C3—C4 | 51.2 (3) |
N4—Ni1—O1—C17 | 171.28 (14) | Ni1—N2—C3—C4 | 172.23 (19) |
N1—Ni1—O1—C17 | 79.59 (14) | N2—C3—C5—C6 | 71.2 (3) |
O2—Ni1—O1—C17 | 0.00 (13) | C4—C3—C5—C6 | −164.7 (2) |
N3—Ni1—O1—C17 | −103.62 (14) | C9—N3—C6—C7 | 163.1 (2) |
N2—Ni1—O2—C17 | 169.89 (14) | Ni1—N3—C6—C7 | −71.0 (2) |
N4—Ni1—O2—C17 | −21.1 (2) | C9—N3—C6—C5 | −76.4 (3) |
N1—Ni1—O2—C17 | −105.97 (14) | Ni1—N3—C6—C5 | 49.4 (3) |
N3—Ni1—O2—C17 | 78.28 (15) | C9—N3—C6—C8 | 44.6 (3) |
O1—Ni1—O2—C17 | 0.00 (13) | Ni1—N3—C6—C8 | 170.46 (18) |
N2—Ni1—N1—C1 | −14.19 (16) | C3—C5—C6—N3 | −61.6 (3) |
N4—Ni1—N1—C1 | 88.57 (16) | C3—C5—C6—C7 | 56.8 (3) |
O2—Ni1—N1—C1 | −116.17 (16) | C3—C5—C6—C8 | 175.3 (2) |
O1—Ni1—N1—C1 | −176.11 (15) | C6—N3—C9—C10 | 174.1 (2) |
N2—Ni1—N1—C14 | −143.61 (18) | Ni1—N3—C9—C10 | 39.7 (2) |
N4—Ni1—N1—C14 | −40.84 (18) | C11—N4—C10—C9 | 169.1 (2) |
O2—Ni1—N1—C14 | 114.42 (17) | Ni1—N4—C10—C9 | 44.6 (2) |
O1—Ni1—N1—C14 | 54.48 (18) | N3—C9—C10—N4 | −59.9 (3) |
N4—Ni1—N2—C2 | −104.54 (16) | C10—N4—C11—C12 | 53.3 (3) |
N1—Ni1—N2—C2 | −15.15 (16) | Ni1—N4—C11—C12 | 171.73 (16) |
O2—Ni1—N2—C2 | 70.77 (16) | C10—N4—C11—C13 | 176.57 (19) |
N3—Ni1—N2—C2 | 169.98 (16) | Ni1—N4—C11—C13 | −65.0 (2) |
O1—Ni1—N2—C2 | 98.6 (2) | N4—C11—C13—C14 | 71.8 (3) |
N4—Ni1—N2—C3 | 131.31 (17) | C12—C11—C13—C14 | −163.2 (2) |
N1—Ni1—N2—C3 | −139.30 (18) | C1—N1—C14—C15 | 163.3 (2) |
O2—Ni1—N2—C3 | −53.38 (18) | Ni1—N1—C14—C15 | −71.2 (2) |
N3—Ni1—N2—C3 | 45.83 (18) | C1—N1—C14—C16 | 46.1 (3) |
O1—Ni1—N2—C3 | −25.6 (3) | Ni1—N1—C14—C16 | 171.49 (16) |
N2—Ni1—N3—C9 | 90.51 (16) | C1—N1—C14—C13 | −75.4 (2) |
N4—Ni1—N3—C9 | −12.31 (16) | Ni1—N1—C14—C13 | 50.1 (2) |
O2—Ni1—N3—C9 | −167.74 (16) | C11—C13—C14—N1 | −61.3 (3) |
O1—Ni1—N3—C9 | −107.87 (16) | C11—C13—C14—C15 | 57.7 (3) |
N2—Ni1—N3—C6 | −40.04 (18) | C11—C13—C14—C16 | 176.0 (2) |
N4—Ni1—N3—C6 | −142.86 (18) | Ni1—O2—C17—O1 | 0.0 (2) |
O2—Ni1—N3—C6 | 61.70 (18) | Ni1—O2—C17—C18 | 179.87 (19) |
O1—Ni1—N3—C6 | 121.58 (18) | Ni1—O1—C17—O2 | 0.0 (2) |
N2—Ni1—N4—C10 | −105.88 (17) | Ni1—O1—C17—C18 | −179.88 (19) |
N1—Ni1—N4—C10 | 169.26 (17) | O2—C17—C18—C19 | 155.0 (2) |
O2—Ni1—N4—C10 | 85.1 (2) | O1—C17—C18—C19 | −25.2 (3) |
N3—Ni1—N4—C10 | −17.14 (17) | O2—C17—C18—C23 | −26.9 (3) |
O1—Ni1—N4—C10 | 66.63 (17) | O1—C17—C18—C23 | 152.9 (2) |
N2—Ni1—N4—C11 | 130.71 (15) | C23—C18—C19—C20 | 0.8 (4) |
N1—Ni1—N4—C11 | 45.86 (16) | C17—C18—C19—C20 | 178.9 (2) |
O2—Ni1—N4—C11 | −38.3 (3) | C18—C19—C20—C21 | −2.2 (4) |
N3—Ni1—N4—C11 | −140.55 (16) | C19—C20—C21—C22 | 1.7 (4) |
O1—Ni1—N4—C11 | −56.77 (16) | C20—C21—C22—C23 | 0.3 (4) |
C14—N1—C1—C2 | 175.3 (2) | C19—C18—C23—N5 | −178.1 (2) |
Ni1—N1—C1—C2 | 41.4 (2) | C17—C18—C23—N5 | 3.8 (4) |
C3—N2—C2—C1 | 169.3 (2) | C19—C18—C23—C22 | 1.1 (3) |
Ni1—N2—C2—C1 | 42.4 (2) | C17—C18—C23—C22 | −176.9 (2) |
N1—C1—C2—N2 | −58.6 (3) | C21—C22—C23—N5 | 177.6 (2) |
C2—N2—C3—C5 | 174.1 (2) | C21—C22—C23—C18 | −1.7 (4) |
Ni1—N2—C3—C5 | −64.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1wi | 0.86 (2) | 2.15 (2) | 2.995 (3) | 166 (2) |
N2—H2···O5ii | 0.86 (2) | 2.56 (2) | 3.304 (8) | 147 (2) |
N2—H2···O5′ii | 0.86 (2) | 2.35 (2) | 3.125 (11) | 150 (3) |
N3—H3···O1 | 0.86 (2) | 2.49 (3) | 2.885 (3) | 109 (2) |
N4—H4···O6ii | 0.86 (3) | 2.61 (2) | 3.343 (6) | 145 (3) |
N4—H4···O6′ii | 0.86 (3) | 2.40 (2) | 3.195 (6) | 155 (3) |
N5—H51···O2 | 0.85 (3) | 2.13 (3) | 2.751 (3) | 129 (2) |
N5—H52···O4′i | 0.85 (1) | 2.32 (1) | 3.155 (6) | 168 (3) |
O1w—H11···O1 | 0.84 (2) | 1.96 (2) | 2.795 (2) | 172 (3) |
O1w—H12···O3 | 0.83 (2) | 2.26 (2) | 3.077 (9) | 167 (3) |
O1w—H12···O3′ | 0.83 (2) | 2.09 (2) | 2.890 (9) | 160 (3) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C7H6NO2)(C16H36N4)]ClO4·H2O |
Mr | 596.79 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 110 |
a, b, c (Å) | 9.6452 (5), 21.5350 (11), 13.5083 (7) |
β (°) | 90.784 (1) |
V (Å3) | 2805.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.84 |
Crystal size (mm) | 0.45 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.818, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6638, 3832, 3667 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.064, 1.08 |
No. of reflections | 3832 |
No. of parameters | 410 |
No. of restraints | 142 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Absolute structure | Flack (1983), 874 Friedel pairs |
Absolute structure parameter | −0.012 (9) |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Ni1—N1 | 2.124 (2) | Ni1—N4 | 2.087 (2) |
Ni1—N2 | 2.084 (2) | Ni1—O1 | 2.1659 (17) |
Ni1—N3 | 2.138 (2) | Ni1—O2 | 2.1280 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1wi | 0.86 (2) | 2.15 (2) | 2.995 (3) | 166 (2) |
N2—H2···O5'ii | 0.86 (2) | 2.35 (2) | 3.125 (11) | 150 (3) |
N3—H3···O1 | 0.86 (2) | 2.49 (3) | 2.885 (3) | 109 (2) |
N4—H4···O6'ii | 0.86 (3) | 2.399 (17) | 3.195 (6) | 155 (3) |
N5—H51···O2 | 0.85 (3) | 2.13 (3) | 2.751 (3) | 129 (2) |
N5—H52···O4'i | 0.85 (1) | 2.316 (14) | 3.155 (6) | 168 (3) |
O1w—H11···O1 | 0.843 (17) | 1.958 (16) | 2.795 (2) | 172 (3) |
O1w—H12···O3 | 0.83 (2) | 2.26 (2) | 3.077 (9) | 167 (3) |
O1w—H12···O3' | 0.83 (2) | 2.094 (18) | 2.890 (9) | 160 (3) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x−1/2, −y+1/2, z+1/2. |
Acknowledgements
We thank the Key Subject Construction Project of Hunan Province (No. 2006–180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023, 05 C736), the NSF of Hunan Province (09 J J3028) and the University of Malaya for supporting this study.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ou, G.-C., Zhang, M. & Yuan, X.-Y. (2008a). Acta Cryst. E64, m1010. Web of Science CrossRef IUCr Journals Google Scholar
Ou, G.-C., Zhang, M., Yuan, X.-Y. & Dai, Y.-Q. (2008b). Acta Cryst. E64, m1588. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Previous studies on (5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel benzoate perchlorate salts have documented a chelating mode for the carboxylate ion. The perchlorate counterion is not directly involved in coordination but forms hydrogen bonds with the amino portions of the macrocycle (Ou et al., 2008a, 2008b). The title substituted benzoate has an additional amino unit that also engages in hydrogen bonding. In the salt, [Ni(C16H36N4)(C7H6NO2)][ClO4].H2O (Scheme I, Fig. 1), the metal atom is O,O'-chelated by the carboxylate anion and N,N',N'',N'''-chelated by the macrocycle to confer an octahedral geometry to the metal center. The cation, anion and lattice water molecules are linked by N–H···O and O–H···O hydrogen bonds into a three-dimensional network.