A no el zinc(II) complex wi h he ligand
2,2000,2000000-(1,4,7- iazanonane-1,4,7- iyl)-
iace a e (NOTA)
I ia Pe ei a-Ga cı
´a, Alejand o Macı
´as,* Ru ina Bas ida
and Lau a Valencia
Depa amen o de Quı
´mica Ino ga
´nica, Facul ade de Quı
´mica, A d. das Ciencias s/n,
Uni e sidade de San iago de Compos ela, 15706-San iago de Compos ela, A
Co un
˜a, Galicia, Spain
Co espondence e-mail: alejand oalbe o.ma[email p o ec ed]
Recei ed 20 Oc obe 2008; accep ed 9 Decembe 2008
Key indica o s: single-c ys al X- ay s udy; T= 100 K; mean (C–C) = 0.005 A
˚;
R ac o = 0.039; wR ac o = 0.084; da a- o-pa ame e a io = 16.6.
The zinc(II) complex wi h NOTA [2,20,200-(1,4,7- iazanonane-
1,4,7- iyl) iace a e] has p e iously been syn hesized and
s udied in solu ion, bu was no isola ed. The co esponding
i le Zn
II
complex pen asodium(I) bis{[2,20,200-(1,4,7- iazano-
nane-1,4,7- iyl) iace a o]zinc(II)} is(pe chlo a e) me hanol
sol a e, Na
5
[Zn(C
12
H
18
N
3
O
6
)]
2
(ClO
4
)
3
CH
3
OH, was c ys al-
lized as a sodium pe chlo a e double sal in me hanol solu ion.
The asymme ic uni con ains wo independen [Zn(NOTA)]
complex anion en i ies, i e sodium ca ions, h ee pe chlo a e
anions and a me hanol sol en molecule. The wo Zn
II
ca ions
exhibi a dis o ed igonal-p isma ic N
3
O
3
coo dina ion wi h
a bi acial a angemen o he dono a oms. Nei he he
me hanol sol en molecule no he pe chlo a e anions appea
o be coo dina ed o he Zn cen es. The c ys al s uc u e
shows a laye a angemen pa allel o (001) gene a ed by
in e ac ions be ween he [Zn(NOTA)]
uni s, he Na
+
ca ions,
wo ClO
4
uni s and he me hanole molecule, leading o an
o e all laye composi ion o [Na
5
[Zn(C
12
H
18
N
3
O
6
)]
2
(ClO
4
)
2.
-
CH
3
OH]
+
. The hi d ClO
4
anion is isola ed and si ua ed
be ween he laye s wi hou any signi ican in e ac ions.
Rela ed li e a u e
De ails on he syn hesis o NOTA a e gi en by Des eux
(1980). Fo NOTA complexes o Al, C , Fe, Co, Ni, Cu, Ga and
In cha ac e ized by X- ay di ac ion s udies, see: Boeyens &
Van de Me we (1997); Bossek e al. (1995); Cla ke & Ma ell
(1991); C aig e al. (1989); Jyo e al. (1990); Van de Me we e
al. (1983, 1985); Moo e e al. (1990); Wiegha d e al. (1982).
Fo gene al backg ound, see: Ge aldes e al. (1985).
Expe imen al
C ys al da a
Na
5
[Zn(C
12
H
18
N
3
O
6
)]
2
(ClO
4
)
3
-
CH
4
O
M
= 1176.67
O ho hombic, Pna21
a= 16.8879 (5) A
˚
b= 9.4723 (3) A
˚
c= 26.4552 (9) A
˚
V= 4232.0 (2) A
˚
3
Z=4
Mo K adia ion
= 1.47 mm
1
T= 100 (2) K
0.22 0.10 0.10 mm
Da a collec ion
B uke APEXII CCD
di ac ome e
Abso p ion co ec ion: mul i-scan
(SADABS; Sheld ick, 1996)
T
min
= 0.738, T
max
= 0.867
31309 measu ed e lec ions
9954 independen e lec ions
8605 e lec ions wi h I>2(I)
R
in
= 0.036
Re inemen
R[F
2
>2(F
2
)] = 0.039
wR(F
2
) = 0.084
S= 1.07
9954 e lec ions
601 pa ame e s
1 es ain
H a oms ea ed by a mix u e o
independen and cons ained
e inemen
max
= 0.56 e A
˚
3
min
=0.58 e A
˚
3
Absolu e s uc u e: Flack (1983),
4585 F iedel pai s
Flack pa ame e : 0.383 (7)
Table 1
Selec ed bond leng hs (A
˚).
Zn1—O5 2.027 (3)
Zn1—O1 2.062 (2)
Zn1—O3 2.066 (2)
Zn1—N2 2.160 (3)
Zn1—N3 2.172 (3)
Zn1—N1 2.189 (3)
Zn2—O23 2.047 (3)
Zn2—O21 2.057 (3)
Zn2—O25 2.072 (3)
Zn2—N22 2.198 (3)
Zn2—N21 2.201 (3)
Zn2—N23 2.201 (3)
Da a collec ion: APEX2 (B uke , 2005); cell e inemen : APEX2;
da a educ ion: SHELXTL (Sheld ick, 2008); p og am(s) used o
sol e s uc u e: SIR92 (Al oma e e al., 1993); p og am(s) used o
e ine s uc u e: SHELXL97 (Sheld ick, 2008); molecula g aphics:
ORTEP-3 o Windows (Fa ugia, 1997); so wa e used o p epa e
ma e ial o publica ion: WinGX (Fa ugia, 1999).
We hank he Xun a de Galicia (Spain; P ojec
PGIDIT07PXIB209039PR) o inancial suppo . The X- ay
da a we e collec ed a he Unidade de Raios X, RIAIDT,
Uni e si y o San iago de Compos ela, Spain.
me al-o ganic compounds
m84 Pe ei a-Ga cı
´ae al. doi:10.1107/S1600536808041895 Ac a C ys . (2009). E65, m84–m85
Ac a C ys allog aphica Sec ion E
S uc u e Repo s
Online
ISSN 1600-5368
Supplemen a y da a and igu es o his pape a e a ailable om he
IUC elec onic a chi es (Re e ence: WM2202).
Re e ences
Al oma e, A., Casca ano, G., Giaco azzo, C. & Guaglia di, A. (1993). J. Appl.
C ys . 26, 343–350.
Boeyens, J. C. A. & Van de Me we, M. J. (1997). Ino g. Chem. 36, 3779–3780.
Bossek, U., Hanke, D., Wiegha d , K. & Nube , B. (1995). Polyhed on,12, 1–5.
B uke (2005). APEX2. B uke AXS Inc., Madison, Wisconsin, USA.
Cla ke, E. T. & Ma ell, A. E. (1991). Ino g. Chim. Ac a,181, 273–280.
C aig, A. S., Helps, I. M., Pa ke , D., Fe guson, G., Bailey, N. A., Smi h, J. A. S.,
Adams, H. & Williams, M. (1989). Polyhed on,8, 2481–2484.
Des eux, J. F. (1980). Ino g. Chem. 19, 1319–1324.
Fa ugia, L. J. (1997). J. Appl. C ys . 30, 565.
Fa ugia, L. J. (1999). J. Appl. C ys . 32, 837–838.
Flack, H. D. (1983). Ac a C ys . A39, 876–881.
Ge aldes, C. F. G. C., Alpoim, M. C., Ma ques, M. P. M., She y, A. D. & Singh,
M. (1985). Ino g. Chem. 24, 3876–3881.
Jyo, A., Kohno, Y., Te azono, Y. & Kawano, S. (1990). Anal. Sci. 6, 629–631.
Moo e, D. A., Fanwick, P. E. & Welch, M. J. (1990). Ino g. Chem. 29, 672–676.
Sheld ick, G. M. (1996). SADABS. Uni e si y o Go
¨ ingen, Ge many.
Sheld ick, G. M. (2008). Ac a C ys . A64, 112–122.
Van de Me we, M. J., Boeyens, J. C. A. & Hancock, R. D. (1983). Ino g. Chem.
22, 3490–3491.
Van de Me we, M. J., Boeyens, J. C. A. & Hancock, R. D. (1985). Ino g. Chem.
24, 1208–1213.
Wiegha d , K., Bossek, U., Chaudhu i, P., He mann, W., Menke, B. C. &
Weiss, J. (1982). Ino g. Chem. 21, 4308–4314.
me al-o ganic compounds
Ac a C ys . (2009). E65, m84–m85 Pe ei a-Ga cı
´ae al. Na
5
[Zn(C
12
H
18
N
3
O
6
)]
2
(ClO
4
)
3
CH
4
Om85
suppo ing in o ma ion
sup-1
Ac a C ys . (2009). E65, m84–m85
suppo ing in o ma ion
Ac a C ys . (2009). E65, m84–m85 [doi:10.1107/S1600536808041895]
A no el zinc(II) complex wi h he ligand 2,2′,2′′-(1,4,7- iazanonane-1,4,7-
iyl) iace a e (NOTA)
I ia Pe ei a-Ga cía, Alejand o Macías, Ru ina Bas ida and Lau a Valencia
S1. Commen
NOTA (1,4,7- iazacyclononane-N, N′, N′′- iace a e) has a well-known p e e ence o small me al ions, and many me al
NOTA complexes (M = Al, C , Fe, Co, Ni, Cu, Ga and In) ha e been s uc u ally cha ac e ized: (Boeyens & Van de
Me we, 1997; Bossek e al., 1995; Cla ke & Ma ell, 1991; C aig e al., 1989; Jyo e al., 1990; Van de Me we e al.,
1983, 1985; Moo e e al., 1990; Wiegha d e al., 1982).
Ou s a ing objec i e was he syn hesis o NOTA (1,4,7- iazacyclononane-N,N′,N′′- iace a e) complexes in aqueous
solu ions and i s isola ion as sal s o he ype [X][M(NOTA)], whe e X+ is a mono alen ca ion and M is ZnII o Cd(II). We
also de eloped a species dis ibu ion diag am o NOTA complexes in aqueous solu ion based on he expe imen al da a
ob ained by Ge aldes e al. (1985). F om hese expe imen s we concluded ha he anionic sal s [Zn(NOTA)]- and
[Cd(NOTA)]-, due o hei ex eme solubili y in aqueous solu ion, do no p ecipi a e as nei he sodium no he alkyl-
ammonium sal s. These di icul ies o isola ing he complexes led us o syn hesize he ZnII and Cd(II) NOTA complexes
in me hanol, a sol en in which he sodium sal s a e less soluble han in aqueous solu ion. A ZnII complex wi h a 1:1
composi ion was p epa ed by eac ion o he NOTA ligand L wi h hyd ous ZnII pe chlo a e in a 1:1 mola a io o
me al:ligand. This complex was syn hesized by a single-s ep p ocedu e as desc ibed and he eac ion e ealed a pu e
p oduc ha was also cha ac e ized by ESI-MS and 1H-NMR spec oscopy.
The molecula s uc u e o he complex en i y [Zn(NOTA)]- and selec ed bond leng hs (Å) and angles (°) o he
coo dina ion en i onmen o ZnII a e gi en in Fig. 1 and Table 1, espec i ely. The asymme ic uni con ains wo
independen mononuclea complex [Zn(NOTA)]- en i ies, i e sodium ca ions, h ee pe chlo a e anions and a me hanol
sol en molecule. The coo dina ion en i onmen , dis ances and angles o bo h independen [Zn(NOTA)]- molecules a e
simila . When he me al cen e coo dina ion equi emen s do no a ou an oc ahed al en i onmen , he me al co e
geome y in NOTA complexes is igonal-p isma ic (Wiegha d e al., 1982). Thus, he ZnII cen es p esen a six-
coo dina ed N3O3 co e in a dis o ed igonal-p isma ic a angemen . Each Zn a om is bound o h ee N a oms om he
mac ocyclic backbone and h ee O a oms om he pendan -a ms. Like in all he o he known s uc u es o NOTA
complexes, in he [Zn(NOTA)]- en i ies he dono a oms a e disposed in a bi acial a angemen . Th ee N a oms occupy
one acial plane o he p ism, and h ee O a oms belong o he o he plane. The a e age Zn—N and Zn—O bond leng hs
a e 2.187 Å and 2.055 Å, espec i ely. These bond leng hs a e in he ange ound o M–N and M–O bonds in o he
NOTA complexes wi h di alen ansi ion me als.
The c ys al s uc u e shows a laye a angemen pa allel (001) gene a ed by in e ac ions be ween he [Zn(NOTA)]- uni s,
he Na+ ca ions, wo ClO4- uni s and he me hanol molecule, leading o an o e all laye composi ion o
[Na5[Zn(C12H18N3O6)]2(ClO4)2.CH3OH]+. The hi d ClO4 anion is isola ed and si ua ed be ween he laye s wi hou any
signi ican in e ac ions (Fig. 2).
suppo ing in o ma ion
sup-2
Ac a C ys . (2009). E65, m84–m85
S2. Expe imen al
Syn hesis o he mac ocycle NOTAH3: The ligand NOTA was p epa ed om i s iazamac ocycle p ecu so TACN by
alkyla ion wi h b omoace ic acid using a modi ica ion o a p e iously epo ed me hod (Des eux, 1980). TACN and
NaOH we e dissol ed in wa e , and o he solu ion was added a b omoace ic acid/ NaOH aqueous solu ion a 273 K. The
eac ion mix u e empe a u e was aised o 323 K, and a NaOH aqueous solu ion was added. The mix u e was main ained
a 323 K unde s i ing o 5 d. Then, concen a ed hyd ob omic acid was added un il a pH o ~ 7 was eached. NOTAH3
does no p ecipi a e om aqueous solu ions in a well-de ined s a e, hus a pu i ica ion s age was needed. A e a liquid-
liquid ex ac ion wi h n-bu anol, a whi e powde cha ac e ized as a sal o he expec ed ligand was inally ob ained.
C12H21N3O6.(CH2B COOH)3:MS (ESI, m/z) 304 [H(LH3)]+, 326 {Na(LH3)]}+, 348 [Na2(LH2)]+; 1H NMR da a: (250 MHz,
D2O, SiMe4): d 3.5 (s, 12 H om –CH2– in he ing), d 3.9 (s, 6 H om CH2B COOH), d 4.3 (s, 6 H om –CH2– in
pendan s).
Syn hesis o he me al complexes: Hyd a ed zinc pe chlo a e was added o a solu ion o he pu i ied ligand NOTAH3 in
me hanol. The eac ion mix u e was hea ed and hen cooled. A concen a ed NaOH me hanolic solu ion was added un il a
pH o 7 was eached. Single c ys als we e ob ained by he di usion apou -phase c ys alliza ion me hod in a MeOH/E 2O
sol en sys em. The ZnII complex was cha ac e ized by ESI-MS, 1HNMR, COSY NMR and X- ay di ac ion.
Na[ZnL]1.5(NaClO4).0.5MeOH: MS(ESI, m/z) 366 [Zn(LH2)]+, 388 {Na[Zn(LH)]}+. Colou : colou less.
The co esponden Cd(II) complex was also ob ained in me hanolic solu ion, bu i has no been isola ed in c ys alline
o m.
S3. Re inemen
The absolu e s uc u e pa ame e was e ined (Flack, 1983) and poin s o acemic winning, wi h a a io o he win
ac ions o app oxima ely 3:2. The hyd ogen a oms a ached o he ca bon a oms we e loca ed in hei calcula ed
posi ions and e ined using a iding model wi h U(H) equal o 1.2× Ueq (1.5 o me hyl g oups) o he pa en a om and C
—H= 0.97 Å. The hyd ogen a om a ached o he oxygen a om in he me hanol molecule was localized in a Fou ie map
and e ined wi h Uiso cons ained o be 1.5 × Ueq o he O a om.
suppo ing in o ma ion
sup-3
Ac a C ys . (2009). E65, m84–m85
Figu e 1
The molecula s uc u e o one [Zn(NOTA)]- complex wi h a om labelling and displacemen ellipsoids d awn a he 50%
p obabili y le el. The s uc u e o he second [Zn(NOTA)]- en i y is e y simila .
suppo ing in o ma ion
sup-4
Ac a C ys . (2009). E65, m84–m85
Figu e 2
The c ys al s uc u e o he i le compound in a p ojec ion along [010], emphasizing he laye a angemen pa allel (001)
as gene a ed by in e ac ions be ween he [Zn(NOTA)]- uni s, he Na+ ca ions, wo ClO4- uni s and he me hanol molecule.
The hi d ClO4 anion is isola ed and si ua ed be ween he laye s wi hou any signi ican in e ac ions.
pen asodium(I) bis[(1,4,7- iazacyclononane-N,N′,N′′- iace a o)zinc(II)] is(pe chlo a e) me hanol sol a e
C ys al da a
Na5[Zn(C12H18N3O6)]2(ClO4)3·CH4O
M = 1176.67
O ho hombic, Pna21
Hall symbol: P 2c -2n
a = 16.8879 (5) Å
b = 9.4723 (3) Å
c = 26.4552 (9) Å
V = 4232.0 (2) Å3
Z = 4
F(000) = 2392
Dx = 1.847 Mg m−3
Mo Kα adia ion, λ = 0.71073 Å
Cell pa ame e s om 9827 e lec ions
θ = 2.4–27.7°
µ = 1.47 mm−1
T = 100 K
P ism, colou less
0.22 × 0.10 × 0.10 mm
Da a collec ion
B uke APEXII CCD
di ac ome e
Radia ion sou ce: ine- ocus sealed ube
G aphi e monoch oma o
ω and φ scans
Abso p ion co ec ion: mul i-scan
(SADABS; Sheld ick, 1996)
Tmin = 0.738, Tmax = 0.867
31309 measu ed e lec ions
9954 independen e lec ions
8605 e lec ions wi h I > 2σ(I)
Rin = 0.036
θmax = 28.3°, θmin = 1.5°
h = −21→22
k = −12→12
l = −35→32
suppo ing in o ma ion
sup-5
Ac a C ys . (2009). E65, m84–m85
Re inemen
Re inemen on F2
Leas -squa es ma ix: ull
R[F2 > 2σ(F2)] = 0.039
wR(F2) = 0.084
S = 1.07
9954 e lec ions
601 pa ame e s
1 es ain
P ima y a om si e loca ion: s uc u e-in a ian
di ec me hods
Seconda y a om si e loca ion: di e ence Fou ie
map
Hyd ogen si e loca ion: in e ed om
neighbou ing si es
H a oms ea ed by a mix u e o independen
and cons ained e inemen
w = 1/[σ2(Fo2) + (0.0392P)2 + 1.4688P]
whe e P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.56 e Å−3
Δρmin = −0.58 e Å−3
Ex inc ion co ec ion: SHELXL97 (Sheld ick,
2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Ex inc ion coe icien : 0.00024 (8)
Absolu e s uc u e: Flack (1983), 4585 F iedel
pai s
Absolu e s uc u e pa ame e : 0.383 (7)
Special de ails
Geome y. All esds (excep he esd in he dihed al angle be ween wo l.s. planes) a e es ima ed using he ull co a iance
ma ix. The cell esds a e aken in o accoun indi idually in he es ima ion o esds in dis ances, angles and o sion angles;
co ela ions be ween esds in cell pa ame e s a e only used when hey a e de ined by c ys al symme y. An app oxima e
(iso opic) ea men o cell esds is used o es ima ing esds in ol ing l.s. planes.
Re inemen . Re inemen o F2 agains ALL e lec ions. The weigh ed R- ac o wR and goodness o i S a e based on F2,
con en ional R- ac o s R a e based on F, wi h F se o ze o o nega i e F2. The h eshold exp ession o F2 > σ(F2) is used
only o calcula ing R- ac o s(g ) e c. and is no ele an o he choice o e lec ions o e inemen . R- ac o s based on F2
a e s a is ically abou wice as la ge as hose based on F, and R- ac o s based on ALL da a will be e en la ge .
F ac ional a omic coo dina es and iso opic o equi alen iso opic displacemen pa ame e s (Å2)
xy z U
iso*/Ueq
Zn1 1.07460 (2) 0.01616 (4) 0.917626 (16) 0.00860 (9)
N1 1.12568 (18) −0.1518 (3) 0.96418 (12) 0.0120 (7)
N2 1.12185 (18) 0.1482 (3) 0.97696 (12) 0.0118 (7)
N3 0.97800 (19) −0.0083 (3) 0.97112 (12) 0.0129 (7)
O1 1.16120 (14) −0.0640 (3) 0.87080 (10) 0.0118 (5)
O2 1.21023 (15) −0.2696 (3) 0.84582 (10) 0.0149 (6)
O3 1.08723 (14) 0.2045 (3) 0.87911 (10) 0.0109 (5)
O4 1.14849 (15) 0.4106 (3) 0.88043 (10) 0.0138 (6)
O5 0.98658 (14) −0.0531 (3) 0.87180 (10) 0.0127 (6)
O6 0.85724 (14) −0.0775 (3) 0.86305 (10) 0.0134 (6)
C1 1.1941 (2) −0.0791 (4) 0.98715 (16) 0.0161 (8)
H1A 1.2341 −0.0596 0.9607 0.019*
H1B 1.2187 −0.1417 1.0127 0.019*
C2 1.1699 (2) 0.0601 (4) 1.01240 (15) 0.0174 (8)
H2A 1.1386 0.0398 1.0432 0.021*
H2B 1.2179 0.1128 1.0226 0.021*
C3 1.0484 (2) 0.2058 (4) 1.00086 (15) 0.0134 (8)
H3A 1.0233 0.2739 0.9774 0.016*
H3B 1.0629 0.2573 1.0321 0.016*
C4 0.9891 (2) 0.0898 (4) 1.01387 (15) 0.0169 (9)
H4A 1.0082 0.0367 1.0437 0.020*
H4B 0.9376 0.1332 1.0227 0.020*
suppo ing in o ma ion
sup-6
Ac a C ys . (2009). E65, m84–m85
C5 0.9838 (2) −0.1590 (4) 0.98620 (15) 0.0157 (8)
H5A 0.9663 −0.2188 0.9576 0.019*
H5B 0.9474 −0.1764 1.0149 0.019*
C6 1.0663 (2) −0.2020 (4) 1.00137 (14) 0.0156 (8)
H6A 1.0787 −0.1621 1.0350 0.019*
H6B 1.0692 −0.3061 1.0039 0.019*
C7 1.1508 (2) −0.2609 (4) 0.92774 (14) 0.0152 (8)
H7A 1.1064 −0.3272 0.9217 0.018*
H7B 1.1955 −0.3151 0.9421 0.018*
C8 1.1760 (2) −0.1946 (4) 0.87764 (14) 0.0095 (7)
C9 1.1674 (2) 0.2606 (4) 0.95153 (14) 0.0140 (8)
H9A 1.2228 0.2292 0.9470 0.017*
H9B 1.1678 0.3460 0.9731 0.017*
C10 1.1323 (2) 0.2972 (4) 0.90042 (14) 0.0107 (8)
C11 0.9056 (2) 0.0144 (4) 0.94157 (15) 0.0128 (8)
H11A 0.8936 0.1166 0.9399 0.015*
H11B 0.8605 −0.0336 0.9582 0.015*
C12 0.9163 (2) −0.0434 (4) 0.88855 (15) 0.0120 (8)
Zn2 0.60272 (2) 0.05820 (4) 0.708125 (16) 0.00988 (9)
N21 0.53471 (18) −0.0972 (3) 0.66409 (11) 0.0111 (7)
N22 0.68311 (18) 0.0323 (3) 0.64345 (12) 0.0137 (7)
N23 0.54514 (19) 0.2003 (3) 0.65352 (12) 0.0141 (7)
O21 0.52931 (15) −0.0254 (3) 0.76249 (10) 0.0134 (6)
O22 0.45361 (15) −0.2103 (3) 0.78197 (10) 0.0168 (6)
O23 0.70301 (16) −0.0144 (3) 0.74292 (10) 0.0160 (6)
O24 0.83384 (17) −0.0339 (3) 0.73661 (12) 0.0267 (7)
O25 0.60456 (15) 0.2484 (3) 0.74679 (10) 0.0142 (6)
O26 0.55583 (15) 0.4664 (3) 0.74935 (10) 0.0145 (6)
C21 0.5825 (2) −0.1491 (4) 0.62115 (14) 0.0129 (8)
H21A 0.5636 −0.1044 0.5895 0.015*
H21B 0.5754 −0.2524 0.6178 0.015*
C22 0.6700 (2) −0.1160 (4) 0.62845 (16) 0.0162 (8)
H22A 0.6920 −0.1791 0.6548 0.019*
H22B 0.6986 −0.1350 0.5965 0.019*
C23 0.6640 (2) 0.1362 (4) 0.60296 (15) 0.0161 (8)
H23A 0.6354 0.0882 0.5752 0.019*
H23B 0.7136 0.1761 0.5891 0.019*
C24 0.6130 (2) 0.2540 (4) 0.62434 (16) 0.0160 (8)
H24A 0.6460 0.3145 0.6465 0.019*
H24B 0.5933 0.3132 0.5962 0.019*
C25 0.4863 (2) 0.1230 (4) 0.62259 (15) 0.0151 (8)
H25A 0.5090 0.1028 0.5888 0.018*
H25B 0.4386 0.1823 0.6179 0.018*
C26 0.4633 (2) −0.0149 (4) 0.64821 (15) 0.0132 (8)
H26A 0.4303 0.0058 0.6783 0.016*
H26B 0.4312 −0.0725 0.6246 0.016*
C27 0.5128 (2) −0.2061 (4) 0.70054 (15) 0.0145 (8)
H27A 0.5563 −0.2757 0.7034 0.017*
suppo ing in o ma ion
sup-7
Ac a C ys . (2009). E65, m84–m85
H27B 0.4650 −0.2564 0.6884 0.017*
C28 0.4961 (2) −0.1420 (4) 0.75278 (14) 0.0121 (8)
C29 0.7628 (2) 0.0498 (4) 0.66439 (15) 0.0175 (9)
H29A 0.7774 0.1510 0.6637 0.021*
H29B 0.8013 −0.0023 0.6432 0.021*
C30 0.7672 (2) −0.0043 (4) 0.71825 (16) 0.0165 (9)
C31 0.5101 (2) 0.3140 (4) 0.68376 (14) 0.0140 (8)
H31A 0.4565 0.2856 0.6950 0.017*
H31B 0.5048 0.3998 0.6627 0.017*
C32 0.5604 (2) 0.3469 (4) 0.72938 (15) 0.0140 (8)
Cl1P 0.90733 (6) 0.49270 (10) 0.94241 (4) 0.0164 (2)
Cl2P 0.76010 (6) 0.50986 (10) 0.57365 (4) 0.0207 (2)
Cl3P 0.85405 (6) 0.29914 (10) 0.79612 (4) 0.0198 (2)
O1P 0.87409 (16) 0.4307 (3) 0.81979 (11) 0.0225 (7)
O2P 0.78137 (15) 0.2457 (3) 0.81750 (11) 0.0215 (7)
O3P 0.91798 (15) 0.2025 (3) 0.80605 (11) 0.0199 (6)
O4P 0.84347 (19) 0.3166 (3) 0.74240 (12) 0.0322 (8)
O5P 0.98116 (16) 0.4732 (3) 0.91612 (13) 0.0264 (7)
O6P 0.92441 (19) 0.5250 (3) 0.99436 (12) 0.0300 (8)
O7P 0.86528 (16) 0.6093 (3) 0.91977 (11) 0.0196 (6)
O8P 0.86005 (19) 0.3672 (3) 0.93927 (13) 0.0326 (8)
O9P 0.81100 (17) 0.6321 (3) 0.57245 (13) 0.0307 (7)
O10P 0.7577 (3) 0.4429 (4) 0.52517 (14) 0.0578 (12)
O11P 0.68191 (19) 0.5555 (3) 0.58564 (16) 0.0445 (10)
O12P 0.78848 (18) 0.4105 (3) 0.61010 (12) 0.0303 (8)
C1S 0.7491 (3) 0.6009 (5) 0.71492 (18) 0.0350 (12)
H1S1 0.7719 0.5133 0.7016 0.053*
H1S2 0.7837 0.6804 0.7064 0.053*
H1S3 0.6967 0.6160 0.6999 0.053*
O1S 0.74181 (18) 0.5907 (3) 0.76745 (11) 0.0238 (7)
H1S 0.708 (3) 0.650 (5) 0.7779 (19) 0.036*
Na1 0.94165 (8) 0.95334 (15) 0.78618 (6) 0.0129 (3)
Na2 0.84425 (8) 0.67402 (15) 0.83292 (6) 0.0180 (3)
Na3 0.52011 (8) 0.11140 (16) 0.83393 (6) 0.0175 (3)
Na4 0.66600 (9) 0.40410 (15) 0.80596 (6) 0.0146 (3)
Na5 0.74113 (8) −0.00225 (14) 0.82877 (6) 0.0121 (3)
A omic displacemen pa ame e s (Å2)
U11 U22 U33 U12 U13 U23
Zn1 0.00958 (19) 0.00826 (19) 0.0080 (2) −0.00044 (15) −0.00002 (19) −0.00020 (19)
N1 0.0161 (16) 0.0096 (15) 0.0102 (16) −0.0003 (12) −0.0014 (13) −0.0001 (13)
N2 0.0135 (16) 0.0102 (16) 0.0117 (16) −0.0013 (12) −0.0008 (13) −0.0011 (13)
N3 0.0172 (18) 0.0110 (16) 0.0106 (16) −0.0007 (12) 0.0024 (14) −0.0027 (13)
O1 0.0138 (13) 0.0109 (13) 0.0106 (13) 0.0039 (10) 0.0041 (11) 0.0003 (11)
O2 0.0156 (14) 0.0128 (14) 0.0164 (14) 0.0043 (10) 0.0033 (12) −0.0003 (11)
O3 0.0119 (13) 0.0117 (13) 0.0092 (13) −0.0018 (10) −0.0016 (11) 0.0001 (11)
O4 0.0160 (14) 0.0092 (13) 0.0162 (14) −0.0019 (10) 0.0031 (11) 0.0019 (11)
suppo ing in o ma ion
sup-14
Ac a C ys . (2009). E65, m84–m85
O21—Zn2—N21 78.35 (11) O4i —Na3—O3Pi 141.14 (10)
O25—Zn2—N21 148.30 (11) O1Pi —Na3—O3Pi 53.95 (9)
N22—Zn2—N21 80.53 (11) O21—Na3—C10i 131.52 (12)
O23—Zn2—N23 150.03 (12) O3i —Na3—C10i 28.26 (9)
O21—Zn2—N23 115.34 (11) O5Pi —Na3—C10i 73.33 (11)
O25—Zn2—N23 78.41 (11) O4i —Na3—C10i 26.73 (9)
N22—Zn2—N23 80.23 (12) O1Pi —Na3—C10i 145.51 (12)
N21—Zn2—N23 80.27 (12) O3Pi —Na3—C10i 115.66 (11)
O23—Zn2—Na3 87.28 (8) O21—Na3—O25 65.18 (9)
O21—Zn2—Na3 35.31 (8) O3i —Na3—O25 81.04 (9)
O25—Zn2—Na3 55.57 (8) O5Pi —Na3—O25 164.93 (10)
N22—Zn2—Na3 164.36 (9) O4i —Na3—O25 90.11 (9)
N21—Zn2—Na3 112.10 (8) O1Pi —Na3—O25 114.70 (10)
N23—Zn2—Na3 110.23 (9) O3Pi —Na3—O25 78.61 (9)
C27—N21—C21 114.3 (3) C10i —Na3—O25 91.59 (10)
C27—N21—C26 110.4 (3) O21—Na3—Cl3Pi 87.13 (8)
C21—N21—C26 113.4 (3) O3i —Na3—Cl3Pi 112.97 (8)
C27—N21—Zn2 104.8 (2) O5Pi —Na3—Cl3Pi 97.78 (9)
C21—N21—Zn2 110.2 (2) O4i —Na3—Cl3Pi 165.21 (9)
C26—N21—Zn2 102.8 (2) O1Pi —Na3—Cl3Pi 27.24 (7)
C29—N22—C22 110.3 (3) O3Pi —Na3—Cl3Pi 27.50 (6)
C29—N22—C23 113.3 (3) C10i —Na3—Cl3Pi 138.69 (9)
C22—N22—C23 113.7 (3) O25—Na3—Cl3Pi 93.66 (7)
C29—N22—Zn2 105.1 (2) O1i —Na4—O25 152.16 (11)
C22—N22—Zn2 102.9 (2) O1i —Na4—O1S 81.39 (10)
C23—N22—Zn2 110.6 (2) O25—Na4—O1S 114.02 (11)
C31—N23—C24 110.2 (3) O1i —Na4—O26 105.71 (10)
C31—N23—C25 113.2 (3) O25—Na4—O26 54.58 (9)
C24—N23—C25 113.8 (3) O1S—Na4—O26 88.20 (11)
C31—N23—Zn2 105.6 (2) O1i —Na4—O2P 109.63 (11)
C24—N23—Zn2 102.2 (2) O25—Na4—O2P 92.77 (10)
C25—N23—Zn2 110.9 (2) O1S—Na4—O2P 94.51 (11)
C28—O21—Zn2 117.5 (2) O26—Na4—O2P 144.57 (11)
C28—O21—Na3 129.0 (2) O1i —Na4—O3i 71.43 (9)
Zn2—O21—Na3 113.50 (12) O25—Na4—O3i 91.22 (10)
C28—O22—Na2i 138.5 (2) O1S—Na4—O3i 152.81 (11)
C28—O22—Na1i 127.0 (2) O26—Na4—O3i 99.40 (10)
Na2i —O22—Na1i 92.88 (11) O2P—Na4—O3i 94.12 (10)
C30—O23—Zn2 116.8 (2) O1i —Na4—C32 131.19 (12)
C30—O23—Na5 104.9 (2) O25—Na4—C32 27.70 (10)
Zn2—O23—Na5 129.88 (13) O1S—Na4—C32 100.22 (12)
C30—O24—Na1iii 164.3 (3) O26—Na4—C32 27.03 (10)
C30—O24—Na5 79.6 (2) O2P—Na4—C32 118.75 (12)
Na1iii—O24—Na5 87.28 (11) O3i —Na4—C32 98.08 (11)
C32—O25—Zn2 116.6 (2) O1i —Na4—Cl3P 106.80 (8)
C32—O25—Na4 92.2 (2) O25—Na4—Cl3P 100.27 (8)
Zn2—O25—Na4 150.14 (13) O1S—Na4—Cl3P 71.34 (8)
C32—O25—Na3 108.3 (2) O26—Na4—Cl3P 138.03 (9)
suppo ing in o ma ion
sup-15
Ac a C ys . (2009). E65, m84–m85
Zn2—O25—Na3 89.79 (9) O2P—Na4—Cl3P 23.25 (7)
Na4—O25—Na3 88.28 (9) O3i —Na4—Cl3P 115.65 (7)
C32—O26—Na1 122.2 (2) C32—Na4—Cl3P 120.02 (9)
C32—O26—Na4 89.6 (2) O4i —Na5—O2 iii 94.98 (11)
Na1 —O26—Na4 117.22 (12) O4i —Na5—O6 118.54 (12)
N21—C21—C22 111.3 (3) O2 iii—Na5—O6 79.66 (10)
N21—C21—H21A 109.4 O4i —Na5—O23 114.38 (11)
C22—C21—H21A 109.4 O2 iii—Na5—O23 94.71 (11)
N21—C21—H21B 109.4 O6—Na5—O23 127.05 (11)
C22—C21—H21B 109.4 O4i —Na5—O2P 84.12 (10)
H21A—C21—H21B 108.0 O2 iii—Na5—O2P 174.83 (12)
N22—C22—C21 112.1 (3) O6—Na5—O2P 96.27 (10)
N22—C22—H22A 109.2 O23—Na5—O2P 90.30 (11)
C21—C22—H22A 109.2 O4i —Na5—O24 157.10 (11)
N22—C22—H22B 109.2 O2 iii—Na5—O24 101.07 (10)
C21—C22—H22B 109.2 O6—Na5—O24 80.68 (10)
H22A—C22—H22B 107.9 O23—Na5—O24 48.48 (9)
N22—C23—C24 109.9 (3) O2P—Na5—O24 81.29 (10)
N22—C23—H23A 109.7 O4i —Na5—C30 134.93 (12)
C24—C23—H23A 109.7 O2 iii—Na5—C30 102.99 (11)
N22—C23—H23B 109.7 O6—Na5—C30 105.29 (11)
C24—C23—H23B 109.7 O23—Na5—C30 24.50 (10)
H23A—C23—H23B 108.2 O2P—Na5—C30 81.10 (11)
N23—C24—C23 112.5 (3) O24—Na5—C30 24.72 (9)
Symme y codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y−1/2, z; (iii) x, y−1, z; (i ) x−1/2, −y+1/2, z; ( ) x−1/2, −y+3/2, z; ( i) x, y+1, z; ( ii) x+1/2, −y+3/2, z;
( iii) x−1/2, −y−1/2, z.
