Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702171X/im2013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702171X/im2013Isup2.hkl |
CCDC reference: 650609
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.020 Å
- R factor = 0.063
- wR factor = 0.141
- Data-to-parameter ratio = 23.2
checkCIF/PLATON results
No syntax errors found
Alert level A EXPT005_ALERT_1_A _exptl_crystal_description is missing Crystal habit description. The following tests will not be performed. CRYSR_01 EXPT010_ALERT_1_A _exptl_crystal_colour (_pd_char_colour for powder) is missing Crystal colour. The following tests will not be performed. CRYSC_01
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 20 PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2 ... ? PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4 ... ? PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 I3
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C8 H20 I4 N4 Zn1 Atom count from _chemical_formula_moiety: PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.90
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Kimura et al. (1997); Shionoya et al. (1993); Wang et al. (2003); Aoki & Kimura (2004).
The title complex was prepared by the direct combination of 1:1 molar equivalents of cyclen, Zn(NO3)2 and KI in ethanol at room temperature for two hours. Then the solution was filtered off and placed directly in the air to evapore the solvent. Single crystals of the title compound suitable for structure analysis were obtained fromn the solution after two weeks.
H atoms were positioned geometrically and refined using a riding model with C—H = 0.97 Å, N—H = 0.91 Å, and with Uiso(H) = 1.2 times Ueq(C or N).
The 1,4,7,10-tetraazacyclododecane (cyclen) is a multipotent ligand which has been used in chemistry, biology and many other fields not only due to its excellent coordination properties but also because of the interesting characteristics of its with metal complexes (Guo et al., 1999). Previously accumulated studies about the intrinsic chemical properties of Zn2+ can be finely tuned by complexation with macrocyclic polyamines such as 1,5,9-triazacyclododecane and 1,4,7,10-tetraazacyclododecane (Kimura et al., 2004). Kimura et al. and others also have investigated the coordination of imides and phosphates to Zn(II)-cyclen complexes in great detail (Kimura et al., 1993; Kimura et al.,1997).
In this paper, we report the crystal structure of a novel Zn(II)-cyclen complex composed of a iodo-(1,4,7,10-tetraazacyclododecane)-zinc(II) cation and a triiodine anion as the counter anion. The asymmetric unit of the title compound is presented in Figure 1. In the cation each zinc atom is coordinated by four nitrogen atoms of the cyclen and one iodo ligand (Fig.1). Weak intermolecular C—H···I interactions seem to be effective in the stabilization of the whole crystal structure in which two neighboring cations are linked into a dimeric unit (C4—H4b···I1i; i: 1 - x,1 - y,1 - z) (Fig. 2). Additional weak intermolecular C—H···I interactions (C7—H7a···I4; C5—H5b···I4ii; ii: -x,1 - y,-z) link all of the dimers into a linear one-dimensional supramolecular structure (Fig. 2).
For related literature, see: Kimura et al. (1997); Shionoya et al. (1993); Wang et al. (2003); Aoki & Kimura (2004).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[ZnI(C8H16N4)]I3 | V = 931.5 (2) Å3 |
Mr = 745.25 | Z = 2 |
Triclinic, P1 | F(000) = 676 |
Hall symbol: -P 1 | Dx = 2.657 Mg m−3 |
a = 8.596 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.120 (1) Å | Cell parameters from 1388 reflections |
c = 12.342 (2) Å | θ = 2.6–22.2° |
α = 94.894 (2)° | µ = 7.94 mm−1 |
β = 104.707 (2)° | T = 298 K |
γ = 91.295 (2)° | 0.26 × 0.24 × 0.22 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3575 independent reflections |
Radiation source: sealed tube | 2260 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
phi and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.15, Tmax = 0.17 | k = −11→8 |
5025 measured reflections | l = −15→14 |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0612P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3 |
3575 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 1.65 e Å−3 |
0 restraints | Δρmin = −1.68 e Å−3 |
[ZnI(C8H16N4)]I3 | γ = 91.295 (2)° |
Mr = 745.25 | V = 931.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.596 (1) Å | Mo Kα radiation |
b = 9.120 (1) Å | µ = 7.94 mm−1 |
c = 12.342 (2) Å | T = 298 K |
α = 94.894 (2)° | 0.26 × 0.24 × 0.22 mm |
β = 104.707 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 3575 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2260 reflections with I > 2σ(I) |
Tmin = 0.15, Tmax = 0.17 | Rint = 0.030 |
5025 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.65 e Å−3 |
3575 reflections | Δρmin = −1.68 e Å−3 |
154 parameters |
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 | ||
C1 | 0.1065 (17) | 0.9305 (16) | 0.3598 (12) | 0.060 (4) | |
H1A | 0.0278 | 0.8883 | 0.2927 | 0.072* | |
H1B | 0.0728 | 1.0259 | 0.3838 | 0.072* | |
C2 | 0.1345 (16) | 0.8207 (17) | 0.4595 (11) | 0.058 (4) | |
H2A | 0.0332 | 0.7984 | 0.4769 | 0.070* | |
H2B | 0.2087 | 0.8677 | 0.5270 | 0.070* | |
C3 | 0.0937 (17) | 0.5709 (16) | 0.3631 (12) | 0.061 (4) | |
H3A | 0.0108 | 0.6177 | 0.3103 | 0.073* | |
H3B | 0.0455 | 0.5244 | 0.4153 | 0.073* | |
C4 | 0.1799 (16) | 0.4582 (15) | 0.3013 (12) | 0.056 (3) | |
H4A | 0.1021 | 0.3834 | 0.2572 | 0.067* | |
H4B | 0.2589 | 0.4101 | 0.3560 | 0.067* | |
C5 | 0.1637 (15) | 0.5576 (14) | 0.1195 (10) | 0.052 (3) | |
H5A | 0.0671 | 0.6034 | 0.1298 | 0.062* | |
H5B | 0.1333 | 0.4650 | 0.0731 | 0.062* | |
C6 | 0.264 (2) | 0.6633 (15) | 0.0640 (12) | 0.067 (4) | |
H6A | 0.3602 | 0.6168 | 0.0540 | 0.080* | |
H6B | 0.1997 | 0.6859 | −0.0089 | 0.080* | |
C7 | 0.1895 (17) | 0.9072 (14) | 0.1314 (12) | 0.056 (3) | |
H7A | 0.0869 | 0.8579 | 0.1280 | 0.067* | |
H7B | 0.1807 | 0.9516 | 0.0616 | 0.067* | |
C8 | 0.2340 (15) | 1.0297 (14) | 0.2343 (13) | 0.061 (4) | |
H8A | 0.1518 | 1.1019 | 0.2278 | 0.073* | |
H8B | 0.3366 | 1.0797 | 0.2388 | 0.073* | |
I1 | 0.64993 (10) | 0.75291 (11) | 0.42815 (8) | 0.0584 (3) | |
I2 | −0.33154 (12) | 1.35959 (11) | 0.26103 (8) | 0.0616 (3) | |
I3 | −0.30693 (10) | 1.06260 (10) | 0.16838 (7) | 0.0498 (2) | |
I4 | −0.28278 (12) | 0.75799 (11) | 0.07214 (8) | 0.0637 (3) | |
N1 | 0.2439 (14) | 0.9392 (12) | 0.3441 (9) | 0.060 (3) | |
H1 | 0.3093 | 0.9926 | 0.4049 | 0.072* | |
N2 | 0.2099 (14) | 0.6659 (12) | 0.4164 (10) | 0.062 (3) | |
H2 | 0.2730 | 0.6263 | 0.4767 | 0.074* | |
N3 | 0.2664 (12) | 0.5358 (11) | 0.2213 (8) | 0.047 (3) | |
H3 | 0.3497 | 0.4818 | 0.2102 | 0.056* | |
N4 | 0.3093 (13) | 0.8072 (13) | 0.1461 (10) | 0.060 (3) | |
H4 | 0.4002 | 0.8507 | 0.1359 | 0.072* | |
Zn1 | 0.35735 (17) | 0.74403 (17) | 0.31372 (12) | 0.0475 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.048 (8) | 0.060 (9) | 0.059 (9) | 0.016 (6) | −0.006 (6) | −0.011 (7) |
C2 | 0.041 (7) | 0.086 (11) | 0.043 (7) | 0.008 (7) | 0.004 (6) | −0.003 (7) |
C3 | 0.057 (8) | 0.070 (9) | 0.052 (8) | −0.030 (7) | 0.007 (6) | 0.018 (7) |
C4 | 0.052 (8) | 0.043 (7) | 0.064 (9) | 0.002 (6) | 0.000 (7) | −0.001 (6) |
C5 | 0.047 (7) | 0.056 (8) | 0.044 (7) | −0.010 (6) | 0.007 (6) | −0.025 (6) |
C6 | 0.105 (13) | 0.050 (8) | 0.052 (8) | 0.018 (8) | 0.028 (8) | 0.014 (7) |
C7 | 0.056 (8) | 0.048 (8) | 0.063 (9) | 0.016 (6) | 0.010 (6) | 0.019 (6) |
C8 | 0.033 (6) | 0.041 (7) | 0.092 (11) | −0.002 (5) | −0.010 (6) | −0.005 (7) |
I1 | 0.0407 (5) | 0.0647 (6) | 0.0574 (6) | 0.0038 (4) | −0.0045 (4) | −0.0113 (4) |
I2 | 0.0593 (6) | 0.0559 (6) | 0.0614 (6) | 0.0094 (4) | 0.0034 (4) | −0.0046 (4) |
I3 | 0.0421 (4) | 0.0550 (5) | 0.0523 (5) | 0.0052 (3) | 0.0100 (4) | 0.0096 (4) |
I4 | 0.0624 (6) | 0.0585 (6) | 0.0646 (6) | 0.0078 (4) | 0.0107 (5) | −0.0099 (5) |
N1 | 0.056 (7) | 0.056 (7) | 0.047 (6) | 0.007 (5) | −0.012 (5) | −0.032 (5) |
N2 | 0.058 (7) | 0.049 (7) | 0.072 (8) | 0.002 (5) | 0.003 (6) | 0.017 (6) |
N3 | 0.038 (5) | 0.048 (6) | 0.043 (6) | 0.011 (4) | −0.007 (4) | −0.007 (5) |
N4 | 0.040 (6) | 0.066 (8) | 0.076 (8) | −0.011 (5) | 0.012 (5) | 0.023 (6) |
Zn1 | 0.0400 (8) | 0.0514 (8) | 0.0455 (8) | 0.0024 (6) | 0.0036 (6) | −0.0050 (6) |
C1—N1 | 1.246 (18) | C7—N4 | 1.379 (16) |
C1—C2 | 1.63 (2) | C7—C8 | 1.581 (19) |
C1—H1A | 0.9700 | C7—I4 | 4.115 (15) |
C1—H1B | 0.9700 | C7—H7A | 0.9700 |
C2—N2 | 1.669 (18) | C7—H7B | 0.9700 |
C2—H2A | 0.9700 | C8—N1 | 1.632 (19) |
C2—H2B | 0.9700 | C8—H8A | 0.9700 |
C3—N2 | 1.308 (16) | C8—H8B | 0.9700 |
C3—C4 | 1.54 (2) | I1—Zn1 | 2.5483 (16) |
C3—H3A | 0.9700 | I2—I3 | 2.8826 (13) |
C3—H3B | 0.9700 | I3—I4 | 2.9599 (14) |
C4—N3 | 1.581 (18) | I4—H7A | 3.1705 |
C4—H4A | 0.9700 | N1—Zn1 | 2.100 (11) |
C4—H4B | 0.9700 | N1—H1 | 0.9100 |
C5—N3 | 1.373 (16) | N2—Zn1 | 2.156 (12) |
C5—C6 | 1.59 (2) | N2—H2 | 0.9100 |
C5—H5A | 0.9700 | N3—Zn1 | 2.151 (10) |
C5—H5B | 0.9700 | N3—H3 | 0.9100 |
C6—N4 | 1.565 (18) | N4—Zn1 | 2.136 (12) |
C6—H6A | 0.9700 | N4—H4 | 0.9100 |
C6—H6B | 0.9700 | ||
N1—C1—C2 | 101.0 (11) | H7A—C7—H7B | 108.4 |
N1—C1—H1A | 111.6 | C7—C8—N1 | 104.3 (10) |
C2—C1—H1A | 111.6 | C7—C8—H8A | 110.9 |
N1—C1—H1B | 111.6 | N1—C8—H8A | 110.9 |
C2—C1—H1B | 111.6 | C7—C8—H8B | 110.9 |
H1A—C1—H1B | 109.4 | N1—C8—H8B | 110.9 |
C1—C2—N2 | 108.7 (10) | H8A—C8—H8B | 108.9 |
C1—C2—H2A | 110.0 | I2—I3—I4 | 179.70 (5) |
N2—C2—H2A | 110.0 | I3—I4—H7A | 81.9 |
C1—C2—H2B | 110.0 | I3—I4—C7 | 80.26 (18) |
N2—C2—H2B | 110.0 | C1—N1—C8 | 108.1 (11) |
H2A—C2—H2B | 108.3 | C1—N1—Zn1 | 118.8 (10) |
N2—C3—C4 | 103.2 (12) | C8—N1—Zn1 | 105.5 (7) |
N2—C3—H3A | 111.1 | C1—N1—H1 | 108.0 |
C4—C3—H3A | 111.1 | C8—N1—H1 | 108.0 |
N2—C3—H3B | 111.1 | Zn1—N1—H1 | 108.0 |
C4—C3—H3B | 111.1 | C3—N2—C2 | 110.4 (12) |
H3A—C3—H3B | 109.1 | C3—N2—Zn1 | 114.6 (10) |
C3—C4—N3 | 111.0 (10) | C2—N2—Zn1 | 102.5 (7) |
C3—C4—H4A | 109.4 | C3—N2—H2 | 109.7 |
N3—C4—H4A | 109.4 | C2—N2—H2 | 109.7 |
C3—C4—H4B | 109.4 | Zn1—N2—H2 | 109.7 |
N3—C4—H4B | 109.4 | C5—N3—C4 | 112.9 (10) |
H4A—C4—H4B | 108.0 | C5—N3—Zn1 | 110.3 (8) |
N3—C5—C6 | 104.4 (10) | C4—N3—Zn1 | 104.0 (7) |
N3—C5—H5A | 110.9 | C5—N3—H3 | 109.8 |
C6—C5—H5A | 110.9 | C4—N3—H3 | 109.8 |
N3—C5—H5B | 110.9 | Zn1—N3—H3 | 109.8 |
C6—C5—H5B | 110.9 | C7—N4—C6 | 113.4 (11) |
H5A—C5—H5B | 108.9 | C7—N4—Zn1 | 109.0 (10) |
N4—C6—C5 | 106.7 (10) | C6—N4—Zn1 | 107.4 (7) |
N4—C6—H6A | 110.4 | C7—N4—H4 | 109.0 |
C5—C6—H6A | 110.4 | C6—N4—H4 | 109.0 |
N4—C6—H6B | 110.4 | Zn1—N4—H4 | 109.0 |
C5—C6—H6B | 110.4 | N1—Zn1—N4 | 83.6 (5) |
H6A—C6—H6B | 108.6 | N1—Zn1—N3 | 132.1 (4) |
N4—C7—C8 | 108.2 (11) | N4—Zn1—N3 | 80.3 (4) |
N4—C7—I4 | 119.4 (8) | N1—Zn1—N2 | 80.5 (5) |
C8—C7—I4 | 110.6 (8) | N4—Zn1—N2 | 134.3 (4) |
N4—C7—H7A | 110.1 | N3—Zn1—N2 | 79.4 (4) |
C8—C7—H7A | 110.1 | N1—Zn1—I1 | 111.8 (3) |
N4—C7—H7B | 110.1 | N4—Zn1—I1 | 117.7 (3) |
C8—C7—H7B | 110.1 | N3—Zn1—I1 | 115.7 (3) |
I4—C7—H7B | 98.0 | N2—Zn1—I1 | 107.9 (3) |
Experimental details
Crystal data | |
Chemical formula | [ZnI(C8H16N4)]I3 |
Mr | 745.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.596 (1), 9.120 (1), 12.342 (2) |
α, β, γ (°) | 94.894 (2), 104.707 (2), 91.295 (2) |
V (Å3) | 931.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 7.94 |
Crystal size (mm) | 0.26 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.15, 0.17 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5025, 3575, 2260 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.141, 1.07 |
No. of reflections | 3575 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.65, −1.68 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
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The 1,4,7,10-tetraazacyclododecane (cyclen) is a multipotent ligand which has been used in chemistry, biology and many other fields not only due to its excellent coordination properties but also because of the interesting characteristics of its with metal complexes (Guo et al., 1999). Previously accumulated studies about the intrinsic chemical properties of Zn2+ can be finely tuned by complexation with macrocyclic polyamines such as 1,5,9-triazacyclododecane and 1,4,7,10-tetraazacyclododecane (Kimura et al., 2004). Kimura et al. and others also have investigated the coordination of imides and phosphates to Zn(II)-cyclen complexes in great detail (Kimura et al., 1993; Kimura et al.,1997).
In this paper, we report the crystal structure of a novel Zn(II)-cyclen complex composed of a iodo-(1,4,7,10-tetraazacyclododecane)-zinc(II) cation and a triiodine anion as the counter anion. The asymmetric unit of the title compound is presented in Figure 1. In the cation each zinc atom is coordinated by four nitrogen atoms of the cyclen and one iodo ligand (Fig.1). Weak intermolecular C—H···I interactions seem to be effective in the stabilization of the whole crystal structure in which two neighboring cations are linked into a dimeric unit (C4—H4b···I1i; i: 1 - x,1 - y,1 - z) (Fig. 2). Additional weak intermolecular C—H···I interactions (C7—H7a···I4; C5—H5b···I4ii; ii: -x,1 - y,-z) link all of the dimers into a linear one-dimensional supramolecular structure (Fig. 2).