Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051422/tk2200sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051422/tk2200Isup2.hkl |
CCDC reference: 667218
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.007 Å
- R factor = 0.046
- wR factor = 0.132
- Data-to-parameter ratio = 23.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.02 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C16 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of N8 = ... S PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn (2) 1.89
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For general background see: Kirin et al. (2005); Storr et al. (2005); Tamamura et al. (2006); Lee et al. (2007) & Ojida et al. (2004). For related literature, see: Addison et al. (1984).
All reagents and solvents were purchased from Aldrich and used without further purification. A mixture of ZnCl2 (0.66 g, 5 mmol) and di(2-picolyl)amine (0.99 g, 5 mmol) in ethanol (20 ml) was stirred at room temperature under an nitrogen atmosphere. The precipitates were filtered off and recrystallized from chloroform to yield (I). 1H NMR for dpa in (I) (d6-DMSO, p.p.m.): δ: 8.76 (d, 2H), 8.00 (m, 2H), 7.55 (t, 4H), 4.90 (t, 1H), 4.13 (s, 4H).
The N8—H atom was refined without constraint. The C-bound H atoms were included in the riding model approximation with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C).
Transition metal complexes with di(2-picolyl)amine (dpa) or substituted-dpa ligands continue to be of interest in many fields in chemistry (Kirin et al., 2005; Storr et al., 2005; Tamamura et al., 2006 & Lee et al., 2007). Among them, Zn(II) complexes exhibit fluorescence and can be applied as fluorescent chemosensors (Ojida et al., 2004). The Zn(II) center in the title [Zn(dpa)Cl2] complex, characterized as a monochloroform solvate, (I), is five-coordinated by the three N atoms of the dpa ligand and two Cl atoms (Fig. 1 & Table 1). The coordination pattern of the three N atoms of the dpa ligand is meridional and forms a planar ZnN3 arrangement and the overall coordination geometry is based on a square pyramid. The calculated trigonality index, τ, for Zn(dpa)Cl2 in (I), of 0.21, is consistent with this conclusion (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid (Addison et al., 1984)). Hydrogen bonding interactions of the type N—H···Cl link molecules into centrosymmetric dimeric aggregates (Table 2). Upon excitation at 400 nm, complex (I) exhibits an intense blue emission at 426 nm in DMF solution.
For general background see: Kirin et al. (2005); Storr et al. (2005); Tamamura et al. (2006); Lee et al. (2007) & Ojida et al. (2004). For related literature, see: Addison et al. (1984).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and 30% probability ellipsoids. |
[ZnCl2(C12H13N3)]·CHCl3 | F(000) = 912 |
Mr = 454.89 | Dx = 1.611 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5802 reflections |
a = 6.9650 (6) Å | θ = 2.5–23.5° |
b = 12.8654 (12) Å | µ = 2.02 mm−1 |
c = 20.9341 (18) Å | T = 295 K |
β = 90.335 (5)° | Block, colourless |
V = 1875.8 (3) Å3 | 0.20 × 0.18 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3104 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.055 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | θmax = 28.4°, θmin = 1.9° |
Tmin = 0.661, Tmax = 0.697 | h = −9→9 |
36984 measured reflections | k = −17→17 |
4676 independent reflections | l = −27→27 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0612P)2 + 1.569P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.132 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.85 e Å−3 |
4676 reflections | Δρmin = −0.76 e Å−3 |
203 parameters |
[ZnCl2(C12H13N3)]·CHCl3 | V = 1875.8 (3) Å3 |
Mr = 454.89 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9650 (6) Å | µ = 2.02 mm−1 |
b = 12.8654 (12) Å | T = 295 K |
c = 20.9341 (18) Å | 0.20 × 0.18 × 0.17 mm |
β = 90.335 (5)° |
Bruker SMART CCD area-detector diffractometer | 4676 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 3104 reflections with I > 2σ(I) |
Tmin = 0.661, Tmax = 0.697 | Rint = 0.055 |
36984 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.85 e Å−3 |
4676 reflections | Δρmin = −0.76 e Å−3 |
203 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. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.58918 (5) | 0.97733 (3) | 0.110162 (18) | 0.04221 (14) | |
Cl1 | 0.69504 (13) | 0.90035 (8) | 0.20260 (4) | 0.0528 (2) | |
Cl2 | 0.80351 (14) | 1.08035 (8) | 0.05874 (4) | 0.0566 (3) | |
N1 | 0.4222 (4) | 1.1003 (3) | 0.15276 (15) | 0.0514 (7) | |
C2 | 0.4828 (7) | 1.1957 (4) | 0.1677 (2) | 0.0665 (11) | |
H2 | 0.6083 | 1.2144 | 0.1581 | 0.08* | |
C3 | 0.3661 (8) | 1.2674 (4) | 0.1968 (2) | 0.0819 (15) | |
H3 | 0.4118 | 1.3332 | 0.207 | 0.098* | |
C4 | 0.1807 (8) | 1.2396 (5) | 0.2105 (2) | 0.0817 (15) | |
H4 | 0.0986 | 1.2869 | 0.2299 | 0.098* | |
C5 | 0.1169 (6) | 1.1420 (4) | 0.1956 (2) | 0.0722 (13) | |
H5 | −0.0084 | 1.1222 | 0.2047 | 0.087* | |
C6 | 0.2417 (5) | 1.0731 (3) | 0.16676 (16) | 0.0521 (9) | |
C7 | 0.1865 (5) | 0.9624 (3) | 0.1518 (2) | 0.0577 (10) | |
H7A | 0.2079 | 0.9192 | 0.1892 | 0.069* | |
H7B | 0.0512 | 0.9592 | 0.1408 | 0.069* | |
N8 | 0.3013 (4) | 0.9232 (3) | 0.09836 (15) | 0.0462 (7) | |
H8 | 0.252 (5) | 0.947 (3) | 0.0644 (19) | 0.045 (11)* | |
C9 | 0.3055 (6) | 0.8096 (3) | 0.0925 (2) | 0.0553 (10) | |
H9A | 0.185 | 0.7851 | 0.0745 | 0.066* | |
H9B | 0.3218 | 0.7785 | 0.1344 | 0.066* | |
C10 | 0.4691 (6) | 0.7776 (3) | 0.04990 (17) | 0.0517 (9) | |
C11 | 0.4684 (8) | 0.6857 (3) | 0.0160 (2) | 0.0721 (13) | |
H11 | 0.3635 | 0.6411 | 0.0176 | 0.087* | |
C12 | 0.6275 (9) | 0.6612 (4) | −0.0206 (2) | 0.0844 (15) | |
H12 | 0.6321 | 0.599 | −0.0431 | 0.101* | |
C13 | 0.7771 (8) | 0.7294 (4) | −0.0231 (2) | 0.0775 (14) | |
H13 | 0.884 | 0.7148 | −0.048 | 0.093* | |
C14 | 0.7680 (6) | 0.8190 (4) | 0.01125 (19) | 0.0597 (10) | |
H14 | 0.8708 | 0.865 | 0.0094 | 0.072* | |
N15 | 0.6173 (4) | 0.8437 (2) | 0.04767 (14) | 0.0482 (7) | |
C16 | 0.9172 (9) | 0.5298 (4) | 0.1609 (2) | 0.0859 (16) | |
H16 | 0.8947 | 0.4975 | 0.2026 | 0.103* | |
Cl3 | 1.1706 (3) | 0.53673 (14) | 0.14969 (12) | 0.1342 (7) | |
Cl4 | 0.8241 (3) | 0.65527 (13) | 0.16368 (8) | 0.1098 (5) | |
Cl5 | 0.8131 (5) | 0.4523 (2) | 0.10431 (13) | 0.1840 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0364 (2) | 0.0507 (2) | 0.0396 (2) | −0.00151 (17) | 0.00611 (15) | −0.00004 (18) |
Cl1 | 0.0524 (5) | 0.0634 (6) | 0.0426 (5) | 0.0039 (4) | 0.0040 (4) | 0.0078 (4) |
Cl2 | 0.0553 (5) | 0.0690 (6) | 0.0458 (5) | −0.0137 (5) | 0.0094 (4) | 0.0064 (4) |
N1 | 0.0486 (17) | 0.057 (2) | 0.0483 (17) | 0.0100 (14) | 0.0022 (13) | 0.0002 (15) |
C2 | 0.071 (3) | 0.063 (3) | 0.066 (3) | 0.008 (2) | 0.001 (2) | −0.010 (2) |
C3 | 0.104 (4) | 0.068 (3) | 0.074 (3) | 0.025 (3) | −0.009 (3) | −0.023 (3) |
C4 | 0.086 (4) | 0.098 (4) | 0.062 (3) | 0.043 (3) | −0.002 (2) | −0.022 (3) |
C5 | 0.055 (2) | 0.106 (4) | 0.056 (3) | 0.025 (3) | 0.0048 (19) | −0.009 (3) |
C6 | 0.045 (2) | 0.074 (3) | 0.0372 (18) | 0.0155 (18) | 0.0046 (15) | 0.0008 (18) |
C7 | 0.0410 (19) | 0.074 (3) | 0.058 (2) | 0.0064 (18) | 0.0086 (17) | 0.008 (2) |
N8 | 0.0393 (15) | 0.058 (2) | 0.0408 (16) | −0.0017 (14) | 0.0009 (13) | 0.0050 (15) |
C9 | 0.053 (2) | 0.055 (2) | 0.059 (2) | −0.0118 (18) | 0.0001 (18) | 0.0050 (18) |
C10 | 0.059 (2) | 0.053 (2) | 0.043 (2) | −0.0036 (18) | −0.0042 (16) | 0.0019 (17) |
C11 | 0.097 (4) | 0.055 (3) | 0.064 (3) | −0.005 (2) | −0.008 (3) | −0.009 (2) |
C12 | 0.117 (5) | 0.069 (3) | 0.067 (3) | 0.011 (3) | −0.001 (3) | −0.023 (3) |
C13 | 0.089 (3) | 0.082 (3) | 0.061 (3) | 0.016 (3) | 0.013 (2) | −0.014 (3) |
C14 | 0.059 (2) | 0.070 (3) | 0.050 (2) | 0.010 (2) | 0.0101 (18) | −0.003 (2) |
N15 | 0.0487 (17) | 0.0533 (18) | 0.0426 (16) | −0.0011 (14) | 0.0044 (13) | −0.0029 (14) |
C16 | 0.128 (5) | 0.071 (3) | 0.059 (3) | 0.006 (3) | 0.009 (3) | −0.001 (2) |
Cl3 | 0.1399 (17) | 0.0955 (12) | 0.168 (2) | 0.0094 (11) | 0.0342 (14) | 0.0047 (12) |
Cl4 | 0.1519 (15) | 0.0851 (10) | 0.0925 (10) | 0.0336 (10) | 0.0029 (10) | 0.0020 (8) |
Cl5 | 0.245 (3) | 0.141 (2) | 0.165 (2) | 0.0070 (19) | −0.077 (2) | −0.0631 (17) |
Zn—N1 | 2.159 (3) | C7—H7B | 0.97 |
Zn—N8 | 2.136 (3) | N8—H8 | 0.85 (4) |
Zn—N15 | 2.170 (3) | C9—C10 | 1.508 (5) |
Zn—Cl1 | 2.2919 (10) | C9—H9A | 0.97 |
Zn—Cl2 | 2.2722 (9) | C9—H9B | 0.97 |
N1—C2 | 1.335 (5) | C10—N15 | 1.338 (5) |
N1—C6 | 1.339 (5) | C10—C11 | 1.380 (6) |
C2—C3 | 1.374 (6) | C11—C12 | 1.386 (7) |
C2—H2 | 0.93 | C11—H11 | 0.93 |
C3—C4 | 1.372 (8) | C12—C13 | 1.364 (7) |
C3—H3 | 0.93 | C12—H12 | 0.93 |
C4—C5 | 1.367 (7) | C13—C14 | 1.360 (6) |
C4—H4 | 0.93 | C13—H13 | 0.93 |
C5—C6 | 1.382 (6) | C14—N15 | 1.340 (5) |
C5—H5 | 0.93 | C14—H14 | 0.93 |
C6—C7 | 1.507 (6) | C16—Cl5 | 1.706 (6) |
N8—C9 | 1.467 (5) | C16—Cl4 | 1.741 (5) |
C7—N8 | 1.468 (5) | C16—Cl3 | 1.784 (7) |
C7—H7A | 0.97 | C16—H16 | 0.98 |
N1—Zn—N8 | 77.23 (12) | C9—N8—Zn | 108.4 (2) |
N1—Zn—N15 | 151.65 (12) | C7—N8—Zn | 108.3 (2) |
N1—Zn—Cl1 | 98.01 (9) | C9—N8—H8 | 108 (3) |
N1—Zn—Cl2 | 97.20 (9) | C7—N8—H8 | 107 (3) |
N8—Zn—N15 | 76.11 (12) | Zn—N8—H8 | 111 (3) |
N8—Zn—Cl1 | 104.71 (9) | N8—C9—C10 | 109.7 (3) |
N8—Zn—Cl2 | 138.97 (9) | N8—C9—H9A | 109.7 |
N15—Zn—Cl1 | 97.87 (9) | C10—C9—H9A | 109.7 |
N15—Zn—Cl2 | 96.59 (8) | N8—C9—H9B | 109.7 |
Cl1—Zn—Cl2 | 116.30 (4) | C10—C9—H9B | 109.7 |
C2—N1—C6 | 119.0 (4) | H9A—C9—H9B | 108.2 |
C2—N1—Zn | 126.9 (3) | N15—C10—C11 | 121.8 (4) |
C6—N1—Zn | 114.1 (3) | N15—C10—C9 | 115.7 (3) |
N1—C2—C3 | 122.3 (5) | C11—C10—C9 | 122.5 (4) |
N1—C2—H2 | 118.9 | C10—C11—C12 | 118.6 (5) |
C3—C2—H2 | 118.9 | C10—C11—H11 | 120.7 |
C4—C3—C2 | 118.6 (5) | C12—C11—H11 | 120.7 |
C4—C3—H3 | 120.7 | C13—C12—C11 | 119.3 (5) |
C2—C3—H3 | 120.7 | C13—C12—H12 | 120.3 |
C5—C4—C3 | 119.8 (4) | C11—C12—H12 | 120.3 |
C5—C4—H4 | 120.1 | C14—C13—C12 | 119.1 (5) |
C3—C4—H4 | 120.1 | C14—C13—H13 | 120.5 |
C4—C5—C6 | 119.0 (5) | C12—C13—H13 | 120.5 |
C4—C5—H5 | 120.5 | N15—C14—C13 | 122.8 (4) |
C6—C5—H5 | 120.5 | N15—C14—H14 | 118.6 |
N1—C6—C5 | 121.4 (4) | C13—C14—H14 | 118.6 |
N1—C6—C7 | 116.1 (3) | C10—N15—C14 | 118.4 (3) |
C5—C6—C7 | 122.4 (4) | C10—N15—Zn | 114.2 (2) |
N8—C7—C6 | 110.1 (3) | C14—N15—Zn | 127.2 (3) |
N8—C7—H7A | 109.6 | Cl5—C16—Cl4 | 114.1 (4) |
C6—C7—H7A | 109.6 | Cl5—C16—Cl3 | 110.8 (3) |
N8—C7—H7B | 109.6 | Cl4—C16—Cl3 | 109.1 (3) |
C6—C7—H7B | 109.6 | Cl5—C16—H16 | 107.5 |
H7A—C7—H7B | 108.2 | Cl4—C16—H16 | 107.5 |
C9—N8—C7 | 114.7 (3) | Cl3—C16—H16 | 107.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl2i | 0.85 (4) | 2.63 (4) | 3.365 (3) | 146 (3) |
Symmetry code: (i) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C12H13N3)]·CHCl3 |
Mr | 454.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 6.9650 (6), 12.8654 (12), 20.9341 (18) |
β (°) | 90.335 (5) |
V (Å3) | 1875.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.02 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.661, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36984, 4676, 3104 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.132, 1.03 |
No. of reflections | 4676 |
No. of parameters | 203 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.85, −0.76 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Zn—N1 | 2.159 (3) | Zn—Cl1 | 2.2919 (10) |
Zn—N8 | 2.136 (3) | Zn—Cl2 | 2.2722 (9) |
Zn—N15 | 2.170 (3) | ||
N1—Zn—N8 | 77.23 (12) | N8—Zn—Cl1 | 104.71 (9) |
N1—Zn—N15 | 151.65 (12) | N8—Zn—Cl2 | 138.97 (9) |
N1—Zn—Cl1 | 98.01 (9) | N15—Zn—Cl1 | 97.87 (9) |
N1—Zn—Cl2 | 97.20 (9) | N15—Zn—Cl2 | 96.59 (8) |
N8—Zn—N15 | 76.11 (12) | Cl1—Zn—Cl2 | 116.30 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl2i | 0.85 (4) | 2.63 (4) | 3.365 (3) | 146 (3) |
Symmetry code: (i) −x+1, −y+2, −z. |
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Transition metal complexes with di(2-picolyl)amine (dpa) or substituted-dpa ligands continue to be of interest in many fields in chemistry (Kirin et al., 2005; Storr et al., 2005; Tamamura et al., 2006 & Lee et al., 2007). Among them, Zn(II) complexes exhibit fluorescence and can be applied as fluorescent chemosensors (Ojida et al., 2004). The Zn(II) center in the title [Zn(dpa)Cl2] complex, characterized as a monochloroform solvate, (I), is five-coordinated by the three N atoms of the dpa ligand and two Cl atoms (Fig. 1 & Table 1). The coordination pattern of the three N atoms of the dpa ligand is meridional and forms a planar ZnN3 arrangement and the overall coordination geometry is based on a square pyramid. The calculated trigonality index, τ, for Zn(dpa)Cl2 in (I), of 0.21, is consistent with this conclusion (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid (Addison et al., 1984)). Hydrogen bonding interactions of the type N—H···Cl link molecules into centrosymmetric dimeric aggregates (Table 2). Upon excitation at 400 nm, complex (I) exhibits an intense blue emission at 426 nm in DMF solution.