


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810028692/hb5556sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810028692/hb5556Isup2.hkl |
CCDC reference: 784038
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.039
- wR factor = 0.099
- Data-to-parameter ratio = 22.8
checkCIF/PLATON results
No syntax errors found
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 29.21 From the CIF: _diffrn_reflns_theta_full 29.21 From the CIF: _reflns_number_total 3560 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3761 Completeness (_total/calc) 94.66% PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 121 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 77
Alert level G PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety C4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 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 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of 4,4'-dimethyl-2,2'-bipyridine (0.20 g, 1.10 mmol) in methanol (10 ml) was added to a solution of ZnBr2 (0.25 g, 1.10 mmol) in methanol (5 ml) at room temperature. Colourless prisms of (I) were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.35 g, 77.7%).
All H atoms were positioned geometrically, with C—H = 0.93Å and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
4,4'-Dimethyl-2,2'-bipyridine (4,4'-dmbipy), is a good bidentate ligand, and numerous complexes with 4,4'-dmbipy have been prepared, such as that of mercury (Kalateh et al., 2008; Yousefi et al., 2008), indium (Ahmadi et al., 2008), iron (Amani et al., 2009), platin (Hojjat Kashani et al., 2008), manganese (Sakamoto et al., 2004), silver (Bellusci et al., 2008), gallium (Sofetis et al., 2006), copper (Willett et al., 2001), iridium (Yoshikawa et al., 2003) and cadmium (Kalateh et al., 2010). Here, we report the synthesis and structure of the title compound.
The asymmetric unit of the title compound, (Fig. 1), contains two half-molecule. The ZnII atom is for-coordinated in distorted tetragonal configurations by two N atoms from one 4,4'-dimethyl-2,2'-bipyridine and two Br atoms. The Zn—Br and Zn—N bond lengths and angles are collected in Table 1.
In the crystal structure, intermolecular C—H···Br hydrogen bonds (Table 2) may stabilize the structure (Fig. 2).
For related structures, see: Ahmadi et al. (2008); Amani et al. (2009); Bellusci et al. (2008); Hojjat Kashani et al. (2008); Kalateh et al. (2008, 2010); Sakamoto et al. (2004); Sofetis et al. (2006); Willett et al. (2001); Yoshikawa et al. (2003); Yousefi et al. (2008).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[ZnBr2(C12H12N2)] | F(000) = 792 |
Mr = 409.43 | Dx = 1.964 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 984 reflections |
a = 13.801 (3) Å | θ = 2.5–29.2° |
b = 8.2454 (16) Å | µ = 7.52 mm−1 |
c = 13.716 (3) Å | T = 120 K |
β = 117.47 (3)° | Prism, colorless |
V = 1384.9 (6) Å3 | 0.30 × 0.22 × 0.10 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 3560 independent reflections |
Radiation source: fine-focus sealed tube | 2963 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
phi and ω scans | θmax = 29.2°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −13→18 |
Tmin = 0.157, Tmax = 0.479 | k = −11→11 |
8352 measured reflections | l = −18→17 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0449P)2 + 2.823P] where P = (Fo2 + 2Fc2)/3 |
3560 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −1.04 e Å−3 |
[ZnBr2(C12H12N2)] | V = 1384.9 (6) Å3 |
Mr = 409.43 | Z = 4 |
Monoclinic, P2/c | Mo Kα radiation |
a = 13.801 (3) Å | µ = 7.52 mm−1 |
b = 8.2454 (16) Å | T = 120 K |
c = 13.716 (3) Å | 0.30 × 0.22 × 0.10 mm |
β = 117.47 (3)° |
Bruker SMART CCD diffractometer | 3560 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2963 reflections with I > 2σ(I) |
Tmin = 0.157, Tmax = 0.479 | Rint = 0.050 |
8352 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.62 e Å−3 |
3560 reflections | Δρmin = −1.04 e Å−3 |
156 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 | 0.3828 (3) | 0.7308 (4) | 0.0326 (3) | 0.0225 (7) | |
H1 | 0.3650 | 0.8327 | 0.0001 | 0.027* | |
C2 | 0.3490 (3) | 0.5946 (5) | −0.0343 (3) | 0.0251 (8) | |
H2 | 0.3082 | 0.6056 | −0.1101 | 0.030* | |
C3 | 0.3767 (3) | 0.4417 (4) | 0.0131 (3) | 0.0234 (7) | |
C4 | 0.3428 (4) | 0.2903 (5) | −0.0556 (4) | 0.0313 (9) | |
H4A | 0.2979 | 0.2252 | −0.0345 | 0.038* | |
H4B | 0.4065 | 0.2299 | −0.0444 | 0.038* | |
H4C | 0.3022 | 0.3191 | −0.1318 | 0.038* | |
C5 | 0.4366 (3) | 0.4324 (4) | 0.1268 (3) | 0.0220 (7) | |
H5 | 0.4562 | 0.3319 | 0.1611 | 0.026* | |
C6 | 0.4671 (3) | 0.5733 (4) | 0.1892 (3) | 0.0185 (7) | |
C7 | 0.1273 (3) | 0.7510 (4) | 0.1512 (3) | 0.0231 (7) | |
H7 | 0.1512 | 0.8521 | 0.1411 | 0.028* | |
C8 | 0.1556 (3) | 0.6153 (5) | 0.1110 (3) | 0.0236 (7) | |
H8 | 0.1977 | 0.6260 | 0.0746 | 0.028* | |
C9 | 0.1209 (3) | 0.4623 (4) | 0.1250 (3) | 0.0208 (7) | |
C10 | 0.1447 (4) | 0.3130 (5) | 0.0775 (4) | 0.0287 (8) | |
H10C | 0.1371 | 0.3370 | 0.0058 | 0.034* | |
H10B | 0.0943 | 0.2289 | 0.0718 | 0.034* | |
H10A | 0.2179 | 0.2774 | 0.1244 | 0.034* | |
C11 | 0.0594 (3) | 0.4535 (4) | 0.1817 (3) | 0.0218 (7) | |
H11 | 0.0357 | 0.3534 | 0.1938 | 0.026* | |
C12 | 0.0334 (3) | 0.5942 (4) | 0.2202 (3) | 0.0181 (7) | |
N1 | 0.4399 (3) | 0.7211 (3) | 0.1415 (3) | 0.0186 (6) | |
N2 | 0.0668 (3) | 0.7419 (3) | 0.2042 (3) | 0.0186 (6) | |
Zn1 | 0.5000 | 0.91089 (6) | 0.2500 | 0.02024 (14) | |
Zn2 | 0.0000 | 0.93068 (6) | 0.2500 | 0.01997 (14) | |
Br1 | 0.37461 (4) | 1.05907 (4) | 0.28513 (4) | 0.02607 (11) | |
Br2 | 0.12396 (4) | 1.07654 (4) | 0.40271 (4) | 0.02828 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0274 (19) | 0.0185 (15) | 0.0221 (19) | 0.0011 (14) | 0.0119 (16) | 0.0019 (13) |
C2 | 0.0263 (19) | 0.0284 (18) | 0.0186 (18) | −0.0019 (15) | 0.0085 (15) | −0.0024 (14) |
C3 | 0.0261 (19) | 0.0232 (16) | 0.0232 (19) | −0.0021 (14) | 0.0134 (16) | −0.0059 (14) |
C4 | 0.035 (2) | 0.0265 (18) | 0.026 (2) | −0.0044 (17) | 0.0089 (18) | −0.0115 (16) |
C5 | 0.0271 (19) | 0.0141 (14) | 0.0249 (19) | −0.0016 (13) | 0.0121 (16) | −0.0035 (12) |
C6 | 0.0262 (18) | 0.0125 (13) | 0.0187 (18) | −0.0021 (12) | 0.0118 (15) | −0.0013 (12) |
C7 | 0.0268 (19) | 0.0184 (15) | 0.025 (2) | −0.0015 (14) | 0.0127 (16) | 0.0010 (13) |
C8 | 0.028 (2) | 0.0240 (16) | 0.025 (2) | 0.0003 (15) | 0.0171 (17) | 0.0010 (14) |
C9 | 0.0227 (18) | 0.0196 (15) | 0.0191 (18) | 0.0039 (13) | 0.0087 (15) | −0.0007 (13) |
C10 | 0.033 (2) | 0.0238 (17) | 0.033 (2) | 0.0066 (16) | 0.0183 (19) | −0.0023 (15) |
C11 | 0.0289 (19) | 0.0138 (14) | 0.0249 (19) | 0.0006 (13) | 0.0142 (16) | −0.0001 (12) |
C12 | 0.0227 (17) | 0.0133 (14) | 0.0192 (18) | 0.0012 (12) | 0.0104 (15) | 0.0003 (11) |
N1 | 0.0222 (15) | 0.0147 (12) | 0.0177 (15) | −0.0004 (11) | 0.0082 (12) | −0.0013 (10) |
N2 | 0.0253 (16) | 0.0129 (12) | 0.0175 (15) | −0.0004 (11) | 0.0097 (13) | 0.0004 (10) |
Zn1 | 0.0277 (3) | 0.0107 (2) | 0.0231 (3) | 0.000 | 0.0123 (3) | 0.000 |
Zn2 | 0.0274 (3) | 0.0106 (2) | 0.0212 (3) | 0.000 | 0.0106 (3) | 0.000 |
Br1 | 0.0329 (2) | 0.01709 (16) | 0.0322 (2) | 0.00397 (14) | 0.01838 (17) | 0.00109 (14) |
Br2 | 0.0317 (2) | 0.01954 (17) | 0.0281 (2) | −0.00180 (14) | 0.00900 (17) | −0.00723 (14) |
C1—N1 | 1.332 (5) | C8—H8 | 0.9300 |
C1—C2 | 1.388 (5) | C9—C11 | 1.394 (5) |
C1—H1 | 0.9300 | C9—C10 | 1.498 (5) |
C2—C3 | 1.388 (5) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | C10—H10B | 0.9600 |
C3—C5 | 1.390 (6) | C10—H10A | 0.9600 |
C3—C4 | 1.503 (5) | C11—C12 | 1.389 (5) |
C4—H4A | 0.9600 | C11—H11 | 0.9300 |
C4—H4B | 0.9600 | C12—N2 | 1.355 (4) |
C4—H4C | 0.9600 | C12—C12ii | 1.488 (7) |
C5—C6 | 1.387 (5) | Zn1—N1 | 2.053 (3) |
C5—H5 | 0.9300 | Zn2—N2 | 2.050 (3) |
C6—N1 | 1.351 (4) | Zn1—N1i | 2.053 (3) |
C6—C6i | 1.487 (8) | Zn1—Br1i | 2.3428 (6) |
C7—N2 | 1.339 (5) | Zn1—Br1 | 2.3428 (6) |
C7—C8 | 1.380 (5) | Zn2—N2ii | 2.050 (3) |
C7—H7 | 0.9300 | Zn2—Br2 | 2.3356 (9) |
C8—C9 | 1.393 (5) | Zn2—Br2ii | 2.3356 (9) |
N1—C1—C2 | 122.5 (3) | C9—C10—H10C | 109.5 |
N1—C1—H1 | 118.7 | C9—C10—H10B | 109.5 |
C2—C1—H1 | 118.7 | H10C—C10—H10B | 109.5 |
C1—C2—C3 | 119.3 (4) | C9—C10—H10A | 109.5 |
C1—C2—H2 | 120.4 | H10C—C10—H10A | 109.5 |
C3—C2—H2 | 120.4 | H10B—C10—H10A | 109.5 |
C2—C3—C5 | 117.9 (3) | C12—C11—C9 | 120.0 (3) |
C2—C3—C4 | 121.4 (4) | C12—C11—H11 | 120.0 |
C5—C3—C4 | 120.6 (4) | C9—C11—H11 | 120.0 |
C3—C4—H4A | 109.5 | N2—C12—C11 | 121.5 (3) |
C3—C4—H4B | 109.5 | N2—C12—C12ii | 115.6 (2) |
H4A—C4—H4B | 109.5 | C11—C12—C12ii | 122.9 (2) |
C3—C4—H4C | 109.5 | C1—N1—C6 | 119.0 (3) |
H4A—C4—H4C | 109.5 | C1—N1—Zn1 | 126.8 (2) |
H4B—C4—H4C | 109.5 | C6—N1—Zn1 | 114.1 (2) |
C6—C5—C3 | 120.0 (3) | C7—N2—C12 | 118.8 (3) |
C6—C5—H5 | 120.0 | C7—N2—Zn2 | 127.2 (2) |
C3—C5—H5 | 120.0 | C12—N2—Zn2 | 113.5 (2) |
N1—C6—C5 | 121.3 (4) | N1—Zn1—N1i | 80.61 (17) |
N1—C6—C6i | 115.6 (2) | N1—Zn1—Br1i | 109.77 (9) |
C5—C6—C6i | 123.1 (2) | N1i—Zn1—Br1i | 117.20 (9) |
N2—C7—C8 | 122.2 (3) | N1—Zn1—Br1 | 117.20 (9) |
N2—C7—H7 | 118.9 | N1i—Zn1—Br1 | 109.77 (9) |
C8—C7—H7 | 118.9 | Br1i—Zn1—Br1 | 117.13 (3) |
C7—C8—C9 | 120.1 (3) | N2—Zn2—N2ii | 81.15 (17) |
C7—C8—H8 | 119.9 | N2—Zn2—Br2 | 114.76 (9) |
C9—C8—H8 | 119.9 | N2ii—Zn2—Br2 | 111.31 (9) |
C8—C9—C11 | 117.4 (3) | N2—Zn2—Br2ii | 111.31 (9) |
C8—C9—C10 | 121.8 (3) | N2ii—Zn2—Br2ii | 114.76 (9) |
C11—C9—C10 | 120.8 (3) | Br2—Zn2—Br2ii | 118.01 (4) |
N1—C1—C2—C3 | −1.1 (6) | C6i—C6—N1—Zn1 | 1.4 (5) |
C1—C2—C3—C5 | 0.8 (6) | C8—C7—N2—C12 | 0.9 (6) |
C1—C2—C3—C4 | −179.6 (4) | C8—C7—N2—Zn2 | −170.8 (3) |
C2—C3—C5—C6 | −0.2 (6) | C11—C12—N2—C7 | −0.8 (6) |
C4—C3—C5—C6 | −179.9 (4) | C12ii—C12—N2—C7 | 179.9 (4) |
C3—C5—C6—N1 | −0.2 (6) | C11—C12—N2—Zn2 | 172.0 (3) |
C3—C5—C6—C6i | −178.8 (4) | C12ii—C12—N2—Zn2 | −7.3 (5) |
N2—C7—C8—C9 | 0.0 (6) | C1—N1—Zn1—N1i | −177.6 (4) |
C7—C8—C9—C11 | −1.0 (6) | C6—N1—Zn1—N1i | −0.5 (2) |
C7—C8—C9—C10 | 176.7 (4) | C1—N1—Zn1—Br1i | −62.0 (3) |
C8—C9—C11—C12 | 1.0 (6) | C6—N1—Zn1—Br1i | 115.1 (3) |
C10—C9—C11—C12 | −176.7 (4) | C1—N1—Zn1—Br1 | 74.9 (3) |
C9—C11—C12—N2 | −0.2 (6) | C6—N1—Zn1—Br1 | −108.0 (3) |
C9—C11—C12—C12ii | 179.1 (4) | C7—N2—Zn2—N2ii | 174.8 (4) |
C2—C1—N1—C6 | 0.7 (6) | C12—N2—Zn2—N2ii | 2.71 (19) |
C2—C1—N1—Zn1 | 177.7 (3) | C7—N2—Zn2—Br2 | −75.8 (3) |
C5—C6—N1—C1 | −0.1 (6) | C12—N2—Zn2—Br2 | 112.2 (3) |
C6i—C6—N1—C1 | 178.7 (4) | C7—N2—Zn2—Br2ii | 61.5 (3) |
C5—C6—N1—Zn1 | −177.4 (3) | C12—N2—Zn2—Br2ii | −110.5 (3) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···Br1iii | 0.96 | 2.89 | 3.772 (5) | 152 |
Symmetry code: (iii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [ZnBr2(C12H12N2)] |
Mr | 409.43 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.801 (3), 8.2454 (16), 13.716 (3) |
β (°) | 117.47 (3) |
V (Å3) | 1384.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.52 |
Crystal size (mm) | 0.30 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.157, 0.479 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8352, 3560, 2963 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.687 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.099, 1.07 |
No. of reflections | 3560 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −1.04 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Zn1—N1 | 2.053 (3) | Zn1—Br1 | 2.3428 (6) |
Zn2—N2 | 2.050 (3) | Zn2—Br2 | 2.3356 (9) |
N1—Zn1—N1i | 80.61 (17) | N2—Zn2—N2ii | 81.15 (17) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···Br1iii | 0.96 | 2.89 | 3.772 (5) | 152 |
Symmetry code: (iii) x, y−1, z. |
4,4'-Dimethyl-2,2'-bipyridine (4,4'-dmbipy), is a good bidentate ligand, and numerous complexes with 4,4'-dmbipy have been prepared, such as that of mercury (Kalateh et al., 2008; Yousefi et al., 2008), indium (Ahmadi et al., 2008), iron (Amani et al., 2009), platin (Hojjat Kashani et al., 2008), manganese (Sakamoto et al., 2004), silver (Bellusci et al., 2008), gallium (Sofetis et al., 2006), copper (Willett et al., 2001), iridium (Yoshikawa et al., 2003) and cadmium (Kalateh et al., 2010). Here, we report the synthesis and structure of the title compound.
The asymmetric unit of the title compound, (Fig. 1), contains two half-molecule. The ZnII atom is for-coordinated in distorted tetragonal configurations by two N atoms from one 4,4'-dimethyl-2,2'-bipyridine and two Br atoms. The Zn—Br and Zn—N bond lengths and angles are collected in Table 1.
In the crystal structure, intermolecular C—H···Br hydrogen bonds (Table 2) may stabilize the structure (Fig. 2).