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Acta Cryst. (2008). E64, m1263    [ doi:10.1107/S1600536808028754 ]

Bis([mu]-N,N'-di-3-pyridyl-2,6-pyridine-2,6-dicarboxamide-[kappa]2N:N')bis[dibromidomercury(II)] N,N-dimethylformamide disolvate

L. Huang and J. Wu

Abstract top

In the dinuclear centrosymmetric title complex, [Hg2Br4(C17H13N5O2)2]·2C3H7NO, the HgII atom is coordinated by two Br atoms and two N atoms from two different ligands in a distorted tetrahedral geometry. The solvent molecule is linked to the 28-atom ring by two hydrogen bonds.

Comment top

Metal-organic frameworks (MOFs) with microporous is currently of great interest because of their interesting structures and potential applications. So far, some interesting microporous MOFs have been documented (Chae et al. 2004, and references cited therein). One of the popular strategies to fabricate such compounds is to design the rigid ligands which have the ability to bridge the metal centers with big ring by utilizing their coordination sites. The rigid conjugated clamp-like multi-pyridine ligand N,N'-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide has been known as a good candidate in the construction of MOFs with big ring (Qin et al. 2003; Baer et al. 2002). In this work, we selected this ligand as linker, generating a new coordination complex, [HgIIBr2(C17N5O2)](DMF), (I), which is reported here. In compound (I) each HgII atom is four-coordinated by two N atoms from two ligands and two Br atoms in a distorted tetrahedral coordination sphere (Fig. 1). The two HgII atoms are bridged with two N,N'-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide ligands to form a microporous MOFs with 28-number ring. The neighbouring units are linked by the interactions to form a two-dimensional network (Fig. 2) and hydrogen bonds arising between the DMF and N,N'-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide ligand (Table 2) complete the structure.

Related literature top

For related literature, see: Baer et al. (2002); Chae et al. (2004 and references cited therein); Qin et al. (2003).

Experimental top

The ligand N,N'-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide (0.05 mmol, 0.016 g) in DMF (5 ml) was added dropwise to a solution of HgBr2 (0.1 mmol, 0.036 g) in methanol (3 ml). The precipitate was filtered and the resulting solution was allowed to stand at room temperature in the dark. After one week good quality colorless crystals were obtained and dried in air.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the title complex, showing the labeling of the non-H atoms and 30% probability ellipsolids. H atoms have been omitted.
[Figure 2] Fig. 2. A view of the crystal packing along the a axis. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Supplementary figure.
Bis(µ-N,N'-di-3-pyridylpyridine-2,6-dicarboxamide- κ2N:N')bis[dibromidomercury(II)] N,N-dimethylformamide disolvate top
Crystal data top
[Hg2Br4(C17H13N5O2)2]·2C3H7NOZ = 1
Mr = 1505.62F(000) = 712
Triclinic, P1Dx = 2.130 Mg m−3
a = 7.7609 (16) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.267 (3) ÅCell parameters from 3306 reflections
c = 13.296 (3) Åθ = 3.2–27.5°
α = 92.27 (3)°µ = 10.00 mm−1
β = 105.82 (3)°T = 293 K
γ = 104.07 (3)°Prism, colourless
V = 1173.7 (4) Å30.20 × 0.18 × 0.17 mm
Data collection top
Rigaku Saturn724
diffractometer		5337 independent reflections
Radiation source: fine-focus sealed tube4364 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 3.2°
dtprofit.ref scansh = −10→10
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2006)		k = −15→15
Tmin = 0.240, Tmax = 0.281l = −17→17
14249 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0274P)2]
where P = (Fo2 + 2Fc2)/3
5337 reflections(Δ/σ)max < 0.001
299 parametersΔρmax = 0.61 e Å−3
2 restraintsΔρmin = −0.71 e Å−3
Crystal data top
[Hg2Br4(C17H13N5O2)2]·2C3H7NOγ = 104.07 (3)°
Mr = 1505.62V = 1173.7 (4) Å3
Triclinic, P1Z = 1
a = 7.7609 (16) ÅMo Kα radiation
b = 12.267 (3) ŵ = 10.00 mm−1
c = 13.296 (3) ÅT = 293 K
α = 92.27 (3)°0.20 × 0.18 × 0.17 mm
β = 105.82 (3)°
Data collection top
Rigaku Saturn724
diffractometer		5337 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2006)		4364 reflections with I > 2σ(I)
Tmin = 0.240, Tmax = 0.281Rint = 0.032
14249 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.067Δρmax = 0.61 e Å−3
S = 1.03Δρmin = −0.71 e Å−3
5337 reflectionsAbsolute structure: ?
299 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg10.35413 (3)0.143038 (15)0.325732 (13)0.04901 (8)
Br10.37301 (7)−0.05158 (4)0.27313 (4)0.05602 (14)
Br20.63842 (7)0.30874 (4)0.39232 (4)0.06222 (15)
O10.8838 (6)0.5153 (3)1.1145 (3)0.0790 (12)
O20.1707 (5)0.0697 (3)0.7966 (2)0.0565 (9)
N10.8086 (5)0.7906 (3)0.8251 (3)0.0394 (8)
N20.7259 (5)0.5300 (3)0.9465 (3)0.0399 (9)
N30.5289 (5)0.3133 (3)0.9248 (2)0.0342 (8)
N40.3039 (5)0.2237 (3)0.7291 (3)0.0375 (8)
N50.1886 (5)0.1582 (3)0.4441 (3)0.0388 (8)
C10.9457 (6)0.8600 (4)0.9012 (3)0.0410 (11)
H10.99480.93350.88880.049*
C21.0151 (6)0.8257 (4)0.9966 (3)0.0458 (11)
H21.10840.87661.04850.055*
C30.9496 (6)0.7169 (4)1.0172 (3)0.0429 (11)
H30.99790.69351.08220.051*
C40.8082 (6)0.6423 (3)0.9377 (3)0.0323 (9)
C50.7417 (6)0.6847 (3)0.8436 (3)0.0356 (10)
H50.64540.63690.79070.043*
C60.7650 (6)0.4739 (4)1.0323 (3)0.0423 (11)
C70.6516 (6)0.3533 (3)1.0186 (3)0.0376 (10)
C80.6773 (7)0.2900 (4)1.1030 (3)0.0466 (12)
H80.76480.32111.16700.056*
C90.5708 (7)0.1802 (4)1.0900 (3)0.0477 (12)
H90.58510.13561.14510.057*
C100.4421 (6)0.1373 (4)0.9935 (4)0.0421 (11)
H100.36790.06330.98270.050*
C110.4256 (6)0.2061 (3)0.9135 (3)0.0353 (10)
C120.2874 (6)0.1602 (3)0.8079 (3)0.0380 (10)
C130.1959 (6)0.1874 (3)0.6234 (3)0.0352 (10)
C140.0045 (6)0.1485 (3)0.5954 (4)0.0418 (11)
H14−0.05820.14440.64620.050*
C15−0.0910 (6)0.1160 (4)0.4913 (4)0.0468 (12)
H15−0.21980.09010.47070.056*
C160.0035 (7)0.1218 (4)0.4176 (4)0.0463 (11)
H16−0.06290.09980.34720.056*
C170.2825 (6)0.1910 (3)0.5445 (3)0.0343 (9)
H170.41110.21750.56270.041*
H220.396 (4)0.283 (2)0.745 (3)0.044 (13)*
H210.642 (4)0.491 (3)0.8924 (19)0.039 (12)*
O30.4162 (5)0.5774 (3)0.2838 (2)0.0568 (9)
N60.1662 (6)0.5374 (3)0.3463 (3)0.0465 (10)
C18−0.0003 (7)0.5662 (5)0.3550 (4)0.0653 (15)
H18A−0.01860.62820.31520.098*
H18B0.01320.58750.42750.098*
H18C−0.10540.50190.32800.098*
C190.2125 (9)0.4419 (4)0.3969 (4)0.0719 (17)
H19A0.31990.42870.38130.108*
H19B0.10990.37590.37150.108*
H19C0.23850.45760.47160.108*
C200.2735 (8)0.5963 (4)0.2962 (3)0.0503 (12)
H20A0.23920.65830.26710.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.06762 (15)0.04080 (12)0.03641 (11)0.01450 (9)0.01118 (9)0.00594 (8)
Br10.0631 (3)0.0433 (3)0.0679 (3)0.0189 (2)0.0251 (3)0.0047 (2)
Br20.0546 (3)0.0547 (3)0.0623 (3)0.0063 (3)0.0000 (3)0.0042 (3)
O10.105 (3)0.053 (2)0.039 (2)−0.011 (2)−0.016 (2)0.0158 (17)
O20.067 (2)0.0389 (18)0.049 (2)−0.0133 (17)0.0173 (17)0.0083 (16)
N10.044 (2)0.035 (2)0.0344 (19)0.0063 (17)0.0071 (17)0.0039 (16)
N20.047 (2)0.037 (2)0.0269 (19)0.0029 (18)0.0026 (17)0.0033 (17)
N30.041 (2)0.0331 (19)0.0315 (19)0.0101 (16)0.0143 (16)0.0078 (16)
N40.042 (2)0.0298 (19)0.034 (2)−0.0031 (17)0.0113 (17)0.0018 (16)
N50.048 (2)0.0330 (19)0.0318 (19)0.0080 (17)0.0082 (17)0.0027 (16)
C10.044 (3)0.031 (2)0.045 (3)0.004 (2)0.013 (2)0.005 (2)
C20.045 (3)0.043 (3)0.036 (2)−0.002 (2)0.001 (2)0.001 (2)
C30.044 (3)0.040 (3)0.035 (2)0.006 (2)0.001 (2)0.004 (2)
C40.036 (2)0.031 (2)0.028 (2)0.0082 (18)0.0086 (18)0.0045 (17)
C50.040 (3)0.033 (2)0.027 (2)0.0048 (19)0.0043 (19)0.0013 (18)
C60.052 (3)0.040 (3)0.030 (2)0.010 (2)0.005 (2)0.010 (2)
C70.046 (3)0.038 (2)0.033 (2)0.013 (2)0.014 (2)0.011 (2)
C80.056 (3)0.051 (3)0.036 (2)0.014 (2)0.016 (2)0.012 (2)
C90.060 (3)0.048 (3)0.038 (3)0.014 (2)0.018 (2)0.018 (2)
C100.052 (3)0.034 (2)0.050 (3)0.013 (2)0.027 (2)0.012 (2)
C110.044 (3)0.030 (2)0.036 (2)0.0066 (19)0.021 (2)0.0063 (18)
C120.044 (3)0.032 (2)0.042 (3)0.009 (2)0.020 (2)0.004 (2)
C130.039 (3)0.027 (2)0.038 (2)0.0062 (18)0.011 (2)0.0052 (18)
C140.041 (3)0.033 (2)0.054 (3)0.010 (2)0.018 (2)0.006 (2)
C150.040 (3)0.032 (2)0.060 (3)0.007 (2)0.003 (2)0.004 (2)
C160.057 (3)0.033 (2)0.042 (3)0.014 (2)0.000 (2)0.004 (2)
C170.036 (2)0.032 (2)0.032 (2)0.0054 (18)0.0080 (19)0.0023 (18)
O30.059 (2)0.053 (2)0.052 (2)−0.0049 (18)0.0235 (18)0.0038 (17)
N60.058 (3)0.038 (2)0.044 (2)0.0050 (19)0.021 (2)0.0033 (18)
C180.063 (4)0.070 (4)0.063 (4)0.018 (3)0.022 (3)−0.010 (3)
C190.104 (5)0.049 (3)0.080 (4)0.024 (3)0.048 (4)0.023 (3)
C200.065 (3)0.041 (3)0.036 (3)0.002 (3)0.010 (3)0.000 (2)
Geometric parameters (Å, °) top
Hg1—N52.315 (3)C7—C81.386 (6)
Hg1—N1i2.351 (3)C8—C91.374 (6)
Hg1—Br12.5108 (8)C8—H80.9300
Hg1—Br22.5289 (12)C9—C101.383 (6)
O1—C61.218 (5)C9—H90.9300
O2—C121.225 (5)C10—C111.382 (6)
N1—C51.335 (5)C10—H100.9300
N1—C11.337 (5)C11—C121.503 (6)
N1—Hg1i2.351 (3)C13—C141.384 (6)
N2—C61.357 (5)C13—C171.389 (5)
N2—C41.394 (5)C14—C151.369 (6)
N2—H210.856 (10)C14—H140.9300
N3—C71.334 (5)C15—C161.370 (6)
N3—C111.342 (5)C15—H150.9300
N4—C121.346 (5)C16—H160.9300
N4—C131.414 (5)C17—H170.9300
N4—H220.859 (10)O3—C201.236 (6)
N5—C171.326 (5)N6—C201.306 (6)
N5—C161.337 (6)N6—C191.446 (6)
C1—C21.361 (6)N6—C181.452 (6)
C1—H10.9300C18—H18A0.9600
C2—C31.374 (6)C18—H18B0.9600
C2—H20.9300C18—H18C0.9600
C3—C41.401 (5)C19—H19A0.9600
C3—H30.9300C19—H19B0.9600
C4—C51.390 (5)C19—H19C0.9600
C5—H50.9300C20—H20A0.9300
C6—C71.502 (6)
N5—Hg1—N1i103.47 (12)C8—C9—H9120.6
N5—Hg1—Br1117.00 (9)C10—C9—H9120.6
N1i—Hg1—Br1107.93 (9)C11—C10—C9118.8 (4)
N5—Hg1—Br2102.81 (9)C11—C10—H10120.6
N1i—Hg1—Br2100.41 (9)C9—C10—H10120.6
Br1—Hg1—Br2122.54 (3)N3—C11—C10123.1 (4)
C5—N1—C1118.4 (4)N3—C11—C12117.5 (3)
C5—N1—Hg1i118.6 (3)C10—C11—C12119.4 (4)
C1—N1—Hg1i122.0 (3)O2—C12—N4123.6 (4)
C6—N2—C4126.9 (4)O2—C12—C11120.7 (4)
C6—N2—H21116 (3)N4—C12—C11115.7 (4)
C4—N2—H21118 (3)C14—C13—C17118.3 (4)
C7—N3—C11117.1 (3)C14—C13—N4122.0 (4)
C12—N4—C13122.6 (4)C17—C13—N4119.8 (4)
C12—N4—H22116 (3)C15—C14—C13118.7 (4)
C13—N4—H22121 (3)C15—C14—H14120.7
C17—N5—C16118.9 (4)C13—C14—H14120.7
C17—N5—Hg1118.2 (3)C14—C15—C16119.9 (4)
C16—N5—Hg1122.4 (3)C14—C15—H15120.0
N1—C1—C2121.6 (4)C16—C15—H15120.0
N1—C1—H1119.2N5—C16—C15121.8 (4)
C2—C1—H1119.2N5—C16—H16119.1
C1—C2—C3121.0 (4)C15—C16—H16119.1
C1—C2—H2119.5N5—C17—C13122.5 (4)
C3—C2—H2119.5N5—C17—H17118.8
C2—C3—C4118.2 (4)C13—C17—H17118.8
C2—C3—H3120.9C20—N6—C19120.5 (4)
C4—C3—H3120.9C20—N6—C18121.7 (4)
C5—C4—N2117.6 (4)C19—N6—C18117.7 (4)
C5—C4—C3117.2 (4)N6—C18—H18A109.5
N2—C4—C3125.2 (4)N6—C18—H18B109.5
N1—C5—C4123.5 (4)H18A—C18—H18B109.5
N1—C5—H5118.2N6—C18—H18C109.5
C4—C5—H5118.2H18A—C18—H18C109.5
O1—C6—N2124.0 (4)H18B—C18—H18C109.5
O1—C6—C7121.1 (4)N6—C19—H19A109.5
N2—C6—C7114.9 (4)N6—C19—H19B109.5
N3—C7—C8123.5 (4)H19A—C19—H19B109.5
N3—C7—C6117.3 (3)N6—C19—H19C109.5
C8—C7—C6119.2 (4)H19A—C19—H19C109.5
C9—C8—C7118.7 (4)H19B—C19—H19C109.5
C9—C8—H8120.7O3—C20—N6126.2 (5)
C7—C8—H8120.7O3—C20—H20A116.9
C8—C9—C10118.8 (4)N6—C20—H20A116.9
N1i—Hg1—N5—C17−141.8 (3)C6—C7—C8—C9179.1 (4)
Br1—Hg1—N5—C1799.7 (3)C7—C8—C9—C10−0.1 (7)
Br2—Hg1—N5—C17−37.6 (3)C8—C9—C10—C110.2 (7)
N1i—Hg1—N5—C1646.8 (3)C7—N3—C11—C10−0.3 (6)
Br1—Hg1—N5—C16−71.7 (3)C7—N3—C11—C12−179.8 (3)
Br2—Hg1—N5—C16151.0 (3)C9—C10—C11—N30.0 (6)
C5—N1—C1—C2−1.1 (6)C9—C10—C11—C12179.5 (4)
Hg1i—N1—C1—C2167.2 (3)C13—N4—C12—O2−4.8 (7)
N1—C1—C2—C31.6 (7)C13—N4—C12—C11174.0 (4)
C1—C2—C3—C4−0.5 (7)N3—C11—C12—O2−169.3 (4)
C6—N2—C4—C5−177.3 (4)C10—C11—C12—O211.2 (6)
C6—N2—C4—C30.9 (7)N3—C11—C12—N411.9 (6)
C2—C3—C4—C5−1.1 (6)C10—C11—C12—N4−167.7 (4)
C2—C3—C4—N2−179.4 (4)C12—N4—C13—C1451.7 (6)
C1—N1—C5—C4−0.7 (6)C12—N4—C13—C17−128.8 (4)
Hg1i—N1—C5—C4−169.4 (3)C17—C13—C14—C15−0.4 (6)
N2—C4—C5—N1−179.9 (4)N4—C13—C14—C15179.2 (4)
C3—C4—C5—N11.8 (6)C13—C14—C15—C160.5 (6)
C4—N2—C6—O1−1.7 (8)C17—N5—C16—C15−1.0 (6)
C4—N2—C6—C7179.3 (4)Hg1—N5—C16—C15170.4 (3)
C11—N3—C7—C80.4 (6)C14—C15—C16—N50.2 (7)
C11—N3—C7—C6−178.9 (4)C16—N5—C17—C131.0 (6)
O1—C6—C7—N3−177.7 (4)Hg1—N5—C17—C13−170.7 (3)
N2—C6—C7—N31.3 (6)C14—C13—C17—N5−0.3 (6)
O1—C6—C7—C83.0 (7)N4—C13—C17—N5−179.9 (4)
N2—C6—C7—C8−178.0 (4)C19—N6—C20—O32.1 (7)
N3—C7—C8—C9−0.2 (7)C18—N6—C20—O3−179.2 (5)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H22···O3i0.86 (1)2.08 (2)2.891 (5)157 (4)
N2—H21···O3i0.86 (1)2.34 (2)3.076 (5)144 (3)
N2—H21···N30.86 (1)2.25 (4)2.685 (5)111 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H22···O3i0.86 (1)2.08 (2)2.891 (5)157 (4)
N2—H21···O3i0.86 (1)2.34 (2)3.076 (5)144 (3)
N2—H21···N30.86 (1)2.25 (4)2.685 (5)111 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank Professor Hou Hong-Wei of Zhengzhou University for his help.

references
References top

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