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In the crystal structure of the title complex, poly­[[di­azido­manganese(II)]-di-μ-1,2-bis­(imidazol-1-yl)­ethane-κ4N3:N3′], [Mn(N3)2(C8H10N4)2]n or [Mn(N3)2(bim)2]n, where bim is 1,2-­bis(imidazol-1-yl)­ethane, each MnII atom is six-coordinated in a distorted octahedral coordination environment to four N atoms from four bim ligands and two N atoms from two azide ligands. The MnII atoms, which lie on inversion centres, are bridged by four bim ligands to form a two-dimensional (4,4)-network. The azide ligands are monodentate (terminal).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014453/jz1634sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014453/jz1634Isup2.hkl
Contains datablock I

CCDC reference: 248128

Comment top

The design of coordination polymers has been developing rapidly because of their fascinating structures and potential applications as functional materials (Batten & Robson, 1998; Blake et al., 1999). A number of infinite one-, two- and three-dimensional frameworks have been synthesized with rigid rod-like organic building blocks, such as 4,4'-bipyridine (Fujita et al., 1994) and 4,4'-azobispyridine (Li et al., 2001). Relatively few studies of flexible ligands have been reported. Recently, we synthesized several coordination polymers with the flexible ligand 1,2-bis(1,2,4-triazol-1-yl)ethane (bte; Li et al., 1999, 2003; Zhu et al., 2004). In order to extend our research, we have now chosen a similar ligand, 1,2-bis(imidazol-1-yl)ethane (bim; Wu et al., 1997). Here, we report the preparation and crystal structure of the title novel two-dimensional coordination polymer incorporating the bim ligand, [Mn(bim)2(N3)2]n, (I). \sch

As shown in Fig. 1, the MnII atom of (I) occupies an inversion centre. The coordination geometry of the MnII atom is distorted octahedral; it is coordinated equatorially by four N atoms from the imidazole rings of four symmetry-related bim ligands, and axially by two N atoms from two symmetry-related azide ligands. The azide anion acts as a monodentate ligand (Ribas et al., 1999). The bim ligands exhibit the anti conformation in (I). The two imidazole ring planes, C1—C3/N1/N2 and C4—C6/N3/N4, are planar, with r.m.s. deviations of 0.0015 (12) and 0.0019 (13) Å, respectively. The dihedral angle between these two imidazole ring planes is 177.85 (15)°. The N2—C7—C8—N4 torsion angle is 57.79 (9)°.

As illustrated in Fig. 2, each bim ligand in (I) coordinates two MnII atoms through its two imidazole N atoms, thus acting as a bridging bidentate ligand. The MnII atoms are bridged by four bim ligands to form a two-dimensional neutral (4,4) network. The networks contain square grids (36-membered ring), with an MnII atom at each corner and a bim ligand at each edge connecting two MnII atoms. Due to the symmetry of the crystal structure, the edge lengths are equal, and the value of 11.7484 (16) Å is similar to what was observed in the related bte ligand compound [Cu(TTA)2]2(bte)] [TTA is 1,1,1-trifloro-3-(2-thenoyl)acetone; Li et al., 1999].

The square-grid sheets are stacked in an off-set fashion parallel to the c direction. The off-set superpositions of each pair of adjacent networks by half of the edges divide the voids into smaller rectangles. The azide anions of one sheet project into the holes of the next sheet. In the superposition structure, the sheets are arranged in the sequence ···A—B—A—B···.

Experimental top

An aqueous solution (10 ml) of NaN3 (0.163 g, 2.5 mmol) was mixed with an aqueous solution (10 ml) of MnSO4·H2O (0.085 g, 0.5 mmol) and stirred for 20 min. Then an ethanol solution (10 ml) of 1,2-bis(imidazol-1-yl)ethane (0.081 g, 0.5 mmol) was added slowly to the above solution. The mixture was stirred at room temperature for 30 min and the resultant solution was filtered. After allowing the filtrate to stand in air at room temperature for two weeks, well formed yellow single crystals of (I) were obtained. The product is stable under an ambient atmosphere and is insoluble in most common inorganic and organic solvents. Analysis, found: C 41.43, H 4.37, N 42.36%; calculated for C16H20MnN14: C 41.47, H 4.35, N 42.33%.

Refinement top

H atoms were placed in idealized positions and refined as riding, with C—H distances of 0.93 (imidazole) and 0.97 Å (CH2), and with Uiso(H) = 1.2Ueq(C). Please check added text.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the local coordination of the MnII atom in (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The two-dimensional sheet of the (4,4) network in (I). The azide anions have been omitted for clarity.
poly[diazidomanganese(II)]-di-µ-1,2-bis(imidazol-1-yl)ethane] top
Crystal data top
[Mn(N3)2(C8H10N4)2]F(000) = 478
Mr = 463.40Dx = 1.464 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4684 reflections
a = 6.9636 (16) Åθ = 3.3–27.5°
b = 14.819 (3) ŵ = 0.66 mm1
c = 10.256 (2) ÅT = 193 K
β = 96.702 (5)°Polyhedron, yellow
V = 1051.1 (4) Å30.51 × 0.32 × 0.25 mm
Z = 2
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
2393 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(North et al., 1968)
h = 99
Tmin = 0.769, Tmax = 0.851k = 1919
11499 measured reflectionsl = 1313
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0335P)2 + 1.025P]
where P = (Fo2 + 2Fc2)/3
2393 reflections(Δ/σ)max < 0.001
142 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
[Mn(N3)2(C8H10N4)2]V = 1051.1 (4) Å3
Mr = 463.40Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.9636 (16) ŵ = 0.66 mm1
b = 14.819 (3) ÅT = 193 K
c = 10.256 (2) Å0.51 × 0.32 × 0.25 mm
β = 96.702 (5)°
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
2393 independent reflections
Absorption correction: multi-scan
(North et al., 1968)
2287 reflections with I > 2σ(I)
Tmin = 0.769, Tmax = 0.851Rint = 0.027
11499 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.07Δρmax = 0.34 e Å3
2393 reflectionsΔρmin = 0.23 e Å3
142 parameters
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
Mn10.00000.00000.00000.01531 (11)
N10.1244 (2)0.14032 (10)0.01270 (16)0.0234 (3)
N20.3487 (2)0.24076 (10)0.04455 (15)0.0231 (3)
N30.8648 (2)0.45944 (10)0.32108 (14)0.0196 (3)
N40.6546 (2)0.40931 (10)0.19334 (15)0.0218 (3)
N50.2775 (2)0.04100 (13)0.11625 (16)0.0285 (4)
N60.3219 (2)0.07325 (11)0.21954 (16)0.0261 (4)
N70.3730 (3)0.10376 (17)0.3224 (2)0.0522 (6)
C10.1044 (3)0.21480 (13)0.0651 (2)0.0281 (4)
H1A0.01040.22140.12180.034*
C20.2414 (3)0.27703 (13)0.0471 (2)0.0296 (4)
H2A0.25930.33280.08820.036*
C30.2731 (3)0.15922 (12)0.07735 (19)0.0244 (4)
H3A0.31970.12080.13810.029*
C40.9450 (3)0.46356 (16)0.19227 (19)0.0314 (5)
H4A1.06880.48450.16390.038*
C50.8175 (3)0.43264 (17)0.1126 (2)0.0355 (5)
H5A0.83670.42820.02150.043*
C60.6900 (3)0.42610 (12)0.31707 (17)0.0205 (4)
H6A0.60190.41550.39090.025*
C70.5205 (3)0.27938 (13)0.0924 (2)0.0266 (4)
H7A0.56420.23980.15820.032*
H7B0.62330.28410.02030.032*
C80.4780 (3)0.37185 (13)0.15148 (19)0.0246 (4)
H8A0.37930.36720.22610.030*
H8B0.43030.41130.08700.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.01532 (19)0.01622 (18)0.01504 (18)0.00171 (14)0.00455 (13)0.00029 (13)
N10.0244 (8)0.0199 (7)0.0270 (8)0.0046 (6)0.0079 (6)0.0001 (6)
N20.0251 (8)0.0196 (7)0.0257 (8)0.0062 (6)0.0082 (6)0.0005 (6)
N30.0196 (7)0.0220 (7)0.0180 (7)0.0013 (6)0.0056 (6)0.0001 (6)
N40.0216 (8)0.0241 (8)0.0205 (7)0.0074 (6)0.0057 (6)0.0010 (6)
N50.0198 (8)0.0419 (10)0.0233 (8)0.0028 (7)0.0005 (6)0.0049 (7)
N60.0256 (8)0.0308 (9)0.0221 (8)0.0111 (7)0.0039 (6)0.0029 (7)
N70.0660 (15)0.0649 (15)0.0260 (10)0.0361 (12)0.0061 (10)0.0092 (10)
C10.0325 (10)0.0239 (9)0.0307 (10)0.0049 (8)0.0157 (8)0.0020 (8)
C20.0383 (11)0.0227 (9)0.0303 (10)0.0079 (8)0.0147 (9)0.0050 (8)
C30.0279 (9)0.0190 (8)0.0278 (9)0.0041 (7)0.0102 (8)0.0014 (7)
C40.0275 (10)0.0459 (12)0.0202 (9)0.0159 (9)0.0012 (8)0.0010 (9)
C50.0360 (11)0.0543 (14)0.0164 (9)0.0224 (10)0.0029 (8)0.0009 (9)
C60.0212 (8)0.0238 (9)0.0167 (8)0.0020 (7)0.0025 (7)0.0020 (7)
C70.0242 (9)0.0227 (9)0.0348 (10)0.0063 (7)0.0114 (8)0.0004 (8)
C80.0213 (9)0.0270 (9)0.0268 (9)0.0059 (7)0.0084 (7)0.0038 (7)
Geometric parameters (Å, º) top
Mn1—N52.2334 (16)N4—C81.458 (2)
Mn1—N5i2.2334 (16)N5—N61.170 (2)
Mn1—N3ii2.2400 (15)N6—N71.164 (2)
Mn1—N3iii2.2400 (15)C1—C21.355 (3)
Mn1—N12.2622 (16)C1—H1A0.9300
Mn1—N1i2.2622 (16)C2—H2A0.9300
N1—C31.323 (2)C3—H3A0.9300
N1—C11.379 (2)C4—C51.355 (3)
N2—C31.345 (2)C4—H4A0.9300
N2—C21.376 (2)C5—H5A0.9300
N2—C71.461 (2)C6—H6A0.9300
N3—C61.319 (2)C7—C81.513 (3)
N3—C41.374 (2)C7—H7A0.9700
N3—Mn1iv2.2400 (15)C7—H7B0.9700
N4—C61.344 (2)C8—H8A0.9700
N4—C51.369 (3)C8—H8B0.9700
N5—Mn1—N5i180.00 (12)C2—C1—H1A124.9
N5—Mn1—N3ii86.80 (6)N1—C1—H1A124.9
N5i—Mn1—N3ii93.20 (6)C1—C2—N2105.94 (17)
N5—Mn1—N3iii93.20 (6)C1—C2—H2A127.0
N5i—Mn1—N3iii86.80 (6)N2—C2—H2A127.0
N3ii—Mn1—N3iii180.00 (4)N1—C3—N2111.79 (16)
N5—Mn1—N191.86 (6)N1—C3—H3A124.1
N5i—Mn1—N188.14 (6)N2—C3—H3A124.1
N3ii—Mn1—N190.05 (6)C5—C4—N3110.08 (17)
N3iii—Mn1—N189.95 (6)C5—C4—H4A125.0
N5—Mn1—N1i88.14 (6)N3—C4—H4A125.0
N5i—Mn1—N1i91.86 (6)C4—C5—N4106.01 (17)
N3ii—Mn1—N1i89.95 (6)C4—C5—H5A127.0
N3iii—Mn1—N1i90.05 (6)N4—C5—H5A127.0
N1—Mn1—N1i180.00 (3)N3—C6—N4111.75 (16)
C3—N1—C1104.99 (15)N3—C6—H6A124.1
C3—N1—Mn1123.41 (13)N4—C6—H6A124.1
C1—N1—Mn1129.59 (12)N2—C7—C8111.09 (16)
C3—N2—C2107.08 (15)N2—C7—H7A109.4
C3—N2—C7125.42 (16)C8—C7—H7A109.4
C2—N2—C7127.39 (16)N2—C7—H7B109.4
C6—N3—C4105.05 (15)C8—C7—H7B109.4
C6—N3—Mn1iv127.14 (12)H7A—C7—H7B108.0
C4—N3—Mn1iv127.81 (12)N4—C8—C7109.30 (15)
C6—N4—C5107.12 (15)N4—C8—H8A109.8
C6—N4—C8127.03 (16)C7—C8—H8A109.8
C5—N4—C8125.84 (16)N4—C8—H8B109.8
N6—N5—Mn1135.64 (14)C7—C8—H8B109.8
N7—N6—N5177.4 (2)H8A—C8—H8B108.3
C2—C1—N1110.20 (17)
N5—Mn1—N1—C3113.76 (16)Mn1—N1—C3—N2164.90 (12)
N5i—Mn1—N1—C366.24 (16)C2—N2—C3—N10.2 (2)
N3ii—Mn1—N1—C3159.44 (16)C7—N2—C3—N1176.25 (17)
N3iii—Mn1—N1—C320.56 (16)C6—N3—C4—C50.0 (3)
N5—Mn1—N1—C184.86 (18)Mn1iv—N3—C4—C5179.86 (15)
N5i—Mn1—N1—C195.14 (18)N3—C4—C5—N40.3 (3)
N3ii—Mn1—N1—C11.94 (18)C6—N4—C5—C40.5 (2)
N3iii—Mn1—N1—C1178.06 (18)C8—N4—C5—C4179.53 (19)
N3ii—Mn1—N5—N6146.2 (2)C4—N3—C6—N40.3 (2)
N3iii—Mn1—N5—N633.8 (2)Mn1iv—N3—C6—N4179.82 (12)
N1—Mn1—N5—N656.3 (2)C5—N4—C6—N30.5 (2)
N1i—Mn1—N5—N6123.7 (2)C8—N4—C6—N3179.53 (17)
C3—N1—C1—C20.4 (2)C3—N2—C7—C8126.5 (2)
Mn1—N1—C1—C2163.58 (14)C2—N2—C7—C857.8 (3)
N1—C1—C2—N20.3 (2)C6—N4—C8—C7113.3 (2)
C3—N2—C2—C10.1 (2)C5—N4—C8—C765.6 (3)
C7—N2—C2—C1176.42 (19)N2—C7—C8—N4177.85 (15)
C1—N1—C3—N20.3 (2)
Symmetry codes: (i) x, y, z; (ii) x1, y+1/2, z+1/2; (iii) x+1, y1/2, z1/2; (iv) x+1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Mn(N3)2(C8H10N4)2]
Mr463.40
Crystal system, space groupMonoclinic, P21/c
Temperature (K)193
a, b, c (Å)6.9636 (16), 14.819 (3), 10.256 (2)
β (°) 96.702 (5)
V3)1051.1 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.66
Crystal size (mm)0.51 × 0.32 × 0.25
Data collection
DiffractometerRigaku Mercury CCD area-detector
diffractometer
Absorption correctionMulti-scan
(North et al., 1968)
Tmin, Tmax0.769, 0.851
No. of measured, independent and
observed [I > 2σ(I)] reflections
11499, 2393, 2287
Rint0.027
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.087, 1.07
No. of reflections2393
No. of parameters142
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.23

Computer programs: CrystalClear (Rigaku, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Mn1—N52.2334 (16)N5—N61.170 (2)
Mn1—N3i2.2400 (15)N6—N71.164 (2)
Mn1—N12.2622 (16)
N5—Mn1—N5ii180.00 (12)N3i—Mn1—N190.05 (6)
N5—Mn1—N3i86.80 (6)N1—Mn1—N1ii180.00 (3)
N3i—Mn1—N3iii180.00 (4)N6—N5—Mn1135.64 (14)
N5—Mn1—N191.86 (6)N7—N6—N5177.4 (2)
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x, y, z; (iii) x+1, y1/2, z1/2.
 

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