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The title compound, [Mn(H2O)6](C7H4N5O2)2, was obtained by the in situ hydro­thermal reaction of MnCl2 with 4-nitro­benzonitrile in the presence of NaN3. The Mn atoms are located on inversion centres. The structure comprises hydrogen-bonded sheets of deprotonated 5-(4-nitro­phen­yl)tetra­zole anions and hexa­aqua­manganese(II) cations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048945/bt2527sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048945/bt2527Isup2.hkl
Contains datablock I

CCDC reference: 667139

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.038
  • wR factor = 0.100
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT110_ALERT_2_B ADDSYM Detects Potential Lattice Centering or Halving . ?
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.88 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Mn1
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.880 Tmax scaled 0.880 Tmin scaled 0.736 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.13
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 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 1 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

Comment top

The tetrazole functional group has found a wide range of applications in coordination chemistry as ligands, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in materials science as high density energy materials (Wang et al.,2005; Dunica et al., 1991; Wittenberger et al., 1993). We report here the crystal structure of the title compound, hexa-aqua-manganese(II) bis-5-(4-nitrophenyl)tetrazolate.

The bond distances and angles of tetrazole ring are comparable to those found in other tetrazole-containing compounds (Wang et al., 2005; ARP et al., 2000). The Mn2+ ions are octahedronally coordinated by six water molecules. For the four of the six water molecules, each of them donates one hydrogen bond; For the other two water molecules, each of them donates two hydrogen bonds. As shown in Fig. 2, the anion and aqua-cations are contacted by H-bonds between O atoms from the coordinated water molecules and the N atoms from tetrazole groups or O atoms from nitro groups.

Related literature top

For the chemisty of tetrazole, see: ARP et al. (2000); Dunica et al. (1991); Wang et al. (2005); Wittenberger & Donner (1993).

Experimental top

A mixture of 4-nitrobenzonitrile (30 mg, 0.2 mmol), NaN3 (26 mg, 0.4 mmol), MnCl2?4H2O(59.3 mg, 0.3 mmol) ethanol (1 ml) and a few drops of water sealed in a glass tube was maintained at 120 °C. Pale-yellow block crystals suitable for X-ray analysis were obtained after 3 days.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, O atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O). The structure shows a pseudo-A centring, but refinement in space group C2/m results in disorder of the water molecules and significantly worse figures of merit.

Structure description top

The tetrazole functional group has found a wide range of applications in coordination chemistry as ligands, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in materials science as high density energy materials (Wang et al.,2005; Dunica et al., 1991; Wittenberger et al., 1993). We report here the crystal structure of the title compound, hexa-aqua-manganese(II) bis-5-(4-nitrophenyl)tetrazolate.

The bond distances and angles of tetrazole ring are comparable to those found in other tetrazole-containing compounds (Wang et al., 2005; ARP et al., 2000). The Mn2+ ions are octahedronally coordinated by six water molecules. For the four of the six water molecules, each of them donates one hydrogen bond; For the other two water molecules, each of them donates two hydrogen bonds. As shown in Fig. 2, the anion and aqua-cations are contacted by H-bonds between O atoms from the coordinated water molecules and the N atoms from tetrazole groups or O atoms from nitro groups.

For the chemisty of tetrazole, see: ARP et al. (2000); Dunica et al. (1991); Wang et al. (2005); Wittenberger & Donner (1993).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1999).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit time-of-flight he title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Atoms labelled with suffix A are generated by the symmetry operator -x + 1, -y, -z + 2.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the b axis. The dashed lines show O—H···N,O—H···O Hydrogen bonds presented in Table 2.
Hexaaquamanganese(II) bis[5-(4-nitrophenyl)tetrazolate] top
Crystal data top
[Mn(H2O)6](C7H4N5O2)2F(000) = 558
Mr = 543.34Dx = 1.637 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2744 reflections
a = 7.954 (7) Åθ = 3.0–27.5°
b = 10.317 (8) ŵ = 0.67 mm1
c = 13.537 (11) ÅT = 293 K
β = 97.157 (16)°Block, yellow
V = 1102.2 (15) Å30.35 × 0.19 × 0.19 mm
Z = 2
Data collection top
Rigaku Mercury2 (2x2 bin mode)
diffractometer
2520 independent reflections
Radiation source: fine-focus sealed tube2221 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = 1010
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1313
Tmin = 0.837, Tmax = 1.000l = 1717
10660 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0518P)2 + 0.2401P]
where P = (Fo2 + 2Fc2)/3
2520 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Mn(H2O)6](C7H4N5O2)2V = 1102.2 (15) Å3
Mr = 543.34Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.954 (7) ŵ = 0.67 mm1
b = 10.317 (8) ÅT = 293 K
c = 13.537 (11) Å0.35 × 0.19 × 0.19 mm
β = 97.157 (16)°
Data collection top
Rigaku Mercury2 (2x2 bin mode)
diffractometer
2520 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
2221 reflections with I > 2σ(I)
Tmin = 0.837, Tmax = 1.000Rint = 0.028
10660 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.08Δρmax = 0.29 e Å3
2520 reflectionsΔρmin = 0.35 e Å3
160 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
Mn10.50000.00001.00000.03147 (14)
C10.6929 (2)0.99094 (13)0.58668 (13)0.0292 (3)
C20.7548 (2)0.99156 (14)0.48888 (12)0.0291 (3)
C30.7496 (2)1.10551 (16)0.43314 (12)0.0384 (4)
H30.70451.18050.45750.046*
C40.8109 (2)1.10797 (18)0.34188 (13)0.0412 (4)
H40.80751.18370.30440.049*
C50.8771 (2)0.99548 (15)0.30807 (13)0.0356 (4)
C60.8825 (2)0.88029 (18)0.36036 (13)0.0410 (4)
H60.92650.80560.33500.049*
C70.8207 (2)0.87909 (17)0.45139 (13)0.0382 (4)
H70.82310.80260.48790.046*
N10.68587 (19)0.88555 (13)0.64346 (10)0.0369 (3)
N20.6243 (2)0.92766 (15)0.72523 (11)0.0403 (3)
N30.5957 (2)1.05356 (15)0.71783 (11)0.0407 (3)
N40.6378 (2)1.09577 (13)0.63085 (10)0.0379 (3)
N50.9448 (2)0.99757 (15)0.21236 (12)0.0438 (4)
O10.9327 (2)1.09802 (15)0.16354 (10)0.0587 (4)
O21.0104 (2)0.89956 (17)0.18422 (12)0.0674 (5)
O30.40897 (18)0.12248 (12)0.87429 (8)0.0444 (3)
H3A0.46200.11460.82260.067*
H3B0.37420.19590.87410.067*
O40.76411 (19)0.04297 (18)0.97221 (10)0.0613 (4)
H4A0.80600.04560.92130.092*
H4B0.83210.05891.01790.092*
O50.50240 (19)0.15689 (12)1.10283 (9)0.0491 (4)
H5A0.45860.14941.15750.074*
H5B0.55290.22681.10890.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0456 (2)0.0249 (2)0.0255 (2)0.00061 (13)0.01037 (15)0.00051 (11)
C10.0320 (7)0.0256 (7)0.0312 (8)0.0010 (6)0.0091 (6)0.0005 (5)
C20.0302 (8)0.0303 (8)0.0280 (8)0.0028 (6)0.0078 (6)0.0005 (5)
C30.0516 (10)0.0296 (8)0.0357 (8)0.0016 (7)0.0128 (7)0.0011 (7)
C40.0540 (11)0.0374 (9)0.0340 (8)0.0028 (8)0.0123 (8)0.0048 (7)
C50.0358 (8)0.0438 (10)0.0286 (8)0.0049 (7)0.0097 (7)0.0006 (6)
C60.0478 (10)0.0386 (9)0.0398 (9)0.0060 (8)0.0178 (8)0.0021 (7)
C70.0462 (9)0.0311 (8)0.0403 (9)0.0036 (7)0.0171 (7)0.0032 (7)
N10.0502 (8)0.0283 (7)0.0354 (7)0.0000 (6)0.0181 (6)0.0015 (6)
N20.0539 (9)0.0344 (7)0.0362 (7)0.0010 (6)0.0201 (7)0.0008 (6)
N30.0580 (9)0.0329 (8)0.0348 (7)0.0022 (7)0.0197 (7)0.0005 (6)
N40.0538 (9)0.0285 (7)0.0348 (7)0.0027 (6)0.0187 (6)0.0007 (6)
N50.0432 (8)0.0585 (11)0.0316 (8)0.0076 (7)0.0127 (7)0.0011 (6)
O10.0856 (11)0.0572 (9)0.0361 (7)0.0196 (8)0.0189 (7)0.0041 (6)
O20.0802 (11)0.0769 (11)0.0526 (8)0.0189 (9)0.0384 (8)0.0027 (8)
O30.0717 (9)0.0328 (6)0.0318 (6)0.0164 (6)0.0184 (6)0.0065 (5)
O40.0510 (8)0.1000 (12)0.0361 (7)0.0124 (8)0.0177 (6)0.0016 (8)
O50.0874 (10)0.0281 (6)0.0373 (7)0.0124 (6)0.0294 (7)0.0083 (5)
Geometric parameters (Å, º) top
Mn1—O52.1334 (17)C5—N51.464 (2)
Mn1—O5i2.1334 (17)C6—C71.382 (2)
Mn1—O3i2.1702 (17)C6—H60.9300
Mn1—O32.1702 (17)C7—H70.9300
Mn1—O4i2.225 (2)N1—N21.338 (2)
Mn1—O42.225 (2)N2—N31.320 (3)
C1—N41.336 (2)N3—N41.336 (2)
C1—N11.337 (2)N5—O21.221 (2)
C1—C21.469 (2)N5—O11.226 (2)
C2—C71.395 (2)O3—H3A0.8644
C2—C31.395 (2)O3—H3B0.8067
C3—C41.384 (2)O4—H4A0.8020
C3—H30.9300O4—H4B0.7867
C4—C51.376 (3)O5—H5A0.8599
C4—H40.9300O5—H5B0.8245
C5—C61.381 (3)
O5—Mn1—O5i180.0C3—C4—H4120.9
O5—Mn1—O3i87.43 (8)C4—C5—C6122.95 (17)
O5i—Mn1—O3i92.57 (8)C4—C5—N5118.70 (15)
O5—Mn1—O392.57 (8)C6—C5—N5118.35 (15)
O5i—Mn1—O387.43 (8)C5—C6—C7118.21 (16)
O3i—Mn1—O3180.0C5—C6—H6120.9
O5—Mn1—O4i88.44 (6)C7—C6—H6120.9
O5i—Mn1—O4i91.56 (6)C6—C7—C2120.55 (16)
O3i—Mn1—O4i88.92 (7)C6—C7—H7119.7
O3—Mn1—O4i91.08 (7)C2—C7—H7119.7
O5—Mn1—O491.56 (6)C1—N1—N2104.92 (14)
O5i—Mn1—O488.44 (6)N3—N2—N1109.52 (13)
O3i—Mn1—O491.08 (7)N2—N3—N4109.13 (12)
O3—Mn1—O488.92 (7)C1—N4—N3105.23 (14)
O4i—Mn1—O4180.00 (7)O2—N5—O1122.65 (18)
N4—C1—N1111.20 (16)O2—N5—C5118.88 (15)
N4—C1—C2124.43 (13)O1—N5—C5118.47 (16)
N1—C1—C2124.36 (14)Mn1—O3—H3A115.5
C7—C2—C3119.45 (16)Mn1—O3—H3B129.1
C7—C2—C1120.52 (14)H3A—O3—H3B106.7
C3—C2—C1120.03 (14)Mn1—O4—H4A130.8
C4—C3—C2120.55 (16)Mn1—O4—H4B118.6
C4—C3—H3119.7H4A—O4—H4B110.5
C2—C3—H3119.7Mn1—O5—H5A121.5
C5—C4—C3118.27 (16)Mn1—O5—H5B133.8
C5—C4—H4120.9H5A—O5—H5B103.8
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···N3ii0.861.982.825 (2)166
O3—H3B···N1iii0.812.022.819 (3)170
O4—H4A···O2iv0.802.243.000 (3)158
O4—H4B···O1v0.792.072.822 (3)159
O5—H5A···N2vi0.861.962.789 (3)161
O5—H5B···N4vii0.821.962.777 (3)170
Symmetry codes: (ii) x, y1, z; (iii) x+1, y1/2, z+3/2; (iv) x+2, y+1, z+1; (v) x, y1, z+1; (vi) x+1, y+1, z+2; (vii) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn(H2O)6](C7H4N5O2)2
Mr543.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.954 (7), 10.317 (8), 13.537 (11)
β (°) 97.157 (16)
V3)1102.2 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.67
Crystal size (mm)0.35 × 0.19 × 0.19
Data collection
DiffractometerRigaku Mercury2 (2x2 bin mode)
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.837, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
10660, 2520, 2221
Rint0.028
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.100, 1.08
No. of reflections2520
No. of parameters160
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.35

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···N3i0.861.982.825 (2)165.9
O3—H3B···N1ii0.812.022.819 (3)170.3
O4—H4A···O2iii0.802.243.000 (3)158.4
O4—H4B···O1iv0.792.072.822 (3)159.2
O5—H5A···N2v0.861.962.789 (3)161.1
O5—H5B···N4vi0.821.962.777 (3)170.3
Symmetry codes: (i) x, y1, z; (ii) x+1, y1/2, z+3/2; (iii) x+2, y+1, z+1; (iv) x, y1, z+1; (v) x+1, y+1, z+2; (vi) x, y+3/2, z+1/2.
 

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