Hexaaqua­manganese(II) bis­[5-(4-nitro­phen­yl)tetra­zolate]

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.

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

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S1. Comment

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

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

S2. Experimental

A mixture of 4-nitrobenzonitrile (30 mg, 0.2 mmol), NaN₃ (26 mg, 0.4 mmol), MnCl_2?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.

S3. Refinement

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 U_iso(H) = 1.2Ueq(C) or U_iso(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.

Computing details

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

	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.
	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]

Crystal data

[Mn(H2O)6](C7H4N5O2)2	F(000) = 558
Mr = 543.34	Dx = 1.637 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2744 reflections
a = 7.954 (7) Å	θ = 3.0–27.5°
b = 10.317 (8) Å	µ = 0.67 mm^−1
c = 13.537 (11) Å	T = 293 K
β = 97.157 (16)°	Block, yellow
V = 1102.2 (15) Å^3	0.35 × 0.19 × 0.19 mm
Z = 2

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer	2520 independent reflections
Radiation source: fine-focus sealed tube	2221 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.837, Tmax = 1.000	l = −17→17
10660 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0518P)^2 + 0.2401P] where P = (Fo^2 + 2Fc^2)/3
2520 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.0000	1.0000	0.03147 (14)
C1	0.6929 (2)	0.99094 (13)	0.58668 (13)	0.0292 (3)
C2	0.7548 (2)	0.99156 (14)	0.48888 (12)	0.0291 (3)
C3	0.7496 (2)	1.10551 (16)	0.43314 (12)	0.0384 (4)
H3	0.7045	1.1805	0.4575	0.046*
C4	0.8109 (2)	1.10797 (18)	0.34188 (13)	0.0412 (4)
H4	0.8075	1.1837	0.3044	0.049*
C5	0.8771 (2)	0.99548 (15)	0.30807 (13)	0.0356 (4)
C6	0.8825 (2)	0.88029 (18)	0.36036 (13)	0.0410 (4)
H6	0.9265	0.8056	0.3350	0.049*
C7	0.8207 (2)	0.87909 (17)	0.45139 (13)	0.0382 (4)
H7	0.8231	0.8026	0.4879	0.046*
N1	0.68587 (19)	0.88555 (13)	0.64346 (10)	0.0369 (3)
N2	0.6243 (2)	0.92766 (15)	0.72523 (11)	0.0403 (3)
N3	0.5957 (2)	1.05356 (15)	0.71783 (11)	0.0407 (3)
N4	0.6378 (2)	1.09577 (13)	0.63085 (10)	0.0379 (3)
N5	0.9448 (2)	0.99757 (15)	0.21236 (12)	0.0438 (4)
O1	0.9327 (2)	1.09802 (15)	0.16354 (10)	0.0587 (4)
O2	1.0104 (2)	0.89956 (17)	0.18422 (12)	0.0674 (5)
O3	0.40897 (18)	0.12248 (12)	0.87429 (8)	0.0444 (3)
H3A	0.4620	0.1146	0.8226	0.067*
H3B	0.3742	0.1959	0.8741	0.067*
O4	0.76411 (19)	0.04297 (18)	0.97221 (10)	0.0613 (4)
H4A	0.8060	0.0456	0.9213	0.092*
H4B	0.8321	0.0589	1.0179	0.092*
O5	0.50240 (19)	0.15689 (12)	1.10283 (9)	0.0491 (4)
H5A	0.4586	0.1494	1.1575	0.074*
H5B	0.5529	0.2268	1.1089	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0456 (2)	0.0249 (2)	0.0255 (2)	0.00061 (13)	0.01037 (15)	−0.00051 (11)
C1	0.0320 (7)	0.0256 (7)	0.0312 (8)	−0.0010 (6)	0.0091 (6)	0.0005 (5)
C2	0.0302 (8)	0.0303 (8)	0.0280 (8)	−0.0028 (6)	0.0078 (6)	−0.0005 (5)
C3	0.0516 (10)	0.0296 (8)	0.0357 (8)	0.0016 (7)	0.0128 (7)	0.0011 (7)
C4	0.0540 (11)	0.0374 (9)	0.0340 (8)	−0.0028 (8)	0.0123 (8)	0.0048 (7)
C5	0.0358 (8)	0.0438 (10)	0.0286 (8)	−0.0049 (7)	0.0097 (7)	−0.0006 (6)
C6	0.0478 (10)	0.0386 (9)	0.0398 (9)	0.0060 (8)	0.0178 (8)	−0.0021 (7)
C7	0.0462 (9)	0.0311 (8)	0.0403 (9)	0.0036 (7)	0.0171 (7)	0.0032 (7)
N1	0.0502 (8)	0.0283 (7)	0.0354 (7)	0.0000 (6)	0.0181 (6)	0.0015 (6)
N2	0.0539 (9)	0.0344 (7)	0.0362 (7)	−0.0010 (6)	0.0201 (7)	0.0008 (6)
N3	0.0580 (9)	0.0329 (8)	0.0348 (7)	0.0022 (7)	0.0197 (7)	−0.0005 (6)
N4	0.0538 (9)	0.0285 (7)	0.0348 (7)	0.0027 (6)	0.0187 (6)	0.0007 (6)
N5	0.0432 (8)	0.0585 (11)	0.0316 (8)	−0.0076 (7)	0.0127 (7)	−0.0011 (6)
O1	0.0856 (11)	0.0572 (9)	0.0361 (7)	−0.0196 (8)	0.0189 (7)	0.0041 (6)
O2	0.0802 (11)	0.0769 (11)	0.0526 (8)	0.0189 (9)	0.0384 (8)	0.0027 (8)
O3	0.0717 (9)	0.0328 (6)	0.0318 (6)	0.0164 (6)	0.0184 (6)	0.0065 (5)
O4	0.0510 (8)	0.1000 (12)	0.0361 (7)	−0.0124 (8)	0.0177 (6)	−0.0016 (8)
O5	0.0874 (10)	0.0281 (6)	0.0373 (7)	−0.0124 (6)	0.0294 (7)	−0.0083 (5)

Geometric parameters (Å, º)

Mn1—O5	2.1334 (17)	C5—N5	1.464 (2)
Mn1—O5^i	2.1334 (17)	C6—C7	1.382 (2)
Mn1—O3^i	2.1702 (17)	C6—H6	0.9300
Mn1—O3	2.1702 (17)	C7—H7	0.9300
Mn1—O4^i	2.225 (2)	N1—N2	1.338 (2)
Mn1—O4	2.225 (2)	N2—N3	1.320 (3)
C1—N4	1.336 (2)	N3—N4	1.336 (2)
C1—N1	1.337 (2)	N5—O2	1.221 (2)
C1—C2	1.469 (2)	N5—O1	1.226 (2)
C2—C7	1.395 (2)	O3—H3A	0.8644
C2—C3	1.395 (2)	O3—H3B	0.8067
C3—C4	1.384 (2)	O4—H4A	0.8020
C3—H3	0.9300	O4—H4B	0.7867
C4—C5	1.376 (3)	O5—H5A	0.8599
C4—H4	0.9300	O5—H5B	0.8245
C5—C6	1.381 (3)
O5—Mn1—O5^i	180.0	C3—C4—H4	120.9
O5—Mn1—O3^i	87.43 (8)	C4—C5—C6	122.95 (17)
O5^i—Mn1—O3^i	92.57 (8)	C4—C5—N5	118.70 (15)
O5—Mn1—O3	92.57 (8)	C6—C5—N5	118.35 (15)
O5^i—Mn1—O3	87.43 (8)	C5—C6—C7	118.21 (16)
O3^i—Mn1—O3	180.0	C5—C6—H6	120.9
O5—Mn1—O4^i	88.44 (6)	C7—C6—H6	120.9
O5^i—Mn1—O4^i	91.56 (6)	C6—C7—C2	120.55 (16)
O3^i—Mn1—O4^i	88.92 (7)	C6—C7—H7	119.7
O3—Mn1—O4^i	91.08 (7)	C2—C7—H7	119.7
O5—Mn1—O4	91.56 (6)	C1—N1—N2	104.92 (14)
O5^i—Mn1—O4	88.44 (6)	N3—N2—N1	109.52 (13)
O3^i—Mn1—O4	91.08 (7)	N2—N3—N4	109.13 (12)
O3—Mn1—O4	88.92 (7)	C1—N4—N3	105.23 (14)
O4^i—Mn1—O4	180.00 (7)	O2—N5—O1	122.65 (18)
N4—C1—N1	111.20 (16)	O2—N5—C5	118.88 (15)
N4—C1—C2	124.43 (13)	O1—N5—C5	118.47 (16)
N1—C1—C2	124.36 (14)	Mn1—O3—H3A	115.5
C7—C2—C3	119.45 (16)	Mn1—O3—H3B	129.1
C7—C2—C1	120.52 (14)	H3A—O3—H3B	106.7
C3—C2—C1	120.03 (14)	Mn1—O4—H4A	130.8
C4—C3—C2	120.55 (16)	Mn1—O4—H4B	118.6
C4—C3—H3	119.7	H4A—O4—H4B	110.5
C2—C3—H3	119.7	Mn1—O5—H5A	121.5
C5—C4—C3	118.27 (16)	Mn1—O5—H5B	133.8
C5—C4—H4	120.9	H5A—O5—H5B	103.8

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N3^ii	0.86	1.98	2.825 (2)	166
O3—H3B···N1^iii	0.81	2.02	2.819 (3)	170
O4—H4A···O2^iv	0.80	2.24	3.000 (3)	158
O4—H4B···O1^v	0.79	2.07	2.822 (3)	159
O5—H5A···N2^vi	0.86	1.96	2.789 (3)	161
O5—H5B···N4^vii	0.82	1.96	2.777 (3)	170

Symmetry codes: (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+1; (v) x, y−1, z+1; (vi) −x+1, −y+1, −z+2; (vii) x, −y+3/2, z+1/2.