Diaqua­bis[5-(2-pyridylmeth­yl)tetra­zolato-κ²N¹,N⁵]manganese(II)

The title complex, [Mn(C₇H₆N₅)₂(H₂O)₂], was obtained by the in situ hydro­thermal reaction of MnCl₂ with 2-(2-pyrid­yl)acetonitrile in the presence of NaN₃. The Mn^II atom, which is located on an inversion centre, has a distorted octa­hedral coordination geometry formed by two water mol­ecules and two chelating ligands. Inter­molecular hydrogen bonds and π–π inter­actions (3.452 Å) stabilize the crystal structure and lead to the formation of a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.059
• wR factor = 0.173
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  C3     ..  C3      ..       3.05 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.802     1.000
            Tmin(prime) and Tmax expected:      0.840     0.902
            RR(prime) =      0.861
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_4_C Tmax/Tmin Range Test RR' too Large .............       0.86
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.90
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

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      0.902
            Tmax scaled      0.902 Tmin scaled      0.723
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

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S1. Comment

Since Sharpless et al. reported the environmentally friendly process for the preparation of tetrazole (Demko & Sharpless, 2001), many novel tetrazole compounds have been reported through 2 + 3 cycloaddition reactions. Work in our group have found that single crystals of coordination polymers can often be generated under hydrothermal conditions through in situ synthesis. (Zhao et al., 2008) The title complex was obtained by the in situ hydrothermal reaction of MnCl₂ with pyridin-2-yl-acetonitrile in the presence of NaN₃.

In the title compound, the central Mn(II) ion is located on an inversion center and coordinated by two water molecules and two 5-(pyridin-2-ylmethyl)tetrazolate ligands through the pyridine N and tetrazole N atoms with a distorted octahedral geometry (Fig. 1). Extensive intermolecular O—H···N and C—H···N hydrogen bonds and π-π interactions stabilize the crystal structure which leads to the formation of a three-dimensional network.

Related literature

For related literature, see: Demko & Sharpless (2001); Zhao et al. (2008). For the synthesis of similar complexes, see: Hu et al. (2007); Liu & Fan (2007).

S2. Experimental

A mixture of pyridin-2-yl-acetonitrile (26 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 105°C. Colorless crystals suitable for X-ray analysis were obtained after a week.

S3. Refinement

The C-bound H atoms were placed in calculated positions (C—H 0.93 Å) and treated in the subsequent refinement as riding atoms, with U_iso(H) = 1.2U_eq(C) while the water H atoms were located in Fourier difference map and refined with U_iso(H) = 1.5U_eq(O).

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, 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

	Fig. 1. The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. [symmetry code: -x, -y+2, -z+2]
	Fig. 2. The packing view of title compound with π···π stacking along the b axis.

Diaquabis[5-(2-pyridylmethyl)tetrazolato-κ²N¹,N⁵]manganese(II)

Crystal data

[Mn(C7H6N5)2(H2O)2]	F(000) = 422
Mr = 411.31	Dx = 1.701 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2050 reflections
a = 6.639 (2) Å	θ = 2.8–27.5°
b = 13.788 (5) Å	µ = 0.86 mm^−1
c = 8.771 (3) Å	T = 293 K
β = 90.01 (5)°	Prism, colorless
V = 802.9 (4) Å^3	0.20 × 0.12 × 0.12 mm
Z = 2

Data collection

Rigaku Mercury2) diffractometer	1836 independent reflections
Radiation source: fine-focus sealed tube	1550 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
Tmin = 0.802, Tmax = 1.000	l = −11→11
8070 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0834P)^2 + 0.8368P] where P = (Fo^2 + 2Fc^2)/3
1836 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.73 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	0.0000	1.0000	1.0000	0.0261 (3)
N5	0.4367 (4)	0.7962 (2)	0.8387 (3)	0.0354 (7)
O1	0.2353 (4)	1.10029 (18)	0.9172 (3)	0.0382 (6)
H1B	0.3241	1.1164	0.9997	0.057*
H1C	0.1730	1.1583	0.8792	0.057*
N3	0.1879 (4)	0.88112 (19)	0.9162 (3)	0.0299 (6)
C7	0.1284 (5)	0.8238 (2)	0.8048 (4)	0.0275 (7)
N2	0.3843 (4)	0.8625 (2)	0.9339 (3)	0.0346 (7)
N4	0.2778 (4)	0.7701 (2)	0.7545 (3)	0.0332 (6)
C6	−0.0793 (5)	0.8223 (2)	0.7415 (4)	0.0317 (7)
H6A	−0.1720	0.8028	0.8214	0.038*
H6B	−0.0860	0.7738	0.6614	0.038*
C5	−0.1465 (5)	0.9175 (2)	0.6782 (4)	0.0289 (7)
C4	−0.2173 (5)	0.9233 (3)	0.5316 (4)	0.0359 (8)
H4A	−0.2262	0.8677	0.4720	0.043*
C3	−0.2743 (6)	1.0105 (3)	0.4737 (4)	0.0371 (8)
H3A	−0.3202	1.0155	0.3738	0.045*
C2	−0.2628 (6)	1.0907 (3)	0.5649 (4)	0.0377 (8)
H2A	−0.3022	1.1513	0.5290	0.045*
C1	−0.1925 (5)	1.0797 (2)	0.7089 (4)	0.0340 (8)
H1A	−0.1832	1.1345	0.7704	0.041*
N1	−0.1363 (4)	0.99533 (17)	0.7671 (3)	0.0273 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0329 (4)	0.0185 (4)	0.0270 (4)	0.0025 (2)	−0.0001 (3)	−0.0016 (2)
N5	0.0353 (15)	0.0297 (15)	0.0413 (16)	0.0058 (12)	−0.0018 (12)	−0.0047 (12)
O1	0.0381 (13)	0.0326 (13)	0.0439 (14)	−0.0103 (10)	−0.0061 (11)	0.0116 (11)
N3	0.0341 (15)	0.0230 (13)	0.0326 (14)	0.0049 (11)	−0.0004 (11)	−0.0030 (11)
C7	0.0324 (16)	0.0155 (13)	0.0345 (16)	0.0003 (11)	0.0025 (13)	−0.0007 (12)
N2	0.0328 (15)	0.0265 (14)	0.0446 (16)	0.0041 (11)	−0.0027 (12)	−0.0019 (12)
N4	0.0371 (15)	0.0253 (13)	0.0371 (16)	0.0054 (11)	−0.0003 (12)	−0.0037 (12)
C6	0.0339 (17)	0.0217 (15)	0.0395 (17)	−0.0018 (12)	−0.0022 (14)	−0.0058 (13)
C5	0.0271 (15)	0.0245 (15)	0.0349 (17)	−0.0007 (12)	−0.0006 (13)	−0.0032 (13)
C4	0.0334 (17)	0.0372 (19)	0.0373 (18)	0.0010 (14)	−0.0045 (14)	−0.0081 (15)
C3	0.0299 (18)	0.051 (2)	0.0303 (17)	−0.0013 (14)	−0.0013 (14)	0.0029 (15)
C2	0.0399 (19)	0.0357 (18)	0.0376 (18)	0.0039 (15)	−0.0015 (15)	0.0079 (15)
C1	0.0417 (19)	0.0246 (16)	0.0357 (17)	0.0038 (13)	0.0001 (14)	0.0003 (13)
N1	0.0289 (14)	0.0239 (14)	0.0291 (14)	0.0009 (9)	0.0012 (11)	0.0003 (10)

Geometric parameters (Å, º)

Mn1—N3	2.187 (5)	C6—H6A	0.9700
Mn1—O1	2.209 (5)	C6—H6B	0.9700
Mn1—N1	2.235 (3)	C5—N1	1.328 (5)
N5—N2	1.286 (5)	C5—C4	1.371 (6)
N5—N4	1.337 (5)	C4—C3	1.359 (6)
O1—H1B	0.9600	C4—H4A	0.9300
O1—H1C	0.9600	C3—C2	1.367 (6)
N3—C7	1.317 (5)	C3—H3A	0.9300
N3—N2	1.338 (6)	C2—C1	1.355 (6)
C7—N4	1.314 (5)	C2—H2A	0.9300
C7—C6	1.487 (6)	C1—N1	1.324 (5)
C6—C5	1.494 (6)	C1—H1A	0.9300
N3—Mn1—O1	87.43 (11)	C7—C6—H6B	108.8
N3^i—Mn1—O1	92.57 (5)	C5—C6—H6B	108.8
N3—Mn1—N1	84.39 (17)	H6A—C6—H6B	107.7
N3^i—Mn1—N1	95.61 (17)	N1—C5—C4	121.4 (3)
O1^i—Mn1—N1	89.79 (18)	N1—C5—C6	118.5 (4)
O1—Mn1—N1	90.21 (18)	C4—C5—C6	120.1 (3)
N2—N5—N4	109.6 (3)	C3—C4—C5	119.9 (3)
Mn1—O1—H1B	109.3	C3—C4—H4A	120.1
Mn1—O1—H1C	109.3	C5—C4—H4A	120.1
H1B—O1—H1C	109.5	C4—C3—C2	118.8 (4)
C7—N3—N2	105.3 (3)	C4—C3—H3A	120.6
C7—N3—Mn1	121.9 (3)	C2—C3—H3A	120.6
N2—N3—Mn1	131.4 (2)	C1—C2—C3	118.3 (4)
N3—C7—N4	111.1 (3)	C1—C2—H2A	120.9
N3—C7—C6	124.3 (3)	C3—C2—H2A	120.9
N4—C7—C6	124.5 (3)	N1—C1—C2	123.7 (3)
N5—N2—N3	109.0 (3)	N1—C1—H1A	118.2
C7—N4—N5	105.0 (3)	C2—C1—H1A	118.2
C7—C6—C5	113.8 (3)	C1—N1—C5	118.0 (4)
C7—C6—H6A	108.8	C1—N1—Mn1	116.2 (2)
C5—C6—H6A	108.8	C5—N1—Mn1	125.5 (2)
O1^i—Mn1—N3—C7	64.4 (3)	C7—C6—C5—C4	125.9 (3)
O1—Mn1—N3—C7	−115.6 (3)	N1—C5—C4—C3	1.5 (5)
N1—Mn1—N3—C7	−25.2 (3)	C6—C5—C4—C3	−178.6 (3)
O1^i—Mn1—N3—N2	−131.9 (3)	C5—C4—C3—C2	−1.1 (6)
O1—Mn1—N3—N2	48.1 (3)	C4—C3—C2—C1	0.8 (6)
N1—Mn1—N3—N2	138.5 (3)	C3—C2—C1—N1	−0.8 (6)
N1^i—Mn1—N3—N2	−41.5 (3)	C2—C1—N1—C5	1.1 (5)
N2—N3—C7—N4	0.8 (4)	C2—C1—N1—Mn1	174.6 (3)
Mn1—N3—C7—N4	168.2 (2)	C4—C5—N1—C1	−1.5 (5)
N2—N3—C7—C6	−177.6 (3)	C6—C5—N1—C1	178.7 (3)
Mn1—N3—C7—C6	−10.2 (4)	C4—C5—N1—Mn1	−174.3 (2)
N4—N5—N2—N3	0.7 (4)	C6—C5—N1—Mn1	5.9 (4)
C7—N3—N2—N5	−0.9 (4)	N3—Mn1—N1—C1	−145.1 (3)
Mn1—N3—N2—N5	−166.6 (2)	N3^i—Mn1—N1—C1	34.9 (3)
N3—C7—N4—N5	−0.3 (4)	O1^i—Mn1—N1—C1	122.3 (3)
C6—C7—N4—N5	178.0 (3)	O1—Mn1—N1—C1	−57.7 (3)
N2—N5—N4—C7	−0.3 (4)	N3—Mn1—N1—C5	27.8 (3)
N3—C7—C6—C5	59.0 (5)	N3^i—Mn1—N1—C5	−152.2 (3)
N4—C7—C6—C5	−119.2 (4)	O1^i—Mn1—N1—C5	−64.8 (3)
C7—C6—C5—N1	−54.2 (4)	O1—Mn1—N1—C5	115.2 (3)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2^ii	0.96	2.04	2.889 (8)	146
O1—H1B···N5^ii	0.96	2.45	3.371 (8)	162
O1—H1C···N4^iii	0.96	1.96	2.786 (8)	142
C6—H6A···N5^iv	0.97	2.60	3.343 (5)	133

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