Diaqua­bis[5-(pyrimidin-2-yl)tetra­zolato]manganese(II)

The title complex, [Mn(C₅H₃N₆)₂(H₂O)₂], possesses a crystallographically imposed center of symmetry occupied by an Mn^II ion, which is coordinated by four N atoms from two 5-(pyrimidin-2-yl)tetra­zolate ligands [Mn—N = 2.2066 (13) and 2.2731 (15) Å] and two water mol­ecules [Mn—O = 2.1868 (14) Å] in a distorted octa­hedral geometry. In the crystal structure, inter­molecular O—H...N hydrogen bonds link the complexes into two-dimensional sheets parallel to the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.076
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
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)       2.08
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 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
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

5-Substituted 1H-tetrazole ligands are often used in metal-organic complexes. With N-heterocyclic substituents, most of metal complexes were structurally characterized, in which 2-position N-containing derivatives always give mono-nuclear complexes. Such as, diaquabis[5-(pyridyl-2-yl)tetrazolato]manganese(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]copper(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]zinc(II) and diaquabis[5-(pyrazin-2-yl)tetrazolato]manganese(II) (Wang et al., 2003; Mo et al., 2004; Rodríguez et al., 2005; Luo et al., 2006; Peng et al., 2007). Herein, 2-(1H-tetrazol-5-yl)pyrimidine (L) ligands were used to give a similar mono-nuclear Mn(II) complex, diaquabis[5-(pyrimidin-2-yl)tetrazolato]manganese(II) (I). With this ligand, two two-dimensional Co(II) and Fe(II) complexes were reported recently (Rodríguez et al., 2005).

In the title complex (I), the central Mn(II) ion is located on an inversion center and coordinated by two deprotonated bidentate L ligands via one of the pyrimidinyl nitrogen and the tetrazole nitrogen in the 1-position and two water molecules with a transoid pseudo-octahedral geometry geometry (Fig. 1). The structure is similar to those of diaquabis[5-(pyridyl-2-yl)tetrazolato]manganese(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]copper(II), diaquabis[5-(pyridyl-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]zinc(II), diaquabis[5-(pyrazin-2-yl)tetrazolato]manganese(II) (Wang et al., 2003; Mo et al., 2004; Rodríguez et al., 2005; Luo et al., 2006; Peng et al., 2007).

An interesting aspect of the structure is the way in which the mononuclear units are interlinked via hydrogen bonds into a two-dimensional network. As shown in Fig. 2, each coordinated water molecule of a mononuclear unit interlinks with the tetrazole rings from two neighboring mononuclear units through O—H···N hydrogen bond, and each tetrazole ring forms two O—H···N hydrogen bonds via the nitrogen atoms at 3- and 4-positions with also two adjacent molecules. Thus, each unit forms a total of eight hydrogen bonds with its four neighbors. The related hydrogen bond parameters are listed in the Table.

Related literature

The synthesis of 2-(1H-tetrazol-5-yl)pyrimidine was described by Demko & Sharpless (2001); for the crystal structures of related complexes, see: Wang et al. (2003), Mo et al. (2004), Rodríguez et al. (2005), Luo et al. (2006), Peng et al. (2007).

S2. Experimental

The ligand, 2-(1H-tetrazol-5-yl)pyrimidine (L) was synthesized according to the literature method (Demko & Sharpless, 2001). A mixture of MnCl₂.4H₂O (40 mg, 0.2 mmol) and ligand L (60 mg, 0.4 mmol) in water (10 ml) was placed in a Teflon-lined stainless-steel Parr bomb that was heated at 393 K for 48 h. Colorless crystals were collected after the bomb allowed to cool to room temperature spontaneously. Yield, 40%.

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) = 1.2 U_eq(C). Two H atoms of the water molecule were located in Fourier difference map and refined with bond restraints O—H = 0.84 (1) Å, and with U_iso(H) = 1.5 U_eq(O).

Computing details

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

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (A) 1 - x, 2 - y, - z].
	Fig. 2. Two-dimensional hydrogen-bonded network.

Diaquabis[5-(pyrimidin-2-yl)tetrazolato]manganese(II)

Crystal data

[Mn(C5H3N6)2(H2O)2]	F(000) = 390
Mr = 385.24	Dx = 1.685 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5442 reflections
a = 8.0084 (16) Å	θ = 3.0–27.5°
b = 13.095 (3) Å	µ = 0.91 mm^−1
c = 7.2958 (15) Å	T = 293 K
β = 97.18 (3)°	Block, colourless
V = 759.1 (3) Å^3	0.16 × 0.14 × 0.02 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1737 independent reflections
Radiation source: fine-focus sealed tube	1431 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
φ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
Tmin = 0.929, Tmax = 1.000	k = −17→16
7203 measured reflections	l = −9→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.1658P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
1737 reflections	Δρmax = 0.30 e Å^−3
122 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (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	1.0000	0.0000	0.03101 (14)
N1	0.54376 (17)	1.16630 (9)	−0.00415 (17)	0.0303 (3)
N2	0.65673 (19)	1.23355 (10)	−0.05190 (19)	0.0359 (3)
N3	0.5993 (2)	1.32610 (10)	−0.02615 (19)	0.0388 (4)
N4	0.4487 (2)	1.32100 (10)	0.03793 (19)	0.0368 (3)
N5	0.27899 (18)	1.07056 (10)	0.12166 (18)	0.0348 (3)
N6	0.1532 (2)	1.23123 (13)	0.1739 (2)	0.0466 (4)
C1	0.4187 (2)	1.22145 (11)	0.0503 (2)	0.0297 (3)
C2	0.2734 (2)	1.17322 (12)	0.1182 (2)	0.0320 (4)
C3	0.1543 (3)	1.02274 (16)	0.1923 (3)	0.0495 (5)
H3A	0.1547	0.9518	0.1987	0.059*
C4	0.0256 (3)	1.07621 (19)	0.2555 (3)	0.0618 (6)
H4A	−0.0606	1.0430	0.3060	0.074*
C5	0.0292 (3)	1.18049 (19)	0.2413 (3)	0.0578 (6)
H5A	−0.0586	1.2178	0.2803	0.069*
O1W	0.64119 (17)	0.99277 (8)	0.27633 (16)	0.0359 (3)
H1WA	0.623 (3)	0.9423 (12)	0.340 (3)	0.054*
H1WB	0.632 (3)	1.0442 (12)	0.344 (3)	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0393 (2)	0.01818 (19)	0.0371 (2)	−0.00146 (14)	0.01063 (15)	−0.00165 (12)
N1	0.0360 (8)	0.0227 (7)	0.0333 (7)	−0.0030 (5)	0.0083 (6)	0.0001 (5)
N2	0.0446 (9)	0.0262 (7)	0.0376 (7)	−0.0071 (6)	0.0081 (6)	0.0014 (5)
N3	0.0563 (10)	0.0219 (7)	0.0377 (8)	−0.0059 (6)	0.0042 (7)	0.0025 (5)
N4	0.0507 (9)	0.0219 (7)	0.0365 (8)	0.0035 (6)	0.0008 (6)	−0.0005 (5)
N5	0.0359 (8)	0.0335 (7)	0.0360 (7)	−0.0051 (6)	0.0086 (6)	−0.0034 (5)
N6	0.0388 (10)	0.0556 (10)	0.0456 (9)	0.0139 (7)	0.0056 (7)	−0.0070 (7)
C1	0.0385 (9)	0.0229 (8)	0.0268 (7)	0.0035 (6)	0.0007 (6)	−0.0017 (5)
C2	0.0338 (9)	0.0339 (9)	0.0276 (8)	0.0040 (7)	0.0011 (6)	−0.0044 (6)
C3	0.0447 (12)	0.0544 (12)	0.0511 (11)	−0.0160 (9)	0.0125 (9)	−0.0017 (8)
C4	0.0387 (13)	0.0904 (18)	0.0594 (13)	−0.0148 (11)	0.0181 (10)	−0.0052 (11)
C5	0.0347 (12)	0.0875 (17)	0.0521 (12)	0.0108 (11)	0.0093 (9)	−0.0123 (10)
O1W	0.0492 (8)	0.0222 (6)	0.0373 (7)	−0.0026 (5)	0.0095 (5)	0.0003 (4)

Geometric parameters (Å, º)

Mn1—O1W	2.1868 (14)	N5—C2	1.345 (2)
Mn1—O1W^i	2.1868 (14)	N6—C2	1.329 (2)
Mn1—N1	2.2066 (13)	N6—C5	1.338 (3)
Mn1—N1^i	2.2066 (13)	C1—C2	1.464 (2)
Mn1—N5^i	2.2731 (15)	C3—C4	1.373 (3)
Mn1—N5	2.2731 (15)	C3—H3A	0.9300
N1—C1	1.335 (2)	C4—C5	1.370 (3)
N1—N2	1.3394 (18)	C4—H4A	0.9300
N2—N3	1.3181 (19)	C5—H5A	0.9300
N3—N4	1.349 (2)	O1W—H1WA	0.830 (9)
N4—C1	1.331 (2)	O1W—H1WB	0.844 (9)
N5—C3	1.335 (2)
O1W—Mn1—O1W^i	180.00 (5)	C3—N5—Mn1	128.04 (13)
O1W—Mn1—N1	89.47 (4)	C2—N5—Mn1	115.14 (11)
O1W^i—Mn1—N1	90.53 (4)	C2—N6—C5	115.28 (18)
O1W—Mn1—N1^i	90.53 (4)	N4—C1—N1	111.16 (15)
O1W^i—Mn1—N1^i	89.47 (4)	N4—C1—C2	127.15 (15)
N1—Mn1—N1^i	180.0	N1—C1—C2	121.67 (13)
O1W—Mn1—N5^i	90.24 (5)	N6—C2—N5	126.13 (16)
O1W^i—Mn1—N5^i	89.76 (5)	N6—C2—C1	119.56 (15)
N1—Mn1—N5^i	105.25 (5)	N5—C2—C1	114.29 (14)
N1^i—Mn1—N5^i	74.75 (5)	N5—C3—C4	121.32 (19)
O1W—Mn1—N5	89.76 (5)	N5—C3—H3A	119.3
O1W^i—Mn1—N5	90.24 (5)	C4—C3—H3A	119.3
N1—Mn1—N5	74.75 (5)	C5—C4—C3	117.3 (2)
N1^i—Mn1—N5	105.25 (5)	C5—C4—H4A	121.4
N5^i—Mn1—N5	180.0	C3—C4—H4A	121.4
C1—N1—N2	106.15 (13)	N6—C5—C4	123.15 (19)
C1—N1—Mn1	113.79 (10)	N6—C5—H5A	118.4
N2—N1—Mn1	140.00 (11)	C4—C5—H5A	118.4
N3—N2—N1	107.96 (14)	Mn1—O1W—H1WA	116.2 (15)
N2—N3—N4	110.30 (12)	Mn1—O1W—H1WB	115.5 (15)
C1—N4—N3	104.43 (13)	H1WA—O1W—H1WB	106 (2)
C3—N5—C2	116.81 (16)
O1W—Mn1—N1—C1	−94.61 (11)	N3—N4—C1—C2	178.01 (14)
O1W^i—Mn1—N1—C1	85.39 (11)	N2—N1—C1—N4	0.21 (17)
N5^i—Mn1—N1—C1	175.28 (10)	Mn1—N1—C1—N4	−177.47 (9)
N5—Mn1—N1—C1	−4.72 (10)	N2—N1—C1—C2	−178.20 (13)
O1W—Mn1—N1—N2	88.86 (16)	Mn1—N1—C1—C2	4.12 (18)
O1W^i—Mn1—N1—N2	−91.14 (16)	C5—N6—C2—N5	1.0 (3)
N5^i—Mn1—N1—N2	−1.25 (16)	C5—N6—C2—C1	−177.15 (16)
N5—Mn1—N1—N2	178.75 (16)	C3—N5—C2—N6	−1.9 (2)
C1—N1—N2—N3	−0.03 (16)	Mn1—N5—C2—N6	176.97 (13)
Mn1—N1—N2—N3	176.67 (11)	C3—N5—C2—C1	176.30 (15)
N1—N2—N3—N4	−0.16 (18)	Mn1—N5—C2—C1	−4.78 (17)
N2—N3—N4—C1	0.28 (18)	N4—C1—C2—N6	0.7 (2)
O1W—Mn1—N5—C3	−86.51 (15)	N1—C1—C2—N6	178.89 (14)
O1W^i—Mn1—N5—C3	93.49 (15)	N4—C1—C2—N5	−177.63 (14)
N1—Mn1—N5—C3	−176.02 (16)	N1—C1—C2—N5	0.5 (2)
N1^i—Mn1—N5—C3	3.98 (16)	C2—N5—C3—C4	1.0 (3)
O1W—Mn1—N5—C2	94.72 (11)	Mn1—N5—C3—C4	−177.80 (14)
O1W^i—Mn1—N5—C2	−85.28 (11)	N5—C3—C4—C5	0.7 (3)
N1—Mn1—N5—C2	5.20 (11)	C2—N6—C5—C4	0.9 (3)
N1^i—Mn1—N5—C2	−174.80 (11)	C3—C4—C5—N6	−1.8 (3)
N3—N4—C1—N1	−0.30 (17)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···N4^ii	0.83 (1)	1.94 (1)	2.7673 (18)	172 (2)
O1W—H1WB···N3^iii	0.84 (1)	1.98 (1)	2.8171 (17)	173 (2)

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+5/2, z+1/2.