Tetra­aqua­bis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN²}manganese(II) dihydrate

The title compound, [Mn(C₄H₃N₈)₂(H₂O)₄]·2H₂O, represents the first structurally characterized transition metal complex of the 1,2-bis­(tetra­zol-5-yl)ethene ligand. The complex mol­ecule occupies a special position on an inversion centre and the Mn atom has a tetra­gonally distorted octa­hedral coordination. The bis­(tetra­zolyl)ethene ligand is planar within 0.0366 (7) Å. All `active' H atoms participate in hydrogen bonds, which link mol­ecules of the complex and the uncoordinated water mol­ecules into an infinite three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.022
• wR factor = 0.069
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          2
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   O1      ..       5.44 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.31

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
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S1. Comment

The 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene ligand (H₂BTAE) was previously reported in its twice deprotonated form in the cystal structure of its sodium salt pentahydrate (Huang et al., 2005). The present paper provides the fist example of its structurally characterized complex with a transition metal; the ligand in this complex is monodeprotonated.

The molecule of Mn(H-BTAE)₂(H₂O)₄ occupies a special position in the inversion centre (Fig. 1); the Mn1 atom has a tetragonally distorted octahedral coordination (Table 1). The H-BTAE ligand has essentailly planar conformation, the maximum deviation of the N6 atom from its mean plane being 0.0366 (7) Å. The geometry of the ligand is similar to the one observed in Huang et al. (2005).

All "active" hydrogen atoms in the structure participate in the H-bonding (Table 2); the extensive H-bond system links molecules of the complex and non-coordinated water molecules into three-dimensional infinite network (Fig. 2).

Related literature

For related literature, see: Huang et al. (2005); Demko & Sharpless (2001)

S2. Experimental

MnCl₂.4H₂O (0.5 mmol, 99 mg) and 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene (1 mmol, 192 mg) (Demko & Sharpless, 2001) were added to 30 ml of water:MeOH (1:1) mixture. After stirring for 30 min at room temperature, the pH value was adjusted to 7 by 1M NaOH, and clear solution was allowed to evaporate in the air. Nice prism-shaped crystals of the title compound were obtained after 3 days. The crystals were filtered, washed by EtOH and dried in the air.

S3. Refinement

All H atoms were located in the difference map and refined isotropically [O—H 0.79 (2)–0.83 (2) Å; C—H 0.91 (1) and 0.96 (1) Å; N—H 0.93 (2) Å].

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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. Molecular structure showing 50% probability displacement ellipsoids. The unlabeled atoms are derived from the reference atoms by means of the (1 - x, -y, 1 - z) symmetry transformation..
	Fig. 2. Packing diagram viewed down the a axis, The hydrogen bonds are shown as dotted lines.

Tetraaquabis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN²}manganese(II) dihydrate

Crystal data

[Mn(C4H3N8)2(H2O)4]·2H2O	Z = 1
Mr = 489.32	F(000) = 251
Triclinic, P1	Dx = 1.676 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2296 (2) Å	Cell parameters from 7983 reflections
b = 7.0093 (2) Å	θ = 3.2–33.5°
c = 12.1212 (3) Å	µ = 0.75 mm^−1
α = 84.405 (1)°	T = 273 K
β = 89.457 (1)°	Prism, brown
γ = 67.016 (1)°	0.36 × 0.28 × 0.16 mm
V = 484.70 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3246 independent reflections
Radiation source: fine-focus sealed tube	3149 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 33.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.717, Tmax = 0.887	k = −10→10
9107 measured reflections	l = −16→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	All H-atom parameters refined
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 0.093P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3246 reflections	Δρmax = 0.37 e Å^−3
179 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (3)

Special details

Experimental. H atoms were located on intermediate difference Fourier map

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	0.5000	0.02323 (6)
O1	0.13139 (12)	0.18659 (13)	0.45633 (6)	0.03342 (15)
O2	0.48182 (15)	0.26842 (14)	0.58308 (6)	0.03732 (17)
O3	0.15295 (14)	0.60925 (13)	0.38023 (6)	0.03452 (15)
H3A	0.108 (4)	0.639 (3)	0.3151 (17)	0.063 (5)*
H3B	0.180 (4)	0.488 (3)	0.3935 (17)	0.068 (6)*
N1	0.80858 (13)	0.13919 (13)	0.30839 (6)	0.02546 (14)
N2	0.60467 (13)	0.13162 (13)	0.34123 (6)	0.02647 (14)
N3	0.46087 (14)	0.17201 (14)	0.25572 (6)	0.02953 (16)
N4	0.56698 (13)	0.20725 (13)	0.16459 (6)	0.02663 (15)
N5	1.08450 (14)	0.30165 (13)	−0.16586 (6)	0.02657 (14)
N6	1.28887 (14)	0.30586 (14)	−0.20234 (6)	0.02983 (16)
N7	1.43373 (14)	0.27581 (14)	−0.12043 (6)	0.03067 (16)
N8	1.32424 (13)	0.25048 (12)	−0.02771 (6)	0.02534 (14)
C1	0.78023 (14)	0.18638 (13)	0.19858 (6)	0.02208 (14)
C2	0.96111 (15)	0.20610 (14)	0.12755 (7)	0.02469 (15)
C3	0.93208 (15)	0.24900 (14)	0.01755 (7)	0.02401 (15)
C4	1.11010 (14)	0.26607 (13)	−0.05597 (6)	0.02185 (14)
H3	0.794 (2)	0.271 (2)	−0.0175 (12)	0.035 (3)*
H2	1.104 (3)	0.186 (2)	0.1658 (12)	0.039 (4)*
H8	1.405 (3)	0.232 (3)	0.0389 (15)	0.057 (5)*
H1A	0.047 (3)	0.239 (3)	0.5070 (15)	0.046 (4)*
H1B	0.050 (3)	0.155 (3)	0.4134 (15)	0.055 (5)*
H2B	0.587 (3)	0.304 (3)	0.5865 (15)	0.052 (4)*
H2A	0.417 (3)	0.280 (3)	0.6422 (17)	0.057 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02135 (10)	0.03467 (10)	0.01477 (8)	−0.01276 (7)	0.00178 (6)	−0.00004 (6)
O1	0.0225 (3)	0.0535 (4)	0.0236 (3)	−0.0133 (3)	−0.0009 (2)	−0.0078 (3)
O2	0.0443 (4)	0.0551 (5)	0.0264 (3)	−0.0324 (4)	0.0122 (3)	−0.0141 (3)
O3	0.0370 (4)	0.0392 (4)	0.0279 (3)	−0.0154 (3)	−0.0016 (3)	−0.0036 (3)
N1	0.0241 (3)	0.0396 (4)	0.0164 (3)	−0.0169 (3)	0.0007 (2)	−0.0007 (2)
N2	0.0249 (3)	0.0414 (4)	0.0161 (3)	−0.0170 (3)	0.0019 (2)	0.0003 (3)
N3	0.0255 (3)	0.0484 (4)	0.0179 (3)	−0.0190 (3)	0.0011 (2)	0.0012 (3)
N4	0.0250 (3)	0.0419 (4)	0.0161 (3)	−0.0174 (3)	0.0002 (2)	0.0011 (3)
N5	0.0283 (3)	0.0380 (4)	0.0167 (3)	−0.0167 (3)	0.0015 (2)	−0.0020 (3)
N6	0.0302 (4)	0.0437 (4)	0.0185 (3)	−0.0178 (3)	0.0051 (3)	−0.0027 (3)
N7	0.0268 (4)	0.0464 (4)	0.0213 (3)	−0.0174 (3)	0.0052 (3)	−0.0024 (3)
N8	0.0230 (3)	0.0373 (4)	0.0172 (3)	−0.0138 (3)	0.0015 (2)	−0.0006 (3)
C1	0.0232 (3)	0.0296 (3)	0.0159 (3)	−0.0133 (3)	0.0014 (2)	−0.0012 (2)
C2	0.0236 (4)	0.0351 (4)	0.0190 (3)	−0.0158 (3)	0.0024 (3)	−0.0014 (3)
C3	0.0234 (4)	0.0332 (4)	0.0189 (3)	−0.0150 (3)	0.0025 (3)	−0.0019 (3)
C4	0.0234 (3)	0.0277 (3)	0.0164 (3)	−0.0122 (3)	0.0017 (2)	−0.0021 (2)

Geometric parameters (Å, º)

Mn1—O2^i	2.1835 (8)	N2—N3	1.3112 (10)
Mn1—O1	2.1923 (7)	N3—N4	1.3336 (9)
Mn1—O2	2.1835 (8)	N4—C1	1.3427 (11)
Mn1—O1^i	2.1923 (7)	N5—C4	1.3304 (10)
Mn1—N2^i	2.2538 (7)	N5—N6	1.3541 (10)
Mn1—N2	2.2538 (7)	N6—N7	1.2931 (11)
O1—H1A	0.823 (18)	N7—N8	1.3420 (10)
O1—H1B	0.833 (18)	N8—C4	1.3403 (11)
O2—H2B	0.790 (18)	N8—H8	0.926 (18)
O2—H2A	0.81 (2)	C1—C2	1.4526 (11)
O3—H3A	0.82 (2)	C2—C3	1.3360 (11)
O3—H3B	0.80 (2)	C2—H2	0.963 (15)
N1—C1	1.3361 (10)	C3—C4	1.4499 (11)
N1—N2	1.3468 (10)	C3—H3	0.914 (14)
O2^i—Mn1—O2	180.0	N3—N2—N1	110.34 (6)
O2^i—Mn1—O1	95.43 (3)	N3—N2—Mn1	115.77 (5)
O2—Mn1—O1	84.57 (3)	N1—N2—Mn1	132.31 (6)
O2^i—Mn1—O1^i	84.57 (3)	N2—N3—N4	108.57 (7)
O2—Mn1—O1^i	95.43 (3)	N3—N4—C1	105.93 (7)
O1—Mn1—O1^i	180.0	C4—N5—N6	105.63 (7)
O2^i—Mn1—N2^i	91.07 (3)	N7—N6—N5	111.07 (7)
O2—Mn1—N2^i	88.93 (3)	N6—N7—N8	106.55 (7)
O1—Mn1—N2^i	89.76 (3)	C4—N8—N7	108.63 (7)
O1^i—Mn1—N2^i	90.24 (3)	C4—N8—H8	134.5 (11)
O2^i—Mn1—N2	88.93 (3)	N7—N8—H8	116.8 (11)
O2—Mn1—N2	91.07 (3)	N1—C1—N4	110.73 (7)
O1—Mn1—N2	90.24 (3)	N1—C1—C2	123.47 (7)
O1^i—Mn1—N2	89.76 (3)	N4—C1—C2	125.79 (7)
N2^i—Mn1—N2	179.999 (2)	C3—C2—C1	122.84 (8)
Mn1—O1—H1A	116.9 (11)	C3—C2—H2	122.3 (9)
Mn1—O1—H1B	125.3 (12)	C1—C2—H2	114.9 (9)
H1A—O1—H1B	106.3 (16)	C2—C3—C4	124.29 (8)
Mn1—O2—H2B	123.3 (13)	C2—C3—H3	121.3 (9)
Mn1—O2—H2A	114.9 (13)	C4—C3—H3	114.4 (9)
H2B—O2—H2A	109.2 (17)	N5—C4—N8	108.11 (7)
H3A—O3—H3B	105.6 (18)	N5—C4—C3	124.43 (8)
C1—N1—N2	104.43 (7)	N8—C4—C3	127.46 (7)
C1—N1—N2—N3	0.04 (10)	N6—N7—N8—C4	−0.01 (10)
C1—N1—N2—Mn1	164.68 (7)	N2—N1—C1—N4	−0.02 (10)
O2^i—Mn1—N2—N3	61.58 (7)	N2—N1—C1—C2	−178.57 (8)
O2—Mn1—N2—N3	−118.42 (7)	N3—N4—C1—N1	−0.01 (10)
O1—Mn1—N2—N3	−33.84 (7)	N3—N4—C1—C2	178.50 (8)
O1^i—Mn1—N2—N3	146.16 (7)	N1—C1—C2—C3	178.52 (9)
O2^i—Mn1—N2—N1	−102.42 (8)	N4—C1—C2—C3	0.19 (14)
O2—Mn1—N2—N1	77.58 (8)	C1—C2—C3—C4	−178.84 (8)
O1—Mn1—N2—N1	162.16 (8)	N6—N5—C4—N8	0.29 (10)
O1^i—Mn1—N2—N1	−17.84 (8)	N6—N5—C4—C3	−179.93 (8)
N1—N2—N3—N4	−0.05 (11)	N7—N8—C4—N5	−0.18 (10)
Mn1—N2—N3—N4	−167.49 (6)	N7—N8—C4—C3	−179.96 (8)
N2—N3—N4—C1	0.03 (10)	C2—C3—C4—N5	177.57 (9)
C4—N5—N6—N7	−0.30 (10)	C2—C3—C4—N8	−2.68 (15)
N5—N6—N7—N8	0.19 (11)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N1^ii	0.833 (18)	2.021 (18)	2.8419 (10)	168.8 (17)
O1—H1A···O3^iii	0.823 (18)	1.940 (18)	2.7599 (11)	174.0 (16)
O2—H2B···O3^iv	0.790 (18)	1.996 (19)	2.7797 (11)	171.4 (18)
O2—H2A···N6^v	0.81 (2)	2.04 (2)	2.8472 (10)	173.7 (18)
O3—H3A···N5^vi	0.82 (2)	2.09 (2)	2.8922 (11)	164.2 (19)
O3—H3B···O1	0.80 (2)	2.30 (2)	3.0693 (12)	160 (2)
N8—H8···N4^vii	0.926 (18)	1.792 (18)	2.7171 (10)	176.6 (16)

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