cis-Tetra­aqua­bis­{5-[4-(1H-imidazol-1-yl-κN3)phen­yl]tetra­zolido}manganese(II) dihydrate

Wang, X.; Yan, S.-W.; Chang, S.-C.; Liang, Y.-C.; Zhang, F.-T.

doi:10.1107/S1600536812010380

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m413-m414

doi:10.1107/S1600536812010380

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cis-Tetraaquabis{5-[4-(1H-imidazol-1-yl-κN³)phenyl]tetrazolido}manganese(II) dihydrate

Xin Wang,^a ^* Shi-Wei Yan,^a Suo-Cheng Chang,^a Yan-Chen Liang ^a and Fu-Tian Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: firefire66@126.com

(Received 13 February 2012; accepted 8 March 2012; online 14 March 2012)

In the title compound, [Mn(C₁₀H₇N₆)₂(H₂O)₄]·2H₂O, the complex unit comprises an Mn²⁺ ion, coordinated by two imidazole N atoms from cis-related monodentate 5-[4-(imidazol-1-yl)phenyl]tetrazolide ligands and four water molecules, together with two water molecules of solvation. The Mn²⁺ ion lies on a twofold rotation axis and has a slightly distorted octahedral geometry. The molecules are connected by O—H⋯N and O—H⋯O hydrogen bonds involving both coordinated and solvent water molecules, generating a three-dimensional structure. Two C atoms of the imidazole ring of the ligand are each disordered over two sites with occupancy factors of 0.75 and 0.25.

Related literature

For general background to the use of nitrogen-containing ligands in the construction of supramolecular coordination compounds, see: Qi et al. (2008 ). For the structure of the anhydrous trans-isomer of the title complex, see: Cheng (2011 ).

Experimental

Crystal data

[Mn(C₁₀H₇N₆)₂(H₂O)₄]·2H₂O
M_r = 585.47
Monoclinic, C 2/c
a = 19.239 (3) Å
b = 13.141 (2) Å
c = 13.417 (2) Å
β = 129.912 (2)°
V = 2601.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 296 K
0.50 × 0.45 × 0.35 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.764, T_max = 0.826
7759 measured reflections
2962 independent reflections
2246 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 1.04
2962 reflections
219 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O3W	0.79 (4)	1.91 (4)	2.690 (4)	169 (2)
O1W—H12W⋯O3Wⁱ	0.82 (3)	1.95 (3)	2.762 (3)	168 (4)
O2W—H21W⋯N4ⁱⁱ	0.79 (4)	2.07 (4)	2.847 (4)	169 (3)
O2W—H22W⋯N5ⁱⁱⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (4)
O3W—H31W⋯N3^iv	0.83 (4)	1.97 (3)	2.786 (3)	167 (3)
O3W—H31W⋯N4^iv	0.83 (4)	2.62 (3)	3.308 (3)	142 (3)
O3W—H32W⋯N6^v	0.82 (3)	1.95 (3)	2.757 (3)	172 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (v) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812010380/zs2184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010380/zs2184Isup2.hkl

checkCIF report

Comment top

In recent years, much study has been focused on using nitrogen-containing ligands and 1,4-benzenedicarboxylic acid to construct supramolecular coordination compounds. The reason is that these supramolecular coordination assemblies exhibit not only a variety of architectures but also have potential applications as functional materials (Qi et al., 2008). In this paper, we report the synthesis and structure of the title complex [Mn(timb)₂(H₂O)₄] . 2H₂O, {Htimb = 5-[4-imidazol-1-yl)phenyl]tetrazole}, synthesized by the hydrothermal reaction of manganese(II) acetate with Htimb in the presence of 1,4-benzenedicarboxylic acid.

In the title compound the coordination polyhedron comprises a Mn²⁺ ion, two monodentate cis-related timb^- ligands and four coordinated water molecules, together with two water molecules of solvation (Fig. 1). The Mn²⁺ lies on a twofold rotation axis and the complex has a slightly distorted octahedral geometry. Both the coordinated and solvent water molecules form intermolecular O—H···O and O—H···N hydrogen-bonding interactions (Table 1) to form a three-dimensional supramolecular network. Two atoms of the imidazole ring (C2, C3) are disordered over two sites (C2A and C3A, respectively), with occupancy factors of 0.75 and 0.25. The structure of the anhydrous trans-isomer of the title complex has previously been reported (Cheng, 2011).

Related literature top

For general background to the use of nitrogen-containing ligands in the construction of supramolecular coordination compounds, see: Qi et al. (2008). For the structure of the anhydrous trans-isomer of the title complex, see: Cheng (2011).

Experimental top

A mixture of Mn(OAc)₂ (0.098 g, 0.4 mmol), 5-[4-imidazol-1-yl)phenyl]tetrazole (Htimb) (0.064 g, 0.3 mmol), 1,4-benzendicarboxylic acid (0.066 g, 0.4 mmol) and water (9 ml) was stirred for 30 min in air. The mixture was then transferred to a 18 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 75 h under autogenous pressure. The product was washed with distilled water and dried, giving the yellow title compound.

Structure description top

For general background to the use of nitrogen-containing ligands in the construction of supramolecular coordination compounds, see: Qi et al. (2008). For the structure of the anhydrous trans-isomer of the title complex, see: Cheng (2011).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular configuration and atom numbering scheme for the title complex, showing the partial disorder in the imidaziole ring of the ligand. Displacement ellipsoids are drawn at the 30% probability level. For symmetry code (i): -x - 1, y, -z + 5/2.

cis-Tetraaquabis{5-[4-(1H-imidazol-1-yl- κN³)phenyl]tetrazolido}manganese(II) dihydrate top

Crystal data top

[Mn(C₁₀H₇N₆)₂(H₂O)₄]·2H₂O	F(000) = 1212
M_r = 585.47	D_x = 1.495 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7759 reflections
a = 19.239 (3) Å	θ = 2.1–27.5°
b = 13.141 (2) Å	µ = 0.57 mm⁻¹
c = 13.417 (2) Å	T = 296 K
β = 129.912 (2)°	Block, yellow
V = 2601.8 (7) Å³	0.50 × 0.45 × 0.35 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	2962 independent reflections
Radiation source: fine-focus sealed tube	2246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
T_min = 0.764, T_max = 0.826	k = −17→16
7759 measured reflections	l = −12→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0453P)² + 1.08P] where P = (F_o² + 2F_c²)/3
2962 reflections	(Δ/σ)_max = 0.002
219 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Mn(C₁₀H₇N₆)₂(H₂O)₄]·2H₂O	V = 2601.8 (7) Å³
M_r = 585.47	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.239 (3) Å	µ = 0.57 mm⁻¹
b = 13.141 (2) Å	T = 296 K
c = 13.417 (2) Å	0.50 × 0.45 × 0.35 mm
β = 129.912 (2)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2962 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2246 reflections with I > 2σ(I)
T_min = 0.764, T_max = 0.826	R_int = 0.027
7759 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.21 e Å⁻³
2962 reflections	Δρ_min = −0.27 e Å⁻³
219 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.50000	0.64609 (3)	1.25000	0.0381 (2)
O1W	0.50199 (14)	0.52591 (12)	1.13954 (19)	0.0494 (6)
O2W	0.35299 (11)	0.62992 (13)	1.09094 (17)	0.0487 (6)
N1	0.53170 (13)	0.76342 (13)	1.16074 (18)	0.0471 (6)
N2	0.58359 (12)	0.81830 (13)	1.06351 (18)	0.0439 (6)
N3	0.72694 (13)	0.88544 (13)	0.73642 (18)	0.0457 (6)
N4	0.73655 (13)	0.84944 (13)	0.65176 (19)	0.0476 (6)
N5	0.70484 (12)	0.75736 (14)	0.61811 (17)	0.0476 (7)
N6	0.67343 (12)	0.72992 (13)	0.67890 (17)	0.0452 (6)
C1	0.54836 (16)	0.74146 (16)	1.0828 (2)	0.0499 (8)
C2	0.5739 (3)	0.8554 (3)	1.2134 (4)	0.0586 (16)	0.750
C3	0.6063 (3)	0.8903 (3)	1.1558 (4)	0.0600 (15)	0.750
C4	0.61025 (13)	0.81709 (14)	0.98504 (19)	0.0371 (6)
C5	0.64673 (17)	0.90308 (16)	0.9751 (2)	0.0500 (8)
C6	0.67239 (17)	0.90067 (16)	0.8996 (2)	0.0503 (8)
C7	0.66198 (13)	0.81344 (14)	0.83318 (19)	0.0358 (6)
C8	0.62672 (15)	0.72795 (16)	0.8463 (2)	0.0469 (7)
C9	0.60114 (15)	0.72957 (16)	0.9219 (2)	0.0495 (8)
C10	0.68777 (13)	0.80981 (14)	0.75070 (19)	0.0358 (6)
C2A	0.5081 (10)	0.8671 (8)	1.1261 (14)	0.067 (5)	0.250
C3A	0.5379 (10)	0.9036 (8)	1.0642 (14)	0.070 (5)	0.250
O3W	0.63171 (12)	0.47411 (14)	1.12748 (17)	0.0481 (6)
H1	0.53660	0.67790	1.04430	0.0600*
H5	0.65400	0.96230	1.01900	0.0600*
H2	0.57970	0.88850	1.27980	0.0710*	0.750
H3	0.63730	0.95100	1.17400	0.0710*	0.750
H9	0.57770	0.67120	0.93000	0.0590*
H11W	0.5443 (19)	0.510 (2)	1.146 (2)	0.065 (9)*
H12W	0.457 (2)	0.524 (2)	1.062 (3)	0.069 (9)*
H21W	0.3226 (18)	0.6277 (18)	1.111 (3)	0.063 (8)*
H22W	0.329 (2)	0.666 (2)	1.023 (3)	0.078 (10)*
H6	0.69710	0.95870	0.89330	0.0600*
H8	0.62010	0.66830	0.80350	0.0560*
H21A	0.47760	0.90570	1.14540	0.0810*	0.250
H31A	0.52910	0.96810	1.02920	0.0830*	0.250
H31W	0.6792 (19)	0.508 (2)	1.171 (3)	0.070 (9)*
H32W	0.6465 (17)	0.415 (2)	1.150 (2)	0.060 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0532 (3)	0.0388 (2)	0.0477 (3)	0.0000	0.0440 (2)	0.0000
O1W	0.0568 (11)	0.0558 (10)	0.0539 (11)	0.0025 (8)	0.0439 (10)	−0.0081 (8)
O2W	0.0539 (10)	0.0631 (10)	0.0514 (10)	0.0093 (8)	0.0440 (9)	0.0084 (8)
N1	0.0636 (12)	0.0482 (10)	0.0584 (11)	−0.0029 (9)	0.0524 (10)	0.0005 (8)
N2	0.0619 (11)	0.0410 (9)	0.0575 (11)	−0.0042 (8)	0.0515 (10)	−0.0015 (8)
N3	0.0657 (12)	0.0424 (9)	0.0591 (12)	−0.0070 (8)	0.0539 (11)	−0.0051 (8)
N4	0.0638 (12)	0.0487 (10)	0.0596 (11)	−0.0038 (9)	0.0530 (11)	−0.0039 (9)
N5	0.0626 (12)	0.0505 (11)	0.0531 (11)	−0.0060 (9)	0.0479 (10)	−0.0068 (8)
N6	0.0611 (11)	0.0448 (10)	0.0509 (10)	−0.0094 (8)	0.0456 (10)	−0.0075 (8)
C1	0.0740 (16)	0.0430 (11)	0.0625 (14)	−0.0077 (11)	0.0574 (14)	−0.0020 (10)
C2	0.089 (3)	0.052 (2)	0.080 (3)	−0.017 (2)	0.075 (2)	−0.0164 (19)
C3	0.092 (3)	0.0465 (18)	0.084 (3)	−0.0215 (19)	0.076 (3)	−0.0183 (18)
C4	0.0430 (11)	0.0414 (10)	0.0436 (11)	0.0005 (8)	0.0354 (10)	0.0034 (8)
C5	0.0795 (16)	0.0366 (11)	0.0686 (15)	−0.0057 (10)	0.0634 (14)	−0.0049 (10)
C6	0.0797 (16)	0.0372 (11)	0.0717 (15)	−0.0079 (10)	0.0658 (15)	−0.0016 (10)
C7	0.0413 (11)	0.0400 (10)	0.0390 (11)	−0.0004 (8)	0.0317 (10)	0.0022 (8)
C8	0.0650 (14)	0.0426 (11)	0.0553 (13)	−0.0131 (10)	0.0488 (13)	−0.0109 (10)
C9	0.0695 (15)	0.0439 (12)	0.0624 (14)	−0.0187 (11)	0.0548 (13)	−0.0082 (10)
C10	0.0420 (11)	0.0375 (10)	0.0399 (11)	0.0011 (8)	0.0318 (10)	0.0019 (8)
C2A	0.108 (10)	0.058 (6)	0.100 (9)	0.028 (7)	0.096 (9)	0.021 (6)
C3A	0.120 (11)	0.045 (5)	0.106 (10)	0.021 (6)	0.101 (9)	0.020 (6)
O3W	0.0543 (11)	0.0420 (9)	0.0597 (10)	0.0019 (8)	0.0420 (9)	−0.0048 (8)

Geometric parameters (Å, º) top

Mn1—O1W	2.183 (2)	N4—N5	1.299 (3)
Mn1—O2W	2.203 (2)	N5—N6	1.339 (4)
Mn1—N1	2.263 (2)	N6—C10	1.329 (3)
Mn1—O1Wⁱ	2.183 (2)	C2—C3	1.347 (9)
Mn1—O2Wⁱ	2.203 (2)	C2A—C3A	1.36 (3)
Mn1—N1ⁱ	2.263 (2)	C4—C5	1.381 (4)
O1W—H12W	0.82 (3)	C4—C9	1.371 (3)
O1W—H11W	0.79 (4)	C5—C6	1.383 (5)
O2W—H21W	0.79 (4)	C6—C7	1.385 (3)
O2W—H22W	0.85 (3)	C7—C10	1.476 (4)
O3W—H32W	0.82 (3)	C7—C8	1.381 (3)
O3W—H31W	0.83 (4)	C8—C9	1.383 (4)
N1—C2	1.372 (5)	C1—H1	0.9300
N1—C1	1.308 (4)	C2—H2	0.9300
N1—C2A	1.417 (11)	C2A—H21A	0.9300
N2—C4	1.437 (4)	C3—H3	0.9300
N2—C3	1.388 (5)	C3A—H31A	0.9300
N2—C3A	1.428 (16)	C5—H5	0.9300
N2—C1	1.331 (4)	C6—H6	0.9300
N3—C10	1.333 (3)	C8—H8	0.9300
N3—N4	1.348 (3)	C9—H9	0.9300

O1W—Mn1—O2W	80.99 (9)	N1—C1—N2	113.9 (2)
O1W—Mn1—N1	90.32 (8)	N1—C2—C3	110.1 (4)
O1W—Mn1—O1Wⁱ	87.31 (8)	N1—C2A—C3A	111.5 (15)
O1W—Mn1—O2Wⁱ	90.98 (8)	N2—C3—C2	106.5 (4)
O1W—Mn1—N1ⁱ	168.63 (10)	N2—C3A—C2A	103.2 (9)
O2W—Mn1—N1	99.64 (8)	N2—C4—C9	119.9 (2)
O1Wⁱ—Mn1—O2W	90.98 (8)	C5—C4—C9	119.9 (3)
O2W—Mn1—O2Wⁱ	168.93 (7)	N2—C4—C5	120.27 (19)
O2W—Mn1—N1ⁱ	87.94 (8)	C4—C5—C6	119.6 (2)
O1Wⁱ—Mn1—N1	168.63 (10)	C5—C6—C7	121.2 (2)
O2Wⁱ—Mn1—N1	87.94 (8)	C6—C7—C10	122.0 (2)
N1—Mn1—N1ⁱ	94.10 (8)	C8—C7—C10	119.89 (19)
O1Wⁱ—Mn1—O2Wⁱ	80.99 (9)	C6—C7—C8	118.1 (3)
O1Wⁱ—Mn1—N1ⁱ	90.32 (8)	C7—C8—C9	121.1 (2)
O2Wⁱ—Mn1—N1ⁱ	99.64 (8)	C4—C9—C8	120.1 (2)
H11W—O1W—H12W	108 (3)	N3—C10—C7	125.22 (18)
Mn1—O1W—H11W	125.7 (18)	N6—C10—C7	123.8 (2)
Mn1—O1W—H12W	115 (2)	N3—C10—N6	111.0 (2)
H21W—O2W—H22W	112 (4)	N2—C1—H1	123.00
Mn1—O2W—H21W	117 (2)	N1—C1—H1	123.00
Mn1—O2W—H22W	117 (3)	N1—C2—H2	125.00
H31W—O3W—H32W	107 (3)	C3—C2—H2	125.00
Mn1—N1—C1	124.09 (14)	C3A—C2A—H21A	124.00
Mn1—N1—C2A	133.7 (9)	N1—C2A—H21A	124.00
C1—N1—C2	103.8 (3)	C2—C3—H3	127.00
C1—N1—C2A	98.1 (8)	N2—C3—H3	127.00
Mn1—N1—C2	126.8 (2)	N2—C3A—H31A	129.00
C3A—N2—C4	121.6 (7)	C2A—C3A—H31A	128.00
C1—N2—C3A	101.7 (8)	C4—C5—H5	120.00
C3—N2—C4	127.3 (3)	C6—C5—H5	120.00
C1—N2—C4	126.86 (19)	C5—C6—H6	119.00
C1—N2—C3	104.6 (3)	C7—C6—H6	119.00
N4—N3—C10	104.79 (18)	C9—C8—H8	120.00
N3—N4—N5	109.4 (2)	C7—C8—H8	119.00
N4—N5—N6	109.5 (2)	C8—C9—H9	120.00
N5—N6—C10	105.31 (19)	C4—C9—H9	120.00

O1W—Mn1—N1—C1	−4.3 (2)	N4—N3—C10—N6	0.1 (3)
O1W—Mn1—N1—C2	−154.2 (4)	N4—N3—C10—C7	−179.0 (2)
O2W—Mn1—N1—C1	−85.2 (2)	N3—N4—N5—N6	0.1 (3)
O2W—Mn1—N1—C2	124.9 (4)	N4—N5—N6—C10	0.0 (3)
O2Wⁱ—Mn1—N1—C1	86.7 (2)	N5—N6—C10—N3	−0.1 (3)
O2Wⁱ—Mn1—N1—C2	−63.3 (4)	N5—N6—C10—C7	179.1 (2)
N1ⁱ—Mn1—N1—C1	−173.8 (2)	N1—C2—C3—N2	0.2 (5)
N1ⁱ—Mn1—N1—C2	36.3 (4)	N2—C4—C5—C6	179.8 (2)
Mn1—N1—C1—N2	−166.66 (17)	C9—C4—C5—C6	1.1 (4)
C2—N1—C1—N2	−11.0 (3)	N2—C4—C9—C8	−180.0 (2)
Mn1—N1—C2—C3	161.0 (3)	C5—C4—C9—C8	−1.3 (4)
C1—N1—C2—C3	6.3 (5)	C4—C5—C6—C7	0.2 (4)
C3—N2—C1—N1	11.3 (4)	C5—C6—C7—C8	−1.2 (4)
C4—N2—C1—N1	179.0 (2)	C5—C6—C7—C10	179.1 (2)
C1—N2—C3—C2	−6.5 (5)	C6—C7—C8—C9	1.0 (4)
C4—N2—C3—C2	−174.1 (3)	C10—C7—C8—C9	−179.3 (2)
C1—N2—C4—C5	−179.5 (2)	C6—C7—C10—N3	3.6 (4)
C1—N2—C4—C9	−0.8 (4)	C6—C7—C10—N6	−175.4 (2)
C3—N2—C4—C5	−14.5 (4)	C8—C7—C10—N3	−176.1 (2)
C3—N2—C4—C9	164.2 (3)	C8—C7—C10—N6	4.9 (4)
C10—N3—N4—N5	−0.1 (3)	C7—C8—C9—C4	0.2 (4)

Symmetry code: (i) −x+1, y, −z+5/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O3W	0.79 (4)	1.91 (4)	2.690 (4)	169 (2)
O1W—H12W···O3Wⁱⁱ	0.82 (3)	1.95 (3)	2.762 (3)	168 (4)
O2W—H21W···N4ⁱⁱⁱ	0.79 (4)	2.07 (4)	2.847 (4)	169 (3)
O2W—H22W···N5^iv	0.85 (3)	1.97 (3)	2.812 (3)	170 (4)
O3W—H31W···N3^v	0.83 (4)	1.97 (3)	2.786 (3)	167 (3)
O3W—H31W···N4^v	0.83 (4)	2.62 (3)	3.308 (3)	142 (3)
O3W—H32W···N6^vi	0.82 (3)	1.95 (3)	2.757 (3)	172 (2)

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₀H₇N₆)₂(H₂O)₄]·2H₂O
M_r	585.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	19.239 (3), 13.141 (2), 13.417 (2)
β (°)	129.912 (2)
V (Å³)	2601.8 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.50 × 0.45 × 0.35

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.764, 0.826
No. of measured, independent and observed [I > 2σ(I)] reflections	7759, 2962, 2246
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 1.04
No. of reflections	2962
No. of parameters	219
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O3W	0.79 (4)	1.91 (4)	2.690 (4)	169 (2)
O1W—H12W···O3Wⁱ	0.82 (3)	1.95 (3)	2.762 (3)	168 (4)
O2W—H21W···N4ⁱⁱ	0.79 (4)	2.07 (4)	2.847 (4)	169 (3)
O2W—H22W···N5ⁱⁱⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (4)
O3W—H31W···N3^iv	0.83 (4)	1.97 (3)	2.786 (3)	167 (3)
O3W—H31W···N4^iv	0.83 (4)	2.62 (3)	3.308 (3)	142 (3)
O3W—H32W···N6^v	0.82 (3)	1.95 (3)	2.757 (3)	172 (2)

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

Acknowledgements

This work was supported by the Science and Technology Foundation of Southwest University (SWUB2007035) and the Science and Technology Innovation Foundation for Students of Southwest University.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc.,Madison Wisconsion, USA. Google Scholar
Cheng, X.-C. (2011). Acta Cryst. E67, m1757. Web of Science CSD CrossRef IUCr Journals Google Scholar
Qi, Y., Che, Y.-X. & Zheng, J.-M. (2008). Cryst. Growth Des. 8, 3602–3608. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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