Aqua­(dicyanamido-κN1)(nitrato-κ2O,O′)(2,3,5,6-tetra-2-pyridylpyrazine-κ3N2,N1,N6)manganese(II)

Callejo, L.; De la Pinta, N.; Vitoria, P.; Cortés, R.

doi:10.1107/S1600536808041755

Aqua(dicyanamido-κN¹)(nitrato-κ²O,O′)(2,3,5,6-tetra-2-pyridylpyrazine-κ³N²,N¹,N⁶)manganese(II)

L. Callejo, N. De la Pinta, P. Vitoria and R. Cortés

In the title compound, [Mn(C₂N₃)(NO₃)(C₂₄H₁₆N₆)(H₂O)], the central manganese(II) ion is heptacoordinated to a tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligand (tppz), a bidentate nitrate ligand, a terminal monodentate dicyanamide ligand (dca) and a water molecule. The structure contains isolated neutral complexes, which are linked by O(water)—H

N hydrogen bonds generating chains along [010].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808041755/fj2176sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808041755/fj2176Isup2.hkl Contains datablock I

CCDC reference: 717195

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.049
wR factor = 0.119
Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       4.38 Ratio
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    --  O1      ..      15.95 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    --  O2      ..      20.29 su

Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.48
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N8     --  C25     ..       5.39 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C26

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

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Only a few examples are known of coordination compounds with the ligands dicyanamido (dca) and 2,3,5,6-tetra-2-pyridylpyrazine (tppz) (Carranza et al., 2003; Hsu et al., 2005).

The molecule of the title compound (I) (Fig. 1) contains a central manganese(II) metal heptacoordinated to a terminal dicyanamide ligand, three nitrogen atoms of the tppz ligand, two oxygen atoms of the nitrate group, and one water molecule.

The central pyrazine ring of the tppz is severely distorted from planarity (N2—C11—C12—N5 = 20.9 (3)°, N2—C13—C14—N5 = 19.9 (2)°) and adopts a twist-boat conformation with a puckering amplitude of 0.215 (2)Å (Spek, 2003). The pyridyl rings are rotated away from planarity with the pyrazine ring, with angles between planes of 25.3 (1) and 21.5 (1)° for the ones coordinated to Mn(II), and larger [31.1 (1), 35.9 (1)°] for the other ones.

The O(water)—H···N hydrogen bonds formed between the water as donor, and a non-coordinated pyridyl ring and the coordinated nitrogen atom of dca as acceptors, generate chains of molecules along the [010] direction (Fig.2).

Related literature top

For related structures containing coordination compounds with the ligands tppz and dca, see: Carranza et al. (2003); Hsu et al. (2005). For related literature, see: Lainé et al. (1995).

Experimental top

The title compound was prepared by mixing two acetonitrile solutions (10 ml each) of Mn(NO₃)₂.4H₂O (125.5 mg, 0.50 mmol) and 2,3,5,6-tetrakis(2-pyridyl)pirazine (97.1 mg, 0.25 mmol). After vigorous stirring for 3 h at a temperature of 30°C, a yellow precipitate appeared. To the resulting solution, a water/acetonitrile (50%) solution (10 ml) of sodium dicyanamide was added, and it was stirred at 40°C for 3 h, and then 2 days at room temperature. The precipitate was filtered off and yellow plaques formed from the resulting solution by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR2004 Burla et al. (2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Detail of the chain generated by the O(water)—H···N hydrogen bonds.

Aqua(dicyanamido-κN¹)(nitrato-κ²O,O')(2,3,5,6-tetra-2- pyridylpyrazine-κ³N²,N¹,N⁶)manganese(II) top

Crystal data top

[Mn(C₂N₃)(NO₃)(C₂₄H₁₆N₆)(H₂O)]	F(000) = 1204
M_r = 589.44	D_x = 1.522 Mg m⁻³ D_m = 1.475 Mg m⁻³ D_m measured by flotation
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2543 reflections
a = 14.0988 (11) Å	θ = 3.2–31.9°
b = 9.7739 (8) Å	µ = 0.57 mm⁻¹
c = 18.7205 (13) Å	T = 298 K
β = 94.491 (6)°	Prism, yellow
V = 2571.8 (3) Å³	0.42 × 0.31 × 0.08 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur 2 diffractometer	7480 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4848 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 8.3504 pixels mm^-1	θ_max = 30.0°, θ_min = 2.7°
ω scans	h = −18→19
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	k = −13→12
T_min = 0.856, T_max = 0.969	l = −26→26
24694 measured reflections

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)] = 0.049	Hydrogen site location: difference Fourier map
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0676P)²] where P = (F_o² + 2F_c²)/3
7480 reflections	(Δ/σ)_max = 0.003
376 parameters	Δρ_max = 0.77 e Å⁻³
2 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Mn(C₂N₃)(NO₃)(C₂₄H₁₆N₆)(H₂O)]	V = 2571.8 (3) Å³
M_r = 589.44	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.0988 (11) Å	µ = 0.57 mm⁻¹
b = 9.7739 (8) Å	T = 298 K
c = 18.7205 (13) Å	0.42 × 0.31 × 0.08 mm
β = 94.491 (6)°

Data collection top

Oxford Diffraction Xcalibur 2 diffractometer	7480 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	4848 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.969	R_int = 0.054
24694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	2 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.77 e Å⁻³
7480 reflections	Δρ_min = −0.31 e Å⁻³
376 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction Ltd., 2007) Analytical numeric absorption correction using a multifaceted crystal model.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.666558 (19)	0.45676 (3)	0.206427 (15)	0.02617 (9)
N1	0.78906 (11)	0.48216 (15)	0.29414 (8)	0.0258 (3)
N2	0.80556 (10)	0.38970 (15)	0.16256 (8)	0.0244 (3)
N3	0.63611 (11)	0.34999 (16)	0.09605 (9)	0.0302 (4)
O1	0.51063 (11)	0.51437 (17)	0.19225 (9)	0.0447 (4)
O2	0.58673 (10)	0.60852 (16)	0.28292 (8)	0.0424 (4)
O1W	0.63075 (10)	0.27874 (16)	0.26656 (9)	0.0386 (4)
H1W	0.5843 (14)	0.239 (3)	0.2725 (15)	0.058*
H2W	0.6758 (15)	0.237 (2)	0.2837 (13)	0.058*
O3	0.44256 (10)	0.67307 (17)	0.25070 (9)	0.0483 (4)
N4	0.84607 (13)	0.11733 (18)	0.00078 (9)	0.0397 (4)
N5	0.97237 (11)	0.37317 (17)	0.10010 (8)	0.0298 (4)
N6	1.03910 (11)	0.63452 (17)	0.22266 (9)	0.0348 (4)
N7	0.70245 (13)	0.64756 (18)	0.14738 (10)	0.0399 (4)
N8	0.77072 (15)	0.6846 (3)	0.03399 (12)	0.0622 (6)
N9	0.6902 (2)	0.7210 (4)	−0.08341 (14)	0.1065 (12)
N10	0.51142 (11)	0.60058 (17)	0.24260 (9)	0.0321 (4)
C1	0.87743 (13)	0.45325 (18)	0.27688 (10)	0.0242 (4)
C2	0.95391 (14)	0.4433 (2)	0.32828 (11)	0.0325 (4)
H2	1.0141	0.4195	0.3153	0.039*
C3	0.93869 (15)	0.4693 (2)	0.39852 (11)	0.0377 (5)
H3	0.9889	0.4644	0.4337	0.045*
C4	0.84871 (15)	0.5027 (2)	0.41657 (11)	0.0360 (5)
H4	0.8373	0.5222	0.4638	0.043*
C5	0.77617 (14)	0.5066 (2)	0.36298 (11)	0.0315 (4)
H5	0.7151	0.5272	0.3753	0.038*
C6	0.71035 (13)	0.33917 (19)	0.05521 (10)	0.0271 (4)
C7	0.69805 (15)	0.3326 (2)	−0.01871 (11)	0.0374 (5)
H7	0.7505	0.3313	−0.0459	0.045*
C8	0.60688 (17)	0.3280 (2)	−0.05189 (12)	0.0472 (6)
H8	0.5971	0.3241	−0.1016	0.057*
C9	0.53124 (16)	0.3294 (2)	−0.01012 (13)	0.0470 (6)
H9	0.4694	0.3213	−0.0309	0.056*
C10	0.54801 (14)	0.3427 (2)	0.06286 (12)	0.0394 (5)
H10	0.4962	0.3470	0.0906	0.047*
C11	0.80572 (13)	0.34520 (18)	0.09524 (9)	0.0253 (4)
C12	0.89402 (13)	0.31643 (19)	0.06821 (10)	0.0281 (4)
C13	0.88645 (12)	0.42660 (18)	0.19952 (10)	0.0242 (4)
C14	0.96892 (13)	0.43718 (19)	0.16272 (10)	0.0266 (4)
C15	1.05445 (13)	0.5179 (2)	0.18756 (10)	0.0292 (4)
C16	1.14420 (14)	0.4738 (2)	0.17324 (12)	0.0371 (5)
H16	1.1523	0.3931	0.1480	0.045*
C17	1.22185 (15)	0.5528 (3)	0.19744 (14)	0.0480 (6)
H17	1.2832	0.5262	0.1887	0.058*
C18	1.20685 (16)	0.6706 (3)	0.23433 (14)	0.0530 (6)
H18	1.2580	0.7242	0.2519	0.064*
C19	1.11509 (16)	0.7090 (2)	0.24518 (13)	0.0459 (6)
H19	1.1056	0.7905	0.2693	0.055*
C20	0.90828 (14)	0.2209 (2)	0.00846 (10)	0.0304 (4)
C21	0.98469 (15)	0.2352 (2)	−0.03278 (11)	0.0406 (5)
H21	1.0265	0.3085	−0.0260	0.049*
C22	0.99719 (19)	0.1369 (3)	−0.08467 (12)	0.0523 (6)
H22	1.0479	0.1432	−0.1134	0.063*
C23	0.9341 (2)	0.0306 (3)	−0.09314 (13)	0.0547 (7)
H23	0.9412	−0.0367	−0.1275	0.066*
C24	0.85993 (19)	0.0258 (2)	−0.04955 (14)	0.0517 (6)
H24	0.8169	−0.0462	−0.0558	0.062*
C25	0.72974 (15)	0.6673 (2)	0.09222 (13)	0.0368 (5)
C26	0.72404 (19)	0.7046 (3)	−0.02745 (15)	0.0559 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02005 (14)	0.03028 (16)	0.02787 (16)	0.00049 (11)	−0.00010 (10)	−0.00116 (12)
N1	0.0219 (8)	0.0282 (8)	0.0271 (8)	0.0000 (6)	−0.0003 (6)	−0.0003 (6)
N2	0.0204 (7)	0.0269 (8)	0.0251 (8)	0.0003 (6)	−0.0021 (6)	−0.0009 (6)
N3	0.0219 (8)	0.0328 (9)	0.0350 (9)	−0.0007 (6)	−0.0036 (7)	−0.0055 (7)
O1	0.0369 (9)	0.0503 (9)	0.0458 (9)	0.0057 (7)	−0.0047 (7)	−0.0149 (8)
O2	0.0284 (8)	0.0533 (10)	0.0436 (9)	0.0041 (7)	−0.0096 (7)	−0.0050 (8)
O1W	0.0255 (8)	0.0370 (9)	0.0528 (9)	−0.0031 (6)	−0.0008 (7)	0.0092 (7)
O3	0.0277 (8)	0.0557 (10)	0.0618 (10)	0.0143 (7)	0.0046 (7)	−0.0050 (8)
N4	0.0423 (10)	0.0398 (10)	0.0380 (10)	−0.0039 (8)	0.0098 (8)	−0.0084 (8)
N5	0.0228 (8)	0.0358 (9)	0.0307 (8)	−0.0010 (6)	0.0025 (7)	−0.0006 (7)
N6	0.0246 (8)	0.0384 (10)	0.0410 (10)	−0.0014 (7)	−0.0009 (7)	−0.0049 (8)
N7	0.0442 (11)	0.0323 (10)	0.0425 (11)	0.0007 (8)	−0.0020 (9)	0.0041 (8)
N8	0.0456 (12)	0.0891 (18)	0.0531 (13)	−0.0092 (12)	0.0118 (11)	0.0062 (12)
N9	0.085 (2)	0.184 (4)	0.0492 (16)	−0.030 (2)	−0.0023 (15)	0.0184 (19)
N10	0.0250 (8)	0.0374 (9)	0.0340 (9)	0.0026 (7)	0.0023 (7)	0.0033 (8)
C1	0.0232 (9)	0.0247 (9)	0.0244 (9)	−0.0010 (7)	−0.0008 (7)	0.0012 (7)
C2	0.0222 (9)	0.0421 (12)	0.0322 (10)	0.0045 (8)	−0.0039 (8)	−0.0009 (9)
C3	0.0352 (11)	0.0465 (13)	0.0293 (10)	0.0023 (9)	−0.0104 (9)	−0.0015 (9)
C4	0.0433 (12)	0.0399 (11)	0.0244 (10)	0.0016 (9)	0.0001 (9)	−0.0035 (8)
C5	0.0298 (10)	0.0349 (10)	0.0301 (10)	0.0015 (8)	0.0044 (8)	−0.0026 (8)
C6	0.0243 (9)	0.0260 (9)	0.0299 (10)	−0.0001 (7)	−0.0042 (8)	−0.0031 (8)
C7	0.0347 (11)	0.0454 (12)	0.0310 (11)	0.0026 (9)	−0.0036 (9)	−0.0008 (9)
C8	0.0478 (14)	0.0553 (15)	0.0355 (12)	0.0057 (11)	−0.0164 (10)	−0.0070 (11)
C9	0.0319 (11)	0.0535 (14)	0.0526 (14)	0.0025 (10)	−0.0161 (10)	−0.0121 (12)
C10	0.0231 (10)	0.0444 (13)	0.0497 (13)	−0.0008 (9)	−0.0051 (9)	−0.0131 (10)
C11	0.0236 (9)	0.0261 (9)	0.0257 (9)	0.0001 (7)	−0.0014 (7)	0.0000 (7)
C12	0.0260 (9)	0.0314 (10)	0.0266 (9)	0.0000 (8)	0.0008 (8)	0.0014 (8)
C13	0.0198 (8)	0.0256 (9)	0.0266 (9)	0.0025 (7)	−0.0025 (7)	−0.0007 (7)
C14	0.0205 (9)	0.0298 (10)	0.0290 (9)	0.0016 (7)	−0.0014 (7)	−0.0006 (8)
C15	0.0204 (9)	0.0357 (11)	0.0310 (10)	−0.0017 (7)	−0.0009 (7)	0.0017 (8)
C16	0.0233 (10)	0.0424 (12)	0.0456 (12)	0.0007 (8)	0.0028 (9)	−0.0035 (10)
C17	0.0205 (10)	0.0605 (15)	0.0624 (16)	−0.0012 (10)	−0.0005 (10)	−0.0021 (13)
C18	0.0262 (11)	0.0605 (16)	0.0708 (17)	−0.0119 (11)	−0.0050 (11)	−0.0108 (14)
C19	0.0358 (12)	0.0441 (13)	0.0565 (14)	−0.0066 (10)	−0.0036 (11)	−0.0125 (11)
C20	0.0305 (10)	0.0349 (11)	0.0257 (9)	0.0040 (8)	0.0021 (8)	0.0001 (8)
C21	0.0350 (11)	0.0513 (13)	0.0367 (12)	0.0006 (10)	0.0103 (9)	−0.0003 (10)
C22	0.0533 (15)	0.0690 (18)	0.0374 (13)	0.0108 (13)	0.0209 (11)	−0.0010 (12)
C23	0.0729 (19)	0.0531 (16)	0.0396 (13)	0.0094 (13)	0.0147 (13)	−0.0128 (11)
C24	0.0624 (17)	0.0437 (14)	0.0500 (14)	−0.0076 (11)	0.0112 (12)	−0.0135 (11)
C25	0.0302 (11)	0.0321 (11)	0.0464 (13)	−0.0029 (8)	−0.0076 (10)	0.0002 (10)
C26	0.0520 (16)	0.0694 (18)	0.0481 (15)	−0.0163 (13)	0.0146 (13)	−0.0007 (13)

Geometric parameters (Å, º) top

Mn1—O1W	2.1537 (15)	C3—H3	0.9300
Mn1—N7	2.2457 (18)	C4—C5	1.376 (3)
Mn1—O1	2.2648 (15)	C4—H4	0.9300
Mn1—N2	2.2796 (15)	C5—H5	0.9300
Mn1—N1	2.3015 (15)	C6—C7	1.383 (3)
Mn1—N3	2.3247 (16)	C6—C11	1.488 (2)
Mn1—O2	2.4021 (15)	C7—C8	1.384 (3)
N1—C5	1.337 (2)	C7—H7	0.9300
N1—C1	1.341 (2)	C8—C9	1.371 (3)
N2—C11	1.333 (2)	C8—H8	0.9300
N2—C13	1.336 (2)	C9—C10	1.374 (3)
N3—C10	1.346 (2)	C9—H9	0.9300
N3—C6	1.348 (2)	C10—H10	0.9300
O1—N10	1.264 (2)	C11—C12	1.408 (3)
O2—N10	1.256 (2)	C12—C20	1.483 (3)
O1W—H1W	0.776 (16)	C13—C14	1.401 (3)
O1W—H2W	0.800 (16)	C14—C15	1.485 (3)
O3—N10	1.221 (2)	C15—C16	1.383 (3)
N4—C24	1.325 (3)	C16—C17	1.387 (3)
N4—C20	1.340 (3)	C16—H16	0.9300
N5—C14	1.333 (2)	C17—C18	1.367 (3)
N5—C12	1.334 (2)	C17—H17	0.9300
N6—C19	1.336 (3)	C18—C19	1.377 (3)
N6—C15	1.342 (3)	C18—H18	0.9300
N7—C25	1.146 (3)	C19—H19	0.9300
N8—C25	1.284 (3)	C20—C21	1.381 (3)
N8—C26	1.294 (4)	C21—C22	1.387 (3)
N9—C26	1.128 (4)	C21—H21	0.9300
C1—C2	1.391 (2)	C22—C23	1.369 (4)
C1—C13	1.487 (2)	C22—H22	0.9300
C2—C3	1.373 (3)	C23—C24	1.377 (3)
C2—H2	0.9300	C23—H23	0.9300
C3—C4	1.377 (3)	C24—H24	0.9300

O1W—Mn1—N7	177.74 (7)	N3—C6—C11	114.99 (16)
O1W—Mn1—O1	89.83 (6)	C7—C6—C11	122.91 (18)
N7—Mn1—O1	89.42 (7)	C6—C7—C8	119.3 (2)
O1W—Mn1—N2	101.50 (6)	C6—C7—H7	120.3
N7—Mn1—N2	80.11 (6)	C8—C7—H7	120.3
O1—Mn1—N2	152.04 (6)	C9—C8—C7	118.7 (2)
O1W—Mn1—N1	84.71 (6)	C9—C8—H8	120.6
N7—Mn1—N1	94.37 (6)	C7—C8—H8	120.6
O1—Mn1—N1	136.40 (6)	C8—C9—C10	119.1 (2)
N2—Mn1—N1	70.72 (5)	C8—C9—H9	120.4
O1W—Mn1—N3	93.87 (6)	C10—C9—H9	120.4
N7—Mn1—N3	88.18 (6)	N3—C10—C9	123.0 (2)
O1—Mn1—N3	84.12 (6)	N3—C10—H10	118.5
N2—Mn1—N3	69.81 (5)	C9—C10—H10	118.5
N1—Mn1—N3	139.34 (6)	N2—C11—C12	118.14 (16)
O1W—Mn1—O2	92.71 (6)	N2—C11—C6	114.86 (16)
N7—Mn1—O2	85.11 (6)	C12—C11—C6	126.90 (17)
O1—Mn1—O2	54.58 (5)	N5—C12—C11	118.71 (17)
N2—Mn1—O2	148.05 (5)	N5—C12—C20	116.28 (16)
N1—Mn1—O2	82.45 (5)	C11—C12—C20	124.94 (17)
N3—Mn1—O2	138.12 (5)	N2—C13—C14	118.22 (16)
C5—N1—C1	117.95 (16)	N2—C13—C1	114.65 (16)
C5—N1—Mn1	123.77 (13)	C14—C13—C1	127.13 (16)
C1—N1—Mn1	117.69 (12)	N5—C14—C13	119.12 (16)
C11—N2—C13	120.85 (16)	N5—C14—C15	116.12 (16)
C11—N2—Mn1	119.97 (11)	C13—C14—C15	124.75 (17)
C13—N2—Mn1	117.31 (12)	N6—C15—C16	123.04 (18)
C10—N3—C6	117.61 (17)	N6—C15—C14	116.53 (17)
C10—N3—Mn1	122.22 (13)	C16—C15—C14	120.42 (18)
C6—N3—Mn1	116.22 (12)	C15—C16—C17	118.3 (2)
N10—O1—Mn1	97.27 (11)	C15—C16—H16	120.9
N10—O2—Mn1	90.98 (11)	C17—C16—H16	120.9
Mn1—O1W—H1W	135 (2)	C18—C17—C16	119.0 (2)
Mn1—O1W—H2W	114.3 (19)	C18—C17—H17	120.5
H1W—O1W—H2W	110 (3)	C16—C17—H17	120.5
C24—N4—C20	117.06 (19)	C17—C18—C19	119.2 (2)
C14—N5—C12	120.17 (16)	C17—C18—H18	120.4
C19—N6—C15	117.48 (18)	C19—C18—H18	120.4
C25—N7—Mn1	133.43 (17)	N6—C19—C18	123.0 (2)
C25—N8—C26	122.9 (2)	N6—C19—H19	118.5
O3—N10—O2	122.18 (17)	C18—C19—H19	118.5
O3—N10—O1	121.26 (17)	N4—C20—C21	123.30 (19)
O2—N10—O1	116.56 (16)	N4—C20—C12	115.50 (17)
N1—C1—C2	122.17 (17)	C21—C20—C12	121.08 (18)
N1—C1—C13	115.05 (15)	C20—C21—C22	118.0 (2)
C2—C1—C13	122.73 (17)	C20—C21—H21	121.0
C3—C2—C1	118.60 (18)	C22—C21—H21	121.0
C3—C2—H2	120.7	C23—C22—C21	119.3 (2)
C1—C2—H2	120.7	C23—C22—H22	120.3
C2—C3—C4	119.67 (19)	C21—C22—H22	120.3
C2—C3—H3	120.2	C22—C23—C24	118.3 (2)
C4—C3—H3	120.2	C22—C23—H23	120.9
C5—C4—C3	118.29 (19)	C24—C23—H23	120.9
C5—C4—H4	120.9	N4—C24—C23	124.0 (2)
C3—C4—H4	120.9	N4—C24—H24	118.0
N1—C5—C4	123.26 (18)	C23—C24—H24	118.0
N1—C5—H5	118.4	N7—C25—N8	172.7 (2)
C4—C5—H5	118.4	N9—C26—N8	174.4 (3)
N3—C6—C7	121.95 (17)

O1W—Mn1—N1—C5	−63.95 (15)	Mn1—N1—C5—C4	170.63 (15)
N7—Mn1—N1—C5	113.98 (16)	C3—C4—C5—N1	−1.4 (3)
O1—Mn1—N1—C5	20.22 (19)	C10—N3—C6—C7	5.5 (3)
N2—Mn1—N1—C5	−168.10 (16)	Mn1—N3—C6—C7	−152.74 (16)
N3—Mn1—N1—C5	−153.72 (14)	C10—N3—C6—C11	−178.84 (17)
O2—Mn1—N1—C5	29.50 (15)	Mn1—N3—C6—C11	23.0 (2)
O1W—Mn1—N1—C1	107.06 (13)	N3—C6—C7—C8	−4.3 (3)
N7—Mn1—N1—C1	−75.01 (14)	C11—C6—C7—C8	−179.65 (19)
O1—Mn1—N1—C1	−168.77 (12)	C6—C7—C8—C9	−0.4 (3)
N2—Mn1—N1—C1	2.91 (12)	C7—C8—C9—C10	3.5 (4)
N3—Mn1—N1—C1	17.29 (17)	C6—N3—C10—C9	−2.1 (3)
O2—Mn1—N1—C1	−159.49 (13)	Mn1—N3—C10—C9	154.67 (18)
O1W—Mn1—N2—C11	100.10 (14)	C8—C9—C10—N3	−2.4 (4)
N7—Mn1—N2—C11	−81.53 (14)	C13—N2—C11—C12	10.4 (3)
O1—Mn1—N2—C11	−12.0 (2)	Mn1—N2—C11—C12	174.40 (13)
N1—Mn1—N2—C11	−179.74 (15)	C13—N2—C11—C6	−166.21 (16)
N3—Mn1—N2—C11	10.18 (13)	Mn1—N2—C11—C6	−2.2 (2)
O2—Mn1—N2—C11	−145.24 (13)	N3—C6—C11—N2	−13.9 (2)
O1W—Mn1—N2—C13	−95.37 (13)	C7—C6—C11—N2	161.74 (19)
N7—Mn1—N2—C13	83.01 (13)	N3—C6—C11—C12	169.79 (18)
O1—Mn1—N2—C13	152.51 (13)	C7—C6—C11—C12	−14.5 (3)
N1—Mn1—N2—C13	−15.21 (12)	C14—N5—C12—C11	10.7 (3)
N3—Mn1—N2—C13	174.72 (14)	C14—N5—C12—C20	−166.23 (17)
O2—Mn1—N2—C13	19.30 (19)	N2—C11—C12—N5	−20.9 (3)
O1W—Mn1—N3—C10	84.37 (16)	C6—C11—C12—N5	155.22 (18)
N7—Mn1—N3—C10	−94.67 (16)	N2—C11—C12—C20	155.68 (18)
O1—Mn1—N3—C10	−5.06 (16)	C6—C11—C12—C20	−28.1 (3)
N2—Mn1—N3—C10	−174.79 (17)	C11—N2—C13—C14	9.5 (3)
N1—Mn1—N3—C10	170.75 (14)	Mn1—N2—C13—C14	−154.90 (13)
O2—Mn1—N3—C10	−14.0 (2)	C11—N2—C13—C1	−170.97 (16)
O1W—Mn1—N3—C6	−118.53 (13)	Mn1—N2—C13—C1	24.63 (19)
N7—Mn1—N3—C6	62.43 (14)	N1—C1—C13—N2	−21.5 (2)
O1—Mn1—N3—C6	152.04 (14)	C2—C1—C13—N2	155.81 (17)
N2—Mn1—N3—C6	−17.70 (13)	N1—C1—C13—C14	157.98 (18)
N1—Mn1—N3—C6	−32.16 (17)	C2—C1—C13—C14	−24.7 (3)
O2—Mn1—N3—C6	143.05 (12)	C12—N5—C14—C13	9.4 (3)
O1W—Mn1—O1—N10	97.99 (12)	C12—N5—C14—C15	−169.43 (17)
N7—Mn1—O1—N10	−79.87 (13)	N2—C13—C14—N5	−19.9 (3)
N2—Mn1—O1—N10	−147.21 (12)	C1—C13—C14—N5	160.60 (17)
N1—Mn1—O1—N10	15.86 (16)	N2—C13—C14—C15	158.84 (17)
N3—Mn1—O1—N10	−168.10 (12)	C1—C13—C14—C15	−20.6 (3)
O2—Mn1—O1—N10	4.54 (10)	C19—N6—C15—C16	−0.9 (3)
O1W—Mn1—O2—N10	−92.39 (11)	C19—N6—C15—C14	−179.71 (19)
N7—Mn1—O2—N10	88.24 (11)	N5—C14—C15—N6	144.16 (18)
O1—Mn1—O2—N10	−4.53 (10)	C13—C14—C15—N6	−34.6 (3)
N2—Mn1—O2—N10	150.67 (11)	N5—C14—C15—C16	−34.7 (3)
N1—Mn1—O2—N10	−176.69 (11)	C13—C14—C15—C16	146.5 (2)
N3—Mn1—O2—N10	6.46 (15)	N6—C15—C16—C17	1.1 (3)
O1—Mn1—N7—C25	−110.2 (2)	C14—C15—C16—C17	179.9 (2)
N2—Mn1—N7—C25	43.7 (2)	C15—C16—C17—C18	0.0 (4)
N1—Mn1—N7—C25	113.3 (2)	C16—C17—C18—C19	−1.3 (4)
N3—Mn1—N7—C25	−26.1 (2)	C15—N6—C19—C18	−0.5 (4)
O2—Mn1—N7—C25	−164.7 (2)	C17—C18—C19—N6	1.6 (4)
Mn1—O2—N10—O3	−171.75 (17)	C24—N4—C20—C21	−0.4 (3)
Mn1—O2—N10—O1	7.42 (17)	C24—N4—C20—C12	−176.33 (19)
Mn1—O1—N10—O3	171.25 (16)	N5—C12—C20—N4	147.61 (18)
Mn1—O1—N10—O2	−7.93 (18)	C11—C12—C20—N4	−29.1 (3)
C5—N1—C1—C2	2.4 (3)	N5—C12—C20—C21	−28.5 (3)
Mn1—N1—C1—C2	−169.16 (14)	C11—C12—C20—C21	154.8 (2)
C5—N1—C1—C13	179.72 (16)	N4—C20—C21—C22	0.0 (3)
Mn1—N1—C1—C13	8.2 (2)	C12—C20—C21—C22	175.8 (2)
N1—C1—C2—C3	−2.6 (3)	C20—C21—C22—C23	0.0 (4)
C13—C1—C2—C3	−179.76 (18)	C21—C22—C23—C24	0.3 (4)
C1—C2—C3—C4	0.8 (3)	C20—N4—C24—C23	0.7 (4)
C2—C3—C4—C5	1.1 (3)	C22—C23—C24—N4	−0.6 (4)
C1—N1—C5—C4	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N6ⁱ	0.78 (2)	2.03 (2)	2.800 (2)	174 (3)
O1W—H2W···N7ⁱ	0.80 (2)	2.24 (2)	3.029 (2)	168 (2)
C5—H5···O2	0.93	2.53	3.122 (2)	122
C7—H7···N4	0.93	2.60	2.966 (3)	104
C10—H10···O1	0.93	2.51	3.027 (3)	116

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(C₂N₃)(NO₃)(C₂₄H₁₆N₆)(H₂O)]
M_r	589.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	14.0988 (11), 9.7739 (8), 18.7205 (13)
β (°)	94.491 (6)
V (Å³)	2571.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.42 × 0.31 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur 2 diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.856, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	24694, 7480, 4848
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.119, 0.93
No. of reflections	7480
No. of parameters	376
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SIR2004 Burla et al. (2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2007), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Selected bond lengths (Å) top

Mn1—O1W	2.1537 (15)	Mn1—N1	2.3015 (15)
Mn1—N7	2.2457 (18)	Mn1—N3	2.3247 (16)
Mn1—O1	2.2648 (15)	Mn1—O2	2.4021 (15)
Mn1—N2	2.2796 (15)