Tris(3,3′-diamino-2,2′-bipyridine)manganese(II) dinitrate

In the title complex, [Mn(C₁₀H₁₀N₄)₃](NO₃)₂, the six-coordinate Mn^II atom is located on the inter­section of one threefold and three twofold axes, while the nitrate anion lies on a threefold axis. In the crystal structure, a two-dimensional network is formed via inter­molecular N—H...N and N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.038
• wR factor = 0.089
• Data-to-parameter ratio = 7.9

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.470
           From the CIF: _refine_ls_abs_structure_Flack_su    0.050
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.47
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.88
PLAT127_ALERT_1_C Implicit Hall Symbol  Inconsistent with Explicit      R 3 2
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.06
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.95
           From the CIF: _reflns_number_total                615
           Count of symmetry unique reflns          615
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Tris(3,3'-diamino-2,2'-bipyridine)manganese(II) dinitrate

Crystal data

[Mn(C10H10N4)3](NO3)2	Dx = 1.481 Mg m^−3
Mr = 737.62	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 1098 reflections
Hall symbol: R 3 2	θ = 2.2–20.3°
a = 14.7149 (16) Å	µ = 0.47 mm^−1
c = 13.229 (3) Å	T = 298 K
V = 2480.8 (7) Å^3	Prism, yellow
Z = 3	0.38 × 0.21 × 0.20 mm
F(000) = 1143

Data collection

Bruker SMART APEX CCD diffractometer	615 independent reflections
Radiation source: fine-focus sealed tube	572 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→18
Tmin = 0.843, Tmax = 0.913	k = −16→18
4198 measured reflections	l = −15→16

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0557P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.003
615 reflections	Δρmax = 0.24 e Å^−3
78 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 480 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.47 (5)

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	1.0000	1.0000	0.0000	0.0381 (3)
N1	0.8489 (2)	0.9409 (2)	0.08403 (18)	0.0430 (7)
C1	0.7767 (2)	0.9562 (2)	0.0367 (2)	0.0429 (8)
C3	0.6406 (3)	0.8140 (4)	0.1305 (3)	0.0677 (10)
H3	0.5703	0.7708	0.1470	0.081*
N2	0.5925 (2)	0.8884 (3)	−0.0063 (3)	0.0816 (12)
H2A	0.5275	0.8437	0.0046	0.098*
H2B	0.6099	0.9336	−0.0541	0.098*
C5	0.8199 (3)	0.8673 (3)	0.1543 (3)	0.0566 (9)
H5	0.8707	0.8572	0.1856	0.068*
C2	0.6686 (3)	0.8874 (3)	0.0528 (3)	0.0555 (9)
C4	0.7160 (3)	0.8053 (3)	0.1822 (3)	0.0677 (11)
H4	0.6978	0.7582	0.2356	0.081*
N3	0.3333	0.6667	0.0445 (3)	0.0483 (9)
O1	0.3971 (2)	0.6352 (2)	0.0446 (2)	0.0737 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0309 (4)	0.0309 (4)	0.0525 (6)	0.01546 (18)	0.000	0.000
N1	0.0398 (13)	0.0346 (15)	0.0531 (14)	0.0174 (11)	0.0026 (10)	0.0053 (11)
C1	0.0359 (16)	0.0328 (15)	0.059 (2)	0.0165 (13)	0.0041 (14)	0.0008 (15)
C3	0.0426 (17)	0.047 (2)	0.093 (2)	0.008 (2)	0.0168 (17)	0.015 (2)
N2	0.0320 (15)	0.065 (2)	0.135 (3)	0.0141 (15)	−0.0022 (18)	0.020 (2)
C5	0.056 (2)	0.053 (2)	0.061 (2)	0.0277 (18)	0.0024 (17)	0.0095 (17)
C2	0.0377 (18)	0.0437 (19)	0.085 (2)	0.0198 (15)	0.0054 (17)	0.0024 (17)
C4	0.067 (3)	0.049 (2)	0.071 (2)	0.0167 (18)	0.019 (2)	0.0216 (19)
N3	0.0442 (14)	0.0442 (14)	0.056 (2)	0.0221 (7)	0.000	0.000
O1	0.0551 (17)	0.0605 (18)	0.116 (2)	0.0371 (16)	0.0009 (15)	−0.0046 (15)

Geometric parameters (Å, º)

Mn1—N1^i	2.237 (2)	C3—C2	1.395 (5)
Mn1—N1^ii	2.237 (2)	C3—H3	0.9300
Mn1—N1^iii	2.237 (2)	N2—C2	1.371 (5)
Mn1—N1^iv	2.237 (2)	N2—H2A	0.8600
Mn1—N1	2.237 (2)	N2—H2B	0.8600
Mn1—N1^v	2.237 (2)	C5—C4	1.382 (6)
N1—C5	1.326 (4)	C5—H5	0.9300
N1—C1	1.344 (4)	C4—H4	0.9300
C1—C2	1.411 (5)	N3—O1^vi	1.237 (2)
C1—C1^ii	1.481 (6)	N3—O1^vii	1.237 (2)
C3—C4	1.363 (6)	N3—O1	1.237 (2)
N1^i—Mn1—N1^ii	92.53 (14)	C2—C1—C1^ii	124.6 (2)
N1^i—Mn1—N1^iii	167.54 (14)	C4—C3—C2	120.2 (3)
N1^ii—Mn1—N1^iii	97.44 (8)	C4—C3—H3	119.9
N1^i—Mn1—N1^iv	97.44 (8)	C2—C3—H3	119.9
N1^ii—Mn1—N1^iv	167.54 (14)	C2—N2—H2A	120.0
N1^iii—Mn1—N1^iv	73.76 (12)	C2—N2—H2B	120.0
N1^i—Mn1—N1	97.44 (8)	H2A—N2—H2B	120.0
N1^ii—Mn1—N1	73.76 (12)	N1—C5—C4	121.6 (4)
N1^iii—Mn1—N1	92.53 (14)	N1—C5—H5	119.2
N1^iv—Mn1—N1	97.44 (8)	C4—C5—H5	119.2
N1^i—Mn1—N1^v	73.76 (12)	N2—C2—C3	120.1 (3)
N1^ii—Mn1—N1^v	97.44 (8)	N2—C2—C1	122.7 (3)
N1^iii—Mn1—N1^v	97.44 (8)	C3—C2—C1	117.2 (3)
N1^iv—Mn1—N1^v	92.53 (14)	C3—C4—C5	119.2 (4)
N1—Mn1—N1^v	167.54 (14)	C3—C4—H4	120.4
C5—N1—C1	120.3 (3)	C5—C4—H4	120.4
C5—N1—Mn1	121.1 (2)	O1^vi—N3—O1^vii	120.000 (2)
C1—N1—Mn1	114.74 (19)	O1^vi—N3—O1	120.000 (2)
N1—C1—C2	120.8 (3)	O1^vii—N3—O1	120.000 (2)
N1—C1—C1^ii	114.48 (19)
N1^i—Mn1—N1—C5	−102.5 (2)	C5—N1—C1—C1^ii	177.5 (3)
N1^ii—Mn1—N1—C5	167.0 (3)	Mn1—N1—C1—C1^ii	−24.3 (4)
N1^iii—Mn1—N1—C5	70.0 (3)	C1—N1—C5—C4	−0.9 (5)
N1^iv—Mn1—N1—C5	−4.0 (3)	Mn1—N1—C5—C4	−157.7 (3)
N1^v—Mn1—N1—C5	−146.8 (3)	C4—C3—C2—N2	173.0 (4)
N1^i—Mn1—N1—C1	99.4 (3)	C4—C3—C2—C1	−5.0 (6)
N1^ii—Mn1—N1—C1	8.96 (17)	N1—C1—C2—N2	−168.2 (4)
N1^iii—Mn1—N1—C1	−88.1 (2)	C1^ii—C1—C2—N2	7.0 (6)
N1^iv—Mn1—N1—C1	−162.0 (2)	N1—C1—C2—C3	9.7 (5)
N1^v—Mn1—N1—C1	55.1 (5)	C1^ii—C1—C2—C3	−175.1 (4)
C5—N1—C1—C2	−6.9 (5)	C2—C3—C4—C5	−2.3 (7)
Mn1—N1—C1—C2	151.4 (3)	N1—C5—C4—C3	5.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N2^ii	0.86	2.41	2.850 (7)	113
N2—H2A···O1^vi	0.86	2.14	2.984 (4)	167

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