X-ray and neutron diffraction studies of the non-linear optical compounds MBANP and MBADNP at 20 K: charge-density and hydrogen-bonding analyses

Neutron-diffraction studies of the compounds 5-nitro-2-{[1-phenylethyl]amino}pyridine (methylbenzylaminonitro­pyridine, hereafter MBANP) and 3,5-dinitro-2-{[1-phenyl­ethyl]amino}pyridine (methylbenzylaminodinitropyridine, hereafter MBADNP) are presented, and a charge-density study of the latter is reported. The studies were conducted in order to relate the structural attributes of these materials to their physical properties. MBANP exhibits a second-harmonic generation (SHG) output, χ⁽²⁾, over eight times higher than that of MBADNP, despite their very similar molecular characteristics and the seemingly more SHG-favourable molecular features present in MBADNP. The neutron-diffraction studies show that intramolecular hydrogen bonding is responsible for this apparent discrepancy. The charge-density study on MBADNP confirms this and reveals that the pyridine group is the principal moiety responsible for the SHG effect on the molecular scale. Moreover, the strong intra­molecular hydrogen bond present in MBADNP is proven to result from an electrostatic interaction. The dipole moment of MBADNP is also deduced from the charge-density study.

S1. Comment

The nature of the hydrogen bonding in two organic non-linear optical compounds, MBANP and MBADNP, as determined by neutron diffraction, is related to their differing second-harmonic-generation outputs. A charge-density study of MBADNP elucidates the nature of the highly influential intramolecular hydrogen-bond and also reveals the nature of the polarizability within the molecule.

Computing details

Data collection: MAD (Barthelemy, 1984) for MBANP; MAD (Bartelemy, 1984) for MBADNP; local program for MBADNPX. Cell refinement: RAFD9 (local program) for MBANP, MBADNP; local program for MBADNPX. Data reduction: RACER (Wilkinson et al., 1988) for MBANP, MBADNP; COLL5N (Lehmann and Wilson, 1987) for MBADNPX. Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for MBANP, MBADNP; SHELXS97 (Sheldrick, 1990) for MBADNPX. Program(s) used to refine structure: SHELXL93 (Sheldrick, 1993) for MBANP, MBADNP; SHELXL97 (Sheldrick, 1997) for MBADNPX. Molecular graphics: SHELXTL-Plus (Sheldrick, 1995) for MBANP, MBADNPX; SHELXTL_PLUS (1995) for MBADNP. Software used to prepare material for publication: SHELXL93 (Sheldrick, 1993) for MBANP, MBADNP; SHELXL97 (Sheldrick, 1997) for MBADNPX.

Figures

(MBANP)

Crystal data

C13H13N3O2	F(000) = 182
Mr = 243.00	Dx = 1.368 Mg m^−3
Monoclinic, P21	Neutron radiation, λ = 0.83717 Å
a = 5.321 (1) Å	Cell parameters from 4 reflections
b = 6.293 (1) Å	θ = 10–12°
c = 17.650 (4) Å	µ = 0.16 mm^−1
β = 93.65 (3)°	T = 20 K
V = 589.8 (2) Å^3	Rectangle, yellow
Z = 2	4.3 × 2.0 × 1.0 mm

Data collection

The high-flux four-circle diffractometer, D9	2619 reflections with I > 2σ(I)
Radiation source: Institut Laue Langevin Reactor, Grenoble, France	Rint = 0.038
Cu (220) monochromator	θmax = 46.5°, θmin = 2.7°
ω–x–θ scans	h = −9→9
Absorption correction: integration Gaussian integration (Coppens et al, 1965)	k = −10→2
Tmin = 0.726, Tmax = 0.857	l = −22→21
4116 measured reflections	1 standard reflections every 50 reflections
2805 independent reflections	intensity decay: none

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)] = 0.073	All H-atom parameters refined
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 2.56	(Δ/σ)max = −0.004
2799 reflections	Δρmax = 1.80 e Å^−3
280 parameters	Δρmin = −1.87 e Å^−3
1 restraint	Absolute structure: Absolute structure known a priori from reagents in synthesis (see paper)
Primary atom site location: structure-invariant direct methods

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 on F² for ALL reflections except for 6 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating the obs R factor 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
O1	0.6458 (6)	0.1528 (5)	0.4698 (2)	0.0103 (5)
O2	0.3175 (6)	0.1837 (5)	0.3915 (2)	0.0114 (5)
N1	0.8817 (3)	0.9896 (3)	0.30042 (12)	0.0080 (3)
H1N	1.0504 (10)	1.0463 (11)	0.3223 (4)	0.0223 (13)
N2	0.5712 (3)	0.7316 (3)	0.30259 (12)	0.0081 (3)
N3	0.5221 (3)	0.2486 (3)	0.41967 (12)	0.0075 (3)
C1	0.8083 (4)	0.9335 (4)	0.1617 (2)	0.0069 (4)
C2	0.6266 (4)	0.9362 (4)	0.1012 (2)	0.0084 (4)
H2	0.4594 (11)	1.0339 (11)	0.1057 (5)	0.0248 (13)
C3	0.6576 (5)	0.8155 (4)	0.0366 (2)	0.0093 (4)
H3	0.5144 (13)	0.8191 (12)	−0.0089 (4)	0.0238 (13)
C4	0.8723 (5)	0.6900 (4)	0.0317 (2)	0.0086 (4)
H4	0.8973 (13)	0.5943 (12)	−0.0180 (4)	0.0241 (13)
C5	1.0539 (4)	0.6858 (4)	0.0915 (2)	0.0082 (4)
H5	1.2218 (11)	0.5898 (12)	0.0879 (4)	0.0241 (13)
C6	1.0243 (4)	0.8075 (4)	0.1567 (2)	0.0080 (4)
H6	1.1690 (11)	0.8058 (12)	0.2031 (4)	0.0219 (12)
C7	0.7761 (4)	1.0788 (4)	0.2293 (2)	0.0067 (4)
H7	0.5722 (9)	1.1041 (10)	0.2343 (4)	0.0177 (10)
C8	0.9068 (5)	1.2913 (4)	0.2160 (2)	0.0101 (4)
H8A	0.8927 (15)	1.3966 (11)	0.2642 (5)	0.0282 (14)
H8B	0.8215 (14)	1.3687 (13)	0.1664 (5)	0.030 (2)
H8C	1.1034 (13)	1.2654 (12)	0.2071 (5)	0.0286 (15)
C9	0.7922 (4)	0.8116 (4)	0.3324 (2)	0.0068 (4)
C10	0.9319 (4)	0.7158 (4)	0.3944 (2)	0.0078 (4)
H10	1.1051 (11)	0.7868 (11)	0.4161 (4)	0.0226 (12)
C11	0.8457 (4)	0.5305 (4)	0.4240 (2)	0.0075 (4)
H11	0.9485 (12)	0.4492 (12)	0.4702 (4)	0.0235 (12)
C12	0.6180 (4)	0.4461 (4)	0.3917 (2)	0.0071 (4)
C13	0.4876 (4)	0.5519 (4)	0.3326 (2)	0.0075 (4)
H13	0.3098 (11)	0.4870 (12)	0.3092 (4)	0.0221 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0090 (10)	0.0066 (11)	0.015 (2)	−0.0026 (8)	−0.0016 (9)	0.0031 (10)
O2	0.0116 (11)	0.0094 (10)	0.013 (2)	−0.0046 (9)	−0.0011 (9)	0.0016 (11)
N1	0.0070 (6)	0.0061 (6)	0.0107 (10)	−0.0021 (5)	−0.0008 (5)	0.0007 (6)
H1N	0.013 (2)	0.024 (3)	0.028 (4)	−0.014 (2)	−0.009 (2)	0.004 (2)
N2	0.0067 (6)	0.0059 (6)	0.0114 (10)	−0.0003 (5)	−0.0013 (5)	0.0013 (6)
N3	0.0062 (6)	0.0060 (6)	0.0100 (9)	−0.0011 (5)	−0.0006 (5)	0.0004 (6)
C1	0.0082 (8)	0.0051 (8)	0.0072 (13)	−0.0008 (7)	−0.0003 (7)	−0.0007 (8)
C2	0.0063 (8)	0.0076 (8)	0.0113 (13)	−0.0004 (7)	−0.0002 (7)	−0.0005 (8)
H2	0.013 (2)	0.025 (3)	0.036 (4)	0.010 (2)	−0.002 (2)	−0.003 (3)
C3	0.0105 (9)	0.0080 (9)	0.0091 (13)	0.0017 (8)	−0.0016 (7)	−0.0015 (9)
H3	0.024 (2)	0.026 (3)	0.021 (3)	0.004 (2)	−0.003 (2)	−0.007 (3)
C4	0.0097 (8)	0.0065 (8)	0.0094 (13)	0.0010 (7)	−0.0001 (7)	−0.0007 (8)
H4	0.029 (3)	0.026 (3)	0.017 (3)	0.006 (2)	−0.001 (2)	−0.009 (2)
C5	0.0061 (8)	0.0071 (8)	0.0112 (13)	0.0017 (7)	−0.0004 (7)	−0.0017 (8)
H5	0.017 (2)	0.026 (3)	0.029 (4)	0.010 (2)	−0.003 (2)	−0.006 (3)
C6	0.0070 (8)	0.0060 (8)	0.0109 (13)	0.0004 (7)	−0.0005 (7)	0.0002 (8)
H6	0.016 (2)	0.026 (3)	0.021 (3)	0.007 (2)	−0.010 (2)	−0.002 (2)
C7	0.0083 (8)	0.0057 (8)	0.0061 (13)	−0.0004 (7)	0.0005 (7)	0.0008 (7)
H7	0.007 (2)	0.021 (2)	0.024 (3)	0.003 (2)	0.000 (2)	0.001 (2)
C8	0.0123 (9)	0.0049 (8)	0.0132 (14)	−0.0021 (7)	0.0018 (8)	−0.0006 (8)
H8A	0.036 (3)	0.019 (3)	0.030 (4)	−0.003 (2)	0.001 (3)	−0.005 (3)
H8B	0.026 (3)	0.026 (3)	0.036 (4)	−0.006 (2)	−0.006 (3)	0.011 (3)
H8C	0.022 (3)	0.022 (3)	0.042 (4)	−0.002 (2)	0.008 (3)	−0.001 (3)
C9	0.0055 (8)	0.0055 (8)	0.0095 (13)	0.0010 (7)	−0.0007 (7)	−0.0009 (8)
C10	0.0048 (7)	0.0060 (9)	0.0123 (14)	−0.0019 (6)	−0.0014 (7)	−0.0004 (8)
H10	0.019 (2)	0.022 (3)	0.026 (3)	−0.006 (2)	−0.004 (2)	0.000 (2)
C11	0.0063 (8)	0.0061 (9)	0.0099 (13)	−0.0016 (6)	−0.0008 (7)	0.0012 (8)
H11	0.022 (2)	0.026 (3)	0.022 (3)	0.002 (2)	−0.005 (2)	0.010 (2)
C12	0.0052 (7)	0.0053 (8)	0.0109 (13)	−0.0012 (6)	0.0001 (7)	0.0003 (8)
C13	0.0062 (8)	0.0060 (8)	0.0100 (13)	−0.0013 (7)	−0.0013 (7)	0.0004 (8)
H13	0.017 (2)	0.023 (3)	0.025 (3)	−0.009 (2)	−0.004 (2)	0.003 (2)

Geometric parameters (Å, º)

O1—N3	1.226 (4)	C4—H4	1.080 (7)
O2—N3	1.237 (3)	C5—C6	1.399 (4)
N1—C9	1.354 (3)	C5—H5	1.084 (6)
N1—C7	1.455 (3)	C6—H6	1.087 (6)
N1—H1N	1.019 (5)	C7—C8	1.532 (4)
N2—C13	1.337 (3)	C7—H7	1.106 (6)
N2—C9	1.354 (3)	C8—H8A	1.085 (8)
N3—C12	1.443 (3)	C8—H8B	1.076 (8)
C1—C2	1.394 (4)	C8—H8C	1.080 (7)
C1—C6	1.404 (3)	C9—C10	1.418 (4)
C1—C7	1.522 (4)	C10—C11	1.369 (4)
C2—C3	1.388 (4)	C10—H10	1.073 (7)
C2—H2	1.089 (6)	C11—C12	1.409 (3)
C3—C4	1.396 (4)	C11—H11	1.082 (7)
C3—H3	1.072 (8)	C12—C13	1.386 (4)
C4—C5	1.385 (4)	C13—H13	1.088 (7)
C9—N1—C7	123.4 (2)	N1—C7—C8	108.3 (2)
C9—N1—H1N	117.2 (4)	C1—C7—C8	109.2 (2)
C7—N1—H1N	118.3 (4)	N1—C7—H7	108.3 (4)
C13—N2—C9	117.6 (2)	C1—C7—H7	108.0 (4)
O1—N3—O2	123.1 (3)	C8—C7—H7	110.1 (4)
O1—N3—C12	119.0 (2)	C7—C8—H8A	111.0 (5)
O2—N3—C12	117.9 (2)	C7—C8—H8B	110.3 (5)
C2—C1—C6	119.3 (2)	H8A—C8—H8B	108.3 (7)
C2—C1—C7	119.1 (2)	C7—C8—H8C	110.1 (4)
C6—C1—C7	121.4 (2)	H8A—C8—H8C	108.8 (6)
C3—C2—C1	120.6 (2)	H8B—C8—H8C	108.2 (7)
C3—C2—H2	120.7 (5)	N2—C9—N1	117.8 (2)
C1—C2—H2	118.7 (5)	N2—C9—C10	122.8 (2)
C2—C3—C4	120.0 (2)	N1—C9—C10	119.5 (2)
C2—C3—H3	119.2 (4)	C11—C10—C9	119.0 (2)
C4—C3—H3	120.8 (5)	C11—C10—H10	121.3 (5)
C5—C4—C3	119.9 (3)	C9—C10—H10	119.7 (4)
C5—C4—H4	119.5 (4)	C10—C11—C12	117.9 (2)
C3—C4—H4	120.6 (4)	C10—C11—H11	121.7 (4)
C4—C5—C6	120.4 (2)	C12—C11—H11	120.4 (4)
C4—C5—H5	120.2 (5)	C13—C12—C11	120.0 (2)
C6—C5—H5	119.4 (5)	C13—C12—N3	120.0 (2)
C5—C6—C1	119.7 (2)	C11—C12—N3	120.0 (2)
C5—C6—H6	120.2 (4)	N2—C13—C12	122.8 (2)
C1—C6—H6	120.1 (4)	N2—C13—H13	118.1 (4)
N1—C7—C1	112.9 (2)	C12—C13—H13	119.2 (4)

(MBADNP)

Crystal data

C13H12N4O4	F(000) = 230
Mr = 288.00	Dx = 1.504 Mg m^−3
Monoclinic, P21	Neutron radiation, λ = 0.83717 Å
a = 8.352 (3) Å	Cell parameters from 4 reflections
b = 8.570 (3) Å	θ = 10–12°
c = 8.909 (4) Å	µ = 0.14 mm^−1
β = 93.98 (2)°	T = 20 K
V = 636.1 (4) Å^3	Hexagonal prism, yellow
Z = 2	3.0 × 2.5 × 1.0 mm

Data collection

High-flux four-circle diffractometer, D9	3267 reflections with I > 2σ(I)
Radiation source: Institut Laue Langevin Reactor, Grenoble, France	Rint = 0.028
Cu (220) monochromator	θmax = 46.6°, θmin = 3.8°
ω–x–2θ scans	h = 0→14
Absorption correction: integration Gaussian integration (Coppens et al, 1965)	k = −10→14
Tmin = 0.757, Tmax = 0.880	l = −15→13
3755 measured reflections	1 standard reflections every 50 reflections
3401 independent reflections	intensity decay: none

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	All H-atom parameters refined
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.47	(Δ/σ)max < 0.001
3397 reflections	Δρmax = 0.82 e Å^−3
298 parameters	Δρmin = −0.91 e Å^−3
1 restraint	Absolute structure: The absolute structure is known a priori from reagents in the synthesis (see paper)
Primary atom site location: structure-invariant direct methods

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 on F² for ALL reflections except for 4 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating the obs R factor 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
O1	−0.15593 (12)	0.96547 (13)	0.73206 (12)	0.0076 (2)
O2	−0.01945 (13)	1.06825 (13)	0.55930 (12)	0.0082 (2)
O3	0.51576 (12)	0.89189 (13)	0.49365 (12)	0.0071 (2)
O4	0.61174 (12)	0.69667 (13)	0.62704 (12)	0.0071 (2)
N1	−0.08104 (7)	0.67472 (7)	0.82438 (7)	0.00506 (9)
H1N	−0.1746 (3)	0.7477 (3)	0.7998 (3)	0.0203 (4)
N2	0.17873 (7)	0.60357 (7)	0.78741 (7)	0.00496 (9)
N3	−0.03933 (7)	0.96757 (7)	0.65345 (7)	0.00438 (9)
N4	0.50107 (7)	0.78427 (7)	0.58286 (7)	0.00431 (9)
C1	−0.24396 (10)	0.55579 (10)	1.00641 (10)	0.00419 (12)
C2	−0.38679 (10)	0.47043 (11)	1.00011 (10)	0.00554 (12)
H2	−0.4081 (3)	0.3772 (3)	0.9181 (3)	0.0199 (4)
C3	−0.50539 (10)	0.50292 (11)	1.09938 (10)	0.00608 (13)
H3	−0.6170 (3)	0.4370 (3)	1.0907 (3)	0.0224 (4)
C4	−0.48078 (10)	0.61863 (11)	1.20866 (10)	0.00586 (13)
H4	−0.5733 (3)	0.6411 (3)	1.2864 (3)	0.0208 (4)
C5	−0.33708 (11)	0.70326 (11)	1.21700 (10)	0.00606 (13)
H5	−0.3150 (3)	0.7913 (3)	1.3034 (3)	0.0217 (4)
C6	−0.22085 (10)	0.67300 (11)	1.11570 (10)	0.00524 (12)
H6	−0.1108 (3)	0.7410 (3)	1.1218 (3)	0.0220 (4)
C7	−0.11286 (10)	0.52602 (10)	0.89968 (9)	0.00404 (12)
H7	−0.0012 (2)	0.4945 (3)	0.9657 (2)	0.0156 (3)
C8	−0.15256 (11)	0.39796 (10)	0.78310 (10)	0.00631 (13)
H8A	−0.1687 (3)	0.2854 (3)	0.8380 (3)	0.0236 (4)
H8B	−0.0542 (3)	0.3866 (3)	0.7081 (3)	0.0237 (4)
H8C	−0.2630 (3)	0.4254 (3)	0.7153 (3)	0.0223 (4)
C9	0.05708 (10)	0.70823 (10)	0.76388 (9)	0.00371 (12)
C10	0.08145 (10)	0.84614 (10)	0.67666 (10)	0.00400 (12)
C11	0.22537 (10)	0.87061 (10)	0.61283 (10)	0.00406 (12)
H11	0.2447 (3)	0.9743 (3)	0.5467 (3)	0.0176 (3)
C12	0.34521 (10)	0.76013 (10)	0.64042 (10)	0.00420 (12)
C13	0.31768 (10)	0.63001 (10)	0.72972 (10)	0.00468 (12)
H13	0.4132 (3)	0.5450 (3)	0.7533 (3)	0.0201 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0064 (3)	0.0062 (3)	0.0106 (4)	0.0020 (3)	0.0039 (3)	0.0023 (3)
O2	0.0086 (4)	0.0077 (4)	0.0087 (4)	0.0028 (3)	0.0028 (3)	0.0047 (3)
O3	0.0066 (3)	0.0071 (4)	0.0080 (4)	0.0007 (3)	0.0027 (3)	0.0030 (3)
O4	0.0046 (3)	0.0072 (4)	0.0094 (4)	0.0009 (3)	0.0007 (3)	0.0012 (3)
N1	0.0046 (2)	0.0042 (2)	0.0066 (2)	0.0007 (2)	0.0019 (2)	0.0017 (2)
H1N	0.0137 (8)	0.0183 (9)	0.0296 (11)	0.0067 (7)	0.0060 (8)	0.0098 (8)
N2	0.0042 (2)	0.0042 (2)	0.0066 (2)	0.0006 (2)	0.0012 (2)	0.0021 (2)
N3	0.0042 (2)	0.0039 (2)	0.0050 (2)	0.0008 (2)	0.0004 (2)	0.0008 (2)
N4	0.0037 (2)	0.0044 (2)	0.0050 (2)	0.0003 (2)	0.0010 (2)	−0.0002 (2)
C1	0.0049 (3)	0.0040 (3)	0.0037 (3)	−0.0006 (2)	0.0003 (2)	−0.0001 (2)
C2	0.0049 (3)	0.0060 (3)	0.0058 (3)	−0.0015 (3)	0.0007 (2)	−0.0011 (3)
H2	0.0201 (8)	0.0204 (9)	0.0196 (9)	−0.0064 (8)	0.0034 (7)	−0.0090 (8)
C3	0.0046 (3)	0.0073 (3)	0.0066 (3)	−0.0012 (2)	0.0015 (2)	−0.0003 (3)
H3	0.0142 (8)	0.0273 (11)	0.0261 (11)	−0.0092 (8)	0.0048 (7)	−0.0043 (9)
C4	0.0058 (3)	0.0060 (3)	0.0060 (3)	0.0009 (3)	0.0019 (2)	0.0005 (3)
H4	0.0166 (8)	0.0261 (11)	0.0210 (9)	−0.0002 (8)	0.0104 (7)	−0.0041 (8)
C5	0.0075 (3)	0.0056 (3)	0.0052 (3)	−0.0002 (3)	0.0015 (2)	−0.0010 (3)
H5	0.0256 (10)	0.0192 (9)	0.0207 (9)	−0.0031 (8)	0.0039 (8)	−0.0114 (8)
C6	0.0059 (3)	0.0045 (3)	0.0054 (3)	−0.0013 (2)	0.0012 (2)	−0.0015 (3)
H6	0.0157 (8)	0.0250 (10)	0.0257 (10)	−0.0110 (8)	0.0048 (7)	−0.0067 (8)
C7	0.0042 (3)	0.0033 (3)	0.0047 (3)	0.0002 (2)	0.0004 (2)	0.0006 (2)
H7	0.0124 (6)	0.0155 (8)	0.0183 (8)	0.0022 (6)	−0.0029 (6)	0.0026 (6)
C8	0.0073 (3)	0.0054 (3)	0.0062 (3)	−0.0007 (3)	0.0007 (3)	−0.0017 (3)
H8A	0.0312 (11)	0.0116 (8)	0.0280 (11)	−0.0027 (8)	0.0028 (9)	0.0024 (8)
H8B	0.0227 (9)	0.0278 (11)	0.0219 (9)	−0.0005 (9)	0.0113 (8)	−0.0071 (9)
H8C	0.0184 (9)	0.0272 (11)	0.0203 (9)	0.0039 (8)	−0.0065 (7)	−0.0037 (8)
C9	0.0040 (3)	0.0031 (3)	0.0041 (3)	0.0000 (2)	0.0008 (2)	0.0006 (2)
C10	0.0040 (3)	0.0034 (3)	0.0046 (3)	0.0002 (2)	0.0006 (2)	0.0007 (2)
C11	0.0041 (3)	0.0033 (3)	0.0048 (3)	0.0005 (2)	0.0007 (2)	0.0006 (2)
H11	0.0181 (8)	0.0135 (8)	0.0214 (8)	0.0004 (7)	0.0037 (7)	0.0076 (7)
C12	0.0032 (3)	0.0040 (3)	0.0056 (3)	0.0003 (2)	0.0013 (2)	0.0007 (2)
C13	0.0039 (3)	0.0039 (3)	0.0064 (3)	0.0003 (2)	0.0009 (2)	0.0017 (2)
H13	0.0123 (7)	0.0177 (9)	0.0306 (11)	0.0072 (7)	0.0034 (7)	0.0074 (8)

Geometric parameters (Å, º)

O1—N3	1.239 (1)	C3—H3	1.089 (2)
O1—H1N	1.971 (3)	C4—C5	1.400 (1)
O2—N3	1.223 (1)	C4—H4	1.090 (2)
O3—N4	1.229 (1)	C5—C6	1.395 (1)
O4—N4	1.234 (1)	C5—H5	1.084 (2)
N1—C9	1.338 (1)	C6—H6	1.086 (2)
N1—C7	1.473 (1)	C7—C8	1.532 (1)
N1—H1N	1.013 (2)	C7—H7	1.101 (2)
N2—C13	1.321 (1)	C8—H8A	1.094 (3)
N2—C9	1.361 (1)	C8—H8B	1.098 (2)
N3—C10	1.454 (1)	C8—H8C	1.093 (2)
N4—C12	1.447 (1)	C9—C10	1.437 (1)
C1—C2	1.397 (1)	C10—C11	1.381 (1)
C1—C6	1.403 (1)	C11—C12	1.387 (1)
C1—C7	1.521 (1)	C11—H11	1.084 (2)
C2—C3	1.401 (1)	C12—C13	1.398 (1)
C2—H2	1.089 (2)	C13—H13	1.090 (2)
C3—C4	1.395 (1)
N3—O1—H1N	105.6 (1)	C1—C6—H6	119.6 (2)
C9—N1—C7	123.85 (6)	N1—C7—C1	107.46 (7)
C9—N1—H1N	117.0 (1)	N1—C7—C8	110.40 (7)
C7—N1—H1N	118.2 (1)	C1—C7—C8	114.39 (7)
C13—N2—C9	119.59 (7)	N1—C7—H7	106.4 (1)
O2—N3—O1	123.21 (9)	C1—C7—H7	109.1 (1)
O2—N3—C10	118.47 (8)	C8—C7—H7	108.8 (1)
O1—N3—C10	118.30 (8)	C7—C8—H8A	110.9 (2)
O3—N4—O4	123.82 (8)	C7—C8—H8B	109.9 (2)
O3—N4—C12	117.98 (7)	H8A—C8—H8B	108.3 (2)
O4—N4—C12	118.20 (7)	C7—C8—H8C	110.8 (2)
C2—C1—C6	118.60 (8)	H8A—C8—H8C	108.1 (2)
C2—C1—C7	122.47 (8)	H8B—C8—H8C	108.8 (2)
C6—C1—C7	118.93 (8)	N1—C9—N2	116.87 (7)
C1—C2—C3	120.65 (8)	N1—C9—C10	123.57 (7)
C1—C2—H2	120.7 (1)	N2—C9—C10	119.56 (7)
C3—C2—H2	118.7 (2)	C11—C10—C9	120.51 (7)
C4—C3—C2	120.37 (8)	C11—C10—N3	116.60 (7)
C4—C3—H3	120.2 (2)	C9—C10—N3	122.87 (7)
C2—C3—H3	119.5 (2)	C10—C11—C12	117.47 (8)
C3—C4—C5	119.32 (8)	C10—C11—H11	121.0 (1)
C3—C4—H4	119.5 (2)	C12—C11—H11	121.5 (1)
C5—C4—H4	121.2 (2)	C11—C12—C13	120.00 (8)
C6—C5—C4	120.13 (8)	C11—C12—N4	119.70 (7)
C6—C5—H5	119.8 (2)	C13—C12—N4	120.22 (7)
C4—C5—H5	120.0 (2)	N2—C13—C12	122.80 (8)
C5—C6—C1	120.92 (8)	N2—C13—H13	117.5 (2)
C5—C6—H6	119.5 (2)	C12—C13—H13	119.7 (2)

(MBADNPX)

Crystal data

C13H12N4O4	F(000) = 300
Mr = 288.27	Dx = 1.505 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.352 (3) Å	Cell parameters from 4 reflections
b = 8.570 (3) Å	θ = 10–12°
c = 8.909 (4) Å	µ = 0.12 mm^−1
β = 93.98 (2)°	T = 20 K
V = 636.1 (4) Å^3	Block, yellow
Z = 2	0.30 × 0.26 × 0.20 mm

Data collection

Fddd cryo- diffractometer at Durham, UK	7613 reflections with I > 2σ(I)
Radiation source: Rotating-anode	Rint = 0.020
Graphite monochromator	θmax = 40.0°, θmin = 2.3°
ω scans	h = −15→15
Absorption correction: integration Gaussian integration (Coppens et al, 1965)	k = −15→15
Tmin = 0.977, Tmax = 0.982	l = −16→16
16427 measured reflections	4 standard reflections every 146 reflections
7873 independent reflections	intensity decay: none

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)] = 0.033	All H-atom parameters refined
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
7873 reflections	Δρmax = 0.61 e Å^−3
238 parameters	Δρmin = −0.27 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 The absolute structure is known a priori from the reagents used in the synthesis (see paper).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.8 (4)

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
O1	−0.15648 (6)	0.96551 (7)	0.73211 (6)	0.01176 (9)
O2	−0.01934 (7)	1.06874 (7)	0.55883 (6)	0.01235 (9)
O3	0.51597 (7)	0.89231 (7)	0.49339 (6)	0.01130 (9)
O4	0.61185 (6)	0.69626 (7)	0.62699 (6)	0.01120 (9)
N1	−0.08107 (7)	0.67476 (7)	0.82450 (6)	0.00877 (8)
H1N	−0.164 (2)	0.742 (2)	0.8061 (19)	0.018 (4)*
N2	0.17858 (7)	0.60322 (7)	0.78756 (6)	0.00886 (8)
N3	−0.03936 (7)	0.96739 (7)	0.65346 (6)	0.00845 (8)
N4	0.50111 (6)	0.78433 (7)	0.58295 (6)	0.00827 (8)
C1	−0.24422 (7)	0.55578 (8)	1.00655 (7)	0.00819 (9)
C2	−0.38688 (8)	0.47035 (8)	1.00010 (7)	0.00953 (9)
H2	−0.4060 (19)	0.397 (2)	0.9235 (16)	0.013 (3)*
C3	−0.50551 (8)	0.50300 (8)	1.09942 (7)	0.01011 (10)
H3	−0.6058 (18)	0.447 (2)	1.0900 (16)	0.014 (3)*
C4	−0.48067 (8)	0.61837 (8)	1.20847 (7)	0.00994 (10)
H4	−0.565 (2)	0.643 (2)	1.2752 (17)	0.018 (3)*
C5	−0.33707 (8)	0.70299 (8)	1.21699 (7)	0.01017 (10)
H5	−0.3217 (17)	0.790 (2)	1.2959 (15)	0.013 (3)*
C6	−0.22103 (8)	0.67317 (8)	1.11588 (7)	0.00942 (9)
H6	−0.1242 (18)	0.734 (2)	1.1210 (15)	0.016 (3)*
C7	−0.11271 (7)	0.52580 (8)	0.89942 (7)	0.00802 (9)
H7	−0.0208 (17)	0.497 (2)	0.9604 (14)	0.011 (3)*
C8	−0.15248 (8)	0.39822 (8)	0.78313 (7)	0.01029 (10)
H8A	−0.1605 (19)	0.297 (2)	0.8342 (18)	0.020 (4)*
H8B	−0.054 (2)	0.386 (2)	0.7126 (16)	0.024 (4)*
H8C	−0.2596 (18)	0.428 (2)	0.7189 (16)	0.018 (4)*
C9	0.05719 (7)	0.70826 (8)	0.76395 (7)	0.00780 (9)
C10	0.08164 (7)	0.84630 (8)	0.67686 (7)	0.00786 (9)
C11	0.22560 (8)	0.87036 (7)	0.61288 (7)	0.00809 (9)
H11	0.250 (2)	0.963 (3)	0.5622 (17)	0.027 (4)*
C12	0.34521 (7)	0.76037 (7)	0.64038 (7)	0.00812 (9)
C13	0.31782 (8)	0.62998 (8)	0.72973 (7)	0.00895 (9)
H13	0.4066 (19)	0.556 (2)	0.7516 (15)	0.017 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.01004 (18)	0.01083 (19)	0.0150 (2)	0.00199 (15)	0.00524 (15)	0.00194 (16)
O2	0.0141 (2)	0.01053 (19)	0.01266 (19)	0.00230 (16)	0.00249 (15)	0.00519 (16)
O3	0.0124 (2)	0.01058 (19)	0.01131 (18)	−0.00007 (16)	0.00365 (14)	0.00289 (15)
O4	0.00880 (18)	0.01028 (19)	0.0145 (2)	0.00173 (15)	0.00053 (14)	0.00138 (16)
N1	0.00862 (18)	0.00752 (19)	0.01038 (19)	0.00028 (15)	0.00225 (15)	0.00205 (15)
N2	0.00833 (18)	0.00780 (19)	0.01059 (19)	0.00079 (15)	0.00171 (14)	0.00115 (16)
N3	0.00894 (18)	0.00714 (18)	0.00932 (18)	0.00076 (15)	0.00099 (14)	−0.00006 (15)
N4	0.00837 (18)	0.00788 (19)	0.00866 (17)	0.00040 (15)	0.00126 (14)	−0.00059 (15)
C1	0.0087 (2)	0.0076 (2)	0.00837 (19)	−0.00015 (16)	0.00117 (15)	−0.00006 (16)
C2	0.0097 (2)	0.0098 (2)	0.0091 (2)	−0.00144 (18)	0.00098 (16)	−0.00049 (18)
C3	0.0093 (2)	0.0106 (2)	0.0105 (2)	−0.00107 (18)	0.00177 (17)	−0.00033 (18)
C4	0.0102 (2)	0.0099 (2)	0.0099 (2)	0.00067 (18)	0.00220 (16)	0.00031 (18)
C5	0.0120 (2)	0.0083 (2)	0.0104 (2)	0.00031 (18)	0.00205 (17)	−0.00059 (18)
C6	0.0096 (2)	0.0086 (2)	0.0102 (2)	−0.00105 (17)	0.00139 (16)	−0.00105 (17)
C7	0.0087 (2)	0.0069 (2)	0.0085 (2)	−0.00009 (16)	0.00134 (15)	0.00042 (16)
C8	0.0112 (2)	0.0093 (2)	0.0106 (2)	−0.00025 (18)	0.00176 (18)	−0.00148 (18)
C9	0.00818 (19)	0.0073 (2)	0.00802 (19)	−0.00015 (16)	0.00104 (15)	0.00029 (16)
C10	0.0084 (2)	0.0068 (2)	0.00844 (19)	0.00085 (16)	0.00094 (15)	0.00053 (16)
C11	0.00839 (19)	0.0076 (2)	0.00835 (19)	0.00010 (16)	0.00112 (15)	0.00035 (16)
C12	0.00795 (19)	0.0075 (2)	0.0091 (2)	−0.00028 (17)	0.00158 (15)	0.00024 (17)
C13	0.0084 (2)	0.0082 (2)	0.0104 (2)	0.00043 (17)	0.00146 (16)	0.00099 (17)

Geometric parameters (Å, º)

O1—N3	1.2422 (8)	C3—H3	0.966 (16)
O2—N3	1.2299 (8)	C4—C5	1.3990 (10)
O3—N4	1.2338 (8)	C4—H4	0.975 (17)
O4—N4	1.2364 (8)	C5—C6	1.3919 (10)
N1—C9	1.3391 (9)	C5—H5	1.026 (16)
N1—C7	1.4729 (10)	C6—H6	0.961 (17)
N1—H1N	0.903 (18)	C7—C8	1.5269 (10)
N2—C13	1.3242 (9)	C7—H7	0.942 (14)
N2—C9	1.3612 (9)	C8—H8A	0.98 (2)
N3—C10	1.4534 (9)	C8—H8B	1.074 (15)
N4—C12	1.4463 (9)	C8—H8C	1.058 (15)
C1—C2	1.3962 (10)	C9—C10	1.4371 (10)
C1—C6	1.4042 (10)	C10—C11	1.3814 (10)
C1—C7	1.5261 (10)	C11—C12	1.3829 (10)
C2—C3	1.4017 (10)	C11—H11	0.94 (2)
C2—H2	0.934 (16)	C12—C13	1.4000 (10)
C3—C4	1.3916 (10)	C13—H13	0.986 (17)
C9—N1—C7	123.73 (6)	N1—C7—C1	107.28 (5)
C9—N1—H1N	117.3 (11)	N1—C7—C8	110.52 (6)
C7—N1—H1N	118.4 (11)	C1—C7—C8	114.38 (6)
C13—N2—C9	119.35 (6)	N1—C7—H7	108.8 (10)
O2—N3—O1	123.07 (6)	C1—C7—H7	106.1 (8)
O2—N3—C10	118.44 (6)	C8—C7—H7	109.6 (10)
O1—N3—C10	118.48 (6)	C7—C8—H8A	109.6 (10)
O3—N4—O4	123.81 (6)	C7—C8—H8B	109.2 (10)
O3—N4—C12	117.95 (6)	H8A—C8—H8B	105.2 (15)
O4—N4—C12	118.24 (6)	C7—C8—H8C	109.4 (10)
C2—C1—C6	118.72 (6)	H8A—C8—H8C	112.1 (14)
C2—C1—C7	122.35 (6)	H8B—C8—H8C	111.1 (11)
C6—C1—C7	118.93 (6)	N1—C9—N2	116.73 (6)
C1—C2—C3	120.52 (6)	N1—C9—C10	123.56 (6)
C1—C2—H2	119.1 (9)	N2—C9—C10	119.71 (6)
C3—C2—H2	120.2 (9)	C11—C10—C9	120.40 (6)
C4—C3—C2	120.32 (6)	C11—C10—N3	116.79 (6)
C4—C3—H3	120.1 (9)	C9—C10—N3	122.80 (6)
C2—C3—H3	119.5 (9)	C10—C11—C12	117.64 (6)
C3—C4—C5	119.47 (6)	C10—C11—H11	123.0 (11)
C3—C4—H4	119.9 (10)	C12—C11—H11	119.0 (11)
C5—C4—H4	120.6 (10)	C11—C12—C13	120.02 (6)
C6—C5—C4	120.16 (6)	C11—C12—N4	119.84 (6)
C6—C5—H5	121.1 (8)	C13—C12—N4	120.07 (6)
C4—C5—H5	118.6 (8)	N2—C13—C12	122.82 (6)
C5—C6—C1	120.78 (6)	N2—C13—H13	118.7 (10)
C5—C6—H6	119.5 (9)	C12—C13—H13	118.5 (10)
C1—C6—H6	119.8 (9)