Quantitative analysis of hydrogen bonding and atomic thermal motion in the organic non-linear optical material DCNP using X-ray and neutron diffraction

A single-crystal neutron diffraction study of the organic non-linear optical material 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (hereafter DCNP), space group Cc, is presented. The study was conducted in order to relate the structural characteristics of the compound to its physical properties. DCNP exhibits a very large second harmonic generation (SHG) output, an extremely large linear electro-optical effect and photoconductive and pyroelectric properties. The nature of the hydrogen-bonding revealed by the study, in part, accounts for the first two of these phenomena. The neutron study also shows that some rather atypical atomic thermal motion is present in part of the molecule. With the aid of a variable-temperature single-crystal X-ray diffraction study, in conjunction with the neutron study, this thermal motion is attributed to libration and is fully characterized. As a result, suitable corrections to the bond geometry and the anisotropic displacement parameters of DCNP are made. The libration is also shown to enhance the SHG effect. The cell parameters from the variable-temperature X-ray study are also used in order to evaluate the thermal expansivity coefficients of DCNP.

S1. Refinement

The flack parameters do not resemble and true meaning since Mo Ka irradiation is not capable of discerning the correct absolute structure for C, H, N only containing compounds.

C1—C3 and C2—C3 are longer than usual due to the extremely electron withdrawing nature of the nitrile group.

Computing details

Data collection: SMART (Siemens Analytical X-ray Instruments, 1995) for 90dcnp, 200dcnp, 290dcnp; SMART (siemens Analytical X-ray Instruments, 1995) for 100dcnp; Local ISIS program for 100Ndcnp. Cell refinement: SMART (Siemens Analytical X-ray Instruments, 1995) for 90dcnp, 100dcnp, 200dcnp, 290dcnp; Local ISIS program for 100Ndcnp. Data reduction: SAINT (Siemens Analytical X-ray Instruments, 1995) for 90dcnp, 100dcnp, 200dcnp, 290dcnp; Local ISIS program for 100Ndcnp. Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for 90dcnp, 100dcnp, 200dcnp, 290dcnp; none for 100Ndcnp. For all compounds, program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

(90dcnp)

Crystal data

C13H10N4	Z = 4
Mr = 222.25	F(000) = 464
Monoclinic, Cc	Dx = 1.312 Mg m^−3
a = 11.5945 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2912 (4) Å	µ = 0.08 mm^−1
c = 7.8944 (2) Å	T = 90 K
β = 90.018 (1)°	Irregular, red
V = 1125.03 (5) Å^3	0.5 × 0.3 × 0.15 mm

Data collection

Siemens SMART-CCD diffractometer	1893 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ω scans	h = −14→15
3921 measured reflections	k = −12→15
2029 independent reflections	l = −10→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Xyz and Uiso refined
R[F^2 > 2σ(F^2)] = 0.035	Calculated w = 1/[σ^2(Fo^2) + (0.0274P)^2 + 0.5936P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max < 0.001
S = 1.16	Δρmax = 0.15 e Å^−3
2028 reflections	Δρmin = −0.16 e Å^−3
195 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0045 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −2.39 (236)

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 1 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 Rfactorobs 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
N1	0.5704 (2)	0.06007 (13)	1.3341 (2)	0.0312 (4)
N2	0.5034 (2)	0.39998 (13)	1.2328 (2)	0.0312 (4)
N3	0.3481 (2)	0.18991 (13)	0.7110 (2)	0.0248 (4)
N4	0.31107 (15)	0.26484 (14)	0.6017 (2)	0.0252 (4)
C1	0.5311 (2)	0.1224 (2)	1.2408 (3)	0.0249 (4)
C2	0.4949 (2)	0.31304 (15)	1.1826 (3)	0.0223 (4)
C3	0.4853 (2)	0.2017 (2)	1.1248 (3)	0.0213 (4)
C4	0.4370 (2)	0.1699 (2)	0.9753 (3)	0.0229 (4)
C5	0.3920 (2)	0.23780 (15)	0.8457 (2)	0.0211 (4)
C6	0.3391 (2)	0.3784 (2)	0.6549 (3)	0.0247 (4)
C7	0.3845 (2)	0.3613 (2)	0.8367 (3)	0.0246 (4)
C8	0.2632 (2)	0.2344 (2)	0.4455 (2)	0.0238 (4)
C9	0.2550 (2)	0.1249 (2)	0.4005 (3)	0.0289 (5)
C10	0.2048 (2)	0.0964 (2)	0.2467 (3)	0.0342 (5)
C11	0.1622 (2)	0.1762 (2)	0.1370 (3)	0.0389 (6)
C12	0.1701 (2)	0.2850 (2)	0.1814 (3)	0.0363 (6)
C13	0.2208 (2)	0.3159 (2)	0.3362 (3)	0.0291 (5)
H4	0.4372 (18)	0.0916 (16)	0.952 (3)	0.023 (6)*
H6A	0.3947 (18)	0.4085 (16)	0.582 (3)	0.023 (5)*
H6B	0.268 (2)	0.4237 (18)	0.653 (3)	0.031 (6)*
H7A	0.458 (2)	0.3947 (19)	0.854 (3)	0.034 (6)*
H7B	0.330 (2)	0.3863 (18)	0.923 (3)	0.031 (6)*
H9	0.283 (2)	0.0716 (19)	0.484 (4)	0.035 (7)*
H10	0.197 (2)	0.018 (2)	0.215 (4)	0.048 (8)*
H11	0.128 (3)	0.157 (3)	0.030 (4)	0.049 (8)*
H12	0.144 (2)	0.346 (2)	0.110 (4)	0.038 (8)*
H13	0.224 (2)	0.397 (2)	0.371 (3)	0.033 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0353 (9)	0.0263 (8)	0.0321 (10)	−0.0005 (7)	−0.0092 (8)	0.0003 (8)
N2	0.0349 (10)	0.0266 (9)	0.0319 (10)	−0.0022 (7)	−0.0076 (8)	−0.0034 (8)
N3	0.0270 (9)	0.0232 (8)	0.0244 (9)	0.0008 (6)	−0.0009 (7)	0.0003 (6)
N4	0.0325 (10)	0.0218 (9)	0.0214 (10)	0.0000 (7)	−0.0031 (8)	−0.0010 (7)
C1	0.0252 (10)	0.0216 (9)	0.0277 (11)	−0.0017 (7)	−0.0019 (9)	−0.0022 (8)
C2	0.0206 (10)	0.0224 (10)	0.0239 (10)	0.0000 (7)	−0.0003 (8)	0.0012 (8)
C3	0.0209 (10)	0.0204 (10)	0.0227 (10)	−0.0026 (7)	0.0000 (8)	−0.0015 (8)
C4	0.0239 (10)	0.0182 (9)	0.0267 (11)	−0.0004 (7)	−0.0002 (8)	−0.0011 (8)
C5	0.0216 (10)	0.0209 (9)	0.0207 (10)	−0.0012 (7)	0.0013 (8)	0.0001 (8)
C6	0.0301 (10)	0.0190 (9)	0.0250 (11)	0.0006 (8)	0.0008 (9)	0.0032 (8)
C7	0.0319 (11)	0.0190 (9)	0.0230 (10)	−0.0012 (8)	0.0011 (8)	0.0006 (8)
C8	0.0189 (10)	0.0321 (10)	0.0205 (10)	−0.0006 (8)	−0.0003 (8)	0.0007 (9)
C9	0.0275 (12)	0.0357 (12)	0.0236 (10)	−0.0066 (9)	0.0008 (9)	−0.0012 (9)
C10	0.0288 (11)	0.0496 (14)	0.0242 (10)	−0.0151 (9)	0.0012 (9)	−0.0076 (9)
C11	0.0238 (12)	0.069 (2)	0.0238 (11)	−0.0120 (10)	−0.0023 (9)	−0.0056 (12)
C12	0.0211 (12)	0.061 (2)	0.0266 (13)	0.0056 (10)	−0.0020 (10)	0.0081 (11)
C13	0.0229 (10)	0.0389 (12)	0.0254 (10)	0.0064 (9)	0.0000 (8)	0.0081 (10)

Geometric parameters (Å, º)

N1—C1	1.156 (3)	C6—H6B	1.00 (2)
N2—C2	1.144 (2)	C7—H7A	0.95 (3)
N3—C5	1.317 (3)	C7—H7B	0.98 (3)
N3—N4	1.333 (2)	C8—C9	1.395 (3)
N4—C8	1.404 (2)	C8—C13	1.411 (3)
N4—C6	1.493 (3)	C9—C10	1.391 (3)
C1—C3	1.439 (3)	C9—H9	0.98 (3)
C2—C3	1.446 (3)	C10—C11	1.399 (4)
C3—C4	1.364 (3)	C10—H10	1.00 (3)
C4—C5	1.420 (3)	C11—C12	1.385 (4)
C4—H4	0.98 (2)	C11—H11	0.96 (3)
C5—C7	1.522 (3)	C12—C13	1.408 (4)
C6—C7	1.543 (3)	C12—H12	0.99 (3)
C6—H6A	0.94 (2)	C13—H13	1.03 (2)
C5—N3—N4	109.8 (2)	C6—C7—H7A	112.3 (15)
N3—N4—C8	120.8 (2)	C5—C7—H7B	108.5 (13)
N3—N4—C6	113.2 (2)	C6—C7—H7B	112.7 (14)
C8—N4—C6	125.6 (2)	H7A—C7—H7B	110 (2)
N1—C1—C3	178.3 (2)	C9—C8—N4	120.5 (2)
N2—C2—C3	178.0 (2)	C9—C8—C13	120.4 (2)
C4—C3—C1	120.5 (2)	N4—C8—C13	119.0 (2)
C4—C3—C2	125.2 (2)	C10—C9—C8	119.5 (2)
C1—C3—C2	114.4 (2)	C10—C9—H9	123.7 (15)
C3—C4—C5	127.3 (2)	C8—C9—H9	116.7 (15)
C3—C4—H4	116.3 (14)	C9—C10—C11	120.8 (2)
C5—C4—H4	116.3 (14)	C9—C10—H10	119.9 (17)
N3—C5—C4	117.4 (2)	C11—C10—H10	119.2 (17)
N3—C5—C7	112.7 (2)	C12—C11—C10	119.8 (2)
C4—C5—C7	129.9 (2)	C12—C11—H11	119.4 (19)
N4—C6—C7	102.04 (15)	C10—C11—H11	120.9 (19)
N4—C6—H6A	110.3 (13)	C11—C12—C13	120.5 (2)
C7—C6—H6A	112.9 (13)	C11—C12—H12	124.4 (16)
N4—C6—H6B	109.7 (13)	C13—C12—H12	115.1 (17)
C7—C6—H6B	111.7 (14)	C12—C13—C8	119.0 (2)
H6A—C6—H6B	110.0 (18)	C12—C13—H13	120.4 (15)
C5—C7—C6	101.5 (2)	C8—C13—H13	120.6 (15)
C5—C7—H7A	111.7 (14)

(100dcnp)

Crystal data

C13H10N4	Z = 4
Mr = 222.25	F(000) = 464
Monoclinic, Cc	Dx = 1.313 Mg m^−3
a = 11.5972 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2873 (2) Å	µ = 0.08 mm^−1
c = 7.8877 (1) Å	T = 100 K
β = 90.021 (1)°	Irregular, red
V = 1123.98 (3) Å^3	0.5 × 0.3 × 0.15 mm

Data collection

Siemens SMART-CCD diffractometer	6421 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 53.7°, θmin = 2.4°
ω scans	h = −26→25
16798 measured reflections	k = −27→23
10048 independent reflections	l = −17→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)] = 0.076	All H-atom parameters refined
wR(F^2) = 0.075	Calculated w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
S = 2.38	(Δ/σ)max = 0.003
9977 reflections	Δρmax = 0.77 e Å^−3
194 parameters	Δρmin = −0.44 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.66 (88)

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 71 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 Rfactorobs 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
N1	0.57031 (6)	0.06009 (5)	1.33401 (9)	0.0314 (2)
N2	0.50383 (6)	0.40003 (5)	1.23365 (9)	0.0314 (2)
N3	0.34807 (6)	0.18977 (5)	0.71094 (9)	0.02323 (14)
N4	0.31106 (6)	0.26461 (5)	0.60155 (8)	0.02438 (14)
C1	0.53098 (7)	0.12240 (6)	1.24063 (10)	0.0243 (2)
C2	0.49505 (7)	0.31263 (6)	1.18214 (10)	0.02133 (15)
C3	0.48533 (6)	0.20168 (6)	1.12553 (10)	0.02010 (15)
C4	0.43697 (7)	0.16978 (6)	0.97498 (10)	0.02107 (15)
C5	0.39183 (6)	0.23780 (6)	0.84573 (9)	0.01953 (14)
C6	0.33923 (7)	0.37837 (6)	0.65496 (10)	0.0234 (2)
C7	0.38457 (7)	0.36109 (6)	0.83672 (10)	0.02311 (15)
C8	0.26309 (6)	0.23429 (6)	0.44577 (9)	0.0222 (2)
C9	0.25490 (7)	0.12493 (7)	0.40025 (10)	0.0275 (2)
C10	0.20489 (7)	0.09619 (8)	0.24698 (11)	0.0340 (2)
C11	0.16224 (7)	0.17644 (9)	0.13673 (12)	0.0391 (2)
C12	0.17053 (7)	0.28461 (9)	0.18307 (12)	0.0368 (2)
C13	0.22085 (7)	0.31530 (7)	0.33606 (11)	0.0286 (2)
H4	0.4365 (7)	0.0961 (6)	0.9541 (11)	0.022 (2)*
H6A	0.3936 (7)	0.4080 (6)	0.5786 (11)	0.023 (2)*
H6B	0.2679 (8)	0.4214 (7)	0.6519 (12)	0.032 (2)*
H7A	0.4611 (8)	0.3925 (7)	0.8514 (12)	0.028 (2)*
H7B	0.3290 (8)	0.3890 (7)	0.9196 (13)	0.035 (2)*
H9	0.2802 (8)	0.0735 (7)	0.4733 (12)	0.026 (2)*
H10	0.2019 (8)	0.0209 (8)	0.2108 (13)	0.037 (3)*
H11	0.1286 (10)	0.1539 (9)	0.0316 (16)	0.048 (3)*
H12	0.1457 (9)	0.3352 (9)	0.1149 (15)	0.045 (3)*
H13	0.2223 (9)	0.3929 (7)	0.3704 (13)	0.031 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0358 (4)	0.0260 (3)	0.0323 (4)	0.0000 (3)	−0.0097 (3)	0.0000 (3)
N2	0.0361 (4)	0.0271 (3)	0.0310 (4)	−0.0028 (3)	−0.0057 (3)	−0.0043 (3)
N3	0.0287 (3)	0.0195 (3)	0.0215 (3)	0.0000 (2)	−0.0001 (3)	0.0007 (2)
N4	0.0326 (4)	0.0198 (3)	0.0207 (3)	0.0004 (3)	−0.0015 (3)	−0.0005 (2)
C1	0.0251 (4)	0.0217 (3)	0.0262 (4)	−0.0019 (3)	−0.0015 (3)	−0.0029 (3)
C2	0.0208 (3)	0.0211 (4)	0.0221 (4)	−0.0010 (3)	−0.0008 (3)	0.0010 (3)
C3	0.0194 (3)	0.0185 (3)	0.0223 (4)	−0.0009 (3)	0.0004 (3)	0.0001 (3)
C4	0.0237 (3)	0.0154 (3)	0.0241 (4)	−0.0006 (3)	0.0012 (3)	−0.0005 (3)
C5	0.0220 (3)	0.0158 (3)	0.0208 (4)	−0.0008 (3)	0.0028 (3)	−0.0009 (3)
C6	0.0306 (4)	0.0157 (3)	0.0239 (4)	0.0010 (3)	0.0023 (3)	0.0025 (3)
C7	0.0321 (4)	0.0157 (3)	0.0216 (4)	0.0003 (3)	0.0021 (3)	0.0005 (3)
C8	0.0193 (4)	0.0293 (4)	0.0180 (4)	0.0002 (3)	0.0009 (3)	0.0004 (3)
C9	0.0268 (4)	0.0330 (4)	0.0228 (4)	−0.0057 (3)	0.0034 (3)	−0.0019 (3)
C10	0.0284 (4)	0.0493 (5)	0.0244 (4)	−0.0155 (4)	0.0028 (3)	−0.0102 (4)
C11	0.0225 (4)	0.0731 (7)	0.0217 (4)	−0.0117 (4)	−0.0009 (3)	−0.0061 (5)
C12	0.0228 (4)	0.0608 (6)	0.0268 (5)	0.0046 (4)	0.0004 (4)	0.0089 (4)
C13	0.0237 (4)	0.0384 (4)	0.0238 (4)	0.0055 (3)	0.0014 (3)	0.0077 (4)

Geometric parameters (Å, º)

N1—C1	1.1561 (10)	C6—H6B	0.982 (9)
N2—C2	1.1527 (10)	C7—H7A	0.975 (9)
N3—C5	1.3175 (10)	C7—H7B	0.980 (9)
N3—N4	1.3319 (9)	C8—C9	1.3941 (11)
N4—C8	1.3992 (9)	C8—C13	1.4069 (11)
N4—C6	1.4960 (10)	C9—C10	1.3864 (12)
C1—C3	1.4328 (11)	C9—H9	0.904 (9)
C2—C3	1.4390 (10)	C10—C11	1.405 (2)
C3—C4	1.3703 (12)	C10—H10	0.968 (10)
C4—C5	1.4183 (10)	C11—C12	1.382 (2)
C4—H4	0.920 (8)	C11—H11	0.957 (13)
C5—C7	1.5190 (10)	C12—C13	1.3923 (14)
C6—C7	1.5416 (12)	C12—H12	0.871 (12)
C6—H6A	0.945 (8)	C13—H13	0.991 (9)
C5—N3—N4	109.72 (6)	C6—C7—H7A	111.5 (5)
N3—N4—C8	120.86 (6)	C5—C7—H7B	110.7 (5)
N3—N4—C6	113.11 (6)	C6—C7—H7B	110.3 (6)
C8—N4—C6	125.65 (6)	H7A—C7—H7B	112.4 (8)
N1—C1—C3	178.24 (8)	C9—C8—N4	120.66 (7)
N2—C2—C3	177.36 (9)	C9—C8—C13	119.99 (8)
C4—C3—C1	120.38 (7)	N4—C8—C13	119.34 (7)
C4—C3—C2	124.88 (8)	C10—C9—C8	119.90 (8)
C1—C3—C2	114.74 (7)	C10—C9—H9	120.9 (6)
C3—C4—C5	127.25 (7)	C8—C9—H9	119.2 (6)
C3—C4—H4	116.0 (5)	C9—C10—C11	120.54 (9)
C5—C4—H4	116.7 (5)	C9—C10—H10	121.0 (6)
N3—C5—C4	117.26 (6)	C11—C10—H10	118.4 (6)
N3—C5—C7	112.81 (7)	C12—C11—C10	119.14 (9)
C4—C5—C7	129.92 (7)	C12—C11—H11	122.4 (7)
N4—C6—C7	101.98 (5)	C10—C11—H11	118.5 (7)
N4—C6—H6A	109.1 (5)	C11—C12—C13	121.26 (10)
C7—C6—H6A	114.7 (5)	C11—C12—H12	120.0 (8)
N4—C6—H6B	108.2 (5)	C13—C12—H12	118.7 (8)
C7—C6—H6B	112.6 (6)	C12—C13—C8	119.15 (9)
H6A—C6—H6B	109.8 (7)	C12—C13—H13	120.3 (6)
C5—C7—C6	101.52 (6)	C8—C13—H13	120.4 (6)
C5—C7—H7A	109.8 (5)

(200dcnp)

Crystal data

C13H10N4	Z = 4
Mr = 222.25	F(000) = 464
Monoclinic, Cc	Dx = 1.295 Mg m^−3
a = 11.7304 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3278 (2) Å	µ = 0.08 mm^−1
c = 7.8844 (2) Å	T = 200 K
β = 90.173 (2)°	Irregular, red
V = 1140.16 (5) Å^3	0.5 × 0.3 × 0.15 mm

Data collection

Siemens SMART-CCD diffractometer	2394 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ω scans	h = −15→15
4054 measured reflections	k = −11→16
2402 independent reflections	l = −9→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Xyz and Uiso refined
R[F^2 > 2σ(F^2)] = 0.046	Calculated w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 1.67	Δρmax = 0.22 e Å^−3
2394 reflections	Δρmin = −0.15 e Å^−3
195 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0200 (22)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 2.33 (205)

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 8 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 Rfactorobs 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
N1	0.5690 (2)	0.06091 (15)	1.3323 (2)	0.0626 (5)
N2	0.5044 (2)	0.39900 (15)	1.2326 (2)	0.0605 (5)
N3	0.3482 (2)	0.19070 (13)	0.7113 (2)	0.0436 (5)
N4	0.31131 (14)	0.26508 (13)	0.6017 (2)	0.0464 (5)
C1	0.5302 (2)	0.1232 (2)	1.2395 (3)	0.0467 (5)
C2	0.4958 (2)	0.3120 (2)	1.1825 (3)	0.0415 (5)
C3	0.4852 (2)	0.2022 (2)	1.1240 (3)	0.0390 (5)
C4	0.4373 (2)	0.1713 (2)	0.9748 (3)	0.0410 (5)
C5	0.3924 (2)	0.23847 (14)	0.8456 (2)	0.0382 (5)
C6	0.3385 (2)	0.3781 (2)	0.6557 (3)	0.0466 (6)
C7	0.3847 (2)	0.3605 (2)	0.8357 (3)	0.0455 (5)
C8	0.2631 (2)	0.2350 (2)	0.4462 (2)	0.0421 (5)
C9	0.2550 (2)	0.1261 (2)	0.4016 (3)	0.0518 (6)
C10	0.2040 (2)	0.0991 (3)	0.2481 (3)	0.0638 (7)
C11	0.1623 (2)	0.1777 (3)	0.1383 (4)	0.0709 (8)
C12	0.1706 (2)	0.2847 (3)	0.1832 (3)	0.0657 (8)
C13	0.2209 (2)	0.3155 (2)	0.3367 (3)	0.0543 (6)
H4	0.4352 (16)	0.0918 (14)	0.950 (3)	0.050 (6)*
H6A	0.3964 (17)	0.4057 (15)	0.585 (3)	0.060 (6)*
H6B	0.2659 (17)	0.4214 (15)	0.650 (2)	0.056 (6)*
H7A	0.4619 (18)	0.3950 (16)	0.855 (3)	0.056 (6)*
H7B	0.3339 (17)	0.3836 (14)	0.924 (3)	0.058 (6)*
H9	0.2856 (19)	0.0702 (17)	0.486 (3)	0.070 (7)*
H10	0.2004 (19)	0.0258 (19)	0.219 (3)	0.063 (7)*
H11	0.123 (2)	0.158 (2)	0.028 (4)	0.079 (8)*
H12	0.143 (2)	0.349 (2)	0.108 (3)	0.080 (9)*
H13	0.224 (2)	0.3918 (18)	0.366 (3)	0.059 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0752 (13)	0.0499 (11)	0.0626 (13)	0.0016 (9)	−0.0200 (10)	0.0029 (10)
N2	0.0719 (13)	0.0485 (11)	0.0608 (13)	−0.0038 (9)	−0.0116 (9)	−0.0100 (9)
N3	0.0550 (11)	0.0343 (9)	0.0414 (11)	−0.0004 (8)	−0.0005 (8)	0.0010 (7)
N4	0.0621 (12)	0.0361 (10)	0.0410 (12)	0.0000 (8)	−0.0016 (9)	−0.0003 (8)
C1	0.0477 (12)	0.0399 (12)	0.0524 (14)	−0.0011 (10)	−0.0051 (10)	−0.0059 (10)
C2	0.0421 (12)	0.0398 (14)	0.0426 (13)	−0.0020 (9)	−0.0010 (9)	0.0009 (9)
C3	0.0409 (13)	0.0367 (12)	0.0395 (12)	−0.0011 (8)	0.0026 (10)	−0.0003 (9)
C4	0.0446 (12)	0.0316 (12)	0.0469 (13)	−0.0013 (9)	0.0023 (9)	−0.0007 (9)
C5	0.0435 (12)	0.0321 (11)	0.0389 (13)	−0.0001 (9)	0.0042 (10)	−0.0022 (9)
C6	0.0565 (14)	0.0358 (12)	0.0475 (14)	0.0012 (10)	0.0020 (11)	0.0028 (10)
C7	0.0571 (14)	0.0337 (11)	0.0456 (12)	−0.0039 (11)	0.0043 (10)	−0.0005 (11)
C8	0.0376 (12)	0.0530 (13)	0.0357 (12)	0.0006 (9)	0.0030 (10)	−0.0014 (10)
C9	0.0519 (14)	0.059 (2)	0.0440 (13)	−0.0089 (12)	0.0060 (10)	−0.0049 (11)
C10	0.0593 (15)	0.083 (2)	0.0496 (14)	−0.0277 (13)	0.0051 (11)	−0.0186 (14)
C11	0.045 (2)	0.126 (3)	0.041 (2)	−0.0186 (14)	−0.0021 (11)	−0.005 (2)
C12	0.045 (2)	0.106 (2)	0.046 (2)	0.0024 (14)	−0.0034 (12)	0.012 (2)
C13	0.0492 (14)	0.068 (2)	0.0456 (13)	0.0081 (12)	0.0037 (10)	0.0114 (13)

Geometric parameters (Å, º)

N1—C1	1.153 (3)	C6—H6B	1.01 (2)
N2—C2	1.147 (2)	C7—H7A	1.01 (2)
N3—C5	1.316 (3)	C7—H7B	0.96 (2)
N3—N4	1.332 (2)	C8—C9	1.391 (3)
N4—C8	1.399 (2)	C8—C13	1.405 (3)
N4—C6	1.490 (3)	C9—C10	1.388 (3)
C1—C3	1.433 (3)	C9—H9	1.02 (2)
C2—C3	1.435 (3)	C10—C11	1.387 (4)
C3—C4	1.357 (3)	C10—H10	0.93 (2)
C4—C5	1.413 (3)	C11—C12	1.369 (4)
C4—H4	1.00 (2)	C11—H11	1.02 (3)
C5—C7	1.509 (3)	C12—C13	1.397 (4)
C6—C7	1.533 (3)	C12—H12	1.04 (3)
C6—H6A	0.95 (2)	C13—H13	0.97 (2)
C5—N3—N4	109.89 (15)	C6—C7—H7A	113.2 (11)
N3—N4—C8	121.08 (15)	C5—C7—H7B	107.1 (11)
N3—N4—C6	112.91 (15)	C6—C7—H7B	114.2 (12)
C8—N4—C6	125.7 (2)	H7A—C7—H7B	108.9 (17)
N1—C1—C3	178.3 (2)	C9—C8—N4	120.3 (2)
N2—C2—C3	178.6 (2)	C9—C8—C13	120.2 (2)
C4—C3—C1	120.7 (2)	N4—C8—C13	119.5 (2)
C4—C3—C2	125.4 (2)	C10—C9—C8	118.7 (2)
C1—C3—C2	113.9 (2)	C10—C9—H9	123.7 (14)
C3—C4—C5	127.8 (2)	C8—C9—H9	117.6 (14)
C3—C4—H4	116.9 (12)	C11—C10—C9	121.8 (3)
C5—C4—H4	115.3 (12)	C11—C10—H10	120.3 (15)
N3—C5—C4	117.5 (2)	C9—C10—H10	117.9 (15)
N3—C5—C7	112.4 (2)	C12—C11—C10	119.1 (2)
C4—C5—C7	130.1 (2)	C12—C11—H11	119.0 (16)
N4—C6—C7	101.9 (2)	C10—C11—H11	121.8 (16)
N4—C6—H6A	108.7 (12)	C11—C12—C13	121.1 (3)
C7—C6—H6A	110.4 (12)	C11—C12—H12	124.4 (16)
N4—C6—H6B	107.7 (11)	C13—C12—H12	114.5 (16)
C7—C6—H6B	114.3 (11)	C12—C13—C8	119.1 (3)
H6A—C6—H6B	113.0 (16)	C12—C13—H13	119.2 (15)
C5—C7—C6	102.1 (2)	C8—C13—H13	121.6 (16)
C5—C7—H7A	111.0 (11)

(290dcnp)

Crystal data

C13H10N4	Z = 4
Mr = 222.25	F(000) = 464
Monoclinic, Cc	Dx = 1.274 Mg m^−3
a = 11.8751 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3735 (5) Å	µ = 0.08 mm^−1
c = 7.8876 (3) Å	T = 290 K
β = 90.412 (2)°	Irregular, red
V = 1158.95 (8) Å^3	0.5 × 0.3 × 0.15 mm

Data collection

Siemens SMART-CCD diffractometer	1557 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ω scans	h = −14→15
4000 measured reflections	k = −13→16
2112 independent reflections	l = −10→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Xyz and Uiso refined
R[F^2 > 2σ(F^2)] = 0.051	Calculated w = 1/[σ^2(Fo^2) + (0.013P)^2 + 0.3922P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max < 0.001
S = 1.31	Δρmax = 0.11 e Å^−3
2098 reflections	Δρmin = −0.10 e Å^−3
195 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0116 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −1.67 (369)

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 14 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 Rfactorobs 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
N1	0.5680 (3)	0.0617 (2)	1.3306 (4)	0.0905 (11)
N2	0.5043 (3)	0.3978 (3)	1.2314 (5)	0.0890 (11)
N3	0.3487 (3)	0.1913 (2)	0.7106 (4)	0.0624 (8)
N4	0.3117 (3)	0.2651 (2)	0.6021 (3)	0.0676 (9)
C1	0.5296 (3)	0.1237 (3)	1.2380 (5)	0.0681 (10)
C2	0.4955 (3)	0.3117 (3)	1.1817 (5)	0.0627 (10)
C3	0.4852 (3)	0.2029 (3)	1.1231 (4)	0.0578 (9)
C4	0.4376 (3)	0.1725 (3)	0.9743 (5)	0.0587 (10)
C5	0.3924 (3)	0.2390 (2)	0.8453 (4)	0.0550 (8)
C6	0.3377 (4)	0.3779 (3)	0.6567 (5)	0.0674 (10)
C7	0.3852 (4)	0.3605 (3)	0.8359 (5)	0.0639 (9)
C8	0.2632 (3)	0.2358 (3)	0.4468 (4)	0.0608 (10)
C9	0.2547 (3)	0.1276 (3)	0.4016 (5)	0.0738 (11)
C10	0.2039 (4)	0.1005 (5)	0.2489 (6)	0.092 (2)
C11	0.1624 (4)	0.1796 (7)	0.1407 (7)	0.104 (2)
C12	0.1710 (4)	0.2852 (5)	0.1856 (6)	0.0930 (15)
C13	0.2215 (3)	0.3157 (4)	0.3378 (6)	0.0778 (11)
H4	0.435 (2)	0.097 (2)	0.950 (4)	0.055 (9)*
H6A	0.391 (3)	0.405 (2)	0.587 (5)	0.072 (10)*
H6B	0.260 (3)	0.419 (3)	0.651 (5)	0.099 (12)*
H7A	0.462 (3)	0.391 (3)	0.861 (5)	0.097 (12)*
H7B	0.331 (3)	0.383 (2)	0.915 (4)	0.069 (9)*
H9	0.285 (3)	0.073 (3)	0.487 (5)	0.082 (12)*
H10	0.197 (3)	0.030 (3)	0.224 (5)	0.081 (12)*
H11	0.129 (4)	0.162 (4)	0.028 (7)	0.107 (16)*
H12	0.139 (3)	0.352 (4)	0.114 (6)	0.099 (15)*
H13	0.224 (3)	0.393 (3)	0.365 (6)	0.087 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.108 (2)	0.072 (2)	0.091 (3)	0.004 (2)	−0.027 (2)	0.004 (2)
N2	0.105 (3)	0.069 (2)	0.092 (3)	−0.003 (2)	−0.016 (2)	−0.012 (2)
N3	0.076 (2)	0.0513 (14)	0.059 (2)	0.0011 (13)	−0.0042 (15)	0.0013 (14)
N4	0.090 (2)	0.053 (2)	0.061 (2)	−0.0020 (15)	−0.001 (2)	0.0009 (15)
C1	0.073 (2)	0.061 (2)	0.071 (3)	−0.001 (2)	−0.010 (2)	0.000 (2)
C2	0.064 (2)	0.058 (2)	0.066 (2)	−0.004 (2)	0.000 (2)	−0.001 (2)
C3	0.057 (2)	0.051 (2)	0.065 (2)	−0.0047 (14)	0.003 (2)	−0.001 (2)
C4	0.067 (2)	0.043 (2)	0.066 (2)	−0.0025 (15)	0.002 (2)	−0.002 (2)
C5	0.063 (2)	0.046 (2)	0.056 (2)	−0.003 (2)	0.006 (2)	0.000 (2)
C6	0.084 (3)	0.050 (2)	0.069 (3)	−0.003 (2)	0.005 (2)	0.004 (2)
C7	0.081 (3)	0.046 (2)	0.065 (2)	0.000 (2)	0.006 (2)	0.001 (2)
C8	0.058 (2)	0.071 (2)	0.054 (2)	0.002 (2)	0.004 (2)	0.002 (2)
C9	0.075 (3)	0.082 (3)	0.064 (2)	−0.013 (2)	0.005 (2)	−0.004 (2)
C10	0.087 (3)	0.120 (4)	0.069 (3)	−0.039 (3)	0.006 (2)	−0.023 (3)
C11	0.071 (3)	0.179 (6)	0.061 (3)	−0.027 (3)	−0.003 (2)	−0.007 (4)
C12	0.069 (3)	0.142 (4)	0.067 (3)	0.006 (3)	−0.008 (3)	0.015 (3)
C13	0.070 (3)	0.093 (3)	0.071 (3)	0.008 (2)	0.003 (2)	0.013 (3)

Geometric parameters (Å, º)

N1—C1	1.151 (4)	C6—H6B	1.06 (4)
N2—C2	1.140 (4)	C7—H7A	1.00 (4)
N3—C5	1.319 (4)	C7—H7B	0.94 (3)
N3—N4	1.324 (4)	C8—C9	1.390 (5)
N4—C8	1.397 (4)	C8—C13	1.398 (5)
N4—C6	1.493 (4)	C9—C10	1.385 (6)
C1—C3	1.433 (5)	C9—H9	1.02 (4)
C2—C3	1.428 (5)	C10—C11	1.387 (8)
C3—C4	1.352 (5)	C10—H10	0.90 (4)
C4—C5	1.411 (5)	C11—C12	1.357 (8)
C4—H4	0.95 (3)	C11—H11	1.00 (5)
C5—C7	1.508 (5)	C12—C13	1.390 (7)
C6—C7	1.534 (5)	C12—H12	1.07 (4)
C6—H6A	0.90 (3)	C13—H13	0.98 (4)
C5—N3—N4	109.8 (2)	C6—C7—H7A	117 (2)
N3—N4—C8	121.4 (2)	C5—C7—H7B	107.7 (18)
N3—N4—C6	113.1 (3)	C6—C7—H7B	108.4 (19)
C8—N4—C6	125.3 (3)	H7A—C7—H7B	112 (3)
N1—C1—C3	178.1 (4)	C9—C8—N4	120.2 (3)
N2—C2—C3	178.7 (4)	C9—C8—C13	119.9 (4)
C4—C3—C2	125.2 (3)	N4—C8—C13	119.9 (3)
C4—C3—C1	120.6 (3)	C10—C9—C8	119.1 (4)
C2—C3—C1	114.2 (3)	C10—C9—H9	124 (2)
C3—C4—C5	128.2 (3)	C8—C9—H9	117 (2)
C3—C4—H4	117.5 (19)	C9—C10—C11	121.0 (5)
C5—C4—H4	114.3 (19)	C9—C10—H10	118 (3)
N3—C5—C4	117.8 (2)	C11—C10—H10	121 (3)
N3—C5—C7	112.6 (3)	C12—C11—C10	119.5 (5)
C4—C5—C7	129.6 (3)	C12—C11—H11	119 (3)
N4—C6—C7	102.0 (3)	C10—C11—H11	122 (3)
N4—C6—H6A	109 (2)	C11—C12—C13	121.2 (5)
C7—C6—H6A	111 (2)	C11—C12—H12	126 (3)
N4—C6—H6B	105 (2)	C13—C12—H12	113 (3)
C7—C6—H6B	115 (2)	C12—C13—C8	119.2 (5)
H6A—C6—H6B	114 (3)	C12—C13—H13	118 (3)
C5—C7—C6	101.9 (3)	C8—C13—H13	123 (3)
C5—C7—H7A	109 (2)

(100Ndcnp)

Crystal data

C13H10N4	Z = 4
Mr = 222.00	F(000) = 388
Monoclinic, Cc	Dx = 1.321 Mg m^−3
a = 11.571 (2) Å	Pulsed neutrons at ISIS, U K radiation, λ = Variable (Time of flight) Å
b = 12.258 (3) Å	µ = Variable because time-of-flight (absorption changes with wavelength) mm^−1
c = 7.868 (2) Å	T = 100 K
β = 90.11 (3)°	Pointed needle, red
V = 1116.0 (4) Å^3	7 × 3 × 2 mm

Data collection

SXD at ISIS, UK diffractometer	1863 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.060
Laue diffraction scans	θmax = 78.0°, θmin = 2.3°
Absorption correction: semi-empirical (using intensity measurements) (Wilson, 1997)	h = 0→34
Tmin = ?, Tmax = ?	k = 0→38
7808 measured reflections	l = −27→23
1867 independent reflections

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)] = 0.073	All parameters refined
wR(F^2) = 0.083	Calculated w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
S = 4.02	(Δ/σ)max = 0.024
1863 reflections	Δρmax = 2.22 e Å^−3
244 parameters	Δρmin = −1.46 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (999)

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 Rfactorobs 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
N1	0.5701 (2)	0.0603 (2)	1.3336 (3)	0.0272 (5)
N2	0.5030 (2)	0.3998 (2)	1.2333 (3)	0.0281 (6)
N3	0.3479 (2)	0.1902 (2)	0.7115 (3)	0.0164 (4)
N4	0.3112 (2)	0.2653 (2)	0.6018 (3)	0.0196 (5)
C1	0.5311 (3)	0.1229 (2)	1.2386 (4)	0.0176 (6)
C2	0.4949 (3)	0.3122 (2)	1.1807 (4)	0.0188 (7)
C3	0.4857 (2)	0.2022 (2)	1.1260 (4)	0.0132 (6)
C4	0.4371 (3)	0.1696 (2)	0.9743 (4)	0.0147 (6)
C5	0.3919 (3)	0.2377 (2)	0.8453 (4)	0.0137 (6)
C6	0.3396 (3)	0.3781 (2)	0.6549 (4)	0.0192 (6)
C7	0.3840 (3)	0.3610 (2)	0.8368 (4)	0.0181 (6)
C8	0.2627 (2)	0.2349 (3)	0.4469 (4)	0.0187 (7)
C9	0.2549 (3)	0.1256 (3)	0.4005 (4)	0.0214 (7)
C10	0.2051 (3)	0.0958 (3)	0.2467 (4)	0.0300 (8)
C11	0.1625 (3)	0.1759 (4)	0.1371 (4)	0.0347 (9)
C12	0.1704 (3)	0.2854 (3)	0.1843 (5)	0.0329 (9)
C13	0.2216 (3)	0.3162 (3)	0.3365 (4)	0.0237 (8)
H4	0.4364 (6)	0.0851 (5)	0.9431 (8)	0.034 (2)
H6A	0.4044 (6)	0.4106 (6)	0.5676 (9)	0.043 (2)
H6B	0.2617 (6)	0.4293 (5)	0.6496 (9)	0.0368 (15)
H7A	0.4669 (6)	0.3991 (5)	0.8556 (9)	0.042 (2)
H7B	0.3234 (7)	0.3909 (5)	0.9306 (8)	0.042 (2)
H9	0.2865 (6)	0.0644 (5)	0.4845 (9)	0.037 (2)
H10	0.1971 (8)	0.0118 (7)	0.2116 (9)	0.057 (2)
H11	0.1231 (7)	0.1564 (10)	0.0156 (11)	0.066 (3)
H12	0.1383 (8)	0.3469 (9)	0.0972 (10)	0.057 (2)
H13	0.2263 (7)	0.3981 (6)	0.3674 (10)	0.047 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0338 (12)	0.0205 (10)	0.0273 (12)	0.0042 (9)	−0.0115 (10)	0.0033 (9)
N2	0.0321 (13)	0.0189 (11)	0.0331 (13)	−0.0034 (9)	−0.0038 (11)	−0.0091 (10)
N3	0.0236 (11)	0.0118 (9)	0.0138 (9)	0.0000 (8)	−0.0022 (8)	−0.0020 (7)
N4	0.0268 (13)	0.0164 (11)	0.0157 (11)	−0.0002 (9)	0.0000 (10)	−0.0006 (9)
C1	0.0181 (14)	0.0170 (13)	0.0177 (15)	0.0008 (11)	−0.0033 (12)	−0.0001 (11)
C2	0.017 (2)	0.0151 (15)	0.025 (2)	−0.0056 (11)	−0.0012 (13)	−0.0040 (12)
C3	0.0129 (14)	0.0120 (12)	0.0147 (13)	−0.0008 (10)	−0.0012 (11)	−0.0019 (11)
C4	0.0173 (14)	0.0105 (12)	0.0163 (13)	0.0025 (10)	0.0012 (11)	−0.0018 (11)
C5	0.0153 (14)	0.0094 (11)	0.0165 (14)	−0.0009 (10)	−0.0004 (12)	−0.0005 (11)
C6	0.023 (2)	0.0149 (14)	0.019 (2)	−0.0007 (11)	0.0025 (13)	0.0009 (12)
C7	0.023 (2)	0.0151 (13)	0.0162 (14)	−0.0008 (12)	0.0023 (12)	0.0010 (12)
C8	0.0139 (15)	0.023 (2)	0.019 (2)	−0.0003 (11)	0.0006 (13)	−0.0017 (12)
C9	0.020 (2)	0.028 (2)	0.0161 (14)	−0.0089 (13)	0.0019 (12)	−0.0014 (13)
C10	0.025 (2)	0.047 (2)	0.0185 (15)	−0.0188 (15)	0.0038 (13)	−0.0088 (15)
C11	0.015 (2)	0.071 (3)	0.018 (2)	−0.010 (2)	−0.0026 (14)	0.001 (2)
C12	0.014 (2)	0.064 (3)	0.021 (2)	0.002 (2)	0.0018 (14)	0.009 (2)
C13	0.015 (2)	0.038 (2)	0.0183 (15)	0.0047 (13)	0.0012 (12)	0.0099 (15)
H4	0.051 (4)	0.017 (3)	0.034 (3)	0.006 (3)	−0.008 (3)	−0.010 (3)
H6A	0.044 (4)	0.044 (4)	0.042 (4)	−0.020 (3)	0.007 (3)	0.013 (3)
H6B	0.037 (3)	0.030 (3)	0.043 (4)	0.013 (3)	0.000 (3)	−0.009 (3)
H7A	0.041 (4)	0.033 (3)	0.052 (4)	−0.017 (3)	−0.015 (3)	0.006 (3)
H7B	0.055 (4)	0.043 (4)	0.027 (3)	0.018 (3)	0.021 (3)	−0.001 (3)
H9	0.047 (4)	0.027 (3)	0.036 (4)	−0.006 (3)	0.004 (3)	0.003 (3)
H10	0.067 (5)	0.067 (5)	0.037 (4)	−0.029 (4)	0.009 (4)	−0.019 (4)
H11	0.037 (5)	0.123 (9)	0.038 (4)	−0.022 (4)	−0.015 (4)	−0.007 (5)
H12	0.044 (5)	0.089 (6)	0.038 (5)	0.015 (4)	0.001 (4)	0.021 (5)
H13	0.055 (5)	0.037 (4)	0.048 (5)	0.020 (4)	−0.004 (4)	0.006 (4)

Geometric parameters (Å, º)

N1—C1	1.161 (3)	C6—H6B	1.100 (7)
N2—C2	1.155 (3)	C7—H7A	1.077 (7)
N3—C5	1.306 (3)	C7—H7B	1.083 (9)
N3—N4	1.331 (3)	C8—C9	1.392 (5)
N4—C8	1.392 (3)	C8—C13	1.405 (4)
N4—C6	1.481 (4)	C9—C10	1.388 (4)
C1—C3	1.416 (4)	C9—H9	1.064 (8)
C2—C3	1.419 (4)	C10—C11	1.396 (6)
C3—C4	1.377 (4)	C10—H10	1.071 (10)
C4—C5	1.413 (4)	C11—C12	1.396 (6)
C4—H4	1.065 (7)	C11—H11	1.085 (8)
C5—C7	1.516 (4)	C12—C13	1.387 (5)
C6—C7	1.534 (4)	C12—H12	1.084 (10)
C6—H6A	1.093 (9)	C13—H13	1.035 (10)
C5—N3—N4	109.7 (2)	C6—C7—H7A	111.4 (5)
N3—N4—C8	120.6 (2)	C5—C7—H7B	110.3 (5)
N3—N4—C6	113.1 (2)	C6—C7—H7B	111.9 (4)
C8—N4—C6	125.9 (2)	H7A—C7—H7B	109.7 (6)
N1—C1—C3	178.0 (3)	N4—C8—C9	120.9 (3)
N2—C2—C3	176.6 (3)	N4—C8—C13	119.2 (3)
C4—C3—C1	119.6 (2)	C9—C8—C13	119.9 (3)
C4—C3—C2	124.6 (3)	C10—C9—C8	120.6 (3)
C1—C3—C2	115.8 (2)	C10—C9—H9	119.9 (5)
C3—C4—C5	127.0 (2)	C8—C9—H9	119.6 (4)
C3—C4—H4	119.0 (4)	C9—C10—C11	120.0 (3)
C5—C4—H4	114.0 (4)	C9—C10—H10	120.9 (5)
N3—C5—C4	117.3 (2)	C11—C10—H10	119.1 (5)
N3—C5—C7	112.7 (2)	C10—C11—C12	119.3 (3)
C4—C5—C7	130.0 (2)	C10—C11—H11	122.4 (8)
N4—C6—C7	102.1 (2)	C12—C11—H11	118.3 (8)
N4—C6—H6A	108.4 (5)	C13—C12—C11	121.2 (3)
C7—C6—H6A	114.1 (4)	C13—C12—H12	120.1 (7)
N4—C6—H6B	109.9 (4)	C11—C12—H12	118.6 (7)
C7—C6—H6B	112.7 (4)	C12—C13—C8	119.0 (3)
H6A—C6—H6B	109.4 (6)	C12—C13—H13	119.3 (5)
C5—C7—C6	101.4 (2)	C8—C13—H13	121.7 (5)
C5—C7—H7A	111.9 (4)