4-Chloro­benzaldehyde (pyrazin-2-ylcarbon­yl)hydrazone

The title compound, C₁₂H₉ClN₄O, was prepared by the reaction of pyrazine-2-carboxylic acid hydrazide and 4-chloro­benzaldehyde in methanol. In the crystal structure, there is an intra­molecular N—H...N hydrogen bond, forming a five-membered ring, and an inter­molecular C—H...O hydrogen bond, resulting in a one-dimensional infinite chain along the a axis. Weak face-to-face π–π stacking inter­actions are also observed between two anti­parallel mol­ecules. These π–π stacking inter­actions further join the mol­ecules into a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.107
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT756_ALERT_4_C H...A   Calc     2.24000, Rep     2.24(3) ......  Senseless su
              H6   -O1      1.555   1.655

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

4-Chlorobenzaldehyde (pyrazine-2-carbonyl)hydrazone

Crystal data

C12H9ClN4O	F(000) = 268
Mr = 260.68	Dx = 1.473 Mg m^−3
Triclinic, P1	Melting point = 479–480 K
a = 5.8860 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.818 (2) Å	Cell parameters from 1017 reflections
c = 13.500 (4) Å	θ = 2.7–25.7°
α = 84.883 (5)°	µ = 0.32 mm^−1
β = 80.500 (5)°	T = 293 K
γ = 73.769 (4)°	Block, colourless
V = 587.7 (3) Å^3	0.22 × 0.18 × 0.10 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2055 independent reflections
Radiation source: fine-focus sealed tube	1350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.925, Tmax = 0.969	k = −9→9
3000 measured reflections	l = −16→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.1868P] where P = (Fo^2 + 2Fc^2)/3
2055 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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
Cl1	0.86529 (15)	−0.25496 (11)	0.97972 (6)	0.0746 (3)
O1	0.0420 (3)	0.3083 (2)	0.46929 (13)	0.0599 (5)
N1	0.0684 (4)	0.6053 (3)	0.19755 (17)	0.0571 (6)
N2	0.4740 (3)	0.4499 (3)	0.29061 (15)	0.0455 (5)
N3	0.4343 (4)	0.2867 (3)	0.47414 (16)	0.0508 (6)
H3A	0.554 (5)	0.311 (4)	0.441 (2)	0.061*
N4	0.4422 (4)	0.1945 (3)	0.56590 (15)	0.0479 (5)
C1	0.4860 (4)	0.5378 (3)	0.20140 (19)	0.0522 (7)
H1	0.6338	0.5489	0.1691	0.063*
C2	0.2867 (5)	0.6125 (3)	0.1555 (2)	0.0529 (7)
H2	0.3053	0.6704	0.0927	0.063*
C3	0.0565 (4)	0.5184 (3)	0.2872 (2)	0.0519 (7)
H3	−0.0923	0.5105	0.3200	0.062*
C4	0.2557 (4)	0.4399 (3)	0.33318 (18)	0.0400 (6)
C5	0.2314 (5)	0.3387 (3)	0.43219 (18)	0.0446 (6)
C6	0.6497 (5)	0.1414 (3)	0.59197 (19)	0.0475 (6)
H6	0.7781	0.1645	0.5481	0.057*
C7	0.6948 (4)	0.0457 (3)	0.68795 (18)	0.0427 (6)
C8	0.5124 (4)	0.0270 (3)	0.76430 (19)	0.0487 (6)
H8	0.3539	0.0776	0.7552	0.058*
C9	0.5636 (5)	−0.0660 (3)	0.85358 (19)	0.0511 (7)
H9	0.4403	−0.0793	0.9039	0.061*
C10	0.7990 (5)	−0.1388 (3)	0.86747 (19)	0.0485 (6)
C11	0.9826 (5)	−0.1205 (4)	0.7936 (2)	0.0547 (7)
H11	1.1409	−0.1706	0.8033	0.066*
C12	0.9299 (5)	−0.0273 (3)	0.7048 (2)	0.0522 (7)
H12	1.0542	−0.0129	0.6554	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0772 (6)	0.0819 (6)	0.0582 (5)	−0.0101 (4)	−0.0222 (4)	0.0172 (4)
O1	0.0577 (12)	0.0717 (13)	0.0549 (12)	−0.0335 (10)	0.0028 (9)	0.0036 (9)
N1	0.0459 (13)	0.0710 (16)	0.0555 (15)	−0.0166 (11)	−0.0157 (11)	0.0100 (12)
N2	0.0392 (12)	0.0512 (13)	0.0452 (12)	−0.0145 (9)	−0.0063 (10)	0.0094 (10)
N3	0.0516 (14)	0.0604 (15)	0.0402 (13)	−0.0224 (11)	0.0000 (11)	0.0110 (11)
N4	0.0556 (14)	0.0517 (13)	0.0365 (12)	−0.0197 (11)	−0.0027 (10)	0.0076 (10)
C1	0.0422 (15)	0.0647 (18)	0.0485 (16)	−0.0177 (13)	−0.0045 (13)	0.0106 (13)
C2	0.0542 (17)	0.0617 (18)	0.0446 (15)	−0.0201 (14)	−0.0133 (13)	0.0133 (13)
C3	0.0385 (14)	0.0639 (18)	0.0535 (16)	−0.0165 (13)	−0.0036 (13)	−0.0002 (14)
C4	0.0379 (13)	0.0403 (14)	0.0423 (14)	−0.0139 (11)	−0.0008 (11)	−0.0027 (11)
C5	0.0472 (15)	0.0457 (15)	0.0428 (15)	−0.0178 (12)	−0.0018 (13)	−0.0034 (12)
C6	0.0492 (16)	0.0526 (16)	0.0418 (14)	−0.0213 (12)	0.0018 (12)	0.0020 (12)
C7	0.0473 (15)	0.0440 (15)	0.0406 (14)	−0.0193 (12)	−0.0053 (12)	−0.0013 (11)
C8	0.0401 (14)	0.0561 (17)	0.0493 (16)	−0.0135 (12)	−0.0079 (12)	0.0045 (12)
C9	0.0478 (16)	0.0592 (17)	0.0452 (15)	−0.0173 (13)	−0.0029 (12)	0.0057 (13)
C10	0.0522 (16)	0.0462 (16)	0.0465 (15)	−0.0112 (12)	−0.0111 (13)	0.0011 (12)
C11	0.0407 (15)	0.0617 (18)	0.0607 (18)	−0.0084 (13)	−0.0142 (14)	−0.0017 (14)
C12	0.0421 (15)	0.0619 (18)	0.0527 (16)	−0.0174 (13)	0.0008 (13)	−0.0063 (13)

Geometric parameters (Å, º)

Cl1—C10	1.739 (3)	C3—H3	0.9300
O1—C5	1.222 (3)	C4—C5	1.498 (3)
N1—C2	1.330 (3)	C6—C7	1.463 (3)
N1—C3	1.335 (3)	C6—H6	0.9300
N2—C1	1.334 (3)	C7—C12	1.390 (3)
N2—C4	1.339 (3)	C7—C8	1.390 (3)
N3—C5	1.350 (3)	C8—C9	1.383 (3)
N3—N4	1.378 (3)	C8—H8	0.9300
N3—H3A	0.83 (3)	C9—C10	1.380 (3)
N4—C6	1.272 (3)	C9—H9	0.9300
C1—C2	1.376 (3)	C10—C11	1.374 (4)
C1—H1	0.9300	C11—C12	1.380 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.381 (3)	C12—H12	0.9300
C2—N1—C3	115.2 (2)	N4—C6—C7	122.9 (2)
C1—N2—C4	115.9 (2)	N4—C6—H6	118.6
C5—N3—N4	121.5 (2)	C7—C6—H6	118.6
C5—N3—H3A	117 (2)	C12—C7—C8	118.2 (2)
N4—N3—H3A	122 (2)	C12—C7—C6	118.9 (2)
C6—N4—N3	114.4 (2)	C8—C7—C6	122.9 (2)
N2—C1—C2	122.1 (2)	C9—C8—C7	120.9 (2)
N2—C1—H1	118.9	C9—C8—H8	119.6
C2—C1—H1	118.9	C7—C8—H8	119.6
N1—C2—C1	122.6 (2)	C10—C9—C8	119.5 (2)
N1—C2—H2	118.7	C10—C9—H9	120.3
C1—C2—H2	118.7	C8—C9—H9	120.3
N1—C3—C4	122.8 (2)	C11—C10—C9	120.8 (2)
N1—C3—H3	118.6	C11—C10—Cl1	119.4 (2)
C4—C3—H3	118.6	C9—C10—Cl1	119.8 (2)
N2—C4—C3	121.4 (2)	C10—C11—C12	119.3 (2)
N2—C4—C5	118.4 (2)	C10—C11—H11	120.3
C3—C4—C5	120.2 (2)	C12—C11—H11	120.3
O1—C5—N3	124.7 (2)	C11—C12—C7	121.3 (2)
O1—C5—C4	121.3 (2)	C11—C12—H12	119.3
N3—C5—C4	113.9 (2)	C7—C12—H12	119.3
C5—N3—N4—C6	174.4 (2)	C3—C4—C5—N3	−172.7 (2)
C4—N2—C1—C2	−0.4 (4)	N3—N4—C6—C7	178.2 (2)
C3—N1—C2—C1	−0.7 (4)	N4—C6—C7—C12	171.8 (2)
N2—C1—C2—N1	1.3 (4)	N4—C6—C7—C8	−9.4 (4)
C2—N1—C3—C4	−0.5 (4)	C12—C7—C8—C9	−1.7 (4)
C1—N2—C4—C3	−0.8 (4)	C6—C7—C8—C9	179.5 (2)
C1—N2—C4—C5	178.4 (2)	C7—C8—C9—C10	0.9 (4)
N1—C3—C4—N2	1.4 (4)	C8—C9—C10—C11	−0.3 (4)
N1—C3—C4—C5	−177.8 (2)	C8—C9—C10—Cl1	179.70 (19)
N4—N3—C5—O1	−1.0 (4)	C9—C10—C11—C12	0.4 (4)
N4—N3—C5—C4	179.1 (2)	Cl1—C10—C11—C12	−179.5 (2)
N2—C4—C5—O1	−171.9 (2)	C10—C11—C12—C7	−1.3 (4)
C3—C4—C5—O1	7.3 (4)	C8—C7—C12—C11	1.9 (4)
N2—C4—C5—N3	8.1 (3)	C6—C7—C12—C11	−179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2	0.83 (3)	2.27 (3)	2.689 (3)	111 (2)
C6—H6···O1^i	0.93	2.24 (3)	3.133 (3)	160 (2)

Symmetry code: (i) x+1, y, z.