(R)-(–)-6-(4-Amino­phen­yl)-5-methyl-4,5-dihydro­pyridazin-3(2H)-one

The title compound, C₁₁H₁₃N₃O, is a key inter­mediate in the synthesis of cardiotonic agents. The asymmetric unit consists of two mol­ecules of the same enanti­omer and the crystal packing is stabilized by inter­molecular N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.046
• wR factor = 0.128
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.11
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4A    ...          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               2743
           Count of symmetry unique reflns         2765
           Completeness (_total/calc)             99.20%
           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         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 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
   4 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

(R)-(-)-6-(4-Aminophenyl)-5-methyl-4,5-dihydropyridazin-3(2H)-one

Crystal data

C11H13N3O	Dx = 1.273 Mg m^−3
Mr = 203.24	Melting point: 474 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2ab	Cell parameters from 13069 reflections
a = 9.765 (2) Å	θ = 3.0–27.5°
b = 11.552 (2) Å	µ = 0.09 mm^−1
c = 18.796 (4) Å	T = 293 K
V = 2120.3 (7) Å^3	Plate, colorless
Z = 8	0.51 × 0.16 × 0.06 mm
F(000) = 864

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer	2743 independent reflections
Radiation source: rotating anode	1914 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
oscillation scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.942, Tmax = 0.995	k = −14→14
20514 measured reflections	l = −24→24

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 0.0063P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2743 reflections	Δρmax = 0.18 e Å^−3
272 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (18)

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	0.3311 (3)	0.09188 (16)	0.19959 (12)	0.0779 (6)
O2	0.4972 (3)	0.71471 (16)	0.45000 (12)	0.0818 (7)
C1	0.2858 (3)	0.7887 (2)	0.30168 (16)	0.0590 (7)
C2	0.3453 (3)	0.7465 (2)	0.23932 (16)	0.0585 (7)
H2A	0.3904	0.7974	0.2090	0.070*
C3	0.3385 (3)	0.6319 (2)	0.22203 (15)	0.0566 (7)
H3A	0.3805	0.6063	0.1805	0.068*
C4	0.2693 (3)	0.5513 (2)	0.26558 (14)	0.0515 (6)
C5	0.2056 (3)	0.5956 (2)	0.32629 (15)	0.0620 (7)
H5A	0.1556	0.5458	0.3552	0.074*
C6	0.2146 (3)	0.7109 (2)	0.34457 (17)	0.0671 (8)
H6A	0.1726	0.7370	0.3860	0.081*
C7	0.2702 (3)	0.4281 (2)	0.24753 (13)	0.0500 (6)
C8	0.3141 (3)	0.1931 (2)	0.21840 (15)	0.0580 (7)
C9	0.2695 (3)	0.2279 (2)	0.29134 (15)	0.0611 (7)
H9A	0.3495	0.2347	0.3216	0.073*
H9B	0.2115	0.1677	0.3109	0.073*
C10	0.1925 (3)	0.3408 (2)	0.29219 (14)	0.0545 (6)
H10A	0.1875	0.3691	0.3413	0.065*
C11	0.0457 (3)	0.3280 (3)	0.2626 (2)	0.0869 (11)
H11A	−0.0039	0.2727	0.2907	0.130*
H11B	0.0498	0.3019	0.2141	0.130*
H11C	0.0000	0.4015	0.2645	0.130*
C12	0.3882 (3)	0.0142 (2)	0.52854 (17)	0.0663 (8)
C13	0.3260 (4)	0.0940 (2)	0.57308 (19)	0.0778 (10)
H13A	0.2799	0.0683	0.6134	0.093*
C14	0.3313 (3)	0.2097 (2)	0.55873 (16)	0.0683 (8)
H14A	0.2869	0.2609	0.5891	0.082*
C15	0.4014 (3)	0.2537 (2)	0.49978 (15)	0.0495 (6)
C16	0.4670 (3)	0.1725 (2)	0.45581 (15)	0.0564 (7)
H16A	0.5162	0.1986	0.4166	0.068*
C17	0.4607 (3)	0.0556 (2)	0.46902 (16)	0.0605 (7)
H17A	0.5043	0.0039	0.4386	0.073*
C18	0.4165 (3)	0.3785 (2)	0.48680 (14)	0.0505 (6)
C19	0.4549 (4)	0.6147 (2)	0.46004 (17)	0.0645 (8)
C20	0.3552 (4)	0.5810 (2)	0.51684 (17)	0.0751 (9)
H20A	0.2633	0.5792	0.4972	0.090*
H20B	0.3570	0.6380	0.5548	0.090*
C21	0.3916 (3)	0.4627 (2)	0.54652 (15)	0.0602 (7)
H21A	0.3149	0.4346	0.5753	0.072*
C22	0.5205 (5)	0.4653 (3)	0.59288 (19)	0.0987 (13)
H22A	0.5388	0.3890	0.6107	0.148*
H22B	0.5067	0.5174	0.6320	0.148*
H22C	0.5969	0.4913	0.5649	0.148*
N1	0.2975 (3)	0.90338 (19)	0.31962 (16)	0.0814 (8)
H1A	0.2604	0.9287	0.3581	0.098*
H1B	0.3420	0.9500	0.2924	0.098*
N2	0.3368 (3)	0.39839 (17)	0.19048 (12)	0.0563 (6)
N3	0.3379 (3)	0.28099 (18)	0.17307 (12)	0.0600 (6)
H3B	0.3554	0.2632	0.1296	0.072*
N4	0.3813 (4)	−0.1023 (2)	0.5425 (2)	0.1115 (13)
H4A	0.3378	−0.1268	0.5793	0.134*
H4B	0.4204	−0.1509	0.5144	0.134*
N5	0.4628 (3)	0.41106 (18)	0.42544 (12)	0.0572 (6)
N6	0.4942 (3)	0.52796 (17)	0.41767 (13)	0.0627 (6)
H6B	0.5443	0.5463	0.3818	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1068 (17)	0.0470 (11)	0.0800 (13)	−0.0139 (11)	0.0161 (14)	−0.0069 (10)
O2	0.1247 (19)	0.0431 (10)	0.0777 (13)	0.0035 (11)	0.0253 (14)	0.0018 (10)
C1	0.0566 (15)	0.0493 (14)	0.0710 (17)	0.0104 (12)	−0.0061 (14)	0.0005 (14)
C2	0.0573 (15)	0.0542 (14)	0.0641 (16)	−0.0019 (13)	0.0013 (14)	0.0071 (13)
C3	0.0593 (15)	0.0527 (15)	0.0578 (16)	−0.0027 (13)	0.0062 (14)	−0.0005 (12)
C4	0.0505 (14)	0.0489 (14)	0.0550 (14)	0.0019 (11)	0.0005 (12)	0.0062 (12)
C5	0.0686 (18)	0.0554 (15)	0.0620 (16)	0.0096 (14)	0.0125 (14)	0.0104 (13)
C6	0.0741 (18)	0.0593 (16)	0.0678 (17)	0.0152 (15)	0.0126 (16)	0.0010 (14)
C7	0.0477 (13)	0.0516 (14)	0.0507 (14)	0.0002 (11)	−0.0028 (11)	0.0068 (12)
C8	0.0642 (16)	0.0494 (14)	0.0605 (16)	−0.0113 (13)	0.0000 (14)	−0.0010 (12)
C9	0.0726 (17)	0.0546 (15)	0.0562 (15)	−0.0053 (13)	0.0024 (14)	0.0091 (13)
C10	0.0598 (16)	0.0540 (14)	0.0498 (14)	−0.0038 (12)	0.0034 (12)	0.0062 (12)
C11	0.0529 (17)	0.101 (3)	0.107 (3)	−0.0113 (16)	−0.0016 (18)	0.027 (2)
C12	0.0785 (19)	0.0413 (13)	0.079 (2)	−0.0056 (14)	0.0130 (16)	−0.0045 (14)
C13	0.095 (2)	0.0522 (16)	0.086 (2)	−0.0113 (16)	0.038 (2)	−0.0043 (15)
C14	0.0782 (19)	0.0477 (14)	0.0791 (19)	0.0000 (14)	0.0290 (17)	−0.0088 (14)
C15	0.0544 (14)	0.0434 (11)	0.0509 (13)	0.0023 (11)	−0.0008 (11)	−0.0050 (10)
C16	0.0667 (17)	0.0522 (14)	0.0503 (14)	0.0041 (13)	0.0045 (13)	−0.0035 (12)
C17	0.0704 (18)	0.0476 (14)	0.0636 (17)	0.0045 (13)	0.0066 (14)	−0.0089 (13)
C18	0.0588 (15)	0.0459 (13)	0.0466 (14)	0.0030 (11)	−0.0033 (12)	−0.0039 (11)
C19	0.088 (2)	0.0427 (15)	0.0627 (18)	0.0111 (13)	0.0038 (16)	0.0026 (13)
C20	0.104 (3)	0.0478 (14)	0.0731 (18)	0.0123 (16)	0.0277 (19)	0.0018 (14)
C21	0.0835 (19)	0.0427 (13)	0.0545 (15)	−0.0007 (13)	0.0107 (15)	−0.0023 (12)
C22	0.152 (4)	0.074 (2)	0.070 (2)	−0.007 (2)	−0.036 (2)	−0.0085 (17)
N1	0.092 (2)	0.0540 (14)	0.099 (2)	0.0059 (14)	0.0178 (17)	−0.0082 (14)
N2	0.0667 (14)	0.0451 (11)	0.0571 (13)	−0.0029 (10)	0.0079 (12)	0.0027 (10)
N3	0.0798 (15)	0.0496 (11)	0.0506 (12)	−0.0065 (11)	0.0054 (12)	−0.0007 (10)
N4	0.162 (3)	0.0435 (14)	0.129 (3)	−0.0089 (17)	0.070 (3)	−0.0045 (16)
N5	0.0769 (15)	0.0416 (11)	0.0532 (13)	0.0043 (10)	0.0004 (11)	−0.0013 (10)
N6	0.0885 (17)	0.0424 (11)	0.0573 (13)	0.0060 (12)	0.0119 (13)	0.0035 (10)

Geometric parameters (Å, º)

O1—C8	1.233 (3)	C13—C14	1.364 (4)
O2—C19	1.241 (3)	C13—H13A	0.9300
C1—N1	1.372 (3)	C14—C15	1.398 (4)
C1—C6	1.394 (4)	C14—H14A	0.9300
C1—C2	1.396 (4)	C15—C16	1.405 (4)
C2—C3	1.364 (4)	C15—C18	1.469 (3)
C2—H2A	0.9300	C16—C17	1.374 (4)
C3—C4	1.412 (4)	C16—H16A	0.9300
C3—H3A	0.9300	C17—H17A	0.9300
C4—C5	1.396 (4)	C18—N5	1.294 (4)
C4—C7	1.464 (3)	C18—C21	1.505 (4)
C5—C6	1.379 (4)	C19—N6	1.337 (3)
C5—H5A	0.9300	C19—C20	1.497 (4)
C6—H6A	0.9300	C20—C21	1.519 (4)
C7—N2	1.300 (3)	C20—H20A	0.9700
C7—C10	1.516 (4)	C20—H20B	0.9700
C8—N3	1.346 (3)	C21—C22	1.531 (5)
C8—C9	1.494 (4)	C21—H21A	0.9800
C9—C10	1.505 (4)	C22—H22A	0.9600
C9—H9A	0.9700	C22—H22B	0.9600
C9—H9B	0.9700	C22—H22C	0.9600
C10—C11	1.545 (4)	N1—H1A	0.8600
C10—H10A	0.9800	N1—H1B	0.8600
C11—H11A	0.9600	N2—N3	1.395 (3)
C11—H11B	0.9600	N3—H3B	0.8600
C11—H11C	0.9600	N4—H4A	0.8600
C12—N4	1.374 (3)	N4—H4B	0.8600
C12—C13	1.385 (4)	N5—N6	1.393 (3)
C12—C17	1.408 (4)	N6—H6B	0.8600
N1—C1—C6	121.5 (3)	C13—C14—H14A	118.9
N1—C1—C2	120.6 (3)	C15—C14—H14A	118.9
C6—C1—C2	117.9 (3)	C14—C15—C16	116.5 (2)
C3—C2—C1	121.2 (3)	C14—C15—C18	122.6 (2)
C3—C2—H2A	119.4	C16—C15—C18	120.8 (2)
C1—C2—H2A	119.4	C17—C16—C15	122.0 (3)
C2—C3—C4	121.7 (3)	C17—C16—H16A	119.0
C2—C3—H3A	119.2	C15—C16—H16A	119.0
C4—C3—H3A	119.2	C16—C17—C12	120.0 (3)
C5—C4—C3	116.5 (2)	C16—C17—H17A	120.0
C5—C4—C7	123.2 (2)	C12—C17—H17A	120.0
C3—C4—C7	120.3 (2)	N5—C18—C15	117.9 (2)
C6—C5—C4	121.9 (3)	N5—C18—C21	122.2 (2)
C6—C5—H5A	119.0	C15—C18—C21	119.6 (2)
C4—C5—H5A	119.0	O2—C19—N6	120.8 (3)
C5—C6—C1	120.7 (3)	O2—C19—C20	124.5 (3)
C5—C6—H6A	119.6	N6—C19—C20	114.7 (2)
C1—C6—H6A	119.6	C19—C20—C21	110.1 (3)
N2—C7—C4	116.8 (2)	C19—C20—H20A	109.6
N2—C7—C10	122.1 (2)	C21—C20—H20A	109.6
C4—C7—C10	121.0 (2)	C19—C20—H20B	109.6
O1—C8—N3	120.7 (3)	C21—C20—H20B	109.6
O1—C8—C9	123.9 (2)	H20A—C20—H20B	108.2
N3—C8—C9	115.4 (2)	C18—C21—C20	110.2 (2)
C8—C9—C10	112.9 (2)	C18—C21—C22	107.8 (3)
C8—C9—H9A	109.0	C20—C21—C22	112.6 (3)
C10—C9—H9A	109.0	C18—C21—H21A	108.7
C8—C9—H9B	109.0	C20—C21—H21A	108.7
C10—C9—H9B	109.0	C22—C21—H21A	108.7
H9A—C9—H9B	107.8	C21—C22—H22A	109.5
C9—C10—C7	108.7 (2)	C21—C22—H22B	109.5
C9—C10—C11	112.1 (3)	H22A—C22—H22B	109.5
C7—C10—C11	109.2 (2)	C21—C22—H22C	109.5
C9—C10—H10A	108.9	H22A—C22—H22C	109.5
C7—C10—H10A	108.9	H22B—C22—H22C	109.5
C11—C10—H10A	108.9	C1—N1—H1A	120.0
C10—C11—H11A	109.5	C1—N1—H1B	120.0
C10—C11—H11B	109.5	H1A—N1—H1B	120.0
H11A—C11—H11B	109.5	C7—N2—N3	117.0 (2)
C10—C11—H11C	109.5	C8—N3—N2	125.7 (2)
H11A—C11—H11C	109.5	C8—N3—H3B	117.1
H11B—C11—H11C	109.5	N2—N3—H3B	117.1
N4—C12—C13	121.0 (3)	C12—N4—H4A	120.0
N4—C12—C17	120.6 (3)	C12—N4—H4B	120.0
C13—C12—C17	118.4 (2)	H4A—N4—H4B	120.0
C14—C13—C12	121.0 (3)	C18—N5—N6	116.9 (2)
C14—C13—H13A	119.5	C19—N6—N5	127.0 (2)
C12—C13—H13A	119.5	C19—N6—H6B	116.5
C13—C14—C15	122.1 (3)	N5—N6—H6B	116.5
N1—C1—C2—C3	177.7 (3)	C14—C15—C16—C17	1.2 (4)
C6—C1—C2—C3	−2.4 (4)	C18—C15—C16—C17	176.4 (3)
C1—C2—C3—C4	1.1 (4)	C15—C16—C17—C12	−0.8 (5)
C2—C3—C4—C5	1.4 (4)	N4—C12—C17—C16	−179.9 (3)
C2—C3—C4—C7	−176.7 (3)	C13—C12—C17—C16	−0.8 (5)
C3—C4—C5—C6	−2.7 (4)	C14—C15—C18—N5	−168.8 (3)
C7—C4—C5—C6	175.3 (3)	C16—C15—C18—N5	16.3 (4)
C4—C5—C6—C1	1.5 (5)	C14—C15—C18—C21	17.1 (4)
N1—C1—C6—C5	−179.0 (3)	C16—C15—C18—C21	−157.7 (3)
C2—C1—C6—C5	1.1 (4)	O2—C19—C20—C21	−143.4 (3)
C5—C4—C7—N2	−178.0 (3)	N6—C19—C20—C21	38.6 (4)
C3—C4—C7—N2	0.0 (4)	N5—C18—C21—C20	29.5 (4)
C5—C4—C7—C10	4.1 (4)	C15—C18—C21—C20	−156.7 (3)
C3—C4—C7—C10	−177.9 (2)	N5—C18—C21—C22	−93.7 (3)
O1—C8—C9—C10	−152.0 (3)	C15—C18—C21—C22	80.1 (3)
N3—C8—C9—C10	29.2 (4)	C19—C20—C21—C18	−48.2 (4)
C8—C9—C10—C7	−46.6 (3)	C19—C20—C21—C22	72.2 (4)
C8—C9—C10—C11	74.2 (3)	C4—C7—N2—N3	−180.0 (2)
N2—C7—C10—C9	35.0 (3)	C10—C7—N2—N3	−2.2 (4)
C4—C7—C10—C9	−147.3 (2)	O1—C8—N3—N2	−172.6 (3)
N2—C7—C10—C11	−87.7 (3)	C9—C8—N3—N2	6.3 (4)
C4—C7—C10—C11	90.1 (3)	C7—N2—N3—C8	−21.2 (4)
N4—C12—C13—C14	−179.1 (4)	C15—C18—N5—N6	−171.3 (2)
C17—C12—C13—C14	1.8 (6)	C21—C18—N5—N6	2.5 (4)
C12—C13—C14—C15	−1.3 (6)	O2—C19—N6—N5	175.3 (3)
C13—C14—C15—C16	−0.2 (5)	C20—C19—N6—N5	−6.7 (5)
C13—C14—C15—C18	−175.3 (3)	C18—N5—N6—C19	−16.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O2^i	0.86	2.11	2.961 (4)	173
N6—H6B···O1^ii	0.86	2.02	2.883 (3)	177
N1—H1B···O1^iii	0.86	2.40	3.153 (4)	147
N3—H3B···O2^iv	0.86	2.15	2.921 (3)	149

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